• 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:
    To provide an organic silicon compound having an average structural formula (1).(Z represents a 2 to 20-valent group containing an organosiloxane structure, each R<sup>1</sup>independently represents an alkyl group or an aryl group, each R<sup>2</sup>independently represents an alkyl group or an aryl group, each R<sup>3</sup>independently represents a hydrogen atom, an alkyl group, an alkoxy group, or an O• (oxy radical), each R<sup>4</sup>independently represents a hydrogen atom or an alkyl group, each A<sup>1</sup>independently represents a single bond or an alkylene group free of a hetero atom, each A<sup>2</sup>independently represents a single bond or a divalent linking group containing a hetero atom, m is a number of 1 to 3, p is a number of 1 to 10, q is a number of 1 to 10, and p + q represents a number satisfying from 2 to 20 corresponding to the valency number of Z.)
    公开号:EP3699182A1
    申请号:EP20156477.0
    申请日:2020-02-10
    公开日:2020-08-26
    发明作者:Tetsuro Yamada；Munenao Hirokami
    申请人:Shin Etsu Chemical Co Ltd；
    IPC主号:C08G77-00
    专利说明:
    [0001] The present invention relates to an organic silicon compound, a method for producing the organic silicon compound, and a curable composition. In more detail, it relates to an organic silicon compound having an organosiloxane structure, a hydrolysable group, and a hindered amine skeleton in the molecule, to methods for producing such organic silicon compound, to curable compositions containing the organic silicon compound, and to uses thereof e.g. as a light stabilizer, and/or for coating or adhesion. BACKGROUND
    [0002] A silane coupling agent is a compound that has in one molecule a part having reactivity to an inorganic substance (a hydrolysable group bonded to a Si atom) and a part capable of performing the impartment of various functions such as reactivity to an organic substance, solubility, and weather resistance, and acts as an adhesive auxiliary at the interface between an inorganic substance and an organic substance, or a resin modifier for an inorganic-organic composite material, and therefore, the silane coupling agent is widely used as a composite resin modifier.
    [0003] On the other hand, a resin material has a problem of degradation over time due to the action of light such as ultraviolet rays. Such time degradation appears as deterioration of physical properties of the resin and of appearance, for example, as a phenomenon such as deterioration in flexibility or an appearance defect (cracking, yellowing, or whitening of the cured product).
    [0004] As a countermeasure against the above time degradation, it has been studied that together with an ultraviolet absorbing agent such as benzotriazole or benzophenone, a stabilizer such as a nickel complex, and an antioxidant such as a hindered phenol-based antioxidant, in particular, 2,6-bis(tert-butyl)-hydroxytoluene, a hindered amine-based light stabilizer that is known to exert an excellent effect in the impartment of light stabilization, particularly of weather resistance is mixed with a resin material.
    [0005] This hindered amine-based light stabilizer (HALS) suppresses time degradation due to action of light such as ultraviolet rays on a resin, in particular, an organic resin, and has been widely used as a resin modifier capable of imparting weather resistance or light resistance to an organic resin. As the HALS, various compounds containing mainly a 2,2,6,6-tetramethylpiperidinyl group, or a 1,2,2,6,6-pentamethylpiperidinyl group have been proposed, and such a study has been conventionally conducted.
    [0006] However, in recent years, the weather resistance properties required for resin materials have become stricter, and there has arisen a problem that the stabilization effect is not sufficiently maintained due to the surface contamination of a resin material by volatilization or bleed-bloom phenomenon of a hindered amine-based light stabilizer during long-term use, or due to the falling of a light stabilizer added along with surface contamination.
    [0007] In order to solve the problem as described above, Patent Document 1 has disclosed a method for binding a hindered amine-based light stabilizer directly to a resin material or a polymer compound, and Patent Document 2 has disclosed increasing the molecular weight by binding multiple hindered amine-based light stabilizers in one molecule.
    [0008] However, it still cannot be said that the weather resistance of these hindered amine-based light stabilizers is sufficient, and further improvement has been desired.
    [0009] On the other hand, in Patent Document 3, in order to improve the weather resistance of a hindered amine-based light stabilizer, a hindered amine-based light stabilizer in which a hydrolysable silyl group is introduced to a hindered amine-based light stabilizer, and a silicone polymer in which a hindered amino group is contained, have been disclosed.
    [0010] The hydrolysable silyl group-introduced hindered amine-based light stabilizer of Patent Document 3 reacts and integrates with a resin, and therefore, can suppress the bleed-bloom phenomenon of the light stabilizer as compared with existing hindered amine-based light stabilizers, however since the compatibility with a resin material is extremely high, it has been difficult to suppress the ultraviolet degradation on a surface of the resin material.
    [0011] Further, in the silicone polymer in which a hindered amino group is contained, due to the production method, an alkoxysilyl group having the highest reactivity with a resin material is preferentially consumed in a dealcoholization condensation reaction, and therefore, there has been a problem that the ability to fix to a resin material is low, and the bleed-bloom phenomenon is easily generated. Citation List
    [0012] Patent Document 1: JP-A 2000-336118 Patent Document 2: JP-A 2005-112809 Patent Document 3: JP 2961541 THE INVENTION
    [0013] The present invention has been made in view of such circumstances, and an object of the present invention is to provide an organic silicon compound that is effective as a hindered amine-based light stabilizer or the like to be added to a resin, particularly a silicone-based resin. Methods for producing the organic silicon compounds, curable compositions containing the organic silicon compounds and uses thereof are further aspects of the proposals.
    [0014] As a result of the intensive studies to solve the problems described above, the present inventors have found certain organic silicon compounds having an organosiloxane structure, a hydrolysable group, and a hindered amine skeleton in the molecule, and a method for producing such organic silicon compounds, further have found that a composition containing the organic silicon compound as a light stabilizer suppresses the time degradation due to action of light such as ultraviolet rays, and gives a cured product capable of exerting favorable weather resistance, crack resistance, and bleed resistance, and therefore, the composition is suitable for a curable composition having high weather resistance, and thus have completed the present invention.
    [0015] That is, the present invention provides the following.1. An organic silicon compound having an average structural formula (1),
    [0016] The organic silicon compounds proposed herein have an organosiloxane structure, a hydrolysable group having high reactivity, and a hindered amine skeleton in the molecule, and we find have characteristics of being excellent in weather resistance, crack resistance and bleed resistance, as compared with conventional hindered amine-based light stabilizers.
    [0017] A composition containing a organic silicon compound according to the present proposals and having such characteristics can be suitably used as a curable composition, particularly, a curable composition having high weather resistance. FURTHER EXPLANATIONS; OPTIONS AND PREFERENCES
    [0018] Hereinafter, the present invention is specifically described.
    [0019] The organic silicon compound according to the present invention has an average structural formula (1).
    [0020] In the formula, R1 and R2 each independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms.
    [0021] R1 and R2 each preferably represent an alkyl group having 1 to 3 carbon atoms, from the viewpoints of weather resistance, crack resistance, and bleed resistance. The alkyl group having 1 to 10 carbon atoms may be any one of a linear, a cyclic, or a branched alkyl group, and is preferably a linear alkyl group.
    [0022] Specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl group, and among them, a methyl, n-propyl, n-hexyl, and n-octyl group are preferred, and a methyl group is more preferred.
    [0023] Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl and naphthyl group, and a phenyl group is preferred.
    [0024] Each R3 independently represents hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 20 carbon atoms, or an O• (oxy radical).
    [0025] R3 preferably represents hydrogen atom or an alkyl group having 1 to 3 carbon atoms, from the viewpoints of weather resistance, crack resistance, and bleed resistance. The alkyl group having 1 to 20 carbon atoms may be any one of a linear, a cyclic, or a branched alkyl group, and is preferably a linear alkyl group.
    [0026] Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, and icosyl group, and among them, a methyl group, and an n-propyl group is preferred, and a methyl group is more preferred.
    [0027] In the alkoxy group having 1 to 20 carbon atoms, an alkyl group in the alkoxy group may be any one of a linear, a cyclic, or a branched alkyl group.
    [0028] Specific examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonyloxy, n-decyloxy, undecyloxy, dodecyloxy, and icosyloxy group, and among them, a methoxy group, and an ethoxy group are preferred, and a methoxy group is more preferred.
    [0029] Each R4 independently represents a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include the same groups as those described for the above R1, and among them, a methyl, n-propyl, n-hexyl, and n-octyl group are preferred, and a methyl group is more preferred.
    [0030] In this regard, some or all of the hydrogen atoms in an alkyl group, an aryl group, or an alkoxy group in these R1 to R4 may be substituted by an alkyl group having 1 to 10 carbon atoms, by halogen atom such as F, Cl, or Br, a by cyano group or the like. Specific examples of such a group include 3-chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, tolyl, and xylyl group, and from the viewpoints of the weather resistance, crack resistance, and bleed resistance, a 3,3,3-trifluoropropyl group is preferred.
    [0031] Each A1 independently represents a single bond, or an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, which is free of a hetero atom.
    [0032] The alkylene group having 1 to 20 carbon atoms, which is free of hetero atom, of A1 may be any one of a linear, a cyclic, or a branched alkylene group. Specific examples of the alkylene group include an alkylene group such as a methylene, ethylene, trimethylene, propylene, isopropylene, tetramethylene, isobutylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, and eicosadecylene group; and a cycloalkylene group such as a cyclopentylene and cyclohexylene group.
    [0033] Among them, A1 is preferably a single bond, an ethylene group, a trimethylene group, or an octamethylene group, and more preferably a single bond, an ethylene group, or a trimethylene group.
    [0034] In this regard, some or all of the hydrogen atoms in the alkylene group of A1 may be substituted by an aryl group having 6 to 20 carbon atoms, such as phenyl group and the like.
    [0035] Each A2 independently represents a single bond, or a divalent linking group comprising (containing or consisting of) hetero atom.
    [0036] Specific examples of the divalent linking group containing a hetero atom of A2 include an ether bond (-O-), a thioether bond (-S-), an amino bond (-NH-), a sulfonyl bond (-S(=O)2-), a phosphinyl bond (-P(=O)OH-), an oxo bond (-C(=O)-), a thiooxo bond (-C(=S)-), an ester bond (-C(=O)O-), a thioester bond (-C(=O)S-), a thionoester bond (-C(=S)O-), a dithioester bond (-C(=S)S-), a carbonic acid ester bond (-OC(=O)O-), a thiocarbonic acid ester bond (-OC(=S)O-), an amide bond (-C(=O)NH-), a thioamide bond (-C(=S)NH-), a urethane bond (-OC(=O)NH-), a thiourethane bond (-SC(=O)NH-), a thionourethane bond (-OC(=S)NH-), a dithiourethane bond (-SC(=S)NH-), a urea bond (-NHC(=O)NH-), a thiourea bond (-NHC(=S)NH-), and a silicon bond (-SiR5R6-, in which R5 and R6 have the same meanings as those in R5 and R6 described later).
    [0037] Among them, A2 is preferably a single bond, an ether bond (-O-), or a silicon bond (-SiR5R6-).
    [0038] In this regard, in a group formed of A1, A2 and Z, a combination in which oxygen atoms form a structure "-O-O-" of continuous oxygen atoms, or a combination in which silicon atoms form a structure "-Si-Si-" of continuous silicon atoms, is not adopted.
    [0039] m is a number of 1 to 3, and from the viewpoint of the bleed resistance, m is preferably a number of 2 to 3, and more preferably 3.
    [0040] p is a number of 1 to 10, q is a number of 1 to 10, and p + q represents a number satisfying from 2 to 20 corresponding to the valency number of Z.
    [0041] From the viewpoints of the weather resistance, crack resistance, and bleed resistance, p is preferably a number of 1 to 5, more preferably a number of 1 to 2, and furthermore preferably a number of 1.
    [0042] From the viewpoints of the weather resistance, crack resistance, and bleed resistance, q is preferably a number of 1 to 5, more preferably a number of 1 to 2, and furthermore preferably a number of 1.
    [0043] Accordingly, from the viewpoints of the weather resistance, crack resistance, and bleed resistance, p + q is preferably a number of 2 to 10, more preferably a number of 2 to 4, and furthermore preferably a number of 2.
    [0044] Z represents a 2 to 20-valent group containing an organosiloxane structure, preferably a 2 to 10-valent group containing an organosiloxane structure, more preferably a 2 to 4-valent group containing an organosiloxane structure, and furthermore preferably a divalent group containing an organosiloxane structure.
    [0045] Z is not particularly limited as long as it is a group containing an organosiloxane structure, and in which a linear structure, a branched structure, or a crosslinking structure may be included.
    [0046] More specifically, as the organosiloxane structure, an organo(poly)siloxane structure including D unit (R1 2SiO2/2 unit), T unit (R1SiO3/2 unit), and/or Q unit (SiO4/2 unit) can be mentioned (where R1 has the same meaning as described above).
    [0047] Each of these units may be a single unit (D unit only, T unit only, or Q unit only), or a combination of multiple units.
    [0048] In particular, from the viewpoints of weather resistance, crack resistance, and bleed resistance, Z is preferably a group that has an organopolysiloxane structure containing one or more D units, and more preferably is a divalent group that has an organopolysiloxane structure containing only D unit.
    [0049] Therefore, among organic silicon compounds according to the present invention, organic silicon compounds having an average structural formula of the following formula (2) are preferred, and by using such a compound, more favorable weather resistance, crack resistance, and bleed resistance are exerted.
    [0050] In formula (2), R5 and R6 each independently represent an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and as these alkyl group and aryl group, the same group options as those described for the above R3 and R1 can be mentioned.
    [0051] In particular, from the viewpoints of the weather resistance, crack resistance, and bleed resistance, R5 and R6 are each preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
    [0052] Further, n represents a number of 1 or more, and from the viewpoints of the weather resistance, the crack resistance, and the bleed resistance, n is preferably a number of 1 to 1,000, more preferably a number of 1 to 100, furthermore preferably a number of 1 to 50, and still more preferably a number of 1 to 10.
    [0053] A weight average molecular weight of the organic silicon compound according to the present invention is not particularly limited, however, with a view to imparting sufficient weather resistance, crack resistance, and bleed resistance to a cured product obtained by curing a curable composition containing the compound, the weight average molecular weight is preferably 400 to 100,000, more preferably 400 to 10,000, furthermore preferably 400 to 5,000, and still more preferably 400 to 1,000. In this regard, the values of weight average molecular weight in the present disclosure are values relative to polystyrene standards as determined by gel permeation chromatography (GPC).
    [0054] In particular, among organic silicon compounds according to the present invention, compounds having the following structural formula (3) or (4) are preferred, and by using such organic silicon compound, we find that the weather resistance, the crack resistance, and the bleed resistance can become more favorable.
    [0055] Organic silicon compounds having the formula (1) can be produced by conventionally known techniques.
    [0056] For example, an organic silicon compound having the above formula (2) can be obtained by reacting an amine compound having an alkenyl group of the following structural formula (5) with a silane compound having an organosiloxane structure of the following average structural formula (6).
    [0057] More specifically, an alkenyl group of an amine compound (5) having the alkenyl group, and a hydrosilyl group (Si-H group) of a silane compound (6) having an organosiloxane structure are subjected to hydrosilylation reaction in the presence of a platinum compound-containing catalyst to add the hydrosilyl group to the alkenyl group, and thus a carbon-silicon bond is formed.
    [0058] Specific examples of the amine compound having an alkenyl group of the above formula (5) include compounds having the following structural formulae, however, the amine compound is not limited thereto.
    [0059] Specific examples of the silane compound having an organosiloxane structure of the above formula (6) include compounds having the following structural formulae, however, the silane compound is not limited thereto. In this regard, the number of repetitions of siloxane units in parentheses represents a number on average, and in a case of being formed of multiple different kinds of siloxane units, the arrangement order of the siloxane units in parentheses is arbitrary.
    [0060] The platinum compound-containing catalyst to be used in the hydrosilylation described above is not particularly limited, and specific examples of the platinum compound-containing catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakis triphenylphosphine platinum, dichlorobis triphenylphosphine platinum, dichlorobis acetonitrile platinum, dichlorobis benzonitrile platinum, dichloro cyclooctadiene platinum, and a supported catalyst such as platinum on carbon, platinum on alumina, or platinum on silica.
    [0061] Among them, from the viewpoint of selectivity, a zero-valent platinum complex is preferred, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex is more preferred.
    [0062] As the amount of the platinum compound-containing catalyst to be used, it is not particularly limited, however, from the viewpoints of the reactivity and the productivity, an amount with which the quantity of the platinum atoms to be included is 1×10-7 to 1×10-2 mol per mol of the amine compound having an alkenyl group of the formula (5) is preferred, and an amount with which the quantity of the platinum atoms to be included is 1×10-7 to 1×10-3 mol per mol of the amine compound having an alkenyl group of the formula (5) is more preferred.
    [0063] Further, a co-catalyst may be used in order to improve the reactivity of hydrosilylation. As the co-catalyst, a co-catalyst that has been commonly used in hydrosilylation can be used, and in the present invention, an ammonium salt of inorganic acid, an acid amide compound, or a carboxylic acid is preferred.
    [0064] Specific examples of the ammonium salt of inorganic acid include ammonium chloride, ammonium sulfate, ammonium amidosulfate, ammonium nitrate, monoammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium hypophosphite, ammonium carbonate, ammonium bicarbonate, ammonium sulfide, ammonium borate, and ammonium fluoroborate, and among them, an ammonium salt of an inorganic acid having a pKa of 2 or more is preferred, and ammonium carbonate, and ammonium bicarbonate are more preferred.
    [0065] Specific examples of the acid amide compound include formamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumaramide, benzamide, phthalamide, palmitic acid amide, stearic acid amide, and among them, formamide, and stearic acid amide are preferred, and formamide is more preferred.
    [0066] Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanoic acid, caproic acid, heptanoic acid, octanoic acid, lactic acid, glycolic acid, trifluoroacetic acid, maleic acid, fumaric acid, succinic acid, tartaric acid, and oxalic acid, and among them, formic acid, acetic acid, lactic acid, maleic acid, fumaric acid, succinic acid, and trifluoroacetic acid are preferred, and acetic acid, trifluoroacetic acid are more preferred.
    [0067] The amount of the co-catalyst to be used is not particularly limited, and from the viewpoint of the reactivity, the selectivity, the cost, or the like, the amount is preferably 1×10-5 to 1×10-1 mol, and more preferably 1×10-4 to 5×10-1 mol, per mol of the amine compound having an alkenyl group of the formula (5).
    [0068] In this regard, the above hydrosilylation reaction proceeds even without using any solvent, but a solvent can be used.
    [0069] Specific examples of the usable solvent include a hydrocarbon-based solvent such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; an ether-based solvent such as diethyl ether, tetrahydrofuran, and dioxane; an ester-based solvent such as ethyl acetate, and butyl acetate; an aprotic polar solvent such as N,N-dimethylformamide; and a chlorinated hydrocarbon-based solvent such as dichloromethane, and chloroform, and these solvents may be used singly alone, or by mixing two or more kinds thereof.
    [0070] The reaction temperature in the above hydrosilylation reaction is not particularly limited, the hydrosilylation reaction can be performed under heating from 0°C, and the reaction temperature is preferably 0 to 200°C.
    [0071] In order to obtain an adequate reaction rate, it is preferred to perform the reaction under heating, and from this point of view, the reaction temperature is more preferably 40 to 110°C, and furthermore preferably 40 to 90°C.
    [0072] In addition, the reaction time is not particularly limited, and is usually around 1 to 60 hours, and the reaction time is preferably 1 to 30 hours, and more preferably 1 to 20 hours.
    [0073] The reaction ratio of the alkenyl group of an amine compound (5) having the alkenyl group to the hydrosilyl group of a silane compound (6) having an organosiloxane structure is preferably 0.8 to 1.3 mol, and more preferably 0.9 to 1.2 mol, per mol of the hydrosilyl group, in view of the suppression of by-products during the hydrosilylation reaction and further of the enhancement of the storage stability and properties of the organic silicon compound to be obtained.
    [0074] The light stabilizer according to the present invention contains at least one kind of the organic silicon compounds (hereinafter, referred to as organic silicon compounds (1)) having the average structural formula (1) described above.
    [0075] The organic silicon compound (1) can be used alone as a light stabilizer, and can also be used as a composition in which an additive agent such as a stabilizer, and an optional component such as a solvent, are appropriately mixed.
    [0076] In this composition, the content of the organic silicon compound (1) is not particularly limited, and can be appropriately set to, for example, 90% by weight or more, 70% by weight or more, 50% by weight or more, 30% by weight or more, 10% by weight or more, 5% by weight or more, or 1% by weight or more, or the like.
    [0077] The curable composition, the coating agent composition, and the adhesive agent composition (hereinafter, these may also be collectively referred to as composition) of the present invention each contain organic silicon compound (1) as disclosed herein.
    [0078] The organic silicon compound (1) is derived from a structure of the organic silicon compound, and this can improve the weather resistance, crack resistance, and bleed resistance of a cured product to be obtained using a composition containing the organic silicon compound (1), as compared with those with a conventional light stabilizer.
    [0079] In a composition of the present invention, the content of the organic silicon compound is not particularly limited, and is preferably around 0.1 to 10% by weight, and more preferably is 0.5 to 5% by weight in the composition. In this regard, in a case where the light stabilizer contains a solvent, the above content means a non-volatile content excluding the solvent.
    [0080] The composition of the present invention is preferably a composition containing a resin as a main agent (base resin). As the resin, an organic resin or a silicone-based resin can be mentioned.
    [0081] The organic resin is not particularly limited, and specific example of the organic resin include an epoxy resin, a phenol resin, polycarbonates, a polycarbonate blend, an acrylic resin, a urethane resin, a urethane acrylic resin, a polyester resin, a polyamide resin, a polyimide resin, polybutadiene, a styrene-butadiene copolymer, an acrylonitrile-styrene copolymer, a styrene-acrylonitrile-butadiene copolymer, a polyvinyl chloride resin, a polystyrene resin, a polyphenylene ether resin, a polymerizable reactive group-containing polyphenylene ether resin, a polystyrene and polyphenylene ether blend, cellulose acetate butyrate, and a polyethylene resin. The organic resin may be appropriately selected from the above depending on the application or the like.
    [0082] In this case, the composition may be mixed with an appropriate curing agent depending on the organic resin to be used, and for example, in a case of using an epoxy resin, the composition may be mixed with a curing agent such as an imidazole compound.
    [0083] Further, depending on the intended purpose for use, various kinds of additive agents such as a curing catalyst, an adhesiveness improving agent, an ultraviolet absorbing agent, a light stabilizer, a storage stability improving agent, a plasticizer, a filler, a pigment, and a solvent, may be added into the composition.
    [0084] In addition, the composition of the present invention is preferably a composition containing a silicone-based resin as a main agent (base resin). As the silicone-based resin, it is not particularly limited, and a commercially available product may be used. Specific examples of the silicone-based resin include X-40-9250, X-40-9246, X-40-9225, KR-500, KR-515, KC-89S, KR-401N, X-40-9227, KR-510, KR-9218, KR-400, X-40-2327, and KR-401, which are manufactured by Shin-Etsu Chemical Co., Ltd.
    [0085] Further, depending on the intended purpose for use, various kinds of additive agents such as a curing catalyst, an adhesiveness improving agent, an ultraviolet absorbing agent, a light stabilizer, a storage stability improving agent, a plasticizer, a filler, a pigment, and a solvent, may be added into the composition.
    [0086] In a case of using the above-described silicone-based resin, the above curing catalyst is a component that promotes a reaction in which hydrolysable groups contained in the silicone-based resin and the organic silicon compound according to the present invention are hydrolysed and condensed with moisture in the air, or a dealcoholization reaction of a silicone-based resin and the organic silicon compound with a silanol group, and also promotes the curing of the composition, and is added to perform the curing efficiently.
    [0087] The curing catalyst is not particularly limited as long as it is a curing catalyst to be used for curing a general moisture condensation curing-type composition. Specific examples of the curing catalyst include an alkyl tin compound such as dibutyltin oxide, and dioctyltin oxide; an alkyltin ester compound such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dioctyltin dioctoate, and dioctyltin diversatate; a titanic acid ester such as tetraisopropoxy titanium, tetra n-butoxy titanium, tetra t-butoxy titanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, titanium diisopropoxybis(ethylacetoacetate), and titanium isopropoxyoctylene glycol, and a titanium chelate compound, and a partial hydrolysate thereof; an organometallic compound such as zinc naphthenate, zinc stearate, zinc 2-ethyloctoate, iron 2-ethylhexoate, cobalt 2-ethylhexoate, manganese 2-ethylhexoate, cobalt naphthenate, aluminum trihydroxide, aluminum alcoholate, aluminum acylate, a salt of aluminum acylate, an aluminosiloxy compound, and an aluminum chelate compound; an aminoalkyl group-substituted alkoxysilane such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl]amine, N,N'-bis[3-(trimethoxysilyl)propyl]ethane-1,2-diamine, N,N'-bis[3-(triethoxysilyl)propyl]ethane-1,2-diamine, and N-phenyl-3-aminopropyltrimethoxysilane; an amine compound such as hexylamine, dodecylamine phosphate, and tetramethyl guanidine, and a salt thereof; a quaternary ammonium salt such as benzyltriethylammonium acetate; a lower fatty acid salt of an alkali metal such as potassium acetate, sodium acetate, and lithium oxalate; a dialkylhydroxylamine such as dimethylhydroxylamine, and diethylhydroxylamine; guanidyl group-containing silane and siloxane such as tetramethyl guanidyl propyl trimethoxysilane, tetramethyl guanidyl propyl methyl dimethoxysilane, tetramethyl guanidyl propyl triethoxysilane, tetramethyl guanidyl propyl methyl diethoxysilane, and tetramethyl guanidyl propyl tris(trimethylsiloxy)silane; and phosphazene base-containing silane and siloxane such as N,N,N',N',N",N"-hexamethyl-N"'-[3-(trimethoxysilyl)propyl]-phosphorimidic triamide. These may be used alone, or in combination of two or more kinds thereof.
    [0088] Among them, from the viewpoint of being more excellent in reactivity, dioctyltin dilaurate, dioctyltin diversatate, tetraisopropoxy titanium, tetra n-butoxy titanium, tetra t-butoxy titanium, titanium diisopropoxybis(ethylacetoacetate), 3-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl] amine, N,N'-bis[3-(trimethoxysilyl)propyl]ethane-1,2-diamine, and tetramethyl guanidyl propyl trimethoxysilane are preferred, and from the viewpoint of the curability of the composition, tetraisopropoxy titanium, tetra n-butoxy titanium, tetra t-butoxy titanium, and titanium diisopropoxybis(ethylacetoacetate) are more preferred, and tetra n-butoxy titanium, and titanium diisopropoxybis(ethylacetoacetate) are furthermore preferred, and further from the viewpoint of the curability of the composition, tetra n-butoxy titanium is particularly preferred.
    [0089] The amount of the curing catalyst to be added is not particularly limited, and is, in view of the improvement of the workability with the adjustment of the curing rate in an adequate range, preferably 0.01 to 15 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the main agent (base resin) component.
    [0090] The above-described coating composition of the present invention is applied onto a surface of a solid substrate, and cured to form a coating layer, as a result of which a coated solid substrate is obtained. The adhesive agent composition of the present invention is applied onto a surface of a solid substrate, and further on the applied solid substrate, another solid substrate is applied or laminated, and then the composition is cured to form an adhesive layer, and as a result of which an adhesive laminate or adhered product is obtained.
    [0091] The method for applying each composition is not particularly limited, specific examples of the method include known methods such as spray coating, spin coating, dip coating, roller coating, brushing, bar coating, and flow coating, and the method may be appropriately selected from the known methods, and used.
    [0092] The solid substrate is not particularly limited, and specific examples of the solid substrate include an organic resin substrate of an epoxy resin, a phenol resin, a polyimide resin, a polycarbonate resin such as polycarbonates and a polycarbonate blend, an acrylic resin such as poly(methyl methacrylate), a polyester resin such as poly(ethylene terephthalate), poly(butylene terephthalate), and an unsaturated polyester resin, a polyamide resin, an acrylonitrile-styrene copolymer resin, a styrene-acrylonitrile-butadiene copolymer resin, a polyvinyl chloride resin, a polystyrene resin, a polystyrene and polyphenylene ether blend, cellulose acetate butyrate, a polyethylene resin or the like; a metal substrate of an iron plate, a copper plate, a steel sheet or the like; a surface applied with a coating material; glass; ceramic; concrete; a slate plate; textile; an inorganic filler of wood, a stone material, a roof tile, (hollow) silica, titania, zirconia, alumina or the like; and a glass fiber product including glass fiber, such as glass cloth, glass tape, glass mat, or glass paper. The material and shape of the substrate are not particularly limited.
    [0093] By bringing the appropriate composition as disclosed herein into contact with moisture in the atmosphere, hydrolysis condensation reaction of a silicone-based resin and the organic silicon compound according to the present invention, or dealcoholization reaction of a silicone-based resin and the organic silicon compound with a silanol group, proceeds. As an index of the moisture in the atmosphere, any humidity of 10 to 100% RH is accepted, and in general, as the humidity is higher, the hydrolysis proceeds more quickly, and therefore moisture may be added to the atmosphere if desired.
    [0094] The curing reaction temperature and the time can be appropriately changed according to a factor such as the substrate to be used, the moisture concentration, the catalyst concentration, or the kind of the hydrolysable group. In general, the curing reaction temperature is preferably ordinary temperature in the vicinity of 25°C from the viewpoint of the workability or the like, however, in order to promote the curing reaction, the curing reaction temperature may be raised within the range not exceeding the heat resistant temperature of the substrate to be used to perform the curing. The curing reaction time is usually around 1 minute to 1 week from the viewpoint of the workability or the like.
    [0095] The curing of the composition of the present invention proceeds favorably even at room temperature, and therefore, in particular, even in a case where room temperature curing is essential at a work site or the like, the stickiness (tack) on a surface of coating disappears within several minutes to several hours. The composition is excellent in curability and workability, and may be subjected to heat treatment within a range not exceeding the heat resistant temperature of the substrate. EXAMPLES
    [0096] Hereinafter, the present invention is further described in more detail by way of Examples and Comparative Examples, but should not be limited by these Examples.
    [0097] In this regard, in the following, the viscosity of each product is a value measured at 25°C with an Ostwald viscometer, and the molecular weight is a weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC) measurement. In addition, the silicone average composition of each product was calculated from the integral values of detection spectra in 1H-NMR and 29Si-NMR by using a 300 MHz-NMR measurement device manufactured by JEOL Ltd. [1] SYNTHESIS OF ORGANIC SILICON COMPOUNDS Example 1-1Synthesis of organic silicon compound 1
    [0098] Into a 300 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 65.0 g of an amine compound having an alkenyl group of the following formula (7), and 0.58 g of a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (5.0×10-5 mol of platinum atom per mol of an amine compound having an alkenyl group) were placed, and the mixture in the flask was heated to 80°C. Into the heated mixture, 83.8 g of a silane compound having an organosiloxane structure of the following formula (8) was added dropwise, and the resultant mixture was heated and stirred at 80°C for 2 hours. The peaks derived from the alkenyl group and hydrosilyl group of the raw material were confirmed to be completely disappeared by 1H-NMR measurement, and then the reaction was terminated. The mixture after the termination of the reaction was distilled off under reduced pressure (80°C, 5 mmHg) for 1 hour, and the resultant mixture was filtered to obtain 148 g of the corresponding organic silicon compound 1.
    [0099] The obtained organic silicon compound 1 was a pale yellow transparent liquid having a viscosity of 13 mm2/s and a weight average molecular weight of 480, and was a compound having the following formula (9).
    [0100] Into a 300 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 69.6 g of an amine compound having an alkenyl group of the following formula (10), and 0.58 g of a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (5.0×10-5 mol of platinum atom per mol of an amine compound having an alkenyl group) were placed, and the mixture in the flask was heated to 80°C. Into the heated mixture, 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was added dropwise, and the resultant mixture was heated and stirred at 80°C for 2 hours. The peaks derived from the alkenyl group and hydrosilyl group of the raw material were confirmed to be completely disappeared by 1H-NMR measurement, and then the reaction was terminated. The mixture after the termination of the reaction was distilled off under reduced pressure (80°C, 5 mmHg) for 1 hour, and the resultant mixture was filtered to obtain 152 g of the corresponding organic silicon compound 2.
    [0101] The obtained organic silicon compound 2 was a yellow transparent liquid having a viscosity of 15 mm2/s and a weight average molecular weight of 490, and was a compound having the following formula (11).
    [0102] Synthesis was performed by a similar procedure as in Example 1-1 except that the 65.0 g of an amine compound having an alkenyl group of the above formula (7) was changed to 74.9 g of an amine compound having an alkenyl group of the following formula (12), and 156 g of the corresponding organic silicon compound 3 was obtained.
    [0103] The obtained organic silicon compound 3 was a yellow transparent liquid having a viscosity of 17 mm2/s and a weight average molecular weight of 510, and was a compound having the following formula (13).
    [0104] Synthesis was performed by a similar procedure as in Example 1-1 except that the 65.0 g of an amine compound having an alkenyl group of the above formula (7) was changed to 69.3 g of an amine compound having an alkenyl group of the following formula (14), and 151 g of the corresponding organic silicon compound 4 was obtained.
    [0105] The obtained organic silicon compound 4 was a brown transparent liquid having a viscosity of 25 mm2/s and a weight average molecular weight of 490, and was a compound having the following formula (15).
    [0106] Synthesis was performed by a similar procedure as in Example 1-1 except that the 65.0 g of an amine compound having an alkenyl group of the above formula (7) was changed to 92.8 g of an amine compound having an alkenyl group of the following formula (16), and 175 g of the corresponding organic silicon compound 5 was obtained.
    [0107] The obtained organic silicon compound 5 was a pale yellow transparent liquid having a viscosity of 20 mm2/s and a weight average molecular weight of 560, and was a compound having the following formula (17).
    [0108] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 108.8 g of a silane compound having an organosiloxane structure of the following formula (18), and 177 g of the corresponding organic silicon compound 6 was obtained.
    [0109] The obtained organic silicon compound 6 was a pale yellow transparent liquid having a viscosity of 18 mm2/s and a weight average molecular weight of 580, and was a compound having the following formula (19).
    [0110] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 96.3 g of a silane compound having an organosiloxane structure of the following formula (20), and 164 g of the corresponding organic silicon compound 7 was obtained.
    [0111] The obtained organic silicon compound 7 was a yellow transparent liquid having a viscosity of 16 mm2/s and a weight average molecular weight of 540, and was a compound having the following formula (21).
    [0112] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 79.1 g of a silane compound having an organosiloxane structure of the following formula (22), and 147 g of the corresponding organic silicon compound 8 was obtained.
    [0113] The obtained organic silicon compound 8 was a pale yellow transparent liquid having a viscosity of 13 mm2/s and a weight average molecular weight of 480, and was a compound having the following formula (23).
    [0114] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 124.2 g of a silane compound having an organopolysiloxane structure of the following average structural formula (24), and 192 g of the corresponding organic silicon compound 9 was obtained.
    [0115] The obtained organic silicon compound 9 was a pale yellow transparent liquid having a viscosity of 24 mm2/s and a weight average molecular weight of 630, and was a compound having the following average structural formula (25).
    [0116] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 136.7 g of a silane compound having an organopolysiloxane structure of the following average structural formula (26), and 204 g of the corresponding organic silicon compound 10 was obtained.
    [0117] The obtained organic silicon compound 10 was a yellow transparent liquid having a viscosity of 26 mm2/s and a weight average molecular weight of 670, and was a compound having the following average structural formula (27).
    [0118] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 119.5 g of a silane compound having an organopolysiloxane structure of the following average structural formula (28), and 187 g of the corresponding organic silicon compound 11 was obtained.
    [0119] The obtained organic silicon compound 11 was a yellow transparent liquid having a viscosity of 21 mm2/s and a weight average molecular weight of 610, and was a compound having the following average structural formula (29).
    [0120] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 190.2 g of a silane compound having an organopolysiloxane structure of the following average structural formula (30), and 257 g of the corresponding organic silicon compound 12 was obtained.
    [0121] The obtained organic silicon compound 12 was a pale yellow transparent liquid having a viscosity of 33 mm2/s and a weight average molecular weight of 850, and was a compound having the following average structural formula (31).
    [0122] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 256.1 g of a silane compound having an organopolysiloxane structure of the following average structural formula (32), and the 300 mL separable flask was changed to a 500 mL separable flask, and 323 g of the corresponding organic silicon compound 13 was obtained.
    [0123] The obtained organic silicon compound 13 was a pale yellow transparent liquid having a viscosity of 45 mm2/s and a weight average molecular weight of 1,080, and was a compound having the following average structural formula (33).
    [0124] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 717.9 g of a silane compound having an organopolysiloxane structure of the following average structural formula (34), and the 300 mL separable flask was changed to a 1 L separable flask, and 780 g of the corresponding organic silicon compound 14 was obtained.
    [0125] The obtained organic silicon compound 14 was a pale yellow transparent liquid having a viscosity of 150 mm2/s and a weight average molecular weight of 2,630, and was a compound having the following average structural formula (35).
    [0126] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 2,235.3 g of a silane compound having an organopolysiloxane structure of the following average structural formula (36), and the 300 mL separable flask was changed to a 3 L separable flask, and 2,282 g of the corresponding organic silicon compound 15 was obtained.
    [0127] The obtained organic silicon compound 15 was a pale yellow transparent liquid having a viscosity of 360 mm2/s and a weight average molecular weight of 7,750, and was a compound having the following average structural formula (37).
    [0128] Synthesis of organic silicon compound 16 Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 83.8 g of a silane compound having an organopolysiloxane structure of the following average structural formula (38), and 150 g of the corresponding organic silicon compound 16 was obtained.
    [0129] The obtained organic silicon compound 16 was a pale yellow transparent liquid having a viscosity of 36 mm2/s and a weight average molecular weight of 990, and was a compound having the following average structural formula (39).
    [0130] Synthesis was performed by a similar procedure as in Example 1-2 except that the 83.8 g of a silane compound having an organosiloxane structure of the above formula (8) was changed to 33.5 g of a silane compound having an organopolysiloxane structure of the following average structural formula (40), and 102 g of the corresponding organic silicon compound 17 was obtained.
    [0131] The obtained organic silicon compound 17 was a pale yellow transparent liquid having a viscosity of 95 mm2/s and a weight average molecular weight of 2,270, and was a compound having the following average structural formula (41).
    [0132] 100 parts by weight of a silicone-based resin (KR-500 manufactured by Shin-Etsu Chemical Co., Ltd.) as a main agent (base resin), 2 parts by weight of an organic silicon compound 1 obtained in Example 1-1 as a light stabilizer, and 2 parts by weight of tetra n-butoxy titanium as a curing catalyst were uniformly mixed by using a stirrer to prepare a composition for coating.
    [0133] The obtained composition for coating was applied on a glass plate at 25°C and 50% RH under the air by using a bar coater No. 14, and cured and dried at 25°C and 50% RH for 1 week under the air to prepare a cured coating film. Examples 2-2 to 2-17
    [0134] Coating compositions and cured coating films were prepared in a similar manner as in Example 2-1 except that the organic silicon compound 1 was changed to each of the organic silicon compounds 2 to 17 obtained in Examples 1-2 to 1-17, respectively. Example 2-18
    [0135] A composition for coating and a cured coating film were prepared in a similar manner as in Example 2-2 except that the silicone-based resin (KR-500 manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to a silicone-based resin (KR-401 manufactured by Shin-Etsu Chemical Co., Ltd.), and the tetra n-butoxy titanium as a curing catalyst was not used. Example 2-19
    [0136] A composition for coating and a cured coating film were prepared in a similar manner as in Example 2-18 except that the organic silicon compound 2 was changed to an organic silicon compound 9 obtained in Example 1-9. Comparative Examples 2-1 to 2-2
    [0137] A composition for coating and a cured coating film were prepared in a similar manner as in Example 2-1 except that the organic silicon compound 1 was changed to a light stabilizer having the following formula (42) or (43).
    [0138] A composition for coating and a cured coating film were prepared in a similar manner as in Example 2-1 except that the organic silicon compound 1 was not used. Comparative Example 2-4
    [0139] A composition for coating and a cured coating film were prepared in a similar manner as in Example 2-18 except that the organic silicon compound 2 was not used.
    [0140] The following evaluations were performed on the cured coating films prepared in Examples 2-1 to 2-19 and Comparative Examples 2-1 to 2-4, respectively. The results are collectively shown in Tables 1 to 3. Weather resistance
    [0141] A test piece obtained by forming a cured coating film on a glass plate by the above application method was subjected to UV irradiation (integrated irradiation dose: 26,000 mJ/cm3) for 2 weeks using a sterilization lamp under air at 25°C and 50% RH. The degree of yellowing of the cured coating film at that time was evaluated as ΔYI (yellowing degree = change width of yellowing degree YI) using a colorimeter (Z-300A, manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.) in accordance with JIS K 7373. It indicates that the smaller the value is, the better the weather resistance is. Crack resistance
    [0142] A test piece obtained by forming a cured coating film on a glass plate by the above application method was subjected to UV irradiation (integrated irradiation dose: 26,000 mJ/cm3) for 2 weeks by using a sterilization lamp under the air at 25°C and 50% RH. The presence or absence of cracks of the cured coating film at that time was observed with the naked eye.
    [0143] In a case where no crack was observed at all, the crack resistance was evaluated as "○", that is, excellent. In a case where one crack was observed, the crack resistance was evaluated as "Δ". In a case where two or more cracks were observed, the crack resistance was evaluated as "X". Bleed resistance
    [0144] A test piece obtained by forming a cured coating film on a glass plate by the above application method was subjected to UV irradiation (integrated irradiation dose: 26,000 mJ/cm3) for 2 weeks by using a sterilization lamp under the air at 25°C and 50% RH. The presence or absence of any bleed-out component on the cured coating film at that time was observed with the naked eye.
    [0145] In a case where no bleed-out component was observed at all, the bleed resistance was evaluated as "○", that is, excellent. In a case where any bleed-out component was observed, the bleed resistance was evaluated as "×". Table 1 Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 Organic silicon compound 1 2 3 4 5 6 7 8 9 10 Silicone-based resin KR-500 KR-500 KR-500 KR-500 KR-500 KR-500 KR-500 KR-500 KR-500 KR-500 Weather resistance ΔYI 0.2 0.2 0.2 0.4 0.3 0.4 0.2 0.2 0.2 0.4 Crack resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Bleed resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Table 2 Example 2-11 2-12 2-13 2-14 2-15 2-16 2-17 2-18 2-19 Organic silicon compound 11 12 13 14 15 16 17 2 9 Silicone-based resin KR-500 KR-500 KR-500 KR-500 KR-500 KR-500 KR-500 KR-401 KR-401 Weather resistance ΔYI 0.3 0.2 0.2 0.3 0.4 0.4 0.3 0.4 0.4 Crack resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ Bleed resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ Table 3 Comparative Example 2-1 2-2 2-3 2-4 Light stabilizer Formula (42) Formula (43) - - Silicone-based resin KR-500 KR-500 KR-500 KR-401 Weather resistance ΔYI 1.0 1.2 1.6 2.6 Crack resistance Δ Δ × × Bleed resistance ○ × ○ ○
    [0146] As shown in Tables 1 to 3, it can be understood that the cured coating films prepared in Examples 2-1 to 2-19 by using the organic silicon compounds 1 to 17 obtained in Examples 1-1 to 1-17 as light stabilizers were excellent in weather resistance, crack resistance, and bleed resistance as compared with those of the cured coating films prepared in each of the Comparative Examples.
    [0147] On the other hand, the cured coating films prepared in Comparative Examples 2-1 to 2-4 had some insufficient points among the weather resistance, crack resistance, and bleed resistance.
    [0148] As described above, by using an organic silicon compound according to the present disclosure, a cured coating film excellent in weather resistance, crack resistance, and bleed resistance, which has been difficult to obtain with conventional light stabilizers, can be obtained. Notes
    [0149] In respect of numerical ranges disclosed in the present description it will of course be understood that in the normal way the technical criterion for the upper limit is different from the technical criterion for the lower limit, i.e. the upper and lower limits are intrinsically distinct proposals.
    [0150] For the avoidance of doubt it is confirmed that in the general description above, in the usual way the proposal of general preferences and options in respect of different features of the organic silicon compound, method, light stabilizer, curable composition, coating agent, adhesive agent, cured articles and uses constitutes the proposal of general combinations of those general preferences and options for the different features, insofar as they are combinable and compatible and are put forward in the same context.
    [0151] The entire contents of Japanese Patent Application No. 2019-031644 filed on February 25, 2019 , the priority of which is claimed herein, are hereby incorporated by reference as a precaution in case of error in translation or transcription.
    [0152] Although some preferred embodiments have been described, many modifications and variations may be made thereto in the light of the above teachings. It is therefore to be understood that the invention may be practised otherwise than as specifically described without departing from the scope of the appended claims or the general teachings herein.
    权利要求:
    Claims (15)
    [0001] An organic silicon compound having an average structural formula (1):
    [0002] Organic silicon compound according to claim 1, having an average structural formula (2):
    [0003] Organic silicon compound according to claim 1 or 2, having a structural formula (3):
    [0004] Organic silicon compound according to claim 1 or 2, having an average structural formula (4):
    [0005] A method for producing an organic silicon compound according to any one of claims 1 to 4, comprisingperforming hydrosilylation reaction of an amine compound having an alkenyl group, of structural formula (5):
    [0006] A light stabilizer, comprising an organic silicon compound according to any one of claims 1 to 4.
    [0007] A curable composition, comprising an organic silicon compound according to any one of claims 1 to 4.
    [0008] A curable composition according to claim 7 in which the content of said organic silicon compound is from 0.1 to 10% by weight, preferably 0.5 to 5% by weight, in the composition.
    [0009] A curable composition according to claim 7 or 8 containing an organic resin or silicone-based resin as base resin in combination with said organic silicon compound.
    [0010] A coating agent, comprising a curable composition according to any one of claims 7 to 9.
    [0011] An adhesive agent, comprising a curable composition according to any one of claims 7 to 9.
    [0012] A cured article obtainable by curing a curable composition according to any one of claims 7 to 9.
    [0013] A cured article, comprising a coating layer obtainable by curing a coating agent according to claim 10.
    [0014] A cured article, comprising an adhesive layer obtainable by curing an adhesive agent according to claim 11.
    [0015] Use of an organic silicon compound according to any one of claims 1 to 4 as a light stabilizer and/or in a coating composition and/or in an adhesive composition.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP2840087B1|2019-04-10|Use of compounds containing semi-organic silicon groups with guanidine groups for curing of compounds containing alkoxysilyl groups
    JP5667326B2|2015-02-12|Curable resin composition, cured product thereof, sealant, and optical semiconductor device
    US9279078B2|2016-03-08|Hardening resin composition and color conversion material using the same
    KR100437516B1|2004-10-08|Improved adhesive curable organopolysiloxane compositions and composites bonded thereto
    EP0664322B1|1998-07-01|Curable organopolysiloxane composition with condensation reaction curing and addition reaction curing
    US6811650B2|2004-11-02|Adhesive for silicone rubber
    US6258914B1|2001-07-10|Silane functional oligomer
    JP5655163B2|2015-01-14|Curable resin composition and cured product thereof
    EP0063863B1|1986-06-04|Latently curable organosilicone compositions
    US20160130402A1|2016-05-12|Curable compositions containing silyl groups and having improved storage stability
    JP4111335B2|2008-07-02|Moisture-curing reactive diluent
    US4302571A|1981-11-24|Room temperature-curable polyoxyalkylene polyether compositions
    JP4612444B2|2011-01-12|Crosslinkable materials based on organosilicon compounds
    US8101677B2|2012-01-24|Multi-component room-temperature-curable silicone rubber composition
    KR100492650B1|2005-08-31|Double Curing Fluid Adhesive
    CN1308407C|2007-04-04|Self-adhesive addition-crosslinking silicone compositions
    EP1776420B1|2010-02-24|Curable organopolysiloxane composition
    JP4217881B2|2009-02-04|Method for forming functional coating and functional coated article
    JP4984086B2|2012-07-25|Room temperature curable organopolysiloxane composition
    US5733996A|1998-03-31|Organosiloxane compositions
    DE60221812T3|2014-05-22|Mixed alkoxysilyl-functionalized polymers
    KR101804832B1|2017-12-05|Moisture curable organopolysiloxane compositions
    WO2014109349A1|2014-07-17|Curable resin composition, and cured product of same
    JP4886717B2|2012-02-29|Method for producing organosilicon compound having organyloxy group
    AU2006225294B2|2011-06-09|Room temperature-curable organopolysiloxane compositions
    同族专利:
    公开号 | 公开日
    CN111607091A|2020-09-01|
    US10975106B2|2021-04-13|
    JP2020132603A|2020-08-31|
    US20200270285A1|2020-08-27|
    KR20200103559A|2020-09-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2020-07-24| PUAI| Public reference made under article 153(3) epc to a published international application that has entered the european phase|Free format text: ORIGINAL CODE: 0009012 |
    2020-07-24| STAA| Information on the status of an ep patent application or granted ep patent|Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED |
    2020-08-26| AK| Designated contracting states|Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
    2020-08-26| AX| Request for extension of the european patent|Extension state: BA ME |
    2021-04-07| 17P| Request for examination filed|Effective date: 20210225 |
    2021-04-07| RBV| Designated contracting states (corrected)|Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
    优先权:
    申请号 | 申请日 | 专利标题
    [返回顶部]