WO2011007789A1 - Curable composition for optical material - Google Patents

Abstract

Disclosed is a curable composition for optical materials which comprises (A) an organic compound having a number-average molecular weight of 10,000 or lower and having, per molecule, at least two carbon-carbon double bonds reactive with an SiH group, (B) a polysiloxane compound which is obtained by reacting a di- or polyfunctional organic compound with a polysiloxane compound and which contains at least two SiH groups per molecule, (C) a hydrosilylation catalyst, and (D) a silicone compound which has a structure represented by the general formula R¹ _nSiO_(4-n)/2 (wherein R¹s may be the same or different and each represents a hydrogen atom or a C_1-50 monovalent organic group optionally substituted by an oxygen, nitrogen, sulfur, or halogen atom, and n is an integer of 1-3) and which has, per molecule, at least two SiH groups and/or carbon-carbon double bonds reactive with an SiH group, the amount of the ingredient (D) being 0.005-10 parts by weight per 100 parts by weight of the sum of the ingredients (A) and (B).

Description

Curable composition for optical materials

The present invention relates to a curable composition for an optical material that gives a cured product excellent in releasability to a substrate, the cured product, and an optical member, an optical component, and an optical semiconductor module using the cured product.

In general, polymer materials for optical materials such as optical components such as lenses and optical fibers, adhesives and coating agents thereof, and optical semiconductors such as LEDs and light receiving elements have high transparency and hardness. Epoxy resins, acrylic resins, polycarbonate resins, cycloolefin resins, etc. are used.

However, due to increasing interest in environmental conservation, the use of low melting point solder containing Pb that has been used so far has been restricted, and the temperature required for solder mounting has increased. In fact, a temperature history exceeding 250 ° C. may be applied, and there is a problem that even resins that have been used so far are discolored or deformed. For this reason, it has been proposed to use a silicone resin having excellent heat resistance and transparency.

For example, Patent Document 1 and Patent Document 2 disclose optical lenses or compositions made of silicone or organopolysiloxane, and propose cured products for optical lenses that ensure heat resistance, transparency, and hardness. However, in general, when a silicone resin is used, the linear expansion coefficient is larger than that of the resin, so that the refractive index dependency with respect to temperature is increased or cracks are generated when a thermal shock is applied. There is.

JP 2000-23002 A JP 2006-324596 A

Accordingly, an object of the present invention is to provide a curable composition that has high transparency and hardness, is excellent in heat discoloration resistance, has low birefringence, and can provide a cured product suitable for an optical material. is there.

That is, the present invention
(A) an organic compound having a number average molecular weight of 10,000 or less, containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(B) a polysiloxane compound containing at least two SiH groups in one molecule, obtained by reacting a bifunctional or higher organic compound with a polysiloxane compound;
(C) a hydrosilylation catalyst, and
(D) The following general formula:
R ¹ _n SiO _{(4-n) / 2}
(R ¹ is hydrogen or a monovalent organic group having 1 to 50 carbon atoms, which may be substituted with oxygen, nitrogen, sulfur or halogen atoms, and each R ¹ may be different or the same. N may be an integer from 1 to 3.)
And a silicone compound having a carbon-carbon double bond having at least two SiH groups and / or reactivity with SiH groups in one molecule, (A) component and (B) The present invention relates to a curable composition for optical materials containing 0.005 to 10 parts by weight with respect to 100 parts by weight as a total of the components.

The viscosity of component (D) at 23 ° C. is preferably 0.001 to 5.0 Pa · s.

The number average molecular weight in terms of polystyrene measured by gel permeation chromatography of component (D) is preferably 300 to 30000.

The component (D) preferably has a weight loss of less than 10% after heating at 100 ° C. for 1 minute in a thermogravimetric apparatus.

(B) component is the following general formula (I):

(Wherein R ² is a monovalent organic group having 1 to 50 carbon atoms, and may be substituted with oxygen, nitrogen, sulfur, or halogen atoms. Each R ² may be different or the same. May be.)
It is preferable that it is obtained from the organic compound more than bifunctional represented by these.

(B) component is the following general formula (II):

(Wherein R ³ is a monovalent organic group having 1 to 50 carbon atoms and may be substituted with an oxygen, nitrogen, sulfur, or halogen atom. Each R ³ may be different or the same. It may preferably be obtained from a bifunctional or higher organic compound represented by

The component (B) is preferably obtained from a bifunctional or higher aliphatic hydrocarbon compound having a cyclic structure.

The component (A) is preferably an aliphatic hydrocarbon compound having a cyclic structure.

The component (A) is represented by the following general formula (I):

(Wherein R ² is a monovalent organic group having 1 to 50 carbon atoms, and may be substituted with oxygen, nitrogen, sulfur, or halogen atoms. Each R ² may be different or the same. May be.)
And a compound represented by the following general formula (II):

(Wherein R ³ is a monovalent organic group having 1 to 50 carbon atoms and may be substituted with an oxygen, nitrogen, sulfur, or halogen atom. Each R ³ may be different or the same. May be.)
It is preferable that it is at least 1 selected from the group which consists of a compound represented by these.

Component (A) is triallyl isocyanurate, diallyl monoglycidyl isocyanurate, divinylbenzene, bisphenol A diallyl ether, bisphenol S diallyl ether, polybutadiene, vinylnorbornene, vinylcyclohexene, and 1,4,6-trivinylcyclohexane. It is preferably at least one selected from the group consisting of

The component (A) preferably contains at least 0.4 mmol of carbon-carbon double bonds having reactivity with SiH groups per 1 g of the component (A).

It is preferable to give a cured product having a light transmittance of 60% or more at a wavelength of 400 nm of the cured product (thickness of 3 mm).

It is preferable to give a cured product having a light transmittance of 60% or more at a wavelength of 400 nm after heat-treating the cured product (3 mm thick) at 280 ° C. for 3 minutes in the air.

It is preferable to give a cured product having a Shore D hardness of 30 or more at 25 ° C.

It is preferable to give a cured product having a linear expansion coefficient at 30 ° C. of 150 ppm / K or less.

The present invention also relates to a transparent cured product obtained by curing the curable composition for optical materials.

Furthermore, the present invention relates to an optical member, an optical component, and an optical semiconductor module that use the transparent cured product.

The curable resin for optical materials of the present invention comprises a silicone compound having a specific structure and having at least two SiH groups and / or carbon-carbon double bonds having reactivity with SiH groups in one molecule. Because it is formulated, it has excellent mold releasability, low birefringence (low curing unevenness), high transparency, heat discoloration and hardness, and suitable for optical materials with low linear expansion coefficient at high temperature. A cured product can be obtained.

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

((A) component)
The component (A) is an organic compound having a number average molecular weight of 10,000 or less, containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule. The molecular structure of the organic compound is not particularly limited, but the organic compound does not include a siloxane unit (Si—O—Si) such as a polysiloxane-organic block copolymer or a polysiloxane-organic graft copolymer. 90% by weight or more of the element is preferably at least one selected from the group consisting of C, H, N, O, S and halogen.

In the case of those containing siloxane units, gas permeability and repelling problems may occur. In addition, when a polymer having a number average molecular weight of 10,000 or more is used, Tg (glass transition temperature) is lowered depending on the skeleton of the organic compound, which causes a problem from the viewpoint of heat resistance of the cured product. The number average molecular weight is more preferably 5000 or less. In the present invention, the number average molecular weight indicates a polystyrene-reduced number average molecular weight by gel permeation chromatography (GPC).

(A) An organic compound having at least two carbon-carbon double bonds that are reactive with a SiH group in one molecule is an organic skeleton portion and the reactivity with the SiH group covalently bonded to the organic skeleton portion. Those consisting of a group having a carbon-carbon double bond having The group having a carbon-carbon double bond having reactivity with the SiH group may be covalently bonded to any part of the organic skeleton.

First, the carbon-carbon double bond having reactivity with the SiH group will be described. The group having a carbon-carbon double bond in the organic compound (A) is not particularly limited as long as it has reactivity with the SiH group. Examples of the group having a carbon-carbon double bond reactive with the SiH group include the following general formula (III):

A group having a structure represented by the formula (wherein R ⁴ represents a hydrogen atom or a methyl group) is preferable because of its high reactivity. From the standpoint of easy availability of raw materials, R ⁴ is particularly preferably a hydrogen atom.

In terms of high heat resistance of the cured product, the group having a carbon-carbon double bond is represented by the following general formula (IV):

(In the formula, R ⁵ represents a hydrogen atom or a methyl group. Each R ⁵ may be the same or different.) In view of the availability of raw materials, R ⁵ is particularly preferably a hydrogen atom.

The group having a carbon-carbon double bond that is reactive with the SiH group may be covalently bonded to the organic skeleton through a divalent or higher functional group.
The divalent or higher functional group is preferably a functional group having 0 to 20 carbon atoms, and more preferably a functional group having 0 to 10 carbon atoms. Although there is no restriction | limiting in particular, As an example of such a functional group, the compound which has the following general formula is mentioned.

Of these, two or more functional groups may be connected by a covalent bond to form one divalent or higher functional group in a larger unit.
Specific examples of the group having a carbon-carbon double bond include vinyl group, allyl group, methallyl group, acrylic group, methacryl 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, 3- (allyloxy) propyl group, 2,2-bis (allyloxymethyl) butyl Groups, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group, and groups represented by the following general formula.

Next, the organic skeleton portion will be described. The organic skeleton is a skeleton mainly composed of elements selected from the group consisting of carbon, hydrogen, nictogen atoms, chalcogen atoms including oxygen, and halogen atoms, and is not particularly limited as long as it is composed of the above elements. For example, organic polymer skeletons such as vinyl, saturated hydrocarbon, ether, ester, acrylate ester, carbonate, arylate, amide, imide, phenol-formaldehyde (phenol resin), Examples thereof include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene, aliphatic hydrocarbons, aliphatic alcohols, cyclic hydrocarbons, and the like, and organic monomer skeletons composed of two or more of these.

The molecular weight of the organic skeleton portion is not particularly limited, but from the viewpoint of handleability, the molecular weight is preferably 10,000 or less, and more preferably 5000 or less. In this invention, molecular weight shows the number average molecular weight of polystyrene conversion by GPC.

Specific examples of the organic polymer skeleton include polyether polymers such as polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polybutadiene. More specific examples:

(Wherein R ⁶ is a monovalent organic group having 0 to 50 carbon atoms, R ⁷ and R ⁸ are divalent organic groups having 1 to 100 carbon atoms, and X and Y are the same or different and are directly bonded or A divalent organic group having 1 to 48 carbon atoms, p, q and r each represents an integer of 1 to 60).
R ⁶ is preferably a monovalent hydrocarbon group having 0 to 6 carbon atoms, R ⁷ and R ⁸ are preferably divalent hydrocarbon groups having 1 to 100 carbon atoms, and more preferably 1 to 100 carbon atoms. An alkylene group, more preferably an alkylene group having 1 to 50 carbon atoms, X and Y are preferably the same or different, and a direct bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, p, q and r are preferably Each represents an integer of 1 to 50.

The organic group herein is not particularly limited, but is preferably a hydrocarbon-based functional group that may have an ether bond, an ester bond, an acetal bond, an imide bond, an amide bond, or a halogen compound. The same applies to the “organic groups” listed below.

Examples of other polymers used as the organic polymer skeleton include dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid, and ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, Polyester polymers obtained by condensation with glycols such as neopentyl glycol or ring-opening polymerization of lactones; ethylene-propylene copolymers; polyisobutylene, copolymers of isobutylene and isoprene, etc .; polychloroprene; polyisoprene , Copolymers of isoprene and butadiene, acrylonitrile, styrene, etc .; copolymers of polybutadiene, butadiene and styrene, acrylonitrile, etc .; polyolefins obtained by hydrogenating polyisoprene (saturated hydrocarbons) Polymers, polyolefin polymers obtained by hydrogenating polybutadiene, polyolefin polymers obtained by hydrogenating copolymers of isoprene and acrylonitrile, styrene, etc., copolymers of butadiene and acrylonitrile, styrene, etc. Polyolefin polymer obtained by hydrogenation of polyacrylic acid ester obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate; acrylic acid ester such as ethyl acrylate and butyl acrylate, vinyl acetate, acrylonitrile, methyl Acrylate ester copolymer with methacrylate, styrene, etc .; Graft polymer obtained by polymerizing vinyl monomer in the organic polymer; Polysulfide polymer; Nylon 6, hexene by ring-opening polymerization of ε-caprolactam Nylon 66 by polycondensation of samethylenediamine and adipic acid, nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, nylon 11 by polycondensation of 11-aminoundecanoic acid, nylon 12 by ring-opening polymerization of laurolactam, Polyamide polymer such as copolymer nylon having two or more components of nylon; polycarbonate polymer produced by polycondensation from bisphenol A and carbonyl chloride; diallyl phthalate polymer; novolac type phenol resin, resole Examples thereof include phenolic resins such as type phenolic resin, ammonia resol type phenolic resin, and benzylic ether type phenolic resin.

Furthermore, as a specific example of the organic compound of the component (A) in which an alkenyl group is introduced into the side chain or terminal of the organic polymer skeleton,

(Wherein R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ and R ¹¹ are the same or different, a divalent organic group having 1 to 100 carbon atoms, X and Y are the same or different and are directly bonded or (The divalent organic group having 1 to 48 carbon atoms, p, q and r each represents an integer of 1 to 100)

(Wherein R ¹² is a hydrogen atom or a methyl group, R ¹³ and R ¹⁴ are the same or different, a divalent organic group having 1 to 100 carbon atoms, and X and Y are the same or different and are directly bonded or (Divalent organic group having 1 to 48 carbon atoms, n represents an integer of 1 to 50)

(Wherein R ¹⁵ is a hydrogen atom or a methyl group, R ¹⁶ and R ¹⁷ are the same or different, a divalent organic group having 1 to 100 carbon atoms, and X and Y are the same or different and are directly bonded or A divalent organic group having 1 to 48 carbon atoms, p and q each represents an integer of 1 to 50, and r represents an integer of 1 to 20)

(Wherein R ¹⁸ is a hydrogen atom or a methyl group, R ¹⁹ , R ²⁰ and R ²¹ are the same or different, a divalent organic group having 1 to 6 carbon atoms, X and Y are the same or different, (Direct bond or divalent organic group having 1 to 48 carbon atoms, p, q and r each represents an integer of 1 to 50, and s represents an integer of 1 to 20)
Etc.

R ¹⁰ , R ¹¹ , R ¹³ and R ¹⁴ are divalent organic groups having 1 to 100 carbon atoms, preferably a hydrocarbon group, and more preferably an alkylene group. The carbon number of the organic group is preferably 1-60.
R ¹⁶ and R ¹⁷ are each a divalent organic group having 1 to 100 carbon atoms, preferably a hydrocarbon group, and more preferably an alkylene group. Also, the organic group preferably has 1 to 6 carbon atoms.
R ¹⁹ , R ²⁰ and R ²¹ are a divalent organic group having 1 to 6 carbon atoms, preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkylene having 1 to 6 carbon atoms. It is a group.
X and Y are a direct bond or a divalent organic group having 1 to 48 carbon atoms, preferably a direct bond or a divalent hydrocarbon group having 1 to 48 carbon atoms. An alkylene group is more preferred. The carbon number of the organic group is preferably 1-12.
p and q are each preferably an integer of 1 to 20, r is preferably an integer of 1 to 20, s is preferably an integer of 1 to 10, and n is preferably an integer of 1 to 10.

Examples of organic monomers include aliphatic chain compounds such as ethane, propane, and isobutane, aliphatic cyclic compounds such as cyclopentane, dicyclopentane, and norbornane, or epoxy, oxetane, furan, and thiophene, Pyrrole, oxazole, isoxazole, thiazole, imidazole, pyrazole, furazane, triazole, tetrazole, pyran, thiine, pyridine, oxazine, thiazine, pyridazine, pyrimidine, pyrazine There are heterocyclic compounds such as a series, a piperazine series, and an isocyanurate series. Here, the heterocyclic ring is not particularly limited as long as it is a cyclic compound having a hetero element in a cyclic skeleton. However, those in which Si is contained in the atoms forming the ring are excluded. The number of atoms forming the ring is not particularly limited and may be 3 or more. From availability, it is preferable that it is 10 or less.

Specific examples of the component (A) comprising an organic monomer include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene, decadiene, cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene, Aliphatic cyclic polyene compounds such as norbornadiene, substituted aliphatic cyclic olefin compounds such as vinylcyclopentene, vinylcyclohexene and vinylnorbornene, diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol Triallyl ether, 1,1,2,2-tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate , Diallyl monoglycidyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably having a purity of 80 to 100% ), Divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, compounds having a group of the following general formula, and the like.

As the component (A), from the viewpoint of further improving the heat resistance, it is preferable to contain 0.4 mmol or more of a carbon-carbon double bond having reactivity with the SiH group per gram of the component (A). Those containing 1.0 mmol or more per gram are more preferable.

The number of carbon-carbon double bonds having reactivity with the SiH group of component (A) should be at least 2 on average per molecule, but it should exceed 2 if it is desired to further improve the mechanical strength. It is preferable that the number is 3 or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of component (A) is 1 or less per molecule, a crosslinked structure is obtained even if it reacts with component (B), resulting in a graft structure. Not.

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), from the viewpoint of high mechanical heat resistance and from the viewpoint that the stringiness of the raw material liquid is small and the moldability, handleability and coating properties are good, the fluidity is at a temperature of 100 ° C. or less. Some are preferred and may be linear or branched. The lower limit of the molecular weight is preferably 50 and the upper limit is 5000. Those having a low molecular weight have high volatility, and if the molecular weight is too large, the raw material becomes highly viscous and inferior in workability, and the effect of crosslinking due to the reaction between the alkenyl group and the SiH group tends to hardly be exhibited.

As the component (A), in order to obtain uniform mixing with other components and good workability, the viscosity is preferably less than 3000 Pa · s at 23 ° C., more preferably less than 2000 Pa · s. Preferably, the one less than 1000 Pa · s is more preferable. 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 compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable. Those not containing a compound having a derivative of are more 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 the 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 that the resulting cured product is less colored and has high light resistance, the component (A) includes vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, and tris (2-acryloyloxyethyl). Isocyanurate, 2,2-bis (4-hydroxycyclohexyl) propane diallyl ether, 1,2,4-trivinylcyclohexane are preferred, triallyl isocyanurate, 2,2-bis (4-hydroxycyclohexyl) propane diallyl Ether and 1,2,4-trivinylcyclohexane are 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 these reactive groups are included, 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 reactive groups, an epoxy group is preferred 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.

In particular, as the component (A), from the viewpoint of high heat resistance and light resistance, the general formula (I):

(Wherein R ² is a monovalent organic group having 1 to 50 carbon atoms, and may be substituted with oxygen, nitrogen, sulfur, or halogen atoms. Each R ² may be different or the same. The compound represented by this may be preferable.

R ^{2 in the} general formula (I) is preferably a monovalent organic group having 1 to 20 carbon atoms from the viewpoint that the heat resistance of the obtained cured product can be further increased. 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are more preferable. Examples of these preferable R ² include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group, and the following.

Preferable specific examples of the organic compound represented by the general formula (I) as described above include triallyl isocyanurate and the following compounds.

A mixture of triallyl isocyanurate and diallyl monoglycidyl isocyanurate is preferred in order to achieve both improved resin strength and light resistance of the cured product. Since the mixture has an isocyanuric ring skeleton, it is also effective from the viewpoint of heat resistance. The mixing ratio can be arbitrarily set, but in order to achieve the above object, triallyl isocyanurate / diallyl monoglycidyl isocyanurate (molar ratio) is preferably 99/1 to 1/99, more preferably 95/5 to 5/95. 90/10 to 10/90 is particularly preferable.

Moreover, it is preferable that (A) component is an aliphatic hydrocarbon compound which has a cyclic structure from a viewpoint that the Abbe number of the hardened | cured material obtained becomes high. For example, vinyl norbornene, vinylcyclohexene, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane and the like can be mentioned.

From the viewpoint of lowering the Abbe number of the resulting cured product, a compound having the skeleton of the general formula (II) is preferable. Further, from the viewpoint of increasing the Abbe number of the obtained cured product, the compound having the skeleton of the general formula (I), the aliphatic hydrocarbon compound having a cyclic structure, and the like are preferable.

Moreover, from the viewpoint that the obtained cured product has high heat resistance and refractive index, the general formula (II):

(Wherein R ³ is a monovalent organic group having 1 to 50 carbon atoms and may be substituted with an oxygen, nitrogen, sulfur, or halogen atom. Each R ³ may be different or the same. The compound represented by this may be preferable.
R ³ is a monovalent organic group having 1 to 50 carbon atoms, preferably a hydrocarbon group, more preferably an alkenyl group. The carbon number of the organic group is preferably 1-30.
Specifically, divinylbenzenes, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, bisphenol A diallyl ether, bis [4- (2-allyloxy) Preferred are those in which part or all of the glycidyl group bonded to an epoxy resin containing an aromatic ring such as) phenyl] sulfone (bisphenol S diallyl ether) or phenol novolac resin is substituted with an allyl group.

As R ^{3 in the} general formula (II), a compound having a plurality of aromatic rings is preferable from the viewpoint that the obtained cured product can have higher heat resistance. Such an aromatic ring preferably has the structure shown below.

From the viewpoint of further improving the heat resistance, the component (A) includes triallyl isocyanurate, diallyl monoglycidyl isocyanurate, divinylbenzene, 1,4,6-trivinylcyclohexane, vinylcyclohexene, vinylnorbornene, bisphenol A. It is preferably selected from diallyl ether and bisphenol S diallyl ether. Among these, bisphenol A diallyl ether and bisphenol S diallyl ether can improve heat resistance while maintaining a low Abbe number.

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

((B) component)
Next, the component (B) will be described.

The component (B) of the present invention is a polysiloxane compound containing at least two SiH groups in one molecule obtained by reacting a bifunctional or higher functional organic compound with a polysiloxane compound. The molecular structure of the organic compound is not particularly limited, but does not include a siloxane unit (Si—O—Si) such as polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, and 90% by weight or more of the constituent elements Is preferably at least one selected from the group consisting of C, H, N, O, S and halogen. This indicates that the component (B) is not a compound composed only of a siloxane skeleton. Here, the siloxane skeleton is
(R ²² ₃ SiO _1/2 ) _p (R ²² ₂ SiO _2/2 ) _q (R ²² SiO _3/2 ) _r (SiO _4/2 ) _t
(R ²² represents the same or different unsubstituted or substituted monovalent hydrocarbon group, p, q, r and t represent the number of moles of each siloxane unit, and p, q, r and t are 0 or positive It is a skeleton consisting of only a continuous SiO bond in the main chain, such as p + q + r + t = 1. When a compound consisting only of a siloxane skeleton has a large value of p or q, the coefficient of linear expansion increases, making it difficult to apply as an optical component. When a value of r or t is large, a thermal shock is applied. Tend to break easily. p is 0 to 300, preferably 0 to 100, q is 0 to 500, preferably 0 to 300, r is 0 to 500, preferably 0 to 300, and t is 0 to 500, preferably 0-300.

From the viewpoint of having good compatibility with the component (A) and from the viewpoint that the problem of outgas from the composition that can lower the volatility of the component (B) is less likely to occur, the component (B) is bifunctional. As the above organic compound, an organic compound (α) containing two or more carbon-carbon double bonds having reactivity with SiH group in one molecule, and at least three in one molecule as a polysiloxane compound It is preferable that it is a compound obtained by hydrosilylating the polyorganosiloxane (β) having a SiH group.

The molecular weight of the component (B) is not particularly limited, and any one can be suitably used. However, from the viewpoint that the fluidity of the curable composition can be more easily controlled, those having a low molecular weight are preferably used. In this case, the lower limit of the preferable molecular weight is 50, and the upper limit of the preferable molecular weight is 100,000, more preferably 10,000, and still more preferably 2,000.

((Α) component)
Here, the component (α) is a number containing at least two carbon-carbon double bonds having reactivity with SiH groups from the viewpoint of compatibility with the components (A) and (D). An organic compound having an average molecular weight of 30000 or less is preferable.

Use the same component (A1) as the organic compound having a number average molecular weight of 10,000 or less and containing at least two carbon-carbon double bonds having reactivity with SiH groups, which is the component (A). Can do. When the component (α1) is used, the resulting cured product has a high crosslink density and tends to be a cured product having high mechanical strength.

As the component (α), an organic compound (α2) containing two carbon-carbon double bonds having reactivity with the SiH group in one molecule and having a molecular weight larger than 10,000 can also be used. However, it is more preferable to use the (α1) component from the viewpoint of heat discoloration of the obtained cured product and transparency at high temperature.

As the component (α), a compound having a skeleton of the general formula (I) or the general formula (II) is preferable from the viewpoint of high heat resistance.

As the component (α), a compound having a cyclic structure, for example, an aliphatic hydrocarbon compound such as vinyl norbornene, or a compound having the skeleton of the general formula (II) described above is preferable from the viewpoint of a high refractive index. Examples of the compound having the skeleton of the general formula (II) include divinylbenzenes, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, bisphenol A diallyl ether, And glycidyl groups bonded to aromatic ring-containing epoxy resins such as bis [4- (2-allyloxy) phenyl] sulfone and phenol novolac resins are substituted with allyl groups.

As the component (α), a compound having the skeleton of the general formula (II) is preferable from the viewpoint that the Abbe number of the obtained cured product is reduced. Further, from the viewpoint of increasing the Abbe number of the obtained cured product, the compound having the skeleton of the general formula (I), the aliphatic hydrocarbon compound having a cyclic structure, and the like are preferable.

((Β) component)
The polyorganosiloxane having at least 3 SiH groups in one molecule that can be used as the (β) component is not particularly limited, and is, for example, a compound described in International Publication No. 96/15194 pamphlet. Those having at least 3 SiH groups can be used.

Of the polyorganosiloxanes having at least 3 SiH groups in one molecule, specific examples of the chain organopolysiloxane include the following general formula (V):

(In the formula, each R ²³ and R ²⁴ represents hydrogen or a monovalent organic group having 1 to 50 carbon atoms, and each R ²³ and R ²⁴ may be different or the same, 3 represents hydrogen, and n represents an integer of 1 to 1000).

R ²³ and R ²⁴ are preferably monovalent organic groups having 1 to 20 carbon atoms, and monovalent organic groups having 1 to 15 carbon atoms from the viewpoint that the resulting cured product can have higher heat resistance. The organic group is more preferably a monovalent organic group having 1 to 10 carbon atoms. Examples of these preferable R ²³ and R ²⁴ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, vinyl group, allyl group, glycidyl group and the like. Can be mentioned. n is preferably an integer of 1 to 300.

Of the polyorganosiloxanes having at least three SiH groups in one molecule, examples of the cyclic polyorganosiloxane include the following general formula (VI):

(Wherein R ²⁵ represents hydrogen or an organic group having 1 to 6 carbon atoms, and each R ²⁵ may be different or the same, but at least three are hydrogen. N is 2 to 10) And a cyclic polyorganosiloxane having at least three SiH groups in one molecule. R ²⁵ in the general formula (VI) is preferably an organic group having 1 to 6 carbon atoms composed of C, H, and O, and more preferably a hydrocarbon group having 1 to 6 carbon atoms. Preferably, it is an alkyl group having 1 to 6 carbon atoms. N is preferably an integer of 3 to 10.
Preferable specific examples of the cyclic polyorganosiloxane represented by the general formula (VI) include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 , 7,9-pentamethylcyclopentasiloxane and the like.

Among these, from the viewpoint of availability, a linear and / or cyclic and / or branched polyorganosiloxane having at least 3 SiH groups in one molecule is preferable. From the viewpoint of compatibility with the component (A), a cyclic polyorganosiloxane or a linear polyorganosiloxane having a molecular weight of 10,000 or less is preferable. From the viewpoint of glass transition temperature, cyclic and branched polyorganosiloxanes are preferred. From the viewpoint of high strength, cyclic polyorganosiloxane is preferred.

The (β) component can be used alone or in combination of two or more.

(Preliminary reaction)
Next, the reaction for obtaining the component (B) will be described.

The mixing ratio of the bifunctional or higher organic compound and the polysiloxane compound in the hydrosilylation reaction is not particularly limited as long as two or more SiH groups remain in one molecule.

When the (α) component and the (β) component are reacted, from the viewpoint of the strength of the resulting cured product, the number of moles of carbon-carbon double bonds having reactivity with SiH groups in the (α) component ( The ratio of X) to the number of moles of SiH groups (Y) in the component (β) is preferably Y / X ≦ 5, and more preferably Y / X ≦ 3. From the viewpoint of the heat resistance of the cured product, 3 ≧ Y / X ≧ 0.7 is preferable, and 2 ≧ Y / X ≧ 0.8 is more preferable.

In the case of hydrosilylation, an appropriate catalyst may be used. As the catalyst, for example, the component (C) described later can be used.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferable addition amount is sufficient for the polyorganosiloxane (β) component having SiH groups in order to have sufficient curability and keep the cost of the curable composition relatively low. ^{10 -10} mol per SiH group 1 mol, more preferably ^{10 -8} mole, the upper limit of the preferable amount is, the polyorganosiloxane (beta) 10 per mole of the SiH group in component having an SiH group ^{- 1} mol, more preferably 10 ^-3 mol.

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 malate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, and amine compounds such as triethylamine. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst is 10 ⁻⁵ mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

Various methods can be used as a catalyst mixing method during the reaction, and a method in which a mixture of the (α) component and the hydrosilylation catalyst (C) is mixed with the (β) component is preferable. In the method of mixing the hydrosilylation catalyst (C) with the mixture of the (α) component and the (β) component, it may be difficult to control the reaction. In the method of mixing the (β) component with the hydrosilylation catalyst (C) and mixing the (α) component, the reaction with the water in which the (β) component is mixed in the presence of the hydrosilylation catalyst (C). Because of its nature, it may be altered.

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 sufficient reaction tends to be long, and if the reaction temperature is high, it may be industrially disadvantageous. The reaction may be carried out at a constant temperature, and 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. The reaction time is not particularly limited. From the economical aspect, it is preferably within 20 hours, more preferably within 10 hours. The pressure is not particularly limited, but is preferably from atmospheric pressure to 5 MPa, more preferably from atmospheric pressure to 2 MPa from the viewpoint that a special apparatus is required and the operation becomes complicated.

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, 1,4-dioxane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

The amount of the solvent used is not particularly limited, but is preferably an amount that can completely dissolve the component (α) in order to make the reaction uniform and promote. (Α) 20 parts by weight or more and 500 parts by weight or less are preferable with respect to 100 parts by weight of the component, and 50 parts by weight or more and 300 parts by weight or less are more preferable.

In addition, various additives may be used for the purpose of controlling reactivity.

Organic compound (α) component containing one carbon-carbon double bond having reactivity with a solvent or unreacted SiH group after hydrosilylation reaction, at least three SiH groups in one molecule It is also possible to remove the polyorganosiloxane (β) component having. By removing these volatile components, the problem of voids and cracks due to volatilization of volatile components during curing is less likely to occur.

Examples of the removal method include treatment with activated carbon, aluminum silicate, silica gel and the like in addition to vacuum devolatilization. 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 120 ° C, more preferably 100 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

Examples of the component (B) obtained by the above method include a reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5,7. -Reaction product of tetramethylcyclotetrasiloxane, reaction product of monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane Reaction product of bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of vinylnorbornene and 1,3,5,7-tetramethylcyclotetrasiloxane, bis [4 -(2-Allyloxy) phenyl] sulfone and 1,3,5,7-tetramethylsilane The reaction product of (b) cyclotetrasiloxane is more preferred.

In this invention, (B) component can be used individually or in mixture of 2 or more types.

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

The hydrosilylation catalyst is not particularly limited as long as it has catalytic activity for the hydrosilylation reaction. For example, platinum alone; solid platinum supported on a support such as alumina, silica, carbon black; 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 (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _a , Pt [(MeViSiO) ₄ ] _b ); platinum-phosphine complexes (eg, 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, u represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and a and b represent an integer.); dicarbonyldichloroplatinum; a Karlstedt catalyst; a platinum-hydrocarbon complex (for example, Ashby) Platinum platinum-hydrocarbon complexes described in US Pat. Nos. 3,159,601 and 3,159,662); platinum alcoholates (eg, platinum alcoholates described in Lamoreaux, US Pat. No. 3,220,972). Catalyst).

In addition, platinum chloride-olefin complexes (eg, the 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.

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.

In addition, a cocatalyst can be used in combination with the catalyst. Examples of promoters include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, acetylene alcohol compounds such as 2-hydroxy-2-methyl-1-butyne, and simple sulfur And the like, amine compounds such as triethylamine, water and the like.

The addition amount of the co-catalyst is not particularly limited, with respect to the hydrosilylation catalyst 1 mol, the lower limit 10 ^-5 mol, the range of the upper limit 10 ² mol, more preferably lower 10 ^-1 mol, the upper limit 10 mols It is.

((D) component)
Next, the following general formula as the component (D):
R ¹ _n SiO _{(4-n) / 2}
(R ¹ is hydrogen or a monovalent organic group having 1 to 50 carbon atoms, which may be substituted with oxygen, nitrogen, sulfur or halogen atoms, and each R ¹ may be different or the same. N may be an integer from 1 to 3.)
A silicone compound having a structure represented by the following formula and having a carbon-carbon double bond having reactivity with at least two SiH groups and / or SiH groups in one molecule will be described.

The component (D) is not particularly limited as long as it is a linear and / or cyclic silicone compound having a carbon-carbon double bond having reactivity with at least two SiH groups and / or SiH groups in one molecule. For example, the compounds described in International Publication WO 96/15194 Pamphlet can be used. Here, the carbon-carbon double bond having reactivity with the SiH group is preferably that described in the description of the component (A).

R ¹ is preferably hydrogen or a monovalent organic group having 1 to 6 carbon atoms, more preferably hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

Since component (D) contains at least two SiH groups and / or carbon-carbon double bonds having reactivity with SiH groups in one molecule, the repetition of components (A) and (B) There is an advantage that it is easy to be taken into the unit, and the obtained cured product has high surface transferability and is difficult to bleed out. From the viewpoints of availability, handling, and compatibility, the number of carbon-carbon double bonds having reactivity with SiH groups and / or SiH groups should be 50 or less per molecule. Is preferred.

Specific examples of the chain silicone compound include the following general formula (V):

(In the formula, each R ²³ and R ²⁴ represents hydrogen or a monovalent organic group having 1 to 50 carbon atoms, and each R ²³ and R ²⁴ may be different or the same. A carbon-carbon double bond having reactivity with at least two hydrogen or SiH groups is contained in the molecule, and n represents an integer of 1 to 1000).
Among the monovalent organic groups having 1 to 50 carbon atoms, a hydrocarbon group is preferable, and an alkyl group is more preferable. The carbon number of the organic group is preferably 1-6. n is preferably an integer of 1 to 500.

Examples of the cyclic silicone compound include the following general formula (VI):

(Wherein R ²⁵ represents hydrogen or a monovalent organic group having 1 to 10 carbon atoms, and each R ²⁵ may be different or the same, but at least two hydrogen atoms or A carbon-carbon double bond having reactivity with SiH groups is included, and n represents an integer of 2 to 10.). R ²⁵ in the general formula (VI) is preferably hydrogen or an organic group having 1 to 6 carbon atoms composed of C, H, and O, and among the organic groups, a hydrocarbon having 1 to 6 carbon atoms. And more preferably an alkyl group having 1 to 6 carbon atoms. N is preferably an integer of 3 to 10.

Preferred examples of these R ²³ , R ²⁴ and R ²⁵ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, vinyl group, allyl group, glycidyl. Group, acryloyl group and the like.

When a compound having an alkoxy group or a hydroxyl group is used as the silicone compound, there is a risk of white turbidity when the cured product is exposed under high humidity conditions, or the adhesion to the substrate tends to be high.

Further, from the viewpoint of compatibility with other components contained in the curable composition, the viscosity of the component (D) at 23 ° C. is preferably 0.001 to 5.0 Pa · s, and 0.003 to 4 More preferably, it is 0.000 Pa · s.
The number average molecular weight in terms of polystyrene measured by GPC as the component (D) is preferably 300 to 30,000. More preferably, it is 300 to 20000, and most preferably 300 to 15000.

In order to suppress the appearance of the obtained cured product, in particular, foaming due to volatile matter or the like, the component (D) preferably has a weight loss of less than 10% after heating at 100 ° C. for 1 minute in a thermogravimetric apparatus. . More preferably, it is less than 5%.

Moreover, it is preferable to use the material in the said range in order to suppress volatilization of (D) component at the time of hardening from a viewpoint of transparency and refractive index of the hardened | cured material obtained.

As the component (D), a linear silicone is preferable from the viewpoint of releasability of a cured product. For example, a linear dimethyl silicone (DMS-V00, DMS-V03, DMS-V05, DMS-V21 manufactured by Gelest) , DMS-H03, DMS-H21, etc.), methylhydrosiloxane-dimethylsiloxane copolymer (HMS-031, HMS-151, HMS-301, etc. manufactured by Gelest), diphenylsiloxane-dimethylsiloxane copolymer (PDV-1625, manufactured by Gelest) PDV-1631, PDV-2331, PDV-2335, etc.) and vinyl-terminated cyclic dimethyl silicone (LS-8670 manufactured by Shin-Etsu Chemical Co., Ltd.).

From the viewpoint of heat resistance and low linear expansion, linear silicones and cyclic siloxanes having a plurality of SiH groups in one molecule are preferable. For example, methyl H siloxane-dimethylsiloxane copolymer (HMS manufactured by Gelest Co., Ltd.) is used as the linear silicone. -031, HMS-151, HMS-301, etc.), and examples of the cyclic siloxane include LS-8600, LS-8670, LS-8990 and the like manufactured by Shin-Etsu Chemical Co., Ltd.

Component (D) is added in an amount of 0.005 to 10 parts by weight, preferably 0.03 to 5 parts by weight, particularly 100 parts by weight of the total weight of components (A) and (B). 0.1 to 3.5 parts by weight are preferred. When the amount is less than 0.005 parts by weight, there is a problem that sufficient releasability from the substrate cannot be ensured or curing unevenness due to a rapid curing reaction occurs. When the amount is more than 10 parts by weight, there are problems that bleed out or surface hardness decreases. In either case, there is a problem that the birefringence of the cured product is increased.
In view of the linear expansion coefficient, the amount is preferably 0.005 to 2.5 parts by weight.

In the present invention, the linear expansion coefficient tends to increase by using the component (D), but by using a specific amount of the component (D), the linear expansion coefficient is kept within a practically acceptable range, and a complex amount is obtained. It can be made into the composition from which the hardened | cured material with low refraction is obtained. Moreover, the mold release property of hardened | cured material can also be improved.

(Curable composition)
The ratio of the component (A) to the component (B) in the curable composition is [number of moles of carbon-carbon double bond having reactivity with the SiH group of the component (A) in the curable composition / The value of the number of moles of SiH groups in the component (B) in the curable composition] is preferably a ratio that is in the range of 0.05 and 10 to the lower limit, and is 0.1 and 5 in the upper limit. A ratio is more preferable. Furthermore, it is more preferable that the ratio is in a range of a lower limit of 0.3 and an upper limit of 2.5. If it is smaller than 0.05, the effect of crosslinking due to the reaction between the carbon-carbon double bond and the SiH group tends to be insufficient, and if it is larger than 10, unreacted component (A) is bleed from the cured product. Tend to come.

From the viewpoint of heat resistance and light discoloration resistance of the cured product, the ratio is preferably 1.5 or less. If it is larger than 1.5, coloring after the environmental test may become large.

The addition amount of the hydrosilylation catalyst of the component (C) in the curable composition is not particularly limited, but in order to impart sufficient curability, the lower limit is 10 ^{− with} respect to 1 mol of the SiH group of the component (A). ¹⁰ mol, more preferably ^{10 -8} mole, in order to reduce the cost of the curable composition, per mole of the SiH group of component (a), the upper limit is ^{10 -2} mol, more preferably 10 ^- The range is ³ moles.

The catalyst does not necessarily need to be added if the remaining amount used at the synthesis of the component (B) shows sufficient curability, but is newly added in the above range in order to adjust curability. It can also be added.

(Other additives)
A curing retarder can be used for the purpose of improving the storage stability of the composition of the present invention 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 compound, and an organic peroxide. These may be used alone or in combination of two or more.

Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. 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 nitrogen-containing compounds 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-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and tert-butyl perbenzoate.

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

Amount of the curing retarder, towards hydrosilylation catalyst 1 mole to be used, the lower limit 10 ^-1 mol, the range of the upper limit 10 ³ moles and preferably, more preferably the lower limit 1 mol, the range of the upper limit 50 mol.

Next, various resins that can be added for the purpose of modifying the characteristics of the curable composition of the present invention will be described. Examples of the resin include polycarbonate resin, polyethersulfone resin, polyarylate resin, epoxy resin, cyanate resin, phenol resin, acrylic resin, polyimide resin, polyvinyl acetal resin, urethane resin, polyester resin, and the like. It is not limited.

You may add an inorganic filler to the curable composition of this invention as needed. Addition of an inorganic filler is effective in increasing the strength of the material and improving flame retardancy. The inorganic filler is preferably in the form of fine particles, and examples thereof include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, talc, barium sulfate, and phosphor. .

Examples of the method for adding the filler include hydrolyzable silane monomers or oligomers such as alkoxysilanes, acyloxysilanes, and halogenated silanes, and metal alkoxides, acyloxides, and halides such as titanium and aluminum. Examples of the method include adding to the curable composition and reacting in the composition or a partial reaction product of the composition to form an inorganic filler in the composition.

You may add antioxidant to the curable composition obtained by 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. Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, 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.

You may add a radical inhibitor to the curable composition obtained by this invention. Examples of radical inhibitors 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′-secondarybutyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine.
Moreover, these radical inhibitors may be used alone or in combination of two or more.

You may add a ultraviolet absorber to the curable composition obtained by this 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.

The curable composition of the present invention includes other flame retardants, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, ion trapping agents such as antimony-bismuth, thixotropic agents, and tackifiers. , Ozone degradation inhibitor, light stabilizer, thickener, plasticizer, antioxidant, heat stabilizer, processing stabilizer, reactive diluent, antistatic agent, radiation blocker, nucleating agent, phosphorus peroxide Decomposing agents, lubricants, pigments, metal deactivators, adhesion-imparting agents, physical property modifiers and the like can be added as long as the object and effect of the present invention are not impaired.

The curable composition of this invention is obtained by mixing said each component.

Moreover, it does not specifically limit as a method of hardening the curable composition of this invention, It can also make it react only by mixing each component, It can also make it react by heating. From the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained, a method of heating and reacting is preferable.

Although various reaction temperatures can be set, a temperature range with a lower limit of 25 ° C. and an upper limit of 300 ° C. is preferred, a lower limit of 50 ° C. and an upper limit of 280 ° C. are more preferred, and a lower limit of 100 ° C. and an upper limit of 260 ° C. are even more preferred. When the temperature is lower than 25 ° C., the reaction time for sufficiently reacting tends to be long. When the temperature is higher than 300 ° C., the product tends to be thermally deteriorated.

The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than carrying out the reaction at a constant temperature, the reaction is preferably carried out while raising the temperature in a multistage manner or continuously in that a uniform cured product without distortion can be easily obtained.

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.

(Cured product)
The cured product obtained by curing the curable composition of the present invention is transparent, and the transmittance is well maintained even in the ultraviolet region. Specifically, it is possible to obtain a cured product having a thickness of 3 mm and a light transmittance of 60% or more at a wavelength of 400 nm. The light transmittance is preferably 70% or more, and more preferably 80% or more.

Furthermore, even if this cured product is heat-treated, the change in light transmittance at a wavelength of 400 nm is extremely small. Specifically, the light transmittance at a wavelength of 400 nm after heat treatment at 280 ° C. for 3 minutes in the atmosphere is 60% or more, and the light transmittance change can be maintained at 10% or less. The light transmittance after heating is preferably 70% or more, and more preferably 80% or more. The change in light transmittance is preferably 5% or less. Thus, the cured product of the present invention has solder reflow resistance. In addition, such high heat resistance can increase the degree of freedom of design and application destinations of optical semiconductors, modules, and optical components.

The cured product obtained by curing the curable composition of the present invention has a small birefringence. The birefringence amount is preferably less than 200 nm, and more preferably less than 100 nm.

The cured product obtained by curing the curable composition of the present invention has a small coefficient of linear expansion. For example, it is possible to obtain a cured product having a linear expansion coefficient at 30 ° C. of 150 ppm / K or less, 150 ppm at 200 ppm / K or less, preferably 185 ppm / K or less. In this way, a cured product with a low coefficient of linear expansion that does not cause a practical problem and a low birefringence can be obtained, so there is little deviation in focus and aberration due to the temperature of the optical component, and the thermal history when the component is fixed Can be reduced in thermal shock and has excellent characteristics for optical components.

Some parts require various coatings such as AR coating. At this time, if the linear expansion coefficient at a high temperature is large, the coating process may restrict the thermal process, which may complicate the process or prevent the coating process. However, the composition according to the present invention is used. The cured product can improve these problems.

The cured product obtained by curing the composition of the present invention has a JIS K6253 type D durometer hardness (Shore D) of 30 or more at 25 ° C., preferably 50 or more, more preferably 55 or more, and still more preferably. It is possible to obtain more than 60. Since the Shore D hardness is high, there is an advantage that there is mechanical strength, the surface is hardly scratched, and dust is difficult to adhere. Furthermore, since mechanical processing such as a cutter or a drill is possible, a complicated shape can be given or corrected after the optical component molding.

The glass transition temperature of the cured product obtained by curing the composition of the present invention is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 120 ° C. or higher. As an optical component, optical characteristics and dimensional accuracy largely change in the vicinity of the glass transition point. If the temperature is less than 60 ° C., the usable temperature range of the obtained molded product tends to be narrowed.

The hardened | cured material obtained by hardening the composition of this invention shows the outstanding mold release property with respect to a base material. It does not specifically limit as a base material, Raw materials, such as metal steel materials and glass used for general plastic molding, are mentioned. On these materials, a material processed by plating such as Cr or Ni or special plating containing fluorine can be used as a mold.

The optical material referred to in the present invention refers to general materials used for applications in which light such as visible light, infrared light, ultraviolet light, X-rays, and laser passes through the material.

The optical material can have various shapes such as a thin film such as a film or a sheet or a bulk material such as a lens or a prism. Applications include optical members such as light guide plates and antireflection films, optical components such as lenses and prisms, and optical semiconductor modules. More specifically, for example, various lenses and prisms used in cameras (steel cameras, digital cameras, security cameras, mobile phone cameras, in-vehicle cameras, etc.), optical measuring devices, optical memory equipment, etc. Examples thereof include various transparent films and sheets such as a sealant, a light guide plate, an antireflection film, a prism sheet, and a deflection plate, and optical semiconductor modules such as LEDs and light receiving elements. Two or more kinds of cured products obtained from the composition for optical materials of the present invention can be used in combination. In particular, in applications where the demand for chromatic aberration is severe, it is necessary to combine a material having a high Abbe number and a material having a low Abbe number. It can be suitably applied to. Examples of the application include an imaging lens unit.

In addition, when these parts are used, there is solder reflow resistance, so that the number of methods that can be applied when assembling the module increases. By devising the construction method, it can be economically advantageous.

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

(NMR)
A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used.
(B) The reaction rate of the allyl group in the component synthesis was measured by adding the reaction solution diluted to about 1% with deuterated chloroform to the NMR tube, the peak of the methylene group derived from the unreacted allyl group, and the reaction. It calculated | required from the peak of the methylene group derived from an allyl group. The reaction rate of the vinyl group was measured by adding a reaction solution diluted to about 1% with deuterated chloroform to an NMR tube. The peak of the CH group derived from the unreacted carbon-carbon double bond and the reaction Si— It was determined from the peak of the C—H group derived from the C bond. As the functional group value of the SiH group-containing compound as the reaction product, the SiH group value (mmol / g) in terms of 1,2-dibromoethane was obtained.

(viscosity)
An E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used. Measurement was performed at a measurement temperature of 23 ° C. using an EHD type 48φ cone.

(Weight reduction rate)
Shimadzu Corporation DTG50H was used. After increasing the temperature from room temperature to 100 ° C. under a temperature of 20 ° C./min under a nitrogen flow (50 ml / min) under a sample amount of 11 ± 1 mg, the weight loss rate after holding at 100 ° C. for 1 minute was determined.

(Synthesis Example 1)
To a 2 L autoclave, 696 g of toluene, 556 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated to an internal temperature of 104 ° C. A mixture of 80 g of triallyl isocyanurate, xylene solution of platinum vinylsiloxane complex (PTVTS-C-3.0X, produced by Umicore Precious Metals, 3 wt% as platinum) and 60 g of toluene was added dropwise. The mixture was heated and stirred for an hour. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure at 80 ° C. and 0.4 kPa.

^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with triallyl isocyanurate (referred to as B1, SiH value: 9.4 mmol / g) I found out that Although the product was a mixture, it contained as a main component the following (B) component of the present invention. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention was contained.

(Synthesis Example 2)
To a 2 L autoclave, 700 g of toluene, 470 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated so that the internal temperature became 105 ° C. Thereto, a mixture of 52 g of bis [4- (2-allyloxy) phenyl] sulfone, 0.06 g of platinum vinylsiloxane complex in xylene (containing 3 wt% as platinum) and 15 g of toluene was dropped, and heated and stirred for 8 hours. . During the dropping, the internal temperature rose to 110 ° C. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene and xylene were distilled off under reduced pressure at 80 ° C. and 0.4 kPa. ^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with bis [4- (2-allyloxy) phenyl] sulfone (referred to as B2, SiH Value: 6.3 mmol / g). Although the product was a mixture, it contained as a main component the following (B) component of the present invention. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention was contained.

(Synthesis Example 3)
To a 2 L four-necked eggplant flask, 600 g of toluene, 600 g of 1,3,5,7-tetramethylcyclotetrasiloxane was added and heated so that the internal temperature was 90 ° C. Thereto was added dropwise a mixture of 73.5 g of divinylbenzene, 0.003 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 73.2 g of toluene. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{According to 1} H-NMR, this is a product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with divinylbenzene (referred to as B3, SiH value: 9.0 mmol / g). I understood it. Although the product was a mixture, it contained as a main component the following (B) component of the present invention. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention was contained.

(Synthesis Example 4)
To a 2 L autoclave was added 600 g of toluene, 360 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the mixture was heated to an internal temperature of 108 ° C. A mixture of 35 g of 5-vinyl 2-norbornene, 0.01 g of a platinum vinylsiloxane complex in xylene (containing 3 wt% as platinum) and 300 g of toluene was added dropwise, and the mixture was heated and stirred for 4 hours. During the dropping, the internal temperature rose to 110 ° C. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene and xylene were distilled off under reduced pressure at 80 ° C. and 0.1 kPa. ^{According to 1} H-NMR, this is a product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with vinylnorbornene (referred to as B4, SiH value: 8.0 mmol / g). I understood it. Although the product was a mixture, it contained as a main component the following (B) component of the present invention. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention was contained.

(Examples 1 to 11 and Comparative Examples 1 to 4)
Blended according to Table 1 below. Triallyl isocyanurate, divinylbenzene, vinylnorbornene, polybutadiene (RICON-130 manufactured by SARTOMER, polystyrene equivalent molecular weight 4600 to 10000) as the component (A), and the synthesized products of Synthesis Examples 1 to 4 are used as the component (B). C) A xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) was used as component (C), and DMS-V05 (vinyl group-terminated linear dimethyl silicone, manufactured by Gelest) was used as component (D) at 23 ° C. Viscosity 6 mPa · s, polystyrene conversion molecular weight 2200, weight reduction rate 4%), DMS-H03 (SiH group-terminated linear dimethyl silicone, viscosity at 23 ° C. 4 mPa · s, polystyrene conversion molecular weight 2100, weight reduction rate 5%) PDV-2331 (Vinyl-terminated linear dimethyl) Diphenyl silicone, viscosity 1 Pa · s at 23 ° C., polystyrene equivalent molecular weight 12000, weight loss 1%, LS-8670 manufactured by Shin-Etsu Chemical Co., Ltd. (vinyl-terminated cyclic dimethyl silicone, viscosity 3 mPa · s at 23 ° C., polystyrene equivalent) X-22-2475 manufactured by Shin-Etsu Chemical Co., Ltd. was used as a monofunctional polyorganosiloxane instead of the component (D). In addition, Irganox 1010 as an anti-aging agent, a xylene solution of a platinum-vinylsiloxane complex as a hydrosilylation catalyst, and 1-ethynyl-1-cyclohexanol as a curing retarder were used in the blending ratio (weight) shown in Table 1. A curable composition was prepared.

A mixture obtained by stirring and defoaming was used as a curable composition. This curable composition was poured into a cell prepared by sandwiching a 3 mm-thick silicone rubber sheet as a spacer between two glass plates, and a cured product was obtained by applying heat up to 180 ° C.

About each obtained hardened | cured material, the transparency, heat resistance, glass transition temperature, linear expansion coefficient, hardness test, mold release property, and birefringence of hardened | cured material were measured by the test method described below.

(Transparency of cured product)
The obtained cured product (3 mm thick) was measured for light transmittance at 400 nm (referred to as “initial transmittance”) with a spectrophotometer (Hitachi spectrophotometer U-3300).

(Heat resistance test)
The cured product was sandwiched between glasses heated to 280 ° C. for 3 minutes to conduct a heat resistance test. For the cured product after the heat resistance test, the light transmittance at 400 nm was measured with a spectrophotometer (Hitachi spectrophotometer U-3300) (referred to as “transmission after heat resistance test”), and the cured product heat resistance according to the following formula The transmittance (change in light transmittance) after the test was derived.
[Transmissivity after heat resistance test of cured product] (%) = [Initial transmittance] (% T) − [Transmittance after heat resistance test] (% T)

(Glass-transition temperature)
A test piece of 30 mm × 5 mm × 3 mm is cut out from the cured product, and a tensile mode, a measurement frequency of 10 Hz, a strain of 0.1%, a static / power ratio of 1.5, and a temperature rise using DVA-200 manufactured by IT Measurement & Control Co., Ltd. Dynamic viscoelasticity measurement was performed under the condition of a lateral degree of 5 ° C./min. The peak temperature of tan δ was taken as the glass transition temperature of the cured product. When there is no clear peak, it is described as ND.

(Linear expansion coefficient)
A test piece of 5 mm × 5 mm × 3 mm was cut out from the cured product, and a thermomechanical analysis measurement was performed using a ThermoPlus TMA8310 manufactured by Rigaku Corporation under conditions of a compression mode and a temperature rising side degree of 10 ° C./min. The linear expansion coefficient was determined from the expansion ratio at 30-40 ° C.

(Hardness test)
The cured product was placed on a blue glass, and the hardness (Shore D) at 25 ° C. was measured with a type D durometer according to JIS K6253.

(Releasability test)
The curable composition was put in an iron ointment can and a glass cell not coated with an external mold release agent, cured under the same curing conditions as in the above examples, and it was examined whether the cured product could be taken out. Those that were peeled off from the substrate after curing were marked with ◎, those that peeled off from the substrate when applied with force were marked with ◯, and those that were not peeled off from the substrate with x.

(Birefringence determination)
A 50 × 50 × 3 mm test piece was cut out and measured several times using a KOBRA-CCD manufactured by Oji Scientific Instruments, and the birefringence of the entire 50 × 50 mm was measured. Those having a birefringence amount of 200 nm or more were evaluated as “x” assuming that there was uneven curing or striae, “Δ” from 100 nm to less than 200 nm, and “◯” as less than 100 nm.

The data measured and evaluated under the above conditions are summarized in Table 1.

A cured product using the curable composition of the present invention has optical transparency, heat discoloration resistance, a low linear expansion coefficient, excellent releasability, and low birefringence.

Claims (19)

1. (A) an organic compound having a number average molecular weight of 10,000 or less, containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule;
   (B) a polysiloxane compound containing at least two SiH groups in one molecule, obtained by reacting a bifunctional or higher organic compound with a polysiloxane compound;
   (C) a hydrosilylation catalyst, and
   (D) The following general formula:
   R ¹ _n SiO _{(4-n) / 2}
   (R ¹ is hydrogen or a monovalent organic group having 1 to 50 carbon atoms, which may be substituted with oxygen, nitrogen, sulfur or halogen atoms, and each R ¹ may be different or the same. N may be an integer from 1 to 3.)
   And a silicone compound having a carbon-carbon double bond having at least two SiH groups and / or reactivity with SiH groups in one molecule, (A) component and (B) A curable composition for optical materials, containing 0.005 to 10 parts by weight with respect to 100 parts by weight as a total of the components.
2. The curable composition for optical materials according to claim 1, wherein the viscosity of component (D) at 23 ° C is 0.001 to 5.0 Pa · s.
3. The curable composition for optical materials according to claim 1 or 2, wherein the number average molecular weight in terms of polystyrene measured by gel permeation chromatography of component (D) is 300 to 30,000.
4. The curable composition for optical materials according to any one of claims 1 to 3, wherein the component (D) has a weight loss of less than 10% after heating at 100 ° C for 1 minute in a thermogravimetric apparatus.
5. (B) component is the following general formula (I):
   

   

   (Wherein R ² is a monovalent organic group having 1 to 50 carbon atoms, and may be substituted with oxygen, nitrogen, sulfur, or halogen atoms. Each R ² may be different or the same. May be.)
   The curable composition for optical materials according to any one of claims 1 to 4, which is obtained from a bifunctional or higher functional organic compound represented by the formula:
6. (B) component is the following general formula (II):
   

   

   (Wherein R ³ is a monovalent organic group having 1 to 50 carbon atoms and may be substituted with an oxygen, nitrogen, sulfur, or halogen atom. Each R ³ may be different or the same. May be.)
   The curable composition for optical materials according to any one of claims 1 to 4, which is obtained from a bifunctional or higher functional organic compound represented by the formula:
7. The curable composition for optical materials according to any one of claims 1 to 4, wherein the component (B) is obtained from a bifunctional or higher functional aliphatic hydrocarbon compound having a cyclic structure.
8. The curable composition for optical materials according to any one of claims 1 to 7, wherein the component (A) is an aliphatic hydrocarbon compound having a cyclic structure.
9. The component (A) is represented by the following general formula (I):
   

   

   (Wherein R ² is a monovalent organic group having 1 to 50 carbon atoms, and may be substituted with oxygen, nitrogen, sulfur, or halogen atoms. Each R ² may be different or the same. May be.)
   And a compound represented by the following general formula (II):
   

   

   (Wherein R ³ is a monovalent organic group having 1 to 50 carbon atoms and may be substituted with an oxygen, nitrogen, sulfur, or halogen atom. Each R ³ may be different or the same. May be.)
   The curable composition for optical materials according to any one of claims 1 to 7, wherein the curable composition for an optical material is at least one selected from the group consisting of compounds represented by:
10. Component (A) is triallyl isocyanurate, diallyl monoglycidyl isocyanurate, divinylbenzene, bisphenol A diallyl ether, bisphenol S diallyl ether, polybutadiene, vinylnorbornene, vinylcyclohexene, and 1,4,6-trivinylcyclohexane. The curable composition for optical materials according to any one of claims 1 to 7, wherein the curable composition for optical materials is at least one selected from the group consisting of:
11. The optical material according to any one of claims 1 to 10, wherein the component (A) contains at least 0.4 mmol of carbon-carbon double bonds having reactivity with SiH groups per gram of component (A). Curable composition.
12. The curable composition for optical materials according to any one of claims 1 to 11, wherein a cured product (3 mm thick) has a light transmittance of 60% or more at a wavelength of 400 nm.
13. The cured product (3 mm thick) is obtained by giving a cured product having a light transmittance of 60% or more at a wavelength of 400 nm after heat treatment at 280 ° C for 3 minutes in the atmosphere. The curable composition for optical materials described in 1.
14. The curable composition for optical materials according to any one of claims 1 to 13, which gives a cured product having a Shore D hardness of 30 or more at 25 ° C.
15. The curable composition for optical materials according to any one of claims 1 to 14, which gives a cured product having a linear expansion coefficient at 30 ° C of 150 ppm / K or less.
16. A transparent cured product obtained by curing the curable composition for optical materials according to any one of claims 1 to 15.
17. An optical member using the transparent cured product according to claim 16.
18. An optical component using the transparent cured product according to claim 16.
19. An optical semiconductor module using the transparent cured product according to claim 16.