JP2652327B2 - Curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] relates FIELD The present invention is a curable resin composition of the industrial, in particular, relates to a curable resin composition excellent in weather resistance and physical properties.

2. Description of the Related Art Conventionally, as a curable resin composition applied to the field of coating, a curable resin composition obtained by mixing a melamine resin or a polyfunctional isocyanate compound as a curing agent with a hydroxyl group-containing resin represented by an acrylic resin or a polyester resin. It has been known. However, the melamine-cured system has the disadvantage that the lower alcohol is eliminated and its volume is reduced, and the triazine skeleton is inferior in weather resistance and durability against acid rain, which has recently been a problem. In addition, there was a problem of deterioration of weather resistance mainly due to yellowing of the coating film.

As a method for improving the weather resistance, a method is known in which an acrylic resin having an alkoxysilyl group introduced into the molecule is subjected to a condensation reaction at room temperature (for example, JP-A-57-36109, JP-A-57-36109).
No. 8-155666), but have the disadvantages that the reaction rate during thermal curing is slow, contamination due to hydrolysis of the remaining alkoxysilyl group occurs, and the rust resistance is poor. Further, a curing system utilizing the reactivity between an alkoxysilyl group and a hydroxyl group of an organic resin (for example, Japanese Patent Publication No. Sho 63
JP-A-335512) has been reported, but has the disadvantage that the reaction rate during thermosetting is slow and the salt water resistance is poor. Further, all of the curing systems are configured as a two-pack type of a resin having a functional group and a curing catalyst thereof, and it is difficult to apply the one-pack curing system with excellent workability.

[0004] On the other hand, a technique of curing vinyl polysiloxane and organohydrogen polysiloxane in the presence of a platinum catalyst (application of hydrosilylation reaction) has been known for a long time. However, since this cured product swells with a solvent, it is resistant to solvents. Poor properties, poor alkali resistance, and poor recoatability have led to little development in the field of coatings.

Examples of the application of the above-mentioned 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 curing agent having an alkenyl group. A curable resin composition composed of a polymer and a hydrosilylation catalyst, which mainly cures to produce a rubbery substance (JP-A-3-9595)
266, JP-A-3-200807) and a curable composition having rubber elasticity (JP-A-1-138230, etc.) composed of an alkenyl group-containing polyether, a hydrosilyl group-containing polyether and a platinum catalyst. However, these are elastic materials 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 organic resin having alkenyl group (acryl, polyester, epoxy resin), organohydrogenpolysiloxane and platinum catalyst. Curable resin composition (JP-A-3-27764)
5) has been reported. However, organohydrogenpolysiloxane, which is a curing agent of this system, has low compatibility with organic resins having alkenyl groups, and it is necessary to design a composition having a high crosslinking density to obtain a cured coating film with sufficient mechanical strength. It was difficult.

According to the present invention, a homo- or copolymer of a heterofunctional organohydrogen macromonomer having a (meth) acryloyloxypropyl group in a chain is used as a curing agent, and an organic resin having an alkenyl group is subjected to a hydrosilylation reaction. Has successfully solved this problem.

[0007] The cured coating film thus obtained also comprises
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 used as a paint, it becomes possible to eliminate a solvent or to make a solid.

Accordingly, a first object of the present invention is to provide a curable resin composition having excellent mechanical strength and excellent 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 to provide moisture resistance, water resistance,
An object of the present invention 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 recoating property.

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

DISCLOSURE OF THE INVENTION The above problem is solved by the present invention. The present invention
(A) a copolymer of a hydrogenpolysiloxane macromonomer having a silicon-hydrogen bond and a 3- (meth) acryloyloxypropyl group bonded to a silicon atom in the molecule, alone or with an ethylenically unsaturated monomer,
A curable resin composition comprising (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 composition formula (1)

Embedded image (Where R is an alkyl or phenyl group having 1 to 6 carbon atoms, R ′ is a hydrogen atom or a methyl group, a, b, and c are 0 ≦ a ≦ 20, 0.5 ≦ b ≦ 3, 0 ≦ represents a real number of c ≦ 10), or average composition formula (2)

Embedded image (Where R, R ', a and b have the same meanings as described above, and d represents a real number satisfying 1 ≦ d ≦ 10) or the average composition formula (3)

Embedded image (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 the case where R ″ is the same as R In other cases-
OSi (R) ₂ H is meant. Having.

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

[0016]

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[0017]

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[0018]

Embedded image (Wherein 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 has become 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]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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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) acrylate.
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) acrylate 2 −
An adduct of hydroxyethyl and poly-ε-caprolactone (for example, Plaxel 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-acrylamide-2-methylpropanesulfonic acid, acid phosphoxypropyl methacrylate,
(Meth) tributyltin acrylate, (meth) acrylamide, (meth) acryloyl isocyanate, (meth)
2-isocyanate ethyl acrylate, silicone macromonomer (for example, Silaprene 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 thereof include N-cyclohexylmaleimide and N-phenylmaleimide.

The 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-mentioned ethylenically unsaturated monomer 80
０0 wt%. If the copolymerization amount of the silicone compound is less than 20% by weight, the crosslink density of the cured composition decreases, and the coating film does not show sufficient mechanical properties. The silicone compound 40 represented by the average composition formula (1) and / or the average composition formula (2) and / or the average composition formula (3)
~ 100wt% and ethylenically unsaturated monomer 60 ~ 0w
Copolymerization with t% is preferred. The number average molecular weight of the copolymer is preferably from 1,000 to 30,000. Further, considering the curability of the cured coating film, the SiH group concentration of the copolymer is 1%.
× 10 ^-3 mol / g or more is desirable.

(B) Component (b) having an alkenyl group has an iodine value of 50 to
Having an alkenyl group of 250 and a number average molecular weight of 300
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.

Examples of the alkenyl group-containing polyether resin include a polyether obtained by ring-opening polymerization of a 1,2-epoxy compound having an alkenyl group with an active hydrogen compound (water, mono- or polyhydric alcohol) as an initiator. 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).
Further, vinylcyclohexane-butanol, allyl alcohol or propargyl alcohol is used 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 Industries, Ltd. (for example, JP-A-4-2382).
9).

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

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

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

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

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

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

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

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Examples of the alkenyl group-containing acrylic resin include, for example, 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
-1: 1 adduct of hydroxyethyl and vinylcyclohexene monoepoxide; homopolymerization of alkenyl group-containing acrylic monomer such as Daicel Chemical Industries, Ltd.) or copolymerization of alkenyl group-containing acrylic monomer with other acrylic monomers. 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 alkenyl alcohol, a transesterification reaction between alkyl (meth) acrylate and alkenyl alcohol, and an addition reaction between isocyanate-containing acrylic monomer and alkenyl alcohol.

Other acrylic monomers copolymerizable with the alkenyl group-containing acrylic monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. I-butyl acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate 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, ( 3-trimethoxysilylpropyl (meth) acrylate, 3-triethoxysilylpropyl (meth) acrylate, 3-dimethoxymethylsilylpropyl (meth) acrylate,
(Meth) acrylic acid 2-acrylamide-2-methylpropanesulfonic acid, acid phosphoxypropyl methacrylate, tributyltin (meth) acrylate, (meth)
Acrylamide, (meth) acryloyl isocyanate, 2-isocyanatoethyl (meth) acrylate, silicone macromonomer (for example, Thylaprene FM
-0711, manufactured by Chisso Corporation).

In addition, styrene,
α-methylstyrene, itaconic acid, maleic acid, vinyl acetate, allyl acetate, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane,
Ethylenically unsaturated monomers other than 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 includes an addition reaction between a hydroxyl group-containing acrylic resin and an alkenyl isocyanate compound and / or an anhydride of an alkenyl group-containing carboxylic acid, and an isocyanate-containing acrylic resin and an alkenyl alcohol. Addition reaction with an alkenyl group-containing epoxy resin, an addition reaction between a carboxyl group-containing acrylic resin and an alkenyl group-containing epoxy compound, and an addition reaction between an epoxy group-containing acrylic resin and an alkenyl group-containing carboxylic acid.

Hydroxyl-containing acrylic resins include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Hydroxyl-containing acrylic monomers such as hydroxypropyl, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and poly-ε-caprolactone (for example, Praxel FM series) Of the acrylic monomer and an ethylenically unsaturated monomer in a range of 50% by weight or less, or by polymerizing with a hydroxyl group-containing acrylic monomer alone.

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

The alkenyl group-containing carboxylic acid anhydrides 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, 2-isocyanatoethyl (meth) acrylate and the other acrylic monomers, and an ethylenically unsaturated monomer within a range of 50% by weight or less. It is obtained by copolymerizing with a monomer or polymerizing with an isocyanate-containing acrylic monomer alone.

Examples of 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, -Methyl-3-butene-
There are 1-ol, 2-methyl-3-buten-2-ol, oleyl alcohol, crotyl alcohol and the like.

The carboxyl group-containing acrylic resin is mixed with 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 a range of 50% by weight or less. It can be obtained by copolymerizing the other acrylic monomer and / or an ethylenically unsaturated monomer within the range of 50% by weight or polymerizing a carboxyl group-containing acrylic monomer alone.

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

As the epoxy group-containing acrylic resin,
For example, an epoxy group-containing acrylic monomer such as glycidyl (meth) acrylate and the other acrylic monomer and an ethylenically unsaturated monomer in a range of 50% by weight or less may be copolymerized, or the epoxy group-containing acrylic monomer alone may be used. Obtained by polymerization.

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 and the like.

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

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,6-hexanediol, diethylene glycol, neopentyl glycol,
Examples thereof include neopentyl glycol hydroxypivalate, trimethylolpropane, and dimethylsiloxane containing an alcoholic hydroxyl group at both ends. Polybasic acids include 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 between the above-mentioned polyhydric alcohol and polybasic acid and the above-mentioned alkenyl group-containing epoxy compound are used. And / or an addition reaction between the hydroxyl group of the polyester resin obtained by the polycondensation reaction of the polyhydric alcohol and the 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, an addition reaction between bisphenol A diglycidyl ether and the alkenyl group-containing carboxylic acid, except for the epoxy group-containing acrylic resin, and the hydroxyl group in the epi-bis type epoxy resin. It can be easily produced by an addition reaction of the above with an alkenyl isocyanate and / or an anhydride of an 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 crosslinked density of the cured product is lowered and sufficient mechanical strength is not produced. 25
If it exceeds 0, the flexibility of the coating film decreases. Preferably, 7
The range is from 0 to 200. Number average molecular weight is 300-20
If it is less than 300, the mechanical strength is reduced, and if it is more than 20,000, the workability in forming a coating film is reduced. Preferably, it is 400 to 10,000.

Further, alkenyl group-containing polyether resins and alkenyl group-containing acrylic resins are preferred.

The addition amount of the component (a) is preferably an amount corresponding to 0.4 to 4 hydrogen atoms bonded to a silicon atom per one alkenyl group of the component (b). By adjusting the amount of the component (a) as described above, a cured product excellent in weather resistance, gloss value and flexibility can be obtained. If the number of hydrogen atoms is less than 0.5 or more than 4, the remaining alkenyl groups and hydrogen atoms may react with moisture or contaminants, or the resin or coating may be deteriorated by ultraviolet rays. Not preferred.

Component (c) Component (c) is a hydrosilylation catalyst for curing the components (a) and (b), and includes a Group VIII transition metal or a compound thereof, for example, platinum, palladium, rhodium,
Each complex of ruthenium can be used.
_{tCl 4, H 2 PtCl 6 ·} 6H 2 O, Pt- vinylsiloxane complexes (e.g., Pt _n (ViMe ₂ SiOSi
Me ₂ ) _m ), a Pt-phosphine complex (eg, 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 (where Me is a methyl group, Vi is a vinyl group, Ph is a phenyl group, Pr is a propyl group, cod is cyclooctadiene, acac is acetylacetonate,
cpd represents cyclooctadiene, and n and m represent integers) and other known hydrosilylation catalysts and mixtures thereof. These catalysts can be used after being diluted with a solvent such as alcohols, aromatic or aliphatic, hydrocarbons, ketones, and a basic solvent, if necessary. Platinum catalysts such as chloroplatinic acid are common.

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

Hereinafter, the present invention will be described in detail 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) were charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel, and heated to 130 ° C. while introducing nitrogen gas. After the temperature was raised, the following mixture (a) was dropped at a constant speed for 3 hours using a dropping funnel.

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

Embedded image Tertiary butyl methacrylate 50 parts 2,2'-azobis (methyl isobutyrate) 6 parts

After the completion of the dropwise addition of the mixture (a), the mixture was heated 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. Obtained. The obtained resin had a number average molecular weight (GPC value in terms of polystyrene) of 3,500, and the resin solution had a nonvolatile content of 49.5% by weight and a Gardner viscosity CD.

Preparation Example 2 90 parts of xylol was charged into a reaction vessel similar to that of Preparation Example 1, and the temperature was raised to 120 ° C. while introducing nitrogen gas. Then, the following mixed solution (b) was dropped for 3 hours using a dropping funnel. The solution was dropped at a constant speed.

Liquid mixture (b) 100 parts of a compound having the following average composition formula

Embedded image 2,2'-azobis (methyl isobutyrate) 3 parts

After the completion of the dropwise addition of the mixture (b), the mixture was heated at 120 ° C. for 1 hour.
After aging for 10 hours, 10 parts of xylol and 2,2'-
0.5 parts of azobis (methyl isobutyrate) was added dropwise over 30 minutes, and the mixture was aged at 120 ° C. for 2 hours and cooled. The resulting resin solution was subjected to polymer purification using methanol as a precipitant. The obtained polymer recovery rate was 75% by weight, which was filtered and dried, and then dried with xylol to obtain a nonvolatile content of 60% by weight.
To give a resin solution B. The number average molecular weight of the obtained resin is 8550, and the resin solution characteristic is a nonvolatile content of 6.
0.2% by weight and Gardner viscosity Z.

Production Example 3 60 parts of xylol was charged into 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 (c) was added using a dropping funnel for 3 hours. The solution was dropped at a constant speed.

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

Embedded image Cyclohexyl methacrylate 30 parts 2,2'-azobis (methyl isobutyrate) 3 parts

After the completion of the dropwise addition of the mixture (c), the mixture was heated at 120 ° C. for 1 hour.
After aging for 2 hours, 6.7 parts of xylol and 2,2 '
0.5 parts of -azobis (methyl isobutyrate) was added dropwise over 30 minutes, the mixture was 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 is 553.
0, the resin solution properties were 58.6% by weight of nonvolatile components and Gardner viscosity V.

Production Example 4 90 parts of Solvesso 100 were charged into a reaction vessel similar to that of Production Example 1, heated to 130 ° C. while introducing nitrogen gas, and then mixed liquid (d) shown below was added using a dropping funnel. The solution was dropped at a constant speed over time.

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

Embedded image Cyclohexyl methacrylate 30 parts Tertiary butyl methacrylate 40 parts 2,2'-azobis (methyl isobutyrate) 3 parts

After the completion of the dropwise addition of the mixed solution (d), the mixture was heated 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, the mixture was aged at 130 ° C. for 2 hours, and then cooled. Obtained. The obtained resin had a number average molecular weight of 4320, resin solution properties of 50.2% by weight of non-volatile content and Gardner viscosity F.

Preparation Example 5 In a reaction vessel similar to that of Preparation Example 1, 100 parts of an alkenyl group-containing polyether resin HPE-1030 (manufactured by Daicel Chemical Industries) was added.
After the temperature was raised to 120 ° C. while introducing nitrogen gas, the following mixture (e) was dropped at a constant speed over 3 hours using a dropping funnel.

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

Embedded image 2-ethylhexyl acrylate 20 parts 2,4-diphenyl-4-methyl-1-pentene 10 parts 2,2'-azobis (methylisobutyrate) 5 parts

After the completion of the dropwise addition of the mixture (e), the mixture was heated at 130 ° C. for 1 hour.
After aging for 2 hours, 0.5 part of 2,2′-azobis (methyl isobutyrate) was divided and charged in 30 minutes, and 1
After aging at 30 ° C. for 2 hours, the mixture was cooled to obtain a resin solution E.
The resulting 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 were charged into the same reaction vessel as in Production Example 1, and the temperature was raised to 120 ° C. while introducing nitrogen gas. The solution was dropped at a constant speed over time.

Mixed solution (f) 3-methyl-3-butenyl methacrylate 50 parts Styrene 30 parts Tertiary butyl methacrylate 20 parts 2,2'-azobis (2-methylbutyronitrile) 5 parts

After the completion of the dropwise addition of the mixture (f), the mixture was heated at 120 ° C. for 1 hour.
After aging for 4.5 hours, 4.5 parts of Solvesso 100 and 0.5 part of 2,2'-azobis (methylbutyronitrile) were added dropwise over 30 minutes, the mixture was aged at 120 ° C. for 2 hours, and then cooled. F was obtained. The resin obtained had a number average molecular weight of 5000, a resin solution characteristic of 51.9% by weight of non-volatile components and a Gardner viscosity H.

Preparation Example 7 90 parts of Solvesso 100 were charged into the same reaction vessel as in Preparation Example 1, and the temperature was raised to 120 ° C. while introducing nitrogen gas. Then, the following mixture (g) was dropped for 3 hours using a dropping funnel. At a constant rate.

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

Embedded image Cyclohexyl methacrylate 30 parts Tertiary butyl methacrylate 20 parts 2,2'-azobis (methyl isobutyrate) 3 parts

After completion of the dropwise addition of the mixed solution (g), the mixture was heated at 120 ° C. for 1 hour.
After aging for 10 hours, 10 parts of Solvesso 100 and 0.5 of 2,2′-azobis (methylisobutyrate) were added.
The mixture was dropped over 30 minutes, aged at 120 ° C. for 2 hours, and then cooled to obtain a resin solution G. The number average molecular weight of the obtained resin was 6,500, the resin liquid property was a nonvolatile matter of 50.5% by weight,
The Gardner viscosity was H.

[0098] Example 1 122 parts of resin solution A, HPE-1030 (manufactured by Daicel Chemical Industries) 39 parts of chloroplatinic acid (H ₂ PtCl ₆ · 6H
2% ethanol solution 1.5 parts of ₂ O) was mixed well, dry film thickness steel plate was coated so that the 20 [mu], after 2 hours settings were baked 25 minutes at 140 ° C.. Table 1 shows the physical properties of the cured coating film. In addition, the measurement of each physical property value was performed as follows.

Pencil hardness: JIS K 5400 No. 6
Measured according to clause 14. Coating film Tg: Dynamic viscoelasticity test (11 Hz / heating rate 2 ° C. /
min) is the temperature at which the maximum value is exhibited in the tan δ temperature dispersion. Xylol wrapping test: 1 impregnated with xylol
The appearance was visually determined after rubbing the coating film 100 times with absorbent cotton having a size of cm × 1 cm. Acid resistance: 0.2 cc of 0.1N sulfuric acid solution applied, 20 ℃
・ After standing still for one day and night at a humidity of 75%, 10 ° C at 60 ° C
After drying for a minute, the state of deterioration of the coating film was visually determined. ：: extremely good, ：: good, Δ: no trace, ×: coating turbidity Initial gloss: 40 parts by weight of titanium oxide (Taipec R-820: manufactured by Ishihara Sangyo) for 100% by weight of each resin solid content, and a ball mill 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 of 60 ° specular gloss after 2000 hours of irradiation with a sunshine weatherometer and the appearance of the coating film.

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 formed in the same manner as in Example 1. Created. Table 1 shows the physical properties of the cured coating film.

Example 3 100 parts of the resin solution C, 40 parts of HPE-1060 (manufactured by Daicel Chemical Industries) and 1.0 part of a 2% ethanol solution of chloroplatinic acid were mixed well, and the mixture was treated in the same manner as in Example 1. A cured coating was formed. Table 1 shows the physical properties of the cured coating film.

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 the dried film thickness was reduced to 20 μm on an iron plate. And dried at room temperature for one week to obtain a normally-dried coating film. Table 1 shows the physical properties of the cured coating film.

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

Example 6 100 parts of the 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. Table 1 shows the physical properties of the cured coating film.

Comparative Example Average Composition Formula

Embedded image Then, 16 parts of methylhydrogenpolysiloxane, 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. Table 1 shows the physical properties of the cured coating film.

[0106]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C09D 151/08 PGX C09D 151/08 PGX 183/07 PMU 183/07 PMU // C08F 299/08 MRY C08F 299/08 MRY C09D 183/05 PMS C09D 183/05 PMS (72) Inventor Hisashi Tanabe 19-17 Ikedanakamachi, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Mitsuhiro Takarada Matsui, Usui-gun, Gunma Prefecture 1-10 Tenmachi Hitomi, Silicon Electronic Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Yuji Yoshikawa 1-10 Hitomi, Matsuidamachi, Usui-gun, Gunma Prefecture, Japan Silicone Electronic Materials Research Laboratory

Claims (4)

(57) [Claims] (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 in combination with an ethylenically unsaturated monomer A curable resin composition comprising: (b) a resin having a plurality of alkenyl groups in the molecule, 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 composition formula (1): ## STR1 ## (Where R is an alkyl group or phenyl group having 1 to 6 carbon atoms, R ′ is a hydrogen atom or a methyl group, a, b, and c are 0 ≦ a ≦ 20, 0.5 ≦ b ≦ 3, 0 ≦ represents a real number of c ≦ 10), or average composition formula (2) (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) (However, wherein R, R 'and c are as defined above, R "means the same or -OSi (R) ₂ H to R, R'" If the same R "within R In other cases-
OSi (R) ₂ H is meant. 2. The curable resin composition according to claim 1, wherein 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.