KR101858638B1 - Silicon-containing curable resin composition - Google Patents

Silicon-containing curable resin composition Download PDF

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KR101858638B1
KR101858638B1 KR1020147011188A KR20147011188A KR101858638B1 KR 101858638 B1 KR101858638 B1 KR 101858638B1 KR 1020147011188 A KR1020147011188 A KR 1020147011188A KR 20147011188 A KR20147011188 A KR 20147011188A KR 101858638 B1 KR101858638 B1 KR 101858638B1
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타카시 스에요시
세이이치 사이토
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가부시키가이샤 아데카
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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Abstract

(A) containing at least two epoxy-containing groups in one molecule and an epoxy siloxane compound having a group represented by the following general formula (1), and a silicone compound containing, as a component (B), 1 to 10 silicon atoms and at least two epoxy- Containing epoxy siloxane compound, and an epoxy-curable compound as a component (C). In the general formula (1), R 1 to R 4 may be the same or different and represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a represents a number of 20 to 10000.

Figure 112014039686618-pct00028

Description

SILICON-CONTAINING CURABLE RESIN COMPOSITION [0002]

The present invention relates to a silicon-containing curable resin composition containing an epoxy group-containing silicon compound and an epoxy curing agent or an epoxy curing catalyst, and a cured product thereof.

Examples of the compound having a siloxane skeleton as a repeating unit and having an epoxy group in an organic group include bisphenol A type epoxy resin, (3 ', 4'-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate , A compound in which a cyclic siloxane group having an epoxy group is linked with a linear polysiloxane group is obtained (for example, in Patent Document 1 (See, for example, Patent Documents 1 to 3) have been known as being excellent in flexibility and suitable as sealing materials for optical semiconductor devices such as light emitting diodes and photodiodes Reference). However, the cured product obtained from such a compound has a drawback that tackiness tends to be generated on the surface, and thus the cured product can not be used for surface coating.

Compared with this, Patent Document 4 discloses that a cyclic siloxane compound having an epoxy group, a cyclic siloxane group having an epoxy group are linked by a straight-chain polysiloxane group, and a compound containing a cyclic siloxane structure having an epoxy siloxane compound crosslinked with a linear (poly) (See Patent Document 4), and a cured product obtained from the composition disclosed in Patent Document 4 has improved surface tackiness, but has insufficient heat resistance, and when used for surface coating applications, There is a problem that cracks tend to occur.

U.S. Patent No. 6313255 International Publication No. 2007/046399 Japanese Patent Application Laid-Open No. 2008-266485 International Publication No. 2008/133108

An object of the present invention is to provide a curable composition which has no surface stickiness and is excellent in heat resistance, and which can hardly cause cracks even when used at a high temperature for a long period of time.

The present invention relates to an epoxy siloxane compound having at least two epoxy-containing groups in one molecule and a group represented by the following general formula (1) as a component (A), at least one silicon- Containing curable resin composition characterized by containing an epoxy silane compound having an epoxy group-containing group and an epoxy silane compound as a component (C).

Figure 112014039686618-pct00001

(Wherein R 1 to R 4 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a represents a number of 20 to 10000)

According to the present invention, it is possible to provide a curable composition which is free of surface stickiness and excellent in heat resistance, and which can hardly cause cracks even when used at a high temperature for a long period of time.

The component (A) of the silicon-containing curable resin composition of the present invention is an epoxy siloxane compound having at least two epoxy-containing groups in one molecule and a group represented by the general formula (1).

In the general formula (1), R 1 to R 4 represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl and the like. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, ethylphenyl, tolyl, cumenyl, xylyl, pseudouric cumenyl, mesityl, t-butylphenyl, phenethyl and the like. As R 1 to R 4 , methyl, ethyl and phenyl are preferable in terms of heat resistance, and methyl and phenyl are more preferable, and phenyl is most preferable. Methyl, ethyl, propyl and butyl are preferable in view of low viscosity and difficulty of crystallization, more preferably methyl and ethyl, and most preferably methyl. Therefore, it is preferable that R 1 to R 4 are a combination of methyl and phenyl, and the ratio of methyl to phenyl in R 1 to R 4 included in the group represented by general formula (1) More preferably from 40:60 to 100: 0, even more preferably from 60:40 to 97: 3, most preferably from 65:35 to 95: 5.

In the general formula (1), a represents a number of 20 to 10000. When a is smaller than 20, the heat resistance of the obtained cured product becomes insufficient, and when it is larger than 10,000, the viscosity becomes large and the handling is hindered. a is preferably from 100 to 5,000, more preferably from 200 to 2,000.

(A) has at least two epoxy-containing groups in one molecule. The number of epoxy groups in the component (A) is preferably at least 3 in view of crack resistance, and more preferably at least 4. When the content of the epoxy group in the component (A) is too small, the cured product tends to become sticky. When the content is too large, the crack resistance tends to be lowered. More preferably from 700 to 20000, and most preferably from 1000 to 10000. On the other hand, the epoxy equivalent refers to the mass (grams) of an epoxy compound containing one equivalent of an epoxy group.

Examples of the epoxy-containing group of the component (A) include the following formulas (5) to (24), and since they are excellent in reactivity and industrially available for the raw materials, 3- glycidyloxypropyl , 2- (3,4-epoxycyclohexyl) ethyl of the formula (16) and 2- (3,4-epoxy-4-methylcyclohexyl) propyl of the formula (17) are preferable, and 3-glycidyloxy Propyl, and 2- (3,4-epoxycyclohexyl) ethyl are more preferable.

Figure 112014039686618-pct00002

Figure 112014039686618-pct00003

Figure 112014039686618-pct00004

The epoxy-containing group may be directly bonded to the group represented by the general formula (1), but it is preferable that the epoxy-containing group is bonded to the group represented by the general formula (1) through a connecting group since the number of epoxy- Do. Examples of the connecting group include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a silane group, a linear siloxane group, and a cyclic siloxane group, and a cyclic siloxane group is preferable because heat resistance is improved. When the component (A) is a compound having an epoxy-containing group bonded through a cyclic siloxane group in the group represented by the general formula (1), the groups represented by the following general formula (2) , The group represented by the general formula (2) and the group represented by the following general formula (3) are preferably an epoxy siloxane compound linked with the group represented by the general formula (1).

Figure 112014039686618-pct00005

(Wherein R 5 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different, E 1 represents an epoxy-containing group, and b represents a number of 2 to 5)

Figure 112014039686618-pct00006

(Wherein c represents a number of 2 to 6 in which b-c + 1 is a number of 0 to 4, and R 5 , E 1 and b have the same meanings as in the general formula (2).)

In the general formula (2), R 5 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups represented by R 1 to R 4 in the general formula (1). As R 5 , methyl and phenyl are preferable, and methyl is most preferable because heat resistance is improved.

In the general formula (2), b represents a number of 2 to 5, and b is preferably 2 to 4, more preferably 2 to 3, and most preferably 3 because industrial raw materials are easily available . E 1 represents an epoxy-containing group, and specific examples thereof include the formulas (5) to (24).

In the general formula (3), c represents a number of 2 to 6 in which b-c + 1 is a number of 0 to 4, and R 1 , E and a have the same meanings as in the general formula (1).

The epoxy siloxane compounds represented by the general formula (2) or the groups represented by the general formula (2) and the group represented by the general formula (3) are connected to the groups represented by the general formula (1) ) Is reacted with a vinyl group of a chain siloxane compound represented by the following general formula (1a), and then an epoxy compound containing a carbon-carbon double bond having reactivity with a SiH group is reacted with a hydrosilyl And then reacting the reaction product.

Figure 112014039686618-pct00007

(Wherein R 1 to R 4 and a have the same meanings as in formula (1)).

Figure 112014039686618-pct00008

(Wherein R 5 and b have the same meanings as in formula (2)).

Among the compounds represented by the general formula (2a), preferred compounds include 2,4,6-trimethylcyclotrisiloxane, 2,4,6-triethylcyclotrisiloxane, 2,4,6-triphenylcyclotrisiloxane, 2 , 4-dimethyl-6-phenylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotrisiloxane, 2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetraphenyl Cyclotetrasiloxane, 2,4,6-trimethyl-8-phenylcyclotetrasiloxane, 2,4-dimethyl-6,8-diphenylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane And the like.

The hydrosilylation reaction between the chain siloxane compound represented by the general formula (1a) and the cyclic siloxane compound represented by the general formula (2a) is preferably carried out using a catalyst, and examples of the hydrosilylation catalyst include platinum Based catalyst, a palladium-based catalyst, and a rhodium-based catalyst. Examples of the platinum-based catalyst include a complex of chloroplatinic acid and chloroplatinic acid with an alcohol, an aldehyde, a ketone, etc., a platinum-olefin complex, a platinum-carbonylvinylmethyl complex (Ossko catalyst), a platinum-divinyltetramethyldisiloxane complex (KaRstedt catalyst), a platinum-cyclopropyl-vinyl siloxane complex, platinum-octyl aldehyde complexes, platinum-phosphine complex (e.g., Pt [P (C 6 H 5) 3] 4, PtCl [P (C 6 H 5 ) 3] 3, Pt [P (C 4 H 9) 3) 4], a platinum-phosphite complex (e.g., Pt [P (OC 6 H 5) 3] 4), Pt [P (OC 4 H 9 ) 3 ] 4 ), and dicarbonyldichloroplatinum. Examples of the palladium-based catalyst or the rhodium-based catalyst include a compound containing a palladium atom or a rhodium atom in place of the platinum atom of the platinum-based catalyst. These may be used alone or in combination of two or more. The hydrosilylation catalyst is preferably a platinum-based catalyst in terms of reactivity, more preferably a platinum-divinyltetramethyldisiloxane complex and a platinum-carbonylvinylmethyl complex, and most preferably a platinum-carbonylvinylmethyl complex. The amount of the catalyst to be used is preferably 5% by mass or less, more preferably 0.0001% by mass to 1.0% by mass, and most preferably 0.001% by mass to 0.1% by mass, based on the total amount of each raw material in view of reactivity. The reaction conditions for the hydrosilylation are not particularly limited and may be carried out under conventionally known conditions using the above catalyst. From the viewpoint of the reaction rate, the reaction is preferably carried out at room temperature (25 ° C) to 130 ° C, , Hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate and the like may be used.

The hydrosilylation reaction between the reaction product of the chain siloxane compound represented by the general formula (1a) and the cyclic siloxane compound represented by the general formula (2a) and the epoxy compound containing a carbon-carbon double bond having reactivity with the SiH group May be carried out under the same conditions as the hydrosilylation reaction between the chain siloxane compound represented by the general formula (1a) and the cyclic siloxane compound represented by the general formula (2a), and after the hydrosilylation reaction, the reaction product is isolated It is preferable to continue the reaction without purification.

Examples of epoxy compounds containing carbon-carbon double bonds having reactivity with SiH groups include compounds represented by the following formulas (5a) to (20a), (22a) to (24a) , The epoxy-containing groups of the above formulas (5) to (20) and (22) to (24) can be respectively introduced.

Figure 112014039686618-pct00009

Figure 112014039686618-pct00010

Figure 112014039686618-pct00011

When a cyclic siloxane compound represented by the general formula (2a) is reacted with a chain siloxane compound represented by the general formula (1a) and an epoxy compound containing a carbon-carbon double bond having reactivity with the SiH group is reacted, The epoxy siloxane compound wherein the groups represented by the general formula (2) are connected to the groups represented by the general formula (1), the group represented by the general formula (2) and the group represented by the general formula (3) Lt; RTI ID = 0.0 > of a < / RTI > epoxy siloxane compound. When an epoxy siloxane compound in which the groups represented by the general formula (2) are connected to the groups represented by the general formula (1) is selectively obtained, the siloxane compound represented by the general formula (2a) can be obtained as compared with the chain siloxane compound represented by the general formula (1a) The cyclosiloxane compound represented by the formula (2a) is removed after the completion of the reaction, and then the carbon having reactivity with the SiH group is removed - carbon double bond in the epoxy resin.

The component (B) of the silicon-containing curable resin composition of the present invention is an epoxy siloxane compound having 1 to 10 silicon atoms and at least two epoxy-containing groups in one molecule. As the component (B), the compound represented by the following general formula (4) is preferable because heat resistance is improved. Examples of the component (B) include compounds represented by the following general formulas (25) to (27).

Figure 112014039686618-pct00012

(Wherein R 6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, E 2 represents an epoxy-containing group, and d represents a number of 3 to 6.)

Figure 112014039686618-pct00013

(Wherein R 7 to R 9 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, E 2 represents an epoxy-containing group, e represents a number of 1 to 3, f and g Independently represent a number of 0 to 6, provided that the sum of the silicon atoms is a number of 1 to 10.)

Figure 112014039686618-pct00014

(Wherein R 10 to R 12 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, E 2 represents an epoxy-containing group, and h represents a number of 0 to 8.)

Figure 112014039686618-pct00015

(Wherein R 13 to R 14 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and E 2 represents an epoxy-containing group.)

In the general formulas (4) and (25) to (27), E 2 represents an epoxy-containing group. Examples of the epoxy-containing groups include the above formulas (5) to (24). The epoxy-containing group of the component (B) is preferably the same group as the epoxy-containing group of the component (A) in order to make the reactivity with the epoxy-containing group of the component (A)

In the general formula (4), R 6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups represented by R 1 to R 4 in the general formula (1). As R 5 , methyl and phenyl are preferable, and methyl is most preferable because heat resistance is improved. d represents a number of 3 to 6 and d is preferably 3 to 5, more preferably 3 to 4, and most preferably 4 because industrial availability of raw materials is easy.

In the general formula (25), R 7 to R 9 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups represented by R 1 to R 4 in the general formula (1). As R 5 , methyl and phenyl are preferable, and methyl is most preferable because heat resistance is improved. e represents a number of 1 to 3; f and g each independently represent a number of 0 to 6; Provided that the total number of silicon atoms is 1 to 10. Since the heat resistance of the cured product is improved, e is preferably 2 to 3. For the same reason, f and g are preferably 0 to 2, more preferably 0 to 1.

In formula (26), R 10 to R 12 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups represented by R 1 to R 4 in the general formula (1). As R 5 , methyl and phenyl are preferable, and methyl is most preferable because heat resistance is improved. h represents 0 to 8, and since the heat resistance of the cured product is improved, the number is preferably 0 to 3, more preferably 0 to 1, and most preferably 0.

In the general formula (27), R 13 and R 14 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups represented by R 1 to R 4 in the general formula (1). As R 5 , methyl and phenyl are preferable, and methyl is most preferable because heat resistance is improved.

The compounds represented by the general formulas (4) and (25) to (27) can be produced by reacting a SiH group of the compound represented by the general formula (4a), (25a) The hydrosilylation reaction can be carried out by reacting a chain siloxane compound represented by the general formula (1a) with a cyclosiloxane compound represented by the general formula (2a) by hydrosilylation The reaction may be carried out under the same conditions as the reaction.

Figure 112014039686618-pct00016

(Wherein R < 6 > And d have the same meanings as in general formula (4).)

Figure 112014039686618-pct00017

(Wherein R 7 to R 9 , e, f and g have the same meanings as in general formula (25).)

Figure 112014039686618-pct00018

(Wherein R 10 to R 12 and h have the same meanings as in formula (26)).

Figure 112014039686618-pct00019

(Wherein R 13 to R 14 have the same meanings as in formula (27)).

(5a) to (20a), (22a) to (24a) are examples of the epoxy compound containing a carbon-carbon double bond having reactivity with SiH groups. Containing groups of formulas (20) and (22) to (24), respectively.

In the silicon-containing curable resin composition of the present invention, when the ratio of the component (B) to the component (A) is too small, the cured product is too soft and tacky on the surface, The content of the component (B) is preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass, and more preferably 7 to 35 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B) Most preferred.

The component (C) of the silicon-containing curable resin composition of the present invention is an epoxy-curable compound. Examples of the epoxy curing compound include an epoxy curing agent and an epoxy curing catalyst. In the present invention, the epoxy curing agent refers to a compound capable of curing the epoxy composition by reacting with an epoxy group. The epoxy curing catalyst is an acidic or alkaline substance which reacts with each other by action of heat or energy rays. Quot; curing "

Examples of the epoxy curing agent include phenolic curing agents such as phenol novolac resin, bisphenol novolac resin and poly p-vinyl phenol; Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamide amine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, m-phenyl (Aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenyl Polyamine type curing agents such as methane and diaminodiphenylsulfone; There may be mentioned phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, methyl-3,6-endomethylenetetrahydro Polycarboxylic acid-based curing agents such as phthalic anhydride, and the like, and phenolic curing agents and polycarboxylic acid-based curing agents are preferable, and polycarboxylic acid-based curing agents are more preferable because cured products having high heat resistance can be obtained.

When an epoxy curing agent is used as the epoxy curing compound as the component (C), a good cured product can be obtained. The amount of the epoxy curing agent to be used is preferably such that the amount of the epoxy curing agent The amount of epoxy reactive groups is preferably from 0.4 to 1.2 mols, more preferably from 0.5 to 0.9 mols. When an epoxy curing agent is used, the amount of the epoxy curing agent to be used is preferably 10 to 50 parts by mass, more preferably 15 to 40 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) More preferred is the addition.

As the epoxy curing catalyst, an epoxy curing catalyst of a type in which an acidic substance is generated from a reaction at a relatively low temperature is preferable, and an organic onium salt curing catalyst is more preferable because of its good storage stability and reactivity. Examples of the organic onium salt curing catalyst include a diazonium salt catalyst, an iodonium salt catalyst, and a sulfonium salt catalyst, and these may be cured by heat or may be cured by energy rays. Generally, aliphatic onium salts are used for curing by heat, and aromatic onium salts are used for curing by energy ray. The organic onium salt curable catalyst can obtain good curing with a small amount of use, and when curing is carried out by an energy ray, the component (C) has good compatibility with the component (A), so that an aromatic iodonium salt, Is preferred. When curing is carried out by heat, the component (C) is preferably an aliphatic sulfonium salt since the compatibility with the component (A) is good.

In the present invention, the aromatic iodonium salt means an iodonium salt in which at least one of the substituents of iodonium is an aryl group. Examples of the aromatic iodonium salt include 4-isopropoxy-4'-methyldiphenyliodonium tetrakispentafluorophenylborate, 4-isopropoxy-4'-methyldiphenyliodonium hexafluorophosphate, 4- (Tolylcumyl) iodonium hexafluorophosphate, (tolylcumyl) iodonium hexafluoroantimonate, (tolylcumyl) iodonium (iodonium) hexafluoroantimonate, (Tert-butylphenyl) iodonium hexafluorophosphate, bis (tert-butylphenyl) iodonium hexafluoroantimonate, bis (tert-butylphenyl) iodonium tetrakispenta Fluorophenylborate, and the like.

In the present invention, the aromatic sulfonium salt means a sulfonium salt in which at least one of the substituents of the sulfonium is an aryl group. Examples of the aromatic sulfonium salts include 4,4'-bis [di (4-heptoxyphenyl) sulfophenyl phenyl] sulfide bishexafluoroantimonate, 4,4'-bis [di (4-heptoxyphenyl) (4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4,4'-bis [bis ([beta] -hydroxyethoxy) phenyl) sulfonio] phenylsulfide bishexafluorophosphate, 4,4'-bis [bis Bis [bis (fluorophenyl) sulfonium] hexafluoroantimonate, 4,4'-bis [bis (fluorophenyl) sulfonio] phenylsulfide bishexafluorophosphate, (Diphenylsulfanyl) phenylsulfide bishexafluorophosphate, 4,4'-bis (diphenylsulfonyl) phenylsulfide bis (diphenylsulfonyl) phenylsulfide bishexafluoroantimonate, 4,4'- Hexafluoroantimonate, 4- ( (4-benzoylphenylthio) phenyl-di- (4- (beta -hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- 4- (4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenylsulfonium hexafluoroantimonate, 4- ), Phenyl 4- (4-benzoylphenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) Phenyl-diphenylsulfonium hexafluoroantimonate, 4- (phenylthio) phenyl-di- (4- (? -Hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- 4- (phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4 - (? - hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4- - (phenylthio) phenyl-di- (4-fluorophenyl) alcohol Diphenylsulfonium hexafluoroantimonate, 4- (phenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyl-diphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimo (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- Phenylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- Phenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-hydroxyphenyl) sulfonium hexafluorophosphate, 4- -Benzoylphenylthio) phenylbis (4-hydroxyphenyl) sulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethyl sulphate 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, and the like can be given.

The aliphatic sulfonium salt in the present invention refers to a sulfonium salt in which all of the substituents of the sulfonium are an aliphatic hydrocarbon group or an aliphatic hydrocarbon having a substituent. Examples of the aliphatic sulfonium salt include dimethylbenzylsulfonium hexafluoroantimonate, tribenzylsulfonium hexafluoroantimonate, dimethylphenylacylsulfonium hexafluoroantimonate, (3-methyl-2-butenyl) dimethyl Sulfonium hexafluoroantimonate, benzyltetrahydrothiophenium hexafluoroantimonate, cinnamyldimethylsulfonium hexafluoroantimonate, 1- (α-naphthylmethyl) tetrahydrothiophenium hexafluoro (Cinnamyl) tetrahydrothiophenium hexafluoroantimonate, 1- (cinnamyl) tetrahydrofuran, tetrahydrothiophenium hexafluorophosphate, 1- (naphthylmethyl) tetrahydrothiophenium hexafluorophosphate, 1- Thiophenium hexafluorophosphate, and the like.

When an epoxy curing catalyst is used as the epoxy curing compound of the component (C), if the content of the epoxy curing catalyst is too small, the curing becomes insufficient. When the content of the epoxy curing catalyst is too small, the heat resistance of the cured product may be adversely affected. The content of the curing catalyst is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, most preferably 0.1 to 1 part by mass based on 100 parts by mass of the total amount of the components (A) and (B).

The silicon-containing curable resin composition of the present invention can be selected as a type of curing by appropriately selecting the kind of the epoxy curing compound as the component (C), by curing by heat, light curing or both light and heat. The curing temperature in the case of thermosetting is preferably 60 to 200 占 폚, more preferably 80 to 150 占 폚. The curing time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours. In the case of photocuring, ultraviolet rays, electron beams, X-rays, radiation, high-frequency waves and the like are used as active energy rays that can be used, and ultraviolet rays are most economically preferable. Ultraviolet light sources include ultraviolet lasers, mercury lamps, high pressure mercury lamps, xenon lamps, sodium lamps, and alkali metal lamps. As the ultraviolet source used here, a high-pressure mercury lamp is preferable. The irradiation energy is usually in the range of 100 to 10000 mJ / cm < 2 > although the optimum condition differs depending on the coated film thickness. In the case of thermosetting after photo-curing, it is usually necessary to heat at 60 to 150 ° C.

The silicon-containing curable resin composition of the present invention may contain other epoxy compounds, curing accelerators, sensitizers, metal oxide fine powders, weather resistance And an additive such as an additive. However, when additives are added to the additives other than the metal oxide fine powder, the total amount of the component (A), the component (B) and the component (C) in the silicon-containing curable resin composition By mass based on the amount excluding the content of the metal oxide fine powder in the range of 90% by mass or more.

In the present invention, the above-mentioned other epoxy resin is a compound having at least one epoxy group in the molecule, and refers to a compound other than the component (A) and the component (B) according to the present invention. Other preferred epoxy resins include 2,2-bis (3,4-epoxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 2- Epoxy) cyclohexyl-5,1-spiro (3,4-epoxy) cyclohexylm-dioxane, bis [(3,4-epoxycyclohexyl) methyl] adipate, 6- Alicyclic epoxy compounds such as hexanecarbonyloxy) hexanoic acid (3,4-epoxycyclohexyl) methyl ester; Bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F and diglycidyl ether of bisphenol S; Novolak type epoxy resins such as phenol novolak epoxy resin, cresol novolac epoxy resin, and hydroxybenzaldehyde phenol novolac epoxy resin; Aromatic epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and polyfunctional epoxy resin such as epoxidized polyvinyl phenol; Polyglycidyl ethers of aliphatic polyhydric alcohols; Polyglycidyl ethers of polyester polyols of aliphatic polyhydric alcohols and aliphatic polyvalent carboxylic acids; Polyglycidyl esters of aliphatic polycarboxylic acids; Polyglycidyl esters of polyester polycarboxylic acids of aliphatic polyhydric alcohols and aliphatic polyvalent carboxylic acids; Dimers, oligomers and polymers obtained by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate; Oligomers, polymers obtained by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers; Epoxylated polybutadiene, and an epoxy siloxane compound represented by the following general formula (28).

Figure 112014039686618-pct00020

(Wherein R 15 to R 19 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, E 3 denotes an epoxy-containing group, X denotes an alkyl group having 1 to 4 carbon atoms, And j and k are numbers from 0 to 1000 where j + k is from 9 to 1000. When j is a number of 0, X represents an epoxy-containing group.

The other epoxy compound preferably has a molecular weight of 100 to 1000 because the improvement in the mechanical strength of the resulting cured product becomes remarkable, and the epoxy equivalent is preferably 100 to 600. If the blending amount of the other epoxy compound is too large, the heat resistance of the obtained cured product may be lowered. Therefore, the amount is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) The addition is more preferable. (A), the component (B) and the epoxy group of the other epoxy compound when the component (C) is an epoxy curing agent. When the component (C) is an epoxy curing agent, ), The component (B) and the other epoxy compound, the amount of the component (C) is suitably changed.

The curing accelerator is a compound for accelerating the reaction between the epoxy group and the epoxy curing agent. It is particularly preferable that the epoxy curing agent is a phenol-based curing agent or a polycarboxylic acid-based curing agent. Examples of the curing accelerator include 3, 3, 4, 5, 6, 7, 8, or 9 kinds of such as 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, Class amines and their salts; Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; Tetraphenylborate salts such as tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. The blending amount of the curing accelerator is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of the component (A), the component (B) and the other epoxy compound in the composition of the present invention.

The sensitizer is a compound capable of expanding an adaptable wavelength range of an energy ray when it is cured by an energy ray. Examples of the sensitizer include benzophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 4,4-dihydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, Phenanone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, 4-methoxybenzophenone, 4,4-dimethoxybenzophenone, 3,3-dimethyl- Benzophenones such as benzophenone, acetophenone, 4-methoxyacetophenone, 2,4-dimethoxyacetophenone, 2,5-dimethoxyacetophenone, 2,6-dimethoxyacetophenone, Acetophenones such as ethoxyacetophenone, 4-ethoxyacetophenone, diethoxyacetophenone, 2,2-diethoxyacetophenone, 2-ethoxy-2-phenylacetophenone and 4-phenylacetophenone, 1,2-benzanthraquinone, 1,4-cyclohexanthraquinone, 2-chloroanthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, anthraquinone sulfonic acid, Ha Anthraquinones such as dodecylanthraquinone (quinizarin), anthraquinones such as anthracene, 1,2-benzoanthracene, 9-cyananoanthracene, 9,10-dicyanoanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9 , And 10-bis (phenylethyl) anthracene, 2,3-dichloro-6-dicyano-p-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, methoxy Benzoquinone, 2,5-dichloro-p-benzoquinone, 2,6-dimethyl-1,4-benzoquinone, 9,10-phenanthrenequinone, camphor quinone, 2,3- 4-naphthoquinone, quinones such as xanthone, thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2 , Dibenzosuberenol, dibenzosuberenol, dibenzosuberane, and the like, such as dibenzosuberenone, dibenzosuberen, dibenzosuberenol, dibenzosuberane, etc., 2-methoxynaphthalene, benzoin isopropyl ether, 4-benzoyldiphenyl, o Aromatic compounds such as benzoylbenzoic acid, methyl o-benzoylbenzoate, 4-benzoyl-4-methyl-diphenylsulfide, benzyl and benzoin methyl ether, and aromatic compounds such as coumarin, thiazine, azine, Acridine-based compounds, and xanthene-based compounds. The addition amount of the sensitizer is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2 parts by mass based on 100 parts by mass of the total of the components (A) and (B).

Examples of the metal oxide fine powder include inorganic materials such as minerals. Specific examples thereof include silicon dioxide such as colloidal silica, silica filler and silica gel; Metal oxides such as aluminum oxide, zinc oxide and titanium oxide; Mica, montmorillonite, silica, diatomaceous earth, sericite, kaolinite, flint, feldspar, vermiculite, attapulgite, And minerals such as talc, minnesotite, pyrophyllite, and the like, and they may be modified by organic modification treatment or the like. Of these, silicon dioxide is preferred.

The particle diameter of the metal oxide fine particles is preferably 100 占 퐉 or less, more preferably 50 占 퐉 or less in terms of heat resistance. The blending amount of the metal oxide fine particles in the silicon-containing curable resin composition of the present invention is preferably 0.1 to 80 mass%, more preferably 0.5 to 70 mass%.

As the weather resistance imparting agent, those generally used such as light stabilizers, ultraviolet absorbers, phenol antioxidants, sulfur antioxidants and phosphorus antioxidants can be used. Examples of the light stabilizer include hindered amines. Examples of the ultraviolet absorber include 2-hydroxybenzophenones, 2- (2-hydroxyphenyl) benzotriazoles, 2- (2-hydroxyphenyl) Diol-1,3,5-triazine, benzoates and cyanoacrylates, and examples of the phenol-based antioxidant include triethylene glycol-bis [3- (3-t- Butyl-5-methyl-4-hydroxyphenyl) propionate], dibutylhydroxytoluene (BHT), 2,6- Zero includes dialkyl thiodipropionates and? -Alkyl mercaptopropionic acid esters, and phosphorus antioxidants include organic phosphites.

When the weathering-imparting agent is used, the content thereof is preferably 0.0001 to 50 mass%, more preferably 0.001 to 10 mass% in the silicon-containing curable resin composition of the present invention in terms of heat resistance, electrical properties, curability, mechanical properties, storage stability, % By mass is more preferable.

The silicon-containing curable resin composition of the present invention has excellent flowability at room temperature (25 DEG C) and is excellent in handling properties. With regard to the fluidity, the viscosity measured by an E-type viscometer at room temperature (25 ° C) is preferably 50 Pa · s or less, more preferably 10 Pa · s or less, in a state not containing a metal oxide fine powder.

The cured product obtained from the silicon-containing curable resin composition of the present invention is excellent in transparency, crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, stain resistance, flame retardancy, moisture resistance, gas barrier property, flexibility, , Low dielectric constant and other mechanical properties, optical properties, electrical characteristics, and the like, and particularly excellent in heat resistance. Accordingly, the silicon-containing curable resin composition of the present invention is useful as a sealing material for display materials, optical materials, recording materials, semiconductors, and the like in the field of electric and electronic materials, high voltage insulating materials, and potting for insulation, dustproofing, a coating material, an interlayer insulating film, an insulating packing, an optical waveguide, an optical fiber protecting material, an optical lens, an adhesive for an optical device, a high heat resistant adhesive, and a heat insulating material. Heat-resistant sealing materials, members for solar cells and fuel cells, insulating coating materials, photosensitive drums for photocopiers, and the like. Particularly, they can be suitably used as coating materials.

Example

Hereinafter, the present invention will be further described with reference to Examples and the like, but the present invention is not limited by these Examples.

Unless specifically stated otherwise, "parts" and "%" in the examples are based on mass standards. The mass average molecular weight was defined as the weight average molecular weight in terms of polystyrene when tetrahydrofuran was used as a solvent and GPC (Gel Permeation Chromatography) analysis was performed. The epoxy equivalent was measured in accordance with JIS K-7236 (method for obtaining an epoxy resin).

[Preparation Example 1: chain siloxane compound a-1]

130 g of ion-exchanged water, 550 g of a 48% aqueous solution of sodium hydroxide and 100 g of toluene as a solvent were charged into a glass reaction vessel equipped with a stirrer, a thermometer and a stirrer, 129 g (1 mol) of dimethyldichlorosilane was added After completion of dropwise addition, stirring was further continued at 105 ° C for 5 hours. The obtained reaction solution was washed with water (washing with water) of 500 g of ion exchange water to remove the purified salt, and the solvent was distilled off under reduced pressure at 60 캜. To the reaction product, 12.1 g (0.1 mol) of dimethylvinylchlorosilane dissolved in 63 g (0.8 mol) of pyridine was added and the mixture was stirred at 70 캜 for 30 minutes. Thereafter, after washing with 100 g of ion-exchanged water, the solvent was distilled off under reduced pressure at 100 캜 to obtain a chain siloxane compound a-1 having vinyl groups at both ends. In the chain siloxane compound a-1, R 1 to R 4 in the general formula (1a) are methyl groups, and the mass average molecular weight by GPC is 40,000 (a is 538).

[Production Example 2: chain siloxane compound a-2]

Except that a mixture of 116 g (0.9 mol) of dimethyldichlorosilane and 25.3 g (0.1 mol) of diphenyldichlorosilane was used in place of 129 g (1 mol) of dimethyldichlorosilane in Production Example 1, To obtain a chain siloxane compound a-2 having a vinyl group. The chain siloxane compound a-3 is a compound in which R 1 to R 2 in the general formula (1a) are methyl groups and R 3 to R 4 are a mixture of a methyl group and a phenyl group (methyl group: phenyl group = 9: 1) The molecular weight was 20,000 (a corresponds to 230).

[Production Example 3: chain siloxane compound a-3]

(1 mol) of dimethyldichlorosilane in Production Example 1 was replaced by a mixture of 90.3 g (0.7 mol) of dimethyldichlorosilane and 75.9 g (0.3 mol) of diphenyldichlorosilane was used in place of 129 g Thereby obtaining a chain siloxane compound a-3 having vinyl groups at both ends thereof. The chain siloxane compound a-3 is a compound represented by the general formula (1a) in which R 1 to R 2 are methyl groups and R 3 to R 4 are a mixture of a methyl group and a phenyl group (methyl group: phenyl group = 7: 3) The molecular weight was 10,000 (a corresponds to 88).

[Preparation Example 4: High molecular weight epoxy siloxane compound A-1]

40 g (1 mmol) of the chain siloxane compound a-1, 1.44 g (6 mmol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 5 g of platinum-divinyltetramethyl di 10 mg of a siloxane complex (Karstedt catalyst) and 50 g of toluene as a solvent were charged and reacted at 105 ° C for 2 hours while stirring. After the unreacted 2,4,6,8-tetramethylcyclotetrasiloxane and the solvent were distilled off under reduced pressure at 80 DEG C, 0.92 g (8 mmol) of allylglycidyl ether and 50 g of toluene as a solvent were added and stirred at 105 DEG C For 3 hours. After completion of the reaction, unreacted allyl glycidyl ether and the solvent were distilled off under reduced pressure at 80 占 폚 to obtain a high molecular weight epoxy siloxane compound A-1. The high molecular weight epoxy siloxane compound A-1 is an epoxy siloxane compound wherein the groups represented by the general formula (2) are connected to the groups represented by the general formula (1), wherein R 1 to R 4 in the general formula (1) Is 538. In the general formula (2), R 5 is a methyl group, E 1 is a 3-glycidyloxypropyl group, and b is 3. The epoxy equivalent of the high molecular weight epoxy siloxane compound A-1 was 6700.

[Preparation Example 5: High molecular weight epoxy siloxane compound A-2]

(1 mmol) of the chain siloxane compound a-2 was used instead of 40 g (1 mmol) of the chain siloxane compound a-1 in Production Example 4 to obtain a high molecular weight epoxy siloxane compound A-2 . The high molecular weight epoxy siloxane compound A-2 is an epoxy siloxane compound wherein the groups represented by the general formula (2) are connected to the groups represented by the general formula (1), wherein R 1 to R 2 in the general formula (1) 3 to R 4 are a mixture of a methyl group and a phenyl group (methyl group: phenyl group = 9: 1), a is 230, R 5 is a methyl group, E 1 is 3-glycidyloxypropyl, b Lt; / RTI > The epoxy equivalent of the high molecular weight epoxy siloxane compound a-2 was 3,400.

[Preparation Example 6: High molecular weight epoxy siloxane compound A-3]

(1 mmol) of the chain siloxane compound a-3 was used instead of 40 g (1 mmol) of the chain siloxane compound a-1 in Production Example 4 to obtain a high molecular weight epoxy siloxane compound A-3 . The high molecular weight epoxy siloxane compound A-3 is an epoxy siloxane compound in which the groups represented by the general formula (2) are connected to the groups represented by the general formula (1), and R 1 to R 2 in the general formula (1) 3 to R 4 are a mixture of a methyl group and a phenyl group (methyl group: phenyl group = 7: 3), a is 88, R 5 is a methyl group, E 1 is 3-glycidyloxypropyl, b Lt; / RTI > The epoxy equivalent of the high molecular weight epoxy siloxane compound A-2 was 1,600.

[Preparation Example 7: High molecular weight epoxy siloxane compound A-4]

Except that 0.99 g (8 mmol) of 1,2-epoxy-4-vinylcyclohexane was used instead of 0.92 g (8 mmol) of allyl glycidyl ether in Production Example 4 to obtain a high molecular weight epoxy siloxane Compound A-4 was obtained. The high molecular weight epoxy siloxane compound A-4 is an epoxy siloxane compound wherein the groups represented by the general formula (2) are connected to the groups represented by the general formula (1), wherein R 1 to R 4 in the general formula (1) Is 538. In the general formula (2), R 5 is a methyl group, E 1 is 2- (3,4-epoxycyclohexyl) ethyl, and b is 3. The epoxy equivalent of the high molecular weight epoxy siloxane compound A-4 was 6700.

[Preparation Example 8: High molecular weight epoxy siloxane compound A-5]

(1 mmol) of the chain siloxane compound a-2 and 0.92 g (8 mmol) of allyl glycidyl ether instead of 40 g (1 mmol) of the chain siloxane compound a-1 in Production Example 4 were replaced with 1,2- Except that 0.99 g (8 mmol) of cyclohexane was used as a polymerization initiator, to obtain a high molecular weight epoxy siloxane compound A-5. The high molecular weight epoxy siloxane compound A-5 is an epoxy siloxane compound wherein the groups represented by the general formula (2) are connected to the groups represented by the general formula (1), wherein R 1 to R 2 in the general formula (1) 3 to R 4 are a mixture of a methyl group and a phenyl group (methyl group: phenyl group = 9: 1), a is 230, R 5 in the general formula (2) is a methyl group, E 1 is 2- (3,4-epoxycyclo Hexyl) ethyl, and b is 3. The epoxy equivalent of the high molecular weight epoxy siloxane compound A-5 was 3,400.

[Preparation Example 9: High molecular weight epoxy siloxane compound A-6]

(0.8 mmol) of the chain siloxane compound a-2, 0.144 g (0.6 mmol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 0.1 g (0.6 mmol) of platinum-divinyltetrasiloxane 10 mg of a methyldisiloxane complex (Karstedt catalyst) and 50 g of toluene as a solvent were charged and reacted at 105 DEG C for 2 hours while stirring, allyl glycidyl ether 0.92 (8 mmol) was added and the reaction was further carried out at 105 DEG C for 3 hours. After completion of the reaction, unreacted allyl glycidyl ether and the solvent were distilled off under reduced pressure at 80 占 폚 to obtain a high molecular weight epoxy siloxane compound A-6. The high molecular weight epoxy siloxane compound A-6 is obtained by reacting an epoxy siloxane compound wherein the groups represented by the general formula (2) are connected to the groups represented by the general formula (1), the group represented by the general formula (2) Wherein R 1 to R 2 are a methyl group and R 3 to R 4 are a mixture of a methyl group and a phenyl group (methyl group: Phenyl group = 9: 1), a is 230, R 5 in the general formulas (2) and (3) is a methyl group, E 1 is 3-glycidyloxypropyl and b is 3. The epoxy equivalent of the high molecular weight epoxy siloxane compound A-6 was 5100.

[Production Example 10: Low molecular weight epoxy siloxane compound B-1]

(0.2 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 114 g (1 mol) of allyl glycidyl ether, and 100 g of platinum-divinyltetramethyldisiloxane complex (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a glass reaction vessel equipped with a stirrer, Karstedt catalyst) and 200 g of toluene as a solvent were charged and reacted at 105 DEG C for 3 hours while stirring. Then, unreacted allyl glycidyl ether and the solvent were distilled off under reduced pressure at 100 占 폚 to obtain a low molecular weight epoxy siloxane compound B-1. The low molecular weight epoxy siloxane compound B-1 was a compound represented by the general formula (4) in which R 6 was methyl, E 2 was 3-glycidyloxypropyl, and d was 4, and the epoxy equivalent was 174.

[Production Example 11: Low molecular weight epoxy siloxane compound B-2]

(1 mol) of 1,2-epoxy-4-vinylcyclohexane was used instead of 114 g (1 mol) of allyl glycidyl ether in Production Example 10 to obtain a low molecular weight epoxy siloxane compound B -2. The low molecular weight epoxy siloxane compound B-2 was a compound represented by the general formula (4) wherein R 6 was a methyl group, E 2 was 2- (3,4-epoxycyclohexyl) ethyl and d was 4, and the epoxy equivalent was 184.

[Preparation Example 12: Low molecular weight epoxy siloxane compound B-3]

The procedure of Production Example 10 was repeated except that 65.6 g (0.2 mol) of tetrakis (dimethylsiloxy) silane was used instead of 48 g (0.2 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane Thereby obtaining a low molecular weight epoxy siloxane compound B-3. The low molecular weight epoxy siloxane compound B-3 is a compound in which R 8 to R 9 in the general formula (25) are methyl groups, E 2 is 3-glycidyloxypropyl group, e is 3, f and g are 1, Was 226.

[Preparation Example 13: comparative epoxy siloxane composition D-1]

According to Example 1 of International Publication No. 2008/133108, a glass reaction vessel equipped with a thermometer and a stirrer was charged with 80 g of 2,4,6,8-tetramethylcyclotetrasiloxane, 37 g of 1,3-divinyltetramethyldisiloxane 37.2 , 2-epoxy-4-vinylcyclohexane (122.6 g) and 1,4-dioxane as a solvent (925 g) were charged and heated and stirred, followed by addition of 10 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) Then, the reaction was carried out at 65 to 100 ° C for 8 hours. After cooling to 30 DEG C, 925 g of acetonitrile was added and stirred at 30 DEG C for 2 hours, 800 g of activated carbon was added, and the mixture was stirred at 30 DEG C for 48 hours. After the activated carbon was removed by filtration, the activated carbon washed by filtration was washed with acetonitrile, and the washing liquid was recovered and mixed with the filtrate obtained earlier. 1,4-dioxane and acetonitrile were distilled off from the mixed solution recovered at a heating temperature of 40 ° C under an evaporator using an evaporator to obtain a comparative epoxy siloxane composition D-1. The epoxy equivalent of the comparative epoxy siloxane composition D-1 was 251.

[Production Example 14: Comparative Composition D-2]

In accordance with Example 14 of International Publication No. 2008/133108, 55.0 g of 2,4,6,8-tetramethylcyclotetrasiloxane and 20.0 g of the polysiloxane compound represented by the following formula (29) were added to a glass reaction vessel equipped with a thermometer and a stirrer, 110 g of 2-epoxy-4-vinylcyclohexane and 1000 g of 1,4-dioxane as a solvent were charged and heated and stirred, and 10 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) was added at 70 캜 Then, the reaction was carried out at 65 to 100 ° C for 8 hours. Then, the same operation as in Production Example 11 was carried out to obtain a comparative epoxy siloxane composition D-2. The epoxy equivalent of the comparative epoxy siloxane composition D-1 was 272.

Figure 112014039686618-pct00021

[Examples 1 to 23, Comparative Examples 1 to 28]

1 to 3 as low-molecular-weight epoxy siloxane compounds B-1 to 3 as components (B), the following compounds C-1 to C-3 as components (C) 1 to 2 and the following compound D-3, and the following compound E-1 as a curing accelerator were used and mixed in the formulations shown in Tables 1 and 2 to obtain the silicon-containing compound of Examples 1 to 23 and Comparative Examples 1 to 28 To prepare a curable resin composition. Using the obtained silicon-containing curable resin composition, a test piece was prepared in accordance with the following <preparation of test piece>.

(C) Component

C-1: 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate as an epoxy curing catalyst

C-2: 1- (cinnamyl) tetrahydrothiophenium hexafluoroantimonate as an epoxy curing catalyst (thermal curing catalyst)

C-3: Methyl hexahydrophthalic anhydride as an epoxy curing agent

Comparative Low molecular weight  Epoxy compound

D-3: phenol novolak type epoxy resin (condensation degree 8) epoxy equivalent 177

Hardening accelerator

E-1: Diazabicyclo undecene octylate

<Preparation of test piece>

Each of the silicon-containing curable resin compositions of Examples 1 to 23 and Comparative Examples 1 to 28 was applied to a square glass substrate having a length of 50 mm, a width of 50 mm and a thickness of 1 mm so as to have a film thickness of 20 m, Curing or thermosetting to obtain the test pieces of Examples 1 to 23 and Comparative Examples 1 to 28. [

(Light curing condition)

The glass substrates coated with the silicon-containing curable resin compositions of Examples 1 to 14 or Comparative Examples 1 to 15 were irradiated with ultraviolet rays at a dose of 10 mJ / cm 2 (365 nm in terms of exposure) using a high-pressure mercury lamp, And then cured by post-baking in a constant temperature bath for 10 minutes.

(Heat curing condition)

The glass substrates coated with the silicon-containing curable resin compositions of Examples 15 to 23 or Comparative Examples 16 to 28 were cured by heating in a thermostatic chamber at 120 占 폚 for 1 hour and then at 150 占 폚 for 2 hours.

Using the obtained test pieces, the following dust adhesion test and heat resistance adhesion test were carried out.

(Dust adhesion test)

The test piece was placed in a container filled with a powdery silica gel (trade name: Wako Gel C-100, manufactured by Wako Pure Chemical Industries, Ltd.) until the entirety was filled. After pulling the test piece from the container, the test piece was dropped three times on the glass plate at a height of 10 cm so that the light screen was vertical. Next, the transmittance of light of 800 nm of the test piece was measured. The results are shown in Tables 1 and 2. The lower the transmittance, the more sticky the surface. On the other hand, the transmittance of light of 800 nm of the test piece before attaching the silica gel was 99% or more.

(Heat Resistance Adhesion Test)

The test piece was placed in a thermostatic chamber at 200 ° C, and a test piece was observed under a microscope every 30 days up to 120 days to investigate peeling and cracking of the cured product. Tables 1 and 2 show the number of days in which peeling or cracks were first detected. On the other hand, it was 120 days or more that no peeling or crack was found even after 120 days.

Figure 112014039686618-pct00022

Figure 112014039686618-pct00023

Claims (9)

(2), or a group represented by the following general formula (2) and a group represented by the following general formula (3) as the component (A) are bonded to the group represented by the general formula (1) An epoxy siloxane compound, an epoxy siloxane compound having 1 to 10 silicon atoms and at least two epoxy-containing groups in one molecule as a component (B), and an epoxy-curable compound as a component (C) As a composition,
Wherein the content of the component (B) is 3 to 50 parts by mass based on 100 parts by mass of the total of the components (A) and (B).
Figure 112018011646236-pct00024

(Wherein R 1 to R 4 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a represents a number of 20 to 10000)
Figure 112018011646236-pct00025

(Wherein R 5 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different, E 1 represents an epoxy-containing group, and b represents a number of 2 to 5)
Figure 112018011646236-pct00026

(Wherein c represents a number of 2 to 6 in which b-c + 1 is a number of 0 to 4, and R 5 , E 1 and b have the same meanings as in the general formula (2).) The method according to claim 1,
Wherein the content of the component (B) is 7 to 35 parts by mass based on 100 parts by mass of the total of the components (A) and (B). 3. The method according to claim 1 or 2,
Wherein the epoxy equivalent of the component (A) is 500 to 50,000. 3. The method according to claim 1 or 2,
Wherein the epoxy equivalent of the component (A) is 1000 to 10,000. 3. The method according to claim 1 or 2,
Wherein the component (B) is an epoxy compound represented by the following general formula (4).
Figure 112018011646236-pct00029

(Wherein R 6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, E 2 represents an epoxy-containing group, and d represents a number of 3 to 6.) The method of claim 3,
Wherein the component (B) is an epoxy compound represented by the following general formula (4).
Figure 112018011646236-pct00030

(Wherein R 6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, E 2 represents an epoxy-containing group, and d represents a number of 3 to 6.) The method of claim 3,
Wherein the content of the component (B) is 7 to 35 parts by mass based on 100 parts by mass of the total of the components (A) and (B). 5. The method of claim 4,
Wherein the content of the component (B) is 7 to 35 parts by mass based on 100 parts by mass of the total of the components (A) and (B). A cured product obtained from the silicon-containing curable resin composition according to claim 1 or 2.
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