WO2013140601A1 - Composition de résine durcissable contenant du silicium - Google Patents

Composition de résine durcissable contenant du silicium Download PDF

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Publication number
WO2013140601A1
WO2013140601A1 PCT/JP2012/057504 JP2012057504W WO2013140601A1 WO 2013140601 A1 WO2013140601 A1 WO 2013140601A1 JP 2012057504 W JP2012057504 W JP 2012057504W WO 2013140601 A1 WO2013140601 A1 WO 2013140601A1
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WIPO (PCT)
Prior art keywords
epoxy
general formula
group
siloxane compound
compound
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PCT/JP2012/057504
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English (en)
Japanese (ja)
Inventor
孝 末吉
斎藤　誠一
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株式会社Adeka
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Priority to CN201280052561.5A priority Critical patent/CN103906783B/zh
Priority to PCT/JP2012/057504 priority patent/WO2013140601A1/fr
Priority to KR1020147011188A priority patent/KR101858638B1/ko
Publication of WO2013140601A1 publication Critical patent/WO2013140601A1/fr

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Classifications

    • 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

Definitions

  • the present invention relates to a silicon compound having an epoxy group, a silicon-containing curable resin composition containing an epoxy curing agent or an epoxy curing catalyst, and a cured product thereof.
  • a compound having a siloxane skeleton as a repeating unit and having an epoxy group as an organic group is a bisphenol A type epoxy resin which has been conventionally used, (3 ', 4'-epoxycyclohexyl) methyl-3,4-epoxycyclohexane carboxylate, etc.
  • Patent Documents 1 to 3 are known to be excellent in flexibility and suitable as a sealing material for optical semiconductor elements such as light emitting diodes and photodiodes (for example, Patent Documents 1 to 3). See 3).
  • a cured product obtained from such a compound has the disadvantage of being easily tacky on the surface, and could not be used for surface coating applications.
  • Patent Document 4 discloses a cyclic siloxane compound having an epoxy group, a compound in which a cyclic siloxane group having an epoxy group is linked by a linear polysiloxane group, and a cyclic siloxane structure is linear in the ring (
  • a composition (see Patent Document 4) containing an epoxy siloxane compound crosslinked with (poly) siloxane group is disclosed, and a cured product obtained from the composition disclosed in Patent Document 4 has an improved surface tack.
  • the heat resistance is insufficient, and when used for surface coating, there has been a problem that when used for a long time at a high temperature, cracks easily occur.
  • An object of the present invention is to provide a curable composition which has a surface tack, is excellent in heat resistance, and is capable of obtaining a cured film which hardly causes a crack even when used at high temperatures for a long time.
  • the present invention is an epoxy siloxane compound having at least two epoxy-containing groups in one molecule as a component (A) and a group represented by the following general formula (1), and 1 to 10 in one molecule as a component (B).
  • the object is to provide a silicon-containing curable resin composition comprising an epoxy siloxane compound having a silicon atom and at least two epoxy-containing groups, and an epoxy curable compound as the component (C). Achieved.
  • a curable composition capable of obtaining a cured film which has no surface tack, is excellent in heat resistance, and hardly causes cracks even when used at high temperatures for a long 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 above general formula (1).
  • R 1 to R 4 each 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, secondary butyl, isobutyl and t-butyl.
  • Examples of the aryl group having 6 to 10 carbon atoms include phenyl, ethylphenyl, toluyl, cumenyl, xylyl, pseudocumenyl, mesityl, t-butylphenyl, phenethyl and the like.
  • R 1 to R 4 in terms of heat resistance, methyl, ethyl and phenyl are preferable, methyl and phenyl are more preferable, and phenyl is most preferable. From the viewpoint of low viscosity and low crystallization, methyl, ethyl, propyl and butyl are preferred, methyl and ethyl are more preferred, and methyl is most preferred.
  • R 1 to R 4 are preferably a combination of methyl and phenyl, and in R 1 to R 4 contained in the group represented by the general formula (1), the ratio of methyl to phenyl is a methyl group
  • the molar ratio of phenyl groups is preferably 40:60 to 100: 0, more preferably 60:40 to 97: 3, and most preferably 65:35 to 95: 5.
  • a represents a number of 20 to 10,000. When a is less than 20, the heat resistance of the resulting cured product is insufficient, and when it is more than 10000, the viscosity is increased, which causes problems in handling. a is preferably 100 to 5,000, and more preferably 200 to 2,000.
  • the component (A) has at least two epoxy-containing groups in one molecule.
  • the number of epoxy groups in the component (A) is preferably at least three, and more preferably at least four, from the viewpoint of crack resistance. If the content of the epoxy group in the component (A) is too small, the cured product tends to be tacky, and if too large, the crack resistance decreases, so the epoxy equivalent of the component (A) is It is preferably 500 to 50000, more preferably 700 to 20000, and most preferably 1000 to 10000.
  • an epoxy equivalent means the mass (gram number) of the epoxy compound containing an epoxy group of 1 equivalent.
  • Examples of the epoxy-containing group of the component (A) include the following formulas (5) to (24), etc., which are excellent in reactivity and easy to industrially obtain raw materials.
  • Glycidyl oxypropyl, 2- (3,4-epoxycyclohexyl) ethyl of formula (16), 2- (3,4-epoxy-4-methylcyclohexyl) propyl of formula (17) are preferred, 3-glycidyloxypropyl, More preferred is 2- (3,4-epoxycyclohexyl) ethyl.
  • the epoxy-containing group may be directly bonded to the group represented by the general formula (1), but since the number of epoxy-containing groups in the component (A) can be increased, the general formula (A) It is preferable that it couple
  • the linking group include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group having a heterocycle, a silane group, a linear siloxane group, a cyclic siloxane group and the like, and the heat resistance is improved. Groups are preferred.
  • the component (A) is a compound in which an epoxy-containing group is bonded to a group represented by the general formula (1) via a cyclic siloxane group
  • the heat resistance is particularly good, and therefore the following general formula (2)
  • an epoxy siloxane compound in which a group represented by the following general formula (2) and a group represented by the following general formula (3) are linked by a group represented by the above general formula (1) Is preferred.
  • 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.
  • groups exemplified for R 1 to R 4 in the general formula (1) can be mentioned.
  • R 5 methyl and phenyl are preferable and methyl is most preferable because heat resistance is improved.
  • b represents a number of 2 to 5, and b is preferably a number of 2 to 4, more preferably a number of 2 to 3, since industrial raw materials are easily obtained. Is most preferred.
  • E 1 represents an epoxy-containing group, and specific examples thereof include the above formulas (5) to (24).
  • c represents a number of 2 to 6 where b-c + 1 is a number of 0 to 4, and R 1 , E and a are as defined in the general formula (1).
  • An epoxy siloxane compound in which groups represented by General Formula (2) or groups represented by General Formula (2) and a group represented by General Formula (3) are connected by a group represented by General Formula (1) After reacting the SiH group of the cyclic siloxane compound represented by the following general formula (2a) with the vinyl group of the chain siloxane compound represented by the following general formula (1a), carbon further having reactivity with the SiH group It can be obtained by hydrosilylation reaction of an epoxy compound containing a carbon double bond.
  • preferred compounds are 2,4,6-trimethylcyclotrisiloxane, 2,4,6-triethylcyclotrisiloxane, 2,4,6-triphenylcyclotrile Siloxane, 2,4-dimethyl-6-phenylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotrisiloxane, 2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8- Tetraphenylcyclotetrasiloxane, 2,4,6-trimethyl-8-phenylcyclotetrasiloxane, 2,4-dimethyl-6,8-diphenylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentan A siloxane etc. are mentioned.
  • 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 performed using a catalyst, and as the hydrosilylation catalyst, for example, a platinum-based catalyst A catalyst, a palladium type catalyst, a rhodium type catalyst etc. are mentioned.
  • platinum catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc., platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalyst), platinum-divinyltetramethyldisiloxane complexes.
  • platinum - cyclovinylmethylsiloxane complex platinum - cyclovinylmethylsiloxane complex, a 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 ], platinum-phosphite complex (eg Pt [P (OC 6 H 5 ) 3 ] 4 ), Pt [P (OC 4 H 9 ) 3 ] 4 And dicarbonyldichloroplatinum.
  • 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
  • platinum-phosphite complex eg Pt [P (OC 6 H 5
  • 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.
  • the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, and most preferably 0.001 to 0.1% by mass from the viewpoint of reactivity. preferable.
  • the reaction conditions for the hydrosilylation are not particularly limited, and the reaction may be carried out under the conventionally known conditions using the above-mentioned catalyst, but from the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 ° C) to 130 ° C. Conventional solvents such as hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate and the like may be used.
  • the hydrosilylation reaction of may be carried out under the same conditions as the hydrosilylation reaction of the linear siloxane compound represented by the general formula (1a) and the cyclic siloxane compound represented by the general formula (2a), and after this hydrosilylation reaction Preferably, the reaction product is subsequently reacted without isolation and purification.
  • Examples of the epoxy compound containing a carbon-carbon double bond having reactivity with an SiH group include compounds of the following formulas (5a) to (20a) and (22a) to (24a).
  • the epoxy-containing groups of the above formulas (5) to (20) and (22) to (24) can be introduced by using such compounds.
  • 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.
  • a compound represented by the following general formula (4) is preferable because heat resistance is improved.
  • Examples of the component (B) further include compounds represented by the following general formulas (25) to (27).
  • E 2 represents an epoxy-containing group.
  • examples of the epoxy-containing group include the aforementioned formulas (5) to (24).
  • the epoxy-containing group of the component (B) is preferably the same as the epoxy-containing group of the component (A) in order to equalize the reactivity with the epoxy-containing group of the component (A).
  • 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.
  • groups exemplified for R 1 to R 4 in the general formula (1) can be mentioned.
  • 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 a number of 3 to 5, more preferably 3 to 4, and most preferably 4 because industrial availability of the raw material is easy.
  • 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.
  • groups exemplified for R 1 to R 4 in the general formula (1) can be mentioned.
  • 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.
  • the total of silicon atoms is a number of 1-10.
  • e is preferably a number of 2 to 3.
  • f and g are preferably a number of 0 to 2, more preferably a number of 0 to 1.
  • each of R 10 to R 12 independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • groups exemplified for R 1 to R 4 in the general formula (1) can be mentioned.
  • R 5 methyl and phenyl are preferable and methyl is most preferable because heat resistance is improved.
  • h represents a number of 0 to 8, and in view of improving the heat resistance of the cured product, the number of 0 to 3 is preferable, the number of 0 to 1 is more preferable, and 0 is most preferable.
  • 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.
  • alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms groups exemplified for R 1 to R 4 in the general formula (1) can be mentioned.
  • 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) have reactivity with the SiH group of the compounds represented by the following general formulas (4a) and (25a) to (27a), respectively.
  • the hydrosilylation reaction can be obtained by hydrosilylation reaction of an epoxy compound containing a carbon-carbon double bond having the following formula, and the hydrosilylation reaction is represented by the chain siloxane compound represented by the general formula (1a) and the general formula (2a) The reaction may be carried out under the same conditions as the hydrosilylation reaction with the cyclic siloxane compound.
  • Examples of the epoxy compound containing a carbon-carbon double bond having reactivity with a SiH group include compounds of formulas (5a) to (20a) and (22a) to (24a), and such compounds
  • the epoxy-containing groups of formulas (5) to (20) and (22) to (24) can be introduced respectively by using
  • the cured product when the ratio of the component (B) to the component (A) is too small, the cured product is too soft and tackiness tends to occur on the surface, and when too large, the cured product
  • the content of the component (B) is preferably 3 to 50 parts by mass with respect to 100 parts by mass in total of the components (A) and (B), since the heat resistance of More preferably, it is part by weight, and most preferably 7 to 35 parts by weight.
  • the component (C) of the silicon-containing curable resin composition of the present invention is an epoxy curable compound.
  • Epoxy curing compounds include epoxy curing agents and epoxy curing catalysts.
  • an epoxy curing agent is a compound capable of curing an epoxy composition by reacting with an epoxy group, and an epoxy curing catalyst causes epoxy to react with each other by the action of heat or energy ray.
  • epoxy curing agents include phenol type curing agents such as phenol novolac resin, bisphenol novolac resin, poly p-vinylphenol, etc .; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamidoamine (polyamide resin), ketimine compound , Isophorone diamine, m-xylene diamine, m-phenylene diamine, 1,3-bis (aminomethyl) cyclohexane, N-aminoethyl piperazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3 ' Polyamine curing agents such as diethyldiphenylmethane and diaminodiphenyl sulfone; Phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride,
  • the amount of the epoxy curing agent used is the epoxy contained in components (A) and (B).
  • the amount of the epoxy reactive group contained in the epoxy curing agent is preferably 0.4 to 1.2 mol, and more preferably 0.5 to 0.9 mol with respect to 1 mol of the group.
  • the amount of the epoxy curing agent used is 10 to 100 parts by weight based on the total amount of components (A) and (B) from the viewpoint of securing the effect of the present invention. 50 parts by mass is preferable, and 15 to 40 parts by mass is more preferable.
  • an epoxy curing catalyst of a type that generates an acidic substance is preferable because the reaction proceeds at a relatively low temperature, and among them, organic onium salt curing is due to good storage stability and reactivity. Catalysts are further preferred.
  • the organic onium salt-based curing catalyst include diazonium salt-based catalysts, iodonium salt-based catalysts, sulfonium salt catalysts, etc. These may be heat-curable or energy-curable. Generally, aliphatic onium salts are used for heat curing, and aromatic onium salts are used for energy curing.
  • An organic onium salt-based curing catalyst can obtain good curing with a small amount used, and when curing is performed by energy rays, as the component (C), compatibility with the component (A) is good.
  • Aromatic iodonium salts and aromatic sulfonium salts are preferred.
  • an aliphatic sulfonium salt is preferable as the component (C) because the compatibility with the component (A) is good.
  • the aromatic iodonium salt refers to an iodonium salt in which at least one of the substituents of iodonium is an aryl group.
  • aromatic iodonium salt 4-isopropoxy-4'-methyldiphenyliodonium tetrakispentafluorophenyl borate, 4-isopropoxy-4'-methyldiphenyliodonium hexafluorophosphate, 4-isopropoxy-4'-methyldiphenyliodonium Hexafluoroantimonate, (trilkamyl) iodonium hexafluorophosphate, (trilkamyl) iodonium hexafluoroantimonate, (trilkamyl) iodonium tetrakis pentafluorophenyl borate, bis (tertiary butyl phenyl) iodonium hexafluoro phosphate, bis (terti
  • the aromatic sulfonium salt refers to a sulfonium salt in which at least one group of sulfonium substituents is an aryl group.
  • aromatic sulfonium salt 4,4′-bis [di (4-heptoxyphenyl) sulfoniophenyl] sulfide bishexafluoroantimonate, 4,4′-bis [di (4-heptoxyphenyl) sulfonioone Phenyl] sulfide bishexafluorophosphate, 4- (4-benzoyl-phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4,4'-bis [bis (( ⁇ -hydroxyethoxy) phenyl) sulfonioone ] Phenyl sulfide bishexafluorophosphate, 4,4'-bis [bis (( ⁇ -hydroxyeth
  • the aliphatic sulfonium salt refers to a sulfonium salt which is an aliphatic hydrocarbon having all of the substituents of sulfonium having an aliphatic hydrocarbon group or a substituent.
  • aliphatic sulfonium salts include dimethylbenzylsulfonium hexafluoroantimonate, tribenzylsulfonium hexafluoroantimonate, dimethylphenacylsulfonium hexafluoroantimonate, (3-methyl-2-butenyl) dimethylsulfonium hexafluoroantimonate, and benzyltetrahydrofuran Thiophenium hexafluoroantimonate, cinnamyl dimethyl sulfonium hexafluoroantimonate, 1- ( ⁇ -naphthylmethyl) tetrahydrothiophenium hexafluoroantimonate, 1- ( ⁇ -naphthylmethyl) tetrahydrothiophenium hexafluorophosphate 1- (cinnamyl) tetrahydrothiophenium hexafluoroantimonate, 1- (cin
  • the content of the epoxy curing catalyst is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and 0.05 It is further more preferable that the amount is -3 parts by mass, and most preferably 0.1 to 1 parts by mass.
  • the silicon-containing curable resin composition of the present invention can be cured by heat curing, photo curing, or both light and heat as the type of curing by appropriately selecting the type of the epoxy curable compound of component (C). You can choose.
  • the curing temperature in the case of heat curing is preferably 60 to 200 ° C., and more preferably 80 to 150 ° C.
  • the curing time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.
  • usable active energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies and the like, and ultraviolet rays are economically most preferable.
  • the ultraviolet light source examples include an ultraviolet laser, a mercury lamp, a high pressure mercury lamp, a xenon lamp, a sodium lamp, and an alkali metal lamp.
  • 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 varies depending on the applied film thickness.
  • heating may usually be performed in the range of 60 to 150 ° C.
  • the silicon-containing curable resin composition of the present invention is not limited to the performance of the silicon-containing curable resin composition of the present invention, and other epoxy compounds, curing accelerators, sensitizers, metal oxide fine powder, weather resistance It may contain any additive such as a modifier. However, when the additives other than the metal oxide fine powder are contained, the total amount of the components (A), (B) and (C) is, from the viewpoint of securing the effect of the present invention, It is preferable to contain in the range used as 90 mass% or more with respect to the quantity except the content of metal oxide fine powder from the silicon-containing curable resin composition of this invention.
  • the 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- (3,4-epoxy) Cyclohexyl-5,1-spiro (3,4-epoxy) cyclohexyl-m-dioxane, bis [(3,4-epoxycyclohexyl) methyl] adipate, 6- (3,4-epoxycyclohexanecarbonyloxy) hexanoic acid (3) Alicyclic epoxy compounds such as 4, 4-epoxycyclohexyl) methyl ester; Diglycidyl ether of bisphenol A, diglycidyl ether of bisferl F,
  • the epoxy equivalent is preferably 100 to 600. If the amount of the other epoxy compound is too large, the heat resistance of the resulting cured product may decrease. Therefore, 1 part per 100 parts by mass of the total of (A) component and (B) component -30 parts by mass is preferable, and 1 to 20 parts by mass is more preferable.
  • the component (C) is an epoxy curing agent, the total content of the epoxy group of the component (A), the component (B) and the other epoxy compound is adjusted. In the case of an epoxy curing catalyst, it is preferable to appropriately change the amount of the component (C) in accordance with the total content of the component (A), the component (B) and the other epoxy compound.
  • the curing accelerator is a compound for accelerating the reaction between the epoxy group and the epoxy curing agent, and in particular, when the epoxy curing agent is a phenolic curing agent or a polycarboxylic acid curing agent, it may be blended. preferable.
  • 1,8-diaza-bicyclo [5.4.0] undecene-7 triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and the like Tertiary amines and salts thereof; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; tributyl phosphine, methyl diphenyl phosphine, triphenyl phosphine, diphenyl phosphine Organic phosphines such as phenyl phosphine; tetraphenylphosphonium tetraphenylboric acid, 2-ethyl-4-methylimidazole tetraphenylboric acid, N-methylmorpholine tetraphenylboric acid And te
  • the sensitizer is a compound capable of expanding the applicable wavelength range of energy rays when curing with energy rays.
  • Examples of sensitizers include benzophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 4,4-dihydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,5-dimethylbenzophenone, and the like.
  • Benzophenones such as 2,4-dimethylbenzophenone, 4-methoxybenzophenone, 4,4-dimethoxybenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4-phenylbenzophenone, acetophenone, 4-methoxyacetophenone, 2,4-dimethoxyphenone Acetophenone, 2,5-dimethoxyacetophenone, 2,6-dimethoxyacetophenone, 4,4-dimethoxyacetophenone, 4-ethoxyacetophenone, diethoxyacetophenone Acetophenones such as 2, 2-diethoxyacetophenone, 2-ethoxy-2-phenylacetophenone, 4-phenylacetophenone, anthraquinone, hydroxyanthraquinone, 1-nitroanthraquinone, aminoanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2 -Anthraquinones such
  • inorganic materials such as a mineral
  • metal oxides such as aluminum oxide, zinc oxide, titanium oxide
  • Minerals such as feldspar powder, vermiculite, attapulgite, talc, minnesite, pyrophyllite and the like may be mentioned, and these may be modified by organic modification treatment or the like.
  • silicon dioxides are preferable.
  • the particle diameter of the metal oxide fine particles is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the compounding amount of the metal oxide fine particles is preferably 0.1 to 80% by mass, and more preferably 0.5 to 70% by mass in the silicon-containing curable resin composition of the present invention.
  • weather resistance imparting agent those generally used in general such as light stabilizers, ultraviolet light absorbers, phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants and the like can be used.
  • light stabilizers include hindered amines
  • ultraviolet light absorbers include 2-hydroxybenzophenones, 2- (2-hydroxyphenyl) benzotriazoles, 2- (2-hydroxyphenyl) -4,6- Diaryl-1,3,5-triazines, benzoates and cyanoacrylates are mentioned, and as a phenolic antioxidant, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxy] is mentioned.
  • Phenyl) propionate dibutylhydroxytoluene (BHT), 2,6-di-t-butyl-paracresol (DBPC), etc.
  • sulfur-based antioxidants such as dialkylthiodipropionates, ⁇ -alkyl Mercapto propionic acid esters are mentioned, As phosphorus system antioxidant, Machine phosphites, and the like.
  • the content thereof is 0 in the silicon-containing curable resin composition of the present invention from the viewpoint of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. .0001 to 50% by mass is preferable, and 0.001 to 10% by mass is more preferable.
  • the silicon-containing curable resin composition of the present invention has good fluidity at room temperature (25 ° C.) and is excellent in handleability. With respect to fluidity, it is preferable that the viscosity measured with an E-type viscometer at room temperature (25 ° C.) in a state not containing the metal oxide fine powder is 50 Pa ⁇ s or less, more preferably 10 Pa ⁇ s or less preferable.
  • the cured product obtained from the silicon-containing curable resin composition of the present invention has transparency, crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, contamination resistance, flame resistance, moisture resistance, gas barrier resistance. It is excellent in flexibility, elongation and strength, mechanical properties such as electrical insulation and low dielectric constant, optical properties, electrical properties and the like, and in particular, the surface tack is small and the heat resistance is excellent. Therefore, the silicon-containing curable resin composition of the present invention is a sealing material for display materials, optical materials, recording materials, semiconductors, etc.
  • high voltage insulating materials, insulation, vibration reduction, water resistance, moisture resistance And sealing materials for plastic parts prototypes of plastic parts, coating materials, interlayer insulation films, packing for insulation, optical waveguides, optical fiber protective materials, optical lenses, adhesives for optical devices, high heat resistant adhesives, high It can be applied to heat dissipating materials, high heat resistant sealing materials, members for solar cells and fuel cells, insulation covering materials, photosensitive drums for copying machines, etc., and in particular, it can be suitably used as a coating material.
  • Production Example 1 Chain-Like Siloxane Compound a-1
  • 130 g of ion exchanged water, 550 g of a 48% aqueous sodium hydroxide solution and 100 g of toluene as a solvent are charged with 129 g (1 mol) of dimethyldichlorosilane at 30 ° C. or less while stirring.
  • the solution was added dropwise over time, and after completion of the dropwise addition, stirring was continued at 105 ° C. for 5 hours.
  • the reaction solution obtained was washed with 500 g of ion-exchanged water to remove purified sodium chloride, and then the solvent was evaporated under reduced pressure at 60 ° C.
  • Preparation Example 2 Chain-Like Siloxane Compound a-2
  • a mixture of 116 g (0.9 mol) of dimethyldichlorosilane and 25.3 g (0.1 mol) of diphenyldichlorosilane is used instead of 129 g (1 mol) of dimethyldichlorosilane in Production Example 1.
  • the procedure was repeated to obtain a linear siloxane compound a-2 having vinyl groups at both ends.
  • R 1 to R 2 are a methyl group
  • the mass average molecular weight by GPC was 20000 (a corresponds to 230).
  • Preparation Example 3 Chain-Like Siloxane Compound a-3
  • Preparation Example 1 a mixture of 90.3 g (0.7 mol) of dimethyldichlorosilane and 75.9 g (0.3 mol) of diphenyldichlorosilane was used instead of 129 g (1 mol) of dimethyldichlorosilane. The same operation was performed to obtain a linear siloxane compound a-3 having a vinyl group at both ends.
  • R 1 to R 2 are a methyl group
  • the mass average molecular weight by GPC was 10000 (a corresponds to 88).
  • the high molecular weight epoxy siloxane compound A-1 is an epoxy siloxane compound in which groups represented by the general formula (2) are connected by a group represented by the general formula (1), and in the general formula (1), R 1 to It is a compound in which R 4 is a methyl group, a is 538, R 5 is a methyl group, E 1 is 3-glycidyloxypropyl, and b is 3 in the general formula (2).
  • the epoxy equivalent of the high molecular weight epoxy siloxane compound A-1 was 6700.
  • the epoxy equivalent of the high molecular weight epoxy siloxane compound A-2 was 3400.
  • the epoxy equivalent of the high molecular weight epoxy siloxane compound A-2 was 1600.
  • Preparation Example 7 High Molecular Weight Epoxy Siloxane Compound A-4
  • 0.99 g (8 mmol) of 1,2-epoxy-4-vinylcyclohexane is used instead of 0.92 g (8 mmol) of allyl glycidyl ether in Production Example 4, and the high molecular weight is obtained.
  • An epoxy siloxane compound A-4 was obtained.
  • the high molecular weight epoxy siloxane compound A-4 is an epoxy siloxane compound in which groups represented by the general formula (2) are connected by a group represented by the general formula (1), and in the general formula (1), R 1 to It is a compound in which R 4 is a methyl group, a is 538, R 5 is a methyl group, E 1 is 2- (3,4-epoxycyclohexyl) ethyl, and b is 3 in the general formula (2).
  • the epoxy equivalent of the high molecular weight epoxy siloxane compound A-4 was 6700.
  • the epoxy equivalent of the high molecular weight epoxy siloxane compound A-5 was 3400.
  • the high molecular weight epoxy siloxane compound A-6 is an epoxy siloxane compound in which groups represented by the general formula (2) are linked by a group represented by the general formula (1), a group represented by the general formula (2) and the following It is a mixture of an epoxy siloxane compound in which a group represented by the general formula (3) is connected by a group represented by the general formula (1), and in the general formula (1), R 1 to R 2 are methyl groups, R 3 To R 4 each represents a mixture of methyl and phenyl (methyl: phenyl: 9: 1), a is 230, and in the general formulas (2) and (3), R 5 is methyl, E It is a compound in which 1 is 3-glycidyloxypropyl and b is 3.
  • Preparation Example 10 Low Molecular Weight Epoxy Siloxane Compound B-1
  • 48 g (0.2 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 114 g (1 mol) of allyl glycidyl ether, platinum-divinyl tetramethyl disiloxane complex 10 mg of Karstedt catalyst and 200 g of toluene as a solvent were charged and reacted at 105 ° C. for 3 hours while stirring. Thereafter, unreacted allyl glycidyl ether and the solvent were removed under reduced pressure at 100 ° C.
  • the low molecular weight epoxy siloxane compound B-1 is a compound in which R 6 is a methyl group, E 2 is 3-glycidyloxypropyl, and d is 4 in the general formula (4), and the epoxy equivalent is 174.
  • Preparation Example 11 Low Molecular Weight Epoxy Siloxane Compound B-2
  • a low molecular weight epoxy siloxane compound B is carried out in the same manner as in Preparation Example 10 except that in Preparation Example 10, 124 g (1 mole) of 1,2-epoxy-4-vinylcyclohexane is used instead of 114 g (1 mol) of allyl glycidyl ether. I got -2.
  • the low molecular weight epoxy siloxane compound B-2 is a compound in which R 6 is a methyl group, E 2 is 2- (3,4-epoxycyclohexyl) ethyl, d is 4 in the general formula (4), and the epoxy equivalent is It was 184.
  • Preparation Example 12 Low Molecular Weight Epoxy Siloxane Compound B-3 Production Example 10 is the same as Production Example 10 except that 65.6 g (0.2 mol) of tetrakis (dimethylsiloxy) silane is used instead of 48 g (0.2 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane. The same operation was performed to obtain a low molecular weight epoxy siloxane compound B-3.
  • the low molecular weight epoxy siloxane compound B-3 is a compound represented by the general formula (25), wherein R 8 to R 9 are methyl groups, E 2 is 3-glycidyloxypropyl, e is 3, f and g are 1. The epoxy equivalent was 226.
  • Examples 1 to 23, Comparative Examples 1 to 28 (A) high molecular weight epoxy siloxane compound A-1 to 5 as component, low molecular weight epoxy siloxane compound B-1 to 3 as component (B), the following compounds C-1 to 3 as component (C), composition for comparison D-1 to 2 and the following compound D-3, and the following compound E-1 as a curing accelerator, were mixed in the formulations shown in Tables 1 and 2 below to obtain Examples 1 to 23 and Comparative Examples 1 to 28.
  • a silicon-containing curable resin composition was prepared. Test pieces were prepared according to the following ⁇ Preparation of test pieces> using the obtained silicon-containing curable resin composition.
  • Component C-1 As an epoxy curing catalyst (photo curing catalyst), 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate
  • C-2 epoxy curing catalyst 1- (cinnamyl) tetrahydrothiophenium hexafluoroantimonate as a thermosetting catalyst
  • C-3 methyl hexahydrophthalic anhydride as an epoxy curing agent
  • Hardening accelerator E-1 diazabicyclo undecen octoate
  • test piece> The silicon-containing curable resin compositions of Examples 1 to 23 and Comparative Examples 1 to 28 were each applied to a square glass substrate 50 mm long, 50 mm wide, and 1 mm thick so as to have a film thickness of 20 ⁇ m. Test pieces of Examples 1 to 23 and Comparative Examples 1 to 28 were obtained by photocuring or heat curing under the conditions.
  • a glass substrate coated with the silicon-containing curable resin composition of Examples 1 to 14 or Comparative Examples 1 to 15 is irradiated with ultraviolet light at 10 mJ / cm 2 (converted to a wavelength of 365 nm exposure) using a high pressure mercury lamp, and then 120 ° C. It was cured by post-baking for 10 minutes in a thermostat bath.
  • Thermal curing conditions The glass substrate coated with the silicon-containing curable resin composition of Examples 15-23 or Comparative Examples 16-28 was cured by heating in a thermostat at 120 ° C. for 1 hour and then at 150 ° C. for 2 hours.
  • the following dust adhesion test and heat resistance adhesion test were performed using the obtained test pieces.
  • the test piece was placed in a container containing powdered silica gel (manufactured by Wako Pure Chemical Industries, Ltd., trade name: Wakogel C-100) until the whole was buried. After pulling up the test piece from the container, it was dropped three times on a glass plate from a height of 10 cm so that the cured surface was vertical. After this, 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 the surface tack is. In addition, the transmittance
  • Test piece was placed in a constant temperature bath at 200 ° C., and the test piece was observed microscopically every 30 days up to 120 days, and peeling of the cured product and occurrence of cracks were examined.
  • Tables 1 and 2 show the number of days for which peeling and cracking were found for the first time. In addition, it was considered as 120 days or more that peeling and a crack were not seen even after 120 days progress.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine durcissable contenant du silicium, comprenant : comme constituant (A), un composé époxy siloxane contenant au moins deux groupes contenant un époxy par molécule et un groupe représenté par la formule générale (1) ; comme constituant (B), un composé époxy siloxane contenant 1 à 10 atomes de silicium et au moins deux groupes contenant un époxy par molécule ; et comme constituant (C), un composé époxy durcissable. Dans la formule générale (1), les R1 à R4 sont identiques ou différents et représentent un groupe alkyle ayant de 1 à 4 atomes de carbone ou un groupe aryle ayant de 6 à 10 atomes de carbone, et a représente un nombre situé dans la plage allant de 20 à 10 000. (1)
PCT/JP2012/057504 2012-03-23 2012-03-23 Composition de résine durcissable contenant du silicium WO2013140601A1 (fr)

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JP2012144678A (ja) * 2011-01-14 2012-08-02 Adeka Corp ケイ素含有硬化性樹脂組成物
JP2016113593A (ja) * 2014-12-18 2016-06-23 信越化学工業株式会社 シリコーン変性エポキシ樹脂と多価カルボン酸化合物を含有するエポキシ樹脂およびその硬化物
JPWO2017010401A1 (ja) * 2015-07-10 2018-04-19 住友精化株式会社 エポキシ樹脂組成物、その製造方法、及び該組成物の用途
WO2018131564A1 (fr) * 2017-01-10 2018-07-19 住友精化株式会社 Composition de résine époxy
WO2020239982A1 (fr) * 2019-05-29 2020-12-03 Elkem Silicones France Sas Méthode de fabrication additive pour produire un article en élastomère silicone
US11091627B2 (en) 2017-01-10 2021-08-17 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11111382B2 (en) 2017-01-10 2021-09-07 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
CN114222779A (zh) * 2019-08-27 2022-03-22 三菱化学株式会社 含有环氧基的聚有机硅氧烷、包含含有环氧基的聚有机硅氧烷的固化性树脂组合物及其固化物
US11292872B2 (en) 2017-01-10 2022-04-05 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11603466B2 (en) 2017-01-10 2023-03-14 Sumitomo Seika Chemicals Co.. Ltd. Epoxy resin composition
CN115894926A (zh) * 2022-11-21 2023-04-04 江南大学 一种环氧基含磷聚硅氧烷及其制备方法与制备的环氧组合物

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CN114031777B (zh) * 2021-11-11 2023-03-24 河南大学 一种含硅聚合物电解质材料及利用其制得的锂电池

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JP2012144678A (ja) * 2011-01-14 2012-08-02 Adeka Corp ケイ素含有硬化性樹脂組成物
JP2016113593A (ja) * 2014-12-18 2016-06-23 信越化学工業株式会社 シリコーン変性エポキシ樹脂と多価カルボン酸化合物を含有するエポキシ樹脂およびその硬化物
US10308803B2 (en) 2014-12-18 2019-06-04 Shin-Etsu Chemical Co., Ltd. Epoxy resin containing silicone-modified epoxy resin and polyvalent carboxylic acid compound, and cured product thereof
US11066510B2 (en) 2015-07-10 2021-07-20 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition, process for producing same, and uses of said composition
JPWO2017010401A1 (ja) * 2015-07-10 2018-04-19 住友精化株式会社 エポキシ樹脂組成物、その製造方法、及び該組成物の用途
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US11603466B2 (en) 2017-01-10 2023-03-14 Sumitomo Seika Chemicals Co.. Ltd. Epoxy resin composition
US11292872B2 (en) 2017-01-10 2022-04-05 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
JPWO2018131564A1 (ja) * 2017-01-10 2019-11-07 住友精化株式会社 エポキシ樹脂組成物
WO2018131564A1 (fr) * 2017-01-10 2018-07-19 住友精化株式会社 Composition de résine époxy
US11111382B2 (en) 2017-01-10 2021-09-07 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
KR20220024167A (ko) * 2019-05-29 2022-03-03 엘켐 실리콘즈 프랑스 에스에이에스 실리콘 엘라스토머 제품 제조용 적층 제조 방법
FR3096606A1 (fr) * 2019-05-29 2020-12-04 Elkem Silicones France Sas Méthode de fabrication additive pour produire un article en élastomère silicone
JP2022534258A (ja) * 2019-05-29 2022-07-28 エルケム シリコンズ フランス ソシエテ パ アクシオンス シンプリフィエ シリコーンエラストマー物品を生成するための付加製造法
WO2020239982A1 (fr) * 2019-05-29 2020-12-03 Elkem Silicones France Sas Méthode de fabrication additive pour produire un article en élastomère silicone
JP7256905B2 (ja) 2019-05-29 2023-04-12 エルケム シリコンズ フランス ソシエテ パ アクシオンス シンプリフィエ シリコーンエラストマー物品を生成するための付加製造法
KR102637455B1 (ko) 2019-05-29 2024-02-15 엘켐 실리콘즈 프랑스 에스에이에스 실리콘 엘라스토머 제품 제조용 적층 제조 방법
CN114222779A (zh) * 2019-08-27 2022-03-22 三菱化学株式会社 含有环氧基的聚有机硅氧烷、包含含有环氧基的聚有机硅氧烷的固化性树脂组合物及其固化物
CN115894926A (zh) * 2022-11-21 2023-04-04 江南大学 一种环氧基含磷聚硅氧烷及其制备方法与制备的环氧组合物

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