grafted copolymer based on acrylic rubber, thermoplastic resin composition, and article

专利摘要:
COPOLYMER WITH ACRYLIC RUBBER GRAFT AND THERMOPLASTIC RESIN COMPOSITION. [Problem] To provide a graft copolymer based on acrylic rubber capable of providing a thermoplastic resin composition of which impact resistance, stiffness and external appearance are all excellent and to provide a thermoplastic resin composition that includes a graft copolymer to the acrylic rubber base. [Solution] A copolymer with a graft based on acrylic rubber is a copolymer with a graft obtained by polymerization with grafting of a vinyl monomer in the presence of a rubber polymer that includes acrylic ester based monomer units and polyfunctional monomer units, wherein the total volume of the polyfunctional monomer units in the rubber polymer is 0.3-3 parts by weight relative to 100 parts by weight of the acrylic ester based monomer units and 30-95% by weight of units of acrylic polyfunctional monomers having two unsaturated bonds and 5-70% by mass of polyfunctional monomer units having three unsaturated bonds in relation to 100 ° / o by mass of polyfunctional monomer units. A thermoplastic resin composition that includes the copolymer with acrylic rubber-based graft (...).
公开号:BR112013025003B1
申请号:R112013025003-8
申请日:2012-03-23
公开日:2020-12-01
发明作者:Kazuhiko Moeda；Takahiro Nakamura；Hironori Matsuyama
申请人:Techno-Umg Co., Ltd.；
IPC主号:

专利说明:

Field of the Invention
[0001] The present invention relates to grafted acrylic rubber copolymers that can be used as various industrial materials and thermoplastic resin compositions and molded articles of thermoplastic resin including copolymers. Background of the Technique
[0002] Thermoplastic resins such as styrene-acrylonitrile copolymer resins, styrene-acrylonitrile copolymer resins and styrene-acrylonitrile-phenylmaleimide copolymer resins are conventionally mixed with graft polymers obtained with graft polymer polymers. monomers that provide compatibility with resins. The resulting materials represented by ABS resins and ASA resins exhibit impact resistance and are widely used. Of these materials, ASA resins that involve such rubber polymers as alkyl (meth) acrylate saturated rubbers exhibit characteristically good weather resistance.
[0003] On the other hand, ASA resins have drawbacks due to the fact that colored molded articles present an unsatisfactory appearance due to reasons such as low color production as well as exhibiting low impact resistance. To improve the balance between mediocre appearance and impact resistance, ASA resins are proposed that involve, as components, rubbery acrylate ester polymers that have a combination of rubber particles with different particle diameter distributions (Patent Literature 1 to 3 ).
[0004] In addition, to complement the defects of ASA resins, a thermoplastic resin composition is proposed which involves an ASA resin in combination with an AES resin that includes an ethylene-propylene rubber component (Patent Literature 4).
[0005] However, these thermoplastic resin compositions are unsatisfactory in any of the properties of impact resistance, stiffness, resistance to weathering and staining with pigment and cannot sufficiently satisfy the recent needs of demand. Patent Literature Citation List
[0006] Patent Literature 1: JP 59-232138A
[0007] Patent Literature 2: JP 4-225051A
[0008] Patent Literature 3: JP 8-134312A
[0009] Patent Literature 4: JP 2004-346187A Purpose and Summary of the Invention
[00010] The present invention was obtained in view of the circumstances described above. It is, therefore, an object of the invention to provide grafted acrylic rubber copolymers which are themselves excellent in impact resistance, stiffness and appearance and are capable of providing thermoplastic resin compositions that exhibit excellent impact resistance, stiffness and appearance, as well as to provide thermoplastic resin compositions that include grafted acrylic rubber copolymers. Solution to the Problem
[00011] The present inventors carried out extensive studies to achieve the above objective. As a result, the present inventors have found that the goal is achieved with a grafted acrylic rubber copolymer obtained by polymerizing a vinyl monomer to a rubbery polymer that includes acrylate ester monomer units and is produced using specific polyfunctional monomers in combination with the acrylate ester monomer.
[00012] The present invention was realized based on the above discovery and is summarized as follows. [1] A grafted copolymer of acrylic rubber obtained by grafting polymerization of a vinyl monomer in the presence of a rubbery polymer that includes acrylate ester monomer units and polyfunctional monomer units, in which the total quantity of the polyfunctional monomer units in the rubbery polymer is 0.3 to 3 parts by weight relative to 100 parts by weight of the acrylate ester monomer units and the polyfunctional monomer units include 30 to 95% by weight of polyfunctional monomer units that have two unsaturated bonds and 5 to 70% by mass of polyfunctional monomer units that have three unsaturated bonds in relation to 100% by mass of the total polyfunctional monomer units. [2] The grafted acrylic rubber copolymer described in [1], wherein the rubbery polymer is a polymer obtained by mixing a copolymer latex obtained by polymerizing a monomer mixture that includes an acrylate ester monomer and polyfunctional monomers together with a copolymer latex that contains an acid group to increase the polymer and thereafter add a monomer that includes an acrylate ester monomer and polymerization of the monomer to the increased polymer. [3] The grafted acrylic rubber copolymer described in [1] or [2], in which the rubbery polymer has an average diameter in particle volume of 300 to 600 nm. [4] A thermoplastic resin composition that includes the grafted acrylic rubber copolymer described in any one of [1] to [3] (hereinafter referred to as "grafted acrylic rubber copolymer (A)"). [5] The thermoplastic resin composition described in [4], wherein the thermoplastic resin composition includes the grafted acrylic rubber copolymer (A) and a grafted acrylic rubber copolymer that has an average particle volume diameter of 70 to 200 nm and obtained by grafting polymerization of a vinyl monomer in the presence of a rubbery polymer that includes acrylate ester monomer units (hereinafter referred to as "grafted acrylic rubber copolymer (B)"). [6] The thermoplastic resin composition described in [5], wherein the thermoplastic resin composition includes the rubber polymers in a total amount of 5 to 30 parts by weight relative to 100 parts by mass of resin components in the composition thermoplastic resin and where the amount of rubbery polymer in the grafted acrylic rubber copolymer (A) is 20 to 70% by weight and the amount of the rubbery polymer in the grafted acrylic rubber copolymer (B) is 30 to 80% by weight in relation to the total of rubber polymers in the thermoplastic resin composition considered as 100% by mass. [7] The thermoplastic resin composition described in [5] or [6], which includes 0 to 90 parts by mass of an additional thermoplastic resin (C) other than the grafted acrylic rubber copolymer (A) and the grafted copolymer of acrylic rubber (B). [8] The thermoplastic resin composition described in any one of [5] to [7], wherein the copolymer grafted from acrylic rubber (B) into a polymer obtained in such a way that 100% by mass of an ester monomer of acrylate is polymerized at a polymerization rate of not less than 3% by mass / minute. [9] A molded article of thermoplastic resin obtained by molding the thermoplastic resin composition described in any one of [4] to [8]. Advantageous Effects of the Invention
[00013] The grafted acrylic rubber copolymers and thermoplastic resin compositions according to the present invention are excellent in impact resistance, stiffness and appearance as well as in the rest of these properties and also exhibit excellent resistance to the weather. As such, these materials are highly valuable in the industry and can be used in automotive materials, construction materials and appliances materials that are recently in increasing demand. Description of Modalities
[00014] Hereinafter, the modalities of the invention will be described in detail.
[00015] In this specification, the term "unit" indicates a part of the structure derived from a monomer compound (a monomer) prior to polymerization. For example, an "acrylate ester monomer unit" means a "part of the structure derived from an acrylate ester monomer".
[00016] In the specification, the term "(meth) acryl" means one or both of "acryl" and "methacryl". [Copolymers grafted from acrylic rubber (A)]
[00017] A grafted acrylic rubber copolymer of the invention (a grafted acrylic rubber copolymer (A)) is a grafted copolymer obtained by polymerizing a graft vinyl monomer in the presence of a rubbery polymer that includes acrylate ester monomer units and polyfunctional monomer units. The total amount of polyfunctional monomer units in the rubber polymer is 0.3 to 3 parts by weight relative to 100 parts by weight of the acrylate ester monomer units. Polyfunctional monomer units include 30 to 95% by mass of polyfunctional monomer units that have two unsaturated bonds and 5 to 70% by mass of polyfunctional monomer units that have three unsaturated bonds relative to 100% by mass of the total polyfunctional monomer units.
[00018] The rubbery polymer used in the grafted acrylic rubber copolymer (A) of the invention (hereinafter, sometimes called "rubbery polymer (a)") includes acrylate ester monomer units and polyfunctional monomer units as essential components.
[00019] Ester acrylate monomers are desirably alkyl acrylate esters having an alkyl group having 1 to 12 carbon atoms. Acrylic acid esters and linear or branched alcohols with 1 to 12 carbon atoms are used as such as alkyl acrylate esters. Examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate. In particular, those having an alkyl group having 1 to 8 carbon atoms are preferable. These esters can be used alone or two or more can be used in combination.
[00020] With respect to 100% by mass of the rubbery polymer (a), the content of the acrylate ester monomer units is preferably not less than 75% by mass, more preferably not less than 85% by mass and particularly of preference is not less than 95% by mass. If the content of the acrylate ester monomer units is less than the lower limit, the grafted acrylic rubber copolymer (A) that can be obtained and the thermoplastic resin composition that can be obtained can be deteriorated in any between weather resistance, impact resistance, stiffness and appearance.
[00021] In the rubbery polymer (a), the total content of the polyfunctional monomer units is 0.3 to 3 parts by weight with respect to 100 parts by weight of the acrylate ester monomer units and preferably not more than 2 parts by mass, particularly preferably not more than 1.5 parts by mass and preferably not less than 0.4 parts by mass, particularly preferably not less than 0.5 parts by mass. If the content of the polyfunctional monomer units exceeds the upper limit, the grafted acrylic rubber copolymer (A) that can be obtained and the thermoplastic resin composition that can be obtained can be deteriorated in impact resistance. Any content below the lower limit can result in a degradation in appearance.
[00022] Polyfunctional monomer units include polyfunctional monomer units that have two unsaturated bonds and polyfunctional monomer units that have three unsaturated bonds. In relation to the total of polyfunctional monomer units in the rubbery polymer (a) considered as 100% by mass, the proportion of polyfunctional monomer units that have two unsaturated bonds is 30 to 95% by mass and that of the polyfunctional monomer units showing three unsaturated bonds is 5 to 70% by mass. The proportion of polyfunctional monomer units which have two unsaturated bonds is most preferably not less than 35% by weight and that of polyfunctional monomer units which have three unsaturated bonds most preferably is not more than 65% by mass and the proportion of polyfunctional monomer units which have two unsaturated bonds particularly preferably is not less than 40% by weight and that of polyfunctional monomer units which have three unsaturated bonds particularly preferably is not more than 60% by weight. In addition, the proportion of polyfunctional monomer units which preferably have two unsaturated bonds is not greater than 90% by weight and that of the polyfunctional monomer units which have three unsaturated bonds preferably is not less than 10% by mass. and the proportion of the polyfunctional monomer units which have two unsaturated bonds particularly preferably is not more than 80% by weight and that of the polyfunctional monomer units which have three unsaturated bonds particularly preferably is not less than 20% by weight.
[00023] If the proportion of polyfunctional monomer units that have two unsaturated bonds is less than the lower limit and that of the polyfunctional monomer units that have three unsaturated bonds is in excess of the upper limit, the grafted acrylic rubber copolymer (A ) that can be obtained and the thermoplastic resin composition that can be obtained may be deteriorated in appearance. If the proportion of polyfunctional monomer units that have two unsaturated bonds is in excess of the upper limit and that of the polyfunctional monomer units that have three unsaturated bonds is less than the lower limit, the grafted acrylic rubber copolymer (A) that can obtained and the thermoplastic resin composition that can be obtained may be deteriorated in impact resistance and stiffness.
[00024] Examples of the polyfunctional monomers having two unsaturated bonds according to the invention include allyl methacrylate, di (di) acrylate esters such as ethylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate and 1, 6-hexanediol, 2-propenyl acrylate and divinylbenzene. In particular, those having an allyl group such as allyl methacrylate and 2-propenyl acrylate are preferable. Allyl methacrylate is particularly preferable in terms of the efficiency in improving the properties of the resin compositions obtainable.
[00025] Examples of polyfunctional monomers that have three or more unsaturated bonds include those that have an aromatic ring such as trialyl isocyanurate, trialyl cyanurate and trialyl trimellitate. In particular, trialyl isocyanurate and trialyl cyanurate having a triazine ring are preferable. In terms of polymerization stability, trialyl isocyanurate is particularly preferable.
[00026] These polyfunctional monomers that have two unsaturated bonds and these polyfunctional monomers that have three unsaturated bonds can each be used alone or as a mixture that includes two or more species of monomers.
[00027] In addition to the acrylate ester monomer and polyfunctional monomers, the rubbery polymer (a) can include an additional copolymerizable monomer with the acrylate ester monomer when necessary.
[00028] Examples of additional copolymerizable monomers with the acrylate ester monomer include aromatic vinyl monomers such as styrene, α-methylstyrene and p-methylstyrene, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile and methacrylate monomer such as methacrylate methyl, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate and 2-ethylhexyl methacrylate. These monomers can be used alone or two or more can be used in combination.
[00029] Furthermore, the rubbery polymer (a) can be a rubber composite formed between a rubbery polymer which includes acrylate ester monomer units and polyfunctional monomer units and a rubbery polymer composed of monomer units other than monomer units of acrylate ester. In this case, the rubbery polymer composed of monomer units other than acrylate ester monomer units can be, for example, ethylene-propylene rubber (EPR), ethylene-propylene-rubber diene (EPDM), rubber diene or polyorganosiloxane . The rubber composite can be obtained by a known method, for example, by polymerizing an acrylate ester monomer and polyfunctional monomers in the presence of a rubbery polymer composed of monomer units other than acrylate ester monomer units or by increasing an acrylate ester monomer. rubbery polymer composed of a monomer other than the acrylate ester monomer, together with a rubbery polymer that includes an acrylate ester monomer and polyfunctional monomers.
[00030] The rubbery polymer (a) according to the invention is preferably produced by emulsion polymerization of a mixture of the above monomers.
[00031] The emulsifier used in emulsion polymerization is preferably an anionic emulsifier because it allows excellent stability of the latex during emulsion polymerization and is responsible for an increase in the polymerization speed.
[00032] Examples of anionic emulsifiers include carboxylate salts (such as sodium sarcosinate, potassium fatty acid, sodium fatty acid, dipotassium alkenyl succinates and colophonium soap), alkyl sulfate ester salts, sodium alkenyl benzene sulfonates, sodium alkenyl sulfonates sodium and polyoxyethylene nonylphenyl ether sodium sulfate esters. From the point of view such as the suppression of hydrolysis of polyfunctional monomers, such emulsifiers as sodium sarcosinate, dipotassic alkenyl succinates, alkyl ester sulphate salts, sodium alkenyl benzene sulphonates, sodium alkyl sulfonates and non-ethylene phenyl isylphenyl ether sodium sulfate esters. . Of these, dipotassium alkenyl succinates are particularly preferable in aspects such as polymerization stability.
[00033] These emulsifiers can be used alone or two or more can be used as a mixture.
[00034] The rubbery polymer (a) used in the grafted acrylic rubber copolymer (A) of the invention is preferably produced by mixing a copolymer latex obtained by polymerizing a monomer mixture that includes an acrylate ester monomer and polyfunctional monomers , together with a copolymer latex that contains an acid group to increase the polymer. It is more preferable that a condensed acid salt is added before the copolymer latex containing the acid group is mixed. The increase in the above manner makes it possible to obtain a rubbery polymer (a) which has a desired volume average particle diameter. The addition of a condensed acid salt prevents the rubbery polymer from having more than 200 nm in particle diameter.
[00035] In the practice of raising the rubbery polymer (a), the condensed acid salt that is added before mixing a copolymer latex containing an acid group is a condensed acid salt of an acid such as phosphoric acid or acid silica with an alkali metal and / or an alkaline earth metal. A salt of pyrophosphoric acid, which is a condensed phosphoric acid, with an alkali metal is preferable. Sodium pyrophosphate or potassium pyrophosphate is particularly preferable. The amount of the condensed acid salt added is preferably 0.1 to 10 parts by weight and more preferably 0.5 to 7 parts by weight relative to 100 parts by weight (in terms of solid content) of the latex of copolymer obtained by polymerizing a monomer mixture that includes an acrylate ester monomer and polyfunctional monomers. If the amount of the condensed acid salt added is less than the lower limit, the increase does not occur sufficiently. If the condensed acid salt is added in excess of the upper limit, the increase may not occur sufficiently or the rubber latex may become unstable and large amounts of clots may form.
[00036] The copolymer latex that contains the acid group used in the augmentation is a latex of a copolymer that contains the acid group obtained by polymerization in water of a monomer mixture that includes a monomer that contains the acid group, a (met) alkyl acrylate monomer and optionally an additional copolymerizable monomer with these monomers.
[00037] The monomer containing the acid group is preferably an unsaturated compound having a carboxyl group. Examples of such compounds include (meth) acrylic acid, itaconic acid and crotonic acid, with (meth) acrylic acid being particularly preferable. The monomer containing the acid groups can be used alone or two or more can be used in combination.
[00038] Examples of alkyl (meth) acrylate ester monomers include esters of acrylic acid and / or methacrylic acid with alcohols having a linear or branched alkyl group with 1 to 12 carbon atoms, such as methyl acrylate , ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylate isobutyl, t-butyl methacrylate and 2-ethylhexyl methacrylate. The alkyl (meth) acrylate esters having an alkyl group having 1 to 8 carbon atoms are particularly preferable. The alkyl (meth) acrylate ester monomers can be used alone or two or more can be used in combination.
[00039] Additional monomers are monomers that can be copolymerized with the monomer that contains the acid groups and alkyl (meth) acrylate ester monomers and that are not monomers that contain the acid group or (meth) acrylate ester monomers alkyl. Examples of additional monomers include aromatic vinyl monomers (for example, styrene, α-methylstyrene and p-methylstyrene), unsaturated nitrile monomers (for example, acrylonitrile and methacrylonitrile) and compounds that have two or more polymerizable functional groups (for example , allyl methacrylate, polyethylene glycol ester dimethacrylate, trialyl cyanurate, trialyl isocyanurate and trialyl trimellitate). Additional monomers can be used alone or two or more can be used in combination.
[00040] The amounts of these used polymerizable monomers are such that in relation to 100% by weight of the acid group copolymer latex, the proportion of the monomer units containing the acid group is preferably 5 to 40% by weight, more preferably 8 to 30% by weight, the proportion of alkyl (meth) acrylate ester monomer units is preferably 60 to 95% by weight, more preferably 70 to 92% by weight and the proportion of units of additional copolymerizable monomers is preferably from 0 to 48% by weight, more preferably from 0 to 30% by weight. If the proportion of the monomer units containing the acid group is less than the lower limit, there will be no substantially increased performance. If the proportion of the monomer units that contain the acid group exceeds the upper limit, large amounts of clots will be formed during the production of the copolymer latex that contains the acid group.
[00041] The copolymer latex containing the acid group can be produced by a common emulsion polymerization method.
[00042] Emulsion polymerization can involve one or two or more species of known emulsifiers such as anionic emulsifiers selected from those emulsifiers that include carboxylic acid emulsifiers such as alkali metal salts of oleic acid, palmitic acid, stearic acid and of colophonium acid and alkali metal salts of alkenyl succinic acids, as well as alkyl sulfate esters, sodium alkenyl benzene sulfonates, sodium alkyl sulfonates and polyoxyethylene nonylphenyl ether sodium sulfate esters.
[00043] Emulsifiers can be used in such a way that the entire amount is added at an early stage of polymerization or such that a part of it is used at an early stage and the remainder is added intermittently or continuously during polymerization. The amount of emulsifiers and the way in which they are used affect the particle diameter of the copolymer latex that contains the acid group and thereby affect the particle diameter of a rubbery polymer latex (a) with a larger particle diameter. Thus, emulsifiers need to be added in an appropriate amount and in an appropriate manner.
[00044] Polymerization initiators such as initiators that can be thermally decomposed and redox initiators can be used in polymerization. Examples of the initiators that can be thermally decomposed include potassium persulfate, sodium persulfate and ammonium persulfate. Examples of the redox initiators include combinations of compounds such as organic peroxides represented by cumene hydroperoxide, sodium formaldehyde sulfoxylate and iron salts. These primers can be used alone or two or more can be used in combination.
[00045] In addition, chain transfer agents can be used to adjust the molecular weight, with examples including mercaptans such as t-dodecylmercaptone and n-octymercylptan, terpinolene and α-methylstyrene dimer. In addition, alkalis and acids can be added for pH adjustment and electrolytes can be added as viscosity-reducing agents.
[00046] The copolymer latex containing the acid group is preferably added in an amount of 0.1 to 10 parts by weight (in terms of solid content) and more preferably from 0.3 to 7 parts by weight with respect to to 100 parts by weight (in terms of solid content) of the copolymer latex obtained by polymerizing the monomer mixture which includes an acrylate ester monomer and polyfunctional monomers. If the amount of the copolymer latex containing the added acid group is less than the lower limit, the increase does not take place at a sufficient level and can result in the generation of large amounts of clots. If the copolymer latex containing the acid group is added in excess of the upper limit, the pH of the increased latex tends to be decreased and the latex tends to become unstable.
[00047] When the condensed acid salt is added before the copolymer latex containing the acid group is added to the copolymer latex obtained by polymerization the monomer mixture which includes an acrylate ester monomer and polyfunctional monomers, the pH of the mixture liquid is preferably not less than 7. If the pH is less than 7, the increase does not occur sufficiently. To obtain a pH of not less than 7, an alkaline compound in general such as sodium hydroxide or potassium hydroxide can be used.
[00048] The condensed acid salt is preferably added in one go before mixing the copolymer latex containing the acid group.
[00049] The copolymer latex containing the acid group is preferably added in one go or intermittently dropwise.
[00050] During the increase, it is necessary to control the agitation appropriately in an appropriate way. Insufficient agitation causes local increase and consequently leaves rubbery polymer components not enlarged. Excessive agitation destabilizes the increased latex and can result in the generation of large amounts of clots. The temperature during the increase is preferably 20 to 90 ° C and more preferably 30 to 80 ° C. If the temperature is outside this range, the increase may not occur sufficiently.
[00051] In the preparation of the rubbery polymer (a) used in the grafted acrylic rubber copolymer (A) of the invention, it is preferable that a monomer that includes an acrylate ester monomer be added further after the increase with the copolymer latex containing the acid group and be polymerized to the increased polymer. By carrying out this operation, the appearance of the grafted acrylic rubber copolymer (A) obtainable and the thermoplastic resin composition obtainable can be further improved.
[00052] The amount of the supplementary monomer that includes an acrylate ester monomer is preferably not more than 50% by weight, more preferably not more than 40% by weight, particularly preferably not more than 30% by weight and preferably not is less than 5% by weight, more preferably not less than 10% by weight, particularly preferably not less than 15% by weight in relation to the total monomers including the acrylate ester monomer used in the production of the rubber polymer ( a) considered as 100% by mass. The additional addition of the monomer that includes an acrylate ester monomer in excess of the upper limit results in the formation of rubbery polymer with a particle diameter of not more than 200 nm and may result in a deterioration in the impact resistance or in the appearance of the grafted copolymer of acrylic rubber (A) that can be obtained and in the thermoplastic resin composition that can be obtained. If the amount of the supplementary monomer that includes an acrylate ester monomer is less than the lower limit, the effects on improving appearance become insufficient.
[00053] The supplementary monomer which includes an acrylate ester monomer can be added in any way such as batch addition, portion addition or successive addition. Successive addition is more preferable to prevent deterioration in impact resistance or appearance due to the formation of rubbery polymer with a particle diameter of not more than 200 nm.
[00054] In this case, the monomer that includes an acrylate ester monomer is any acrylate ester monomer, the additional optional polyfunctional monomers and copolymerizable monomers mentioned above with these monomers and includes at least one acrylate ester monomer. That is, the monomer (s) can be an acrylate ester monomer (s) alone or it can be a mixture that includes an acrylate ester monomer and a polyfunctional monomer or a mixture which includes an acrylate ester monomer, a polyfunctional monomer and an additional monomer. A mixture that includes an acrylate ester monomer and a polyfunctional monomer is particularly preferable.
[00055] When monomers that include an acrylate ester monomer are added additionally, the polyfunctional monomers and optional additional monomers used before and after the increase can be added with different proportions. That is, the polyfunctional monomers and the optional additional monomers used in the polymerization stage the supplementary monomers that include an acrylate ester monomer after the increase can be added with different proportions than those of the polyfunctional monomers and the optional additional monomers used in the polymerization stage of the monomers that include an acrylate ester monomer prior to the increase. However, the total amount of the polyfunctional monomers and the optional additional monomers used after polymerization was completed to produce the rubbery polymer needed to be within the range mentioned above. The balance between impact strength, stiffness and appearance of the grafted acrylic rubber copolymer (A) obtainable and the thermoplastic resin composition obtainable tends to be improved by the use of relatively small amounts of polyfunctional monomers in the polymerization stage of monomers that include an acrylate ester monomer prior to the increase and by using relatively large amounts of polyfunctional monomers in the polymerization stage of supplementary monomers that include an acrylate ester monomer after the increase. In this case, as long as the proportion of the acrylate ester monomer used before the increase is X% by mass relative to the total amount of the acrylate ester monomer considered to be 100% by mass, the polyfunctional monomers used before the increase can be added in no greater than X% by weight, for example, 0.3X to X% by weight and the polyfunctional monomers used in the polymerization stage of supplementary monomers that include an acrylate ester monomer after the increase can be added in no less than (100 - X)% by weight, for example, (100 - X) to 2 x (100 - X)% by weight, in relation to the total amount of polyfunctional monomers considered to be 100% by weight.
[00056] The rubbery polymer (a) used in the grafted acrylic rubber copolymer (A) of the invention preferably has an average particle volume diameter of not less than 300 nm and more preferably not less than 350 nm. If the average particle diameter in volume is less than the lower limit, the grafted acrylic rubber copolymer (A) that can be obtained and the thermoplastic resin composition that can be obtained may exhibit low impact resistance. The volume average diameter of the rubbery polymer particle (a) is preferably not more than 600 nm and more preferably not more than 550 nm. If the average diameter by volume of the particle exceeds the upper limit, the grafted acrylic rubber copolymer (A) that can be obtained and the thermoplastic resin composition that can be obtained may exhibit mediocre appearance.
[00057] It is preferable that the content of rubber polymer having a particle diameter of not more than 200 nm is not more than 20% by weight and more preferably not more than 10% by weight relative to 100% by weight of the polymer rubbery. If the content of rubbery polymer having a particle diameter of not more than 200 nm exceeds the upper limit, the grafted acrylic rubber copolymer (A) that can be obtained and the thermoplastic resin composition that can be obtained may exhibit low strength impact.
[00058] The grafted acrylic rubber copolymer (A) of the invention is obtained by grafting polymerization of a vinyl monomer in the presence of the rubbery polymer (a).
[00059] The vinyl monomers used in grafting polymerization preferably include an unsaturated nitrile monomer and an aromatic vinyl monomer and optionally an additional monomer when needed.
[00060] Examples of unsaturated nitrile monomers include acrylonitrile and methacrylonitrile. These can be used alone or two or more can be used in combination.
[00061] Examples of aromatic vinyl monomers include styrene, α-methylstyrene and vinyltoluene. These can be used alone or two or more can be used in combination.
[00062] Additional monomers are monomers that can be polymerized with unsaturated nitrile monomers and with aromatic vinyl monomers and that are not unsaturated nitrile monomers or aromatic vinyl monomers. Examples of additional monomers include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, ethyl 2-hydroxymethacrylate, glycidyl methacrylate, N , Ethyl N-dimethylaminomethacrylate, acrylamide, methacrylamide, maleic acid anhydride and N-substituted maleimide. Additional monomers can be used alone or two or more can be used in combination.
[00063] The vinyl monomer that is polymerized by grafting to the rubbery polymer (a) is preferably a monomer mixture that includes an aromatic vinyl monomer such as styrene and an unsaturated nitrile monomer such as acrylonitrile because an excellent is obtained resistance to the impact of molded articles obtainable. A mixture of styrene and acrylonitrile is particularly preferable.
[00064] In the mixture of graft polymerized monomers with rubbery polymer (a), the proportion of unsaturated nitrile monomers is preferably 3 to 50% by weight and more preferably 10 to 40% by weight in the monomer mixture (100% by mass). When the proportion of unsaturated nitrile monomers is not less than the lower limit, the molded articles that can be obtained exhibit good impact resistance. When the proportion of unsaturated nitrile monomers does not exceed the upper limit, the molded articles that can be obtained do not undergo discoloration due to heating.
[00065] The proportion of aromatic vinyl monomers is preferably from 20 to 97% by weight and more preferably from 30 to 80% by weight in the monomer mixture (100% by weight). When the proportion of aromatic vinyl monomers is not less than the lower limit, good molding properties are obtained. When the proportion of aromatic vinyl monomers does not exceed the upper limit, the molded articles that can be obtained exhibit good impact resistance.
[00066] In the monomer mixture (100% by weight), the proportion of additional monomers is preferably not more than 50% by weight and more preferably not more than 40% by weight. When the proportion of additional monomers does not exceed the upper limit, a good balance between impact resistance and appearance is achieved.
[00067] Preferably, the grafted acrylic rubber copolymer (A) of the invention is produced by emulsion polymerization of the above monomer mixture in the presence of the rubber polymer latex (a).
[00068] Similar to the production of the rubbery polymer (a), the emulsifier used in emulsion polymerization is preferably an anionic emulsifier. From the point of view such as suppression of hydrolysis of polyfunctional monomers, dipotassium alkenyl succinates are preferable.
[00069] Examples of polymerization initiators used in emulsion polymerization include peroxides, azo initiators and redox initiators that include combinations of oxidizing agents and reducing agents.
[00070] Emulsion polymerization can involve chain transfer agents to adjust the graft ratio and the molecular weights of grafted components.
[00071] In emulsion polymerization, monomers such as aromatic vinyl monomers and unsaturated nitrile monomers can be added by a method such as batch addition, portion addition or successive addition. These methods can be used in combination such that, for example, a portion is added at once and the remaining portion is added in succession. It is also possible to adopt a method in which the monomers are kept for a period of time after they are added and after that the polymerization initiator is added to initiate the polymerization.
[00072] After emulsion polymerization, the grafted acrylic rubber copolymer (A) can be recovered from the latex of the grafted acrylic rubber copolymer (A) by the following method.
[00073] The grafted copolymer latex is added to the hot water in which a coagulating agent has been dissolved, thereby solidifying the grafted copolymer. Next, the grafted solidified copolymer is redispersed in water or warm water to provide a suspension and the copolymer is washed by eluting the residual emulsifier that remains in the grafted copolymer in the water. Subsequently, the suspension is dehydrated with a device such as a dehydrator and the resulting solid is dried with a dryer such as an air dryer, thereby recovering the grafted copolymer as a powder or particles.
[00074] In one embodiment, the graft copolymer of acrylic rubber (A) in latex can be mixed together with a graft copolymer of acrylic rubber (B) in latex described later and optionally with an additional latex polymer and after that the copolymer can be recovered in the manner described above.
[00075] Examples of coagulants include inorganic acids (such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid) and metal salts (such as calcium chloride, calcium acetate and aluminum sulfate). Coagulants are selected appropriately according to the type of emulsifier. For example, any coagulant can be used in the event that a carboxylate salt (such as a fatty acid salt or a colophonium soap) alone is used as the emulsifier. An inorganic acid does not work sufficiently and it is necessary that a metal salt be used in the event that the emulsifier is one that exhibits stable emulsifying power even in an acidic region such as sodium alkylbenzenesulfonate.
[00076] In the grafted acrylic rubber copolymer (A), the content of the rubbery polymer (a) is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight and particularly preferably 30 to 70 parts by weight in relation to 100 parts by weight of the grafted acrylic rubber copolymer (A). When the content of the rubbery polymer (a) is not less than the lower limit, the grafted acrylic rubber copolymer (A) obtainable and the thermoplastic resin composition obtainable achieve an even higher impact resistance. When the content of the rubber polymer (a) is not greater than the upper limit, the grafted acrylic rubber copolymer (A) obtainable and the thermoplastic resin composition obtainable can maintain a good appearance.
[00077] The graft ratio of the grafted acrylic rubber copolymer (A) is preferably 30 to 90% and particularly preferably 50 to 80%. This range of the graft proportion of the acrylic rubber grafted copolymer (A) ensures that a good appearance is maintained. The graft ratio of the grafted acrylic rubber (A) copolymer can be determined by a method described later in the Examples.
[00078] Furthermore, it is preferable that the reduced viscosity of the grafted copolymer components of acetone-soluble acrylic rubber (A) are from 0.40 to 1.00 g / dL and particularly preferably from 0.50 to 0.80 g / dL. Impact resistance can also be increased when the reduced viscosity of the grafted copolymer components of acetone-soluble acrylic rubber (A) is not less than the lower limit. When the reduced viscosity does not exceed the upper limit, good-looking and molding properties can be maintained. The reduced viscosity of the grafted copolymer components of acrylic rubber (A) soluble in acetone can be determined by a method described later in EXAMPLES. [Thermoplastic resin compositions]
[00079] The thermoplastic resin composition according to the present invention includes the grafted acrylic rubber copolymer (A) of the invention described above. Preferably, the thermoplastic resin composition includes the grafted acrylic rubber copolymer (A) of the invention and a grafted acrylic rubber copolymer (B) which is obtained by polymerizing a vinyl monomer in the presence of a rubbery polymer that includes rubber units. acrylate ester monomer (hereinafter, sometimes called "rubbery polymer (b)") and having an average particle volume diameter of 70 to 200 nm (hereinafter, sometimes called "grafted acrylic rubber copolymer ( B) of the invention ").
[00080] The rubbery polymer (b) used in the grafted acrylic rubber copolymer (B) of the invention includes acrylate ester monomer units as essential components.
[00081] The acrylate ester monomers are desirably alkyl acrylate esters having an alkyl group with 1 to 12 carbon atoms. Esters of acrylic acid and linear or branched alcohols with 1 to 12 carbon atoms are used as such alkyl acrylate esters. Examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate. In particular, those having an alkyl group having 1 to 8 carbon atoms are preferable. These esters can be used alone or two of the same or more can be used in combination.
[00082] The rubbery polymer (b) can include polyfunctional monomer units in addition to the acrylate ester monomer units. In such cases, the polyfunctional monomers used in the rubbery polymer (b) are not particularly limited and can be any of the known polyfunctional monomers. Examples of such known polyfunctional monomers include diol di (meth) acrylate esters such as ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol diacrylate, as well as trialyl cyanurate, trialyl isocyanurate, trimellitate trialyl and allyl methacrylate. These can be used alone or two or more can be used in combination.
[00083] In addition, the rubbery polymer (b) can include an additional monomer when necessary that can be copolymerized with the acrylate ester monomer. Examples of the additional copolymerizable monomers with the acrylate ester monomer include aromatic vinyl monomers such as styrene, a-methylstyrene and p-methylstyrene, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile and methacrylate ester monomer such as methacrylate such as methacrylate ester such as methacrylate ethyl, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate and 2-ethylhexyl methacrylate. These monomers can be used alone or two or more can be used in combination.
[00084] Furthermore, the rubbery polymer (b) used in the grafted acrylic rubber copolymer (B) of the invention can be a rubber composite formed between a rubbery polymer that includes acrylate ester monomer units and a rubbery polymer composed of units of monomer other than acrylate ester monomer units. For example, the rubbery polymer composed of monomer units other than acrylate ester monomer units may be ethylene-propylene rubber (EPR), ethylene-propylene-rubber diene (EPDM), rubber diene or polyorganosiloxane. The rubber composite can be obtained by a known method, for example, by polymerizing an acrylate ester monomer in the presence of a rubbery polymer composed of monomer units other than acrylate ester monomer units.
[00085] With respect to 100% by weight of the rubbery polymer (b), the content of the acrylate ester monomer units is preferably not less than 75% by weight, more preferably not less than 85% by weight and particularly of preference is not less than 95% by mass. If the content of the acrylate ester monomer units is less than the lower limit, the thermoplastic resin composition that can be obtained can be deteriorated in any one between weather resistance, impact resistance, stiffness and appearance.
[00086] In the rubbery polymer (b), the content of the polyfunctional monomer units preferably does not exceed 3 parts by weight, more preferably it does not exceed 2 parts by weight, particularly preferably it does not exceed 1 part by weight and preferably it is not less than 0.05 parts by weight, more preferably it is not less than 0.1 parts by weight, particularly preferably it is not less than 0.15 parts by weight, relative to 100 parts by weight of the units of acrylate ester monomer. If the content of the polyfunctional monomer units in the rubbery polymer (b) exceeds the upper limit, the thermoplastic resin composition that can be obtained can be deteriorated in impact resistance. Any content below the lower limit can result in a decrease in appearance.
[00087] In the case where the rubbery polymer (b) includes units of additional copolymerizable monomers with the acrylate ester monomer, their content in the rubbery polymer (b) is preferably not more than 25% by weight, more preferably not is greater than 15% by weight and particularly preferably not more than 5% by mass. If the content of additional monomer units exceeds the upper limit, the thermoplastic resin composition that can be obtained can be deteriorated in any one between weather resistance, impact resistance, stiffness and appearance.
[00088] A rubbery polymer latex (b) for the grafted acrylic rubber copolymer (B) is preferably produced by emulsion polymerization. In particular, it is preferable that the latex is produced by a batch emulsion polymerization method with batch addition of the acrylate ester monomer in such a way that 100% by mass of all the acrylate ester monomer used in the production of the rubber polymer (b) is polymerized at a polymerization rate of not less than 3% by mass / minute and particularly not less than 3.5% by mass / minute. If the polymerization speed is lower than the lower limit, the appearance of the thermoplastic resin composition that can be obtained can be deteriorated. The upper limit of the polymerization speed is not particularly limited. In industrial production, however, removal of heat from polymerization is more difficult when the rate of polymerization increases. Thus, the rate of polymerization is usually not more than 20% by weight / minute and more preferably not more than 10% by weight / minute.
[00089] Because a detailed structural analysis of the rubbery polymer (b) is impossible, the detailed reasons why the above polymerization speed provides an improvement in. However, a change in the crosslinking structure of the rubbery polymer (b) is likely to occur.
[00090] Redox initiators that include combinations of oxidizing agents and reducing agents are preferable as the polymerization initiators used in emulsion polymerization. The use of initiators that can be thermally decomposed such as peroxides and azo initiators is disadvantageous in the industry because large amounts of initiators need to be used to control the polymerization speed within the above range as well as because the polymerization causes high temperatures. When a redox initiator is used, the rate of polymerization can be adjusted by controlling the amount of metal ions as a catalyst as well as the amounts of the oxidizing agent and reducing agent.
[00091] The rubbery polymer (b) used in the grafted acrylic rubber copolymer (B) preferably has an average diameter in particle volume that is not less than 70 nm, more preferably not less than 80 nm and not more than 200 nm, more preferably not more than 170 nm, particularly preferably not more than 150 nm. If the average volume diameter of the rubbery polymer particle (b) is less than the lower limit, the thermoplastic resin composition that can be obtained may have its mechanical strength deteriorated. If the average diameter by volume of the particle exceeds the upper limit, the appearance may be deteriorated.
[00092] The grafted acrylic rubber copolymer (B) is obtained by grafting polymerization of a vinyl monomer in the presence of the rubbery polymer (b).
[00093] The vinyl monomers used in this case may be similar to the vinyl monomers used in the grafted acrylic rubber (A) copolymer. Preferred examples and amounts of the vinyl monomers are also similar to those described above.
[00094] The grafted acrylic rubber copolymer (B) can be produced by a known production method such as emulsion polymerization or continuous polymerization. Of such methods, an emulsion polymerization method is particularly preferable. The agents used in emulsion polymerization such as emulsifiers, initiators and chain transfer agents can be known agents similar to those used in the production of the grafted acrylic rubber copolymer (A).
[00095] After emulsion polymerization, the grafted acrylic rubber copolymer (B) can be recovered from the latex of the grafted acrylic rubber copolymer (B) by the same method as recovering the grafted acrylic rubber copolymer (A).
[00096] As already described above, the grafted copolymer of acrylic rubber (A) in latex, the grafted copolymer of acrylic rubber (B) in latex and optionally an additional latex polymer can be mixed together and after that the copolymer can be recovered the way before.
[00097] In the grafted acrylic rubber copolymer (B), the content of the rubbery polymer (b) is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight and particularly preferably 30 to 70 parts by weight in relation to 100 parts by weight of the grafted acrylic rubber copolymer (B). When the rubbery polymer content (b) is not less than the lower limit, the thermoplastic resin composition that can be obtained reaching an even higher impact resistance. When the rubbery polymer content does not exceed the upper limit, the thermoplastic resin composition that can be obtained can maintain a good appearance.
[00098] The graft ratio of the grafted acrylic rubber copolymer (B) is preferably 30 to 90% and particularly preferably 35 to 70%. This range of graft ratio of the grafted acrylic rubber copolymer (B) ensures that a good appearance is maintained. The graft ratio of the grafted acrylic rubber copolymer (B) can be determined by a method described later in the examples.
[00099] Furthermore, it is preferable that the reduced viscosity of the grafted copolymer components of acetone-soluble acrylic rubber (B) is from 0.40 to 1.00 g / dL and particularly preferably from 0.50 to 0.80 g / dL. Impact strength can also be increased when the reduced viscosity of the components of the grafted acrylic rubber (B) copolymer soluble in acetone is not less than the lower limit. When the reduced viscosity is not less than the upper limit, good good-looking and molding properties can be maintained. The reduced viscosity of grafted copolymer components of acetone-soluble acrylic rubber (B) can be determined by a method described later in the examples. [Thermoplastic resins (C)]
[000100] The thermoplastic resin compositions of the invention may contain an additional thermoplastic resin (C) other than the grafted acrylic rubber copolymers (A) and the grafted acrylic rubber copolymers (B). In this case, examples of thermoplastic resins (C) include styrene resins, methyl styrene methacrylate copolymers (MS resins), (meth) acrylic resins, methyl polymethacrylates, polycarbonates (PC), polybutylene terephthalates (PBT), terephthalates polyethylene (PET), polyvinyl chlorides, polyolefins such as polyethylene and polypropylene, styrene elastomers such as styrene-butadiene-styrene (SBS), styrene-butadiene (SBR), hydrogenated SBS and styrene-isoprene-styrene (SIS), olefin elastomers, polyester elastomers, polyacetals, modified polyphenylene ethers (modified PPE resins), ethylene-vinyl acetate copolymers, polyphenylene sulfides (PPS), polyethersulfones (PES), polyethersulfones (PEEK), polyalylates, resins, polyalylates liquid crystal polyester and polyamides (nylons). These thermoplastic resins can be used alone or two or more can be used in combination.
[000101] Of these resins, polybutylene terephthalates (PBT) are preferable from the point of view of an improvement in chemical resistance; polyethylene terephthalates (PET) and styrene resins are preferable from the point of view of an improvement in the handling capacity for molding and modified polyphenylene ethers (modified PPE) and polyamides are preferable from the point of view of an improvement in thermal resistance. In terms of the balance of properties between impact resistance and molding, styrene resins are particularly preferable. From the point of view of an improvement in weather resistance, (meth) acrylic resins are particularly preferable. In terms of the balance between impact resistance and thermal resistance, polycarbonate resins are particularly preferable.
[000102] Styrene resins are resins that contain aromatic vinyl monomer units as essential components and optional comonomers, for example, unsaturated nitrile monomers such as vinyl cyanide, unsaturated carboxylic acid anhydrides and N-substituted maleimides. These monomer units can be used alone or two or more species can be used in combination.
[000103] Particularly preferred styrene resins are acrylonitrile-styrene copolymers, acrylonitrile-alpha-methylstyrene copolymers, acrylonitrile-styrene-N-phenylmaleimide copolymers, acrylonitrile-styrene-alpha-methyl-styrene-copolymers and phenyl-methyl-styrene-alpha-methyl styrene styrene-N-phenylmaleimide.
[000104] In the styrene resin, the proportion of aromatic vinyl monomer units is preferably 20 to 100% by weight, more preferably 30 to 90% by weight and particularly preferably 50 to 80% by weight relative to to the monomer mixture (100% by mass) used in the production of the styrene resin. When the proportion of aromatic vinyl monomers is not less than the lower limit, the thermoplastic resin composition that can be obtained exhibits good molding properties.
[000105] In the styrene resin, the proportion of unsaturated nitrile monomer units is preferably from 0 to 50% by weight and more preferably from 10 to 40% by weight relative to a monomer mixture (100% mass) used in the production of styrene resin. When the proportion of unsaturated nitrile monomers is below the upper limit, the coloring of molded articles that can be obtained due to heat is eliminated.
[000106] In styrene resin, the proportion of comonomers is preferably not more than 55% by weight and more preferably not more than 40% by weight compared to the monomer mixture (100% by weight) used in the production of the resin styrene. When the proportion of comonomers is not higher than the upper limit, the molded articles that can be obtained exhibit a good balance between impact resistance and appearance.
[000107] (meth) acrylic resins are resins that are polymer compound components formed from methacrylate ester monomers such as methyl methacrylate or copolymer components formed from methacrylate ester monomers as well as acrylate ester monomers such as methyl acrylate and / or additional copolymerizable monomers with methacrylate ester monomers and acrylate ester monomers. In (meth) acrylic resin, the mass ratio of the acrylate ester monomer to the acrylate ester monomer is preferably in the range of 100/0 to 50/50 and more preferably from 99/1 to 80/20, if the proportion of the acrylate ester monomer is higher than this range, the thermoplastic resin composition that can be obtained tends to deteriorate in thermal stability and thermal resistance.
[000108] It is preferable that methyl methacrylate is used as the acrylate ester monomer and methyl acrylate is used as the acrylate ester monomer.
[000109] Specific examples of (meth) acrylic resins include "ACRYPET VHS" and "ACRYPET MD" manufactured by Mitsubishi Rayon Co., Ltd. and "PARAPET G" manufactured by KURARAY CO., LTD. commercially available
[000110] Polycarbonate (PC) resins preferably have an average molecular weight in viscosity (Mv) in the range of 10,000 to 45,000 and particularly preferably 13,000 to 40,000. If the viscosity average molecular weight of the polycarbonate resin is less than this range, the impact resistance tends to deteriorate. If an average molecular weight in viscosity exceeds this range, fluidity is impaired to result in poor molding properties and the appearance of products tends to be less.
[000111] Specific examples of polycarbonate (PC) resins include "Iupilon series" and "NOVAREX series" manufactured by Mitsubishi Engineering-Plastics Corporation and "TARFLON series" manufactured by commercially available Idemitsu Kosan Co., Ltd.
[000112] Additional thermoplastic resins (C) can be produced by known production methods such as emulsion polymerization, polymerization and suspension and continuous mass polymerization. [Resin components]
[000113] Like the resin components, the thermoplastic resin composition of the invention essentially contains the grafted acrylic rubber copolymer (A) and preferably furthermore contains the grafted acrylic rubber copolymer (B) and optionally the additional thermoplastic resin (C ).
[000114] The thermoplastic resin composition of the invention preferably includes the rubber polymers in a total amount of 5 to 30 parts by weight and more preferably from 7 to 25 parts by weight relative to 100 parts by weight of the resin components in the composition of thermoplastic resin. When the content of rubber polymers in the thermoplastic resin composition is not less than the lower limit, the impact resistance of the thermoplastic resin composition that can be obtained is also increased. When the content of rubber polymers does not exceed the upper limit, the thermoplastic resin composition that can be obtained can maintain good appearance and fluidity.
[000115] In the thermoplastic resin composition of the invention, it is preferable that the amount of the rubber polymer (a) in the grafted acrylic rubber copolymer (A) is from 20 to 70% by weight and the amount of the rubber polymer (b) in o grafted copolymer of acrylic rubber (B) is 30 to 80% by weight in relation to the total of rubber polymers in the thermoplastic resin composition considered to be 100% by weight. More preferably, the amount of the rubbery polymer (a) in the grafted acrylic rubber copolymer (A) is 30 to 60% by weight and the amount of the rubbery polymer (b) in the grafted acrylic rubber copolymer (B) is 40 to 70 % in large scale. The impact resistance of the thermoplastic resin composition that can be obtained is also increased when the amount of rubber polymer (a) in the grafted acrylic rubber copolymer (A) is not less than the lower limit and the amount of rubber polymer (b) in grafted acrylic rubber copolymer (B) is not higher than the upper limit. The thermoplastic resin composition that can be obtained can maintain a good appearance when the amount of rubber polymer (a) in the grafted acrylic rubber copolymer (A) is not greater than the upper limit and the amount of rubber polymer (b) in the grafted copolymer of acrylic rubber (B) is not less than the lower limit.
[000116] When the thermoplastic resin composition which includes the grafted acrylic rubber copolymer of the invention also contains the additional thermoplastic resin (C), the content thereof is preferably from 0 to 70 parts by weight and more preferably from 10 to 65 parts by mass relative to 100 parts by mass of the resin components in the thermoplastic resin composition. A good appearance can be maintained when the amount of additional thermoplastic resin (C) used is not greater than the upper limit. [Additional components]
[000117] The thermoplastic resin compositions of the invention can contain other components when necessary such as colorants including pigments and dyes, thermal stabilizers, light stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants, plasticizers, antistatic agents and processing aids. [Production Method of Thermoplastic Resin Compositions]
[000118] For example, the thermoplastic resin composition of the invention is produced by mixing the grafted acrylic rubber copolymer (A) with the grafted acrylic rubber copolymer (B) and optionally with the additional thermoplastic resin (C) and additional components by using a mixer such as a twin-cylinder blender or a Henschel mixer and kneading the mixture in the molten state discharged from the mixer. The mixture can be kneaded the mixture in the molten state with a kneader such as a single screw or twin screw extruder, a Banbury mixer, a heated mixer or cylinders. [Thermoplastic Resin Molded Items]
[000119] Molded thermoplastic resin articles of the invention that are produced by molding thermoplastic resin compositions of the invention can be used in various applications.
[000120] Examples of methods for molding thermoplastic resin compositions include injection molding, extrusion, blow molding, compression molding, calendering and blow film extrusion.
[000121] The thermoplastic resin composition of the invention can be used as a material to form a coating layer on substrates such as other resins or other metals.
[000122] In this case, examples of other resins that form the substrates on which a coating layer of the inventive thermoplastic resin composition needs to be deposited include resins described above as additional thermoplastic (C) resins, modified rubber thermoplastic resins such as resins and ABS and styrene resins (HIPS) for high impact pulleys such as thermoset resins such as phenolic resins and melamine resins.
[000123] By applying a thermoplastic resin composition coating on such resinous or metallic substrates of the invention, projected objects resistant to the weather and having good appearance can be produced.
[000124] Molded articles can be used in various applications. For example, molded articles can be used appropriately in industry as parts for vehicles, in particular various external and internal parts used without paint, construction parts such as materials for walls and window frames, edible utensils, toys parts for electronic devices households such as vacuum cleaner cases, television cases and air conditioner cases, internal parts, marine vessel parts and electrical equipment cases such as communication device cases, laptop case cases, terminal case cases wireless movers and enclosures for liquid crystal projectors. EXAMPLES
[000125] The present invention will also be described in detail for purposes of examples. However, the scope of the invention is not limited by such examples. In the following examples, the term "part (s)" is (are) in bulk unless otherwise mentioned.
[000126] The properties of rubber polymers and copolymers grafted from acrylic rubber and the characteristics of molded articles obtained were measured and evaluated by the following methods. <Solid content>
[000127] Exactly 1 g of a latex was weighed. The volatile components were evaporated at 200 ° C for a period of 20 minutes and the mass of the residue was measured. The solids content in the latex was determined by the following equation. Solid content (%) = mass of residue / mass of latex x 100 <Polymerization with conversion>
[000128] After measuring the solids content, conversion polymerization was determined by the following equation.
[000129] Polymerization with conversion (%) = {S ^ 100 x total mass of materials - mass of materials other than monomers and water} / total mass of monomers x 100
[000130] In the equation, S is the solid content (%) and the total mass of materials is the total mass of materials such as monomers and water added to the reactor. <Graft ratio>
[000131] The graft ratio of a grafted copolymer was calculated by the following method.
[000132] Acetone 80 ml was added to 2.5 g of the grafted copolymer and the mixture was left to reflux in a hot water bath at 65 ° C for 3 hours to extract
[000133] components soluble in acetone. The residual acetone-soluble components were separated by centrifugal separation and dried. The dry weight was measured and the weight ratio of the components insoluble in acetone was calculated. The graft ratio was calculated by the following equation based on the mass proportion of the acetone-insoluble components in the grafted copolymer. [Mat. 1]
[000134] Graft ratio (%) = (mass ratio of components insoluble in acetone - mass ratio of rubber polymer) / mass ratio of rubber polymer x 100 <Reduced Viscosity>
[000135] The reduced viscosity was measured against a solution of 0.2 g / dL of a copolymer in N, N-dimethylformamide with a Ubbelohde viscometer at 25 ° C. the measurement of the reduced viscosity was carried out using the acetone-soluble components of the grafted copolymer that had been extracted in acetone in the measurement of the graft ratio. <Average molecular weight in viscosity>
[000136] To determine an average molecular weight in viscosity (Mv), a solution in methylene chloride of the polycarbonate resin was analyzed with an Ubbelohde viscometer at 20 ° C to measure the intrinsic viscosity fo]. An average molecular weight in viscosity was calculated using the following equation. fo] = 1.23 x 10-4 x (Mv) 0.83 <Average Particle Diameter in Volume and proportion of particles with a particle diameter of not more than 200 nm>
[000137] These properties were determined by a Dynamic Light Diffusion method using Nanotrac UPA-EX150 manufactured by NIKKISO CO., LTD. <Volume Rate in the Cast State>
[000138] The melt volume rate of the thermoplastic resin composition was measured by a method according to ISO 1133 at a barrel temperature of 220 ° C and a load of 98 N. The melt volume rate is one fluidity indicator of the thermoplastic resin composition. <Charpy Impact Resistance>
[000139] The Charpy Impact Strength of a molded article was measured by a method according to ISO 179 in relation to a V-notch test piece that had been conditioned in an atmosphere at 23 ° C for at least 12 hours . <Flex Module>
[000140] To determine the flexural modulus of a molded article, a specimen with a thickness of 4 mm was tested by a method according to the ISO 178 testing method at a measurement temperature of 23 ° C. <Deflection temperature under load>
[000141] The deflection temperature under load of a molded article was measured by a method in the plane with 1.83 MPa and 4 mm according to ISO the test method 75. <Bright>
[000142] To determine the surface gloss of a molded article, the thermoplastic resin composition was injection molded (injection rate: 40 g / s) in a 100 mm x 100 mm x 3 mm plate and the gloss was obtained by reflectance measured at an angle of incidence of 60 ° and at an angle of reflection of 60 ° with a digital gonophotometer UGV-5D manufactured by Suga Test Instruments Co., Ltd.
[000143] In EXAMPLES 11 to 28 and COMPARATIVE EXAMPLES 3 to 5, the gloss was measured in the same way as above with respect to the surface of 100 x 100 x 2 mm of flat specimens obtained by injection molding at a rate of injection of 10 g / s or 40 g / s. <Color Production Properties>
[000144] The thermoplastic resin composition was molded by injection (injection rate: 40 g / sec.) In a 100 mm x 100 mm x 3 mm plate and L * was measured with a CM-508D colorimeter manufactured by Minolta. A lower value of L * indicates better color-producing properties.
[000145] In EXAMPLES 11 to 28 and COMPARATIVE EXAMPLES 3 to 5, the color production properties were measured in the same way as above with respect to the surface of 100 x 100 x 2 mm flat plate specimens obtained by molding with injection at an injection rate of 10 g / s or 40 g / s. [SYNTHETIC EXAMPLE 1: Production of copolymer latex containing acid group (K)]
[000146] Under a stream of nitrogen, a reactor equipped with a reagent injection container, a condenser tube, a heating jacket and a stirrer was loaded with: deionized water (here, simply, water) 200 parts, 2 parts potassium oleate, 4 parts sodium dioctylsulfosuccinate, 0.003 part ferrous sulfate, 0.009 part disodium ethylene diaminetetraacetate and 0.3 part sodium formaldehyde sulfate. The temperature was increased to 60 ° C. When the temperature reached 60 ° C, a mixture consisting of: 82 parts n-butyl acrylate, 18 parts methacrylic acid and 0.5 parts cumene hydroperoxide, was added dropwise continuously over a period of 120 minutes. After the dropwise addition was completed, aging was carried out at 60 ° C for 2 hours. In this way, a copolymer latex was obtained which contains an acid group (K) which had a solids content of 33%, a polymerization conversion of 96% and an average volume diameter of the particle of the copolymer containing 150 acid group. nm. [SYNTHETIC EXAMPLE 2: Production of rubbery polymer in latex (a-1)] <First stage>
[000147] While stirring, a reactor equipped with a reagent injection container, a condenser tube, a heating jacket and a stirrer was loaded with: water 310 parts, dipotassium alkenyl succinate (LATEMUL ASK manufactured by Kao Corporation) 1 part, n-butyl acrylate 80 parts, allyl methacrylate 0.48 parts, trialyl isocyanurate 0.4 parts and t-butyl hydroperoxide 0.2 part. The reactor was then purged with nitrogen and the temperature of the contents was increased. At an internal temperature of 55 ° C, an aqueous solution was added which consists of: 0.3 part sodium formaldehyde, 0.0001 part ferrous sulfate, 0.0003 part disodium ethylene diaminetetraacetate and 10 part water and polymerization has started. After the generation of the polymerization heat was observed, the jacket temperature was controlled to 75 ° C. Polymerization was carried out continuously until the generation of polymerization heat ceased and the System was left to stand for 1 hour. The rubbery polymer obtained had an average particle volume diameter of 100 nm. To the Polymerization System, 1 part was added in terms of the solid content of a 5% aqueous solution of sodium pyrophosphate. (The pH of the liquid mixture was 9.1.) The temperature of the jacket was controlled so that the internal temperature became 70 ° C.
[000148] At an internal temperature of 70 ° C, the copolymer latex containing the acid group (K) was added in an amount of 3 parts in terms of solid content. The mixture was stirred for 30 minutes while maintaining the internal temperature at 70 ° C, thereby increasing the particles. The volume average diameter of the particle after the increase was 420 nm. <Second stage>
[000149] At an internal temperature of 70 ° C, an aqueous solution consisting of: 0.03 part sodium formaldehyde sulfate, 0.002 part ferrous sulfate, 0.006 part disodium ethylene diaminetetraacetate and 80 parts water, was added. Subsequently, a liquid mixture consisting of: 20 parts n-butyl acrylate, 0.12 part allyl methacrylate, 0.1 part trialyl isocyanurate and 0.02 part t-butyl hydroperoxide was added dropwise over a period of 1 hour time period. After the dropwise addition was complete, the system was maintained at a temperature of 70 ° C for 1 hour and thereafter cooled. In this way, a rubber latex polymer (a-1) was obtained which had a solid content of 18% and an average diameter by volume of the rubber polymer particle of 450 nm. The polymerization conversion was 97% and the proportion of particles with a particle diameter not exceeding 200 nm was 10%. [SYNTHETIC EXAMPLE 3: Production of rubber latex polymers (a-2) to (a-5) and rubber latex polymers (x-1) to (x-2)]
[000150] Latex rubber polymers (a-2) to (a-5) and latex rubber polymers (x-1) to (x-2) were obtained in the same way as in SYNTHETIC EXAMPLE 2, except that methacrylate was used of allyl and trialyl isocyanurate in quantities as described in Table 1. [SYNTHETIC EXAMPLE 4: Production of rubbery polymer in latex (a-6)]
[000151] A rubber latex polymer (a-6) was obtained in the same way as in SYNTHETIC EXAMPLE 2, except that the 5% aqueous solution of sodium pyrophosphate and the copolymer latex containing the acid group (K) were added in quantities of 2 parts and 3 parts in terms of solid content, respectively, in the increase. The volume average diameter of the particle after the increase was 510 nm. The volume average diameter of the particle after the polymerization of 20 parts of n-butyl acrylate was 550 nm. [SYNTHETIC EXAMPLE 5: Production of rubbery polymer latex (a-7)]
[000152] A rubber latex polymer (a-7) was obtained in the same way as in SYNTHETIC EXAMPLE 2, except that the 5% aqueous solution of sodium pyrophosphate and the copolymer latex containing the acid group (K) were added in quantities of 1 part and 4 parts in terms of solid content, respectively, in the increase. The volume average diameter of the particle after the increase was 325 nm. The volume average diameter of the particle after the polymerization of 20 parts of n-butyl acrylate was 350 nm. [SYNTHETIC EXAMPLE 6: Production of rubbery polymer latex (a-8)]
[000153] A rubber latex polymer (a-8) was obtained in the same manner as in SYNTHETIC EXAMPLE 2, except that the initial charge of materials such as monomers was changed as described in Table 1 and that the polymerization of monomers such as acrylate of n-butyl after the increase was not performed. The volume average diameter of the particle after the increase was 430 nm. [SYNTHETIC EXAMPLE 7: Rubber latex polymer production (a-9)]
[000154] A rubbery latex polymer (a-9) was obtained in the same way as in SYNTHETIC EXAMPLE 2, except that a 5% aqueous solution of sodium pyrophosphate and the copolymer latex containing the acid group (K) in quantities of 3 parts and 3 parts in terms of solid content, respectively, in the increase. The volume average diameter of the particle after the increase was 600 nm. The volume average diameter of the particle after the polymerization of 20 parts of n-butyl acrylate was 650 nm. [SYNTHETIC EXAMPLE 8: Production of rubbery polymer in latex (a-10)]
[000155] A rubber latex polymer (a-10) was obtained in the same way as in SYNTHETIC EXAMPLE 2, except that a 5% aqueous solution of sodium pyrophosphate and the copolymer latex containing the acid group (K) were added in quantities of
[000156] 1 part and 5 parts in terms of solid content, respectively, in the increase. The volume average diameter of the particle after the increase was 280 nm. The volume average diameter of the particle after the polymerization of 20 parts of n-butyl acrylate was 300 nm.
[000157] The conditions for the synthesis of rubbery polymer latexes (a-1) to (a-10) and (x-1) to (x-2), as well as properties such as the diameter of the particles of the rubber polymers obtained are described in Table 1. Table 1
* 1: parts by weight with respect to 100 parts by weight of acrylate ester monomer * 2:% by weight with respect to 100% by weight of the total amount of polyfunctional monomers [EXAMPLE 1: Production of grafted copolymer (A-1 )]
[000158] A reactor equipped with a reagent injection container, a condenser tube, a heating jacket and a stirrer was loaded with: water (including water in the rubber latex polymer) 230 parts, rubber latex polymer (a -1) 50 parts (in terms of solid content), dipotassium alkenyl succinate (LATEMUL ASK manufactured by Kao Corporation) 0.5 part and 0.3 part sodium sulfoxylate formaldehyde. The reactor was purged completely with nitrogen. Thereafter, the internal temperature was increased to 70 ° C while stirring.
[000159] Thereafter, the temperature was raised to 80 ° C while a liquid mixture consisting of: 15 parts acrylonitrile, 35 parts styrene and t-butyl hydroperoxide is added dropwise over a period of 100 minutes. 0.5 part.
[000160] After the dropwise addition was completed, the system was maintained at a temperature of 80 ° C for 30 minutes and thereafter cooled. In this way, a latex-grafted copolymer (A-1) was obtained.
[000161] Subsequently, 100 parts of a 1.5% aqueous solution of sulfuric acid were heated to 80 ° C and 100 parts of the grafted copolymer (A-1) in latex were gradually added dropwise to the aqueous solution while maintaining agitation of the aqueous solution, thereby solidifying the grafted copolymer. In addition, the temperature was raised to 95 ° C and the system was kept at temperature for 10 minutes.
[000162] Next, the solid was dehydrated, washed and dried to provide a powdered grafted copolymer (A-1). [EXAMPLES 2 TO 10 AND COMPARATIVE EXAMPLES 1 TO 2]
[000163] Copolymers grafted in powder (A-2) to (A-10) and (X-1) to (X-2) were obtained in the same way as in EXAMPLE 1, except that the rubber latex polymer was varied as described in Table 2.
[000164] The conditions for the synthesis of graft copolymers (A-2) to (A-10) and (X-1) to (X-2), as well as the results of property evaluations are described in Table 2. Table 2

[SYNTHETIC EXAMPLE 9: Production of grafted copolymer (B-1)]
[000165] While stirring, a reactor equipped with a reagent injection container, a condenser tube, a heating jacket and a stirrer was loaded with: water 240 parts, dipotassium alkenyl succinate (LATEMUL ASK manufactured by Kao Corporation) 0 , 7 part, n-butyl acrylate 50 parts, allyl methacrylate 0.15 part, dimethacrylate of 1,3-butanediol 0.05 part and t-butyl hydroperoxide 0.1 part. The reactor was then purged with nitrogen and the temperature of the contents was increased.
[000166] At an internal temperature of 55 ° C, an aqueous solution consisting of: sodium formaldehyde sulfoxylate 0.2 part, ferrous sulfate heptahydrate 0.00015 part, ethylene diaminetetraacetate 0.00045 part and water 10 parts , was added and polymerization started. After the generation of polymerization heat was observed, the jacket temperature was controlled to 75 ° C. Polymerization was carried out continuously until the generation of polymerization heat ceased and the system was left to stand for 1 hour. The generation of polymerization heat ceased within 20 minutes after observation. Upon confirmation that heat generation had ceased, the polymerization conversion was 92% and the polymerization speed was 4.6% / minute. The volume average diameter of the rubbery polymer particle obtained was 105 nm.
[000167] While controlling the internal temperature at 70 ° C, an aqueous solution consisting of: dipotassium alkenylsuccinate (LATEMUL ASK manufactured by Kao Corporation) 0.2 part, formaldehyde sodium sulfoxylate 0.3 part, ferrous sulfate heptahydrate 0.001 part, disodium ethylenediaminetetraacetate 0.003 part and water 10 parts, was added. Subsequently, the temperature was raised to 80 ° C while a liquid mixture consisting of 12 parts acrylonitrile, 28 parts styrene and 0.2 part t-butyl hydroperoxide was added dropwise over a period of 80 minutes. .
[000168] After the dropwise addition was completed, the system was maintained at a temperature of 80 ° C for 30 minutes and was thereafter cooled to 75 ° C. Subsequently, a liquid mixture consisting of: 3-part acrylonitrile, 7-part styrene, 0.02 part normal octylmercaptan and 0.05 part t-butyl hydroperoxide, was added dropwise over a period of 20 minutes. After the dropwise addition was complete, the system was maintained at a temperature of 75 ° C for 60 minutes and thereafter cooled. In this way, a latex-grafted copolymer (B-1) was obtained.
[000169] Subsequently, 100 parts of a 2.0% aqueous solution of sulfuric acid were heated to 40 ° C and 100 parts of the grafted copolymer (B-1) in latex were added dropwise gradually to the aqueous solution stirring the aqueous solution, thereby solidifying the grafted copolymer. In addition, the temperature was raised to 95 ° C and the system was kept at temperature for 10 minutes.
[000170] Next, the solid was dehydrated, washed and dried to provide a powdered grafted copolymer (B-1). [SYNTHETIC EXAMPLE 10: Production of grafted copolymer (B-2)]
[000171] A graft copolymer (B-2) powder was obtained in the same manner as in SYNTHETIC EXAMPLE 9, except that the amount of dipotassium alkenyl succinate added in the polymerization of n-butyl acrylate was varied to 0.3 part.
[000172] The generation of heat by the polymerization of n-butyl acrylate ceased in 22 minutes after being observed. In the confirmation that the heat generation had ceased, the polymerization with conversion was 94% and the polymerization speed was 4.3% / minute. The volume average diameter of the rubbery polymer particle was 155 nm. [SYNTHETIC EXAMPLE 11: Production of grafted copolymer (B-3)]
[000173] A graft copolymer (B-3) powder was obtained in the same manner as in SYNTHETIC EXAMPLE 9, except that the amounts of ferrous sulfate heptahydrate and disodium ethylene diaminetetraacetate added in the polymerization of n-butyl acrylate were exchanged to 0.0000375 part and 0.0001125 part, respectively.
[000174] The generation of heat by the polymerization of n-butyl acrylate ceased in 40 minutes after being observed. Upon confirmation that the heat generation had ceased, the polymerization with conversion was 91% and the polymerization speed was 2.3% / minute. The volume average diameter of the particle was 130 nm.
[000175] The conditions for the synthesis of grafted copolymers (B-1) to (B-3), as well as the results of property evaluations are described in Table 3. Table 3
AMA: BDMA allyl methacrylate: 1,3-butanediol dimethacrylate * 1: parts by weight with respect to 100 parts by weight of acrylate ester monomer [SYNTHETIC EXAMPLE 12: Production of thermoplastic resins (C-1) and (C -two)]
[000176] Copolymers (C-1) and (C-2) of the thermoplastic resins (C-1) and (C-2) were obtained by a known method of suspension polymerization. The chemical compositions and reduced viscosities of the resins are described in Table 4. [SYNTHETIC EXAMPLE 13: Production of thermoplastic resin (C-3)]
[000177] A copolymer (C-3) was obtained as a thermoplastic resin (C-3) by a known continuous method of solution polymerization. The chemical composition and reduced viscosity of the resin are described in Table 4. [SYNTHETIC EXAMPLE 14: Production of thermoplastic resin (C-4)]
[000178] A copolymer (C-4) was obtained as a thermoplastic resin (C-4) by a known method of suspension polymerization. The chemical composition and reduced viscosity of the resin are described in Table 4.
[000179] Polycarbonate resin (Iupilon S-3000 (average molecular weight in viscosity (Mv): 21,000), manufactured by Mitsubishi Engineering-Plastics Corporation) was used as the thermoplastic resin (C-5).
[000180] The monomer compositions and reduced viscosities of the copolymers (C-1) to (C-4) are described in Table 4. Table 4
AN: acrylonitrile ST: styrene AMS: alpha-methylstyrene PMID: N-phenylmaleimide MMA: methyl methacrylate MA: methyl acrylate [EXAMPLE 11: Production of thermoplastic resin composition]
[000181] 16 parts of the grafted copolymer (A-1), 24 parts of the grafted copolymer (B-1), 30 parts of the thermoplastic resin (C-1), 30 parts of the thermoplastic resin (C-1) were mixed in a Henschel mixer -2), 0.5 part of ethylene bisstearylamide, 0.5 part of ADEKASTAB LA-63PK (manufactured by ADEKA CORPORATION) and 1 part of carbon black No. 960 (manufactured by Mitsubishi Chemical Corporation) as a colorant. The mixture was extruded with a twin screw degassing extruder (TEX30a manufactured by The Japan Steel Works, Ltd.) at a barrel temperature of 240 ° C to form pellets. The pellets were tested to determine the melt volume rate. The results are described in Table 5.
[000182] The resin pellets were molded with a 113 gram (4 ounce) injection molding machine (manufactured by The Japan Steel Works, Ltd.) at 220 to 260 ° C to provide the desired specimens. The specimens were tested to determine the impact resistance of Charpy, the Flexion Module and the Deflection Temperature under load. In addition, gloss and color-producing properties were measured against the surface of 100 x 100 x 2 mm flat specimens obtained by injection molding at an injection rate of 10 g / s or 40 g / s . The results are described in Table 5. [EXAMPLES 12 to 28 and COMPARATIVE EXAMPLES 3 to 5: Production of thermoplastic resin compositions]
[000183] Pellets of thermoplastic resin compositions were obtained in the same manner as in EXAMPLE 11, except that acrylic rubber grafted copolymers (A), acrylic rubber grafted copolymers (B), grafted copolymers (X) and resins thermoplastic (C) were added in the quantities described in Table 5. The properties were measured, the results being described in Table 5. Table 5

[Discussions] From Table 5, the following was demonstrated.
[000184] COMPARATIVE EXAMPLE 3 resulted in an inferior appearance with mediocre luster and poor color production properties due to the use of the grafted acrylic rubber copolymer (X-1) free of allyl methacrylate-derived units which was an essential polyfunctional monomer which have two unsaturated bonds in the present invention. The balance between impact resistance, brightness and color-producing properties was poor in COMPARATIVE EXAMPLE 4 which involved the grafted acrylic rubber copolymer (X-2) free from units derived from trialyl isocyanurate which was a polyfunctional monomer that had three bonds not saturated. In addition, COMPARATIVE EXAMPLE 5 which did not involve grafted acrylic rubber (A) copolymers according to the invention resulted in a mediocre balance between impact resistance and the Flexion Module. In all COMPARATIVE EXAMPLES, the articles exhibited significant variations in brightness and color-producing properties depending on whether they had been produced by low speed molding or high speed molding. Thus, it was demonstrated that these compositions have a high dependence on the injection rate.
[000185] In contrast, the thermoplastic resin compositions of EXAMPLES 11 to 28 of the invention, which contained the grafted acrylic rubber copolymer (A) according to the invention, achieved good properties in terms of mechanical strength such as impact resistance and Flexion module as well as in terms of appearance such as brightness and color-producing properties. [EXAMPLES 29 to 44 and COMPARATIVE EXAMPLES 6 to 8: Production of thermoplastic resin compositions]
[000186] Pellets of thermoplastic resin compositions were obtained in the same manner as in EXAMPLE 11, except that the thermoplastic resins (C-1) and (C-2) in EXAMPLE 11 were changed to the thermoplastic resin (C-4) which was a (meth) acrylic resin and that grafted acrylic rubber copolymers (A), grafted acrylic rubber copolymers (B), grafted copolymers (X) and thermoplastic resins (C) were added in the quantities described in Table 6 The properties were measured, the results are described in Table 6. Table 6
[Discussions] From Table 6, the following was demonstrated.
[000187] COMPARATIVE EXAMPLE 6 resulted in an inferior appearance with mediocre luster and poor color production properties due to the use of the grafted acrylic rubber copolymer (X-1) free of allyl methacrylate derived units which was an essential polyfunctional monomer which has two unsaturated bonds in the present invention. The balance between impact resistance, gloss and color-producing properties was poor in COMPARATIVE EXAMPLE 7 which involved the grafted acrylic rubber copolymer (X-2) free from units derived from trialyl isocyanurate which was a polyfunctional monomer that has three bonds not saturated. In addition, COMPARATIVE EXAMPLE 8 which did not involve grafted acrylic rubber copolymers (A) according to the invention resulted in a mediocre balance between impact resistance and the Flexion Module.
[000188] In contrast, the thermoplastic resin compositions of EXAMPLES 29 to 44 of the invention, which contained the grafted acrylic rubber copolymer (A) according to the invention, achieved good properties in terms of mechanical strength such as impact resistance and Flexural modulus as well as in terms of appearance such as gloss and color-producing properties, even when methacrylic resin (C-4) was used as the thermoplastic resin (C). [EXAMPLE 45: Production of thermoplastic resin composition]
[000189] 6 parts of the grafted copolymer (A-1), 9 parts of the grafted copolymer (B-1), 45 parts of the thermoplastic resin (C-1), 40 parts of the thermoplastic resin (C-1) were mixed in a Henschel mixer -5), 0.5 part of a paraffin wax, 0.5 part of ADEKASTAB LA-63PK (manufactured by ADEKA CORPORATION) and 1 part of carbon black No. 960 (manufactured by Mitsubishi Chemical Corporation) as a colorant. The mixture was extruded with a degassing twin screw extruder (TEX30a manufactured by The Japan Steel Works, Ltd.) at a barrel temperature of 250 ° C to form pellets. The pellets were tested to determine the melt volume rate. The results are described in Table 7.
[000190] The resin pellets were molded with a 113 gram (4 ounce) injection molding machine (manufactured by The Japan Steel Works, Ltd.) at 250 to 270 ° C to provide desired specimens. The specimens were tested to determine the impact resistance of Charpy, the Flexural Module and the Deflection Temperature under load, the brightness and the properties of color production. The results are described in Table 7. [EXAMPLES 46 to 63 and COMPARATIVE EXAMPLES 9 to 12: Production of thermoplastic resin compositions]
[000191] Pellets of thermoplastic resin compositions were obtained in the same manner as in EXAMPLE 45, except that the grafted acrylic rubber copolymers (A), the grafted acrylic rubber copolymers (B), the grafted copolymers (X) and the resins thermoplastic (C-1) and (C-5) were added in the quantities described in Table 7. The properties were measured, the results being described in Table 7. Table 7

[Discussions] From Table 7, the following was demonstrated.
[000192] COMPARATIVE EXAMPLE 9 resulted in an inferior appearance with mediocre luster and poor color-producing properties due to the use of the grafted acrylic rubber copolymer (X-1) free of units derived from ally methacrylate which was an essential polyfunctional monomer which has two unsaturated bonds in the present invention. The balance between impact resistance, gloss and color-producing properties was poor in COMPARATIVE EXAMPLE 10 which involved the grafted acrylic rubber copolymer (X-2) free from units derived from trialyl isocyanurate which was a polyfunctional monomer that has three bonds not saturated. In addition, COMPARATIVE EXAMPLE 11 which did not involve grafted acrylic rubber (A) copolymers according to the invention resulted in a mediocre balance between impact resistance and the Flexion Module. In COMPARATIVE EXAMPLE 12, a marked decrease in impact resistance was caused due to the small amount of total rubber polymers in the thermoplastic resin composition.
[000193] In contrast, the thermoplastic resin compositions of EXAMPLES 45 to 63 of the invention which contained the grafted acrylic rubber copolymer (A) according to the invention achieved good properties in terms of mechanical strength such as impact resistance and modulus of resistance. Flexion as well as appearance such as gloss and color-producing properties, even when styrene resin (C-1) and polycarbonate resin (C-5) were used as thermoplastic resins (C). Industrial Applicability
[000194] The grafted acrylic rubber (A) copolymers and the thermoplastic resin compositions according to the present invention present an excellent balance between impact resistance, rigidity and appearance and in addition exhibit excellent resistance to the weather. In this way, these materials are used appropriately in automotive materials, construction materials and home appliance materials that have recently come into use.
[000195] Although the present invention has been described in detail in relation to some specific embodiments, the person skilled in the art will consider that various modifications are possible within the spirit and scope of the invention.
[000196] This patent application is based on a Japanese patent application (JP 2011-072129), filed on March 29, 2011, the total content of which is incorporated herein by reference.

权利要求:
Claims (10)
[0001]
1. Grafted acrylic rubber copolymer, characterized by the fact that it is obtained by polymerization by grafting vinyl monomer, in the presence of a rubber polymer, including acrylate ester monomer units and polyfunctional monomer units, the amount being total units of polyfunctional monomer in the rubber polymer is 0.3 to 3 parts by weight with respect to 100 parts by mass of acrylate ester monomer units, with polyfunctional monomer units including 30 to 95% in mass of polyfunctional monomer units with two unsaturated bonds and 5 to 70% by weight of polyfunctional monomer units with three unsaturated bonds in relation to 100% by mass of the total polyfunctional monomer units, and polyfunctional monomer units with two unsaturated bonds are selected from the group consisting of allyl methyl acrylate and 2-propenyl acrylate.
[0002]
2. A grafted acrylic rubber copolymer according to claim 1, characterized by the fact that the rubbery polymer is a polymer obtained by mixing a copolymer latex obtained by the polymerization of a monomer mixture, including an acrylate ester monomer and polyfunctional monomers together with a copolymer latex containing an acid group to increase the polymer, and further adding a monomer including an acrylate ester monomer and polymerizing the monomer to the increased polymer.
[0003]
3. Grafted acrylic rubber copolymer, according to claim 1 or 2, characterized by the fact that the rubber polymer has an average particle diameter in volume of 300 to 600 nm.
[0004]
4. Acrylic rubber grafted copolymer according to any one of claims 1 to 3, characterized in that the polyfunctional monomer units with two unsaturated bonds are allyl methacrylate.
[0005]
5. Thermoplastic resin composition, characterized in that it comprises the grafted acrylic rubber copolymer, as defined in any of claims 1 to 4 (hereinafter, referred to as "grafted acrylic rubber copolymer (A)").
[0006]
6. Thermoplastic resin composition according to claim 5, characterized in that the thermoplastic resin composition comprises the grafted acrylic rubber copolymer (A) and an grafted acrylic rubber copolymer having an average particle diameter in volume of 70 to 200 nm and obtained by grafting polymerizing a vinyl monomer in the presence of a rubber polymer, which includes acrylate ester monomer units (hereinafter referred to as "grafted acrylic rubber copolymer (B)").
[0007]
7. Thermoplastic resin composition according to claim 6, characterized in that the thermoplastic resin composition includes the rubber polymers in a total amount of 5 to 30 parts by weight in relation to 100 parts by weight of components of resin in the thermoplastic resin composition and the amount of rubber polymer in the grafted acrylic rubber copolymer (A) is 20 to 70% by weight and the amount of rubber polymer in the grafted acrylic rubber copolymer (B) is 30 to 80% by weight in relation to the total of rubber polymers in the thermoplastic resin composition taken as 100% by weight.
[0008]
8. Thermoplastic resin composition according to claim 6 or 7, characterized in that it comprises 0 to 90 parts by mass of an additional thermoplastic resin (C) other than the grafted acrylic rubber copolymer (A) and the grafted copolymer of acrylic rubber (B).
[0009]
9. Thermoplastic resin composition according to any one of claims 6 to 8, characterized in that the grafted acrylic rubber copolymer (B) is a polymer obtained in such a way that 100% by weight of an ester monomer of acrylate is polymerized at a polymerization rate of not less than 3% by mass / min.
[0010]
10. Article in the form of thermoplastic resin, characterized by the fact that it is obtained by modeling the composition of thermoplastic resin, as defined in any one of claims 5 to 9.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

JPS5034592B1|1970-12-18|1975-11-10|

---

JPS5230996B2|1972-05-15|1977-08-11|

---

JPH0134461B2|1983-06-15|1989-07-19|Mitsubishi Monsanto Chem|

---

JPH0436170B2|1983-11-24|1992-06-15|Mitsubishi Rayon Co|

---

JPS62230841A|1985-11-29|1987-10-09|Mitsubishi Rayon Co Ltd|Impact-resistant methacrylate resin composition|

---

JPH0366329B2|1986-02-06|1991-10-17|Mitsubishi Rayon Co|

---

JPH0725965B2|1986-06-24|1995-03-22|電気化学工業株式会社|Weather resistant heat resistant resin composition|

---

DE3743199A1|1987-12-19|1989-06-29|Roehm Gmbh|IMPACT MODIFIER FOR PLASTICS|

---

DE4011162A1|1990-04-06|1991-10-10|Basf Ag|THERMOPLASTIC MOLDING|

---

JPH07304824A|1994-05-13|1995-11-21|Sekisui Chem Co Ltd|Production of vinyl chloride-based resin|

---

JP3630182B2|1994-11-15|2005-03-16|株式会社カネカ|Resin composition with excellent impact resistance|

---

JP3507581B2|1995-04-27|2004-03-15|積水化学工業株式会社|Vinyl chloride resin composition|

---

US7488775B2|2000-12-25|2009-02-10|Mitsubishi Rayon Co., Ltd.|Graft copolymer and thermoplastic resin composition|

---

JP2002194034A|2000-12-25|2002-07-10|Mitsubishi Rayon Co Ltd|Graft copolymer, thermoplastic resin composition and molded product using the composition|

---

JP4346956B2|2003-05-22|2009-10-21|三菱レイヨン株式会社|Thermoplastic resin composition and molded article|

---

JP2004346237A|2003-05-23|2004-12-09|Umg Abs Ltd|Thermoplastic resin composition and molded product|

---

JP2006016524A|2004-07-02|2006-01-19|Umg Abs Ltd|Thermoplastic resin composition and molded product thereof|

---

JP2006241283A|2005-03-02|2006-09-14|Nippon A & L Kk|Thermoplastic resin composition and resin molded product composed of the same|

---

JP2007091970A|2005-09-30|2007-04-12|Nippon A & L Kk|Thermoplastic resin composition, material for lighting fixture of vehicle and housing part for lighting fixture of vehicle|

---

CN102132212B|2008-09-04|2013-08-28|日立化成株式会社|Positive-type photosensitive resin composition, method for producing resist pattern, and electronic component|JP2012214702A|2011-03-31|2012-11-08|Unitika Ltd|Resin composition and molded article made of the resin composition|

---

KR20150002267A|2013-06-28|2015-01-07|제일모직주식회사|Thermoplastic resin composition and molded article using the same|

---

KR101681212B1|2013-09-03|2016-11-30|롯데첨단소재|Molded article for automobile using thermoplastic resin composition|

---

KR101750679B1|2013-12-06|2017-06-27|현대모비스 주식회사|Thermoplastic resin composition having excellent weatherability and improved deposition|

---

US10100190B2|2014-02-06|2018-10-16|Toray Industries, Inc.|Thermoplastic resin composition|

---

JP5742994B1|2014-03-19|2015-07-01|ユーエムジー・エービーエス株式会社|Thermoplastic resin composition and resin molded product|

---

JP6149783B2|2014-03-31|2017-06-21|ユーエムジー・エービーエス株式会社|Thermoplastic resin composition and molded article thereof|

---

US10208202B2|2014-06-13|2019-02-19|Umg Abs, Ltd.|Thermoplastic resin composition containing polycarbonate resin, graft copolymer, and copolymer, and molded article thereof|

---

JP6276116B2|2014-06-17|2018-02-07|ユーエムジー・エービーエス株式会社|Thermoplastic resin composition and vehicle lamp housing using the same|

---

KR101671297B1|2015-01-07|2016-11-02|금호석유화학 주식회사|Method for preparing acrylic graft copolymer having superior coloring properties and impact strength|

---

JP6597403B2|2015-03-23|2019-10-30|東レ株式会社|Thermoplastic resin composition|

---

JP6554870B2|2015-03-31|2019-08-07|東レ株式会社|Thermoplastic resin composition|

---

KR101957854B1|2015-05-13|2019-03-14|주식회사 엘지화학|Acrylate based processing aid and vinyl chloride resin composition comprising thereof|

---

KR101884972B1|2015-12-04|2018-08-02|주식회사 엘지화학|Thermoplastic resin composition having gloss and reduced gloss and molded article made from same|

---

JP6885345B2|2016-01-21|2021-06-16|テクノＵｍｇ株式会社|Rubbery polymer, graft copolymer and thermoplastic resin composition|

---

JP6962724B2|2017-07-06|2021-11-05|テクノＵｍｇ株式会社|Three-way polymer, graft polymer and thermoplastic resin composition|

---

WO2019009203A1|2017-07-06|2019-01-10|テクノＵｍｇ株式会社|Polymer, graft polymer, and thermoplastic resin composition|

---

JP6980445B2|2017-07-28|2021-12-15|テクノＵｍｇ株式会社|Thermoplastic resin compositions and molded products|

---

KR102185742B1|2017-11-22|2020-12-02|주식회사 엘지화학|Method for preparing graft copolymer powder|

---

KR102060530B1|2017-12-28|2019-12-30|금호석유화학 주식회사|An acrylic graft copolymer and a method for prepairng the same|

---

SG11202010603TA|2018-04-27|2020-11-27|Zeon Corp|Method for producing acrylic rubber, and acrylic rubber obtained by said production method|

---

WO2021039895A1|2019-08-30|2021-03-04|三菱エンジニアリングプラスチックス株式会社|Polycarbonate resin composition, and molded product thereof|

法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-02-27| B25A| Requested transfer of rights approved|Owner name: TECHNO-UMG CO., LTD. (JP) |

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2020-05-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-01| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2011072129|2011-03-29|

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JP2011-072129|2011-03-29|

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PCT/JP2012/057525|WO2012133190A1|2011-03-29|2012-03-23|Acrylic rubber-based graft copolymer and thermoplastic resin composition|

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