• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PURPOSE: A thermoplastic resin composition having a good shock resistance and a plasticity is provided which is mixed with a butadiene based rubber graft copolymer and nonlinear acrylonitrilstyrene copolymer resin having a crosslinking point, so it manufactures large plastic goods and is used for various utilities of structural material. CONSTITUTION: A thermoplastic resin composition having a good shock resistance and plasticity is composed of 20-50 wt.pts. of graft copolymer(11) which is made by a copolymerization of rubber copolymer(B) with cyanovinyl compound(A) and aliphaticvinyl compound(S) or (A), (S) and monomer(E), wherein the weight average molecular weight of copolymer(II) is 120,000-600,000. The copolymerized weight average molecular weight is more 18,000 by containing 0.01-3 wt.pts. of the composition composed of 1-99 wt% of multifunctional mercaptan and 99-1 wt% of vinyl benzene based compound, and contains an ingredient(II-1) having more 0.6 of intrinsic viscosity. The graft copolymer(I) is composed of 20-80 wt% of graft copolymer(I-1) having 0.1-0.2 micrometer of particle size and 80-20 wt% of graft copolymer(I-2) having 0.28-0.40 micrometer of particle size.
    公开号:KR20000046092A
    申请号:KR1019980062768
    申请日:1998-12-31
    公开日:2000-07-25
    发明作者:안경현；김성국；정종훈；안성희
    申请人:유현식；제일모직 주식회사；
    IPC主号:
    专利说明:

    Thermoplastic resin composition excellent in impact resistance and moldability
    The present invention relates to a thermoplastic resin composition, and more particularly, in preparing a composition of acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as "ABS resin"), two kinds of butadienes having different sizes of rubber particles A method for producing a thermoplastic resin composition having excellent impact resistance and moldability by mixing a rubbery graft copolymer and a non-new acrylonitrile-styrene copolymer resin having a crosslinking point (hereinafter referred to as "SAN resin") and its To a composition.
    In general, ABS resins have excellent mechanical and thermal properties, such as physical properties such as processability of styrene, stiffness and chemical resistance of acrylonitrile, and impact resistance of butadiene rubber, and have excellent appearance characteristics such as helmets, pipes, electrical and electronic products, It is widely used in the field of rigid molded products from daily necessities such as automobile parts and general office supplies to industrial goods.
    Most of these molded products are manufactured by injection molding, but in the case of the size of the molded products being large or curved on the outside of the molded products, they are produced by vacuum molding or the like. Vacuum molding is a plastic sheet that obtains a product of a desired shape by extruding a sheet and manufacturing a sheet sheet first, and then softening the sheet in a vacuum molding machine and simultaneously performing vacuum or pressure and vacuum to adhere the softened sheet to a mold. It is a kind of molding method.
    However, the conventional general ABS resin has a problem that a lot of thickness variation occurs during the vacuum molding, so that a very thin portion locally occurs, so that a lot of defects such as tearing occur at the portion. In order to solve this problem, the use of SAN copolymer having a large molecular weight and molecular weight distribution can reduce the thickness variation somewhat, but due to the deterioration of fluidity, the extruder load increases during compounding and sheet production, resulting in a decrease in productivity and color change. There is this. In addition, the application range of ABS resin by vacuum molding has been gradually increased in recent years, and is used as structural materials for various uses. Unlike conventional sheets, very high impact resistance is required. There is a need for a new concept of resin having excellent impact resistance and moldability.
    On the other hand, blow molding is a molding technique in which a molten thermoplastic resin is extruded onto a pipe, held in a mold, adhered to a mold wall surface by air pressure, and cooled to produce a hollow product such as a plastic bottle. Increasingly, the scope of development has been expanded to manufacture large structural materials. The blow molding method is inexpensive compared to injection molding, and the structure can be curved in a variety of designs, and in the case of a large structure, its use is gradually expanding due to the advantage of having a low residual stress.
    When polyolefins such as low density polyethylene are used for the production of large molded articles by blow molding method, the moldability is excellent, but when coating is required, application of the structural material is low due to low adhesion strength of the coating film, and in the case of modified polyphenylene ether, coating film adhesion It is excellent in heat resistance, but its chemical resistance is poor, so stress cracks due to thinner or the like occur during painting, and the surface is often worsened. On the other hand, ABS resin has been widely used for injection molding and vacuum molding because of its excellent mechanical properties, ease of molding, and beautiful appearance, but it is used for blow molding due to the heavy draw down and the thick thickness of the molded product. It is often difficult to be.
    Japanese Patent Publication No. 95-15039 discloses a technique for applying ABS resin having excellent paintability to blow molding of large parts by using a resin composition having a slightly larger molecular weight and molecular weight distribution than conventional ABS resin. However, simply increasing the molecular weight and molecular weight distribution does not significantly improve the blow moldability of the ABS resin.
    On the other hand, Japanese Patent Publication No. 95-5820 discloses a technique using a copolymer copolymerized with an organic silane compound to improve blow property of ABS resin, but this method is manufactured by solution polymerization, which makes it difficult to mass-produce. There is a problem that the manufacturing cost increases.
    SUMMARY OF THE INVENTION An object of the present invention is to overcome the problems of the prior art as described above, and to produce a non-linear acrylonitrile-styrene copolymer resin having a crosslinking point with two butadiene-based rubbery graft copolymers having different sizes of rubber particles. By mixing, the thickness variation during vacuum molding can be reduced to reduce the fluidity, and the vacuum forming is improved. The parison has a large strength and a small drawdown, so it is suitable for blow molding of large parts with a small thickness thickness of blow molded products. It is to provide a thermoplastic resin composition with significantly improved impact resistance.
    That is, the present invention is a graft copolymer (I) obtained by copolymerizing a vinyl cyanide compound (A) with an aromatic vinyl compound (S) or a monomer (E) copolymerizable with (A) or (S) in a rubbery polymer (B). It consists of 20-50 weight part and 80-50 weight part of copolymers (II) which consist of (A), (S) or (A), (S), and (E), and the weight average molecular weight of copolymer (II) It is 120,000-600,000, and the weight average molecular weight copolymerized with 0.01-3 weight part of the mixture which consists of 1-99 weight% of polyfunctional mercaptans and 99-1 weight% of vinylbenzene compounds in the composition of (II) is 180,000. A thermoplastic resin composition comprising component (II-1) having an intrinsic viscosity of 0.6 or more, wherein the graft copolymer (I) has a graft copolymer (I-1) having a particle diameter of 0.1 to 0.2 µm and a particle diameter of 0.28. The graft copolymer (I-2) having a ˜0.40 μm ratio of 20 to 80 and 80 to 20 wt%, respectively, relative to 100 parts by weight of the graft copolymer (I) To provide a thermoplastic resin composition, characterized in that in the composition.
    Hereinafter, the present invention will be described in more detail.
    First, the graft copolymer (I) is composed of a graft copolymer (I-1) having a particle size of 0.1-0.2 µm and a graft copolymer (I-2) having a particle size of 0.28-0.40 µm. The copolymer is a graft copolymer emulsified or bulk polymerized by a conventional method using 10-50 parts by weight of acrylonitrile and 90-50 parts by weight of styrene in the presence of 30-60 parts by weight of polybutadiene latex, respectively. It is appropriate that the grafted acrylonitrile-styrene copolymer is 35 to 60 parts by weight, and the content of acrylonitrile is 15 to 45 parts by weight in the grafted acrylonitrile-styrene copolymer. If the content of acrylonitrile in the grafted acrylonitrile-styrene copolymer is out of the above range, the compatibility with the ungrafted acrylonitrile-styrene copolymer (II) is insufficient and the mechanical properties are deteriorated. Is not good because it can occur. The content ratio of the graft copolymer is an impact resistance increase effect can be obtained when the content ratio of the graft copolymer (I-1) is 20 to 80% by weight based on 100 parts by weight of the graft copolymer (I) More preferably, the effect is most noticeable when it is 30 to 60% by weight. The graft copolymer (I) having the particle size distribution described above may be prepared by copolymerizing and mixing two graft copolymers having respective particle size distributions or having the particle distribution as described above by a two-step reaction in the polymerization step. Can be.
    On the other hand, the vinyl cyanide compound-aromatic vinyl compound copolymer (II), which may be represented by an acrylonitrile-styrene copolymer, is prepared in a conventional manner using 10 to 50 parts by weight of a vinyl cyanide compound and 90 to 50 parts by weight of an aromatic vinyl compound. Polymerized copolymers generally have a linear structure. Copolymer (II-1) having a nonlinear structure is a copolymer polymerized including a mixture of a polyfunctional multicaptan and a vinylbenzene compound of 3 parts by weight or less with respect to 100 parts by weight of a vinyl cyanide compound and an aromatic vinyl compound. In particular, in order to improve vacuum formation of ABS resin, the copolymer (II-1) should have a PS reduction weight average molecular weight of 180,000 or more by GPC and an intrinsic viscosity of 0.6 or more in tetrahydrofuran solvent. . If the molecular weight and intrinsic viscosity are out of the above range, regardless of the content of the copolymer, the vacuum forming of ABS does not improve clearly, so that the uniform thickness distribution cannot be obtained. Not suitable for
    Multifunctional mulcaptans that can be used in the present invention include trifunctional and tetrafunctional mulcaptans. The trifunctional mercaptans include trimetholpropane tri (3-mercaptopropionate), trimetholpropane tri (3-mercaptoacetate), trimetholpropane tri (4-mercaptobutanate) and trimetholamide. Tyrolpropane tri (5-mercaptopentanate), trimetholpropane tri (6-mercaptohexaonate) and the like can be used. Tetrafunctional mercaptans include pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (4-mercaptobutanate), and pentaerythrate. Lititol tetrakis (5-mercaptopentanate), pentaerythritol tetrakis (6-mercaptohexanate), and the like. In the present invention, the multifunctional mulcaptan may be used alone or in combination of two or more of the above compounds. In the present invention, as the vinylbenzene compound, divinylbenzene is preferable. The above compounds are only for illustrating the present invention and do not have a limiting meaning.
    U.S. Patent No. 4,918,159 discloses a method for producing a non-linear styrene resin using a multifunctional multicaptan, but when using the multifunctional multicaptan alone, the reactivity is slow and the dispersion system becomes very unstable as the polymerization proceeds. This may cause problems in the polymerization reaction control, such as a problem that the entire polymerization system is hardened.
    On the other hand, Japanese Patent Application Laid-Open No. 59-149912 discloses that the copolymer made of a polyaromatic compound and a polyfunctional compound copolymerizable with a vinyl cyanide compound improves the fluidity and mechanical properties. In this case, there is a problem in that the reactivity is not easy to control the molecular structure of the resin.
    The present invention can overcome the above problems, in the preparation of non-linear copolymer (II-1), the reactivity is controlled by using a highly functional divinylbenzene and a polyfunctional multicaptan which is slow and easy to gelation And, by limiting the range of the weight average molecular weight and the intrinsic viscosity of the polymerized copolymer, it is characterized by improving the moldability of the ABS resin by greatly improving the stretching characteristics. The content of the mixture consisting of the polyfunctional mercaptan and the vinylbenzene compound used in the present invention is 0.01-3 parts by weight, more preferably 0.1-2 parts by weight, based on 100 parts by weight of the vinyl cyanide compound and the aromatic vinyl compound. The mixing ratio of the mercaptan and the vinylbenzene compound is a ratio of 99-1% by weight of the vinylbenzene compound to 1-99% by weight of the polyfunctional mercaptan. In the present invention, when the content of the mixture consisting of the multifunctional mercaptan and the vinylbenzene compound is less than 0.01 part by weight, the effect of improving the stretching property is not obvious. When the content exceeds 3 parts by weight, the gelation reaction proceeds and the copolymer is usable. Not formed. In addition, when the PS-reduced weight average molecular weight by GPC is less than 180,000 or the intrinsic viscosity is less than 0.6 in a tetrahydrofuran solvent, the effect of improving the stretching property is not obvious, and the upper limit of the allowable weight average molecular weight and intrinsic viscosity is for use. The range may not be limited unless gelation proceeds sufficiently as it may be applied differently according to the present invention.
    In the present invention, the weight average molecular weight of the copolymer (II) is preferably 120,000-600,000 when expressed in terms of styrene by gel permeation chromatography (GPC). If the weight average molecular weight is less than 120,000, it is difficult to obtain a molded article having a uniform thickness distribution due to the drawdown is severe, and when exceeding 600,000, there is a problem that the productivity is lowered and the color change occurs due to a lot of extrusion load during molding.
    In the present invention, the rubbery polymer (B) is an acrylic such as a diene rubbery polymer such as polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butyl acrylate-methyl methacrylate-methacrylate ester copolymer, etc. Saturated rubber polymers, such as rubber | gum and ethylene propylene copolymer rubber, etc. can be used. The content of the rubbery component in the resin is appropriately 10-30 parts by weight. If it is less than 10 parts by weight, the impact resistance is weak, and if it exceeds 30 parts by weight, problems such as insufficient rigidity of the molded article may occur.
    Acrylonitrile or methacrylonitrile may be used as the vinyl cyanide compound constituting the copolymer (I) or (II) or (II-1) in the thermoplastic resin composition of the present invention. , Alphamethylstyrene, or a mixture of styrene and alphamethylstyrene may be used, and methacrylic acid ester compounds such as methyl methacrylate or butyl acrylate, N phenylmaleimide, N cyclohexyl maleimide, maleic anhydride, and the like. This may be copolymerized.
    The amount of the cyanide compound unit in the resin is appropriately 10-50 parts by weight of the resin component except for the rubbery polymer, if less than 10 parts by weight stress cracking occurs due to paint or thinner may cause problems in the appearance of the molded article. On the contrary, if it exceeds 50 parts by weight, problems such as discoloration of the resin may occur during reuse.
    In the present invention, as the method for producing the copolymers (I) and (II), known methods, that is, emulsion polymerization method, suspension polymerization method, solution polymerization method and the like can be used. Supplementary ingredients, such as stabilizers, lubricants, may be added.
    The invention will be further elucidated by the following examples which are set forth for the purpose of illustrating the invention and are not intended to limit the scope of the invention.
    EXAMPLE
    Preparation Example 1 Preparation of Graft Copolymer (G-1)
    45 parts by weight of polybutadiene latex (rubber average particle size 0.32㎛) and 200 parts by weight of deionized water were added to a polymerization reactor equipped with a stirring device, a reflux cooler, a thermometer, and a preparation device. 7 parts by weight of a 4% aqueous potassium perchlorate solution while stirring under a nitrogen stream. And 60 parts by weight of styrene and 40 parts by weight of acrylonitrile were added to the monomer mixture, and 0.1 parts by weight of t-dodecyl mercaptan was continuously added for 3 hours to polymerize at 70 ° C. The latex obtained here was dropped into 4% aqueous sulfuric acid solution heated to 90 ° C, washed, dehydrated and dried to obtain a graft copolymer (G-1). The graft ratio of the obtained copolymer was 50% and the weight average molecular weight of the ungrafted acrylonitrile styrene copolymer was 45,000.
    Preparation Example 2 Preparation of Graft Copolymer (G-2)
    A graft copolymer G-2 was prepared by the same method as Preparation Example 1, except that 50 parts by weight of a monomer mixture of styrene and acrylonitrile were mixed with 50 parts by weight of polybutadiene rubber having a rubber particle diameter of 0.12 μm.
    Preparation Example 3 Preparation of Copolymer (II-1)
    Styrene 71%, acrylonitrile 29%, ion exchanged water 150 parts, tricalcium phosphate 0.4 part, carboxylic acid anionic surfactant 0.03 part, polyoxyethylene alkyl ether phosphate ester, And 0.5 part of trimetholpropane tri (3-mercaptopropionate) trivalent as a polyfunctional mercaptan and 0.1 part of divinylbenzene were mixed with 0.5 part of 2,2'-azobisisobutylonitrile as an initiator. After the reactor was completely sealed, the mixture was sufficiently stirred to disperse, and then the internal temperature of the reactor was raised to proceed with polymerization at 75 ° C. for 6 hours. Subsequently, the inside of the reactor was cooled to room temperature to terminate the reaction, and then the obtained polymer was washed, dehydrated and dried to obtain a bead-like copolymer (II-1). The weight average molecular weight by GPC of the copolymer obtained at this time was 320,000.
    Preparation Example 4 Preparation of Copolymer (II-2)
    A copolymer (II-2) was prepared in the same manner as in Preparation Example 3, except that 1 part of trimetholpropane tri (3-mercaptopropionate) and 0.02 part of divinylbenzene were mixed and used.
    Preparation Example 5 Copolymer (S-1) to Copolymer (S-3)
    Copolymers (S-1) to (S-3) used in this example are as follows.
    S-1: Acrylonitrile-styrene copolymer whose weight average molecular weight is 260,000-350,000, and the content of acrylonitrile is 23-28 weight%.
    S-2: Acrylonitrile-styrene copolymer whose weight average molecular weight is 100,000-160,000, and the content of acrylonitrile is 36-42 weight%.
    S-3: Acrylonitrile-styrene copolymer having a weight average molecular weight of 100,000 to 120,000 and an acrylonitrile content of 23 to 28% by weight.
    Example 1
    Graft copolymers (G-1) and (G-2) and acrylonitrile-styrene copolymers (II-1) and (S-2) are respectively mixed in a ratio of 20: 20: 30: 30, and 0.4 parts by weight of a conventional heat stabilizer and a lubricant were mixed with respect to 100 parts by weight of the resin, and pellets were prepared by using a twin screw extruder having a diameter of 40 mm. The prepared pellets were made of injection specimens according to the ASTM D236 method, and the impact strength of the 1/4 inch specimens was measured. In addition, the prepared pellets were made into compressed specimens of 400 mm × 400 mm × 2 mm using a press, and then the lattice of 50 mm width and width was displayed on the prepared compression specimens, and then 300 mm (L) through a vacuum molding machine. A vacuum molded article of × 30 mm (W) × 200 mm (H) was prepared, and the physical properties of the vacuum molded article were evaluated and shown in Table 1 below.
    Example 2
    Except for changing the acrylonitrile-styrene copolymer (S-2) to (S-3) was carried out in the same manner as in Example 1 to prepare a vacuum molded article and to evaluate the overall physical properties are shown in Table 1 below. .
    Example 3
    Except for changing the acrylonitrile-styrene copolymer (II-1) to (II-2) was carried out in Example 1 to prepare a vacuum molded article and to evaluate the overall physical properties are shown in Table 1 together.
    Example 4
    Except for changing the acrylonitrile-styrene copolymer (II-1) to (II-2) was carried out in the same manner as in Example 2 to prepare a vacuum molded article and to evaluate the overall physical properties are shown in Table 1 below. .
    Comparative Example 1
    Vacuum was carried out in Example 1 except that the graft copolymer (G-1) was mixed with the acrylonitrile-styrene copolymers (S-1) and (S-2) in a ratio of 40:30:30. To prepare a molded article and to evaluate the overall physical properties are shown in Table 1 below.
    Comparative Example 2
    The same procedure as in Example 1 was carried out except that the graft copolymer (G-2) was mixed with the acrylonitrile-styrene copolymers (S-1) and (S-3) in a ratio of 40:30:30. To prepare a vacuum molded article and to evaluate the overall physical properties are shown in Table 1 below.
    Comparative Example 3
    Except for changing the acrylonitrile-styrene copolymer (II-1) to (S-1) was carried out in the same manner as in Example 1 to prepare a vacuum molded article and to evaluate the overall physical properties are shown in Table 1 below. .
    Comparative Example 4
    The same procedure as in Example 1 was carried out except that the graft copolymer (G-1) was mixed with the acrylonitrile-styrene copolymers (II-1) and (S-3) in a ratio of 40:30:30. To prepare a vacuum molded article and to evaluate the overall physical properties are shown in Table 1 below.
    Comparative Example 5
    A vacuum molded article was prepared in the same manner as in Comparative Example 4 except that (G-1) and (G-2) were mixed at a ratio of 90 parts by weight and 10 parts by weight, respectively, based on 100 parts by weight of the graft copolymer. And the physical properties were evaluated and shown in Table 1 below.
    Notch Impact Strength (kg-cm / cm)Thickness (mm)Standard deviation (mm)Swellby (-)Draw time (sec) Example 1400.500.101.961 Example 2360.520.122.062 Example 3390.480.121.859 Example 4350.500.131.960 Comparative Example 1300.300.251.440 Comparative Example 2250.320.231.338 Comparative Example 3400.300.241.339 Comparative Example 4270.500.132.058 Comparative Example 5280.510.131.957
    [Property evaluation method]
    (1) minimum thickness and standard deviation
    For the vacuum molded article, the thickness of the intersection point of the lattice was measured with a thickness meter with an accuracy of 1/100 mm. Large minimum thickness and small standard deviation can be said to be excellent in vacuum forming.
    (2) Swellby and Draw Time
    The pellets were extruded using a blow molding machine having a diameter of 50 mm at a cylinder temperature of 220 ° C. and a screw speed of 30 rpm to measure swell ratio and draw time from a parison formed. Swellby is defined as the diameter of the parison tip divided by the diameter of the die, and the draw time is defined as the time it takes for the ferry to leave the 1.2m high die from the ground and reach the ground. In general, the greater the swell ratio, the longer the draw time, the greater the parison's strength and the better formability.
    The thermoplastic resin composition of the present invention has the advantage of being suitable for blow molding of large parts by reducing the thickness variation without deteriorating fluidity, and excellent in vacuum forming, high strength of parison, low drawdown, and low thickness sheeting of blow molded articles. In addition, the thermoplastic resin composition of the present invention is excellent in impact resistance, it is possible to develop a use as a structural material of various applications.
    权利要求:
    Claims (3)
    [1" claim-type="Currently amended] 20 to 50 parts by weight of a graft copolymer (I) obtained by copolymerizing a vinyl cyanide compound (A) with an aromatic vinyl compound (S) or a monomer (E) copolymerizable with (A) and (S) to a rubbery polymer (B) And (A), (S) or 80 to 50 parts by weight of copolymer (II) consisting of (A), (S) and (E), the weight average molecular weight of the copolymer (II) is 120,000-600,000, In the composition of (II), 0.01-3 parts by weight of a mixture composed of 1-99% by weight of polyfunctional mercaptan and 99-1% by weight of a vinylbenzene compound was copolymerized, and the weight average molecular weight of the copolymer was 180,000 or more and the intrinsic viscosity A thermoplastic resin composition comprising component (II-1) having 0.6 or more, wherein the graft copolymer (I) is a graft copolymer (I-1) having a particle size of 0.1 to 0.2 µm and a graft having a particle diameter of 0.28 to 0.40 µm. The copolymer (I-2) at 20 to 80 and 80 to 20% by weight, based on 100 parts by weight of the graft copolymer (I) Thermoplastic resin composition characterized in that.
    [2" claim-type="Currently amended] The method of claim 1, wherein the multifunctional mercaptan is trimetholpropane tree (3-mercaptopropionate), trimetholpropane tree (3-mercaptoacetate), trimetholpropane tree (4-mercapto) Butanate), trimetholpropane tri (5-mercaptopentanate), trimetholpropane tri (6-mercaptohexaonate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetra Keith (3-Mercaptopropionate), Pentaerythritol Tetrakis (4-Mercaptobutanate), Pentaerythritol Tetrakis (5-Mercaptopentanate), Pentaerythritol Tetrakis (6-Mercaptohexa) Nate) is at least one member selected from the group consisting of a thermoplastic resin composition.
    [3" claim-type="Currently amended] The thermoplastic resin composition according to claim 1, wherein the vinylbenzene compound is divinylbenzene.
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    同族专利:
    公开号 | 公开日
    KR100430890B1|2004-10-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-12-31|Application filed by 유현식, 제일모직 주식회사
    1998-12-31|Priority to KR10-1998-0062768A
    2000-07-25|Publication of KR20000046092A
    2004-10-12|Application granted
    2004-10-12|Publication of KR100430890B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR10-1998-0062768A|KR100430890B1|1998-12-31|1998-12-31|Thermoplastic composition with excellent impact resistance and formability|
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