TW201434883A - Organopolysiloxane and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an organopolysiloxane represented by the average unit formula: (R1R2SiO2/2)a(R3SiO3/2)b(XO1/2)c, wherein R1 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, or a phenyl group; R2 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, a phenyl group, or an epoxy group-containing organic group, provided that at least one R2 in a molecule is the epoxy group-containing organic group; R3 is a condensed polycyclic aromatic group or a condensed polycyclic aromatic group-containing organic group; X is an alkyl group having from 1 to 3 carbon atoms or a hydrogen atom; a is a number from 0.20 to 0.60, b is a number from 0.40 to 0.80, a sum of a and b is 1.00, and c is a number from 0 to 0.5. The organopolysiloxane has a high refractive index, and is monodispersed and curable to form a cured product having an adequate elastic modulus.

Description

Organic polyoxyalkylene and manufacturing method thereof

The present invention relates to an organopolyoxane comprising an epoxy group-containing organic group and a condensed polycyclic aromatic group or an organic group containing a condensed polycyclic aromatic group, and a process for producing the same.

The present application claims priority to Japanese Patent Application No. 2013-043000, filed on March 5, 2013, the content of which is incorporated herein by reference.

The oxirane unit (M unit) represented by the formula R ₃ SiO _1/2 , the oxoxane unit (D unit) represented by the formula R ₂ SiO _2/2, represented by the formula RSiO _3/2 An organopolyoxane unit of any combination of a oxoxane unit (T unit) and a _oxoxane unit (Q unit) represented by the formula SiO _4/2 (in this formula, R is the same or different monovalent hydrocarbon group) Alkanes are used as optical materials such as sealants for LEDs and lens molding materials because of their excellent heat resistance, light resistance and transparency. Among these applications, organopolyoxyalkylenes having a high refractive index are particularly preferred. In order to increase the refractive index of the organopolyoxane, it is known to introduce a condensed polycyclic aromatic group such as a naphthyl group or an organic group containing a condensed polycyclic aromatic group such as naphthylethyl group into the molecular chain. As an organic group. It is also known to introduce an epoxy group-containing organic group as another organic functional group (see Patent Documents 1 and 2).

For example, Patent Document 1 discloses bis(1-naphthyl)dimethoxydecane or 1-naphthylmethyldimethoxydecane and 3-glycidoxypropyltrimethoxydecane or 3-glycidyloxy group. Propyl Hydrolysis and condensation of methyl dimethoxydecane. Further, Patent Document 2 discloses hydrolysis and condensation reaction of 9-phenanthryl triethoxydecane, 3-glycidoxypropyltrimethoxydecane and methyltriethoxydecane, and 1-naphthyltriethoxy group Hydrolysis and condensation of decane, 3-glycidoxypropyltrimethoxynonane and triethoxydecane.

However, the organopolyoxane prepared in Patent Document 1 contains a condensed polycyclic aromatic group (such as a naphthyl group) in the D unit, and an epoxy group-containing organic group in another D unit or in the T unit. group. The organopolysiloxane has a large degree of molecular weight dispersion, and the problem is that the cured product obtained by curing the organopolysiloxane has a remarkably low modulus of elasticity.

Further, the organopolyoxane prepared in Patent Document 2 contains a condensed polycyclic aromatic group (such as a naphthyl group) in a T unit, and an epoxy group-containing organic group in another T unit. Although the organopolyoxane has a lower degree of molecular weight dispersion, the problem is that the cured product obtained by curing the organopolysiloxane has a remarkably high modulus of elasticity.

Prior technical literature Patent literature

Patent Document 1: Japanese Unexamined Patent Publication No. 2010-007057A

Patent Document 2: Japanese Unexamined Patent Publication (Translation of PCT Application) No. 2011-504958A

It is an object of the present invention to provide an organopolyoxane having a high refractive index, monodisperse, and curable to form a cured product having a suitable modulus of elasticity, and a method of making the same.

The organopolyoxyalkylene of the present invention is represented by the following average unit formula: (R ¹ R ² SiO _2/2 ) _a (R ³ SiO _3/2 ) _b (XO _1/2 ) _c

Wherein R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a phenyl group; and R ² is an alkyl group having 1 to 12 carbon atoms and having 2 to 12 carbon atoms An alkenyl group, a phenyl group or an epoxy group-containing organic group, provided that at least one R ² in the molecule is an epoxy group-containing organic group; R ³ is a condensed polycyclic aromatic group or contains a condensation group An organic group of a cyclic aromatic group; X is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, a is a number from 0.20 to 0.60, b is a number from 0.40 to 0.80, and the sum of a and b is 1.00. And c is a number from 0 to 0.5.

In the formula, the epoxy group-containing organic group for R ² is preferably a glycidoxyalkyl group, an epoxycyclohexylalkyl group or an epoxyethylalkyl group, and R ^{3 is} preferably a naphthyl group. Or naphthylethyl. Further, at least 10 mol% of all of R ¹ and R ² in the molecule are preferably an epoxy group-containing organic group.

The production method of the present invention is a method for producing the above organopolyoxane. The production method includes a step of subjecting a substance to hydrolysis and condensation reaction in the presence of an acid or a base: a decane compound represented by the following formula (I): R ¹ R ⁴ SiY ₂

Wherein R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a phenyl group; R ⁴ is an epoxy group-containing organic group; and Y is a hydrolyzable group; / or a oxoxane compound represented by the following formula (II): HO (R ¹ R ⁴ SiO) _m H

Wherein R ¹ and R ⁴ are the same as those described above, and m is an integer from 1 to 100; and, if necessary, a decane compound represented by the following formula (III): R ¹ ₂ SiY ₂

Wherein R ¹ and Y are the same as those described above; and/or a oxoxane compound represented by the following formula (IV): HO(R ¹ ₂ SiO) _n H

Wherein R ¹ is the same as the above, and n is an integer from 1 to 100; and a decane compound represented by the following formula (V): R ³ SiY ₃

Wherein R ³ is a condensed polycyclic aromatic group or an organic group containing a condensed polycyclic aromatic group, and the Y system is the same as the above.

In the decane compound represented by the formula (I) and the oxirane compound represented by the formula (II), R ^{4 is} preferably a glycidoxyalkyl group, an epoxycyclohexylalkyl group or an epoxyethyl group. alkyl. In the decane compound represented by the general formula (V), R ^{3 is} preferably a naphthyl group or a naphthylethyl group.

The organopolyoxane of the present invention is characterized by having a high refractive index, being monodisperse, and curable to form a cured product having an appropriate modulus of elasticity. Further, the production method of the present invention is characterized in that the organopolyoxane can be efficiently produced.

First, the organopolyoxane of the present invention will be described in detail.

The organopolyoxyalkylene of the present invention is represented by the following average unit formula: (R ¹ R ² SiO _2/2 ) _a (R ³ SiO _3/2 ) _b (XO _1/2 ) _c .

In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a phenyl group. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a cyclopentyl group, and a cyclooctyl group. Among these, a methyl group is preferred. Examples of the alkenyl group for R ¹ include a vinyl group, an allyl group, and a butenyl group. Among these, a vinyl group is preferred.

In the formula, R ² is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a phenyl group or an epoxy group-containing organic group. Examples of the alkyl group for R ² include the same groups as described for R ¹ . Among these, a methyl group is preferred. Examples of alkenyl groups for R ² include the same groups as described for R ¹ . Among these, a vinyl group is preferred. Examples of the epoxy group-containing organic group for R ² include glycidoxyalkyl groups such as 2-glycidoxyethyl group, 3-glycidoxypropyl group, and 4-glycidoxybutyl group; Oxocycloalkylalkyl such as 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, 2-(3,4-epoxy Decylalkyl)ethyl and 2-(3,4-epoxy-3-methylcyclohexyl)-2-methylethyl; and epoxyethylalkyl such as 4-epoxyethylbutyl And 8-epoxyethyloctyl. Among these, a glycidoxyalkyl group is preferred, and a 3-glycidoxypropyl group is particularly preferred. It should be noted that at least one and preferably at least two R ² in the molecule are organic groups containing an epoxy group. In particular, since the organopolysiloxane of the present invention is excellent in curability, the epoxy group-containing organic group preferably accounts for at least 10 mol% of all R ¹ and R ² in the molecule, and more preferably Good for at least 15 moles.

In the formula, R ³ is a condensed polycyclic aromatic group or an organic group containing a condensed polycyclic aromatic group. Examples of the condensed polycyclic aromatic group for R ³ include a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group and a hydrogen atom thereof by an alkyl group such as a methyl group or an ethyl group; an alkoxy group such as a methoxy group or an ethoxy group Or a condensed polycyclic aromatic group substituted by a halogen atom such as a chlorine atom or a bromine atom. Among these, a naphthyl group is preferred. Examples of the organic group containing a condensed polycyclic aromatic group for R ³ include an alkyl group having a condensed polycyclic aromatic group such as naphthylethyl, naphthylpropyl, decylethyl, phenethylethyl And a mercaptoethyl group; and the condensed polycyclic ring in which a hydrogen atom is replaced by an alkyl group such as a methyl group or an ethyl group; an alkoxy group such as a methoxy group or an ethoxy group; or a halogen atom such as a chlorine atom or a bromine atom; Aromatic group. The organic group containing a condensed polycyclic aromatic group for R ³ is preferably an alkyl group having a condensed polycyclic aromatic group, and particularly preferably a naphthylethyl group. An organopolyoxane comprising an organic group containing a condensed polycyclic aromatic group as R ³ has a relatively low viscosity, and thus can reduce a curable polyoxynium containing the organopolysiloxane as a main component The viscosity of the composition.

In the formula, X is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Examples of the alkyl group for X include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group is preferred.

In the formula, a represents the ratio of the D unit and is a number from 0.20 to 0.60, and b represents T The ratio of the cells is a number from 0.40 to 0.80. It should be noted that the sum of a and b is 1.00. This is because, when the value of a is greater than or equal to the lower limit of the above range, the cured product of the organopolysiloxane will exhibit an excellent elastic modulus, and when the value of a is less than or equal to the upper limit of the above range, the organic Polyoxyalkylene will exhibit a high refractive index and become monodisperse.

In the formula, c represents the ratio of the unit represented by the formula XO _1/2 formed in the process of producing the organopolyoxane of the present invention, and is a number from 0 to 0.5. This is because, when the value of c is less than or equal to the upper limit of the above range, the stability of the organopolyoxyalkylene itself is enhanced. The organopolysiloxane preferably comprises the above unit because the adhesion of the curable polyoxynoxy composition comprising the organopolysiloxane of the present invention as a main component can be enhanced, and/or the curable polycondensation can be enhanced. The bonding of the cured product of the oxygen composition to the substrate.

The molecular weight of such an organic polyoxoxane of the present invention is not particularly limited, but from the viewpoint of excellent handling/processability and the like, such as the weight average of standard polystyrene measured by gel permeation chromatography The molecular weight is preferably in the range of from 400 to 5,000, more preferably in the range of from 500 to 3,000, and particularly preferably in the range of from 1,000 to 2,000. The form of the organic polyoxyalkylene of the present invention at 25 ° C is not particularly limited, and examples of the form include oily, paste-like, resin-like, gum-like, and solid (powder).

Further, the organic polysiloxane of the present invention preferably has a refractive index at a wavelength of 25 ° C and 632.8 nm of greater than or equal to 1.50, and particularly preferably greater than or equal to 1.53.

Since the molecule of the organopolyoxane of the present invention contains an epoxy group-containing organic group, a curable polyoxo oxygen combination can be formed by mixing a curing agent and a curing accelerator in the organopolyoxane of the present invention. Things.

The curing agent is not particularly limited as long as the curing agent reacts with the epoxy group in the organopolyoxane of the present invention to be cured. Examples of the curing agent include phenol resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl Bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, bisphenol, dihydroxynaphthalene, 1,1,1-indolyl (4-hydroxyphenyl)methane, 4,4-( 1-(4-(1-(4-hydroxyl) Phenyl)-1-methylethyl)phenyl)ethylidene)bisphenol, phenol novolac resin, cresol novolac resin, bisphenol A phenolic resin, bromophenol phenolic resin and bromobisphenol A phenolic resin; Hydrogenated aromatic ring polyols of such phenolic resins; alicyclic acid anhydrides such as polysebacic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic acid Anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-di Carboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride, cyclohexane-1,2,3-tricarboxylic acid-1,2-anhydride and cyclohexane-1,2,4-tricarboxylate An acid-1,2-anhydride; and an alkyl-substituted glutaric anhydride such as 3-alkylglutaric anhydride (for example, 3-methylpentane which may be a branched chain and an alkyl group having 1 to 8 carbon atoms) a dianhydride), which may be a branched chain and a 2,3-dialkylglutaric anhydride (for example, 2-ethyl-3-propylglutaric anhydride) having an alkyl group having 1 to 8 carbon atoms, and may be a branch a chain and a 2,4-dialkylglutaric anhydride comprising an alkyl group having 1 to 8 carbon atoms (eg 2,4-diethylglutaric anhydride and 2,4- Methyl glutaric anhydride); and aromatic anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride.

Although the compounding amount of the curing agent is not particularly limited, since the organic polyoxyalkylene of the present invention can be sufficiently cured and the resulting cured product exhibits excellent heat resistance and weather resistance, the mixing amount is preferably from 1 to 200 parts by weight. Within the range, and particularly preferably in the range of from 20 to 160 parts by weight per 100 parts by weight of the organopolyoxane of the invention.

The curing accelerator is not particularly limited as long as the curing accelerator accelerates the curing reaction between the curing agent and the organopolyoxane of the present invention. Examples of such curing accelerators include aliphatic amines such as ethylenediamine, tri-ethylhexamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminophene And an isophorone diamine; an aromatic amine such as m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl fluorene, 4,4'-diaminodiphenyl hydrazine, 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl ether; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl Imidazole and 2-phenyl-4-methylimidazole; tertiary amines such as dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene and its salts; phosphine , such as triphenylphosphine; a phosphonium salt such as triphenylphosphonium bromide and methyltributylphosphonium dimethyl phosphate; Aminotriazole; tin compounds such as tin octoate and dibutyltin dilaurate; zinc compounds such as zinc octoate; and acetoacetate such as metals of aluminum, chromium, cobalt and zirconium.

Although the compounding amount of the curing accelerator is not particularly limited, since the curing of the organopolysiloxane of the present invention can be sufficiently accelerated and the resulting cured product exhibits excellent heat resistance and weather resistance, the mixing amount is preferably from 0.01 to 5 Within the range of parts by weight, and particularly preferably from 0.1 to 5 parts by weight per 100 parts by weight of the organopolyoxane of the present invention.

Further, from the viewpoint of enhancing the light resistance and heat resistance of the resulting cured product, such as 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, adipic acid double An epoxy compound of (3,4-epoxycyclohexylmethyl), vinylcyclohexene dioxide, and hydrogenated bisphenol A diglycidyl ether can be mixed into the organic polysiloxane containing the present invention as a main group A portion of the curable polydecene oxide composition. Although the compounding amount of the epoxy compound is not particularly limited, the compounding amount is preferably not more than 200 parts by weight, and particularly preferably not more than 100 parts by weight per 100 parts by weight of the organopolysiloxane of the present invention.

The organopolysiloxane of the present invention can be cured to form a cured product which is transparent and has a high refractive index and a suitable modulus of elasticity. Although the elastic modulus of the cured product is not particularly limited, for example, the storage elastic modulus is preferably in the range of 1 to 50 MPa.

The method for producing the organopolyoxane of the present invention will now be described in detail.

The decane compound represented by the following general formula (I) R ¹ R ⁴ SiY ₂ is a raw material for introducing a D unit having an epoxy group-containing organic group into the obtained organic polysiloxane.

In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a phenyl group, and examples thereof are the same as the above groups. Among these, a methyl group is preferred.

In the formula, examples of the epoxy group-containing organic group for R ⁴ include glycidoxyalkyl groups such as 2-glycidoxyethyl, 3-glycidoxypropyl and 4-glycidol. Oxybutyl; epoxy cycloalkylalkyl, such as 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, 2-( 3,4-epoxynorbornyl)ethyl and 2-(3,4-epoxy-3-methylcyclohexyl)-2-methylethyl; and epoxyethylalkyl, such as 4-epoxyethylbutyl and 8-epoxyethyloctyl. Among these, a glycidoxyalkyl group is preferred, and a 3-glycidoxypropyl group is particularly preferred.

In the formula, Y is a hydrolyzable group, and examples thereof include an alkoxy group, a decyloxy group, and a halogen atom. Examples of the alkoxy group for Y include a methoxy group, an ethoxy group, and a propoxy group. Examples of the methoxy group for Y include an ethoxy group. Examples of the halogen atom for Y include a chlorine atom and a bromine atom.

Examples of the decane compound include 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropylethyl dimethyl Oxydecane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxydecane, 4-epoxyethylbutylmethyldimethoxydecane, 8-epoxyethyloctylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxymethoxydecane, 3-shrinkage Glyceryloxypropylethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxydecane, 3-glycidoxypropylmethyldichloride Decane, 3-glycidoxypropylethyldichlorodecane and 2-(3,4-epoxycyclohexyl)ethylmethyldichlorodecane.

The oxoxane compound represented by the following general formula (II) HO(R ¹ R ⁴ SiO) _m H is also a raw material for introducing a D unit having an epoxy group-containing organic group into the obtained organic polysiloxane.

In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a phenyl group, and examples thereof are the same as the above groups. Among these, a methyl group is preferred. Further, in the formula, R ⁴ is an epoxy group-containing organic group, and examples thereof are the same as the above groups. Among these, a glycidoxyalkyl group is preferred, and a 3-glycidoxypropyl group is particularly preferred. Further, in the formula, m is an integer of 1 to 100, preferably an integer of 1 to 50, and particularly preferably an integer of 1 to 20.

The decane compound represented by the following general formula (III) R ¹ ₂ SiY ₂ is an optional raw material for introducing a D unit containing no epoxy group-containing organic group into the obtained organic polysiloxane.

In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a phenyl group, and examples thereof are the same as the above groups. Among these, a methyl group is preferred. Further, Y is a hydrolyzable group, and examples thereof are the same as the above groups.

Examples of the decane compound include dimethyldimethoxydecane, dimethyldiethoxydecane, methylphenyldimethoxydecane, methylphenyldiethoxydecane, and methylethyldimethyl Oxydecane, ethyl phenyl dimethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, dimethyl diethoxy decane, methyl phenyl di oxime Alkane, ethylphenyldiethoxydecane, diphenyldiethoxydecane, dimethyldichlorodecane, methylphenyldichlorodecane, and diphenyldichlorodecane.

The oxoxane compound represented by the following general formula (IV) HO(R ¹ ₂ SiO) _n H is also an optional one for introducing the D unit containing no epoxy group-containing organic group into the obtained organic polyoxane. raw material.

In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a phenyl group, and examples thereof are the same as the above groups. Among these, a methyl group is preferred. Further, in the formula, n is an integer of from 1 to 100, preferably an integer of from 1 to 50, and particularly preferably an integer of from 1 to 20.

The decane compound represented by the following general formula (V) R ³ SiY ₃ is a metal unit for introducing a T unit having a condensed polycyclic aromatic group or an organic group containing a condensed polycyclic aromatic group into the obtained organic polydecane Raw materials.

In the formula, R ³ is a condensed polycyclic aromatic group or an organic group containing a condensed polycyclic aromatic group, and examples thereof are the same as the above groups. Among these, a naphthyl group and a naphthylethyl group are preferred. Further, in the formula, Y is a hydrolyzable group, and examples thereof are the same as the above groups.

Examples of the decane compound include naphthyltrimethoxydecane, decyltrimethoxydecane, phenanthryltrimethoxydecane, decyltrimethoxydecane, naphthyltriethoxydecane,decyltriethoxydecane, Fenyl triethoxy decane, decyl triethoxy decane, naphthylethyl Trimethoxydecane, naphthylpropyltrimethoxydecane, decylethyltrimethoxydecane, naphthyltriethoxydecane,decyltriethoxydecane,phenanthryltriethoxydecane, Mercapto triethoxy decane, naphthyl trichloro decane, decyl trichloro decane, phenanthryl chloride, and decyl trichloro decane.

The production method of the present invention is characterized in that the following substances are subjected to hydrolysis and condensation reaction in the presence of an acid or a base: a decane compound represented by the formula (I) and/or a oxoxane compound represented by the formula (II), And a decane compound represented by the formula (III) and/or a oxane compound represented by the formula (IV) and a decane compound represented by the formula (V), as the case requires.

In the production method of the present invention, the mixing amount of each raw material is such that the D unit introduced into the obtained organopolyoxane (by using the decane compound represented by the general formula (I) and/or by the general formula (II) The ratio of the oxane compound to be represented, and optionally the decane compound represented by the formula (III) and/or the oxane compound represented by the formula (IV) as a raw material, will be a value of 0.20 to 0.60, and The ratio of the T unit introduced into the obtained organopolyoxane (by using the decane compound represented by the general formula (V) as a raw material) will be a value of 0.40 to 0.80.

Further, a decane compound represented by the formula (I) or a decane compound represented by the formula (II) for introducing a D unit, and a decane compound represented by the formula (III) or a formula The proportion of the oxoxane compound represented by (IV) is not particularly limited. However, from the viewpoint that the curability of the obtained organopolyoxane is excellent, the ratio of the compounds is such that the ratio of R ⁴ to all of R ¹ and R ⁴ is preferably at least 10 mol%, and more preferably Jia will be at least 15% by mole.

Examples of the acid which can be used in the production method of the present invention include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acid, trifluoromethanesulfonic acid, and ion exchange resin. Further, examples of the base which can be used in the production method of the present invention include inorganic bases such as potassium hydroxide, sodium hydroxide and barium hydroxide; and organic base compounds such as triethylamine, diethylamine, monoethanolamine, diethanolamine , triethanolamine, aqueous ammonia, tetramethylammonium hydroxide, alkoxydecane having an amine group, and aminopropyltrimethoxydecane.

In the production method of the present invention, an organic solvent can be used. Examples of the organic solvent include ethers, ketones, acetates, aromatic or aliphatic hydrocarbons, and 3-butyrolactone; and mixtures of two or more of such solvents. Specifically, examples of such organic solvents are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monobutylene. Ether, 3-butyrolactone, toluene and xylene.

In order to accelerate the hydrolysis and condensation reaction of the components in the production method of the present invention, it is preferred to add water or a mixed solution of water and an alcohol. Preferred examples of the alcohol include methanol and ethanol. If an organic solvent is used and the reaction is accelerated by heating, the reaction is preferably carried out at the reflux temperature of the organic solvent.

Instance

The organopolyoxane of the present invention and a method for producing the same will now be described in more detail by way of examples. Further, in the formula, Me is a methyl group, wherein Ph is a phenyl group, wherein Naph is a 1-naphthyl group, and Ep is a 3-glycidoxypropyl group. Further, the characteristics of the organopolyoxane are evaluated as follows.

[Weight average molecular weight and dispersion]

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the standard polystyrene of the organopolyoxane were determined by gel permeation chromatography using an RI detector. The degree of dispersion (Mw/Mn) was determined from these values.

[refractive index]

The refractive index of the organopolyoxane at 25 ° C was measured using an Abbe refractometer. Visible light (632.8 nm) was used as a light source.

[viscosity]

The viscosity of the organopolyoxane at 25 ° C was measured using a rotational viscometer VG-DA (manufactured by Shibaura System Co., Ltd.).

[epoxy equivalent weight]

The organic polymerization is determined by the structure identified by analysis using nuclear magnetic resonance spectroscopy The epoxy equivalent weight (g/mol) of the decane.

[methoxy content]

The methoxy group content (% by weight) in the organopolyoxane was determined from the structure identified by analysis using nuclear magnetic resonance spectroscopy.

Further, the characteristics of the curable polydecene oxide composition containing the organopolysiloxane as a main component and in which a curing agent and a curing accelerator are mixed, and the characteristics of the cured product thereof are evaluated as follows.

[Viscosity of the curable polyanthracene composition]

The viscosity of the curable polyanthracene composition at 25 ° C was measured using an AR 500 (manufactured by TA Instruments). Note that the viscosity is measured using a cone having a cone diameter of 20 mm and a cone angle of 2° of 20 s ^-1 .

[Storage modulus of the cured product]

The curable polyoxynoxy composition was heated at 150 ° C for 1 hour to produce a film-like cured product having a thickness of 0.5 mm. Next, the 0.5 mm thick film sample was sandwiched between parallel plates having a diameter of 8 mm by using an MCR 301 rheometer (manufactured by Anton Paar GmbH), and storage at 25 ° C was measured by applying the following conditions. Elastic modulus values: strain: 0.1%; frequency: 1 Hz; vertical force: a constant pressure of 5 N; and the temperature was raised from -10 ° C to 50 ° C at a rate of 3 ° C/min.

[Refractive index of the cured product]

The refractive index of the cured product prepared by the above method at 25 ° C was measured by a prism coupler method. A 632.8 nm laser source was used for this measurement.

[Transparency of the cured product]

The transparency of the cured product prepared by the above method was visually confirmed.

[Actual Example 1]

49.67 g of 1-naphthyltrimethoxynonane, 14.69 g of 3-glycidoxypropylmethyldimethoxydecane and 47.49 g of toluene were placed in a mixer, thermometer, reflux tube and drops. The reaction funnel was placed in the reaction vessel and stirred. A mixture of 0.07 g of a 50% aqueous potassium hydroxide solution, 9.90 g of water and 9.90 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. After cooling, the resulting product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 47.00 g of a clear brown solid (at room temperature) was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the solid was an organic polyoxane represented by the following average unit formula: (EpMeSiO _2/2 ) _0.24 (NaphSiO _3/2 ) _0.76 (MeO _1/2 ) _0.05 .

The organopolyoxyalkylene had an epoxy equivalent weight of 740 g/mol. The organic polyoxyalkylene had a methoxy group content of 0.8% by weight. The weight average molecular weight (Mw) was 1,400. The degree of dispersion (Mw/Mn) was 1.12. The refractive index is 1.615.

[Actual example 2]

37.25 g of 1-naphthyltrimethoxynonane, 33.05 g of 3-glycidoxypropylmethyldimethoxydecane and 53.03 g of toluene were placed in a reaction vessel provided with a stirrer, a thermometer, a reflux tube and a dropping funnel. And stir. A mixture of 0.07 g of a 50% aqueous potassium hydroxide solution, 10.12 g of water and 10.12 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. After cooling, the resulting product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 53.70 g of a clear brown gum-like substance (at room temperature) was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the solid was an organopolyoxane represented by the following average unit formula: (EpMeSiO _2/2 ) _0.50 (NaphSiO _3/2 ) _0.50 .

The organopolyoxyalkylene had an epoxy equivalent weight of 350 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1% by weight. The weight average molecular weight (Mw) was 1,800. The degree of dispersion (Mw/Mn) was 1.20. The refractive index is 1.568.

[Actual Example 3]

37.25 g of 1-naphthyltrimethoxynonane, 33.05 g of 3-glycidoxypropylmethyldimethoxydecane and 58.22 g of toluene were placed in a reaction vessel provided with a stirrer, a thermometer, a reflux tube and a dropping funnel. And stir. A mixture of 0.07 g of a 50% aqueous potassium hydroxide solution, 4.73 g of water and 4.73 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. After cooling, the resulting product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 56.95 g of a clear yellow liquid having a viscosity of 1,600 mPa ̇s was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the liquid was an organic polyoxane represented by the following average unit formula: (EpMeSiO _2/2 ) _0.49 (NaphSiO _3/2 ) _0.51 (MeO _1/2 ) _0.20 .

The organopolyoxyalkylene had an epoxy equivalent weight of 370 g/mol. The organic polyoxyalkylene had a methoxy group content of 3.4% by weight. The weight average molecular weight (Mw) was 1,200. The degree of dispersion (Mw/Mn) was 1.26. The refractive index is 1.543.

[Actual Example 4]

49.67 g of 1-naphthyltrimethoxynonane, 14.69 g of 3-glycidoxypropylmethyldimethoxydecane and 47.49 g of toluene were placed in a reaction vessel provided with a stirrer, a thermometer, a reflux tube and a dropping funnel. And stir. A mixture of 0.10 g of cesium hydroxide monohydrate, 9.90 g of water and 9.90 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. cool down Thereafter, the obtained product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 48.77 g of a clear pale yellow liquid (at room temperature) was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the liquid was an organopolyoxane represented by the following average unit formula: (EpMeSiO _2/2 ) _0.24 (NaphSiO _3/2 ) _0.76 (MeO _1/2 ) _0.01 .

The organopolyoxyalkylene had an epoxy equivalent weight of 740 g/mol. The organic polyoxyalkylene had a methoxy group content of 0.1% by weight. The weight average molecular weight (Mw) was 1,300. The degree of dispersion (Mw/Mn) was 1.07. The refractive index is 1.600.

[Actual Example 5]

37.25 g of 1-naphthyltrimethoxynonane, 33.05 g of 3-glycidoxypropylmethyldimethoxydecane and 58.22 g of toluene were placed in a reaction vessel provided with a stirrer, a thermometer, a reflux tube and a dropping funnel. And stir. A mixture of 0.12 g of cesium hydroxide monohydrate, 4.73 g of water and 4.73 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. After cooling, the resulting product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 58.63 g of a clear yellow liquid having a viscosity of 800 mPa ̇s was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the liquid was an organic polyoxane represented by the following average unit formula: (EpMeSiO _2/2 ) _0.51 (NaphSiO _3/2 ) _0.49 (MeO _1/2 ) _0.23 .

The organopolyoxyalkylene had an epoxy equivalent weight of 360 g/mol. The organic polyoxyalkylene had a methoxy group content of 3.9% by weight. The weight average molecular weight (Mw) was 1,200. The degree of dispersion (Mw/Mn) was 1.27. The refractive index is 1.539.

[Actual Example 6]

77.48 g of 1-naphthyltrimethoxynonane, 7.05 g of 3-glycidoxypropylmethyldimethoxydecane and 4.16 g of dimethylpolyanion represented by the formula HO(Me ₂ SiO) ₁₀ H The oxane and 56.69 g of toluene were placed in a reaction vessel provided with a stirrer, a thermometer, a reflux tube and a dropping funnel, and stirred. A mixture of 0.11 g of cesium hydroxide monohydrate, 13.50 g of water and 13.50 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. After cooling, the resulting product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 66.53 g of a slightly yellow solid (at room temperature) was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the solid was an organic polyoxane represented by the following average unit formula: (Me ₂ SiO _2/2 ) _0.14 (EpMeSiO _2/2 ) _0.08 (NaphSiO _3/2 ) _0.78 .

The organopolyoxyalkylene had an epoxy equivalent weight of 2,100 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1% by weight. The weight average molecular weight (Mw) was 1,300. The degree of dispersion (Mw/Mn) was 1.13. The refractive index is 1.614.

[Comparative Example 1]

50.00 g of 1-naphthylmethyldimethoxydecane, 50.85 g of 3-glycidoxypropyltrimethoxydecane and 76.13 g of toluene were placed in a reaction vessel provided with a stirrer, a thermometer, a reflux tube and a dropping funnel. And stir. A mixture of 0.07 g of cesium hydroxide monohydrate, 14.51 g of water and 14.51 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. After cooling, the resulting product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 76.20 g of a slightly yellow solid (at room temperature) was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the solid was an organic polyoxane represented by the following average unit formula: (NaphMeSiO _2/2 ) _0.49 (EpSiO _3/2 ) _0.51 .

The organopolyoxyalkylene had an epoxy equivalent weight of 350 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1% by weight. The weight average molecular weight (Mw) was 1,800. The degree of dispersion (Mw/Mn) was 1.36. The refractive index is 1.569.

[Comparative Example 2]

50.00 g of 1-naphthylmethyldimethoxydecane, 50.85 g of 3-glycidoxypropyltrimethoxydecane and 3.54 g of dimethylpolyanion represented by the formula HO(Me ₂ SiO) ₁₀ H The oxane and 79.65 g of toluene were placed in a reaction vessel provided with a stirrer, a thermometer, a reflux tube and a dropping funnel, and stirred. A mixture of 0.08 g of cesium hydroxide monohydrate, 14.51 g of water and 14.51 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. After cooling, the resulting product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 79.22 g of a slightly yellow solid (at room temperature) was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the solid was an organic polyoxane represented by the following average unit formula: (NaphMeSiO _2/2 ) _0.45 (Me ₂ SiO _2/2 ) _0.10 (EpSiO _3/2 ) _0.45 .

The organopolyoxyalkylene had an epoxy equivalent weight of 370 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1% by weight. The weight average molecular weight (Mw) was 1,700. The degree of dispersion (Mw/Mn) was 1.41. The refractive index is 1.561.

[Comparative Example 3]

59.40 g of phenyltrimethoxydecane, 66.10 g of 3-glycidoxypropylmethyldimethoxydecane and 91.00 g of toluene were placed in a reaction vessel provided with a stirrer, a thermometer, a reflux tube and a dropping funnel, and Stir. A mixture of 0.13 g of a 50% aqueous potassium hydroxide solution, 20.25 g of water and 20.25 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. After cooling, the resulting product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 90.80 g of a transparent yellow liquid having a viscosity of 13,400 mPa ̇s was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the liquid was an organopolyoxane represented by the following average unit formula: (EpMeSiO _2/2 ) _0.51 (PhSiO _3/2 ) _0.49 .

The organopolyoxyalkylene had an epoxy equivalent weight of 300 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1% by weight. The weight average molecular weight (Mw) was 2,600. The degree of dispersion (Mw/Mn) was 1.34. The refractive index is 1.513.

[Comparative Example 4]

59.40 g of phenyltrimethoxydecane, 66.10 g of 3-glycidoxypropylmethyldimethoxydecane and 101.35 g of toluene were placed in a reaction vessel provided with a stirrer, a thermometer, a reflux tube and a dropping funnel, and Stir. A mixture of 0.13 g of a 50% aqueous potassium hydroxide solution, 9.45 g of water and 9.45 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. After cooling, the resulting product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 99.35 g of a transparent yellow liquid having a viscosity of 100 mPa ̇s was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the liquid was an organic polyoxane represented by the following average unit formula: (EpMeSiO _2/2 ) _0.51 (PhSiO _3/2 ) _0.49 (MeO _1/2 ) _0.21 .

The organopolyoxyalkylene had an epoxy equivalent weight of 310 g/mol. The organic polyoxyalkylene had a methoxy group content of 4.1% by weight. The weight average molecular weight (Mw) was 1,400. Dispersion (Mw/Mn) was 1.28. The refractive index is 1.491.

[Comparative Example 5]

49.67 g of 1-naphthyltrimethoxynonane, 15.76 g of 3-glycidoxypropyltrimethoxydecane and 47.03 g of toluene were placed in a reaction vessel provided with a stirrer, a thermometer, a reflux tube and a dropping funnel, and stirred. . A mixture of 0.07 g of a 50% aqueous potassium hydroxide solution, 10.80 g of water and 10.80 g of methanol was gradually added to the reaction vessel using a dropping funnel. After the addition was completed, the mixture was refluxed for 1 hour. The produced methanol and excess water were removed by azeotropic dehydration, and then the resulting product was reacted in toluene for 8 hours under reflux. After cooling, the resulting product was neutralized with acetic acid. After neutralizing the salt by filtration, toluene and a low-boiling component were heated under reduced pressure to be removed by distillation. Thus, 56.95 g of a clear pale yellow powder (at room temperature) was obtained.

It was confirmed by analysis by nuclear magnetic resonance spectroscopy that the powder was an organic polyoxane represented by the following average unit formula: (EpSiO _3/2 ) _0.24 (NaphSiO _3/2 ) _0.76 .

The organopolyoxyalkylene had an epoxy equivalent weight of 720 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1% by weight. The weight average molecular weight (Mw) was 2,200. The degree of dispersion (Mw/Mn) was 1.37. The refractive index is 1.623.

[Application Example 1]

1.02 g of an organopolyoxane represented by the following average unit formula (EpMeSiO _2/2 ) _0.24 (NaphSiO _3/2 ) _0.76 (MeO _1/2 ) _0.05 , 0.98 g of an epoxy compound prepared in Practical Example 1 (3',4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; Celloxide 2021P, manufactured by Daicel Chemical Industries Ltd.), 1.58 g of an acid anhydride-based curing agent (3- or 4-methyl-hexahydrophthalic anhydride; HN 5500E, manufactured by Hitachi Chemical Co., Ltd.) and 0.0236 g of a curing accelerator (methyltributylphosphonium dimethyl phosphate; Hishicolin PX-4MP, Nippon Chemical Industrial Co., Ltd.) was mixed to prepare a liquid curable polydecene oxide composition.

The curable polydecene oxide composition was coated on a quartz glass plate and cured by heating at 150 ° C for 1 hour. The cured product obtained was transparent and colorless, and had a storage elastic modulus of 1.84 MPa and a refractive index of 1.5284.

[Application Example 2]

2.04 g of an organic polyoxane represented by the following average unit formula (EpMeSiO _2/2 ) _0.50 (NaphSiO _3/2 ) _0.50 , 0.95 g of an acid anhydride-based curing agent (3- or 4-A) prepared in Practical Example 2 Base-hexahydrophthalic anhydride; HN 5500E, manufactured by Hitachi Chemical Co., Ltd., 0.0300 g of curing accelerator (methyltributylphosphonium dimethyl phosphate; Hishicolin PX-4MP, by Nippon Chemical Industrial) Co., Ltd., manufactured by Co., Ltd., and additional toluene were mixed to prepare a toluene solution (concentration: about 30% by weight) of the curable polyoxynene composition.

The curable polydecene oxide composition was coated on a quartz glass plate. After the toluene was volatilized by air drying for 1 day, the curable polydecene oxide composition was cured by heating at 150 ° C for 1 hour. The cured product obtained was transparent and colorless, and had a storage elastic modulus of 30.3 MPa and a refractive index of 1.5524.

[Application Example 3]

1.99 g of an organic polyoxane represented by the following average unit formula (EpMeSiO _2/2 ) _0.49 (NaphSiO _3/2 ) _0.51 (MeO _1/2 ) _0.05 , 0.94 g of an acid anhydride-based curing agent prepared in Practical Example 3 (3- or 4-methyl-hexahydrophthalic anhydride; HN 5500E, manufactured by Hitachi Chemical Co., Ltd.), 0.0195 g of a curing accelerator (methyltributylphosphonium dimethyl phosphate; Hishicolin PX) -4MP, manufactured by Nippon Chemical Industrial Co., Ltd.) and additional toluene were mixed to prepare a toluene solution (concentration: about 30% by weight) of the curable polyxanylene composition.

The curable polydecene oxide composition was coated on a quartz glass plate. After the toluene was volatilized by air drying for 1 day, the curable polydecene oxide composition was cured by heating at 150 ° C for 1 hour. The cured product obtained was transparent and colorless, and had a storage elastic modulus of 12.9 MPa and a refractive index of 1.5484.

[Control application example 1]

2.07 g of an organic polyoxane represented by the following average unit formula (NaphMeSiO _2/2 ) _0.49 (EpSiO _3/2 ) _0.51 , 0.95 g of an acid anhydride-based curing agent (3- or 4-A) prepared in Comparative Example 1 Base-hexahydrophthalic anhydride; HN 5500E, manufactured by Hitachi Chemical Co., Ltd., 0.0214 g of a curing accelerator (methyltributylphosphonium dimethyl phosphate; Hishicolin PX-4MP, by Nippon Chemical Industrial) (manufactured by Co., Ltd.), 0.0158 g of an antioxidant, 10.8 wt% of a solution of isovalerol [3-(3,5-di-t-butyl-hydroxyphenyl)propionic acid] in toluene and Additional toluene was mixed to prepare a toluene solution (concentration: about 30% by weight) of the curable polydecane oxide composition.

The curable polydecene oxide composition was coated on a quartz glass plate. After the toluene was volatilized by air drying for 1 day, the curable polydecene oxide composition was cured by heating at 150 ° C for 1 hour. The cured product obtained was transparent and colorless, and had a storage elastic modulus of 0.89 MPa and a refractive index of 1.5481.

[Control application example 2]

1.07 g of an organopolyoxane represented by the following average unit formula (EpMeSiO _2/2 ) _0.51 (PhSiO _3/2 ) _0.49 and 0.97 g of an epoxy compound (3', 4'-) prepared in Comparative Example 3 were prepared. Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; Celloxide 2021P, manufactured by Daicel Chemical Industries Ltd.), 1.86 g of an acid anhydride-based curing agent (3- or 4-methyl-hexahydrogen) Phthalic anhydride; HN 5500E, manufactured by Hitachi Chemical Co., Ltd.) and 0.0208 g of a curing accelerator (methyltributylphosphonium methacrylate; Hishicolin PX-4MP, by Nippon Chemical Industrial Co., Ltd.) . Manufacture) mixing to prepare a liquid curable polydecene oxide composition.

The curable polydecene oxide composition was coated on a quartz glass plate and cured by heating at 150 ° C for 1 hour. The cured product obtained was transparent and colorless, and had a storage elastic modulus of 8.0 MPa and a refractive index of 1.5073.

[Control application example 3]

2.00 g of an organic polyoxoxane represented by the following average unit formula (EpMeSiO _2/2 ) _0.51 (PhSiO _3/2 ) _0.49 (MeO _1/2 ) _0.21 , 1.07 g of an acid anhydride-based curing agent prepared in Comparative Example 4 (3- or 4-methyl-hexahydrophthalic anhydride; HN 5500E, manufactured by Hitachi Chemical Co., Ltd.) and 0.0154 g of a curing accelerator (methyltributylphosphonium dimethyl phosphate; Hishicolin PX) -4MP, manufactured by Nippon Chemical Industrial Co., Ltd.) was mixed to prepare a liquid curable polydecane oxygen composition.

The curable polydecene oxide composition was coated on a quartz glass plate and cured by heating at 150 ° C for 1 hour. The cured product obtained was transparent and colorless, and had a storage elastic modulus of 11.8 MPa and a refractive index of 1.5098.

[Control application example 4]

2.01 g of an organic polyoxane represented by the following average unit formula (EpSiO _3/2 ) _0.24 (NaphSiO _3/2 ) _0.76 , 0.49 g of an acid anhydride-based curing agent (3- or 4-A) prepared in Comparative Example 5 Base-hexahydrophthalic anhydride; HN 5500E, manufactured by Hitachi Chemical Co., Ltd., 0.0236 g of a curing accelerator (methyltributylphosphonium dimethyl phosphate; Hishicolin PX-4MP, by Nippon Chemical Industrial) Co., Ltd., manufactured by Co., Ltd., and additional toluene were mixed to prepare a toluene solution (concentration: about 30% by weight) of the curable polyoxynene composition.

The curable polydecene oxide composition was coated on a quartz glass plate. After the toluene was volatilized by air drying for 1 day, the curable polydecene oxide composition was cured by heating at 150 ° C for 1 hour. The cured product obtained was transparent and colorless, and had a storage elastic modulus of 68.7 MPa and a refractive index of 1.6029.

Industrial applicability

Since the organopolysiloxane of the present invention can be cured by the reaction of an epoxy group and forms a cured product having transparency and a high refractive index and a suitable modulus of elasticity, the organopolysiloxane of the present invention is preferably used for optics. Materials such as photoresists, coatings, films, sheets, adhesives, coating materials, sealing materials, lenses, light guides and optical waveguides, and particularly good for sealing materials, coating agents or adhesives for LED components; Electrodes or classes around the component a coating of the object; or a lens forming material.

Claims (7)

An organopolyoxane which is represented by the following average unit formula: (R ¹ R ² SiO _2/2 ) _a (R ³ SiO _3/2 ) _b (XO _1/2 ) _c wherein R ¹ has 1 to An alkyl group of 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a phenyl group; and R ² is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a phenyl group or An epoxy group-containing organic group, provided that at least one R ² in the molecule is an epoxy group-containing organic group; and R ³ is a condensed polycyclic aromatic group or an organic group containing a condensed polycyclic aromatic group; a group; X is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom; a is a number from 0.20 to 0.60, b is a number from 0.40 to 0.80, a sum of a and b is 1.00, and c is from 0 to 0.5. digital. The organopolyoxane of claim 1, wherein the epoxy group-containing organic group for R ² is a glycidoxyalkyl group, an epoxycycloalkylalkyl group or an epoxyethylalkyl group. The organopolyoxane of claim 1 wherein R ³ is naphthyl or naphthylethyl. The organopolyoxane of claim 1, wherein at least 10 mole % of all of R ¹ and R ^{2 in} the molecule is an epoxy group-containing organic group. A process for producing an organopolyoxane according to claim 1, which comprises the steps of subjecting a substance to hydrolysis and condensation in the presence of an acid or a base: a decane compound represented by the following formula (I) R ¹ R ⁴ SiY ₂ wherein R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a phenyl group; R ⁴ is an epoxy group-containing organic group; and Y a hydrolyzable group; and/or a oxoxane compound represented by the following formula (II): HO(R ¹ R ⁴ SiO) _m H wherein R ¹ and R ⁴ are the same as described above, and m is An integer of from 1 to 100; and, if necessary, a decane compound represented by the following formula (III): R ¹ ₂ SiY ₂ wherein R ¹ and Y are the same as those described above; and/or from the following formula (IV) a halogenated alkane compound: HO(R ¹ ₂ SiO) _n H wherein R ¹ is the same as the above, and n is an integer from 1 to 100; and a decane compound represented by the following formula (V): R ³ SiY ₃ wherein R ³ is a condensed polycyclic aromatic group or an organic group containing a condensed polycyclic aromatic group, and the Y system is the same as the above. The production method of claim 5, wherein, in the decane compound represented by the formula (I) and the oxirane compound represented by the formula (II), R ⁴ is a glycidoxyalkyl group or an epoxy group Alkyl or epoxyethylalkyl. The production method of claim 5, wherein in the decane compound represented by the general formula (V), R ³ is a naphthyl group or a naphthylethyl group.