JP2011105869A - White curable composition and reflective coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a white curable composition which gives a while cured product having high heat and light resistance and a reflective coating material using the same. <P>SOLUTION: The white curable composition has (A) a compound having at least two carbon-carbon double bonds having reactivity with an SiH group in the molecule, (B) a compound containing at least two SiH groups in the molecule, (C) a hydrosilylating catalyst, and (D) a white pigment as essential components. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a white curable composition, and more particularly to a white curable composition that gives a white cured product having high heat and light resistance, and its use, particularly a reflective coating material using the same. .

  Reflective coating materials for light-emitting diode substrates, reflective coating materials used for backlight units of liquid crystal display devices, reflective coating materials for concentrating panels of solar cells, or reflective coating materials used for roofs, rooftops, or outer walls of buildings, and lighting fixtures There has been a demand for a reflective coating material having heat resistance and light resistance, such as a reflective coating material used in the above-described methods, that is, maintaining a high reflectance even in an environment exposed to high temperature or high energy light.

  As a white curable composition, what filled the white pigment in the epoxy resin is proposed (patent documents 1, 2). However, heat resistance and light resistance are not sufficient, and there is a problem that the reflectance is lowered due to gradual coloring in an environment where the light is exposed to high temperature or high energy light for a long time.

  In addition, as a white curable composition having high heat resistance, a silicone resin filled with a white pigment has been proposed (Patent Documents 3 and 4). However, when used as a reflective coating material, there is a problem that the surface hardness is low and the durability is inferior, or that high adhesion to a substrate is difficult to obtain.

  Further, an organic compound (A) having at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule, a curing agent (B) having at least two SiH groups in one molecule, and hydrosilyl A curable composition containing a fluorination catalyst (C) and a white pigment has also been proposed (Patent Documents 5 and 6). However, the use as a reflective coating material is not disclosed.

JP 2007-129173 A JP 2009-194222 A JP 2009-155415 A JP 2009-256400 A International Publication WO / 04-076585 JP 2005-146191 A

  Accordingly, an object of the present invention is to provide a white curable composition that gives a white cured product having high heat and light resistance, and a reflective coating material using the same.

  In order to solve this problem, the present inventors have conducted intensive research, and as a result, have a compound with a specific structure containing two carbon-carbon double bonds reactive with SiH groups in one molecule, and at least in one molecule. The present inventors have found that the above-mentioned problems can be solved by using a compound having a specific structure containing two SiH groups and a hydrosilylation catalyst as essential components to form a curable composition.

That is, the present invention
(A) a compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a compound containing at least two SiH groups in one molecule, (C) hydrosilyl A white curable resin composition (Claim 1), characterized by containing an oxidization catalyst, (D) a white pigment as an essential component,
The content of silicon atoms in the component (A) and the component (B) is 10 to 30% by weight of the total amount of the component (A) and the component (B). A white curable composition (claim 2),
The white curable composition according to claim 1, wherein the content of silicon atoms in the liquid component of the curable composition is 10 to 30% by weight of the total amount of the liquid components (claim). 3)
The component (A) is an organic compound containing at least two carbon-carbon double bonds having reactivity with a SiH group in one molecule. The white curable composition according to claim 4 (Claim 4),
The component (A) is represented by the following general formula (I)

(In the formula, R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms and does not include a carbon-carbon double bond having reactivity with the SiH group). The white curable composition according to claim 4, which is an organic compound (claim 5),
The component (B) is represented by the following general formula (II)

(In the formula, R ² is a monovalent organic group having 1 to 50 carbon atoms, and represents a group not containing a carbon-carbon double bond having reactivity with the SiH group, and n represents a number of 3 to 10). )) And (α) a compound obtained by hydrosilylation reaction of a compound containing at least one carbon-carbon double bond having reactivity with SiH group in one molecule. A white curable composition according to any one of claims 1 to 5 (claim 6),
It is a reflective coating material (Claim 7) which consists of a white curable composition of any one of Claims 1 thru | or 6.

  Since the white curable composition of the present invention gives a white cured product having high heat resistance and light resistance, it can maintain a high reflectance even in an environment exposed to high temperature and high energy light. Useful.

  Hereinafter, preferred embodiments for carrying out the present invention will be specifically described.

(A) Component The (A) component of the present invention is a compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule.

  The component (A) used here is not particularly limited as long as it is a compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule, and various compounds can be used. .

  The compound (A) is preferably an organic compound. In the case of a polysiloxane-based compound, the gas permeability of the resulting cured product tends to be high, and the reliability of electronic parts may be impaired, and the problem of repellency may easily occur and industrial applicability may be difficult. .

  The organic compound (A) can be classified into an organic polymer compound and an organic monomer compound. Examples of organic polymer compounds include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde (phenolic resin) ), Polyimide compounds can be used. Examples of the organic monomer compounds include aromatic hydrocarbon compounds such as phenol, bisphenol, benzene, and naphthalene; aliphatic hydrocarbon compounds such as linear and alicyclic; heterocyclic rings such as triazine. Series compounds and mixtures thereof can be used.

  The bonding position of the carbon-carbon double bond having reactivity with the SiH group contained in these compounds is not particularly limited, and is present anywhere in the molecule, such as in the skeleton, as a substituent, or at the end of the polymer. May be.

  (A) Although it does not specifically limit as a carbon-carbon double bond which has reactivity with SiH group of a component, In the point that the reactivity of hydrosilylation reaction is favorable, following General formula (III)

A group represented by the formula (wherein R ³ represents a hydrogen atom or a methyl group) is preferred. Among them, from the point that it is easier to obtain raw materials,

The groups shown are particularly preferred.

  On the other hand, in the point that the heat resistance of the obtained cured product is likely to be high, the carbon-carbon double bond having reactivity with the SiH group of the component (A) is represented by the following general formula (IV).

An alicyclic group represented by the formula (wherein R ⁴ represents a hydrogen atom or a methyl group) is preferred. Among them, from the point that it is easier to obtain raw materials,

The alicyclic groups shown are particularly preferred.

  The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the component (A) or may be covalently bonded via a divalent or higher valent substituent. In this case, the divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but those containing only C, H, N, O, S, and halogen as constituent elements are preferable. Examples of these substituents include

Etc. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

  Examples of the group containing a carbon-carbon double bond having reactivity with the SiH group as described above and bonded to the skeleton include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy group. -3- (allyloxy) propyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group 2- (allyloxy) ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group,

Etc.

  As the component (A), a low molecular weight compound such as butadiene, which is difficult to express by dividing into a skeleton portion and an alkenyl group as described above, can also be used.

  Specific examples of the component (A) as described above include aliphatic chain polyene compounds such as butadiene, isoprene, octadiene, decadiene; cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene. Aliphatic cyclopolyene compounds such as norbornadiene; substituted aliphatic cyclic olefin compounds such as vinylcyclopentene, vinylcyclohexene, and vinylnorbornene; diallyl phthalate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, diarylidenepentaerythlit, Diallyl monoglycidyl isocyanurate, divinylbenzene, divinylbiphenyl, diisopropenylbenzene

In addition, a compound in which a part or all of the glycidyl group of a conventionally known epoxy resin is replaced with an allyl group, and a compound containing at least two allyl groups in one molecule can be mentioned.

  The component (A) preferably contains 0.001 mol or more of a carbon-carbon double bond having reactivity with the SiH group per 1 g of the component (A) from the viewpoint of further improving the heat resistance. What contains 0.005 mol or more per is more preferable, and what contains 0.007 mol or more is still more preferable.

  The component (A) preferably has a molecular weight of less than 900 from the viewpoint of high mechanical heat resistance and from the viewpoint that the obtained component (A) is not high in viscosity and has good moldability and handleability. , Less than 700 is more preferred, and less than 500 is more preferred.

  As the component (A), those having a low content of phenolic hydroxyl group and / or a compound having a phenolic hydroxyl group derivative are preferable from the viewpoint of coloration of the obtained cured product, particularly yellowing, and phenolic hydroxyl group and / or Or the thing which does not contain the compound which has a derivative of a phenolic hydroxyl group is preferable. In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.

  From the viewpoint of good optical properties such as low birefringence and low photoelastic coefficient and good weather resistance, the component weight ratio in the aromatic ring (A) component is 50 wt. % Or less, preferably 40% by weight or less, more preferably 30% by weight or less. Most preferred are those that do not contain an aromatic hydrocarbon ring.

  From the viewpoint that the obtained cured product is less colored, has high optical transparency, and has high light resistance, the component (A) is vinylcyclohexene, dicyclopentadiene, 2,2-bis (4-hydroxycyclohexyl) propane. Diallyl ether of the following general formula (I)

(In the formula, R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms and does not include a carbon-carbon double bond having reactivity with the SiH group). Organic compounds are preferred, and triallyl isocyanurate or diallyl monoglycidyl isocyanurate is particularly preferred.

  (A) As a component, you may have another reactive group. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high.

  The component (A) may be a compound that can be obtained by hydrosilylation reaction of the compound described as an example of the component (A) with a compound containing at least one SiH group in one molecule. In this case, the compatibility between the component (A) and the component (B) tends to be improved.

  (A) component can be used individually or in mixture of 2 or more types.

Component (B) The component (B) of the present invention is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. For example, it is a compound described in International Publication WO 96/15194. Those having at least two SiH groups in one molecule can be used.

  Of these, a chain and / or cyclic organopolysiloxane having at least two SiH groups in one molecule is preferable in that it is relatively easily industrially available. From the viewpoint that the compatibility with the component (A) and the compatibility of the obtained component (B) with the component (A) are easily improved, the following general formula (II)

(In the formula, R ² is a monovalent organic group having 1 to 50 carbon atoms, and represents a group not containing a carbon-carbon double bond having reactivity with the SiH group, and n represents a number of 3 to 10). The cyclic organopolysiloxane having at least two SiH groups in one molecule represented by.

The substituent R ² in the compound represented by the general formula (II) is preferably composed of C, H and O, more preferably a hydrocarbon group, a methyl group or a phenyl group. More preferably it is.

  The compound represented by the general formula (II) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane from the viewpoint of availability.

  The component (B) is a carbon-carbon having reactivity with the above-mentioned chain and / or cyclic organopolysiloxane and (α) SiH group in that compatibility with the component (A) is likely to improve. More preferably, the compound is obtained by hydrosilylation reaction with a compound containing at least one double bond in one molecule.

  In this case, as the component (α), the compounds listed as examples of the component (A) and preferred examples can be used. A compound containing one carbon-carbon double bond having reactivity with the SiH group in one molecule can also be used.

  Here, examples of the compound containing one carbon-carbon double bond reactive with the SiH group in one molecule include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1 -Octene, 1-nonene, 1-decene, 1-dodecene, 1-undecene, Idemitsu Petrochemical's linearene, 4,4-dimethyl-1-pentene, 2-methyl-1-hexene, 2,3,3- Chain aliphatic hydrocarbon compounds such as trimethyl-1-butene, 2,4,4-trimethyl-1-pentene, cyclohexene, methylcyclohexene, methylenecyclohexane, norbornylene, ethylidenecyclohexane, vinylcyclohexane, camphene, carene Cycloaliphatic hydrocarbon compounds such as α-pinene, β-pinene, styrene, α-methylstyrene, indene, Aromatic hydrocarbon compounds such as nylacetylene, 4-ethynyltoluene, allylbenzene, 4-phenyl-1-butene, allyl ethers such as alkyl allyl ether, allyl glycidyl ether, allyl phenyl ether, glycerin monoallyl ether , Aliphatic compounds such as ethylene glycol monoallyl ether, 4-vinyl-1,3-dioxolan-2-one, and aromatic compounds such as 1,2-dimethoxy-4-allylbenzene, o-allylphenol And substituted isocyanurates such as monoallyl dibenzyl isocyanurate and monoallyl diglycidyl isocyanurate, and silicon compounds such as vinyltrimethylsilane, vinyltrimethoxysilane and vinyltriphenylsilane. Furthermore, polyether resins such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide, hydrocarbon resins such as one-end allylated polyisobutylene, one-end allylated polybutyl acrylate, one-end allylated polymethyl methacrylate Examples thereof also include polymers or oligomers having a vinyl group at one end, such as acrylic resins.

  The component (α) may have other reactive groups. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high. Specific examples include monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyloxyethyl methacrylate, allyloxyethyl acrylate, vinyltrimethoxysilane, and the like.

  As the (α) component as described above, a single component may be used, or a plurality of components may be used in combination.

  The molecular weight of the component (B) is not particularly limited and any one can be suitably used, but a low molecular weight is preferably used from the viewpoint of easier expression of fluidity. In this case, the lower limit of the preferred molecular weight is 50, and the upper limit of the preferred molecular weight is 100,000, more preferably 1,000, and still more preferably 700.

  Component (B) can be used alone or in combination of two or more.

Ratio of component (A) and component (B) The mixing ratio of component (A) and component (B) in the composition of the present invention is not particularly limited as long as the required strength is not lost, but in component (B) The ratio of the number of SiH groups (M) to the number of carbon-carbon double bonds (N) in the component (A) is preferably 2.0 ≧ M / N ≧ 0.5, 1.5 ≧ M / N ≧ 0.7 is more preferable. When 2.0> M / N or M / N <0.5, sufficient curability may not be obtained and sufficient strength may not be obtained. When M / N <0.5 The carbon-carbon double bond is excessive and tends to cause coloring.

The amount of component (A) and component (B) in the curable composition The total amount of component (A) and component (B) in the composition of the present invention is the component involved in the hydrosilylation reaction in the composition ( That is, it is usually 70% by weight or more, more preferably 80% by weight or more, and further preferably 90% by weight or more based on the total amount of the component having a carbon-carbon double bond or SiH group). 95% by weight or more is particularly preferable.

Component (C) Next, the hydrosilylation catalyst as component (C) will be described.

The hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, a platinum simple substance, a support made of alumina, silica, carbon black or the like on which solid platinum is supported, chloroplatinic acid, platinum chloride Complexes of acids with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (eg Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ), platinum-vinyl Siloxane complexes (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complexes (for example, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phos Fight complexes _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me represents a methyl group, Bu a butyl group, Vi represents a vinyl group Ph represents a phenyl group, and n and m represent integers.), Dicarbonyldichloroplatinum, Karstedt catalyst, and also described in Ashby US Pat. Nos. 3,159,601 and 3,159,662. Platinum-hydrocarbon complexes, as well as platinum alcoholate catalysts described in Lamoreaux US Pat. No. 3,220,972. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.

  As the catalyst for the component (C), it is also possible to use the component (A) or / and the component contained in the component (B) as the component (C).

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The addition amount of the catalyst is not particularly limited, but in order to have sufficient curability and keep the cost of the curable composition relatively low, it is 10 ⁻¹ to 10 ⁻⁸ mol relative to 1 mol of SiH group. A range is preferable, and a range of 10 ⁻² to 10 ⁻⁶ mol is more preferable.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. The addition amount of the cocatalyst is not particularly limited, but is preferably in the range of 10 ⁻² to 10 ² mol, more preferably in the range of 10 ⁻¹ to 10 mol, with respect to 1 mol of the catalyst.

(D) component (D) component of this invention is a white pigment.

  Various types of white pigments are used. For example, silica, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, glass fiber and other silicon oxides White metal oxides such as aluminum oxide, magnesium oxide, calcium oxide, titanium oxide, zinc oxide and zirconium oxide, white metal nitrides such as silicon nitride, boron nitride and aluminum nitride, white such as silicon carbide and titanium carbide Examples thereof include metal carbides, white metal sulfides such as barium sulfide and zinc sulfide. Other examples include basic lead carbonate, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, magnesium carbonate, potassium titanate, calcium silicate, and aluminum silicate.

  Of these, silica, alumina, and titanium oxide are preferable, and titanium oxide is more preferable in terms of industrial availability and high reflectance. Alumina is preferable in that heat dissipation is likely to be high. In addition, glass fiber, potassium titanate, and calcium silicate are preferable in that the reinforcing effect is high and the strength of the coating film tends to be high.

  The white pigment may be appropriately surface treated. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like.

  Examples of the coupling agent in this case include a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be exemplified.

  In addition, there is a method of adding a white pigment. For example, a hydrolyzable silane monomer or oligomer such as alkoxysilane, acyloxysilane, or halogenated silane, or an alkoxide, acyloxide, or halide of a metal such as titanium or aluminum is added to the composition of the present invention. There can also be mentioned a method in which a white pigment is produced in the composition by reacting in the composition or in a partial reaction product of the composition.

  As the average particle size and particle size distribution of the white pigment, various types are used without particular limitation, but the lower limit of the average particle size that is usually used is 0.1 μm, and preferably 0 from the viewpoint that fluidity tends to be good. The upper limit of the average particle size usually used is 120 μm, and preferably 60 μm, more preferably 15 μm from the viewpoint that fluidity tends to be good.

  As the shape of the white pigment, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape are used. Various aspect ratios are used. The aspect ratio of 10 or more is preferable in that the strength of the obtained cured product tends to increase. From the viewpoint of isotropic shrinkage of the resin, a powder form is preferable to a fiber form. Or a spherical thing is preferable at the point that a fluidity | liquidity tends to improve also at the time of high filling.

  These white pigments may be used alone or in combination of two or more.

  The addition amount of the white pigment is not particularly limited, but from the viewpoint that the reflectance tends to be high and the fluidity of the composition is good, the preferred lower limit of the addition amount is 3% by weight in the total composition, more preferably Is 5% by weight, more preferably 10% by weight, and the upper limit of the preferred addition amount is 95% by weight in the total composition, more preferably 85% by weight.

  As the mixing order of the inorganic filler, various methods can be used. However, in the point that the storage stability of the intermediate raw material of the composition tends to be good, the component (A) and the white pigment are added to the component (A). A method of mixing the mixture and the component (B) is preferable. When the method of mixing the component (A) with the component (B) mixed with the component (B) and / or the white pigment, the component (B) is added in the presence or absence of the component (C). Since it has reactivity with moisture or / and inorganic fillers in the environment, it may be altered during storage. In addition, (A) component, (B) component, (C) in that (A) component, (B) component, and (C) component which are reaction components are well mixed and a stable molded product is easily obtained. It is preferable to mix a white pigment into a mixture of components. On the other hand, in the point that the dispersibility of the white pigment in the resin component is likely to improve, a method of mixing the component (B) with the white pigment and the method of mixing the component (A) and the component (C) is preferable.

  As a means for mixing these white pigments, various means conventionally used and / or proposed for epoxy resins and the like can be used. For example, a two-roll or three-roll, a planetary stirring and deaerator, a stirrer such as a homogenizer, a dissolver, and a planetary mixer, a ball mill, a bead mill, and the like can be given. The white pigment may be mixed at room temperature or heated. Moreover, you may carry out under a normal pressure and may carry out in a pressure-reduced state. In view that sufficient dispersibility of the inorganic filler is easily obtained even at high filling, it is preferable to mix in a heated state, and it is easy to obtain sufficient dispersibility by improving the wettability of the inorganic filler surface. Is preferably mixed under reduced pressure.

Other ingredients (curing retarder)
In the composition of the present invention, a curing retarder can be used for the purpose of improving the storage stability or adjusting the reactivity of the hydrosilylation reaction during the production process. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol. And maleate esters such as ene-yne compounds and dimethyl malate. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Among these curing retarders, from the viewpoint of good retarding activity and good raw material availability, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred.

Although the addition amount of the curing retarder can be variously set, the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst to be used is 10 ⁻¹ mol, more preferably 1 mol, and the upper limit of the preferable addition amount is 10 ³ mol, more preferably Is 50 moles.

  Moreover, these hardening retarders may be used independently and may be used together 2 or more types.

(Adhesion improver)
An adhesion improver can also be added to the composition of the present invention. In addition to commonly used adhesives as adhesion improvers, for example, various coupling agents, epoxy compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene-vinyltoluene A copolymer, polyethylmethylstyrene, aromatic polyisocyanate, etc. can be mentioned.

  Examples of coupling agents include silane coupling agents and titanate coupling agents.

  The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and / or hydrolyzable silicon group in the molecule. The group reactive with the organic group includes at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, a carbamate group, and a ureido group from the viewpoint of handleability. From the viewpoint of curability and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) silanes having an epoxy functional group such as ethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltri Silica having methacrylic group or acrylic group such as ethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane , Vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane and other silanes having a vinyl group, γ-mercaptopropyltrimethoxysilane, γ-mercapto Mercaptosilanes such as propylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxy Silane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, N-β- (N-vinylbenzylamino) Silanes having amino groups such as (til) -γ-aminopropyltrimethoxysilane, silanes such as methyltrimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, etc. Is mentioned.

  Titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2 , 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate , Isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate DOO, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate.

  The addition amount of the coupling agent can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is 0.1 parts by weight, more preferably 0.5 parts by weight. The upper limit of the preferable addition amount is 50 parts by weight, more preferably 25 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  Examples of the epoxy compound include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexylene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl iso Cyanurate, mention may be made of diallyl monoglycidyl isocyanurate and the like.

  Although the addition amount of the epoxy compound can be variously set, the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is preferably 1 part by weight, more preferably 3 parts by weight. The upper limit of the addition amount is 50 parts by weight, more preferably 25 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  These coupling agents, silane coupling agents, epoxy compounds, etc. may be used alone or in combination of two or more.

  In the present invention, a silanol condensation catalyst can be further used to enhance the effect of the coupling agent or the epoxy compound, and the adhesion can be improved and / or stabilized. Such a silanol condensation catalyst is not particularly limited, but is preferably a boron compound or / and an aluminum compound or / and a titanium compound. Examples of the aluminum compound used as the silanol condensation catalyst include aluminum alkoxides such as aluminum triisopropoxide, sec-butoxyaluminum diisoflopoxide, aluminum trisec-butoxide, ethyl acetoacetate aluminum diisopropoxide, aluminum tris ( Ethyl acetoacetate), aluminum chelate M (manufactured by Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), etc. Aluminum chelates are more preferable from the viewpoint of handleability. Titanium compounds used as silanol condensation catalysts include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium: titanium chelates such as titanium tetraacetylacetonate: general residues having residues such as oxyacetic acid and ethylene glycol And titanate coupling agents.

  Examples of the boron compound that serves as a silanol condensation catalyst include boric acid esters. Examples of borate esters include tri-2-ethylhexyl borate, normal trioctadecyl borate, tri-octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, tri-butyl borate, tri-sec-butyl borate, tri-borate triborate -Tert-butyl, triisopropyl borate, trinormalpropyl borate, triallyl borate, triethyl borate, trimethyl borate, and boron methoxyethoxide can be preferably used.

These borate esters may be used alone or in combination of two or more. Mixing may be performed in advance or may be performed at the time of producing a cured product.
Of these borate esters, trimethyl borate, triethyl borate, and trinormal butyl borate are preferable, and trimethyl borate is more preferable among them because it is easily available and has high industrial practicality.

  From the point that the volatility at the time of curing can be suppressed, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, tri-sec-butyl borate, boric acid Tri-tert-butyl, triisopropyl borate, tripropylpropyl borate, triallyl borate, and boron methoxyethoxide are preferred. Among these, normal trioctadecyl borate, tri-tert-butyl borate, triphenyl borate, and tributyl normal borate are more preferred. preferable.

  From the viewpoint of suppression of volatility and good workability, trinormal butyl borate, triisopropyl borate and trinormal propyl borate are preferable, and trinormal butyl borate is more preferable.

  From the viewpoint of low colorability at high temperatures, trimethyl borate and triethyl borate are preferred, and trimethyl borate is more preferred.

  The amount used in the case of using a silanol condensation catalyst can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound is 0.1 parts by weight, more preferably 1 part by weight. The upper limit of the preferable addition amount is 50 parts by weight, more preferably 30 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  These silanol condensation catalysts may be used alone or in combination of two or more.

  In the present invention, a silanol source compound can be further used in order to further enhance the effect of improving adhesiveness, and the adhesiveness can be improved and / or stabilized. Examples of such a silanol source include silanol compounds such as triphenylsilanol and diphenyldihydroxysilane, and alkoxysilanes such as diphenyldimethoxysilane, tetramethoxysilane, and methyltrimethoxysilane.

  The amount used in the case of using a silanol source compound can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound is 0.1 parts by weight, more preferably 1 part by weight. The upper limit of the preferable addition amount is 50 parts by weight, more preferably 30 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  Moreover, these silanol source compounds may be used independently and may be used together 2 or more types.

  In the present invention, carboxylic acids and / or acid anhydrides can be used to enhance the effect of the coupling agent or epoxy compound, and adhesion can be improved and / or stabilized. Such carboxylic acids and acid anhydrides are not particularly limited, but 2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylhymic acid, Norbornene dicarboxylic acid, hydrogenated methyl nadic acid, maleic acid, acetylenedicarboxylic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenecarboxylic acid Examples include acids, naphthalenedicarboxylic acids, and single or complex acid anhydrides thereof.

  Of these carboxylic acids and / or acid anhydrides, they react with SiH groups in that they have hydrosilylation reactivity and are unlikely to impair the physical properties of the resulting cured product with little possibility of seepage from the cured product. What contains the carbon-carbon double bond which has property is preferable. Preferred carboxylic acids and / or acid anhydrides include, for example, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and single or complex acid anhydrides thereof.

  The amount used in the case of using carboxylic acids or / and acid anhydrides can be variously set, but the lower limit of the preferred addition amount with respect to 100 parts by weight of the coupling agent or / and epoxy compound epoxy compound is 0.1 parts by weight, More preferably, it is 1 part by weight, and the upper limit of the preferable addition amount is 50 parts by weight, more preferably 10 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  Moreover, these carboxylic acids or / and acid anhydrides may be used alone or in combination of two or more.

  In the composition of the present invention, the above silane compound can be used. The silane compound contributes to improving the adhesion with the substrate and is effective in preventing moisture from entering from the interface. Illustrative examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, and the like, with dimethyldimethoxysilane being particularly preferred.

(Thermosetting resin)
Various thermosetting resins can be added to the composition of the present invention for the purpose of modifying the properties. Examples of the thermosetting resin include, but are not limited to, epoxy resins, cyanate ester resins, phenol resins, polyimide resins, urethane resins, bismaleimide resins, and the like. Among these, an epoxy resin is preferable from the viewpoint of excellent practical properties such as adhesiveness.

  Examples of the epoxy resin include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexylene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanate Curing epoxy resins such as nurate and diallyl monoglycidyl isocyanurate with aliphatic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and hydrogenated methyl nadic anhydride Is mentioned. These epoxy resins or curing agents may be used alone or in combination.

  The addition amount of the thermosetting resin is not particularly limited, but the lower limit of the preferable use amount is 5% by weight of the entire curable composition, more preferably 10% by weight, and the upper limit of the preferable use amount is the curable composition. The content is 50% by weight, more preferably 30% by weight. If the addition amount is small, it is difficult to obtain the intended effects such as adhesiveness, and if the addition amount is large, the addition tends to be brittle.

  These thermosetting resins may be used alone or in combination.

  The thermosetting resin may be a resin raw material and / or a cured product dissolved in the component (A) or / and the component (B) and mixed in a uniform state, or may be pulverized and mixed in a particle state. Alternatively, it may be dispersed by dissolving in a solvent and mixing. In the point that the obtained hardened | cured material tends to become more transparent, it is preferable to melt | dissolve in (A) component or / and (B) component, and to mix as a uniform state. Also in this case, the thermosetting resin may be directly dissolved in the component (A) or / and the component (B), or may be uniformly mixed using a solvent or the like. It is good also as a dispersed state or / and a mixed state.

  When the thermosetting resin is used in a dispersed state, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle diameters, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. The coefficient of variation is preferably 10% or less.

(Thermoplastic resin)
Various thermoplastic resins may be added to the composition of the present invention for the purpose of modifying the properties. Various thermoplastic resins can be used. For example, a homopolymer of methyl methacrylate or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and other monomers (for example, Hitachi Chemical) Optretz, etc.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3, A polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like is copolymerized alone or copolymerized. Cycloolefin resins such as fat, norbornene derivative ring-opening metathesis polymer, or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene and Olefin-maleimide resins such as maleimide copolymers (eg TI-PAS manufactured by Tosoh Corporation), bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, and diols such as diethylene glycol Polyester resins such as polyester obtained by polycondensation of phthalic acids and aliphatic dicarboxylic acids such as terephthalic acid and isophthalic acid (eg O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, Polyethylene resin Polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, not natural rubber, but the rubber-like resin is exemplified such EPDM is not limited thereto.

  As a thermoplastic resin, you may have the carbon-carbon double bond or / and SiH group which have a reactivity with SiH group in a molecule | numerator. In the point that the obtained cured product tends to be tougher, the molecule has one or more carbon-carbon double bonds or / and SiH groups having reactivity with SiH groups in the molecule on average. It is preferable.

  The thermoplastic resin may have other crosslinkable groups. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the obtained cured product tends to be high, it is preferable to have one or more crosslinkable groups in one molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less in that the compatibility with the component (A) or the component (B) is likely to be good. More preferably, it is 5,000 or less. On the contrary, the number average molecular weight is preferably 10,000 or more, more preferably 100,000 or more in that the obtained cured product tends to be tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably, it is as follows.

  The blending amount of the thermoplastic resin is not particularly limited, but a preferable lower limit of the amount used is 5% by weight of the entire curable composition, more preferably 10% by weight, and a preferable upper limit of the amount used is in the curable composition. Is 50% by weight, more preferably 30% by weight. When the addition amount is small, the obtained cured product tends to be brittle, and when it is large, the heat resistance (elastic modulus at high temperature) tends to be low.

  A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

  The thermoplastic resin may be dissolved in the component (A) or / and the component (B) and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed. It may be in a dispersed state. In the point that the obtained hardened | cured material tends to become more transparent, it is preferable to melt | dissolve in (A) component or / and (B) component, and to mix as a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the component (A) or / and the component (B), or may be mixed uniformly using a solvent or the like, and then the solvent is removed and uniform dispersion is performed. It is good also as a state or / and a mixed state.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle diameters, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. The coefficient of variation is preferably 10% or less.

(Anti-aging agent)
An antioxidant may be added to the composition of the present invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.

  As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.

  Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.

  Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

(Radical inhibitor)
A radical inhibitor may be added to the composition of the present invention. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.

  Moreover, these radical inhibitors may be used alone or in combination of two or more.

(UV absorber)
An ultraviolet absorber may be added to the composition of the present invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned.

  Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.

(solvent)
The composition of the present invention can be used by dissolving in a solvent. Solvents that can be used are not particularly limited. Specific examples include hydrocarbon solvents such as mesitylene, xylene, toluene, decane, and octane, propylene glycol methyl ether acetate, octanol, ethyl lactate, and methyl isobutyl ketone. Can be mentioned.

Although the amount of solvent to be used can be set as appropriate, the lower limit of the preferred amount of use with respect to 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferred amount of use is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also from a cost standpoint. It is disadvantageous and the industrial utility value decreases. (In this respect, it is preferable not to include a solvent.)
These solvents may be used alone or as a mixed solvent of two or more.

(Other additives)
In addition, the composition of the present invention includes a release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, an anti-fogging agent, an ion trapping agent such as antimony-bismuth, and thixotropy. Imparting agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity imparting agent, antistatic Agents, radiation shielding agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, metal deactivators, thermal conductivity-imparting agents, physical property modifiers, etc. are added within a range that does not impair the purpose and effect of the present invention. Can do.

Preparation method of white curable composition The composition of this invention can be made into a white curable composition by mixing each component previously.

  After mixing, only a part of the functional group in the composition can be reacted (B-stage) by controlling the reaction conditions or using the difference in the reactivity of the substituents to obtain an adhesive and a sealant. Viscosity can be easily adjusted by these methods. In the case of B-stage, the required amount of each component (A), (B), (C) may be mixed and reacted at one time, but the remaining amount after mixing and reacting partly A method of mixing and further reacting can also be employed.

Content of silicon atom in white curable composition In the white curable composition of the present invention, the preferred lower limit of the content of silicon atom in the component (A) and the component (B) is the component (A) and (B) It is 10 weight% of the total amount of a component, More preferably, it is 13 weight%, More preferably, it is 15 weight%. Moreover, the upper limit with preferable content of the silicon atom in (A) component and (B) component is 30 weight% of the total amount of (A) component and (B) component, More preferably, it is 28 weight%. Yes, more preferably 25% by weight.

  Moreover, the preferable lower limit of content of the silicon atom in the liquid component of a white curable composition is 10 weight% of the total amount of (A) component and (B) component, More preferably, it is 13 weight%. More preferably, it is 15% by weight. Moreover, the upper limit with preferable content of the silicon atom in (A) component and (B) component is 30 weight% of the total amount of (A) component and (B) component, More preferably, it is 28 weight%. Yes, more preferably 25% by weight. In this case, a liquid component means the supernatant liquid obtained by processing a white curable composition with a centrifuge.

  When the content of silicon atoms is small, the heat and light resistance tends to be low, and conversely, when the content is high, problems such as low adhesiveness or low strength of the cured product are likely to occur.

Curing Method The white curable composition of this reaction can be cured by reacting a part or all of SiH groups with a carbon-carbon double bond having reactivity with SiH groups in the composition.

  As a curing method, the reaction can be performed by simply mixing, or the reaction can be performed by heating. A method of heating and reacting is preferable from the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained.

  Although various reaction temperatures can be set, for example, a temperature of 30 to 300 ° C. can be applied, 100 to 250 ° C. is more preferable, and 150 to 200 ° C. is more preferable. If the reaction temperature is low, the reaction time for sufficient reaction will be long, and if the reaction temperature is high, molding will tend to be difficult.

  The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. It is preferable to carry out the reaction while raising the temperature in a multistage manner or continuously, as compared with the case of performing the treatment at a constant temperature, because a uniform cured product without distortion can be easily obtained.

  Although various reaction times can be set, it is preferable to react at a relatively low temperature for a long time rather than reacting at a high temperature for a short time because a uniform cured product without distortion can be easily obtained. On the other hand, in terms of high industrial productivity, it is preferable to react at a high temperature for a short time.

  The pressure during the reaction can be variously set as required, and the reaction can be carried out at normal pressure, high pressure or reduced pressure.

  Various coating methods can be employed including the methods used for coating conventional inks, paints, resists, and the like. For example, spin coating, spray coating, die coating, curtain coating, slit coating, bar coating, dip coating, screen printing, pad printing, gravure printing, flexographic printing, offset printing, inkjet printing, dispensing coating, etc. are applied as appropriate. be able to.

  Various treatments can also be performed as necessary at the time of application. For example, to suppress voids generated during molding, the composition or partially reacted composition is defoamed by centrifugation, reduced pressure, etc., applied under reduced pressure, applied under heating, etc. Can be applied.

Applications The white curable composition of the present invention can be widely applied to applications used for reflecting or / and shielding light under an environment exposed to high temperature and / or light.

  The light in this case includes various light rays such as infrared rays, ultraviolet rays, and visible rays, and includes not only monochromatic light in a specific wavelength region but also white light and light in which a plurality of wavelengths are combined. The light source is not limited and can be applied to various light sources such as sunlight, fluorescent lamp, cold cathode tube, incandescent lamp, arc lamp, HID, discharge lamp, light emitting diode, organic EL, and laser.

  The reflective coating material of the present invention can be used for the purpose of reflecting or / and shielding the light from the applied surface side, or it can be applied to a transparent substrate or the like to reflect or / and shield the light from the substrate surface side. It can also be used for applications.

  The purpose of the reflective coating is to reflect the light from the light source in the target direction, and to reflect the light so that it does not hit the object (that is, to block the light). In some cases.

  Specific applications include reflective coating materials for light-emitting diode substrates, white resists, reflective coating materials used in backlight units for liquid crystal display devices, reflective coating materials for solar cell condensing panels, roofs and rooftops of buildings, Examples thereof include a reflective coating material used for an outer wall, a reflective coating material used for a lighting apparatus, a paint used for an exterior of an automobile, a train, an aircraft, a ship, a rocket, an artificial satellite, and a plastic surface protective coating material.

  Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

(Synthesis Example 1)
A stirrer, a condenser tube, and a dropping funnel were set in a 5 L four-necked flask. To this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and heated and stirred in an oil bath heated to 120 ° C. in a nitrogen atmosphere. To this flask, 200 g of triallyl isocyanurate as component (α) and 1.44 mL of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum) diluted with 200 g of toluene were added dropwise from a dropping funnel over 50 minutes. The mixture was heated and stirred at the same temperature for 6 hours and then allowed to cool. Then, 2.95 g of 1-ethynylcyclohexanol was added and mixed, and volatile matter was distilled off under reduced pressure to give 723 g of a pale yellow slightly viscous liquid (Reactant A). Got.

¹ H-NMR revealed that a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane reacted with triallyl isocyanurate. In addition, ¹ H-NMR measurement using 1,2-dibromoethane as an internal standard revealed that the product contained 9.15 mmol / g SiH group and 0.164 mmol / g allyl group.

(Synthesis Example 2)
To a 2 L autoclave, 525 g of toluene, 570 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated so that the internal temperature became 105 ° C. There, a mixture of 120 g of diallyl monoglycidyl isocyanurate as component (α), 0.05 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 120 g of toluene was dropped. During the dropping, the internal temperature rose to 109 ° C. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a pale yellow slightly viscous liquid (Reactant B).

¹ H-NMR revealed that a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane reacted with diallyl monoglycidyl isocyanurate. Further, ¹ H-NMR measurement using 1,2-dibromoethane as an internal standard revealed that the product contained 7.7 mmol / g of SiH groups.

(Examples 1 and 2)
Each component was mixed with the formulation shown in Table 1 to obtain a white curable composition. The mixing method is that the component (C) is added to the component (A) and stirred and mixed, the component (B) and the curing retarder are added and stirred, and then the adhesion improver is added and mixed. (D) component was added to the obtained liquid curable composition, and it mixed with the planetary stirring deaerator.

(Comparative Example 1)
A liquid curable composition was obtained by mixing 33 g of 3,4-cyclohexylmethyl-3,4-cyclohexanecarboxylate, 66 g of methylhexahydrophthalic anhydride, and 1.0 g of 2-ethyl-4-methylimidazole. 350 g of spherical alumina (manufactured by Showa Denko, rounded alumina AS-40) and 30 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Tyco R-820) were added thereto and mixed with a planetary stirring deaerator to obtain a white curable composition. Obtained.

(Measurement example)
The white curable composition was applied onto a glass epoxy substrate with a film thickness of 100 μm using a bar coater, and heated in a hot air dryer at 150 ° C./1 hour and 180 ° C./30 minutes to obtain a coated sample.

  The obtained sample was subjected to a heat and light resistance test under the following conditions, and the change of the sample was visually examined.

  Heat resistance test: Heat treatment was performed at 200 ° C./24 hours in a hot air dryer.

  Light resistance test: Light was irradiated with a metering weather meter M6T manufactured by Suga Test Instruments Co., Ltd. under the condition of an integrated irradiation intensity of 100 MJ (black panel temperature = 120 ° C.).

  The results are shown in Table 2.

  As shown in the table, the white cured product of the example maintained white, but the white cured product of the comparative example was colored and the visible light reflectance was decreased. It was shown that the white curable composition of the present invention is useful as a reflective coating material because it gives a white cured product having high heat and light resistance and maintains white color.

Claims (7)

  (A) a compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a compound containing at least two SiH groups in one molecule, (C) hydrosilyl A white curable resin composition comprising an oxidization catalyst and (D) a white pigment as an essential component.   The content of silicon atoms in the component (A) and the component (B) is 10 to 30% by weight of the total amount of the component (A) and the component (B). White curable composition.   The white curable composition according to claim 1, wherein the content of silicon atoms in the liquid component of the curable composition is 10 to 30% by weight of the total amount of the liquid components.   The component (A) is an organic compound containing at least two carbon-carbon double bonds having reactivity with a SiH group in one molecule. The white curable composition described in 1. The component (A) is represented by the following general formula (I)

(In the formula, R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms and does not include a carbon-carbon double bond having reactivity with the SiH group). The white curable composition according to claim 4, wherein the white curable composition is an organic compound. The component (B) is represented by the following general formula (II)

(In the formula, R ² is a monovalent organic group having 1 to 50 carbon atoms, and represents a group not containing a carbon-carbon double bond having reactivity with the SiH group, and n represents a number of 3 to 10). )) And (α) a compound obtained by hydrosilylation reaction of a compound containing at least one carbon-carbon double bond having reactivity with SiH group in one molecule. The white curable composition according to claim 1, wherein the white curable composition is a white curable composition.   A reflective coating material comprising the white curable composition according to claim 1.