JP2012107114A - Curable composition for optical material and cured material of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition for optical material providing a cured material which has high heat resistance and transparency, has a satisfactory molding property and appearance, and does not cause distortion, and to provide the cured material of the curable composition for optical material.SOLUTION: The curable composition for optical material has, as indispensable components: an organic compound which contains at least two carbon-carbon double bonds having reactivity with SiH group in one molecule; a compound which contains at least two SiH groups in one molecule; a hydrosilylation catalyst; and acetylene alcohols as a (D) component; wherein the rate of weight decrease at 100°C of the (D) component is 10% or less.

Description

  The object of the present invention is a curable composition for optical materials that can be filled at high temperature, can be molded by short-time curing, has high heat resistance and transparency, has a good appearance, and has a reduced birefringence variation. Product and cured product.

  In general, high transparency and hardness are required for polymer materials for optical materials such as camera lenses and optical fibers attached to digital cameras and mobile phones. Acrylic resins, polycarbonate resins, cycloolefin resins, etc. Thermoplastic resins have been used. In recent years, for the purpose of miniaturization and cost reduction, a method of manufacturing a lens unit and a light receiving sensor unit in a batch by a solder reflow process is being introduced. However, a temperature history exceeding 250 degrees may be applied, and it has been used so far. There has been a limit in the thermoplastic resins that have been developed, and thermosetting resins with high heat resistance have attracted attention. For example, thermosetting resin compositions containing a siloxane skeleton with excellent heat discoloration have been proposed. (Patent Document 1).

  In the molding of lenses, the uniformity of optical properties such as birefringence is important, and it is required to be cured uniformly. However, when molding is performed isothermally using the resin composition described in Patent Document 1, birefringence variations are likely to occur.

  Moreover, in the molding of the thermosetting resin, a molding method in which the temperature at the time of filling is lowered from the curing temperature, that is, the temperature is raised and cooled may be taken (Patent Document 2). In the molding method in which the temperature is raised and cooled, it is desirable that the difference between the filling temperature and the curing temperature is small from the viewpoint of molding cycle time. However, the resin composition described in Patent Document 1 has room for improvement because it cures quickly at a low temperature and the filling temperature is low.

JP 2009-84437 A JP 2010-89293

  The object of the present invention is a curable composition for optical materials that can be filled at high temperature, can be molded by short-time curing, has high heat resistance and transparency, has a good appearance, and has a reduced birefringence variation. It is in providing a thing and a hardened | cured material.

  In view of the above circumstances, as a result of extensive studies by the present inventors, the present invention has the following configuration.

That is, the present invention
1). (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) hydrosilyl And (D) the following general formula (I):

(Wherein R ¹ is an alkyl group or an aryl group, and each R ¹ may be connected; R ² is a hydrogen group, an alkyl group or an aryl group) A curable composition for optical materials, wherein the molecular weight of component (D) is 130 or more.

2). The curable composition for optical materials according to 1), wherein R ² in the general formula (I) is a hydrogen group.

  3). (D) The curable composition for optical materials according to any one of 1) to 2), wherein the weight loss rate of the component at 100 ° C. is within 10%.

  4). (D) The component is at least one compound selected from 2-phenyl-3-butyn-2-ol and 3,7,11-trimethyl-1-dodecyn-3-ol 1) to 3) The curable composition for optical materials as described in any one.

  5). (A) The curable composition for optical materials according to 1), wherein the component contains 1 mmol or more of carbon-carbon double bonds having reactivity with SiH groups per 1 g of component (A).

  6). (B) The curable composition for molding optical materials according to 1), wherein the component is a compound containing a linear and / or cyclic polysiloxane skeleton.

  7). The curable composition for optical materials according to any one of 1) to 6), further comprising an anti-aging agent.

  8). The curable composition for optical materials according to any one of 1) to 7), which comprises a release agent.

  9). Hardened | cured material formed by hardening | curing the curable composition in any one of 1) -8).

  10). 9) An optical component using the cured product described in 9).

  11). An optical module using the optical component according to 10).

  According to the present invention, the curability for optical materials that can be filled at a high temperature, can be molded in a short time, has high heat resistance and transparency, has a good appearance, and has a small birefringence variation. It is possible to provide a composition.

  Hereinafter, the present invention will be described in detail.

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

  First, a group having a carbon-carbon double bond reactive with the SiH group will be described. The carbon-carbon double bond of the component (A) is not particularly limited as long as it has reactivity with the SiH group, but the carbon-carbon double bond represented by the following general formula (II) is reactive. Is preferred.

(In the formula, R ³ represents a hydrogen atom or a methyl group.) From the viewpoint of availability of raw materials, R ³ is more preferably a hydrogen atom.

  General formula (III) is suitable from the point that the heat resistance of hardened | cured material is high.

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and each R ⁴ may be different or the same.) From the viewpoint of availability of raw materials, R ⁴ should be a hydrogen atom. Is more preferable.

  The carbon-carbon double bond may be covalently bonded to the skeleton of the component (A) via a substituent, and the substituent is selected from C, H, N, O, S and halogen as constituent elements. Those containing only atoms are preferred. The following are mentioned as an example of a substituent.

  Two or more of these substituents may be connected by a covalent bond to form a substituent.

  Examples of the group covalently bonded to the skeleton as described above include 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 (allyl) Examples include oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group, and those shown below.

  Next, the organic skeleton part will be described. The organic skeleton of the component (A) is not particularly limited, and an organic polymer skeleton or an organic monomer skeleton may be used.

  Examples of organic polymer skeletons include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, poly (meth) acrylate, polyamide, phenol-formaldehyde (Phenol resin type), polyimide type and the like.

  In particular, polyesters, polycarbonates, and poly (meth) acrylic acid esters are preferable from the viewpoint of heat resistance and transparency.

  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 and vinylcyclohexene, 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 mono Ricidyl 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%), divinyl Biphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene,

Etc.

  As the above-mentioned component (A), from the viewpoint that the heat resistance can be further improved, a component containing 0.1 mmol or more of carbon-carbon double bond having reactivity with SiH group per 1 g of component (A) is preferable. Furthermore, what contains 0.5 mmol or more per 1g is preferable, and what contains 1 mmol or more is especially preferable.

  The number of carbon-carbon double bonds having reactivity with the SiH group of component (A) should be on average at least two per molecule, but may exceed 2 if it is desired to further improve the mechanical strength. Preferably, it 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, only a graft structure is formed even if it reacts with component (B). Don't be.

  From the viewpoint of high mechanical heat resistance and from the viewpoint of low stringiness of the raw material liquid and good moldability, handleability and filling properties, the component (A) preferably has a molecular weight of less than 900, and less than 700 Are more preferred, and those less than 500 are even more preferred.

  In order to obtain good workability, the component (A) preferably has a viscosity at 23 ° C. of less than 100 Pa · s, more preferably less than 50 Pa · s, and even more preferably less than 30 Pa · s. The viscosity here refers to a value measured by an E-type viscometer.

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

  From the viewpoint that the resulting cured product is less colored and has high light resistance, the component (A) is vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, tris (2-acryloyloxyethyl). Preferred isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane, triallyl isocyanurate, diallyl of 2,2-bis (4-hydroxycyclohexyl) propane Ether and 1,2,4-trivinylcyclohexane are particularly preferred.

  In particular, as the component (A), an isocyanuric acid derivative represented by the following general formula (IV) is particularly preferable from the viewpoint of high heat discoloration.

(Wherein R ⁵ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ⁵ may be different or the same).

R ^{5 in the} general formula (IV) is preferably a monovalent organic group having 1 to 30 carbon atoms from the viewpoint that the heat resistance of the resulting cured product can be further increased. 20 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 10 carbon atoms are even more preferable. Examples of these preferable R ⁵ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group and the like.

  Preferred examples of the compound represented by the above general formula (IV) include triallyl isocyanurate, trimethallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monophenyl isocyanate. And nurate, tris (2-acryloyloxyethyl) isocyanurate, and the like.

  From the viewpoint of high heat distortion resistance and high refractive index, as the component (A), divinylbenzenes represented by the following general formula (V), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-di Some or all of glycidyl groups bonded to aromatic ring-containing epoxy resins such as isopropenylbenzene, oligomers thereof, bisphenol A diallyl ether, bis [4- (2-allyloxy) phenyl] sulfone, and phenol novolac resins Those substituted with an allyl group are preferred.

(In the formula, R ⁶ represents an organic group which may be substituted with monovalent oxygen, nitrogen, sulfur or halogen atom having 1 to 50 carbon atoms, and each R ⁶ may be different or the same. It is good.)

R ^{6 in the} general formula (V) preferably has a plurality of aromatic rings from the viewpoint that the resulting cured product can have higher heat resistance.
From the viewpoint of high light resistance, the (A) component is preferably an alicyclic compound. Specific examples include vinylcyclohexene, dicyclopentadiene, 1,2,4-trivinylcyclohexane, vinyl norbornene, and the like.
(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) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. For example, chain polyorganosiloxane, cyclic polyorganosiloxane, network polyorganosiloxane, polyorganosiloxane and organic A product obtained by partially reacting a compound can be used.

  From the viewpoint of high hardness of the cured product, it preferably contains a chain polyorganosiloxane and / or a cyclic polyorganosiloxane skeleton.

  Specific examples of the chain polyorganosiloxane include the following general formula (VI):

(In the formula, each of R ⁷ and R ⁸ represents hydrogen or a monovalent organic group having 1 to 50 carbon atoms, and each of R ⁷ and R ⁸ may be different or the same, 2 represents hydrogen, and n represents a number of 1 to 1000).
R ⁷ and R ⁸ are each preferably a monovalent organic group having 1 to 20 carbon atoms, and monovalent having 1 to 15 carbon atoms from the viewpoint that the heat resistance of the resulting cured product can be higher. The organic group is more preferably a monovalent organic group having 1 to 10 carbon atoms. Examples of these preferable R ⁷ and R ⁸ 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.

  Examples of the cyclic polyorganosiloxane include the following general formula (VII):

(Wherein R ⁹ represents hydrogen or an organic group having 1 to 6 carbon atoms, and each R ⁹ may be different or the same, but at least two are hydrogen. N is 2 to 10) And a cyclic polyorganosiloxane having at least two SiH groups in one molecule. Note that R ⁹ in the general formula (VII) 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. preferable. R ⁷ is particularly preferably a methyl group from the viewpoint of availability and heat resistance, and particularly preferably a phenyl group from the viewpoint of increasing the strength of the cured product. N is preferably a number of 3 to 10.

  Preferable specific examples of the cyclic polyorganosiloxane represented by the general formula (VII) include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 , 7,9-pentamethylcyclopentasiloxane and the like.

  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 3000.

  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 reduce the volatility of the component (B) is less likely to occur, the component (B) is a SiH group. Hydrosilylation of an organic compound (B1) containing at least one carbon-carbon double bond having reactivity with a polyorganosiloxane (B2) having at least two SiH groups in one molecule A compound that can be obtained by reaction is preferred.

((B1) component)
The component (B1) is an organic compound containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule. As the component (B1), the same component (B11) as the component (A) described above, which is the same as the organic compound containing at least two carbon-carbon double bonds reactive with the SiH group in one molecule is used. Can do. When the component (B11) is used, the resulting cured product has a high crosslink density and tends to be a cured product having high mechanical strength.

  In addition, an organic compound (B12) containing one carbon-carbon double bond having reactivity with the SiH group in one molecule can also be used. When the component (B12) is used, the obtained cured product tends to have low elasticity.

  The bonding position of the carbon-carbon double bond having reactivity with the SiH group of the component (B12) is not particularly limited, and may be present anywhere in the molecule. Further, the carbon-carbon double bond having reactivity with the SiB group of the component (B12) is not particularly limited, but the functional group described in the component (A) is preferable.

  The compound of the component (B12) can be classified into a polymer compound and a monomer compound, and each skeleton is preferably the skeleton explained in the component (A).

  From the viewpoint of high heat discoloration, the above-described general formula (IV) is used as the component (B1).

A compound having the following skeleton is preferred.
From the viewpoint of a high refractive index, the general formula (V) described above is used as the component (B1).

  A compound having the following skeleton is preferred.

From the viewpoint of high light resistance, an alicyclic compound is preferred as the component (B1).
(B1) A component can be used individually or in mixture of 2 or more types.

((B2) component)
The component (B2) is not particularly limited as long as it is a polyorganosiloxane containing at least two SiH groups in one molecule. Specific examples of each compound include those described for the component (B).
(B2) A component can be used individually or in mixture of 2 or more types.

(Preliminary reaction)
Reacting an organic compound (B1) component containing at least one carbon-carbon double bond in one molecule with a polyorganosiloxane (B2) component having at least two SiH groups in one molecule (B) A reaction for obtaining a compound containing at least two SiH groups in one molecule as a component will be described.

  When the (B1) component and the (B2) component are subjected to a hydrosilylation reaction, the mixing ratio of the (B1) component and the (B2) component is particularly limited as long as two or more SiH groups remain in one molecule. Not.

  When considering the strength of the resulting cured product, the number of moles (X) of carbon-carbon double bonds having reactivity with SiH groups in component (B1) and the number of moles of SiH groups in component (B2) The ratio with (Y) is preferably Y / X ≧ 2, and more preferably Y / X ≧ 3.

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

Although the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is sufficient with respect to 1 mol of SiH groups of the component (B2) in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ⁻¹⁰ mol, more preferably 10 ⁻⁸ mol, and the upper limit of the preferable addition amount is 10 ⁻¹ mol, more preferably 10 ⁻² mol, per 1 mol of SiH group of the component (B2).

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, amine compounds such as triethylamine, and the like. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst is 10 ⁻² 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 component (B1) mixed with a hydrosilylation catalyst is mixed with component (B2) is preferable. In some cases, it is difficult to control the reaction in the method of mixing the hydrosilylation catalyst with the mixture of the component (B1) and the component (B2). Further, in the method of mixing the component (B1) with the mixture of the component (B2) and the hydrosilylation catalyst, the component (B2) is reactive in the presence of the hydrosilylation catalyst, and therefore, changes in quality. Sometimes.

  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. Specific examples include 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 solvent and / or unreacted compound may be removed after the synthesis reaction. Examples of the removal method include 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.

  In order to improve storage stability, storage at 10 ° C. or lower is preferable in an inert gas atmosphere such as nitrogen or argon, storage at 0 ° C. or lower is particularly preferable, and storage at −10 ° C. or lower is further preferable. .

Examples of (B) obtained from the above reaction include a reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5, Reaction product of 7-tetramethylcyclotetrasiloxane, reaction product of monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, divinylbenzene and 1,3,5,7-tetramethylcyclotetra Reaction product of siloxane, reaction product of bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, bis [4- (2-allyloxy) phenyl] sulfone and 1,3,5,7-tetra More preferred is a reaction product of methylcyclotetrasiloxane.
(B) A 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 of component (C) is not particularly limited as long as it has catalytic activity for the hydrosilylation reaction. For example, platinum alone; solid platinum supported on a carrier such as alumina, silica, carbon black; Platinum acid; complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc .; platinum-olefin complex (for example, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ); Platinum-vinylsiloxane complex (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _a , Pt [(MeViSiO) ₄ ] _b ); 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 Til group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and a and b represent an integer.); Dicarbonyldichloroplatinum; Karlstedt catalyst; platinum-hydrocarbon complex (for example, Platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,662; platinum alcoholate catalysts (eg, described in US Pat. No. 3,220,972 of Lamoreaux). And platinum alcoholate 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.

The addition amount of the component (C) is not particularly limited, but the preferable lower limit of the addition amount is 1 mol of SiH groups of the component (B) in order to have sufficient curability and keep the cost of the curable composition relatively low. ^{10 -8} mol relative to, more preferably from ^{10 -7} moles, preferable amount of the upper limit is ^{10 -1} moles per mole of the SiH group in component (B), more preferably ^{10 -2} mol .

  In addition, a cocatalyst can be used in combination with the catalyst. Examples of the cocatalyst include a sulfur-based compound such as simple sulfur, and an amine-based compound such as triethylamine.

The addition amount of the cocatalyst is not particularly limited, but a lower limit of 10 ⁻² mol and an upper limit of 10 ² mol are preferable, and a lower limit of 10 ⁻¹ mol and an upper limit of 10 mol are preferable with respect to 1 mol of the hydrosilylation catalyst. It is.
((D) component)
Next, the component (D) will be described.

  Component (D) is represented by the following general formula (I)

(Wherein R ¹ is an alkyl group or an aryl group, and each R ¹ may be connected; R ² is a hydrogen group, an alkyl group or an aryl group), and a compound having a molecular weight of 130 or more It is. By using a compound having a molecular weight of 130 or more, curing at 110 ° C. or lower can be suppressed, filling can be performed at a high temperature, and a cured product with little variation in birefringence can be created in a short time.

  The component (D) is not particularly limited as long as it is suitable for the above conditions and is compatible with the resin, and 2-phenyl-3-butyn-2-ol, 3,7,11-trimethyl-1-dodecyne- 3-ol, 1,1-dicyclohexyl-2-propyn-1-ol, 1-tetradecin-3-ol, 1,1,1-trifluoro-2-phenyl-3-butyn-2-ol, 1 -(3,4-dimethoxyphenyl) -2-propyn-1-ol, 2- (2-fluorophenyl) -3-butyn-2-ol, 2- (3-fluorophenyl) -3-butyn-2- All, 2- (4-fluorophenyl) -3-butyn-2-ol and the like are exemplified.

From the viewpoint of storage stability at room temperature, R ² in formula (I) is preferably a hydrogen group.

  From the viewpoint of mold contamination during molding, the component (D) is preferably a compound having a weight reduction rate at 100 ° C. of within 10%. Here, the weight reduction rate is defined by the weight reduction rate when 25 ° C. is used as a reference when TGA measurement is performed by flowing nitrogen gas at 50 mL / min and raising the temperature at 10 ° C./min. When a compound having a weight reduction rate of more than 10% is used, the mold may be contaminated by volatile components during molding.

  From the viewpoint of compatibility with the resin, the component (D) is preferably liquid at 23 ° C. When a solid compound is used at 23 ° C., heating or long-time stirring may be required to dissolve it in the resin.

From the viewpoint of the amount added, R ¹ in formula (I) is preferably an aryl group. When R ¹ is an aryl group, the effect can be obtained even if the added part by weight is small. Preferred examples include 2-phenyl-3-butyn-2-ol, 2- (2-fluorophenyl) -3-butyn-2-ol, and 2- (3-fluorophenyl) -3-butyn-2-ol. All, 2- (4-fluorophenyl) -3-butyn-2-ol, and the like.
From the viewpoint of availability, 2-phenyl-3-butyn-2-ol and 3,7,11-trimethyl-1-dodecin-3-ol are preferable.

  (D) A component may be used independently and may be used together 2 or more types.

The amount of component (D) added is preferably in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 200 mol, relative to 1 mol of the hydrosilylation catalyst as component (C).

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

  Various types of hindered phenol-based anti-aging agents such as Irganox 1010 available from Ciba Specialty Chemicals are used.

Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

(Release agent)
You may add a mold release agent to the curable composition for optical materials of this invention. The release agent is not particularly limited as long as it is compatible with the resin, does not impair the transparency of the cured product, and improves the release property from the mold. Examples of such a release agent include fluorine compounds, silicone compounds, and long chain hydrocarbon compounds. Examples of the fluorine-based compound include perfluoroalkyl-containing oligomers, perfluoroalkylethylene oxide, perfluoroalkenyl ethylene oxide, and the like. Examples of the silicone compound include dimethyl silicone and polyether-modified silicone having a reactive functional group such as a carbon-carbon double bond and SiH group. Examples of the long-chain hydrocarbon compound include stearic acid derivatives and palmitic acid derivatives.
Moreover, these mold release agents may be used independently and may be used together 2 or more types.

(UV absorber)
You may add a ultraviolet absorber to the curable composition for optical materials of 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.

(Inorganic filler)
An inorganic filler may be added to the curable composition for optical materials of the present invention. Addition of an inorganic filler is effective in increasing the strength of the material and improving flame retardancy. The inorganic filler is preferably a fine particle, and examples thereof include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, barium sulfate, and a phosphor.

  As a method for adding the filler, for example, hydrolyzable silane monomers or oligomers such as alkoxysilane, acyloxysilane, and halogenated silane, metal alkoxides such as titanium and aluminum, acyloxide, or halides, and the like are cured according to the present invention. Examples thereof include a method in which an inorganic filler is produced in the composition by adding to the functional composition and reacting in the composition or a partial reaction product of the composition.

(solvent)
When the curable composition for optical materials of the present invention has a high viscosity, it can be dissolved in a solvent and used. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. Ether solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), ethylene glycol diethyl ether, chloroform, methylene chloride, A halogen-based solvent such as 1,2-dichloroethane can be preferably used.

  As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane, propylene glycol-1-monomethyl ether-2-acetate, and chloroform are preferable.

  Although the amount of solvent to be used can be set as appropriate, the lower limit of the preferred amount of use with respect to 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferred amount of use is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as lowering the viscosity. If the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also in terms of cost. It is disadvantageous and the industrial utility value decreases.

  These solvents may be used alone or as a mixed solvent of two or more.

  The curable composition of the present invention includes other colorants, storage stabilizers, flame retardants, flame retardant aids, surfactants, emulsifiers, leveling agents, anti-fogging agents, ion trapping agents such as antimony-bismuth, thixo Property imparting agent, anti-ozone degradation agent, light stabilizer, thickener, antifoaming agent, plasticizer, reactive diluent, antioxidant, thermal stabilizer, conductivity imparting agent, antistatic agent, radiation blocking agent Further, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity-imparting agent, a physical property adjusting agent and the like can be added within a range that does not impair the object and effect of the present invention.

  The preparation method of a curable composition is not specifically limited, It can prepare with various methods. Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance. After mixing all the components, only a part of the functional groups in the composition may be reacted by utilizing reaction control conditions or differences in functional group reactivity. When additives such as thermoplastic resins are used for the purpose of improving physical properties, these additives and a platinum compound as a curing catalyst are mixed and stored in advance, and each predetermined amount is mixed immediately before curing. It may be prepared.

(Cured product)
Although 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, and 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, the lower limit of the preferable temperature is 30 ° C, more preferably 60 ° C, and still more preferably 90 ° C. The upper limit of the preferable temperature is 300 ° C, more preferably 250 ° C, and still more preferably 200 ° C. When the reaction temperature is low, the reaction time for sufficient reaction is prolonged. If the reaction temperature is high, coloring or bulging may occur. If the reaction temperature is low, the reaction time for sufficient reaction tends to be long, and if the reaction temperature is high, coloring or bulging may occur.

  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, it is preferable to carry out the reaction while raising the temperature in a multistage or continuous manner from the viewpoint that both workability during resin filling and shortening of the curing time can be achieved.

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.
The cured product obtained by curing the composition of the present invention is preferably a 1 mm thick sample having a light transmittance of 80% or more at a wavelength of 400 nm. Furthermore, even if this cured product is heat-treated at 280 ° C. for 3 minutes, the change in light transmittance at a wavelength of 400 nm can be maintained at 10% or less, and therefore, it is considered that there is solder reflow resistance. Such high heat resistance can increase the degree of design freedom and application destinations of optical semiconductors, modules, and optical components.

  The cured product obtained by curing the composition of the present invention preferably has a hardness (Shore D) according to JIS K6253 type D durometer of 50 or more, more preferably 55 or more, and particularly preferably 60 or more. When the hardness by Shore D is high, there is mechanical strength, and mechanical processing such as a cutter and a drill is possible. Therefore, a complicated shape can be given or corrected after optical component molding.

  The cured product obtained by curing the composition of the present invention preferably has a linear expansion coefficient at 30 ° C. of 110 ppm / K or less, more preferably 100 ppm / K or less. By reducing the linear expansion coefficient, it is possible to reduce the deviation of the focus and aberration due to the temperature of the optical component, and to reduce the thermal shock when a thermal history is applied when the component is fixed.

(Use)
The curable composition of the present invention is used for optical materials. The optical material here is a material used for the purpose of allowing light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material, and specific examples thereof include the following.

  For example, camera lenses such as (digital) cameras, mobile phones, and in-vehicle cameras, optical lenses such as projection lenses, f-θ lenses, and pickup lenses, optical films, optical sheets, dicing tape, insulating materials (printed boards, wire coatings) Etc.), high voltage insulation materials, interlayer insulation films, insulation coating materials, coating materials (including hard coats, sheets, films, release paper coats, optical disc coats, optical fiber coats, etc.), molding materials (sheets) , Film, FRP, etc.), potting material, optical semiconductor sealing material, resist material, liquid resist material, colored resist, dry film resist material, solder resist material, color filter material, stereolithography, solar cell material, It can be applied to display materials, recording materials, and photosensitive drums for copying machines.

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

(Synthesis Example 1)
Into a 2 L autoclave, 650 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 600 g of toluene were added, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed solution of 90 g of triallyl isocyanurate, 110 g of toluene and 3.5 g of a xylene solution of platinum vinylsiloxane complex (containing 0.03 wt% as platinum) was added in 10 divided portions. After 6 hours of heating and stirring from the end of dropping, ¹ H-NMR confirmed that the allyl group reaction rate was 95% or more, and the reaction was terminated by cooling. The reaction was terminated by cooling.

Toluene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were devolatilized under reduced pressure at 60 ° C. for 2 hours and at 80 ° C. for 2 hours to obtain a colorless and transparent liquid. ^{According to 1} H-NMR, this product was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with the allyl group of triallyl isocyanurate (referred to as (β1). Although it was a mixture, it was found that it contains the following compounds containing 9 SiH groups in one molecule as the main component). Further, when the SiH group value was determined by ¹ H-NMR using 1,2-dibromoethane as an internal standard, it was found to be 9 mmol / g.

(Examples 1 to 3, Comparative Example 1)
A curable composition was prepared with the blending composition shown in Table 1 (the blending amount was by weight, and (D) component was added to component (C)).

(Measurement, test)
(Creation of isothermal molded cured product)
3 g of the curable composition blended with the above composition was dropped on a glass preheated to 135 ° C., and the glass was covered from above with a 1 mm-thick silicone rubber sheet as a spacer. Heated in air for 8 minutes to obtain a transparent cured product.

(Birefringence)
The in-plane birefringence of the isothermal molded cured product prepared by the above method was measured using a KOBRA-CCD manufactured by Oji Scientific Instruments. A sample having a birefringence variation of less than 50 nm was evaluated as ◯, and a sample having a birefringence of 50 nm or more as ×.

(Gel time)
An aluminum foil was laid on an as-one hot plate heated to a predetermined temperature (actual measurement value), and a drop of the resin composition was dropped here and stirred at a constant speed using a toothpick. The time from when the curable composition was dropped to when the curing started was measured with a stopwatch and used as the gel time. It can be said that the longer the gelation time, the slower the curing at a predetermined temperature and the easier the resin filling.

(Molding cycle)
Using the curable composition as a sample, a temperature range of 25 ° C. to 350 ° C. is measured at a sample amount of 15 mg, nitrogen gas of 30 mL / min, and a temperature increase rate of 10 ° C./min using a DSC manufactured by Shimadzu Corporation. The reaction rate at each temperature was determined. The temperature at which the reaction rate reached 10% was set as the filling temperature, the temperature at which the reaction rate reached 80% was set as the curing temperature, and the difference between the filling temperature and the curing temperature was set as Δt. It can be said that the larger Δt, the longer the temperature rise and cooling of the mold, and the worse the molding cycle property.
(Reaction rate) = (Integrated value of calorific value over time obtained every second) / (Total calorific value) × 100
The total of the temperature rise and cooling time required when the temperature was raised and cooled at 5 ° C./min was defined as the temperature raising and cooling time.

(SiH base value)
A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used. (B) Reaction tracking in component synthesis was measured by adding a reaction solution diluted to about 1% with deuterated chloroform to an NMR tube and measuring the peak of unreacted SiH groups or unreacted carbon-carbon double bond groups. It calculated | required from the peak of the methylene group derived from, and the peak of the methylene group derived from the reaction carbon-carbon double bond group. As the functional group value of the component (B), the SiH group value (mmol / g) in terms of dibromoethane was determined.

(Weight reduction rate)
Using a DTG-50 manufactured by Shimadzu Corporation, measure a temperature range of 25 ° C to 300 ° C at a sample amount of 6 mg, nitrogen gas of 50 mL / min, and a rate of temperature increase of 10 ° C / min, based on the weight at 25 ° C. The weight reduction rate at 100 ° C. was determined.

Claims (11)

(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) hydrosilyl And (D) the following general formula (I):

(Wherein R ¹ is an alkyl group or an aryl group, and each R ¹ may be connected; R ² is a hydrogen group, an alkyl group or an aryl group) A curable composition for optical materials, wherein the molecular weight of component (D) is 130 or more. The curable composition for optical materials according to claim 1, wherein R ² in the general formula (I) is a hydrogen group.   The curable composition for optical materials according to any one of claims 1 to 2, wherein the weight reduction rate of the component (D) at 100 ° C is within 10%. The component (D) is at least one compound selected from 2-phenyl-3-butyn-2-ol and 3,7,11-trimethyl-1-dodecyn-3-ol. The curable composition for optical materials as described in any one. The curable composition for optical materials according to claim 1, wherein the component (A) contains at least 1 mmol of carbon-carbon double bonds having reactivity with SiH groups per gram of component (A). The curable composition for molding an optical material according to claim 1, wherein the component (B) is a compound containing a linear and / or cyclic polysiloxane skeleton. An aging inhibitor is contained, The curable composition for optical materials as described in any one of Claims 1-6 characterized by the above-mentioned.   The curable composition for optical materials according to any one of claims 1 to 7, further comprising a release agent. Hardened | cured material formed by hardening | curing the curable composition in any one of Claims 1-8.   An optical component using the cured product according to claim 9.   An optical module using the optical component according to claim 10.