JP2010018719A - Silicon-containing curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicon-containing curable composition which is hardly discolored due to light deterioration or thermal deterioration and is made hard, to which dust is hardly stuck and which is useful as electric/electronic materials, particularly as a sealing agent for a light emitting element. <P>SOLUTION: The silicon-containing curable composition contains: as a component (A), a prepolymer which is obtained by subjecting a cyclic siloxane compound having two or more Si-H groups in one molecule thereof and a trivinylcyclohexane compound to a hydrosilylation reaction by such a ratio that two or more Si-H groups remains in one molecule of the prepolymer and which has two or more Si-H groups in one molecule thereof; as a component (B), a cyclic siloxane compound having two or more carbon-carbon double bonds, each of which has reactivity with the Si-H group, in one molecule thereof; and as a component (C), a hydrosilylation catalyst. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a silicon-containing curable composition and a cured product obtained by curing the composition. Specifically, the present invention relates to a silicon-containing curable composition useful as an electric / electronic material such as an LED sealing material and a cured product thereof.

Light-emitting elements such as light-emitting diodes (LEDs) are usually sealed with a sealant because their light-emitting characteristics deteriorate rapidly due to moisture in the atmosphere or floating dust when they come into direct contact with the atmosphere. It has a structure. As a sealant for sealing such a light emitting element, an epoxy resin such as a bisphenol type epoxy resin or an alicyclic epoxy resin has been used because of its high adhesive strength and excellent mechanical durability (for example, , See Patent Document 1). In recent years, LEDs have come to be used in applications that require high brightness, such as automotive headlights and lighting, and sealants that seal light emitting elements are high enough to withstand an increase in the amount of heat generated during lighting. In addition to heat resistance, high light resistance is required to prevent light deterioration associated with higher brightness.
However, it is difficult to say that a conventional sealant using an epoxy resin has sufficient heat resistance and light resistance. For applications that require high brightness such as automotive headlights and lighting, a sealant made of an epoxy resin is difficult. In some cases, it was not possible to use a stop agent. In addition, epoxy resin has low transmittance for light having a short wavelength in the blue to ultraviolet region, and may cause coloration due to light deterioration or heat deterioration. Therefore, recently developed blue light emitting diodes, ultraviolet light emitting diodes, and However, there is a problem in that they may not be used for sealants such as white light emitting diodes in which these are combined with a phosphor.
On the other hand, since the silicone resin has high transparency to short-wavelength light in the blue to ultraviolet region, a method of using it as a sealant for sealing a light emitting element of an LED instead of an epoxy resin is known (for example, (See Patent Documents 2 and 3). However, silicone resin has many outgas components (volatile components), so its use is limited due to contamination problems in the manufacturing process of electronic components, etc., and since it is soft and has surface tackiness, dust on the surface is easy. There was a drawback that the light transmittance was reduced due to adhesion. As a silicone resin having a small outgas component, a prepolymer containing two or more Si-H groups in one molecule and two carbon-carbon double bonds having reactivity with Si-H groups are contained in one molecule. A silicone resin (for example, see Patent Document 4) obtained by reacting at least one cyclic siloxane compound is known, but it does not improve photodegradation or surface tack.

JP 2003-277473 A JP 2002-88244 A JP 2002-314142 A JP 2006-232970 A

Accordingly, an object of the present invention is to provide a silicon-containing curable composition which is less colored due to light deterioration and heat deterioration, is hard and has little dust adhesion, and is useful as a sealing agent for electrical and electronic materials, particularly light emitting devices. It is in.

As a result of intensive studies to solve the above problems, the present inventors have focused on the structure and prepolymer of a specific silicon-containing compound, and have completed the present invention.
That is, the present invention
As the component (A), a cyclic siloxane compound (a-1) represented by the following general formula (1) having two or more Si-H groups in one molecule and the following general formula (2) In the molecule obtained by subjecting the alicyclic structure-containing unsaturated compound (a-2) to a hydrosilylation reaction in such a ratio that two or more Si-H groups remain in one molecule after the reaction. A prepolymer having two or more Si-H groups;
As the component (B), a cyclic siloxane compound represented by the following general formula (3) having two or more carbon-carbon double bonds having reactivity with the Si-H group in one molecule;
As component (C), a hydrosilylation catalyst,
The above object is achieved by providing a silicon-containing curable composition characterized by containing.

^(Wherein, R 1, ^{R 2} and ^{R 3} represent different and have a good C 1 -C 6 alkyl group or a phenyl group each identical, a is a number from 2 to 10, b is 0 Represents the number 8)

(Wherein ^a R 4, ^{R 5} and an alkyl group or a phenyl group ^{R 6} is 1 to 6 carbon atoms which may the same as or different from each other, p is a number from 2 to 10, q is 0 It is a number of 8.)
Moreover, this invention provides the silicon-containing hardened | cured material which heat-hardened the said silicon-containing curable composition.

According to the present invention, it is possible to provide a silicon-containing curable composition that is less colored due to light degradation and heat degradation, is hard and has little dust adhesion, and is useful as an encapsulant for electric / electronic materials, particularly light-emitting elements.

Hereinafter, the silicon-containing curable composition of the present invention will be described in detail based on preferred embodiments.

First, the prepolymer which is the component (A) according to the present invention will be described.
The prepolymer of the component (A) according to the present invention has a cyclic siloxane compound (a-1) represented by the above general formula (1) having two or more Si—H groups in one molecule, and the above general Hydrosilylation reaction of the alicyclic structure-containing unsaturated compound (a-2) represented by the formula (2) at such a ratio that two or more Si-H groups remain in one molecule after the reaction. Is a compound having two or more Si—H groups in one molecule.

In the general formula ^(1), the alkyl group having 1 to 6 carbon atoms represented by R 1, ^{R 2} and ^{R 3,} methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, t- butyl , Pentyl, isopentyl, secondary pentyl, t-pentyl, hexyl and secondary hexyl groups. R ¹ is preferably a methyl group because it is easily available industrially, and R ² and R ³ are preferably a methyl group or a phenyl group because the outgas component in the silicon-containing curable composition of the present invention can be lowered. Further, a methyl group is more preferable because photodegradation is less likely to occur. As a, since the crosslinking density of hardening reaction becomes high and it becomes hard and dust adhesion decreases, 3-7 are preferable and 4-6 are still more preferable. In view of ease of production, the value of a + b is preferably 4 to 8, more preferably 4 to 6, and most preferably 4 to 5.

Specific examples of the component (a-1) include 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethyl. -2-phenylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4-diphenylcyclotetrasiloxane, 2,4,6-tetramethyl-8-phenylcyclotetrasiloxane, 2,4-tetramethyl -6,8-diphenylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10,12-hexamethylcyclohexasiloxane, etc. Are easily available and the number of Si-H functional groups is appropriate, so that 2,4,6,8-tetramethylcyclotetrasiloxane and 2,4,6,8 Preferably 10 pentamethylcyclopentasiloxane, more preferably 2,4,6,8-tetramethylcyclotetrasiloxane. The component (a-1) may be used alone or in combination of two or more.

The component (a-2) is an alicyclic structure-containing unsaturated compound represented by the general formula (2). Specific examples thereof include 1,2,3-trivinylcyclohexane and 1,2,4-trivinyl. Although cyclohexane and 1,3,5-trivinylcyclohexane are mentioned, 1,2,4-trivinylcyclohexane is preferable because it is easily available industrially.

The prepolymer of the component (A) according to the present invention is obtained by subjecting the component (a-1) and the component (a-2) to a hydrosilylation reaction. If the blending ratio of the component (a-1) and the component (a-2) is a blending ratio that contains two or more Si—H groups in one molecule of the prepolymer (A), Although not particularly limited, preferably, from the point of viscosity of the prepolymer, the reaction between the number (X) of Si-H groups in the component (a-1) and the Si-H groups in the component (a-2) The ratio to the number of carbon-carbon double bonds having a property (Y) is preferably X: Y = 10: 1 to 8: 1, more preferably X: Y = 7: 1 to 5: 1, and X: Y = 4: 1 to 2: 1 is most preferable.

The concentration of the Si—H group of the prepolymer of the component (A) according to the present invention is preferably 0.0001 to 100 mmol / g, more preferably 0.01 to 40 mmol / g, from the viewpoint of curability and storage stability. 0.1-20 mmol / g is most preferable. The concentration of Si-H groups ^can be determined from the ratio of the integrated value of the peaks of the 1 H-NMR analysis is.

The prepolymer of the component (A) according to the present invention preferably has a weight average molecular weight of 500 to 500,000, more preferably 1,000 to 300,000, most preferably 5,000 to 50,000, from the viewpoint of heat resistance and handling properties. preferable. In addition, the weight average molecular weight of this prepolymer means the weight average molecular weight of polystyrene conversion calculated | required by GPC measurement which used tetrahydrofuran as the solvent.
The number of Si—H groups contained in the prepolymer (A) can be determined from the product of the concentration of Si—H groups and the weight average molecular weight.

The hydrosilylation reaction between the component (a-1) and the component (a-2) is preferably performed using a catalyst. Examples of the hydrosilylation catalyst include a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst. Can be mentioned. Examples of platinum-based catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc., platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane complexes. (KaRstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (for example, Pt [P (C ₆ H ₅ ) ₃ ] ₄ , PtCl [P (C ₆ H ₅ ) ₃ ] ₃ , Pt [P (C ₄ H ₉ ) ₃ ) ₄ ], platinum-phosphite complexes (eg, Pt [P (OC ₆ H ₅ ) ₃ ] ₄ ), Pt [P (OC ₄ H ₉ ) ₃ ] ₄ ), Dicarbonyldichloroplatinum and the like. Examples of the palladium catalyst or rhodium catalyst include compounds containing a palladium atom or a rhodium atom instead of the platinum atom of the platinum catalyst. These may be used alone or in combination of two or more. The hydrosilylation catalyst is preferably a platinum-based catalyst from the viewpoint of reactivity, more preferably a platinum-divinyltetramethyldisiloxane complex and a platinum-carbonylvinylmethyl complex, and most preferably a platinum-carbonylvinylmethyl complex. Moreover, the usage-amount of a catalyst is 5 mass% or less of the total amount of (a-1) component and (b-1) component from a reactive point, and 0.0001-1.0 mass% is still more preferable. 0.001 to 0.1% by mass is most preferable.

The reaction conditions for hydrosilylation of the component (a-1) and the component (a-2) are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst. 25 ° C.) to 130 ° C., and a conventionally known solvent such as toluene, hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used during the reaction.

The prepolymer of the component (A) according to the present invention is a cyclic siloxane compound represented by the general formula (1) having two or more Si-H groups in one molecule, and the component (a-1) The ratio of the component (a-2) which is an alicyclic structure-containing unsaturated compound represented by the general formula (2) such that two or more Si-H groups remain in one molecule after the reaction. It is a compound having two or more Si—H groups in one molecule, obtained by hydrosilylation reaction. In the present invention, since a low-boiling point product can be removed by making it a prepolymer and then using it as a blending component of the curable composition, a cured composition having an extremely small outgas component can be obtained. Moreover, in this invention, since (a-2) component is an alicyclic structure, hardened | cured material with small cure shrinkage property is obtained. Furthermore, since the component (a-1) according to the present invention is a cyclic siloxane compound, the physical strength (rigidity), crack resistance, etc. of the cured product are improved as compared with the case of a chain compound. Can do.

Next, the component (B) according to the present invention will be described. The component (B) of the present invention is a cyclic siloxane compound represented by the above general formula (3) having two or more carbon-carbon double bonds having reactivity with Si-H groups in one molecule. . Examples of the alkyl group represented by R ⁴ , R ⁵ and R ⁶ include the groups exemplified in the description of the general formula (1). As R ⁴ , R ⁵ and R ⁶ , a methyl group or a phenyl group is preferable because it is easily available industrially. p is preferably 2 to 4 from the viewpoint of the crosslinking density of the cured product, and the value of p + q is preferably 4 to 8 and more preferably 4 to 6 in terms of ease of production.

Specific examples of the component (B) that are preferable from the viewpoint of physical properties of the cured product include 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6,6,8,8- Hexamethyl-2,4-divinylcyclotetrasiloxane, 2,4,6,8,8-pentamethyl-2,4,6-trivinylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4 6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetramethyl-8-phenyl-2,4,6-trivinylcyclotetrasiloxane, 2,4,6,8-tetramethyl-6, 8-diphenyl-2,4-divinylcyclotetrasiloxane, 2,4,6,8-tetraphenyl-2,4,6,8-tetravinylcyclotetrasiloxane 2,4,6,8,10-pentamethyl-2 , , 6,8,10- penta vinyl cyclopentasiloxane, 2,4,6,8,10,12-hexamethyl-2,4,6,8,10,12-hexa vinyl cyclohexasiloxane and the like.

2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetramethyl-8-phenyl-2 because of industrial availability , 4,6-trivinylcyclotetrasiloxane, 2,4,6,8-tetramethyl-6,8-diphenyl-2,4-divinylcyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2 4,6,8,10-pentavinylcyclopentasiloxane, 2,4,6,8,10,12-hexamethyl-2,4,6,8,10,12-hexavinylcyclohexasiloxane is preferred. , 4,6,8,10-pentamethyl-2,4,6,8,10-pentavinylcyclopentasiloxane, 2,4,6,8,10,12-hexamethyl-2,4,6,8,10 , 12-hex Vinyl cyclohexanol siloxane, and most preferably 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane.

Since the component (B) according to the present invention is a cyclic siloxane compound containing two or more carbon-carbon double bonds having reactivity with Si-H group in one molecule, it is compared with a component that is not a siloxane compound. In addition, since it is excellent in heat resistance, transparency, and the like, and is a cyclic compound, the physical strength (rigidity), base resistance, crack resistance, and the like of the cured product are excellent as compared with the chain compound.

In the silicon-containing curable composition of the present invention, the content of the component (A) and the component (B) considers the ratio of Si—H groups and carbon-carbon double bonds that are reactive with Si—H groups. The equivalent ratio of the Si-H group and the carbon-carbon double bond having reactivity with the Si-H group is preferably 0.9 to 10, and preferably 1.0 to 5.0. More preferred is 1.1 to 3.0. In terms of mass%, the content of the component (A) is preferably 50 to 98 mass%, more preferably 70 to 97 mass%, and most preferably 85 to 95 mass%. The content of the component (B) is preferably 2 to 50% by mass, more preferably 3 to 30% by mass, and most preferably 5 to 15% by mass.

Next, the hydrosilylation catalyst which is the component (C) according to the present invention will be described.
The component (C) according to the present invention is not particularly limited as long as it has catalytic activity for hydrosilylation reaction, and a known compound can be used. Examples of such a catalyst include a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst. Examples of platinum-based catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc., platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane complexes. (KaRstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (for example, Pt [P (C ₆ H ₅ ) ₃ ] ₄ , PtCl [P (C ₆ H ₅ ) ₃ ] ₃ , Pt [P (C ₄ H ₉ ) ₃ ) ₄ ]), platinum-phosphite complexes (eg, Pt [P (OC ₆ H ₅ ) ₃ ] ₄ , Pt [P (OC ₄ H ₉ ) ₃ ] ₄ ), Dicarbonyldichloroplatinum and the like. Examples of the palladium catalyst or rhodium catalyst include compounds containing a palladium atom or a rhodium atom instead of the platinum atom of the platinum catalyst. These may be used alone or in combination of two or more. The hydrosilylation catalyst is preferably a platinum-based catalyst from the viewpoint of reactivity, more preferably a platinum-divinyltetramethyldisiloxane complex and a platinum-carbonylvinylmethyl complex, and most preferably a platinum-carbonylvinylmethyl complex. Further, the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass of the total amount of the component (a-1) and the component (b-1) from the viewpoint of reactivity. 0.001 to 0.1% by mass is most preferable.

In the silicon-containing curable composition of the present invention, the content of the component (C) is preferably 5% by mass or less, preferably 0.0001 to 1.0% by mass from the viewpoints of reactivity, curability and storage stability. More preferred is 0.001 to 0.1% by mass. In addition, when the catalyst used at the time of the reaction of the prepolymer of the component (A) according to the present invention remains without being deactivated, the remaining catalyst may be used as the component (C).

The silicon-containing curable composition of the present invention may contain a weather resistance imparting agent, an inorganic filler, an antistatic agent and the like, if necessary, in addition to the components (A) to (C).

Examples of the weather resistance-imparting agent include a light stabilizer, an ultraviolet absorber, a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Examples of the light stabilizer include hindered amines, and examples of the ultraviolet absorber include 2-hydroxybenzophenones, benzotriazoles, 2- (2-hydroxyphenyl) triazines, benzoates, and cyanoacrylates. Examples of phenolic antioxidants include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,6-di-t-butyl-methylphenol (BHT or DBPC) and the like, examples of the sulfur-based antioxidant include dialkylthiodipropionates, β-alkyl mercaptopropionic acid esters, and the like, and examples of the phosphorus-based antioxidant include organic phosphites. . The content of the weather resistance imparting agent in the silicon-containing curable composition of the present invention is 0.0001 to 10% by mass in terms of transparency, heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling. Is preferable, 0.005-5 mass% is still more preferable, and 0.05-1 mass% is the most preferable.

The inorganic filler refers to a so-called filler, an inorganic material such as a mineral, and a material obtained by modifying the inorganic material by an organic modification treatment or the like. Specifically, for example, silicon dioxides such as colloidal silica, silica filler, silica gel; metal oxides such as aluminum oxide, zinc oxide, titanium oxide, beryllium oxide; mica, montmorillonite, silica, diatomaceous earth, sericite, kaori Minerals such as knight, flint, feldspar powder, aragonite, attapulgite, talc, minnesotite, pyrophyllite; ceramics such as silicon nitride, aluminum nitride, boron nitride, silicon carbide; these have been modified by organic modification treatment, etc. Things. The particle size of these inorganic fillers is preferably 100 μm or less and more preferably 50 μm or less from the viewpoint of heat resistance. The inorganic filler content in the silicon-containing curable composition of the present invention is preferably 0 to 10% by mass because it is not used or is preferably used as little as possible when importance is placed on transparency. When used for the purpose of imparting thixotropy, 10 to 90% by mass is preferable.

Examples of the antistatic agent include cationic antistatic agents such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, trialkylmethylammonium salts, alkylbenzyldimethylammonium salts, polyamine quaternary salts; higher fatty acid salts, alkenylsuccinic acid Salt, N-acyl amino acid salt, alkylamino fatty acid salt, alkyl sulfonate, alpha olefin sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alpha sulfo fatty acid ester salt, higher alcohol sulfate ester salt, higher alcohol ethylene oxide Anionic antistatic agents such as adduct sulfate ester salt, higher alcohol phosphate ester salt, higher alcohol ethylene oxide adduct phosphate ester salt; polyhydric alcohol alkyl ether Nonionic antistatic agents such as polyethylene glycol fatty acid ester, ethylene oxide adduct of polyhydric alcohol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid ester polyethylene glycol, higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, diethanolamine fatty acid amide; Examples include amphoteric antistatic agents such as amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine, imidazoline amphoteric activators, and alkylamine oxides. The content of the weather resistance imparting agent in the silicon-containing curable composition of the present invention is preferably 0.0001 to 10% by mass, more preferably 0.005 to 5% by mass, and most preferably 0.05 to 1% by mass. .

Next, the cured product of the present invention will be described.
The silicon-containing curable composition of the present invention can be cured by heating and can be a cured product. This curing reaction may be performed by any method, such as a method of mixing the compounding components of the silicon-containing curable composition of the present invention immediately before use, a method of mixing all in advance and curing by heating or the like when performing the curing reaction. You may go. The temperature for curing is preferably 35 to 350 ° C, more preferably 50 to 250 ° C, and most preferably 100 to 230 ° C. The curing reaction may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. The curing time is preferably from 0.01 to 10 hours, more preferably from 0.05 to 6 hours.

The shape of the cured product is not particularly limited because it can take various forms depending on the application, but can be, for example, a film shape, a sheet shape, a tube shape, a rod shape, a coating film shape, a bulk shape, or the like.
The method for molding the cured product of the present invention can be various methods including a conventional method for molding a thermosetting resin. 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.

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 to improve releasability from the mold.

When the cured product of the present invention is molded, various treatments can be performed as necessary. For example, a treatment for defoaming a composition or a partially reacted composition by centrifugation, decompression, etc., or a treatment for releasing pressure once during pressing can be applied to suppress voids generated during molding.

The silicon-containing curable composition of the present invention has few outgas components and is excellent in transparency, and the cured product is excellent in heat resistance, crack resistance and dust resistance, and hardly undergoes light deterioration and heat deterioration. For this reason, the silicon-containing curable composition of the present invention can be used for various applications including optical materials. The optical material means a general material used for the purpose of allowing light to pass through the material. In addition to the LED sealant, the following materials can be mentioned.

In the liquid crystal display field, it is a film for a liquid crystal such as a substrate material, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, and a polarizer protective film.
In the field of plasma displays, they are sealing agents for plasma displays, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitute materials, and the like.
In LED display devices, they are LED molding materials, LED sealants, front glass protective films, front glass substitute materials, and the like.

In the organic EL (electroluminescence) display field, it is a protective film for a front glass, a front glass substitute material, and the like.

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, sealants and the like.

In the field of optical equipment, it is a lens material, a finder prism, a target prism, a finder cover, a light receiving sensor part, a finder, a protective film, and the like.

In the field of optical components, optical fiber materials, lenses, waveguides, device sealants, ferrules, optical passive components, and optical circuit components include lenses, waveguides, device sealants, and the like.

In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, corrosion-resistant coatings, switch parts, headlamps, electrical parts, various interior and exterior products, interior panels, interior materials, protective and binding wireness, glass It is an alternative product.

Applications other than optical materials include general applications in which thermosetting resins such as epoxy resins are used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.) In addition to insulating materials (including printed circuit boards and wire coatings), 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 Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these Examples. In the examples, “parts” and “%” are based on mass.

[Synthesis Example 1] Component (A): Synthetic nitrogen gas introduction tube of prepolymer A-1, thermometer, condenser, and 500 ml flask equipped with a stirrer were 2, 4, 6, 8 as component (a-1). -54 g (0.225 mol) of tetramethylcyclotetrasiloxane, 16.2 g (0.1 mol) of 1,2,4-trivinylcyclohexane as component (a-2), platinum-divinyltetramethyldisiloxane complex 0 as catalyst 0.002 g and 80 g of toluene as a solvent were charged and reacted at 105 ° C. for 2 hours. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C. to obtain Prepolymer A-1. The weight average molecular weight determined by GPC analysis of the prepolymer A-1 was 16,000, the content of SiH groups per gram determined by H-NMR analysis was 8.5 mmol, and the weight average molecular weight and Si-H The number of Si—H groups per molecule obtained from the group concentration is 142.

Synthesis Example 2 Component (A): Synthesis of Prepolymer A-2 As component (a-1), 77.1 g (0.225 mol) of 2,4,6-tetramethyl-8-phenylcyclotetrasiloxane was used. Except that, prepolymer A-2 was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight determined by GPC analysis of the prepolymer A-2 was 12,000, the content of SiH groups per gram determined by H-NMR analysis was 6.4 mmol, and the weight average molecular weight and Si-H The number of Si—H groups per molecule obtained from the group concentration is 77.

[Synthesis Example 3] Component (A): Synthesis of Prepolymer A-3 Synthesis Example except that 24.3 g (0.15 mol) of 1,2,4-trivinylcyclohexane was used as the component (a-2). The same operation as 2 was performed to obtain a prepolymer A-3. The weight average molecular weight determined by GPC analysis of prepolymer A-3 was 8,000, the content of SiH groups per gram determined by H-NMR analysis was 5.4 mmol, and the weight average molecular weight and Si-H The number of Si—H groups per molecule obtained from the group concentration is 43.

[Comparative Product] Comparative Prepolymer A′-1
In Synthesis Example 1, 1,2,4-trivinylcyclohexane is a linear polydimethylsiloxane having vinyl groups at both ends (molecular weight 20000, content of Si-H groups per molecule is 2) 100 g (0 0.005 mol), prepolymer A′-1 was obtained in the same manner. The weight average molecular weight determined by GPC analysis of prepolymer A′-1 was 25000, the content of SiH groups per gram determined by H-NMR analysis was 0.35 mmol, the weight average molecular weight and the content of Si—H groups The number of Si—H groups per molecule obtained from is 8.75.

[Comparative Product] Comparative Prepolymer A'-2
A prepolymer A′-2 was obtained in the same manner as in Synthesis Example 1 except that 1,2,4-trivinylcyclohexane was changed to 13 g (0.1 mol) of p-divinylbenzene. The weight average molecular weight determined by GPC analysis of the prepolymer A′-2 was 30,000, the content of SiH groups per gram determined by H-NMR analysis was 5.9 mmol, and the weight average molecular weight and Si—H group were The number of Si—H groups per molecule obtained from the content of 177 is 177.

[Example 1]
100 parts of the prepolymer A-1 obtained in Synthesis Example 1 as the component (A) and 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane as the component (B) 10 parts of was mixed to obtain a silicon-containing curable composition 1 of the present invention. In addition, 100 parts of silicon-containing curable composition 1 contains 0.003 part of a platinum-divinyltetramethyldisiloxane complex (corresponding to the component (C)) derived from the prepolymer A-1.
Place a 3mm thick silicone sheet with square holes of 20mm in length and 20mm in width on a glass plate. After pouring the silicon-containing curable composition 1 from which bubbles were removed by light pressure reduction into the holes, place the glass plate on it. It was. This was put in a thermostatic bath, heated at 130 ° C. for 1 hour, and further heated at 200 ° C. for 3 hours to obtain a cured product of Example 1.

[Example 2]
The cured product of Example 2 was obtained by performing the same operation as in Example 1 except that the prepolymer A-2 obtained in Synthesis Example 2 was used as the component (A). In addition, 100 parts of silicon-containing curable composition 2 contains 0.003 part of platinum-divinyltetramethyldisiloxane complex (corresponding to component (C)) derived from prepolymer A-2.

[Example 3]
The same operation as in Example 1 was performed except that 2,4,6,8-tetramethyl-8-phenyl-2,4,6-trivinylcyclotetrasiloxane was used as the component (B). A cured product was obtained. In addition, 100 parts of silicon-containing curable composition 4 contains 0.003 part of platinum-divinyltetramethyldisiloxane complex (corresponding to component (C)) derived from prepolymer A-1.

[Comparative Example 1]
As a highly transparent epoxy resin, 43 parts of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, 56 parts of 4-methylcyclohexene-1,2-dicarboxylic acid anhydride and a catalyst (air products) An epoxy resin composition was obtained by blending 1 part of a trade name, Ancamine K54). A cured product of Comparative Example 1 was obtained by performing the same operation as in Example 1 except that the curing conditions were changed to 150 ° C. for 1 hour.

[Comparative Example 2]
30 parts of comparative prepolymer A-1 ′ and linear polydimethylsiloxane having vinyl groups at both ends (25000, Si—H groups are 0.35 mmol of SiH groups per gram from H-NMR) The cured product of Comparative Example 2 was obtained by performing the same operation as in Example 1, except that 70 parts of was used.

[Comparative Example 3]
Example 1 except that 90 parts of comparative prepolymer A-2 ′ and 10 parts of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasilosane were used. Operation was performed and the hardened | cured material of the comparative example 3 was obtained.
About the hardened | cured material of Examples 1-4 and Comparative Examples 1-3, thermal coloring property, hardness, dust adhesion, and a weather resistance were measured by the method shown below. The results are shown in Table 1.

[Thermal coloring test method]
A cured product test piece having a thickness of 3 mm was heated and stored in a thermostat bath at 200 ° C. for 6 hours, and the thermal colorability was evaluated by measuring the transmittance of light at 400 nm and 700 nm before and after heating. It shows that coloring is so large that the fall of the transmittance | permeability before and behind a heating is large.

[Hardness test method]
In accordance with JIS K6253 (vulcanized rubber and thermoplastic rubber—how to obtain hardness), the durometer hardness (Shore hardness) of the cured specimen was measured. In the table, A indicates a type A durometer, and D indicates a value of a type D durometer.

[Dust adhesion test method]
The cured product test piece was put in a beaker containing powdered silica gel (manufactured by Wako Pure Chemical Industries, Ltd., trade name: Wakogel C-100) until it was completely filled. The test piece was dropped on a glass plate from a position 5 cm apart in the vertical direction, and the presence or absence of silica gel was visually determined on the surface. When silica gel is adhered, it indicates that the surface is tacky and dust tends to adhere.

[Light resistance test method]
The cured product test piece was irradiated with a light beam having an illuminance of 5000 mW / cm ² from a distance of 5 mm for 24 hours at a temperature of 100 ° C., then the appearance was visually observed, and the light resistance was evaluated according to the following criteria. In addition, for irradiation, a light beam obtained by cutting a wavelength component of 300 nm or less with a spectral filter (manufactured by Asahi Techno Glass Co., Ltd., trade name UV-33) using an ultra-high pressure mercury lamp (manufactured by Mitsunaga Electric Co., Ltd., trade name UVF352S) as a light source. Was used.
○: The test piece is transparent and does not change.
Δ: Some turbidity is observed in the test piece.
X: Obvious turbidity of the test piece is observed.

Claims (2)

As the component (A), a cyclic siloxane compound (a-1) represented by the following general formula (1) having two or more Si-H groups in one molecule and the following general formula (2) In the molecule obtained by subjecting the alicyclic structure-containing unsaturated compound (a-2) to a hydrosilylation reaction in such a ratio that two or more Si-H groups remain in one molecule after the reaction. A prepolymer having two or more Si-H groups;
As the component (B), a cyclic siloxane compound represented by the following general formula (3) having two or more carbon-carbon double bonds having reactivity with the Si-H group in one molecule;
As component (C), a hydrosilylation catalyst,
Silicon-containing curable composition characterized by containing.

(Wherein R ¹ , R ² and R ³ each represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be the same or different, a represents a number of 2 to 10 and b represents 0 to 0; Represents the number 8)

^(Wherein, R 4, ^{R 5} and ^{R 6} each represent an alkyl group or a phenyl group having 1 to 6 carbon atoms which may be the same or different, p is a number from 2 to 10, q is 0 Represents the number 8) A silicon-containing cured product obtained by heat-curing the silicon-containing curable composition according to claim 1.