JP2011225733A - Curable composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition and a cured product, more in detail, a cured product solving many problems caused due to an internal stress.SOLUTION: The curable composition contains: (A) an organic compound containing at least 2 carbon-carbon double bonds, which are reactive with an SiH group, in one molecule; (B) a compound containing at least two SiH groups in one molecule; and (C) a hydrosilylating catalyst, as indispensable components. The component (A) is an isocyanuric acid derivative, the component (B) is a mixture of a compound β1 (compound B1) which can be obtained through a hydrosilylation reaction of an (α) component and a polyorganosiloxane having at least three SiH groups in one molecule, and a compound β2 (compound B2) which can be obtained through a hydrosilylation reaction of the (α) component and a linear polyorganosiloxane having at least two SiH groups in one molecule, wherein a rate of the compound B2 to the sum of the compound B1 and the compound B2 is 10-90% by weight ratio.

Description

  The present invention relates to a curable composition and a cured product, and more particularly, to provide a cured product that solves various problems caused by internal stress.

  High transparency and heat resistance are required for optical materials including various protective coating agents used in liquid crystal display devices, LED sealants and die bond agents, and various sensor coating agents (Patent Documents 1 to 3). . On the other hand, when a high internal stress is generated in the cured product used for the optical material, it causes cracking, peeling, and warping of the coated substrate, and thus needs to be improved. On the other hand, as a method for reducing internal stress, a curable composition can be designed so that internal stress is lowered by introducing a crosslinkable component having a high molecular weight into the composition.

  However, if a large amount of components that reduce internal stress is used, stickiness (tackiness) occurs on the surface of the material, which may cause adhesion between materials and adhesion of dust and dust in the air, which is not preferable. .

JP 2006-152316 A JP2004-131518 JP2002-317048

  An object of the present invention is to provide an internal stress in an optical material composition comprising an organic compound containing a carbon-carbon double bond that is reactive with SiH groups, a compound containing SiH groups, and a hydrosilylation catalyst. To provide a curing method for obtaining a highly practical composition for optical materials having warpage resistance and crack resistance by reducing and having no tackiness, and a liquid crystal display device and LED using the same It is.

  In order to solve this problem, the present inventors have intensively researched and completed the present invention.

  That is, the present invention includes (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) containing at least two SiH groups in one molecule. A curable composition containing (C) a hydrosilylation catalyst as an essential component, wherein the component (A) is represented by the following general formula (I):

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same), and
The component (B) is a hydrosilylation reaction between an organic compound containing two (α) SiH group-reactive carbon-carbon double bonds in one molecule and (β) a polyorganosiloxane having a SiH group. The component (B) can be obtained by hydrosilylation reaction of the component (α) with (β1) a polyorganosiloxane having 3 or more SiH groups in one molecule. A compound (compound B2) that can be obtained by hydrosilylation reaction of a compound (compound B1) that can be obtained with the above-mentioned (α) component and a linear polyorganosiloxane having two SiH groups in one molecule (β2) And a ratio of the compound B2 to the sum of the compound B1 and the compound B2 is 10 to 90% by weight (Claim 1),
The linear polyorganosiloxane is represented by the following general formula (II)

(Wherein R ² represents a monovalent organic group having 1 to 6 carbon atoms, and a plurality of R ² may be different or the same. N is a number of 0 to 1000). A curable composition characterized in that (Claim 2),
An LED encapsulant, a die-bonding agent, an adhesive, and a coating agent (Claim 3) comprising the curable composition according to claim 1 or 2.

  The curable composition of the present invention can be used as a coating agent for various optical materials, an LED sealant, and a die bond agent because it has a reduced storage elastic modulus and has warpage resistance.

((A) component)
First, the component (A) in the present invention will be described.
The component (A) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. The organic compound is preferably a compound other than a compound containing a siloxane unit (Si—O—Si), such as polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, and C, H, N, O as constituent elements. , Compounds containing no elements other than S and halogen are more preferred. In the case of a compound containing a siloxane unit, there are problems of gas permeability and repelling.

  The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule. (A) A component may be used independently and may be used in combination of 2 or more types. The compound of the component (A) can be classified into an organic polymer compound and an organic monomer compound.

  Although it does not specifically limit as an organic polymer type compound, For example, polyether type, polyester type, polyarylate type, polycarbonate type, saturated hydrocarbon type, unsaturated hydrocarbon type, polyacrylate ester type, polyamide type, phenol-formaldehyde Examples thereof include a phenolic compound and a polyimide compound.

Although it does not specifically limit as an organic monomer type compound, For example, aromatic hydrocarbon type, such as phenol type, bisphenol type, benzene, and naphthalene; And the like.
Although it does not specifically limit as a carbon-carbon double bond which has reactivity with SiH group of (A) component, The following general formula (III)

A group represented by the formula (wherein R ³ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. Among the groups represented by the general formula (III), from the availability of raw materials

Is particularly preferred.
Furthermore, as the carbon-carbon double bond having reactivity with the SiH group of component (A), an alicyclic group having a partial structure represented by the following general formula (IV) in the ring is a cured product. This is preferable from the viewpoint of high heat resistance.

(In the formula, R ⁴ represents a hydrogen atom or a methyl group. Two R ⁴ may be the same or different.) Among these, from the availability of raw materials, it is represented by the following formula. An alicyclic group having a partial structure in the ring is 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 through a divalent or higher valent substituent. Although the divalent or higher valent substituent is not particularly limited, a substituent having 0 to 10 carbon atoms is preferable, and a substituent that does not contain elements other than C, H, N, O, S, and halogen is more preferable as a constituent element. . Examples of the divalent or higher substituent are as follows:

Is mentioned. Further, two or more of the exemplified divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

Examples of the group covalently bonded to the skeleton of the component (A) include a vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-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,

Is mentioned.
Specific examples of the component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane. Diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane, divinylbenzenes (purity 50 -100%, preferably 80-100% purity), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, oligomers thereof, 1,2-polybutadiene (1, 2 ratio 10 100% of those, preferably 1,2 ratio 50-100% of those), allyl ether of novolak phenol, allylated polyphenylene oxide,

And those in which part or all of the glycidyl group of the epoxy resin is replaced with an allyl group.

  As the component (A), low molecular weight compounds that are difficult to express separately for the skeleton portion and the carbon-carbon double bond can also be used. Specific examples of the low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, aliphatic groups such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

  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 is more preferable, and what contains 0.008 mol or more is further more preferable.

  The number of carbon-carbon double bonds reactive with the SiH group of component (A) should be at least two per molecule, but it is preferable to exceed two when it is desired to further improve the mechanical strength, More preferably, it is 3 or more. However, when the component (A) is a mixture of various compounds and the number of the carbon-carbon double bonds of each compound cannot be identified, the average of the carbon-carbon double bonds per molecule for the whole mixture The number is obtained and used as the number of the carbon-carbon double bonds of the component (A). When the number of carbon-carbon double bonds having reactivity with the SiH group of component (A) is 1 or less per molecule, only a graft structure is formed even if it reacts with component (B). Don't be.

  From the viewpoint of good reactivity as the component (A), it is preferable that one or more vinyl groups are contained in one molecule, and two or more vinyl groups are contained in one molecule. Is more preferable. Further, from the viewpoint that the storage stability tends to be good, it is preferable that 6 or less vinyl groups are contained in one molecule, and it is more preferable that 4 or less vinyl groups are contained in one molecule.

  As the component (A), those having a molecular weight of less than 900 are preferable from the viewpoint of high mechanical heat resistance, and from the viewpoint of low stringiness of the raw material liquid and good moldability and handleability. Those less than 700 are more preferred, and those less than 500 are more preferred.

  As the component (A), in order to obtain uniform mixing with other components and good workability, the viscosity is preferably less than 100 Pa · s at 23 ° C., more preferably less than 30 Pa · s. More preferred is less than 3 Pa · s. The viscosity can be measured with an E-type viscometer.

  As the component (A), from the viewpoint of suppression of coloring (particularly yellowing), those having a small content of a phenolic hydroxyl group and a compound having a phenolic hydroxyl group derivative are preferable. What does not contain the compound which has is more preferable. In the present invention, the phenolic hydroxyl group refers to a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus such as a benzene ring, naphthalene ring, anthracene ring, etc. And an alkyl group such as an ethyl group, an alkenyl group such as a vinyl group and an allyl group, and an acyl group such as an acetoxy group.

  From the viewpoints of good optical properties such as low birefringence and low photoelastic coefficient, and good weather resistance, the component (A) is preferably an aliphatic compound. In this case, the aliphatic compound means one that does not contain an aromatic ring or has a low content. Specifically, the component weight ratio in the component (A) of the aromatic ring is preferably 50% by weight or less, more preferably 40% by weight or less, and even 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) includes vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, 2,2-bis (4 -Hydroxycyclohexyl) propane diallyl ether, 1,2,4-trivinylcyclohexane is preferred, triallyl isocyanurate, 2,2-bis (4-hydroxycyclohexyl) propane diallyl ether, 1,2,4-trivinyl Cyclohexane is particularly preferred.

  The component (A) may have a reactive group other than the carbon-carbon double bond having reactivity with the SiH group. Although it does not specifically limit as said reactive group, For example, an epoxy group, an amino group, a radically polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, an alkoxysilyl group etc. are mentioned. When it has the said reactive group, the adhesiveness of the composition for optical materials obtained tends to become high, and the intensity | strength of the hardened | cured material obtained tends to become high. Of these reactive groups, an epoxy group is preferred from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable that the average of the said reactive group is 1 or more in 1 molecule from the point that the heat resistance of the hardened | cured material obtained becomes high easily.

(General formula (I))
The component (A) is preferably a compound represented by the following general formula (I) from the viewpoint of high heat resistance and transparency.

(In the formula, R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same.)
As R < ¹ > of the said general formula (I), from a viewpoint that the heat resistance of the hardened | cured material obtained can become higher, a C1-C20 monovalent organic group is preferable, and it is C1-C10 one. A valent organic group is more preferable, and a monovalent organic group having 1 to 4 carbon atoms is more preferable. Examples of preferable R ¹ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

Etc.
From the viewpoint that the adhesiveness of the obtained cured product to various materials can be improved, at least one of the three R ^{1 s in} the general formula (I) has 1 to 50 carbon atoms including one or more epoxy groups. Is preferably a monovalent organic group,

It is more preferable that it is a C1-C50 monovalent organic group containing 1 or more of epoxy groups represented by these. Examples of the monovalent organic group having 1 to 50 carbon atoms including one or more epoxy groups include a glycidyl group,

Is preferred.

As R ¹ of the general formula (I), from the viewpoint that chemical thermal stability of the resulting cured product can be improved, it contains 2 or less oxygen atoms and is composed of C, H, N as constituent elements. And a monovalent organic group having 1 to 50 carbon atoms which does not contain any element other than O and O, preferably 1 to 50 carbon atoms which contain 2 or less oxygen atoms and which do not contain any elements other than C, H and O as constituent elements. Are more preferable, and a monovalent hydrocarbon group having 1 to 50 carbon atoms is more preferable. Examples of these preferable R ¹ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

Etc.
From the viewpoint of improving the reactivity, at least one of the three R ^{1 in} the general formula (I) is:

In preferably a group represented by a one or more containing monovalent organic group having 1 to 50 carbon atoms, at least one of the three R ^1, the following general formula (III)

(Wherein R ³ represents a hydrogen atom or a methyl group), more preferably a monovalent organic group having 1 to 50 carbon atoms containing at least one group represented by at least ^one of the three R ¹ groups. Two are the following general formula (V)

(Wherein R ⁵ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group. The plurality of R ⁵ and R ⁶ may be the same even if they are different from each other. It is more preferable that it is an organic group represented by.

R ^{5 in the} general formula (V) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the heat resistance of the obtained cured product can be further increased, the direct bond or carbon A divalent organic group having 1 to 20 carbon atoms is preferable, a direct bond or a divalent organic group having 1 to 10 carbon atoms is more preferable, and a direct bond or a divalent organic group having 1 to 4 carbon atoms is more preferable. Particularly preferred examples of R ⁵ include

Etc.

As R ⁵ of the general formula (V), from the viewpoint that the chemical thermal stability of the obtained cured product can be improved, it is a direct bond, or contains two or less oxygen atoms and is a constituent element. A divalent organic group having 1 to 48 carbon atoms containing no elements other than C, H and O is preferred, and a direct bond or a divalent hydrocarbon group having 1 to 48 carbon atoms is more preferred. Particularly preferred examples of R ⁵ include

Is mentioned.

R ^{6 in the} general formula (V) is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of good reactivity.
However, even in the organic compound represented by the general formula (I), it is necessary to contain at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. From the viewpoint that heat resistance can be further improved, an organic compound containing three or more carbon-carbon double bonds having reactivity with SiH groups in one molecule is more preferable.
Organic compounds represented by general formula (I)

(In the formula, R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same.)
Preferable specific examples include triallyl isocyanurate and the like. For improving adhesiveness, triallyl isocyanurate is preferred as the component (A).

((B) component)
Next, the compound which has SiH group which is (B) component is demonstrated.

  In the present invention, the component (B) comprises hydrosilylating an organic compound containing two (α) SiH group-reactive carbon-carbon double bonds in one molecule and a polyorganosiloxane having (β) SiH group. The compound (B) obtained by hydrosilylation reaction of the component (α) and the (β1) polyorganosiloxane having 3 or more SiH groups in one molecule. A compound (compound B1) that can be obtained by hydrosilylation reaction of the above component (α) and (β2) a linear polyorganosiloxane having two SiH groups in one molecule ( It is a mixture containing compound B2). Here, the total amount of the compound B1 and the compound B2 is preferably 60 to 100% by weight, more preferably 80 to 100% by weight, and 90 to 100% by weight in all the components (B). Is more preferable, and it is most preferable that it is 95 to 100 weight%.

((Α) component)
As the component (α), an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group, which is the component (A), can be used. The component (α) may be used alone or in combination of two or more.

((Β) component)
The (β) component in the present invention is a polyorganosiloxane having a SiH group, and is a mixture of the following (β1) component and (β2) component.

((Β1) component)
The component (β1) is a compound (compound B1) that can be obtained by a hydrosilylation reaction with a polyorganosiloxane having 3 or more SiH groups in one molecule. From the viewpoint of easy compatibility with the component (α), the following general formula (VI)

(In the formula, R ² represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10).

The substituent R ² in the compound represented by the general formula (VI) is preferably a substituent not containing an element other than C, H and O as a constituent element, more preferably a hydrocarbon group, and still more preferably a methyl group. As the compound represented by the general formula (VI), 1,3,5,7-tetramethylcyclotetrasiloxane is preferable from the viewpoint of availability. The (β1) component may be used alone or in combination of two or more.

((Β2) component)
The component (β2) is a linear polyorganosiloxane having two SiH groups in one molecule. For example, the following general formula (II)

(Wherein R ² represents a monovalent organic group having 1 to 6 carbon atoms, and a plurality of R ² may be different or the same. N is a number of 0 to 1000). be able to. Specific examples of R ^{2 in the} general formula (II) include a hydrogen atom, a methyl group, a phenyl group, an ethyl group, an octyl group, a vinyl group, a cyano group, a trifluoromethyl group, a methoxy group, an ethoxy group, and a propoxy group. And a butoxy group.

  Among these, from the viewpoint of good industrial availability, a hydrogen atom, a methyl group and a phenyl group are preferable, a methyl group and a phenyl group are more preferable, and a methyl group is most preferable. In the general formula (II), n is preferably a number of 0 to 10, more preferably a number of 0 to 3, and most preferably 0 from the viewpoint of good compatibility with other components. More specific examples of the compound represented by the general formula (II) include 1,1,3,3-tetramethyldisiloxane, 1,1,2,2,3,3-hexamethyltrisiloxane, and the like. can give.

  In the present invention, the ratio of the compound B2 to the sum of the compound B1 and the compound B2 may be appropriately changed, but is preferably 10 to 90% by weight, more preferably 30 to 70%, and particularly preferably 40. -60%.

(Reaction of (α) component and (β) component)
When the component (B) is a reaction product of a chain siloxane compound (β) component containing SiH groups at both ends and the component (α), a chain siloxane compound containing SiH groups at both ends ( The explanation of the (β) component and the (α) component, and preferred examples thereof are the same as those described above.

  Specific examples of the component (B) include a reaction product of 1,1,3,3-tetramethyldisiloxane and triallyl isocyanurate, 1,1,2,2,3,3-hexamethyltrisiloxane and triaryl. Reaction product of allyl isocyanurate, reaction product of 1,1,3,3-tetramethyldisiloxane and diallyl monoglycidyl isocyanurate, 1,1,2,2,3,3-hexamethyltrisiloxane and diallyl monoglycidyl A reaction product with isocyanurate can be mentioned.

  With respect to the method of reacting the chain siloxane compound containing SiH groups at both ends and the component (α), the hydrosilylation reaction is carried out in the presence of a hydrosilylation catalyst, if necessary, with chains containing SiH groups at both ends. It can be carried out, for example, by mixing the siloxane compound and the component (α).

  The description of the hydrosilylation catalyst in this case is the same as the description of the component (C) of the present invention described later.

  The mixing ratio of the chain siloxane compound containing SiH groups at both ends as described above and the component (α) is such that the component (B) obtained contains at least two SiH groups in one molecule. In general, the number of SiH groups in the chain siloxane compound containing SiH groups at both ends (Y), and the number of carbon-carbon double bonds reactive with the SiH groups in the component (α). The ratio with (X) is preferably 5 ≧ Y / X> 1, and more preferably 3 ≧ Y / X ≧ 1.5.

  Various methods can be applied as a mixing method, but in order to suppress gelation during the reaction, there is a method in which the component (A) is gradually added to the chain siloxane compound containing SiH groups at both ends. preferable.

  The mixing ratio of the (α) component and the (β) component in the composition of the present invention is not particularly limited as long as the necessary strength is not lost, but the (α) of the number of SiH groups (Y) in the (β) component ) The ratio of carbon-carbon double bonds (X) in the component is preferably 2.0 ≧ Y / X ≧ 0.5, more preferably 1.5 ≧ Y / X ≧ 0.7 . If 2.0> Y / X or Y / X <0.5, sufficient curability may not be obtained, and sufficient strength may not be obtained. If Y / X <0.5, The carbon-carbon double bond is excessive and tends to cause coloring.

  The molecular weight of the component (β) is not particularly limited, and any one can be suitably used. By increasing the molecular weight of the component (β), the molecular weight of the cross-linked portion is increased, and the degree of freedom of the molecular chain in the cross-linked product is increased. As a result, the storage elastic modulus can be lowered.

In this case, the lower limit of the preferable molecular weight is 500, and the upper limit of the preferable molecular weight is 100,000, more preferably 20,000, and still more preferably 1,000. The (β) component may be used alone or in combination of two or more.
When the (α) component and the (β) component are subjected to a hydrosilylation reaction, an appropriate catalyst may be used. The catalyst is not particularly limited as long as it has a catalytic activity for hydrosilylation reaction. For example, platinum alone, alumina, silica, carbon black or the like supported on solid platinum, chloroplatinic acid, chloroplatinic acid and alcohol , Complexes with aldehydes, ketones, etc., platinum-olefin complexes (for example, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ), platinum-vinylsiloxane complexes ( For example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complex (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complex ( For _{example, 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 is phenyl N and m are integers.), Dicarbonyldichloroplatinum, Karstedt catalyst, Ashby US Pat. Nos. 3,159,601 and 3,159,662 And the platinum alcoholate catalyst described in US Pat. No. 3,220,972 to Lamoreaux. 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 and the} like. It is done.

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

  The amount of the catalyst to be added is not particularly limited, but in order to have sufficient curability and to keep the cost of the composition for optical materials relatively low, the content of 3% solution as platinum of the component (C) is all components. The upper limit is preferably 0.1 parts by weight with respect to 100 parts by weight, more preferably 0.03 parts by weight, and the lower limit is preferably 0 parts or more, more preferably 0.001 parts or more.

  A co-catalyst can be used in combination with the above catalyst, for example, phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, 2-hydroxy-2-methyl-1-butyne Acetylene alcohol compounds such as sulfur, sulfur compounds such as simple sulfur, and amine compounds such as triethylamine.

  As the method of mixing the (α) component, the (β) component and the catalyst in the reaction, various methods can be used, but the (α) component mixed with the catalyst is mixed with the (β) component. The method is preferred. In the case of a method in which a catalyst is mixed with a mixture of the (α) component and the (β) component, it is difficult to control the reaction. When the method of mixing the (β) component with the mixture of the (β) component and the catalyst, the (β) component is reactive in the presence of the catalyst and may be altered due to its reactivity with water. .

Although various reaction temperatures can be set, the lower limit of the preferred temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferred temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.
Various reaction times and pressures during the reaction can be set as required.

A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specifically, hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.
In addition, various additives may be used for the purpose of controlling reactivity.
After reacting the (α) component and the (β) component, the solvent, the unreacted (α) component and / or the (β) component can also be removed. By removing these volatile components, the component (B) obtained does not have volatile components, so that the problem of voids and cracks due to volatilization of the volatile components hardly occurs in the case of curing with the component (A). Examples of the removing method include treatment with activated carbon, aluminum silicate, silica gel and the like in addition to devolatilization under reduced pressure. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 100 ° C, more preferably 60 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

(Mixing of component (A) and component (B))
About the combination of (A) component and (B) component, the combination of what was mentioned as an example of (A) component and those various mixtures / example of (B) component, and those various mixtures. Can be mentioned.

  The mixing ratio of the component (A) and the component (B) is not particularly limited as long as the necessary strength is not lost, but the number of SiH groups in the component (B) (Y) is the carbon-carbon in the component (A). In the ratio to the number of double bonds (X), the lower limit of the preferred range is Y / X ≧ 0.3, more preferably Y / X ≧ 0.5, and even more preferably Y / X ≧ 0.7, which is preferable. The upper limit of the range is 3 ≧ Y / X, more preferably 2 ≧ Y / X, and even more preferably 1.5 ≧ Y / X. When it deviates from the preferred range, sufficient strength may not be obtained or thermal deterioration may easily occur.

((C) component)
Next, the component (C) in the present invention will be described.
The hydrosilylation catalyst that is component (C) is not particularly limited as long as it has catalytic activity for hydrosilylation reaction. For example, a catalyst in which solid platinum is supported on a carrier such as a simple substance of platinum, alumina, silica, or carbon black, Chloroplatinic acid, complexes of chloroplatinic acid 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 ), a platinum-vinylsiloxane complex (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), a platinum-phosphine complex (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ )) _4), platinum - phosphite complex _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me represents a methyl group, Bu is a butyl group Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer.), Dicarbonyldichloroplatinum, Karlstedt catalyst, Ashby US Pat. Nos. 3,159,601 and 3,159,662 And the platinum alcoholate catalyst described in US Pat. No. 3,220,972 of Lamoreaux. 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 and the} like. It is done.
Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. The said catalyst may be used independently and may use 2 or more types together.

  The addition amount of the hydrosilylation catalyst is not particularly limited, but in order to have sufficient curability and keep the cost of the composition for optical materials relatively low, the content of 3% solution as platinum of the component (C) is The upper limit is preferably 0.1 parts by weight, more preferably 0.03 parts by weight, and the lower limit is preferably 0 parts or more, more preferably 0.001 parts or more, relative to 100 parts by weight of all components. is there.

(Additive)
Next, optional components in the present invention will be described.
(Curing retarder)
The composition for optical materials of the present invention can contain a curing retarder for the purpose of improving storage stability or adjusting the reactivity of the hydrosilylation reaction during the production process. Although it does not specifically limit as a hardening retarder, For example, the compound containing an aliphatic unsaturated bond, an organic phosphorus compound, a sulfur containing compound, a nitrogen containing compound, a tin type compound, an organic peroxide etc. are mentioned.

  As the compound containing an aliphatic unsaturated bond, propargyl alcohols such as 2-hydroxy-2-methyl-3-butyne, 2-hydroxy-2-phenyl-3-butyne, 1-ethynyl-1-cyclohexanol, Examples include en-in compounds and maleic esters such as dimethyl maleate. Examples of the organic phosphorus compound include triorganophosphines such as triphenylphosphine, diorganophosphines, organophosphones, and triorganophosphites. Examples of sulfur-containing compounds include elemental sulfur, organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, 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 the above-mentioned curing retardants, benzothiazole, thiazole, dimethyl maleate, 2-hydroxy-2-methyl-3-butyne, 1-ethynyl-1-cyclo is preferable from the viewpoint of good delay activity and good raw material availability. Hexanol is preferred.

The addition amount in the case of using the above-mentioned curing retardant is not particularly limited and can be variously set. However, the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst is 10 ⁻¹ mol, more preferably 1 mol, and the upper limit of the preferable addition amount. Is 10 ³ mol, more preferably 50 mol. Moreover, these hardening retarders may be used independently and may be used together 2 or more types.

(Adhesion improver)
You may mix | blend an adhesive improvement agent with the composition for optical materials of this invention. The adhesion improver is not particularly limited. For example, commonly used adhesives, coupling agents, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene-vinyltoluene Examples thereof include polymers, polyethylmethylstyrene, and aromatic polyisocyanates.

An example of the coupling agent is a silane coupling agent. The silane coupling agent is a compound having at least one functional group reactive with an organic group and at least one hydrolyzable silicon group in the molecule. The functional group reactive with the organic group is not particularly limited, but at least one selected from a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, a carbamate group, and a glycidyl group from the viewpoint of handleability. A functional group is preferable, and a methacryl group, an acrylic group, and a glycidyl group are particularly preferable from the viewpoints of curability and adhesiveness. Although it does not specifically limit as a hydrolysable silicon group, The alkoxy silyl group is preferable from the point of handleability, and a methoxy silyl group and an ethoxy silyl group are especially preferable from a reactive point.
Preferred silane coupling agents include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane. , Alkoxysilanes having a methacrylic group or an acrylic group such as methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, and 3-glycidoxypropyltrimethoxysilane (trade name: A- 187) and 3-glycidoxypropylmethyldiethoxysilane (trade name: AZ-6165) and other alkoxysilanes having a glycidyl group.

The amount of addition in the case of using the above-mentioned adhesion improver is not particularly limited and can be variously set. However, the lower limit of the preferable amount of addition with respect to 100 parts by weight of [(A) component + (B) component] is 0.1. The upper limit of the preferred amount added is 50 parts by weight, more preferably 25 parts by weight. If the addition amount is small, the effect of improving the adhesiveness is hardly exhibited, and if the addition amount is large, the physical properties of the cured product may be adversely affected.
The said adhesive improvement agent may be used independently and may use 2 or more types together.

(Anti-aging agent)
You may mix | blend an antioxidant with the composition for optical materials of this 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.

  Although it does not specifically limit as sulfur type anti-aging agent, For example, sulfides, such as mercaptans, mercaptan salts; sulfide carboxylic acid esters, hindered phenol sulfides; polysulfides, dithiocarboxylates, thioureas, thio Examples include phosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides. The above antioxidants may be used alone or in combination of two or more.

(Properties of composition for optical material)
As described above, the optical material composition of the present invention can be used in various combinations as described above. However, in terms of good workability by filling a narrow gap and coating, the viscosity of the composition is high. It is preferably 1000 Pa · s or less at 23 ° C., more preferably 10 Pa · s or less, even more preferably less than 5.0 Pa · s, and particularly preferably 1.0 Pa · s or less. And most preferably 0.1 or less. For the same reason, it is preferably 10 Pa · s or less at 100 ° C., more preferably 1.0 Pa · s or less, and further preferably 0.1 Pa · s or less. Various types of viscosity temperature dependency (thixotropic properties) can be used. The viscosity can be measured with an E-type viscometer.

  The curability of the composition for optical materials of the present invention can be arbitrarily set, but the gelation time at 120 ° C. is preferably within 120 seconds, and more preferably within 60 seconds. Further, the gelation time at 150 ° C. is preferably within 60 seconds, and more preferably within 30 seconds. Further, the gelation time at 100 ° C. is preferably within 180 seconds, and more preferably within 120 seconds. When the curability is slow, workability as a composition is deteriorated. On the other hand, when it is fast, the storage stability may be easily deteriorated. The gelation time can be examined as follows. An aluminum foil having a thickness of 50 μm is placed on a hot plate adjusted to a set temperature, and the time until gelation is performed by dropping 100 mg of the composition thereon is defined as the gelation time.

(Curing)
The composition for optical materials of the present invention is prepared by mixing each component in advance and reacting a part or all of SiH groups with a carbon-carbon double bond having reactivity with SiH groups in the composition. It can be used as an optical material.

  In the case where the composition for optical material is reacted and cured, the required amounts of the components (A), (B), and (C) may be mixed and reacted at one time. After reacting, reacting only part of the functional group in the composition by controlling the reaction conditions after mixing and using the difference in reactivity of the substituents (B-stage) It is also possible to take a method such as molding and then further curing. According to these methods, viscosity adjustment at the time of molding becomes easy.

  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.

(Curing temperature)
In the present invention, the curable composition is heated at 60 to 90 ° C. for 0.5 to 10 hours, and then heated at 100 to 250 ° C. for 0.5 to 12 hours. In the present invention, preliminary heat treatment can be performed at a temperature of less than 60 ° C. as long as the heat treatment conditions are followed. The temperature of the preliminary heat treatment is preferably 30 ° C. or more and less than 60 ° C. The upper limit temperature in the heat treatment of the present invention is preferably 250 ° C, more preferably 220 ° C, and particularly preferably 190 ° C. If the heat treatment temperature is too low, the curing time for sufficient reaction may be long, and if the heat treatment temperature is too high, the molding process tends to be difficult. In the present invention, the curing reaction is performed in multiple stages or continuously by changing the temperature. However, it is more uniform and distortion-free if the reaction is performed in multiple stages or continuously while raising the temperature than in a constant temperature. It is preferable in that a cured product is easily obtained.

(Gel time)
Unlike the above heat treatment time, the reactivity and the crosslinking rate of the curable composition can be evaluated by measuring the gelation time of the composition. The gelation time can be variously set. For example, the gelation time at a temperature range of 110 to 130 ° C. is preferably 0.1 to 7 minutes, more preferably 0.3 to 5 minutes, and particularly preferably 0.5 to 3 minutes. If the gelling time is too long, the production efficiency is lowered, and if it is too short, a distorted and non-uniform cured product is not preferable.

(Optical material)
The optical material as used in the field of this invention shows the general material used for the use which permeate | transmits light, such as visible light, infrared rays, an ultraviolet-ray, an X-ray, a laser, in the material. Although it does not specifically limit, For example, the material used for light emitting diodes (LED), such as a mold member and die bond agents, etc. which are used for liquid crystal display devices, such as a color filter protective film, TFT planarization film | membrane, and substrate materials. In addition, the mold member in this specification is a concept including a molding agent or a sealing agent.

Substrate materials, light guide plates, prism sheets, deflector plates, retardation plates, viewing angle correction films, polarizer protective films, color filters, etc. in the liquid crystal display field; various coating agents, protective films, mold members, adhesives used for them And so on.
Examples include LED element mold members, LED mold members, front glass protective films, front glass substitute materials used in LED display devices; various coating agents, protective films, mold members, and adhesives used for these.

  Color PDP (plasma display) anti-reflection film, optical correction film, housing material, front glass protective film, front glass substitute material, etc .; various coating agents, protective films, mold members, adhesives, etc. used for them . Substrate materials, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films, polarizer protective films for plasma addressed liquid crystal (PALC) displays; various coating agents, protective films, mold members, and adhesives used for them And so on. A protective film for the front glass in an organic EL (electroluminescence) display, a substitute material for the front glass; various coating agents, protective films, mold members, adhesives, and the like used for them. Various film substrates in a field emission display (FED), a protective film for a front glass, a substitute material for a front glass; various coating agents, protective films, mold members, adhesives and the like used for them.

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films; various coating agents, protective films, mold members, adhesives and the like used for them.

  In the field of optical equipment, steel camera lens materials, finder prisms, target prisms, finder covers, light receiving sensor parts; various coating agents, protective films, molding members, adhesives, and the like used for them. Examples include photographing lenses and finders of video cameras; various coating agents, protective films, mold members, adhesives and the like used for them. Examples include projection lenses and protective films for projection televisions; various coating agents, protective films, mold members, adhesives, and the like used for them. Materials for lenses of optical sensing devices, various films; various coating agents, protective films, mold members, adhesives and the like used for them.

  In the field of optical components, fiber materials, lenses, waveguides, elements around optical switches in optical communication systems; various coating agents, protective films, mold members, adhesives and the like used for them are also included. Examples include optical fiber materials and ferrules around optical connectors; various coating agents, protective films, mold members, adhesives and the like used for them. In optical passive components and optical circuit components, lenses, waveguides; various coating agents, protective films, mold members, adhesives and the like used for them are also included. Examples include substrate materials and fiber materials around an optoelectronic integrated circuit (OEIC); various coating agents, protective films, mold members, adhesives and the like used for them.

  In the field of optical fibers, lighting for optical displays, light guides, etc., sensors for industrial use, displays / signs, etc., optical fibers for communication infrastructure and home digital equipment connection; various coating agents used for them, protective films, A mold member, an adhesive agent, etc. are also mentioned.

  Examples of peripheral materials for semiconductor integrated circuits include resist materials for microlithography for LSI and VLSI materials.

  In the field of automobiles and transportation equipment, lamp materials such as head lamps, tail lamps and interior lamps for automobiles, lamp reflectors, lamp lenses, various interior and exterior products such as exterior panels and interior panels, glass substitutes; various coating agents used for them , Protective films, mold members, adhesives and the like. Examples include exterior parts for railway vehicles, glass substitutes; various coating agents, protective films, mold members, adhesives and the like used for them. Aircraft exterior parts, glass substitutes; various coating agents, protective films, mold members, adhesives and the like used for them.

In the construction field, glass intermediate films, glass substitutes, solar cell peripheral materials; various coating agents, protective films, mold members, adhesives and the like used for them are also included.
For agriculture, a house covering film is also included.
Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Examples of the mold member include various coating agents, protective films, mold members, and adhesives used for them.

  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 dropping funnel, and a condenser tube were set in a 5 L four-necked flask. Into this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, heated and stirred in an oil bath at 120 ° C. A mixed solution of 200 g of diallyl monoglycidyl isocyanurate, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3% as platinum) was added dropwise over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours, and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{By 1} H-NMR, it was found that this was a product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane was reacted with diallyl monoglycidyl isocyanurate (synthesized product b1). Further, when the content of SiH group was determined by ¹ H-NMR using 1,2-dibromomethane as an internal standard, it was found to contain 6.7 mmol / g SiH group. Although the product is a mixture, it contains as a main component the following compounds corresponding to the compound B1 of the present invention.

(Synthesis Example 2)
500 g of toluene and 188 g of 1,1,3,3-tetramethyldisiloxane are placed in a 2 L autoclave equipped with a stirrer, addition pot and temperature controller so that the temperature inside the autoclave becomes 103-108 ° C. And stirred. A mixed solution of 186 g of diallyl monoglycidyl isocyanurate, 500 g of toluene and 0.18 g of a xylene solution of platinum vinylsiloxane complex (containing 3% as platinum) was added dropwise every 5 to 10 minutes in 10 portions. The obtained solution was heated and stirred as it was for 5 hours, then cooled to 50 ° C. and left overnight. Unreacted 1,1,3,3-tetramethyldisiloxane and toluene were distilled off under reduced pressure. ^{By 1} H-NMR, it was found that a part of the SiH group of 1,1,3,3-tetramethyldisiloxane was reacted with diallyl monoglycidyl isocyanurate (synthesized product b2). Further, when the content of SiH groups was determined by ¹ H-NMR using 1,2-dibromomethane as an internal standard, it was found to contain 2.46 mmol / g SiH groups. Although the product is a mixture, it contains as a main component the following compounds corresponding to the compound B2 (crosslinkable component having a large molecular weight) of the present invention.

(Where n is a number from 1 to 3)

( ¹ H-NMR) A 400 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used. The reaction rate of the allyl group in the synthesis was measured by adding the reaction solution diluted to about 1% with deuterated chloroform to the NMR tube and measuring the peak of the methylene group derived from the unreacted allyl group and the reaction allyl group derived. It calculated | required from the peak of the methylene group.

Example 1
Triallyl isocyanurate 4.32 g, diallyl monoglycidyl isocyanurate 41.32 g, platinum-divinyltetramethyldisiloxane complex in xylene solution (containing 3% platinum), trimethyl borate 0.48 g, anti-aging agent (product) Name: irganox 1010) After mixing 3 g and heating at 70 ° C. for 2 hours, the mixture was stirred and defoamed with a planetary stirring and defoaming machine to make liquid A. In addition, 46.18 g of the synthetic b1 prepared in Synthesis Example 1, 24.88 g of the synthetic b2 prepared in Synthesis Example 2, 0.3 g of 1-ethynylcyclohexanol, and 3-glycidoxypropyltrimethoxysilane (trade name: A-187) 2.5 g was mixed and stirred and degassed in the same manner as above to obtain a solution B. Thereafter, liquid A and liquid B were mixed, and stirring and defoaming were performed in the same manner as above to obtain a one-liquid mixture.

(Example 2)
The liquid B was prepared in the same manner as in Example 1 except that the composition b1 was 38.03 g and the composition b2 was 49.76 g.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that the anti-aging agent was not added to the liquid A and the composition of the liquid B was 54.36 g of the synthetic product b1.

(Comparative Example 2)
It carried out similarly to the said Example 1 except having performed by the mixing | blending which shows the composition of A liquid and B liquid in a table | surface.

(Glass transition temperature (Tg))
15 g of the one-component mixture prepared in Examples 1 and 2 and Comparative Example 1 was poured into a glass cell with a 3 mm spacer in between, and in a perfect oven (HT310S manufactured by ETAC), 60 ° C./6 hours, 70 ° C. / 1 hour, 80 ° C./1 hour, 120 ° C./1 hour, 150 ° C./1 hour, 180 ° C./30 minutes, and cured by heating. The obtained cured product (thickness 3 mm) was cut into 5 mm × 30 mm, and the temperature was raised at 5 ° C./min in the temperature range of −20 ° C. to 200 ° C. using Rheogel-E4000FA manufactured by UBM. Measurement of dynamic viscoelasticity (DMA) in free end / bending mode at speed, and glass transition temperature (Tg) was determined from the peak temperature of tan δ calculated from the values of storage elastic modulus and loss elastic modulus .

(Warp test)
0.5 g of one-component mixture prepared in Examples and Comparative Examples was applied onto a 33 mm × 33 mm, 0.3 mm thick glass epoxy resin sheet surrounded by a dam material, and a perfect oven (manufactured by ETAC) HT310S) to cure by heating at step cure conditions of 60 ° C / 6 hours, 70 ° C / 1 hour, 80 ° C / 1 hour, 120 ° C / 1 hour, 150 ° C / 1 hour, 180 ° C / 30 minutes. It was. After cooling the cured product to room temperature, one corner of the test piece was pressed with a finger on the flat plate, and the distance between the opposite end of the lifted plate and the flat plate was measured to determine the warpage.

(Crack resistance)
The one-component mixture produced in the examples and comparative examples is put in an LED cup having four dummy chips, and is heated in a hot air dryer at 60 ° C./6 hours, 70 ° C./1 hour, 80 ° C./1 hour, 120 ° C./1 hour, 150 ° C./1 hour, 180 ° C./30 minutes were heated and cured. Using a thermal shock tester, the state of cracks was observed after 100 cycles of a cycle consisting of leaving at −40 ° C./30 minutes and leaving at 100 ° C./30 minutes were observed. The observation results are shown in the table according to the following evaluation criteria.
○: No abnormality △: Small amount of cracks or small amount of peeling in sealing resin ×: Large amount of cracks or large amount of peeling in sealing resin

(reagent)
The reagents used are shown below.
・ Triallyl isocyanurate: Degussa reagent ・ Diallyl monoglycidyl isocyanurate: Shikoku Kasei ・ 1,3,5,7-tetramethylcyclotetrasiloxane: In-house ・ 1,1,3,3-tetramethyldisiloxane ( LS-7040): Shin-Etsu Chemical Co., Ltd., xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% platinum): E. Chemcat, 1-ethynylcyclohexanol: Aldrich, trimethoxyborane: Wako Pure Chemical, 3-glycidoxypropyltrimethoxysilane (A-187): GE Toshiba Silicone

  The results of blending and various physical properties of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in the table.

  As shown in the table, it can be seen that the warpage is smaller in Examples 1 and 2 than in Comparative Example 1. From this, the composition (Examples 1 and 2 and Comparative Example 1) containing the crosslinkable component (Compound B2) having a large molecular weight is higher than the composition (Comparative Example 1) using only the compound B1 as the B component. It can be seen that the substrate is highly resistant to warpage.

  On the other hand, in Comparative Example 2 where the content of compound B2 is the highest, although resistance to substrate warpage is high, Tg is around 25 ° C. and room temperature, so that there is tackiness of materials, adhesion between materials and in the air It is not preferable from the viewpoint that dust and dust adhere. On the other hand, in Examples 1 and 2, since the Tg is 88 and 67 ° C., respectively, the material has no tackiness and is highly resistant to substrate warpage.

  Moreover, it turns out that crack resistance is recognized in Example 2 and the comparative example 2 with many ratios of compound B2 about crack resistance.

  From the above test results, the compositions of Examples 1 and 2 having warpage resistance and no tackiness are preferable, and among them, the composition of Example 2 having crack resistance is particularly preferable.

Claims (3)

(A) an organic 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) A curable composition containing a hydrosilylation catalyst as an essential component, wherein the component (A) is represented by the following general formula (I):

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same), and
The component (B) is a hydrosilylation reaction between an organic compound containing two (α) SiH group-reactive carbon-carbon double bonds in one molecule and (β) a polyorganosiloxane having a SiH group. The component (B) can be obtained by hydrosilylation reaction of the component (α) with (β1) a polyorganosiloxane having 3 or more SiH groups in one molecule. A compound (compound B2) that can be obtained by hydrosilylation reaction of a compound (compound B1) that can be obtained with the above-mentioned (α) component and a linear polyorganosiloxane having two SiH groups in one molecule (β2) And a ratio of the compound B2 to the sum of the compound B1 and the compound B2 is 10 to 90% by weight. The linear polyorganosiloxane is represented by the following general formula (II)

(Wherein R ² represents a monovalent organic group having 1 to 6 carbon atoms, and a plurality of R ² may be different or the same. N is a number of 0 to 1000). A curable composition characterized by that.   LED sealing agent, die-bonding agent, adhesive, and coating agent comprising the curable composition according to claim 1 or 2.