WO2020066993A1 - Composition, cured object, laminate, and light resistant coating material - Google Patents

Abstract

The present invention provides a composition that contains a polysiloxane having a reactive group, a base generating agent, and an inorganic filler, and that is characterized in that the amount of the inorganic filler blended therein is 1-15 wt% of the non-volatile portion of the composition. Also provided is said composition that contains an ultraviolet ray absorbing agent. The present invention also provides: a cured object obtained by curing said composition; and a weather resistant coating material and a light resistant coating material, which contain said composition.

Description

Compositions, cured products, laminates and lightfast paints

(4) The present invention relates to a composition containing a polysiloxane, a base generator, and an inorganic filler.

BACKGROUND ART Transparent resin materials typified by polycarbonate and the like are widely used in various applications because of their low specific gravity and light weight. In particular, there is a great demand for use outdoors or under strong illumination, such as resin glass utilizing transparency, and building materials utilizing lightweight.
On the other hand, resin materials have problems such as that the surface is easily damaged, gloss and transparency are easily lost, and solvent resistance, weather resistance, and heat resistance are weak. Therefore, the resin material is often used by being coated with various protective films for the purpose of improving its surface characteristics.

For example, there is a method of providing a silicon dioxide thin film by a sol-gel method using tetraalkoxysilane. This method has the drawback of being brittle and easily broken. As a method for improving this, there has been proposed to add polyethylene glycol to eliminate fragility (Patent Document 1). In the method proposed in Patent Document 1, although a certain degree of surface hardness and flexibility is achieved, heating for a long time in the processing method may have an adverse effect on the base material. In order to improve, an active energy ray-curable hard coat agent which achieves a high surface hardness changed to an active ultraviolet curable type, and has excellent transparency and adhesion has been proposed (Patent Document 2).
However, these methods still have problems in light resistance and weather resistance that can be used outdoors or under strong lighting.

JP-A-2001-79980 JP 2011-6620

課題 An object of the present invention is to provide a resin composition having a hard coat property and capable of obtaining a cured product having excellent light resistance and weather resistance.

As a result of intensive studies, the present inventors have found that the above problems can be solved by providing a composition containing a polysiloxane having a reactive group, a base generator, and an inorganic filler.

That is, the present invention relates to a composition containing a polysiloxane having a reactive group, a base generator, and an inorganic filler, wherein the amount of the inorganic filler is 1 to 15 wt% or less in the composition nonvolatile component. A composition is provided.

The present invention also provides a cured product obtained by curing the composition, and a laminate having the cured product layer.

The present invention also provides a light-resistant paint and a weather-resistant paint containing the composition of the present invention.

組成 The composition of the present invention has a hard coat property and can obtain a cured product excellent in light resistance and weather resistance, and therefore, is a paint capable of protecting the plastic layer even under strong illumination or outdoors.

The present invention relates to a composition containing a polysiloxane having a reactive group, a base generator, and an inorganic filler, wherein the amount of the inorganic filler is 1 to 15% by weight or less in the nonvolatile components of the composition. It is intended to provide a composition characterized by the above.

<Polysiloxane having a reactive group>
In the polysiloxane having a reactive group of the present invention, the reactive group may be any yellow having reactivity, for example, a group having a polymerizable double bond, an epoxy group, an amino group, a ureido group, and an isocyanate group. , Isocyanurate groups, mercapto groups, acid anhydrides and the like. Among them, a group having a polymerizable double bond and an epoxy group are preferable.
Examples of the group having a polymerizable double bond include a vinyl group, a (meth) acryloyl group, a styryl group, an allyl group, and a maleimide group, and a (meth) acryloyl group is particularly preferred.

ポ リ A polysiloxane having a reactive group can be obtained by condensing a silane compound having a silanol group and / or a hydrolyzable silyl group. At this time, a reactive group can be introduced into the polysiloxane by using a silane compound having a reactive group other than the silanol group and / or the hydrolyzable silyl group.

For example, when a group having a polymerizable double bond is introduced, examples of a silane compound having both a group having a polymerizable double bond and a silanol group and / or a hydrolyzable silyl group include vinyltrimethoxy. Silane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethylvinylether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrichlorosilane, 8- (meth) acryloyloxyoctyltri Tokishishiran, in combination 8- (meth) acryloyloxy octyltriethoxysilane like. Among them, vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane are preferred because the hydrolysis reaction can easily proceed and by-products after the reaction can be easily removed.

In addition, an epoxy group-containing silane compound may be used to introduce an epoxy group into the reactive group. Epoxy group-containing silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltriacetoxysilane, γ-glycidoxypropyldimethoxymethylsilane, γ-glycidoxypropyldiethoxymethylsilane, γ-glycidoxypropyldimethoxyethoxymethylsilane, γ-glycidoxypropyldiacetoxy Methylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethoxymethylsilane, β -(3,4-epoxycyclohexyl) ethyldiacetoxymethylsilane, γ-glycidoxypropyldimethoxyethylsilane, γ-glycidoxypropyldiethoxyethylsilane, γ-glycidoxypropyldimethoxyethoxyethylsilane, γ-gly Sidoxypropyldiacetoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxyethylsilane, β- (3,4-epoxycyclohexyl) Tyldimethoxyethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldiacetoxyethylsilane, γ-glycidoxypropyldimethoxyisopropylsilane, γ-glycidoxypropyldiethoxyisopropylsilane, γ-glycidoxypropyldimethoxy Ethoxyisopropylsilane, γ-glycidoxypropyldiacetoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxyisopropylsilane, β- ( 3,4-epoxycyclohexyl) ethyldimethoxyethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldiacetoxyisopropylsilane, γ-glycidoxypropylmethoxydi Methylsilane, γ-glycidoxypropylethoxydimethylsilane, γ-glycidoxypropylmethoxyethoxydimethylsilane, γ-glycidoxypropylacetoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxydimethylsilane, γ-glycidoxypropyl Methoxydiethylsilane, γ-glycidoxypropylethoxydiethylsilane, γ-glycidoxypropylmethoxyethoxydiethylsilane, γ-glycidoxypropylacetoxydiethylsilane, β- (3,4-epoxy Clohexyl) ethylmethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxy Diethylsilane, γ-glycidoxypropylmethoxydiisopropylsilane, γ-glycidoxypropylethoxydiisopropylsilane, γ-glycidoxypropylmethoxyethoxydiisopropylsilane, γ-glycidoxypropylacetoxydiisopropylsilane, β- (3,4 -Epoxycyclohexyl) ethylmethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) e Tylmethoxyethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxydiisopropylsilane, γ-glycidoxypropylmethoxyethoxymethylsilane, γ-glycidoxypropylacetoxymethoxymethylsilane, γ-glycidoxypropylacetoxy Ethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyacetoxymethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxyacetoxymethyl Silane, γ-glycidoxypropylmethoxyethoxyethylsilane, γ-glycidoxypropylacetoxymethoxyethylsilane, γ-glycidoxypropylacetoxyethoxyethylsila , Β- (3,4-epoxycyclohexyl) ethylmethoxyethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyacetoxyethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxyacetoxyethylsilane, γ -Glycidoxypropylmethoxyethoxyisopropylsilane, γ-glycidoxypropylacetoxymethoxyisopropylsilane, γ-glycidoxypropylacetoxyethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyacetoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethylethoxyacetoxyisopropylsilane, glycidoxymethyl Rutrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxymethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxymethyltrimethoxy Silane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxy Silane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxy Silane, β-glyci Xybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxy Silane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltryptoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- ( 3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxy Cyclohexyl) butyl Liethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxy Silane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropyl Methyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ Glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxy Examples include silane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, 8-glycidoxyoctyltrimethoxysilane, and 8-glycidoxyoctyltriethoxysilane.

In addition, a silane compound having no reactive group may be used. For example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane Various organotrialkoxysilanes such as ethoxysilane; various diorganodialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, methylcyclohexyldimethoxysilane; methyltrimethoxysilane Chlorosilanes such as chlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane and the like can be mentioned.

Further, a tetrafunctional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane or tetra-n-propoxysilane or a partially hydrolyzed condensate of the tetrafunctional alkoxysilane compound may be used in combination as long as the effects of the present invention are not impaired. it can. When the tetrafunctional alkoxysilane compound or the partially hydrolyzed condensate thereof is used in combination, the silicon atoms of the tetrafunctional alkoxysilane compound are more than 20 mol% based on all silicon atoms constituting the polysiloxane. It is preferable to use them together so that the range is not within the range.

市 販 As the polysiloxane having a reactive group, a commercially available product can also be used. For example, X-12-1048 (Shin-Etsu Chemical Co., Ltd.), X-12-1050 (Shin-Etsu Chemical Co., Ltd.), KR-513 (Shin-Etsu Chemical Co., Ltd.), X-40-9308 (Shin-Etsu Chemical Co., Ltd.) ), KR-517 (Shin-Etsu Chemical Co., Ltd.), X-40-2670 (Shin-Etsu Chemical Co., Ltd.), X-24-9590 (Shin-Etsu Chemical Co., Ltd.), KR-516 (Shin-Etsu Chemical Co., Ltd.), X40-9296 (manufactured by Shin-Etsu Chemical Co., Ltd.), TM-100 (manufactured by Toa Gosei), TA-100 (manufactured by Toa Gosei), M-100 (SiliXan), M-140 (SiliXan) and the like. .

<Base generator>
The composition of the present invention is characterized by containing a base generator. Since the base generator promotes the condensation reaction of the polysiloxane, the hardness of the obtained composition is improved. In addition, crack resistance during exposure is improved.

In the present invention, a known base generator can be used. For example, M
. Shirai, and M.S. Tsunooka, Prog. Polym. Sci.
, 21, 1 (1996); Masahiro Kadooka, Polymer Processing, 46, 2 (1997); Kuta
1, Coord. Chem. Rev .. , 211, 353 (2001); Kaneko
, A. Sarker, and D.S. Neckers, Chem. Mater. , 11,
170 (1999); Tachi, M .; Shirai, and M.S. Tsunoo
ka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000
); Winkle, and K. Graziano, J. et al. Photopolym.
Sci. Technol. , 3,419 (1990); Tsunooka, H .; Ta
chi, and S.C. Yoshitaka, J .; Photopolym. Sci. Te
chnol. , 9, 13 (1996); Suyama, H .; Araki, M .; Shi
rai, J .; Photopolym. Sci. Technol. , 19, 81 (2006
), The base component forms a salt, such as those having a structure such as a transition metal compound complex or an ammonium salt, or those in which the amidine moiety is latentized by forming a salt with a carboxylic acid. Ionic compounds, carbamate derivatives, oxime derivatives, oxime ester derivatives, nonionic compounds in which the base component is latentized by urethane bonds or oxime bonds such as acyl compounds, amide derivatives, Examples include imide derivatives, α-cobalt complexes, imidazole derivatives, and cinnamic acid amide derivatives.

Examples of the basic substance generated from the base generator include, but are not particularly limited to, a compound having an amino group, particularly a monoamine, a polyamine such as a diamine, or an amidine. The generated basic substance is preferably a compound having a more basic amino group. This is because the catalyst has a strong catalytic action on the dehydration-condensation reaction and the like in the imidization of the polyimide precursor, and the addition of a smaller amount enables the manifestation of the catalytic effect on the dehydration-condensation reaction and the like at lower temperatures. That is, since the generated basic substance has a large catalytic effect, the apparent sensitivity of the negative photosensitive resin composition is improved. Amidines and aliphatic amines are preferred from the viewpoint of the above catalytic effect.

Further, from the above reasons, as the base generator, it is preferable that the base generated as described above is latentized using a covalent bond, and the generated base uses an amide bond, a carbamate bond, or an oxime bond. It is preferably latent. Examples of the base generator according to the present invention include base generators having a cinnamic acid amide structure as disclosed in JP-A-2009-80452 and WO2009 / 123122, and JP-A-2006-189591. And a base generator having a carbamate structure as disclosed in JP-A-2008-247747, an oxime structure and a carbamoyl oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581. And the like. However, the present invention is not limited thereto, and other known base generator structures can be used.

Other examples of the base generator include paragraph No. 0185 of JP-A-2012-93746.
-0188, 0199-0200 and 0202, JP-A-2013-194
No. 205, paragraphs [0022] to [0069], compounds described in JP-A-2013-20401.
No. 9, the compounds described in paragraphs [0026] to [0074], and WO2010
Compounds described in paragraph No. 0052 of JP / 0464631 are exemplified.

Commercially available base generators include WPBG-266, WPBG-300, WPGB-3
45, WPGB-140, WPBG-165, WPBG-027, PBG-018, WP
GB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-1
66, WPGB-158, WPGB-025, WPGB-168, WPGB-167 and WPBG-082 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) can also be used.

1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate (WPBG-266, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 1,2-dicyclohexyl-4 4,4,5,5-Tetramethylbiguanidium-n-butyltriphenylborate (WPBG-300, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) is preferable from an industrial viewpoint.

塩 基 The content of the base generator in the composition of the present invention is preferably 0.01 to 10 wt% in the nonvolatile components of the composition. When the content is 0.01% by weight or more, the weather resistance is improved. When the content is 10% by weight or less, excessive curing is unlikely to occur, so that the strength of the cured product is easily maintained. Preferably, when the content is 0.1% by weight or more, the weather resistance is improved, and when the content is 5% by weight or less, excessive curing is unlikely to occur, so that the strength of the cured product is easily maintained.

<Inorganic filler>
The composition of the present invention contains an inorganic filler. By containing an inorganic filler, various properties can be imparted to the paint. For example, when the purpose is to improve the hard coat property, it is preferable to mix silica.

The silica is not particularly limited, and known silica fine particles such as powdered silica and colloidal silica can be used. Commercially available silica fine particles in the form of powder include, for example, Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121 and H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silica Industry Co., Ltd. , E220, SYLYSIA 470 manufactured by Fuji Silysia Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
Examples of commercially available colloidal silica include methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, MEK-ST, PGM-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned.

Reactive silica may be used as the silica. Examples of the reactive silica include silica modified with a reactive compound. Examples of the reactive compound include a reactive silane coupling agent having a hydrophobic group, a compound having a (meth) acryloyl group, a compound having a maleimide group, and a compound having a glycidyl group.
Examples of commercially available powdery silica modified with a compound having a (meth) acryloyl group include commercially available colloidal silica modified with a compound having a (meth) acryloyl group, such as Aerosil RM50 and R711 manufactured by Nippon Aerosil Co., Ltd. Examples include MIBK-SD, MIBK-SD-L, MIBK-AC-2140Z, and MEK-AC-2140Z manufactured by Nissan Chemical Industries, Ltd. Further, silica modified with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane and then subjected to an addition reaction with acrylic acid or a compound having a hydroxyl group and a (meth) acryloyl group with 3-isocyanatopropyltriethoxysilane and a urethane is used. Silica modified with a compound subjected to a chemical reaction is also included as a reactive silica.

The shape of the silica fine particles is not particularly limited, and may be spherical, hollow, porous, rod-like, plate-like, fibrous, or irregular. For example, as commercially available hollow silica fine particles, Silex available from Nippon Steel Mining Co., Ltd. can be used.
The primary particle size is preferably in the range of 5 to 200 nm. When it is 5 nm or more, the dispersion of the inorganic fine particles in the composition becomes sufficient, and when it is 200 nm or less, a sufficient strength of the cured product can be maintained.

無機 Also, inorganic fillers other than silica can be used. The shape of the inorganic filler is not limited, and examples thereof include particulate, plate-like, and fibrous fillers.

For example, those having excellent heat resistance include alumina, magnesia, titania, and zirconia; and those having excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, and silicon oxide. As a material having excellent conductivity, a metal filler and / or a metal-coated filler using a metal alone or an alloy (eg, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); Examples of excellent properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, and barium sulfate. , Zinc oxide, magnesium hydroxide; refraction High barium titanate, zirconia, titanium oxide, etc .; titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, terium, nickel, iron , Cobalt, silver, molybdenum, strontium, chromium, barium, photocatalytic metals such as lead, composites of the above-mentioned metals, oxides thereof, etc .; as those having excellent wear resistance, metals such as alumina, zirconia, magnesium oxide, And their composites and oxides; metals having excellent conductivity such as silver and copper; tin oxide and indium oxide; and those having excellent ultraviolet shielding properties include titanium oxide and zinc oxide.
These inorganic fine particles may be appropriately selected depending on the application, and may be used alone or in combination of two or more. In addition, since the inorganic fine particles have various characteristics in addition to the characteristics described in the examples, they may be appropriately selected according to the intended use.

The compounding amount of the inorganic filler in the composition of the present invention is 1 to 15% by weight based on the nonvolatile content of the composition. If the amount is less than 1 wt%, the strength of the coating film becomes insufficient, and the coating film may be cracked or the hard coat property may not be exhibited. If the amount is more than 15% by weight, the cured product may become brittle and easily cracked.
The preferred amount of the inorganic filler is 3 to 12% by weight, particularly preferably 5 to 10% by weight, based on the nonvolatile content of the composition.

<Ultraviolet absorber>
The composition of the present invention may have a compound other than the above-mentioned polysiloxane having a reactive group, a base generator, and an inorganic filler.
For example, it may have an ultraviolet absorber. By blending an ultraviolet absorber, the light resistance of the coating film is improved.

Examples of the ultraviolet absorber include a triazine-based ultraviolet absorber, a triazole-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber. Preferred are triazine-based ultraviolet absorbers.

The triazine-based ultraviolet absorber is an ultraviolet absorber having a triazine skeleton, for example, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxy-phenyl] -4. 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxy-phenyl] -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2-ethyl-hexyloxy) propyl) oxy] -2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyroxyphenyl) -6- (2,4-bis-butyroxy Enyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine And 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxy-phenyl, and oxirane [(C10- Reaction product with C16 {primarily C12-C13 alkyloxy) methyl] oxirane, 2- (2,4-dihydroxy-phenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5- Reaction product of triazine and (2-ethyl-hexyl) -glycidic acid ester, 2,4-bis “2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3-5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine Commercial products include TINUVIN 400 (manufactured by BASF), TINUVIN 405 (manufactured by BASF), TINUVIN 460 (manufactured by BASF), TINUVIN 477 (manufactured by BASF), TINUVIN 479 (manufactured by BASF), ADK STAB LA-46 (manufactured by ADEKA), ADK STAB LA-F70 is available.

The triazole-based ultraviolet absorber is an ultraviolet absorber having a triazole skeleton, for example, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-
1-phenylethyl) phenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-5- (2- (meth) acryloyloxyethyl) phenyl] -2H -Benzotriazole and the like. Commercial products include TINUVIN PS (manufactured by BASF), TINUVIN99-2 (manufactured by BASF), TINUVIN326 (manufactured by BASF), TINUVIN328 (manufactured by BASF), TINUVIN384-2 (manufactured by BASF), and RUVA-93 (manufactured by Otsuka). Chemicals), UVA-1935LH (manufactured by BASF), LA-29 (manufactured by ADEKA), LA-31G (manufactured by ADEKA), LA-31RG (manufactured by ADEKA), LA-32 (manufactured by ADEKA), LA-36 (made by ADEKA) is available.

The benzophenone-based ultraviolet absorber is an ultraviolet absorber having a benzophenone skeleton, such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone. As commercially available products, 1413 (manufactured by ADEKA), Hostabin ARO8 (manufactured by CLARIANT), and Hostabin 3041 (manufactured by CLARIANT) can be used.

(1) The ultraviolet absorber is preferably added in an amount of 1 to 15 parts by weight based on 100 parts by weight of the solid content in the composition. When the amount is 1 part by weight or more, the ultraviolet absorbing ability is sufficiently exhibited, and when the amount is 15 parts by weight or less, bleed-out hardly occurs. Preferably it is 2 to 13 parts by weight, more preferably 3 to 9 parts by weight.

<Other compounds>
The composition of the present invention may have other compounds as long as the effects of the present invention are not impaired. For example, various resins, reactive compounds, catalysts, polymerization initiators, organic fillers, organic solvents, inorganic pigments, organic pigments, extenders, clay minerals, waxes, surfactants, stabilizers, flow regulators, coupling agents, Dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers and the like may be added.

Examples of the organic solvent include ester solvents, ketone solvents, ether solvents, aliphatic solvents, aromatic solvents, and alcohol solvents.
Specifically, ester solvents such as ethyl acetate-, propyl acetate and butyl acetate, ketone-based solvents such as acetone, 2-butanone, methyl ethyl-ketone and methyl isobutyl ketone, and ether-based solvents such as tetrahydrofuran, Examples of aliphatic solvents such as dioxolane and the like, hexane and cyclohexane, aromatic solvents such as toluene and xylene, and alcohol solvents such as ethanol, methanol, propanol, butanol and propylene glycol monomethyl ether can be given. .

液状 Also, a liquid organic polymer may be used for adjusting the viscosity. The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and includes, for example, a modified carboxyl group-containing polymer (Floren G-900, NC-500: Kyoeisha), an acrylic polymer (Floren WK-20: Kyoeisha), Specific modified phosphate ester amine salts (HIPLAAD @ ED-251: Kusumoto Kasei), modified acrylic block copolymers (DISPERBYK2000; BYK Chemie) and the like.

As various resins, a thermosetting resin or a thermoplastic resin can be used.

Thermosetting resin is a resin having a property of being substantially insoluble and infusible when cured by heating, radiation, or a catalyst. As a specific example, a thermosetting resin is a resin having a property of being substantially insoluble and infusible when cured by heating, radiation, a catalyst or the like. Specific examples thereof include phenol resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, epoxy resin, silicone resin, urethane resin, furan resin, ketone resin, xylene Resins, thermosetting polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, styrene / maleic anhydride (SMA) resins, and the like. These thermosetting resins can be used alone or in combination of two or more.

The thermosetting resin may be mixed with the composition in the form of a monomer or oligomer before the reaction, or may be mixed with the composition as a resin after the reaction. Preferably, it is a case where it is blended with a monomer or oligomer before the reaction.
As the monomer, for example, a compound having a polymerizable double bond may be blended. Examples of the compound having a polymerizable double bond include a (meth) acryloyl compound and a vinyl compound. Above all, examples of the (meth) acryloyl-based compound include a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.

Examples of the monofunctional (meth) acrylate include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone-modified hydroxy (meth) acrylate (for example, trade name “Daicel Chemical Industries, Ltd.” Praxel ”), mono (meth) acrylate of polyester diol obtained from phthalic acid and propylene glycol, mono (meth) acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene glycol mono (meth) acrylate, polypropylene glycol Mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, (meth) acrylic acid adducts of various epoxy esters It can be mentioned.

Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, glycerol tri (meth) acrylate modified with ethylene oxide, glycerol tri (meth) acrylate modified with propylene oxide, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate modified with hydroxypivalic acid Trimethylolpropane tri (meth) acrylate modified with ethylene oxide, trimethylol propane tri (meth) acrylate modified with propylene oxide, ethylene oxide Modified phosphoric acid tri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, Tripentaerythritol octa (meth) acrylate, dipentaerythritol hexa modified with ethylene oxide ( (T) acrylate, dipentaerythritol hexa (meth) acrylate modified with propylene oxide, urethane (meth) acrylate compound obtained by reacting isocyanate compound and alcohol compound, polyhydric alcohol and (meth) acrylic acid and polyfunctional carboxylic acid Examples thereof include a polyester (meth) acrylate compound synthesized by a condensation reaction with an acid, and an epoxy (meth) acrylate compound synthesized by an addition reaction of a bisphenol-type epoxy resin or a novolak-type epoxy resin with (meth) acrylic acid.

For example, a compound having an epoxy group may be blended. Examples of the compound having an epoxy group include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, polyhydroxybenzene epoxy resin, polyhydroxynaphthalene epoxy resin, and biphenyl epoxy resin. Epoxy resin, liquid epoxy resin such as tetramethylbiphenyl type epoxy resin, brominated epoxy resin such as brominated phenol novolak type epoxy resin, solid bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenyl Methane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin , Phenylene ether epoxy resin, naphthylene ether epoxy resin, naphthol novolak epoxy resin, naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolak epoxy resin, naphthol-cresol co-condensed novolak epoxy resin, aromatic hydrocarbon Examples thereof include a formaldehyde resin-modified phenol resin-type epoxy resin and a biphenyl-modified novolak-type epoxy resin.

Thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, and polyvinyl chloride resin. Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone Fat, polyarylate resins, thermoplastic polyimide resins, polyamideimide resins, polyether ether ketone resin, polyketone resin, liquid crystal polyester resins, fluorine resins, syndiotactic polystyrene resin, cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

場合 When the composition of the present invention contains a polymerizable double bond, it can be cured with an active energy ray. At this time, it is preferable to use a polymerization initiator, particularly a photopolymerization initiator. Any known photopolymerization initiator may be used, and for example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used. Examples of the acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, -(2-hydroxy-ethoxy) phenyl- (2-hydroxy-2-propyl) ketone and the like. Examples of the benzyl ketals include 1-hydroxy-cyclohexyl-phenyl ketone, benzyl dimethyl ketal, and the like. Examples of the benzophenones include benzophenone and methyl o-benzoylbenzoate. Examples of the benzoins include benzoin, benzoin methyl ether, benzoin isopropyl ether, and the like. The photopolymerization initiator may be used alone or in combination of two or more. The amount of the photopolymerization initiator to be used is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, based on 100% by weight of the nonvolatile content of the composition.

硬化 When the composition of the present invention contains an epoxy group, a curing agent capable of reacting with the epoxy compound may be used. The curing agent is not particularly limited as long as it can react with the epoxy compound, and examples thereof include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. .

For example, as amine compounds, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, polypropyleneglycoldiamine, aliphatic polyamines such as diethylenetriamine, triethylenetetramine, pentaethylenehexamine, and meta-xylylenediamine, diaminodiphenylmethane, phenylenediamine And polyaliphatic polyamines such as 1,3-bis (aminomethyl) cyclohexane, isophoronediamine and norbornanediamine, and dicyandiamide.

Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, polypropylene glycol maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and hexahydroanhydride. Examples include phthalic acid and methylhexahydrophthalic anhydride.

Phenol compounds include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin Naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, aminotriazine-modified phenol resin, and modified products thereof. Further, examples of the latent catalyst include imidazole, BF3-amine complex, and guanidine derivative.

Examples of the amide compound include an aliphatic polyamide synthesized from a polycarboxylic acid and a polyamine, an aromatic polyamide having an aromatic ring introduced therein, an aliphatic polyamide adduct obtained by adding an epoxy compound to the polyamide, and an aromatic polyamide. Adducts and the like.

Examples of the carboxylic acid compound include carboxylic acid-terminated polyesters, carboxylic acid polymers such as polyacrylic acid and maleic acid-modified polypropylene glycol.

場合 When using these curing agents, only one curing agent may be used, or two or more curing agents may be mixed.

<Surface modifier>
To the composition of the present invention, various surface modifiers may be added for the purpose of enhancing the leveling property at the time of application and for the purpose of enhancing the slipperiness of the cured film to enhance the scratch resistance. As the surface modifier, various additives for modifying the surface properties, which are commercially available under the names of a surface conditioner, a leveling agent, a slipperiness imparting agent, and an antifouling agent, can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred.
Specific examples include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, fluorine polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, Fluorinated polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain, and the like. One or more of these may be used. For the purpose of, for example, increasing the sustainability of the slip property, a compound containing a (meth) acryloyl group in the molecule may be used. As specific surface modifiers, EBECRYL350 (Daicel Ornex Co., Ltd.), BYK-333 (Big Chemie Japan KK), BYK-377 (Big Chemie Japan KK), BYK-378 (Big Chemie Japan KK) ), BYK-UV3500 (Big Chemie Japan KK), BYK-UV3505 (Big Chemie Japan KK), BYK-UV3576 (Big Chemie Japan KK), MegaFac RS-75 (DIC Corporation), MegaFak RS- 76-E (DIC Corporation), Megafax RS-72-K (DIC Corporation), Megafax RS-76-NS (DIC Corporation), Megafax RS-90 (DIC Corporation), Megafax RS- 91 (DIC Corporation), Gaffa RS-55 (DIC Corporation), Optool DAC-HP (Daikin Industries, Ltd.), ZX-058-A (T & K TOKA Corporation), ZX-201 (T & K TOKA Corporation), ZX-202 (T & K Corporation) TOKA), ZX-212 (T & K TOKA Corporation), ZX-214-A (T & K TOKA Corporation), X-22-164AS (Shin-Etsu Chemical Co., Ltd.), X-22-164A (Shin-Etsu Chemical Co., Ltd.) , X-22-164B (Shin-Etsu Chemical Co., Ltd.), X-22-164C (Shin-Etsu Chemical Co., Ltd.), X-22-164E (Shin-Etsu Chemical Co., Ltd.), X-22-174DX (Shin-Etsu Chemical Co., Ltd.) Company), and the like.

<Laminate>
The laminate of the present invention can be obtained by laminating a substrate and a molded article of the resin composition of the present invention. The material of the substrate is not particularly limited and may be appropriately selected depending on the application.Examples include wood, metal, metal oxide, plastic, paper, silicon, and modified silicon, and are obtained by joining different materials. Substrate may be used. The shape of the substrate is not particularly limited, and may be an arbitrary shape according to the purpose, such as a flat plate, a sheet, or a surface having a curvature on the entire surface or a part thereof. There is no limitation on the hardness, thickness, etc. of the substrate.

組成 The composition of the present invention has particularly high adhesion to a plastic substrate. There is no particular limitation as long as it is a resin, and for example, the above-described thermosetting resin or thermoplastic resin may be used. The substrate may be a single resin or a substrate in which a plurality of types of resins are blended, or may have a single layer or a laminated structure of two or more layers. These plastic substrates may be fiber reinforced (FRP).

When the laminate of the present invention is formed as a transparent laminate, it is preferable that the plastic layer be made of a polycarbonate resin (for example, an aliphatic polycarbonate, an aromatic polycarbonate, an alicyclic polycarbonate, or the like), a polymethyl methacrylate resin, or a polystyrene resin.

In addition, as long as the effects of the present invention are not impaired, the base material may contain a known antistatic agent, antifogging agent, antiblocking agent, ultraviolet absorber, antioxidant, pigment, organic filler, or inorganic filler, if necessary. And known additives such as a light stabilizer, a crystal nucleating agent, and a lubricant.

The laminate can be obtained by laminating the above-mentioned molded body on a base material. The molded article to be laminated on the substrate may be formed by directly coating or directly molding the substrate, or a molded article of the composition may be laminated. In the case of direct coating, there is no particular limitation on a coating method, and a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, a doctor blade method, a curtain coating method, a slit coating method, A screen printing method, an ink jet method, and the like can be given. In the case of direct molding, in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding and the like can be mentioned. When laminating a molded article of the composition, the uncured or semi-cured composition layer may be cured after laminating on the substrate, and the cured product layer in which the composition is completely cured is laminated on the substrate. You may.

積 層 The laminate of the present invention may further have a second substrate on the substrate and the cured product layer of the present invention. The material of the second substrate is not particularly limited, and examples thereof include wood, metal, metal oxide, plastic, paper, silicon, and modified silicon, and may be a substrate obtained by joining different materials. . The shape of the substrate is not particularly limited, and may be an arbitrary shape according to the purpose, such as a flat plate, a sheet, or a surface having a curvature on the entire surface or a part thereof. There is no limitation on the hardness, thickness, etc. of the substrate.

積 層 Since the laminate of the present invention has high adhesiveness to both plastics and inorganic substances, it can be preferably used as an interlayer material of different materials. Particularly preferably, the substrate is a plastic and the second substrate is an inorganic layer. Examples of the inorganic layer include quartz, sapphire, glass, optical films, ceramic materials, inorganic oxides, evaporated films (CVD, PVD, sputter), magnetic films, reflective films, Ni, Cu, Cr, Fe, stainless steel, etc. Metal, paper, plastic layers such as SOG (Spin On Glass), SOC (Spin On Carbon), polyester, polycarbonate, polyimide, TFT array substrate, PDP electrode plate, conductive base materials such as ITO and metal, insulating base Materials, silicon-based substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon.

(Cured)
Since the base generator contained in the composition of the present invention can activate the base generator by irradiation with active energy rays or heat, the composition can be cured by either irradiation with active energy rays or heat.

(In case of active energy ray curing)
It refers to curing by irradiating the coating material with active energy rays. Active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. Among these, ultraviolet (UV) is particularly preferred from the viewpoint of curability and convenience.
Light used for ultraviolet curing may be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an argon laser, a helium-cadmium laser, or the like. By using these, ultraviolet rays having a wavelength of about 180 to 400 nm are applied to the application surface of the coating product, whereby the coating film is cured to form a cured product layer, thereby obtaining a laminate. The irradiation amount of the ultraviolet ray is appropriately selected depending on the type and amount of the base generator used and the type and amount of the radical polymerization initiator used.

(In case of heat curing)
It means that the coating is cured by heating. Examples of the heating method include heating with a hot air dryer or an IR dryer.
By heating the coating using these materials, it is possible to cure the coating film to form a cured product layer and obtain a laminate. The heating temperature and the heating time are appropriately selected depending on the type and amount of the base generator used, the type and amount of the radical polymerization initiator, and the polysiloxane and resin used.

Further, active energy ray curing and thermal curing may be used in combination, for example, thermal curing after active energy ray curing and active energy curing after thermal curing.

(Application)
Since the laminate of the present application is excellent in light resistance and weather resistance, it can be particularly suitably used as various protective materials. For example, for building materials, housing equipment, transportation vehicles such as automobiles, ships, aircraft, railways, etc., electronic materials, recording materials, optical materials, lighting, packaging materials, protection of outdoor installations, optical fibers It can be used for coating and for protecting resin glass.

Next, the present invention will be described in detail with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified.

Synthesis example: PSi-1
In a 0.5 L separable flask equipped with a stirrer and an air blowing tube, 138.5 parts by weight of 3-methacryloyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts by weight of propylene glycol monomethyl ether, dibutylhydroxyl 0.2 parts by weight of toluene (BHT), 0.02 parts by weight of hydroquinone monomethyl ether (MEHQ) and 0.31 parts by weight of butyl acid phosphate (A-4, manufactured by SC Organic Chemicals) are charged, and the liquid temperature is 75 ° C. 30.2 parts by weight of water was added dropwise with stirring.
After the completion of the dropwise addition, the mixture was stirred at 75 ° C for 4 hours, and the temperature was lowered to 50 ° C. Thereafter, the pressure was reduced to 80 hPa, and methanol and water were distilled off until the liquid temperature reached 70 ° C. The reaction product was diluted with propylene glycol monomethyl ether so as to have a solid content of 50 wt%, to obtain 230.7 parts by weight of a polysiloxane-containing liquid having a reactive group, PSi-1.

Synthesis example: PSi-2
In a 0.5 L separable flask equipped with a stirrer and an air blowing tube, 55.4 parts by weight of KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 85.7 parts of methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.) Parts by weight, 100 parts by weight of propylene glycol monomethyl ether, 0.2 parts by weight of dibutylhydroxytoluene (BHT), 0.02 parts by weight of hydroquinone monomethyl ether (MEHQ) and 0.43 parts by weight of A-4 (manufactured by SC Organic Chemicals) Then, 42.7 parts by weight of water was added dropwise while stirring the solution at 75 ° C.
After the completion of the dropwise addition, the mixture was stirred at 75 ° C for 4 hours, and the temperature was lowered to 50 ° C. Thereafter, the pressure was reduced to 80 hPa, and methanol and water were distilled off until the liquid temperature reached 70 ° C. The reaction product was diluted with propylene glycol monomethyl ether to a solid content of 50 wt% to obtain 243.3 g of a polysiloxane-containing liquid having a reactive group, PSi-2.

Synthesis example: PSi-3
In a 0.5 L separable flask equipped with a stirrer and an air blowing tube, 53.1 parts by weight of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.), 85.7 parts by weight of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.), propylene glycol 100 parts by weight of monomethyl ether, 0.2 parts by weight of dibutylhydroxytoluene (BHT), 0.02 parts by weight of hydroquinone monomethyl ether (MEHQ) and 0.43 parts by weight of A-4 (manufactured by SC Organic Chemicals) were charged. While stirring at a temperature of 75 ° C., 42.7 parts by weight of water was added dropwise.
After the completion of the dropwise addition, the mixture was stirred at 75 ° C for 4 hours, and the temperature was lowered to 50 ° C. Thereafter, the pressure was reduced to 80 hPa, and methanol and water were distilled off until the liquid temperature reached 70 ° C. The reaction product was diluted with propylene glycol monomethyl ether to a solid content of 50 wt% to obtain 233.1 parts by weight of a polysiloxane-containing liquid having a reactive group, PSi-3.

Synthesis example: PSi-4
In a 3 L separable flask equipped with a stirrer and an air blowing tube, 45.9 parts by weight of phenyltrimethoxysilane (KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.) and 85.7 parts by weight of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts by weight of propylene glycol monomethyl ether, 0.2 parts by weight of dibutylhydroxytoluene (BHT), 0.02 parts by weight of hydroquinone monomethyl ether (MEHQ) and 0.43 parts by weight of A-4 (manufactured by SC Organic Chemicals). 42.7 parts by weight of water was added dropwise while charging and stirring at a liquid temperature of 75 ° C. After the completion of the dropwise addition, the mixture was stirred at 75 ° C for 4 hours, and the temperature was lowered to 50 ° C. Thereafter, the pressure was reduced to 80 hPa, and methanol and water were distilled off until the liquid temperature reached 70 ° C. The reaction product was diluted with propylene glycol monomethyl ether to a solid content of 50 wt% to obtain 198.1 parts by weight of a polysiloxane-containing liquid having no reactive group, PSi-4.

<Example 1>
(Preparation of composition)
160 parts by weight of the synthesized PSi-1, 33.3 parts by weight of PGM-ST (unmodified silica, solid content: 30 wt%) as an inorganic filler, 33.3 parts by weight of pentaerythritol tetraacrylate (M-450, Toa Gosei) (Manufactured by the company) and 10 parts by weight. To the obtained compound, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate (WPBG-266, Fujifilm Wako Pure Chemical Industries, Ltd.) was used as a base generator. 2.0 parts by weight based on the total amount of the resin solid content and the inorganic filler solid content, and Omnirad 819 (IGM Co., Ltd., photoinitiator) as the radical initiator was used as the resin solid content and the inorganic filler solid content. Of propylene glycol monomethyl ether (PGM), 14.6 parts by weight with respect to the total amount of the resin solid content and the solid content of the inorganic filler, and methyl ethyl ketone (MEK). ) Was diluted with 20 parts by weight based on the total amount of the resin solid content and the inorganic filler solid content, and the composition 1 having a nonvolatile content of 43 parts by weight was diluted. Obtained.

<Examples 2 to 8> Preparation of Compositions 2 to 8 Compositions 2 to 8 were obtained in the same manner as in Example 1, except that the blending ratio was changed to the blending ratio shown in Table 1. The amounts of the light stabilizer (HALS) and the ultraviolet absorber (UVA) were determined based on the total amount of the resin solid content and the solid content of the inorganic filler, similarly to the base generator.

(Production of laminate)
The obtained composition was used to produce a laminate under the following conditions. Various tests were performed on the obtained laminate.

<Coating>
-Bar coater coating White enamel coating Chromate-treated metal plate (white plate) or polycarbonate plate (L-1225LZ manufactured by Teijin, thickness 3 mm), the coating thickness after drying the composition 1 prepared in Table 1 is about 10 to It was applied so as to have a thickness of 20 μm, and dried at 80 ° C. for 6 minutes.

<Curing>
The UV irradiation was performed using a high-pressure mercury lamp manufactured by GS-YUASA Co., Ltd., and the irradiation energy per pass was set at a peak irradiance of 200 mW / cm ^{2 in} the UV-A region of UV POWER PUCK II manufactured by EIT. 1000 mJ / cm ² and so as lamp output, lamp height, and to adjust the conveyor speed, to the irradiation curing reaction in one pass (total 1000 mJ / cm ²⁾ or 2-pass (total 2000 mJ / cm ^2), the laminate I got

<Evaluation>
[Taber abrasion test]
The surface of the laminate was rubbed in a Taber abrasion test by a method based on ASTM D1044 (wear wheel: CS-10F, load: 500 g, number of rotations: 100), and the difference in cloudiness value from the initial state, that is, haze The value change ΔH (%) is measured. The smaller the difference, the higher the abrasion resistance, indicating that ΔHaze ≦ 10.0 was a pass value. In addition, the Taber abrasion test was carried out on a laminate coated on a polycarbonate plate (L-1225LZ, Teijin, 3 mm in thickness).
With respect to the obtained laminate after the abrasion test, the light transmittance of the test piece was measured using a haze meter, and was calculated by the following equation (unit:%).

[Lightfastness]: Xenon accelerated weathering test Using Iwasaki Denki's accelerated weathering tester, i-Super Xenon tester, illuminance: 180 W / m2 (wavelength: 300-400 nm), filter: (quartz / # 275), Test cycle: Irradiation only, black panel temperature (BPT): 63 ± 2 ° C., humidity: 50 ± 5% After the obtained laminate was tested for 500 hours and taken out, each of the above samples was returned to room temperature, The change in the surface layer of the laminate was visually confirmed.
：: No crack.
×: Cracked

[Weather resistance]: SUV accelerated weather resistance test Irradiation for 4 hours (irradiation intensity: 90 mW, black panel temperature: 63 ° C., humidity: 70%) and darkness for 4 hours using an accelerated weather tester, Super UV Tester (SUV) manufactured by Iwasaki Electric Co., Ltd. A 360-hour test was conducted with one cycle consisting of 12 hours of condensation (black panel temperature of 63 ° C. and 90% humidity) and 4 hours of condensation (black panel temperature of 30 ° C. and 95% humidity).

(Whitening)
Using a color meter (SpectroEye manufactured by X-rite), the L * value of the test piece was measured based on JIS Z8781, and the change in L * value, that is, ΔL * was measured.
：: ΔL * <3.0
×: ΔL * ≧ 3.0

(crack)
○: No crack ×: Crack

(Adhesion)
In the laminate, the adhesion to the polycarbonate plate was evaluated according to the following criteria by checking the time at which peeling occurred spontaneously from the end during the test.
○: No peeling
×: Peeled

PGM-ST (manufactured by Nissan Chemical Industries, Ltd.) unmodified silica, solid content 30 wt%
MEK-AC Nissan Chemical Industries, Ltd.) Methacryloyl-modified silica Solid content 40 wt%
BTA-705 (Rohm & Haas): Elastic rubber particles, solid content 30 wt%
M-315 (manufactured by Toa Gosei Co., Ltd.): 2-hydroxyethyl triacrylate isocyanurate M-450 (manufactured by Toa Gosei Co., Ltd.): pentaerythritol tetraacrylate Tinuvin 123 (manufactured by BASF): hindered amine HALS
Tinuvin 479 (manufactured by BASF): Triazine-based UVA

<Comparative Examples 1 to 4> Preparation of Comparative Compositions 1 to 4 Comparative Examples 1 to 4 and laminates 1 to 4 were prepared in the same manner as in Example 1 except that the blending ratio was changed to the blending ratio shown in Table 2. 4 was obtained and evaluated.

組成 The composition of the present invention has a hard coat property, and a cured product excellent in light resistance and weather resistance can be obtained, so that it can be suitably used as a coating agent for plastics. It is particularly suitable for outdoor use and use under strong lighting.

Claims (8)

1. A composition containing a polysiloxane having a reactive group, a base generator, and an inorganic filler, wherein the compounding amount of the inorganic filler is 1 to 15 wt% in the nonvolatile content of the composition. Composition.
2. 2. The composition according to claim 1, wherein the reactive group is at least one of a group having a polymerizable double bond and an epoxy group.
3. 組成 The composition according to claim 1 or 2, further comprising an ultraviolet absorber.
4. (4) The composition according to any one of (1) to (3), wherein the content of the base generator is 0.01 to 10 wt% in the nonvolatile content of the composition.
5. (5) A cured product obtained by curing the composition according to any one of (1) to (4).
6. (5) A laminate obtained by laminating the base material and the cured product layer according to claim 5.
7. (4) A light-resistant paint containing the composition according to any one of (1) to (4).
8. (5) A weather-resistant paint containing the composition according to any one of (1) to (4).