JP2012233118A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which has a high refractive index and a low Abbe number, and is suitable for an optical material, and to provide a hardened material.SOLUTION: The curable composition comprises, as essential components: (A) an organic compound containing at least two carbon-carbon double bonds having reactivity with an SiH group in one molecule; (B) cyclic polyorganosiloxane containing at least two SiH groups in one molecule; (C) a hydrosilylation catalyst; and (D) a condensed ring compound having a carbon-carbon double bond having reactivity with an SiH group in one molecule.

Description

  For example, the present invention makes it possible to provide a curable composition and a cured product having a high refractive index and a low Abbe number.

In recent years, plastic lenses are suitably used for compact cameras, camera-equipped mobile phones, and the like that are excellent in low cost and portability. As such plastic lens materials, thermoplastic resins such as polymethyl acrylate, polycarbonate, and cyclic olefin polymers are used. As a method of mounting a camera module having such a plastic lens on a camera-equipped mobile phone or the like, a method of mounting by solder reflow processing has been proposed. In this method, connector parts are not required, so that the thickness can be reduced, and the cost can be reduced by shortening the process. However, when the above-described thermoplastic plastic material is used in the proposed mounting method, there is a defect that the plastic material is deformed or colored by the heat of the reflow process, and the heat resistance requirement for the plastic material is increasing.

  As a material to compensate for these drawbacks, there is a thermosetting silicone material excellent in heat distortion resistance and heat discoloration, but simultaneously satisfies high refractive index, high and / or low Abbe number, and also has high hardness. No material has been found.

  For example, Patent Document 1 discloses a composition in which inorganic particles are added to an organic resin, and a cured product that maintains transparency and can control the refractive index and the Abbe number is proposed. However, the viscosity of the composition is high, which may cause a problem from the viewpoint of operability. Furthermore, the haze is about several percent, which is not sufficient for the imaging system from the viewpoint of transparency. In addition, with the increasing temperature of solder mounting, there is still room for improvement in heat resistance. From the above viewpoint, development of a lens material having high heat resistance and high refractive index and high and / or low Abbe number is required.

JP 2008-001841 A

  Accordingly, an object of the present invention is to provide a curable composition and a cured product that have, for example, good heat discoloration and moderate hardness, and have a high refractive index and are suitable for an optical material having a low Abbe number.

As a result of intensive studies, the present inventors have
(A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) a cyclic polyorganosiloxane containing at least two SiH groups in one molecule. (C) The hydrosilylation catalyst, (D) The curable composition comprising a condensed ring compound having one carbon-carbon double bond reactive with SiH group in one molecule can solve the above-mentioned problems. I found.

That is, the present invention has the following configuration.
1). (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) a cyclic polyorganosiloxane containing at least two SiH groups in one molecule. (C) a hydrosilylation catalyst, (D) a curable composition comprising a condensed ring compound having one carbon-carbon double bond reactive with a SiH group in one molecule as an essential component.

2). (D) A condensed ring compound having one carbon-carbon double bond having reactivity with a SiH group in one molecule contains a structure represented by the following general formula (I): The curable composition as described. (In the formula, R ¹ is a hydrogen atom, a halogen atom, or an organic group, and R ² is a group having an ethylenically unsaturated bond.)

3). (D) The curing according to 2), wherein the condensed ring compound having one carbon-carbon double bond reactive with the SiH group in one molecule is 1-vinylnaphthalene or 2-vinylnaphthalene. Sex composition.

  4). The organic compound in which the cyclic polyorganosiloxane containing at least two SiH groups in one molecule as the component (B) has at least two carbon-carbon double bonds reactive with SiH groups in one molecule. The curable composition according to 1), which is a compound obtainable by hydrosilylation reaction of (α) and a cyclic polyorganosiloxane (β) having at least two SiH groups in one molecule.

  5). The cyclic polyorganosiloxane (β) having at least two SiH groups in one molecule is 1,3,5,7-tetramethyltetracyclosiloxane and / or 1,3,5,7,9-penta. The curable composition according to 4), which is methylcyclopentasiloxane.

  6). An optical component obtained by curing the curable composition according to any one of 1) to 5).

  According to the curable resin for optical materials of the present invention, a cured product having good heat discoloration and moderate hardness and suitable for an optical material having a high refractive index and a low Abbe number can be obtained.

  Hereinafter, the present invention will be described in detail.

  First, the component (A) in the present invention will be described.

  The component (A) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule.

  Examples of the organic compound include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as straight chain and alicyclics: heterocyclic compounds, and mixtures thereof. Can be mentioned.

  The carbon-carbon double bond having reactivity with the SiH group of the component (A) is not particularly limited, but the following general formula (II)

(In the formula, R ³ represents a hydrogen atom or a methyl group. In this case, each R ³ may be the same or different.) An alkenyl group represented by the formula is preferable from the viewpoint of reactivity. For example,

The alkenyl group shown by can be used suitably.

  As a carbon-carbon double bond having reactivity with the SiH group of the component (A), the following general formula (III)

A carbon-carbon double bond contained in the ring of the alicyclic compound represented by the formula (wherein R ⁴ represents a hydrogen atom or a methyl group) is preferable from the viewpoint of high heat resistance of the cured product. For example

The carbon-carbon double bond contained in the ring of the alicyclic compound shown by can be used suitably.
The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the component (A) or may be covalently bonded via a divalent or higher valent substituent. Although it will not specifically limit if it is a C1-C10 substituent as a substituent more than bivalence, The thing containing only C, H, N, O, S, and a halogen is preferable as a structural element. Examples of these substituents include

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

  Examples of the group 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) Oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group,

Is mentioned. From the viewpoint of high heat resistance and light resistance, a vinyl group and an allyl group are preferable.

  Specific examples of the component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2, -tetraallyloxy. Ethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzene, divinylnaphthalene, divinylbiphenyl, 1, 3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene, allyl ether of novolak phenol, allylated polyphenylene Kisaido, vinyl norbornene,

Is mentioned.

The component (A) is preferably a compound containing an aromatic ring such as benzene, naphthalene, bisphenol, and fluorene from the viewpoint of optical characteristics, for example, Abbe number, and isocyanuric ring from the viewpoint of colorability of the cured product. preferable. From the above viewpoint, as component (A), divinylfluorene, diallylfluorene, fluorene bisphenoxyethyl acrylate, fluorene bisphenoxyethyl vinyl ether, fluorene bisphenoxyethyl allyl ether, fluorene bisphenoxy acrylate, fluorene bisphenoxy vinyl, fluorene bisphenoxy allyl, More preferred are triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl isocyanurate, diallyl monophenyl isocyanurate, bisphenol F diallyl ether, bisphenol A diallyl ether, bisphenol S diallyl ether, divinylbenzene and divinylnaphthalene.
Moreover, the above component (A) may be used alone or in combination of two or more.

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

  The number of carbon-carbon double bonds reactive with the SiH group of component (A) should be on average at least two per molecule, but if it is less than two, the strength may be insufficient. There is.

As the component (A), in order to obtain uniform mixing with other components and good workability, those having fluidity at a temperature of 100 ° C. or less are preferable, and may be linear or branched, and the molecular weight may be Although there is no restriction | limiting in particular, Arbitrary things of 50-100,000 can be used conveniently. When the molecular weight is 100,000 or more, the raw material generally has a high viscosity and is inferior in workability, and the effect of crosslinking due to the reaction between the alkenyl group and the SiH group is hardly exhibited. From the viewpoint that the cured product obtained as the component (A) has high hardness, a compound having a molecular weight of 3,000 or less is preferable.
Next, the component (B) will be described.

  The component (B) of the present invention is not particularly limited as long as it is a cyclic polyorganosiloxane containing at least two SiH groups in one molecule.

  In the case where 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 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 unlikely to occur, the component (B) has a carbon-carbon double bond having reactivity with the SiH group in one molecule. A condensed ring compound having one carbon-carbon double bond reactive with an SiH group which is an organic compound (α) and / or a component (D) described later in one molecule, and 1 A compound obtained by hydrosilylation reaction of a cyclic polyorganosiloxane (β) having at least two SiH groups in the molecule is preferable.

  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 preferred molecular weight is 50, and the upper limit of the preferred molecular weight is 100,000, more preferably 10,000, and even more preferably 5,000.

[(Α) component]
Here, the component (α) is the same as the component (A), which is the same as the organic compound containing at least two carbon-carbon double bonds reactive with the SiH group in the molecule. Can be used as The component (α) is preferably a compound containing an aromatic ring, such as the above-mentioned isocyanuric ring system, benzene system, naphthalene system, bisphenol system, fluorene system, from the viewpoint of, for example, the Abbe number.

[(Β) component]
The cyclic polyorganosiloxane having at least two SiH groups in one molecule that can be used in the present invention is not particularly limited, and specific examples thereof include, for example, the following general formula (IV):

(Wherein R ⁵ represents hydrogen or an organic group having 1 to 6 carbon atoms, and each R ⁵ 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. R ⁵ in the general formula (IV) 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. An alkyl group having 1 to 6 carbon atoms is more preferable. N is preferably a number of 3 to 10.

  Among these, from the viewpoint of availability, a cyclic polyorganosiloxane having at least two SiH groups in one molecule is preferable. From the aspect of compatibility with the component (A), a cyclic polyorganosiloxane having at least two SiH groups in one molecule is preferable. From the viewpoint of heat resistance, a cyclic polyorganosiloxane having at least 3 SiH groups in one molecule is preferable.

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

Various (β) components as described above can be used alone or in admixture of two or more.
(Reaction of (α) component and / or (D) component with (β) component)
Regarding the component (B) described above, the organic compound (α) containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule and / or SiH as the component (D) described later Hydrosilylation reaction of a condensed ring compound having one carbon-carbon double bond reactive with a group in one molecule and a cyclic polyorganosiloxane (β) having at least two SiH groups in one molecule The reaction for obtaining the compound will be described.

  An organic compound (α) containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule and / or one carbon-carbon double bond reactive with SiH groups in one molecule. (Α) component and / or (D) in the case of subjecting (D) component, which is a fused ring compound, and cyclic polyorganosiloxane (β) having at least two SiH groups in one molecule to hydrosilylation reaction The mixing ratio of the component () and the component (β) is not particularly limited as long as at least two SiH groups remain in one molecule after the hydrosilylation reaction.

  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 (α) and the reactivity with SiH groups in component (D) The ratio of the number of moles of carbon-carbon double bonds (Y) and the number of moles of SiH groups (Z) in the component (β) is preferably Z / (X + Y) ≧ 2. More preferably, (X + Y) ≧ 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.

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 polyorganosiloxane (beta) ¹⁰ per mole of the SiH group in component ^-1 having SiH groups 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, 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 at the time of the reaction, and a method in which the (α) component and / or the (D) component mixed with the hydrosilylation catalyst (C) is mixed with the (β) component. Is preferred. In the method of mixing the hydrosilylation catalyst (C) with the component (α) and / or the mixture of the component (D) and the component (β), it may be difficult to control the reaction. In the method of mixing the (β) component and the hydrosilylation catalyst (C) with the (α) component and / or the (D) component, the (β) component is mixed in the presence of the hydrosilylation catalyst (C). It may be altered due to its reactivity with water.

  Although various reaction temperatures can be set, the lower limit of the preferred temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferred temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for 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. Although the pressure is not particularly limited, it is preferably atmospheric pressure −5 MPa, more preferably atmospheric pressure −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 amount of the solvent used is not particularly limited, but an amount capable of completely dissolving the component (α) and / or the component (D) is preferable in order to make the reaction uniform and promote. 20 parts by weight or more and 500 parts by weight or less are preferable, and 50 parts by weight or more and 300 parts by weight or less are more preferable with respect to 100 parts by weight of component (α) and / or component (D).

In addition, various additives may be used for the purpose of controlling reactivity.
After the hydrosilylation reaction, an organic compound (α) containing one carbon-carbon double bond reactive with a solvent and / or an unreacted SiH group in one molecule and at least two SiH in one molecule The cyclic polyorganosiloxane (β) having a group can also be removed. By removing these volatile components, the component (B) obtained does not have volatile components, so that problems of voids and cracks due to volatilization of volatile components are less likely to occur during curing. 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) as described above include a reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, divinylbenzene and 1,3,5,7-tetramethylcyclohexane. A reaction product of tetrasiloxane, a reaction product of bisphenol S diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane is more preferable.
In this invention, (B) component can be used individually or in mixture of 2 or more types.
Next, the hydrosilylation catalyst as component (C) will be described.

The hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, platinum having a solid platinum supported on a carrier such as simple substance of alumina, alumina, silica, carbon black, chloroplatinic acid, platinum chloride, etc. 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) _n , Pt [(MeViSiO) ₄ ] _m ), 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 Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent integers.), Dicarbonyldichloroplatinum, a Karstedt catalyst, and Ashby U.S. Pat. No. 3,159,601. And platinum-hydrocarbon complexes described in US Pat. No. 3,159,662 and platinum alcoholate catalysts described in Lamoreaux US Pat. No. 3,220,972. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

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

  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 above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, and amine compounds such as triethylamine. The amount of the cocatalyst added is not particularly limited, but is preferably in the range of 10 ⁻² to 10 ² mol, more preferably in the range of 10 ⁻¹ to 10 mol, with respect to 1 mol of the catalyst.
Next, the component (D) will be described.

The component (D) is a component for controlling optical characteristics, for example, the Abbe number, and is not particularly limited as long as it is a condensed ring compound having one carbon-carbon double bond having reactivity with the SiH group in one molecule. .
A condensed ring compound represented by the following general formula is preferred.

(In the formula, R ¹ is a hydrogen atom, a halogen atom, or an organic group, and R ² is a group having an ethylenically unsaturated bond.)

The organic group R ¹ in component (D), a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group are preferred. Furthermore, a hydrogen atom, a phenyl group, and a naphthyl group are more preferable from a heat resistant viewpoint. The group R ² having an ethylenically unsaturated bond is preferably a vinyl group, an allyl group, a methallyl group, an acrylic group, or a methacryl group. Furthermore, a vinyl group and an allyl group are preferable from the viewpoint of reactivity.

Component (D) is added in an amount of 1 to 100 parts by weight, preferably 2 to 80 parts by weight, more preferably 5 to 50 parts by weight, with 100 parts by weight of component (A) + (B).
If the amount added is too small, the Abbe number may not be lowered sufficiently, and if it is too large, the heat resistance may be deteriorated.

  Examples of the component (D) include 1-vinylnaphthalene and 2-vinylnaphthalene. In this invention, (D) component can be used individually or in mixture of 2 or more types.

  The hardness of the optical material obtained by curing is not particularly limited, but it is usually preferably 40 or more, more preferably 50 or more, still more preferably 60 or more as a hardness meter Shore D for use as an optical material. is there. If the hardness by Shore D is high, there is mechanical strength, and mechanical processing such as a cutter and a drill is possible, so that a complicated shape can be given or corrected after optical component molding.

  Next, various resins that can be added for the purpose of modifying the properties of the composition and the curing agent of the present invention will be described.

  Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, ether solvents such as tetrahydrofuran, 1,4-dioxane, and diethyl ether, and acetone. And ketone solvents such as 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 and chloroform are preferable. The amount of solvent to be used is preferably used in the range of lower limit 0 mL and upper limit 10 mL, more preferably in the range of lower limit 0.5 mL and upper limit 5 mL, and lower limit 1 mL and upper limit 3 mL with respect to 1 g of the reactive component used. It is particularly preferable to use within a range.

  Furthermore, 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-based compound, and an organic peroxide, and these may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, 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, thiazole, benzothiazole, 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-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

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

The addition amount of the storage stability improving agent is preferably in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 50 mol, with respect to 1 mol of the hydrosilylation catalyst used.

  You may add an inorganic filler to the composition of this invention as needed. Addition of an inorganic filler is effective in preventing fluidity of the composition and increasing the strength of the material. The inorganic filler is preferably in the form of fine particles that do not deteriorate the optical properties, and examples thereof include alumina, fused silica, crystalline silica, ultrafine powder amorphous silica, hydrophobic ultrafine silica, and barium sulfate.

  Furthermore, various resins can be added for the purpose of modifying the properties of the composition of the present invention. Examples of the resin include, but are not limited to, polycarbonate resin, polyethersulfone resin, polyarylate resin, epoxy resin, cyanate resin, phenol resin, acrylic resin, polyimide resin, polyvinyl acetal resin, urethane resin, and polyester resin. It is not something.

  The composition of the present invention can be directly formed into a film or the like, but the composition can be dissolved in an organic solvent to form a varnish. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, ether solvents such as tetrahydrofuran, 1,4-dioxane, and diethyl ether, and acetone. And ketone solvents such as 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 and chloroform are preferable. The amount of the solvent used is preferably in the range of 0 to 10 mL, more preferably in the range of 0.5 to 5 mL, and in the range of 1 to 3 mL with respect to 1 g of the reactive (A) component to be used. Is particularly preferred. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent will remain in the material and easily cause problems such as thermal cracks. It is disadvantageous and the industrial utility value decreases.

  In addition, the composition of the present invention includes an anti-aging agent, a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, a surfactant, a storage stability improver, an ozone degradation inhibitor, a light stabilizer, a thickening agent. Agent, plasticizer, coupling agent, antioxidant, heat stabilizer, conductivity enhancer, antistatic agent, radiation blocking agent, nucleating agent, phosphorus peroxide decomposing agent, lubricant, pigment, metal deactivator Further, physical property modifiers and the like can be added within a range that does not impair the object and effect of the present invention.

  The composition for optical material of the present invention is mixed in advance and cured by reacting a part of or all of the SiH group with a carbon-carbon double bond having reactivity with the SiH group in the composition. It can be.

  As the mixing method, various methods can be used, and a method in which the component (A) and the component (D) are mixed with the component (C) and the method of mixing the component (B) are preferable. It is difficult to control the reaction by mixing the component (C) with the component (A) and the mixture of the component (D) and the component (B). When the method of mixing the component (A) and the component (D) with the component (B) mixed with the component (B), the component (B) is reactive with moisture in the presence of the component (C). Therefore, it may be altered during storage.

  In the case of curing by reacting the composition, the necessary amounts of the respective components (A), (B), (C), and (D) may be mixed and reacted at one time. After reacting, react only a part of the functional group in the composition by mixing the remaining amount, reacting after mixing, controlling reaction conditions and utilizing the reactivity difference of substituents It is also possible to take a method of further curing by performing a treatment such as molding. According to these methods, viscosity adjustment at the time of molding becomes easy.

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

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

  The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

  Various reaction times can be set.

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

  The shape of the optical material obtained by curing can be variously selected depending on the application and is not particularly limited. For example, the shape may be a film shape, a sheet shape, a tube shape, a rod shape, a coating shape, a bulk shape, or the like. it can.

  Various molding methods can be used including a conventional thermosetting resin molding method. For example, a molding method such as a cast method, a press method, a casting method, a transfer molding method, a coating method, or a RIM method can be applied. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied. In addition, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be applied in order to improve releasability from the mold.

Various treatments can be performed as necessary during molding. For example, a treatment for defoaming the composition or a partially reacted composition by centrifugation, decompression, or the like for releasing the pressure once during pressing may be applied to suppress voids generated during molding.
The cured product obtained in the present invention can be used for various applications including optical materials.
The optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material.

  More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned.

  It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive.

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

  In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices.

  In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC).

  In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection.

  As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material.

  In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings.

In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film.
Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

  Other uses of optical materials include general uses in which thermosetting resins such as epoxy resins are used, including, for example, adhesives, paints, coating agents, molding materials (sheets, films, FRP, etc.) ), Insulating materials (including printed circuit boards, wire coatings, etc.), sealants, additives to other resins, and the like.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for sealing, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.

  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 was placed 300.0 g of toluene, 130.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane, the gas phase was replaced with nitrogen, and then heated at a jacket temperature of 115 ° C. and an internal temperature of 110 ° C. , Stirred. 286 g of divinylbenzene, 300 g of toluene, and a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) 0. 015 g of the mixture was added in 10 portions. Reacted for 1 hour after completion of the dropwise addition, to confirm that ¹ H- N M R in reaction rate of the allyl group is 95% or more, the reaction was terminated by cooling. Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid. ^{According to 1} H-N M R, this is a product in which a part of S i H group is reacted with divinylbenzene (the following chemical formula, referred to as reactant B1), S i H value: 9.8 mm / g / g )

(Synthesis Example 2)
To a 500 mL flask, 80.0 g of toluene and 130.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated to an internal temperature of 90 ° C. Then, a slurry solution of 33.0 g of bisphenol S diallyl ether, a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) 0.65 g, and 33.0 g of toluene was divided into 5 parts at intervals of 30 minutes. Added. Heated to reflux for 2 hours from the final addition. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{According to 1} H-N M R, this is a product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane is reacted with bisphenol S diallyl ether (the following chemical formula, referred to as reactant B2) , S i H value: 6.8 mmol / g).

(Examples 1-4 and Comparative Examples 1-7)
Blended according to Table 1 below. For the examples, divinylbenzene as the component (A), the compound B1 of Synthesis Example 1 or the compound B2 of Synthesis Example 2 as the component (B), and xylene of a platinum-divinyltetramethyldisiloxane complex as the component (C) A curable composition was prepared using a solution (containing 3% by weight of platinum) and 2-vinylnaphthalene as the component (D) at a blending ratio (weight) shown in Table 1. As for the comparative example, divinylbenzene as the component (A), FX-T180 (K) -A manufactured by Adeka as a phenyl silicone monomer having a high refractive index and a low Abbe number, and Synthesis Example 1 as the component (B) Compound B1 of Synthesis Example 2, Compound B2 of Synthesis Example 2, and TSF484 made by Momentive Co., which is a linear polyorganosiloxane containing at least two SiH groups in one molecule, and platinum-divinyltetra A curable composition was prepared using a xylene solution of methyldisiloxane complex (containing 3% by weight of platinum) and styrene and 2-vinylnaphthalene as the component (D).

(Evaluation method)
The following evaluation was performed and the results are shown in Table 1.

  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 1 mm-thick silicone rubber sheet between two glass plates as a spacer. All examples and comparative examples were 60 ° C. for 6 hours, 80 ° C. for 1 hour, 100 ° C. Heated at 120 ° C. for 1 hour and 180 ° C. for 30 minutes to obtain a cured product.

(Refractive index and Abbe number)
Apparatus: Prismatic coupler 2010 / M manufactured by Metaricon
Measurement conditions: The refractive index at 404, 594, and 827 nm was continuously measured three times in the half mode, and the average value was defined as the refractive index of each wavelength. The refractive index (n) at 486, 589, and 656 nm was obtained by the Cauchy approximation formula of the built-in software, and the Abbe number was calculated.

(Transparency of cured product)
The light transmittance at 450 nm and 400 nm of the obtained cured product (1 mm thickness) was measured with a spectrophotometer (U-3300, Hitachi).

(Heat resistance test)
The cured product was heated at 260 ° C. for 5 minutes to conduct a heat resistance test. For the cured product after the heat resistance test, the light transmittance at 450 nm and 400 nm was measured with a spectrophotometer (U-3300, Hitachi) (transmittance after heat resistance test), and before and after the heat resistance test according to the following formula at each wavelength. The change of transmittance was derived numerically. Here, as the “initial transmittance”, the light transmittances of 450 nm and 400 nm of the cured product before the heat resistance test were used.
Rate of change (%) = transmittance after heat test / initial transmittance × 100
(Hardness of cured product)
The cured product (1 mm thick) was placed on a blue glass, and the hardness was measured by a type D durometer according to JIS K6253.

(Storage modulus)
A test piece of 1 mm × 5 mm × 30 mm was cut out from the produced cured product, and using a DVA-200 manufactured by IT Measurement Control Co., Ltd., a tensile mode, a measurement frequency of 10 Hz, a strain of 0.1%, a static / power ratio of 1.5, and an increase Dynamic viscoelasticity measurement was performed under the condition of a temperature rate of 5 ° C./min. The storage elastic modulus at 25 ° C. is described.

  In consideration of molding these curable compositions as optical parts, for example, in optical lens applications, the hardness at Shore D is preferably 75 or more, and the refractive index is 1.55 or more from the viewpoint of reducing the height of the lens. Is desirable. In order to solve the problem of chromatic aberration, it is desirable that the material having a low Abbe number is 33 or less from the viewpoint of combining lens materials having an Abbe number difference. It is desirable that the change rate of the light transmittance of each wavelength before and after the heat resistance test can maintain 85% or more.

  The cured product using the curable composition of the present invention has a smaller Abbe number and a refractive index equal to or higher than those of Comparative Examples 1 to 4, and the addition of the component (D) reduces the Abbe number and increases the refractive index. It is clear that In addition to Comparative Examples 2 and 3 using styrene as the component (D), Examples 1 and 2 have higher hardness and elastic modulus in addition to optical properties, and excellent heat discoloration, and the effect of the condensed ring compound is clear. It is. In addition to the excellent optical properties, Examples 1 to 4 had higher hardness than Comparative Examples 5 and 6, and thus the effect of cyclic siloxane was also shown. In Comparative Example 7, the cured product became cloudy and a transparent cured product could not be obtained.

  From the results in Table 1, it was shown that a cured product using the curable composition of the present invention has a high refractive index and a low Abbe number, and has good heat discoloration and appropriate hardness.

Claims (6)

(A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) a cyclic polyorganosiloxane containing at least two SiH groups in one molecule. (C) a hydrosilylation catalyst, (D) a curable composition comprising a condensed ring compound having one carbon-carbon double bond reactive with a SiH group in one molecule as an essential component. (D) A condensed ring compound having one carbon-carbon double bond having reactivity with a SiH group in one molecule contains a structure represented by the following general formula (I): The curable composition according to 1. (In the formula, R ¹ is a hydrogen atom, a halogen atom, or an organic group, and R ² is a group having an ethylenically unsaturated bond.)

(D) The condensed ring compound having one carbon-carbon double bond reactive with SiH group in one molecule is 1-vinylnaphthalene or 2-vinylnaphthalene. Curable composition. The organic compound in which the cyclic polyorganosiloxane containing at least two SiH groups in one molecule as the component (B) has at least two carbon-carbon double bonds reactive with SiH groups in one molecule. The curable composition according to claim 1, which is a compound obtained by hydrosilylation reaction of (α) and a cyclic polyorganosiloxane (β) having at least two SiH groups in one molecule. The cyclic polyorganosiloxane (β) having at least two SiH groups in one molecule is 1,3,5,7-tetramethyltetracyclosiloxane and / or 1,3,5,7,9-penta. The curable composition according to claim 4, which is methylcyclopentasiloxane. The optical component formed by hardening | curing the curable composition as described in any one of Claims 1-5.