JPH0711141A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a curable resin compsn. excellent in weatherability, resistances to solvents, alkali, acid, and salt water, mechanical strengths, etc., by compounding a specific hydrogenpolysiloxane macromonomer, a specific resin, and a catalyst. CONSTITUTION:This curable resin compsn. comprises a hydrogenpolysiloxane macromonomer having Si-H bonds and 3-(meth)acryloyloxypropyl groups bonded to Si in the molecule (e.g. a compd. of formula I) of its copolymer with an ethylenically unsatd. monomer (e.g. tertiary-butyl methacrylate), a resin having alkenyl groups in the molecule, a number average mol.wt of 300-20,000, and an iodine value of 50-250) (e.g. HPE-1030, a product of Diul Chemical Industries, Ltd. a compd. of formula II), and a hydrosilylation catalyst (e.g. chloroplatinic acid).

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition, and more particularly to a curable resin composition excellent in weather resistance and physical properties.

2. Description of the Related Art Conventional curable resin compositions applied to the coating field are those obtained by compounding a melamine resin or a polyfunctional isocyanate compound as a curing agent with a hydroxyl group-containing resin typified by an acrylic resin or a polyester resin. It has been known. However, in the melamine curing system, lower alcohols are eliminated and the volume is reduced, and the triazine skeleton has a drawback that it is inferior in weather resistance and durability against acid rain which has recently been a problem. There was a problem of deterioration in weather resistance mainly due to yellowing of the coating film.

As a method for improving weather resistance, a method of subjecting an acrylic resin having an alkoxysilyl group introduced into its molecule to a condensation reaction at room temperature (see, for example, JP-A-57-36109 and JP-A-5-36109).
No. 8-155666, etc.) has been reported, but there are drawbacks that the reaction rate at the time of heat curing is slow, contamination occurs due to hydrolysis of the residual alkoxysilyl group, and the anticorrosive property is poor. Further, a curing system utilizing the reactivity of an alkoxysilyl group and a hydroxyl group of an organic resin (for example, Japanese Examined Patent Publication 63
However, it has a drawback that the reaction rate during thermosetting is slow and the salt water resistance is poor. Further, each of the curing systems is configured as a two-pack type of a resin having a functional group and a curing catalyst thereof, and it is difficult to apply it to a one-pack type curing system excellent in workability.

On the other hand, a technique for curing vinyl polysiloxane and organohydrogen polysiloxane in the presence of a platinum catalyst (application of hydrosilylation reaction) has been known for a long time, but since this cured product swells with a solvent, it is solvent resistant. Since it has poor properties, poor alkali resistance, and poor recoatability, it has hardly been developed in the paint field.

Examples of applying the above hydrosilylation reaction to a curing system of an organic resin having excellent mechanical properties and solvent resistance include a polymer having a hydrosilyl group or an organic curing agent which is not a polymer, and an organic compound having an alkenyl group. A curable resin composition composed mainly of a polymer and a hydrosilylation catalyst, which mainly cures to form a rubber-like substance (JP-A-3-953).
266, JP-A-3-200807, etc.) and a curable composition having rubber elasticity composed of an alkenyl group-containing polyether, a hydrosilyl group-containing polyether and a platinum catalyst (JP-A-1-138230). However, these are elastic bodies such as liquid rubber, and it is difficult to apply them to the coating field where mechanical strength is essential. In addition, various physical properties (weather resistance, solvent resistance, acid resistance, alkali resistance, mechanical strength, etc.) composed of alkenyl group-containing organic resins (acrylic, polyester, epoxy resins), organohydrogenpolysiloxane, and platinum catalysts. Excellent curable resin composition (JP-A-3-27764
5) has been reported. However, the organohydrogenpolysiloxane, which is a curing agent of this system, has low compatibility with the organic resin having an alkenyl group, and a composition having a high crosslinking density is designed in order to obtain a cured coating film having sufficient mechanical strength. Was difficult.

In the present invention, a homo- or copolymer of a heterofunctional organohydrogen macromonomer having a (meth) acroyloxypropyl group in the chain is used as a curing agent, and an organic resin having an alkenyl group is subjected to a hydrosilylation reaction. We succeeded in solving this problem by cross-linking by.

The cured coating film thus obtained also has
It has excellent physical properties such as weather resistance, solvent resistance, alkali resistance, acid resistance, water resistance, salt water resistance, rust resistance, and stain resistance.
Further, when it is used as a paint, it can be solvent-free or high solid.

Therefore, a first object of the present invention is to provide a curable resin composition having excellent mechanical strength and weather resistance.

A second object of the present invention is to provide a curable resin composition which does not cause a decrease in volume after curing and can be used as a molding resin.

A third object of the present invention is moisture resistance, water resistance,
It is to provide a curable resin composition having excellent salt water resistance and the like.

A fourth object of the present invention is to provide a curable resin composition having excellent solvent resistance, alkali resistance, acid resistance and recoatability.

Further, a fifth object of the present invention is to provide a solventless or high solid type curable resin composition which does not cause air pollution by an organic solvent.

DISCLOSURE OF THE INVENTION The above problems are solved by the present invention. The present invention is
(A) a hydrogen polysiloxane macromonomer having a silicon-hydrogen bond and a 3- (meth) acryloyloxypropyl group bonded to a silicon atom in the molecule, alone or as a copolymer with an ethylenically unsaturated monomer,
There is provided a curable resin composition containing (b) a resin having a plurality of alkenyl groups in the molecule, a number average molecular weight of 300 to 20,000, an iodine value of 50 to 250, and (c) a hydrosilylation catalyst.

Preferably, the hydrogen macromonomer has an average compositional formula (1).

[Chemical 4] (However, in the formula, R is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ′ is a hydrogen atom or a methyl group, and a, b, and c are 0 ≦ a ≦ 20, 0.5 ≦ b ≦ 3, 0 ≦. c represents a real number of 10) or an average composition formula (2).

[Chemical 5] (Wherein R, R ′, a and b have the same meaning as described above, and d represents a real number satisfying 1 ≦ d ≦ 10) or the average composition formula (3).

[Chemical 6] (Wherein R, R ′ and c have the same meanings as described above, R ″ is the same as R or —OSi (R) ₂ H, and R ′ ″ is the same when R ″ is the same as R. Hydrogen atom otherwise-
It means OSi (R) ₂ H. Have.

Detailed Discussion Component (a) Hydrogen polysiloxane macromonomers having a silicon-hydrogen bond and a 3- (meth) acryloyloxypropyl group bonded to a silicon atom in the molecule are known. For example, JP-A-4-169589 discloses a hydrogen polysiloxane having the following average composition formulas (1), (2) and (3).

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9] (In the formula, the symbols are the same as above.)

However, homopolymers of these macromonomers and copolymers with other ethylenically unsaturated monomers are not known.

By changing the design of the macromonomer itself and / or by selecting the type and ratio of the monomers to be copolymerized, it becomes possible to give the cured coating various properties. Can be used for this purpose (meta)
As the acroyl group-containing hydrogen polysiloxane macromonomer, those containing a phenyl-substituted siloxane unit are particularly preferable, and the following compounds can be exemplified as those corresponding to the average composition formula (1).

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

[0025]

[Chemical 14]

[0026]

[Chemical 15]

[0027]

[Chemical 16]

The following compounds can be exemplified as those corresponding to the average composition formula (2).

[0029]

[Chemical 17]

[0030]

[Chemical 18]

[0031]

[Chemical 19]

[0032]

[Chemical 20]

[0033]

[Chemical 21]

The following compounds can be exemplified as those corresponding to the average composition formula (3).

[0035]

[Chemical formula 22]

[0036]

[Chemical formula 23]

[0037]

[Chemical formula 24]

[0038]

[Chemical 25]

[0039]

[Chemical formula 26]

The monomers copolymerizable with the (meth) acryloyl group-containing hydrogen polysiloxane macromonomer include acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and (meth).
N-butyl acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate,
Phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid 2 −
Addition product of hydroxyethyl and poly-ε-caprolactone (for example, Praxel FM manufactured by Daicel Chemical Industries, Ltd.)
1), glycidyl (meth) acrylate, 3-trimethoxysilylpropyl (meth) acrylate, 3-triethoxysilylpropyl (meth) acrylate, 3-dimethoxymethylsilylpropyl (meth) acrylate, (meth) acrylic Acid 2-acrylamido-2-methylpropanesulfonic acid, acid phosphoxypropyl methacrylate,
Tributyltin (meth) acrylate, (meth) acrylamide, (meth) acryloyl isocyanate, (meth)
2-isocyanatoethyl acrylate, silicone macromonomer (for example, Silaplane FM-0711,
Manufactured by Chisso).

Other than acrylic monomers, styrene, α-methylstyrene, itaconic acid, maleic acid, vinyl acetate, allyl acetate, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, Examples include N-cyclohexylmaleimide, N-phenylmaleimide and the like.

Homopolymerization or copolymerization of the hydrogen polysiloxane macromonomer can be carried out by a known solution polymerization method. Alkenyl group-containing resin (b)
In-situ polymerization in solution may be performed.

The polymer (a) having a SiH group is a silicone compound 20 represented by the average composition formula (1) and / or the average composition formula (2) and / or the average composition formula (3).
~ 100 wt% and the above ethylenically unsaturated monomer 80
It is a copolymer with .about.0 wt%. When the copolymerization amount of the silicone compound is less than 20% by weight, the crosslink density of the cured composition is lowered and the coating film does not exhibit sufficient mechanical properties. Silicone compound 40 represented by average composition formula (1) and / or average composition formula (2) and / or average composition formula (3)
-100 wt% and ethylenically unsaturated monomer 60-0w
Copolymerization with t% is preferred. The number average molecular weight of the copolymer is preferably 1,000 to 30,000. Furthermore, considering the curability of the cured coating film, the SiH group concentration of the copolymer is 1
It is preferably × 10 ^-3 mol / g or more.

The polymer (b) having an alkenyl group as the component (b) has an iodine value of 50 to 50.
Number average molecular weight of 300 having 250 alkenyl groups
˜20,000 polymers. Specific examples include alkenyl group-containing polyether resins, alkenyl group-containing acrylic resins, alkenyl group-containing polyester resins, and alkenyl group-containing epoxy resins.

As an example of the alkenyl group-containing polyether resin, a poly (ethylene glycol) obtained by ring-opening polymerization of an alkenyl group-containing 1,2-epoxy compound with an active hydrogen compound (water, mono- or polyhydric alcohol) as an initiator is used. There is ether. For example, a polyether obtained by ring-opening polymerization of allyl glycidyl ether using ethylene glycol as an initiator is commercially available as SANTLINK XI-100 (number average molecular weight 1200, iodine value 212).
In addition, vinylcyclohexane-using butanol, allyl alcohol or propargyl alcohol as an initiator
A polyether having the following average composition and properties obtained by ring-opening polymerization of 1,2-epoxide is provided by Daicel Chemical Co., Ltd. (for example, JP-A-4-2382).
9).

HPE-1030 (number average molecular weight 450,
Iodine value 170)

[Chemical 27]

HPE-1060 (number average molecular weight 820,
Iodine value 185)

[Chemical 28]

HPE-10601A (number average molecular weight 89
0, iodine value 170)

[Chemical 29]

HPE-10602A (number average molecular weight 98
0, iodine value 130)

[Chemical 30]

HPE-10601C (number average molecular weight 78
0, iodine value 196)

[Chemical 31]

HPE-10602C (number average molecular weight 75
0, iodine value 170)

[Chemical 32]

HPE-Pr3 (number average molecular weight 430, iodine value 236)

[Chemical 33]

Examples of the alkenyl group-containing acrylic resin include allyl (meth) acrylate, 2-butenyl (meth) acrylate, 3-methyl-3-butenyl (meth) acrylate, and 3-methyl-2 (meth) acrylate. -Butenyl,
Cyclohexenylmethyl (meth) acrylate, (meth)
2-Methyl-2-propenyl acrylate, 3-heptenyl (meth) acrylate, 4-hexenyl (meth) acrylate, Cyclomer MF-401 (methacrylic acid 2
A 1: 1 addition product of hydroxyethyl and vinylcyclohexene monoepoxide; homopolymerization of an alkenyl group-containing acrylic monomer such as Daicel Chemical Industries, Ltd. or co-polymerization of an alkenyl group-containing acrylic monomer with another acrylic monomer Obtained by polymerization.

The alkenyl group-containing acrylic monomer is
For example, it can be synthesized by a reaction between (meth) acrylic acid chloride and an alkenyl alcohol, a transesterification reaction between an alkyl (meth) acrylate and an alkenyl alcohol, an addition reaction between an isocyanate-containing acrylic monomer and an alkenyl alcohol, and the like.

Other acrylic monomers that can be copolymerized with the alkenyl group-containing acrylic monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic. I-Butyl acid, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxyethyl, 2-hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, an adduct of 2-hydroxyethyl (meth) acrylate and poly-ε-caprolactone (for example, Praxel FM1 manufactured by Daicel Chemical Industries, Ltd.), glycidyl (meth) acrylate, ( (Meth) acrylic acid 3-trimethoxysilylpropyl, (meth) acrylic acid 3-triethoxysilylpropyl, (meth) acrylic acid 3-dimethoxymethylsilylpropyl,
(Meth) acrylic acid 2-acrylamido-2-methylpropanesulfonic acid, acid phosphoxypropyl methacrylate, (meth) acrylic acid tributyltin, (meth)
Acrylamide, (meth) acryloyl isocyanate, 2-isocyanatoethyl (meth) acrylate, silicone macromonomer (for example, silaplane FM
-0711, manufactured by Chisso Corporation).

Further, styrene within the range of 50% by weight,
α-methylstyrene, itaconic acid, maleic acid, vinyl acetate, allyl acetate, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane,
Ethylenically unsaturated monomers other than the acrylic monomers exemplified by vinylmethyldiethoxysilane, N-cyclohexylmaleimide, N-phenylmaleimide and the like can also be copolymerized.

Still another method for synthesizing an alkenyl group-containing acrylic resin is an addition reaction of a hydroxyl group-containing acrylic resin with an alkenyl isocyanate compound and / or an anhydride of an alkenyl group-containing carboxylic acid, an isocyanate-containing acrylic resin and an alkenyl alcohol. And an alkenyl group-containing epoxy compound, an addition reaction between an epoxy group-containing acrylic resin and an alkenyl group-containing carboxylic acid, and the like.

The hydroxyl group-containing acrylic resin is 2-hydroxyethyl (meth) acrylate, 2-methacrylate (meth) acrylate.
Acrylic monomers containing hydroxyl groups such as hydroxypropyl, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and poly-ε-caprolactone (for example, Praxel FM series), and other than the above It can be obtained by copolymerizing the acrylic monomer and the ethylenically unsaturated monomer within the range of 50% by weight, or by polymerizing the hydroxyl group-containing acrylic monomer alone.

Examples of the alkenyl isocyanate include allyl isocyanate, (meth) acryloyl isocyanate, and 2-isocyanatoethyl (meth) acrylate.

Examples of the alkenyl group-containing carboxylic acid anhydride include itaconic anhydride, maleic anhydride, tetrahydrophthalic anhydride and the like.

The isocyanate-containing acrylic resin is an isocyanate-containing acrylic monomer such as (meth) acryloyl isocyanate and 2-isocyanatoethyl (meth) acrylate, the other acrylic monomer, and ethylenically unsaturated within 50% by weight. It can be obtained by copolymerizing with a monomer or by polymerizing with an isocyanate-containing acrylic monomer alone.

The alkenyl alcohols include allyl alcohol, vinyl alcohol, 3-buten-1-ol, 2- (allyloxy) ethanol, glycerin diallyl ether, cyclohexenemethanol, 3-methyl-2-buten-1-ol, 3 -Methyl-3-butene-
1-ol, 2-methyl-3-buten-2-ol, oleyl alcohol, crotyl alcohol and the like.

The carboxyl group-containing acrylic resin is a carboxyl group-containing acrylic monomer such as (meth) acrylic acid and / or a carboxyl group-containing ethylenically unsaturated monomer such as itaconic acid and maleic acid within the range of 50% by weight. It can be obtained by copolymerizing the other acrylic monomer and / or ethylenically unsaturated monomer within the range of 50% by weight or by polymerizing the carboxyl group-containing acrylic monomer alone.

Examples of the alkenyl group-containing epoxy compound include allyl glycidyl ether and the like.

As the epoxy group-containing acrylic resin,
For example, copolymerizing an epoxy group-containing acrylic monomer such as glycidyl (meth) acrylate with the other acrylic monomer and an ethylenically unsaturated monomer within a range of 50% by weight or using an epoxy group-containing acrylic monomer alone. Obtained by polymerizing.

The alkenyl group-containing carboxylic acids include
Allyl acetic acid, (meth) acrylic acid, 2-butenoic acid, 3
-Butenoic acid, crotonic acid, undecylenic acid, linoleic acid etc.

The alkenyl group-containing polyester resin is easily produced by the polycondensation reaction of the above-mentioned alkenyl alcohols and polyhydric alcohols with polybasic acids.

As the polyhydric alcohol, ethylene glycol, propylene glycol, 1,6-hexanediol, diethylene glycol, neopentyl glycol,
Examples thereof include hydroxypivalic acid neopentyl glycol ester, trimethylolpropane, and dimethylsiloxane having alcoholic hydroxyl groups at both ends. As the polybasic acid, phthalic anhydride, isophthalic acid, terephthalic acid,
Adipic acid, azelaic acid, trimellitic acid and the like are exemplified. If necessary, a monohydric alcohol or a monobasic acid may be partially used.

As another method for synthesizing the alkenyl group-containing polyester resin, for example, the carboxyl group of the polyester resin obtained by the polycondensation reaction of the polyhydric alcohol and the polybasic acid described above and the alkenyl group-containing epoxy compound described above are used. Addition reaction and / or addition reaction of the hydroxyl group of the polyester resin obtained by polycondensation reaction of polyhydric alcohols and polybasic acid with the above-mentioned alkenyl isocyanate and / or alkenyl group-containing carboxylic acid anhydride Can be mentioned.

The alkenyl group-containing epoxy resin is, for example, the addition reaction of bisphenol A diglycidyl ether with the above-mentioned alkenyl group-containing carboxylic acids, and the hydroxyl group in the epi-bis type epoxy resin, except for the above-mentioned epoxy group-containing acrylic resin. It can be easily produced by an addition reaction or the like with the above-mentioned alkenyl isocyanate and / or the anhydride of the alkenyl group-containing carboxylic acid.

The alkenyl group-containing polyether resin, acrylic resin, epoxy resin and polyester resin have an iodine value of 50 to 250. If the iodine value is less than 50, the crosslink density of the cured product is lowered and sufficient mechanical strength does not occur. 25
When it exceeds 0, the flexibility of the coating film decreases. Preferably 7
It is in the range of 0 to 200. Number average molecular weight is 300 to 20
If it is less than 300, the mechanical strength will decrease, and if it is more than 20,000, the workability in forming a coating film will decrease. It is preferably 400 to 10,000.

Further, alkenyl group-containing polyether resin and alkenyl group-containing acrylic resin are preferable.

The component (a) is preferably added in an amount corresponding to 0.4 to 4 hydrogen atoms bonded to silicon atoms with respect to one alkenyl group in the component (b). By adjusting the addition amount of the component (a) in this way, it becomes possible to obtain a cured product excellent in weather resistance, gloss value and flexibility. If the number of hydrogen atoms is less than 0.5 or more than 4, the residual alkenyl groups and hydrogen atoms may react with moisture or contaminants, or the resin or coating film may deteriorate due to ultraviolet rays. Not preferable.

Component (c) Component (c) is a hydrosilylation catalyst for curing component (a) and component (b), and is a Group VIII transition metal or compound thereof, such as platinum, palladium, rhodium,
Each complex of ruthenium can be used, and specifically P
tCl ₄ , H ₂ PtCl ₆ · 6H ₂ O, Pt-vinylsiloxane complex (for example, Pt _n (ViMe ₂ SiOSi
Me ₂ ) _m ), Pt-phosphine complex (for example, Pt
(PPh) ₄ ), Pt-olefin complex (for example, Pt
Cl ₂ (cod)), Pt (acac) ₂ , trans
- or cis- [PtCl ₂ (NH ₂ Pr) _2], P
dCl ₂ (PPh ₃ ) ₂ , PdCl ₂ (PhCN) ₂ ,
RhCl ₂ (PPh ₃ ) ₃ , [RhClcod] ₂ , R
u (cpd) ₂ (wherein Me is a methyl group, Vi is a vinyl group, Ph is a phenyl group, Pr is a propyl group, cod is a cyclooctadiene, acac is an acetylacetonate,
(cpd represents cyclooctadiene, n and m represent integers) and other known hydrosilylation catalysts and mixtures thereof. If necessary, these catalysts can be diluted with a solvent such as alcohols, aromatics or aliphatics, hydrocarbons, ketones and basic solvents before use. Platinum catalysts such as chloroplatinic acid are common.

The compounding amount of (c) is 5 to 1000 relative to 100 parts by weight of the solid content of the mixture of the components (a) and (b).
0 ppm is preferable and 20 to 1000 ppm is particularly preferable. If it is less than 5 ppm, the curability is poor and 10,000 p
If it exceeds pm, the cured coating film may be colored by the color of the catalyst.

The present invention will be described in detail below with reference to production examples and examples. In these, "part" and "%"
Is based on weight.

Production Example 1 90 parts of Solvesso 100 (manufactured by Esso Standard Petroleum) was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introducing pipe and a dropping funnel, and the temperature was raised to 130 ° C. while introducing nitrogen gas. After the temperature was raised, the following mixed solution (a) was added dropwise at a constant rate over 3 hours using a dropping funnel.

Mixed liquid (a) 50 parts of compound having the following average composition formula

[Chemical 34] Tertiary butyl methacrylate 50 parts 2,2'-azobis (methyl isobutyrate) 6 parts

After the addition of the mixed solution (a) was completed, the mixture was kept at 130 ° C. for 1 hour.
After aging for 10 hours, 10 parts of Solvesso 100 and 0.5 part of 2,2′-azobis (methylisobutyrate) were added dropwise over 30 minutes, and the mixture was aged at 130 ° C. for 2 hours and then cooled to obtain a resin solution A. Obtained. The number average molecular weight (polystyrene conversion value of GPC) of the obtained resin was 3500, the resin solution characteristics were a nonvolatile content of 49.5 wt% and Gardner viscosity CD.

Production Example 2 90 parts of xylol was charged in the same reaction vessel as in Production Example 1 and the temperature was raised to 120 ° C. while introducing nitrogen gas. Then, the following mixed solution (b) was added in 3 hours using a dropping funnel. It was dropped at a constant speed.

Mixture (b) 100 parts of compound having the following average composition formula

[Chemical 35] 2,2'-azobis (methylisobutyrate) 3 parts

After the dropping of the mixed solution (b) was completed, 1
After aging for a while, then 10 parts of xylol and 2,2'-
0.5 part of azobis (methyl isobutyrate) was added dropwise over 30 minutes, and the mixture was aged at 120 ° C. for 2 hours and cooled. The obtained resin solution was subjected to polymer purification using methanol as a precipitant. The obtained polymer recovery rate was 75% by weight, and after filtering and drying it, the nonvolatile content was 60% by weight by xylol.
To obtain a resin solution B. The number average molecular weight of the obtained resin was 8550, and the resin solution had a nonvolatile content of 6
The weight was 0.2% by weight and the Gardner viscosity was Z.

Production Example 3 60 parts of xylol was charged in the same reaction vessel as in Production Example 1 and the temperature was raised to 120 ° C. while introducing nitrogen gas, and then the following mixed solution (c) was used for 3 hours using a dropping funnel. It was dropped at a constant speed.

Mixture (c) 70 parts of compound having the following average composition formula

[Chemical 36] Cyclohexyl methacrylate 30 parts 2,2'-azobis (methyl isobutyrate) 3 parts

After the dropping of the mixed solution (c) was completed, the mixture was kept at 120 ° C. for 1 hour.
After aging for a while, then 6.7 parts of xylol and 2,2 '
-0.5 parts of azobis (methylisobutyrate) was added dropwise over 30 minutes, aged at 120 ° C for 2 hours, and then cooled to obtain a resin solution C. The number average molecular weight of the obtained resin was 553.
0, the resin solution characteristics were 58.6% by weight of non-volatile content and Gardner viscosity V.

Production Example 4 90 parts of Solvesso 100 was charged in the same reaction vessel as in Production Example 1, heated to 130 ° C. while introducing nitrogen gas, and the following mixed solution (d) was added to the reaction vessel using a dropping funnel. It was added dropwise at a constant rate over time.

Mixture (d) 30 parts of compound having the following average composition formula

[Chemical 37] Cyclohexyl methacrylate 30 parts Tert-butyl methacrylate 40 parts 2,2'-azobis (methyl isobutyrate) 3 parts

After the dropwise addition of the mixed solution (d) was completed, the mixture was kept at 130 ° C. for 1 hour.
After aging for 10 hours, 10 parts of Solvesso 100 and 0.5 part of 2,2′-azobis (methylisobutyrate) were added dropwise over 30 minutes, and the solution was aged at 130 ° C. for 2 hours and then cooled to obtain a resin solution D. Obtained. The number average molecular weight of the obtained resin was 4320, the resin solution characteristics were a nonvolatile content of 50.2% by weight, and the Gardner viscosity F.

Production Example 5 In a reaction container similar to that of Production Example 1, 100% of an alkenyl group-containing polyether resin HPE-1030 (manufactured by Daicel Chemical Industries, Ltd.) was used.
After charging a part and raising the temperature to 120 ° C. while introducing nitrogen gas, the following mixture solution (e) was added dropwise at a constant rate over 3 hours using a dropping funnel.

Liquid mixture (e) 70 parts of compound having the following average composition formula

[Chemical 38] 2-Ethylhexyl acrylate 20 parts 2,4-diphenyl-4-methyl-1-pentene 10 parts 2,2′-azobis (methylisobutyrate) 5 parts

After the addition of the mixed solution (e) was completed, the mixture was heated at 130 ° C. for 1 hour.
After aging for 2 hours, 0.5 part of 2,2'-azobis (methylisobutyrate) was then added in 30 minutes in a divided manner.
After aging at 30 ° C. for 2 hours, it was cooled to obtain a resin solution E.
The obtained resin solution had a nonvolatile content of 98.2% by weight and a Gardner viscosity of Z1-Z2.

Production Example 6 90 parts of Solvesso 100 was charged in the same reaction vessel as in Production Example 1, heated to 120 ° C. while introducing nitrogen gas, and the following mixed solution (f) was added to the reaction vessel using a dropping funnel. It was added dropwise at a constant rate over time.

Mixture (f) 3-methyl-3-butenyl methacrylate 50 parts styrene 30 parts tert-butyl methacrylate 20 parts 2,2'-azobis (2-methylbutyronitrile) 5 parts

After the dropping of the mixed solution (f) was completed, the mixture was mixed at 120 ° C. for 1 hour.
After aging for 4 hours, 4.5 parts of Solvesso 100 and 0.5 part of 2,2'-azobis (methylbutyronitrile) were added dropwise over 30 minutes, and the mixture was aged at 120 ° C for 2 hours and then cooled to obtain a resin solution. I got F. The number average molecular weight of the obtained resin was 5,000, the resin solution characteristics were a nonvolatile content of 51.9% by weight, and the Gardner viscosity H.

Production Example 7 90 parts of Solvesso 100 was charged in the same reaction vessel as in Production Example 1, heated to 120 ° C. while introducing nitrogen gas, and then the following mixed solution (g) was added for 3 hours using a dropping funnel. At constant speed.

Mixture (g) 40 parts of compound having the following average composition formula

[Chemical Formula 39] Cyclohexyl methacrylate 30 parts Tertiary methacrylate 20 parts 2,2'-azobis (methyl isobutyrate) 3 parts

After the addition of the mixed solution (g) was completed, the mixture was kept at 120 ° C. for 1 hour.
After aging for a period of time, 10 parts of Solvesso 100 and 0.5 parts of 2,2'-azobis (methylisobutyrate) were then added.
Parts were added dropwise over 30 minutes, aged at 120 ° C. for 2 hours and then cooled to obtain a resin solution G. The obtained resin has a number average molecular weight of 6500, a resin liquid property of non-volatile content of 50.5% by weight,
The Gardner viscosity was H.

Example 1 122 parts of resin solution A, 39 parts of HPE-1030 (manufactured by Daicel Chemical Industries) and chloroplatinic acid (H ₂ PtCl ₆ · 6H)
1.5 parts of a 2% ethanol solution of ₂ O) was mixed well, coated on an iron plate so that the dry film thickness would be 20 μm, and after setting for 2 hours, baked at 140 ° C. for 25 minutes. The physical properties of the cured coating film are shown in Table 1. In addition, the measurement of each physical property value was performed as follows.

Pencil hardness: JIS K 5400 No. 6-
Measured according to paragraph 14. Coating film Tg: dynamic viscoelasticity test (11 Hz / heating rate 2 ° C. /
The temperature at which the temperature dispersion of tan δ in (min) has a maximum value. Xylol wrapping test: 1 impregnated with xylol
The appearance after visually rubbing the coating film 100 times with absorbent cotton of cm x 1 cm size is judged visually. Acid resistance: 0.2 cc of 0.1N sulfuric acid solution is applied at 20 ° C
・ Stand at room temperature with humidity of 75% for 1 day and then 10 at 60 ℃
After drying for a minute, the state of deterioration of the coating film was visually determined. ◎: Very good, ○: Good, △: Traces, ×: Whitening of coating film Initial gloss: 40 parts of titanium oxide (Taipaque R-820: made by Ishihara Sangyo Co., Ltd.) was added to 100% by weight of each resin solid, and a ball mill was used. The dispersed white paint was cured in the same manner as the coating films of Examples and Comparative Examples, and the specular gloss at 60 ° C. was measured. Weather resistance: The weather resistance was measured by visually judging the retention rate of 60 ° specular gloss and the appearance of the coating film after irradiation for 2000 hours with a sunshine weatherometer.

Example 2 71 parts of the resin solution B, 114 parts of the resin solution F and 1.5 parts of a 2% ethanol solution of chloroplatinic acid were mixed well, and a cured coating film was prepared in the same manner as in Example 1 below. Created. The physical properties of the cured coating film are shown in Table 1.

Example 3 100 parts of the resin solution C, 40 parts of HPE-1060 (manufactured by Daicel Chemical Industries, Ltd.) and 1.0 part of a 2% ethanol solution of chloroplatinic acid were mixed well, and the same procedure as in Example 1 was carried out. A cured coating film was prepared. The physical properties of the cured coating film are shown in Table 1.

Example 4 67 parts of the resin solution D, 67 parts of HPE-10601C (manufactured by Daicel Chemical Industries, Ltd.) and 3.0 parts of a 2% ethanol solution of chloroplatinic acid were mixed well, and a dry film thickness was 20 μm on an iron plate. It was applied as described above and dried at room temperature for 1 week to obtain an always dry coating film. The physical properties of the cured coating film are shown in Table 1.

Example 5 100 parts of resin solution E and 1.5 parts of a 2% ethanol solution of chloroplatinic acid were mixed well, and a dry film thickness of 20 μm was formed on an iron plate.
And a cured coating film was prepared in the same manner as in Example 1. The physical properties of the cured coating film are shown in Table 1.

Example 6 100 parts of Resin Solution G, 25 parts of HPE-1030 and 1.0 part of a 2% ethanol solution of chloroplatinic acid were mixed well and a cured coating film was prepared in the same manner as in Example 1. did. The physical properties of the cured coating film are shown in Table 1.

Comparative Example Average composition formula

[Chemical 40] 16 parts of methylhydrogenpolysiloxane of Example 1, 100 parts of resin solution F and 1 part of a 2% ethanol solution of chloroplatinic acid were mixed well, and a cured coating film was prepared in the same manner as in Example 1. The physical properties of the cured coating film are shown in Table 1.

[0106]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 183/07 PMV // C08F 299/08 MRY (72) Inventor Hisashi Tanabe Ikeda, Neyagawa, Osaka 19-17 Nakamachi Japan Paint Co., Ltd. (72) Inventor Mitsuhiro Takarada 1 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Yuji Yoshikawa Gunma Prefecture 1 Hitomi, Oita, Matsuida-cho, Usui-gun 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (4)

[Claims] 1. A hydrogen polysiloxane macromonomer having (a) a silicon-hydrogen bond and a 3- (meth) acryloyloxypropyl group bonded to a silicon atom in the molecule, alone or in combination with an ethylenically unsaturated monomer. A curable resin composition containing (b) a resin having a plurality of alkenyl groups in the molecule, having a number average molecular weight of 300 to 20,000 and an iodine value of 50 to 250, and (c) a hydrosilylation catalyst. 2. The hydrogen macromonomer has an average compositional formula (1): (However, in the formula, R is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ′ is a hydrogen atom or a methyl group, and a, b, and c are 0 ≦ a ≦ 20, 0.5 ≦ b ≦ 3, 0 ≦. represents a real number of c ≦ 10) or an average composition formula (2) (Wherein R, R ′, a and b have the same meaning as described above, and d represents a real number of 1 ≦ d ≦ 10) or the average composition formula (3) (Wherein R, R ′ and c have the same meaning as described above, R ″ is the same as R or —OSi (R) ₂ H, and R ′ ″ is when R ″ is the same as R. Hydrogen atom otherwise-
It means OSi (R) ₂ H. ) The curable resin composition according to claim 1. 3. The cured resin composition according to claim 1, wherein the component (b) is a polyether resin, polyester resin, epoxy resin or acrylic resin having a plurality of alkenyl groups in the molecule. 4. The curable resin composition according to claim 1, wherein the component (c) is a platinum catalyst.