JP2009280747A - Silicon-containing curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicon-containing curable composition which scarcely causes discoloration due to light deterioration and thermal deterioration, is rigid, has less dust attachment, and is useful as a sealant for electric or electronic materials, and, inter alia, light emitting devices. <P>SOLUTION: The silicon-containing curable composition contains: (A) a prepolymer having not less than two Si-H groups in one molecule obtained by hydrosilylating (a-1) a compound having not less than two Si-H groups in the molecule and (a-2) an unsaturated compound having an alicyclic structure, an ether group, and not less than two carbon-carbon double bonds in one molecule reactive with the Si-H groups in the compound (a-1) in a ratio at which not less than two Si-H groups are left in one molecule after the reaction; (B) a cyclic siloxane compound having not less than two carbon-carbon double bonds in one molecule reactive with the Si-H groups; and (C) a hydrosilylating 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 same. 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-based resin has sufficient heat resistance and light resistance, and is composed of an epoxy resin in applications requiring high brightness such as automotive headlights and lighting. In some cases, the sealant could not cope. 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 in the manufacturing process of electronic parts due to contamination problems, and it is soft and has surface tackiness, so dust easily adheres to the surface. However, there is a drawback that the light transmittance is lowered. 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 compound (a-1) having two or more Si—H groups in one molecule, and a carbon-carbon two compound having reactivity with the Si—H group in the compound (a-1). An unsaturated compound (a-2) having an alicyclic structure and an ether group having two or more heavy bonds in one molecule so that two or more Si-H groups remain in one molecule after the reaction. A prepolymer having two or more Si-H groups in one molecule, obtained by hydrosilylation reaction in a small proportion;
As the component (B), a cyclic siloxane compound 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.

  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 reacts with the compound (a-1) having two or more Si—H groups in one molecule and the Si—H group in the compound (a-1). An unsaturated compound (a-2) having an alicyclic structure and an ether group having two or more carbon-carbon double bonds having a property in one molecule is converted into two or more Si in one molecule after the reaction. It is a compound having two or more Si-H groups in one molecule, obtained by hydrosilylation reaction at such a ratio that -H groups remain.

  The component (a-1) is a compound having two or more Si—H groups in one molecule. The component (a-1) may be chain or cyclic, but is preferably a cyclic siloxane compound represented by the following general formula (1) because of excellent compatibility with the component (a-2).

（式中、Ｒ¹、Ｒ²及びＲ³は、それぞれ、炭素原子数１〜６のアルキル基又はフェニル基を表し、同一でも異なっていても良い。ａは２〜１０の数を表し、ｂは０〜８の数を表す。）

(In the formula, R ¹ , R ² and R ³ each represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different. A represents a number of 2 to 10; Represents a number from 0 to 8.)

In the general formula (1), the alkyl group having 1 to 6 carbon atoms represented by R ¹ , R ² and R ³ is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl. , Amyl, isoamyl, t-amyl, hexyl and cyclohexyl groups. As R ¹ , a methyl group is preferable because it is easily available on the industry, and as R ² and R ³ , the outgas component in the silicon-containing curable composition of the present invention can be lowered. Preferably, a methyl group is more preferable because photodegradation hardly occurs. As a, since the crosslinking density of hardening reaction becomes high and it is hard and dust adhesion decreases, 3-7 are preferable and 4-6 are more preferable. Moreover, it is preferable that the value of a + b is 4-8 from the ease of manufacture, and it is more preferable that it is 4-6.

  Specific examples of the component (a-1) include 2,4,6,8-tetramethylcyclotetrasiloxane, 2,2,4,6,8-pentamethylcyclotetrasiloxane, 2,2,4,4, 6,8-hexamethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10,12-hexamethylcyclohexasiloxane, etc. 2,4,6,8-tetramethylcyclotetrasiloxane and 2,4,6,8,10-pentamethylcyclopentasiloxane are preferred because they are readily available and have an appropriate number of Si-H functional groups. 2,4,6,8-tetramethylcyclotetrasiloxane is more preferable. The component (a-1) may be used alone or in combination of two or more.

  Component (a-2) is a compound having two or more carbon-carbon double bonds reactive with the Si—H group in compound (a-1) in one molecule and having an alicyclic structure and an ether group. Preferred examples include saturated compounds and compounds represented by the following general formula (2) or general formula (4) from the viewpoint of heat resistance and crack resistance.

（式中、Ｒ⁴及びＲ⁵は、それぞれ、ビニル基又はアリル基を表し、同一でも異なっていても良い。Ｒ⁶は水素原子、−ＣＨ₂−Ｏ−ＣＨ＝ＣＨ₂基又は−ＣＨ₂−Ｏ−ＣＨ₂ＣＨ＝ＣＨ₂基を表す。）

(In the formula, R ⁴ and R ⁵ each represent a vinyl group or an allyl group, and may be the same or different. R ⁶ is a hydrogen atom, —CH ₂ —O—CH═CH ₂ group or —CH _2. It represents an -O-CH ₂ CH = CH ₂ group.)

（式中、Ｒ¹⁰及びＲ¹¹は、それぞれ、ビニル基又はアリル基を表し、同一でも異なっていても良い。）

(In the formula, R ¹⁰ and R ¹¹ each represent a vinyl group or an allyl group, and may be the same or different.)

  Examples of the compound represented by the general formula (2) include 1,2-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,2, 4-cyclohexanetrimethanol trivinyl ether, 1,2-cyclohexanedimethanol diallyl ether, 1,3-cyclohexanedimethanol diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, 1,2,4-cyclohexanetrimethanol triallyl ether Examples of the compound represented by the general formula (4) include 1,2-bis (4-vinyloxycyclohexyl) propane, 1,2-bis (4-allyloxycyclohexyl) propane, and the like. Be

As the unsaturated compound (a-2), a compound represented by the above general formula (2) is more preferable because it is less colored due to thermal degradation or photodegradation. Among them, R ⁴ and R ⁵ are vinyl groups. R ⁶ is preferably a hydrogen atom or a —CH ₂ —O—CH═CH ₂ group.

  Specific examples of preferred compounds include 1,2-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and 1,2,4-cyclohexanetrimethanol trivinyl ether. 1,4-cyclohexane dimethanol divinyl ether is preferable because it is easy to obtain industrially. The component (a-2) may be used alone or in combination of two or more.

  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 values of the peaks of ¹ H-NMR analysis.

  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.

  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 hydrosilylation catalyst. Examples of the hydrosilylation catalyst include platinum-based catalysts, palladium-based catalysts, and rhodium-based catalysts. Etc. Examples of platinum-based catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, and ketones, platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), and 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 complex (for example, 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 (a-2) 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 the hydrosilylation of the component (a-1) and the component (a-2) are not particularly limited, and may be performed under the conventionally known conditions using the hydrosilylation catalyst. From the viewpoint of the reaction rate, It is preferable to carry out at room temperature (25 degreeC) -130 degreeC, and you may use conventionally well-known solvents, such as toluene, hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate, at the time of reaction.

The prepolymer of the component (A) according to the present invention is a compound (a-1) that is a compound having two or more Si-H groups in one molecule, and the Si-H group in the component (a-1). And a prepolymer obtained by a hydrosilylation reaction of (a-2) component, which is an unsaturated compound having an alicyclic structure and an ether group, having two or more carbon-carbon double bonds having reactivity with each other. It is a polymer. In the present invention, a low-boiling point product can be removed by converting it into a prepolymer and then using it as a blending component of the curable composition, so that a curable composition with very few outgas components can be obtained. Further, in the present invention, since the component (a-2) has an alicyclic structure, the curing shrinkage is small, and since it has an ether group, it is flexible, so that a cured product having excellent crack resistance at high temperatures is obtained. It is done. Furthermore, when the component (a-1) according to the present invention is a cyclic siloxane compound, the physical strength (rigidity), crack resistance and the like of the cured product are improved as compared with the case of a chain compound. be able to.

Next, the component (B) according to the present invention will be described.

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 groups in one molecule. The number of double bonds is preferably 2 to 10, and more preferably 2 to 6 from the viewpoint of the crosslink density of the cured product. Further, examples of the carbon-carbon double bond having reactivity with the Si-H group include an alkenyl group and a vinyl group. Particularly, from the viewpoint of reactivity, a vinyl group bonded to a silicon atom (Si-CH ═CH ₂ group). Moreover, as a preferable (B) component from the point of the physical property of hardened | cured material, the compound represented by following General formula (3) is preferable.

（式中、Ｒ⁷、Ｒ⁸及びＲ⁹は、それぞれ、炭素原子数１〜６のアルキル基又はフェニル基を表し、同一でも異なっていても良い。ｐは２〜１０の数を表し、ｑは０〜８の数を表す。）

(Wherein R ⁷ , R ⁸ and R ⁹ each represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different. P represents a number of 2 to 10 and q Represents a number from 0 to 8.)

In the said General formula (3), group illustrated by description of the said General formula (1) is mentioned as a C1-C6 alkyl group represented by R < ⁷ >, R < ⁸ > and R < ⁹ >. R ⁷ , R ⁸ and R ⁹ are preferably a methyl group or a phenyl group because they are easily available in industry. p is preferably 2 to 4 from the viewpoint of crosslinking density, and the value of p + q is preferably 4 to 8 and more preferably 4 to 6 from the viewpoint 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.

  The component (B) according to the present invention is a cyclic siloxane compound containing two or more carbon-carbon double bonds having reactivity with the Si-H group in one molecule, so that it is compared with a non-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 the Si-H group and the carbon-carbon double bond having reactivity with the Si-H group. 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.

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,
0.001-0.1 mass% is the most preferable. 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 light stabilizers, ultraviolet absorbers, phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. 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 inorganic materials such as so-called fillers and minerals and those modified by 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 content of the inorganic filler 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 transparency is important. 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 salt, dialkyldimethylammonium salt, trialkylmethylammonium salt, alkylbenzyldimethylammonium salt, polyamine quaternary salt; higher fatty acid salt, alkenyl succinic 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 polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid esters ethylene oxide adducts, polyethylene glycol fatty acid esters, fatty acid esters polyethylene glycol, higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, diethanolamine fatty acid amides; Examples include amphoteric antistatic agents such as amphoteric alkylbetaines such as dimethylaminoacetic acid betaine, imidazoline type amphoteric activators, and alkylamine oxides. The content of the antistatic 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 of the present invention is not particularly limited because it can take various forms depending on the application. For example, it can be in the form of a film, a sheet, a tube, a rod, a coating, a bulk, 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.

  Various treatments can be applied as necessary when the cured product of the present invention is molded. For example, in order to suppress voids generated during molding, a process of defoaming the composition or a partially reacted composition by centrifugation, decompression, or the like, a process of releasing the pressure once during pressing, or the like can be applied.

  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 adhesion, and is less colored due to 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 components, 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 for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, dipping, transfer mold sealing, pottings for ICs, LSIs such as COB, COF, TAB, etc., flip chip For example, underfill for sealing, etc., sealing (reinforcing underfill) when mounting IC packages such as BGA, CSP, and the like can be given.

  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): Synthesis of Prepolymer A-1 In a 500 ml flask equipped with a nitrogen gas introduction tube, a thermometer, a cooling tube and a stirrer, , 8-tetramethylcyclotetrasiloxane 33.6 g (0.14 mol), (a-2) component cyclohexanedimethanol divinyl ether 19.6 g (0.1 mol), platinum-divinyltetramethyldisiloxane as catalyst 0.002 g of the complex 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 150,000, the content of Si—H groups per gram determined by ¹ H-NMR analysis was 5.0 mmol, and the weight average molecular weight The number of Si—H groups per molecule obtained from the concentration of Si—H groups is 750.

[Synthesis Example 2] Component (A): Synthesis of Prepolymer A-2 Same as Synthesis Example 1 except that 33.3 g (0.17 mol) of cyclohexanedimethanol divinyl ether was used as the component (a-2). To obtain prepolymer A-2. The weight average molecular weight determined by GPC analysis of the prepolymer A-2 was 30,000, the content of Si—H groups per gram determined by ¹ H-NMR analysis was 4.2 mmol, and the weight average molecular weight The number of Si—H groups per molecule obtained from the content of Si—H groups is 126.

Synthesis Example 3 Component (A): Synthesis of Prepolymer A-3 As component (a-1), 100.8 g (0.75 mol) of 1,1,3,3-tetramethyldisiloxane, (a- 2) A prepolymer A-3 was obtained in the same manner as in Synthesis Example 1 except that 49 g (0.25 mol) of cyclohexanedimethanol divinyl ether was used as the component. The weight average molecular weight determined by GPC analysis of the prepolymer A-3 is 150,000, the content of Si-H groups per gram determined by ¹ H-NMR analysis is 5.0 mmol, and the weight average molecular weight The number of Si—H groups per molecule obtained from the concentration of Si—H groups is 900.

[Synthesis Example 4] Component (A): Synthesis of Prepolymer A-4 As component (a-1), 40.9 g (0.14 mol) of 1,2-bis (4-vinyloxycyclohexyl) propane was used. Except for the above, the same operation as in Synthesis Example 1 was performed to obtain Prepolymer A-4. The weight average molecular weight determined by GPC analysis of the prepolymer A-4 is 150,000, the content of Si—H groups per gram determined by ¹ H-NMR analysis is 5.0 mmol, and the weight average molecular weight The number of Si—H groups per molecule obtained from the concentration of Si—H groups is 750.

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

[Comparative Synthesis Example 2] Comparative prepolymer A′-2
A prepolymer A′-2 was obtained in the same manner as in Synthesis Example 1 except that cyclohexane dimethanol divinyl ether 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 is 30000, the content of Si—H groups per gram determined by ¹ H-NMR analysis is 5.9 mmol, and the weight average molecular weight and Si The number of Si—H groups per molecule obtained from the content of —H groups is 177.

[Example 1]
As component (A), 100 parts of prepolymer A-1 obtained in Synthesis Example 1, and as component (B), 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl 10 parts of cyclotetrasiloxane was blended to obtain the silicon-containing curable composition 1 of the present invention. In addition, the silicon-containing curable composition 1 contains 0.003% of a platinum-divinyltetramethyldisiloxane complex (corresponding to the component (C)) derived from the prepolymer A-1. The resulting silicon-containing curable composition 1 was gently depressurized to remove bubbles.
Next, a 3 mm thick silicone sheet provided with square holes of 20 mm length and 20 mm width is prepared as a mold and placed on a glass plate. After the silicon-containing curable composition 1 from which bubbles were removed was uniformly poured into holes provided in the silicon sheet, a glass plate was placed on the silicon sheet. 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]
(A) The silicon-containing curable composition 2 of this invention was obtained like Example 1 except having used prepolymer A-2 obtained by the synthesis example 2 as a component. The silicon-containing curable composition 2 contains 0.003% of a platinum-divinyltetramethyldisiloxane complex (corresponding to the component (C)) derived from the prepolymer A-2. The same operation as in Example 1 was performed from the silicon-containing curable composition 2 to obtain a cured product of Example 2.

[Example 3]
As the component (A), the silicon-containing curable composition 3 of the present invention was obtained in the same manner as in Example 1 except that the prepolymer A-3 obtained in Synthesis Example 3 was used. The silicon-containing curable composition 3 contains 0.003% of a platinum-divinyltetramethyldisiloxane complex (corresponding to the component (C)) derived from the prepolymer A-3. The same operation as in Example 1 was performed from the silicon-containing curable composition 3 to obtain a cured product of Example 3.

[Example 4]
(A) The silicon-containing curable composition 4 of this invention was obtained like Example 1 except having used prepolymer A-4 obtained by the synthesis example 4 as a component. The silicon-containing curable composition 4 contains 0.001% of a platinum-divinyltetramethyldisiloxane complex (corresponding to the component (C)) derived from the prepolymer A-4. The same operation as in Example 1 was performed from the silicon-containing curable composition 4 to obtain a cured product of Example 4.

[Example 5]
The silicon-containing composition of the present invention was the same as Example 1 except that 2,4,6,8-tetramethyl-8-phenyl-2,4,6-trivinylcyclotetrasiloxane was used as the component (B). A curable composition 5 was obtained. The silicon-containing curable composition 5 contains 0.003% of a platinum-divinyltetramethyldisiloxane complex derived from the prepolymer A-1 (corresponding to the component (C)). The same operation as in Example 1 was performed from the silicon-containing curable composition 5 to obtain a cured product of Example 5.

[Comparative Example 1]
As highly transparent epoxy resin, 43 parts of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, 56 parts of 4-methylcyclohexene-1,2-dicarboxylic anhydride, and catalyst An epoxy resin composition was obtained by blending 1 part of (Product name: Ancamine K54, manufactured by Air Products). 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 ′, linear polydimethylsiloxane having vinyl groups at both ends (weight average molecular weight determined by GPC analysis is 25000, and calculated per 1 g determined by ¹ H-NMR analysis The content of Si—H groups is 0.35 mmol, and the number of Si—H groups per molecule obtained from the weight average molecular weight and the content of Si—H groups is 8.75). Except having used, operation similar to Example 1 was performed and the hardened | cured material of the comparative example 2 was obtained.

[Comparative Example 3]
Example 1 except that 90 parts of the comparative prepolymer A-2 ′ and 10 parts of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane were used. Operation was performed and the hardened | cured material of the comparative example 3 was obtained.

  About the hardened | cured material of Examples 1-5 and Comparative Examples 1-3, thermal coloring property, hardness, dust adhesion, and light resistance were measured by the method shown below. The results are shown in Table 1.

[Thermal coloring test method]
A cured product specimen having a thickness of 3 mm was heated and stored in a thermostat set 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. The greater the decrease in transmittance before and after heating, the greater the coloration, indicating poorer heat resistance.

[Hardness test method]
Based on 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 then the presence or absence of silica gel adhering to the surface was visually determined. 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. For irradiation, an ultrahigh pressure mercury lamp (trade name: UVF352S, manufactured by Mitsunaga Electric Co., Ltd.) is used as a light source, and a wavelength component of 300 nm or less is cut with a spectral filter (trade name: UV-33, manufactured by Asahi Techno Glass Co., Ltd.). Used light rays.
○: The test piece is transparent, has no change, and has excellent light resistance.
Δ: Some turbidity is observed in the test piece, and the light resistance is slightly inferior.
X: Obvious turbidity is seen in the test piece and light resistance is inferior.

Claims (5)

As the component (A), a compound (a-1) having two or more Si—H groups in one molecule, and a carbon-carbon two compound having reactivity with the Si—H group in the compound (a-1). An unsaturated compound (a-2) having an alicyclic structure and an ether group having two or more heavy bonds in one molecule so that two or more Si-H groups remain in one molecule after the reaction. A prepolymer having two or more Si-H groups in one molecule, obtained by hydrosilylation reaction in a small proportion;
As the component (B), a cyclic siloxane compound 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. The silicon-containing curable composition according to claim 1, wherein the compound (a-1) is a cyclic siloxane compound represented by the following general formula (1).

(In the formula, R ¹ , R ² and R ³ each represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different. A represents a number of 2 to 10; Represents a number from 0 to 8.) The silicon-containing curable composition according to claim 1 or 2, wherein the unsaturated compound (a-2) is a compound represented by the following general formula (2).

(In the formula, R ⁴ and R ⁵ each represent a vinyl group or an allyl group, and may be the same or different. R ⁶ is a hydrogen atom, —CH ₂ —O—CH═CH ₂ group or —CH _2. It represents an -O-CH ₂ CH = CH ₂ group.) The silicon-containing curable composition according to any one of claims 1 to 3, wherein the cyclic siloxane compound as the component (B) is a compound represented by the following general formula (3).

(Wherein R ⁷ , R ⁸ and R ⁹ each represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different. P represents a number of 2 to 10 and q Represents a number from 0 to 8.)   The silicon-containing hardened | cured material which heat-hardened the silicon-containing curable composition in any one of Claims 1-4.