WO2011111667A1 - Curable composition, hardened material, and method for using curable composition - Google Patents
Curable composition, hardened material, and method for using curable composition Download PDFInfo
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- WO2011111667A1 WO2011111667A1 PCT/JP2011/055273 JP2011055273W WO2011111667A1 WO 2011111667 A1 WO2011111667 A1 WO 2011111667A1 JP 2011055273 W JP2011055273 W JP 2011055273W WO 2011111667 A1 WO2011111667 A1 WO 2011111667A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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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
- 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
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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
- 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
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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
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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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
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/06—Triglycidylisocyanurates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
- H01L2924/097—Glass-ceramics, e.g. devitrified glass
- H01L2924/09701—Low temperature co-fired ceramic [LTCC]
Definitions
- the present invention relates to a curable composition from which a cured product having excellent transparency and heat resistance and high adhesive strength can be obtained, a cured product obtained by curing the composition, and the composition as an optical element fixing material.
- the present invention relates to a method for use as an adhesive for optical devices or a sealant for optical element fixing materials.
- curable compositions have been improved in various ways depending on the application, and have been widely used in industry as raw materials for optical parts and molded articles, adhesives, coating agents, and the like.
- a curable composition that forms a cured product having excellent transparency is used as a raw material for optical components and a coating agent thereof, and a curable composition that forms a cured product having a high adhesive force is used as an adhesive or coating.
- curable compositions have also been used as compositions for optical element fixing materials, such as adhesives for optical element fixing materials and sealing agents for optical element fixing materials, when producing optical element sealing bodies. It is coming.
- the optical element examples include various lasers such as a semiconductor laser (LD), light emitting elements such as a light emitting diode (LED), a light receiving element, a composite optical element, and an optical integrated circuit.
- LD semiconductor laser
- LED light emitting diode
- a composite optical element a composite optical element
- optical integrated circuit an optical integrated circuit
- the cured product of the composition for optical element fixing materials is exposed to higher energy light and higher temperature heat generated from the optical element for a long time, and deteriorates and cracks. The problem of generating or peeling occurred.
- Patent Documents 1 to 3 propose compositions for optical element fixing materials containing a polysilsesquioxane compound as a main component.
- a cured product of a composition for optical element fixing materials mainly composed of a polysilsesquioxane compound described in Patent Documents 1 to 3 heat resistance and transparency can be maintained while maintaining sufficient adhesive force. It was sometimes difficult to get.
- Patent Document 4 proposes an epoxy resin composition using an alicyclic epoxy resin
- Patent Document 5 proposes an epoxy resin composition containing a polythiol compound. ing.
- these compositions are used, there is a case where sufficient light deterioration resistance accompanying a change with time cannot be satisfied or the adhesive force is lowered.
- JP 2004-359933 A JP 2005-263869 A JP 2006-328231 A Japanese Patent Laid-Open No. 7-309927 JP 2009-001752 A
- the present invention has been made in view of the actual situation of the prior art, and is a curable composition that is excellent in heat resistance and transparency and that can provide a cured product having high adhesive strength. It is an object of the present invention to provide a cured product and a method for using the composition as an adhesive for optical element fixing materials or an encapsulant for optical element fixing materials.
- the present inventors have (A) a specific silane compound copolymer, (B) an epoxy compound having an isocyanurate skeleton, and (C) an alicyclic group having a carboxyl group.
- the cured product of the composition containing the acid anhydride-containing curing agent and (D) the silane coupling agent having an acid anhydride structure has excellent transparency and heat resistance over a long period of time, and at a high temperature.
- the present invention has been completed.
- the following curable compositions [1] to [9] are provided. [1] (A) In the molecule, the following formulas (i), (ii) and (iii)
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- X 0 represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group for a hydroxyl group) D) represents a single bond or a linking group.
- R 2 represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted phenyl group.
- the content ratio of the components (A), (B), (C), and (D) is a mass ratio of (A) and [(B) + (C) + (D)].
- the curable composition according to [1] or [2], wherein [(B) + (C) + (D)] 90:10 to 50:50.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- X 0 represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group for a hydroxyl group) D) represents a single bond or a linking group.
- R 3 represents an alkyl group having 1 to 6 carbon atoms
- X 1 represents a halogen atom
- p represents an integer of 0 to 3.
- Q represents an integer of 0 to 3.
- the curing agent (C) is composed of one or more selected from alicyclic acid anhydrides having a carboxyl group and other alicyclic acid anhydrides, and the mass ratio thereof is (carboxyl group
- the curable composition according to [1] or [4], wherein: (an alicyclic acid anhydride): (other alicyclic acid anhydride) 100: 0 to 10:90.
- the curable composition according to [1] or [4] which is a composition for an optical element fixing material.
- the following [10] and [11] cured products are provided.
- [10] A cured product obtained by curing the curable composition according to [1] or [4].
- [11] The cured product according to [10], which is an optical element fixing material.
- [12] A method of using the curable composition according to [1] or [4] as an adhesive for an optical element fixing material.
- [13] A method of using the curable composition according to [1] or [4] as a sealant for an optical element fixing material.
- the curable composition of the present invention even when irradiated with high energy light or in a high temperature state, it does not color and does not deteriorate transparency, and has excellent transparency over a long period of time. In addition, a cured product having a high adhesive force even at a high temperature can be obtained.
- the curable composition of the present invention can be used when forming an optical element fixing material, and particularly preferably used as an adhesive for an optical element fixing material and an encapsulant for an optical element fixing material. it can.
- Curable composition of the present invention comprises: (A) In the molecule, the following formulas (i), (ii) and (iii)
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- X 0 represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group for a hydroxyl group) D) represents a single bond or a linking group.
- R 2 represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted phenyl group.
- the curable composition of the present invention comprises (i) and (i) of the repeating units represented by the formulas (i), (ii) and (iii) as the component (A). having a repeating unit of ii), (i) and (iii), (ii) and (iii), or (i), (ii) and (iii), and having a weight average molecular weight of 1,000 to 30,000 A silane compound copolymer (hereinafter sometimes referred to as “silane compound copolymer (A)”).
- the silane compound copolymer (A) may have one type of repeating unit represented by (i), (ii), or (iii), or may have two or more types.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom.
- alkyl group having 1 to 6 carbon atoms represented by R 1 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, s- Examples thereof include a butyl group, an n-pentyl group, and an n-hexyl group.
- X 0 represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a cyano group; or a group represented by the formula: OG.
- G represents a protecting group for a hydroxyl group.
- the well-known protecting group known as a hydroxyl-protecting group is mentioned.
- acyl protecting groups silyl protecting groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group; methoxymethyl group, methoxyethoxymethyl group, 1-ethoxyethyl group
- An acetal type protective group such as tetrahydropyran-2-yl group or tetrahydrofuran-2-yl group; an alkoxycarbonyl type protective group such as t-butoxycarbonyl group; methyl group, ethyl group, t-butyl group, octyl group
- ether-based protecting groups such as allyl group, triphenylmethyl group, benzyl group, p-
- the acyl-based protecting group is specifically a group represented by the formula: —C ( ⁇ O) R 5 .
- R 5 represents carbon such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and n-pentyl group.
- Examples of the substituent of the phenyl group which may have a substituent represented by R 5 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i -Alkyl groups such as butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and i-octyl; halogen atoms such as fluorine, chlorine and bromine An alkoxy group such as a methoxy group or an ethoxy group;
- a chlorine atom a group represented by the formula: OG ′ (wherein G ′ is an acyl group) And a group selected from a cyano group, a group selected from a chlorine atom, an acetoxy group and a cyano group is more preferable, and an acetoxy group is particularly preferable.
- D represents a single bond or a linking group.
- the linking group include a divalent organic group that may have a substituent.
- the organic group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
- Examples of the divalent organic group that may have a substituent include an alkylene group that may have a substituent, an alkenylene group that may have a substituent, and a substituent.
- alkynylene group which may have a substituent an alkynylene group which may have a substituent, an arylene group which may have a substituent, an arylene group which may have a substituent (an alkylene group, an alkenylene group or an alkynylene group) and an arylene group which may have a substituent; And a divalent group consisting of the above-mentioned combinations.
- alkylene group of the alkylene group which may have a substituent a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc., having 1 to 20 carbon atoms, preferably And an alkylene group having 1 to 10 carbon atoms.
- the alkenylene group of the alkenylene group which may have a substituent is an alkenylene group having 2 to 20 carbon atoms such as vinylene group, propenylene group, butenylene group or pentenylene group, preferably an alkenylene group having 2 to 10 carbon atoms. Is mentioned.
- alkynylene group which may have a substituent examples include alkynylene groups having 2 to 20 carbon atoms such as ethynylene group and propynylene group, preferably alkynylene groups having 2 to 10 carbon atoms.
- the arylene group of the arylene group which may have a substituent is preferably an arylene group having 6 to 20 carbon atoms such as an o-phenylene group, an m-phenylene group, a p-phenylene group, or a 2,6-naphthylene group, Includes an arylene group having 6 to 10 carbon atoms.
- Examples of the substituent for the alkylene group, alkenylene group, and alkynylene group include a halogen atom such as a fluorine atom and a chlorine atom; an alkoxy group such as a methoxy group and an ethoxy group; an alkylthio group such as a methylthio group and an ethylthio group; a methoxycarbonyl group; An alkoxycarbonyl group such as an ethoxycarbonyl group; and the like.
- substituents for the arylene group include: a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; And alkylthio groups such as ethylthio group; and the like.
- substituents may be bonded at arbitrary positions in groups such as an alkylene group, an alkenylene group, an alkynylene group, and an arylene group, and a plurality of them may be bonded in the same or different manner.
- the divalent group consisting of a combination of an optionally substituted (alkylene group, alkenylene group, or alkynylene group) and an optionally substituted arylene group has the above substituents.
- a group in which at least one kind of (alkylene group, alkenylene group, or alkynylene group) which may be present and at least one kind of arylene group which may have the substituent are bonded in series. Specific examples include groups represented by the following formula.
- D is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and a methylene group or an ethylene group is preferable because a cured product having high adhesive strength can be obtained. Particularly preferred.
- R 2 represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted phenyl group.
- alkyl group having 1 to 20 carbon atoms represented by R 2 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t- Examples include a butyl group, n-pentyl group, n-hexyl group, n-octyl group, i-octyl group, n-nonyl group, n-decyl group, n-dodecyl group and the like.
- Examples of the substituent of the phenyl group which may have a substituent represented by R 2 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i -Alkyl groups such as butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and i-octyl; alkoxy groups such as methoxy and ethoxy; fluorine atoms And halogen atoms such as chlorine atom.
- curing material which is excellent in transparency and adhesiveness, and excellent in heat resistance is obtained.
- the amount of the group represented by the formula: R 1 —CH (X 0 ) —D— and R 2 can be quantified by, for example, measuring the NMR spectrum of the silane compound copolymer (A).
- the silane compound copolymer (A) may be any copolymer such as a random copolymer, a block copolymer, a graft copolymer, and an alternating copolymer, but a random copolymer is particularly preferable. .
- the weight average molecular weight (Mw) of the silane compound copolymer (A) is in the range of 1,000 to 30,000, preferably in the range of 1,500 to 6,000. By being in the said range, the hardened
- a weight average molecular weight (Mw) can be calculated
- the molecular weight distribution (Mw / Mn) of the silane compound copolymer (A) is not particularly limited, but is usually in the range of 1.0 to 3.0, preferably 1.1 to 2.0. By being in the said range, the hardened
- the silane compound copolymer (A) can be used alone or in combination of two or more.
- the silane compound copolymer (A) is a polysilsesquioxane compound having a ladder structure.
- the fact that the silane compound copolymer has a ladder structure can be confirmed, for example, by performing infrared absorption spectrum measurement, X-ray diffraction measurement, and NMR measurement of the reaction product.
- the component (A) is (A ′) Formula (1): R 1 —CH (X 0 ) —D—Si (OR 3 ) p (X 1 ) 3-p [Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X 0 represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group for a hydroxyl group) D) represents a single bond or a linking group. R 3 represents an alkyl group having 1 to 6 carbon atoms, X 1 represents a halogen atom, and p represents an integer of 0 to 3.
- silane compound copolymer having a weight average molecular weight of 1,000 to 30,000 (hereinafter referred to as “silane compound copolymer”) obtained by condensing a mixture of silane compounds containing at least one silane compound (2) represented by Polymer (A ′) ”), and the silane compound copolymer (A) is preferably a silane compound copolymer (A ′).
- the silane compound (1) is a compound represented by the formula (1): R 1 —CH (X 0 ) —D—Si (OR 3 ) p (X 1 ) 3-p .
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom. Specific examples include those exemplified as R 1 in the silane compound copolymer (A).
- X 0 is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a cyano group, or a group represented by the formula: OG (wherein, G represents a protecting group for a hydroxyl group).
- D represents a single bond or a linking group. Specific examples of those represented by X 0 and D, respectively, those exemplified as X 0 and D in the silane compound copolymer (A).
- R 3 is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc.
- X 1 represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
- p represents an integer of 0 to 3. When p is 2 or more, the ORs 3 may be the same or different. When (3-p) is 2 or more, X 1 may be the same or different.
- silane compound (1) examples include chloromethyltrimethoxysilane, bromomethyltriethoxysilane, 2-chloroethyltripropoxysilane, 2-bromoethyltributoxysilane, 3-chloropropyltrimethoxysilane, 3-chloro Propyltriethoxysilane, 3-chloropropyltripropoxysilane, 3-chloropropyltributoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 3-bromopropyltripropoxysilane, 3-bromopropyltri Butoxysilane, 3-fluoropropyltrimethoxysilane, 3-fluoropropyltriethoxysilane, 3-fluoropropyltripropoxysilane, 3-fluoropropyltributoxysilane, 3-iodopropylto Methoxysilane, 2-chlor
- trialkoxysilane compounds in which X 0 is a halogen atom, trialkoxysilane in which X 0 is a cyano group Compounds, or trialkoxysilane compounds in which X 0 is a group represented by the formula: OG are preferred, trialkoxysilane compounds having a 3-chloropropyl group, trialkoxysilane compounds having a 3-acetoxypropyl group More preferred are trialkoxysilane compounds having a 2-cyanoethyl group or trialkoxysilane compounds having a 3-cyanopropyl group.
- the silane compound (2) is a compound represented by the formula (2): R 2 Si (OR 4 ) q (X 2 ) 3-q .
- R 2 represents an alkyl group having 1 to 20 carbon atoms or a phenyl group which may have a substituent. Specific examples include those exemplified as R 2 in the silane compound copolymer (A).
- R 4 represents the same alkyl group having 1 to 6 carbon atoms as R 3 .
- X 2 represents the same halogen atom as X 1 .
- q represents an integer of 0 to 3. When q is 2 or more, OR 4 may be the same or different. When (3-q) is 2 or more, X 2 may be the same or different.
- silane compound (2) examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, i-butyltrimethoxy.
- Alkyltrialkoxysilane compounds such as silane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, i-octyltriethoxysilane, dodecyltrimethoxysilane, methyldimethoxyethoxysilane, methyldiethoxymethoxysilane;
- Alkylhalogenoalkoxysilane compounds such as methylchlorodimethoxysilane, methyldichloromethoxysilane, methylchlorodiethoxysilane, ethylchlorodimethoxysilane, ethyldichloromethoxysilane, n-propylchlorodimethoxysilane, n-propyldichloromethoxysilane;
- Alkyltrihalogenosilane compounds such as methyltrichlorosilane, methyltribromosilane, eth
- phenyltrimethoxysilane 4-methoxyphenyltrimethoxysilane, 2-chlorophenyltrimethoxysilane, phenyltriethoxysilane, 2-methoxyphenyltriethoxysilane, phenyldimethoxyethoxysilane, phenyldiethoxymethoxysilane
- phenyltrialkoxysilane compounds Phenylhalogenoalkoxysilane compounds which may have a substituent such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, phenylchloromethoxyethoxysilane, phenylchlorodiethoxysilane, phenyldichloroethoxysilane
- phenyltrihalogenosilane compounds which may have a substituent such as phenyltrichlorosilane, phenyltribro
- the method for condensing the mixture of the silane compounds is not particularly limited, but the silane compound (1), the silane compound (2), and other silane compounds as required are dissolved in a solvent, and a predetermined amount of catalyst is added. And a method of stirring at a predetermined temperature.
- the catalyst used may be either an acid catalyst or a base catalyst.
- the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid and trifluoroacetic acid; Can be mentioned.
- Base catalysts include trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, aniline, picoline, 1,4-diazabicyclo [2 2.2]
- Organic bases such as octane and imidazole;
- Organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide;
- Metals such as sodium methoxide, sodium ethoxide, sodium t-butoxide, and potassium t-butoxide Alcoholates;
- Metal hydrides such as sodium hydride and calcium hydride;
- Metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide;
- Metal carbonates such as sodium carbonate, potassium carbonate and magnesium carbonate; Carbonated water And the like are; sodium, metal hydrogen carbonates such as potassium hydrogen carbon
- an acid catalyst is preferable, and an inorganic acid is more preferable.
- the amount of catalyst used is usually in the range of 0.1 mol% to 10 mol%, preferably 1 mol% to 5 mol%, based on the total molar amount of the silane compound.
- the solvent to be used can be appropriately selected according to the type of the silane compound.
- water aromatic hydrocarbons such as benzene, toluene and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone and cyclohexanone; methyl And alcohols such as alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, s-butyl alcohol and t-butyl alcohol.
- aromatic hydrocarbons such as benzene, toluene and xylene
- esters such as methyl acetate, ethyl acetate, propyl acetate and methyl propionate
- ketones such as acetone, methyl ethyl ket
- water, aromatic hydrocarbons, and a mixed solvent thereof are preferable, and a mixed solvent of water and toluene is particularly preferable.
- the ratio of water to toluene (volume ratio) is preferably 1: 9 to 9: 1, more preferably 7: 3 to 3: 7.
- the amount of the solvent used is such that the total molar amount of the silane compound per liter of solvent is usually 0.1 mol to 10 mol, preferably 0.5 mol to 10 mol.
- the temperature at which the silane compound is condensed (reacted) is usually in the temperature range from 0 ° C. to the boiling point of the solvent used, preferably in the range of 20 ° C. to 100 ° C. If the reaction temperature is too low, the progress of the condensation reaction may be insufficient. On the other hand, if the reaction temperature is too high, it is difficult to suppress gelation. The reaction is usually completed in 30 minutes to 20 hours.
- an acid catalyst After completion of the reaction, when an acid catalyst is used, an alkaline aqueous solution such as an aqueous sodium hydrogen carbonate solution is added to the reaction solution. When a basic catalyst is used, an acid such as hydrochloric acid is added to the reaction solution. Neutralization is performed, and the salt generated at that time is removed by filtration or washing with water, etc., and the desired silane compound copolymer can be obtained.
- the curable composition of the present invention contains an epoxy compound having an isocyanurate skeleton (hereinafter sometimes referred to as “epoxy compound (B)”) as the component (B). To do. Since the curable composition of the present invention contains the epoxy compound (B), a cured product having excellent heat resistance and transparency can be obtained even after heat history.
- epoxy compound (B) an epoxy compound having an isocyanurate skeleton
- the epoxy compound (B) is not particularly limited as long as it is a compound having an isocyanurate skeleton (the following (c), in the formula,-represents a bond) and an epoxy ring in the molecule.
- the isocyanurate skeleton (c) may have a tautomer as shown below (cyanurate skeleton (c ′), wherein — represents a bond), and an epoxy having this skeleton is present.
- the compound is also included in the epoxy compound (B) used in the present invention.
- epoxy compound (B) as shown in the following formulas (c-1) to (c-3), at least one of hydrogen atoms bonded to the nitrogen atoms at the 1, 3, and 5 positions of the isocyanurate ring is used.
- a compound in which one is substituted with a group (E) having an epoxy ring is preferred.
- E represents a group having an epoxy ring
- R represents an arbitrary group other than a group having an epoxy ring such as a hydrogen atom or an organic group.
- group (E) having an epoxy ring for example, the following formula
- a, b and c each represents an integer of 1 to 20, and the methylene group may be substituted with an alkyl group such as a methyl group or an ethyl group).
- epoxy compound (B) examples include glycidyl isocyanurate, diglycidyl isocyanurate, tris (2,3-epoxypropyl) isocyanurate, tris (glycidoxy) from the viewpoint of obtaining a cured product having high adhesive strength.
- glycidyl isocyanurate diglycidyl isocyanurate
- tris (2,3-epoxypropyl) isocyanurate tris (glycidoxy) from the viewpoint of obtaining a cured product having high adhesive strength.
- Propyl) isocyanurate tris ( ⁇ -methylglycidyl) isocyanurate, and a mixture containing two or more of these compounds.
- epoxy compound (B) those commercially available as epoxy compounds having an isocyanurate skeleton (for example, trade names: TEPIC-S, TEPIC-PAS B22, trade names: TEPIC-PAS B26, etc. are all Nissan) Chemical Industries, Ltd.) can also be used as it is.
- the compounding amount of the epoxy compound (B) is not particularly limited, but from the viewpoint of obtaining a cured product having higher adhesive strength, the epoxy equivalent is preferably 50 to 300 g / eq, particularly preferably 100 to 200 g / eq.
- the epoxy equivalent is a value measured according to JIS K7236: 2001.
- curable composition of the present invention may be referred to as a curing agent (hereinafter referred to as “curing agent (C)”) containing an alicyclic acid anhydride having a carboxyl group as the component (C). )including. Since the curable composition of this invention contains a hardening
- the alicyclic acid anhydride having a carboxyl group is an acid anhydride having an alicyclic structure in which at least one carboxyl group is substituted.
- Examples of the alicyclic structure include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene, cycloalkyne) structure.
- the alicyclic acid anhydrides include 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, 3- Methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, Examples include methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride, and the like.
- the carboxyl group may be substituted at any position of the alicyclic structure of the alicyclic acid anhydride, and the position of substitution and the number of carboxyl groups to be substituted are not particularly limited.
- cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride and cyclohexane-1,2,3-tricarboxylic acid-1,2 anhydride in which a carboxyl group is substituted with hexahydrophthalic anhydride are preferable.
- Cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride is particularly preferable. This compound may exist as a stereoisomer, but may be any isomer.
- the alicyclic acid anhydride having a carboxyl group can be used alone or in combination of two or more.
- the curing agent (C) may further contain another curing agent.
- Other curing agents include alicyclic acid anhydrides having no carboxyl group (hereinafter referred to as “other alicyclic acid anhydrides”), polyazeline acid anhydrides and other aliphatic acid anhydrides, aliphatic Examples include amine curing agents, alicyclic amine curing agents, secondary or tertiary amine curing agents, aromatic amine curing agents, dicyandiamide, boron trifluoride amine complex salts, and imidazole compounds.
- curing agent can be used individually by 1 type or in combination of 2 or more types.
- other alicyclic acid anhydrides are preferable because cured products having high adhesive force even at high temperatures are obtained.
- the other alicyclic acid anhydrides include those exemplified as the alicyclic acid anhydride of the alicyclic acid anhydride having a carboxyl group. Of these, 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride are preferable, and 4-methyl-hexahydrophthalic anhydride is particularly preferable.
- curing agent (C) consists of 1 type, or 2 or more types chosen from the alicyclic acid anhydride which has a carboxyl group, and other alicyclic acid anhydrides,
- the mass ratio is (it has a carboxyl group.
- Alicyclic acid anhydride): (other alicyclic acid anhydrides) 100: 0 to 10:90 is preferable, and 50:50 to 10:90 is more preferable.
- the curable composition of the present invention has a silane coupling agent having an acid anhydride structure as the component (D) (hereinafter sometimes referred to as “silane coupling agent (D)”). including. Since the curable composition of this invention contains a silane coupling agent (D), it can obtain the hardened
- the silane coupling agent (D) is an organosilicon compound having both a group (Y) having an acid anhydride structure and a hydrolyzable group (OR b ) in one molecule. Specifically, it is a compound represented by the following formula (d).
- Y represents an acid anhydride structure
- R a represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group
- R b represents an alkyl group having 1 to 6 carbon atoms.
- I represents an integer of 1 to 3
- j represents an integer of 0 to 2
- k represents an integer of 1 to 3
- i + j + k 4.
- the alkyl group having 1 to 6 carbon atoms represented by R a and R b is the same as that exemplified above as the alkyl group having 1 to 6 carbon atoms represented by R 1 .
- the phenyl group which may have a substituent represented by R a is exemplified above as the phenyl group which may have a substituent represented by R 2 .
- the same group is mentioned.
- the compound represented by the formula (d) the following formula (d-1)
- R b , h, i, j and k represent the same meaning as described above.
- the compound represented by these is preferable.
- h is preferably 2 to 8.
- silane coupling agent represented by the formula (d-1) examples include 2-trimethoxysilylethyl succinic anhydride and 3-triethoxysilylpropyl succinic anhydride.
- a silane coupling agent (D) can be used individually by 1 type or in combination of 2 or more types.
- the content ratio of the components (A), (B), (C) and (D) is (A) and [(B) + (C) + (D)].
- each component in such a ratio it is possible to obtain a curable composition capable of obtaining a cured product having excellent transparency and heat resistance over a long period of time and having a high adhesive force even at high temperatures.
- the curable composition of the present invention may further contain other components as long as the object of the present invention is not impaired.
- other components include a curing catalyst, an antioxidant, an ultraviolet absorber, a light stabilizer, and a diluent.
- a curing catalyst is added to accelerate curing.
- the curing catalyst include 2-methylimidazole and triphenylphosphine. These curing catalysts can be used alone or in combination of two or more.
- An antioxidant is added to prevent oxidative degradation during heating.
- examples of the antioxidant include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants and the like.
- Phosphorous antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butylphenyl) ) Phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2,4 -Phosphites such as -di-t-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4-
- phenolic antioxidants examples include 2,6-di-t-butyl-p-cresol, dibutylhydroxytoluene, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl- ⁇ - Monophenols such as (3,5-di-t-butyl-4-hydroxyphenyl) propionate; 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis (4- Ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- ⁇ - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ ethyl] 2,4,8 Bisphenols such as 1,10-tetraoxaspiro [5,5]
- sulfur-based antioxidants examples include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like.
- antioxidants can be used alone or in combination of two or more.
- the curable composition of the present invention contains the component (B) and the component (D)
- oxidative deterioration during heating hardly occurs even without an antioxidant.
- the amount used is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the silane compound copolymer (A) or (A ′).
- the ultraviolet absorber is added for the purpose of improving the light resistance of the resulting cured product.
- the ultraviolet absorber include salicylic acids such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy- Benzophenones such as 5-sulfobenzophenone; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-3 ', 5'-di-t
- ultraviolet absorbers can be used alone or in combination of two or more.
- the amount of the ultraviolet absorber used is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the silane compound copolymer (A) or (A ′).
- the light stabilizer is added for the purpose of improving the light resistance of the resulting cured product.
- the light stabilizer include poly [ ⁇ 6- (1,1,3,3, -tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6 , 6-tetramethyl-4-piperidine) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidine) imino ⁇ ] and the like.
- light stabilizers can be used alone or in combination of two or more.
- the amount of the light stabilizer used is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the silane compound copolymer (A) or (A ′).
- a diluent is added in order to adjust the viscosity of the curable composition.
- the diluent include glycerin diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cyclohexane dimethanol diglycidyl ether, alkylene diglycidyl ether, polyglycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
- Examples include ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, and the like. These diluents can be used alone or in combination of two or more.
- the curable composition of the present invention is, for example, known by blending the above-mentioned components (A) or (A ′), (B), (C), (D), and other components as required in a predetermined ratio. It can be obtained by mixing and defoaming by a method.
- the curable composition of the present invention obtained as described above, even when irradiated with high energy light or in a high temperature state, it is not colored and the transparency is not lowered, and it is long-term. It is possible to obtain a cured product having excellent transparency and high adhesive strength. Therefore, the curable composition of the present invention is suitably used as a raw material for optical parts and molded articles, an adhesive, a coating agent, and the like. In particular, since the problem relating to deterioration of the optical element fixing material accompanying the increase in luminance of the optical element can be solved, the curable composition of the present invention can be suitably used as a composition for optical element fixing material. it can.
- the second of the present invention is a cured product obtained by curing the curable composition of the present invention.
- Heat curing is mentioned as a method of hardening the curable composition of this invention.
- the heating temperature for curing is usually 100 to 200 ° C., and the heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.
- the cured product of the present invention has excellent transparency over a long period of time, even when irradiated with high energy light or in a high temperature state, without being colored and having a reduced transparency, and High adhesive strength. Therefore, the hardened
- the cured product of the present invention has a high adhesive force, for example, by measuring the adhesive force as follows. That is, the curable composition is applied to the mirror surface of the silicon chip, and the coated surface is placed on the adherend and pressure-bonded, and then heated and cured. This is left for 30 seconds on a measurement stage of a bond tester that has been heated to a predetermined temperature (for example, 23 ° C., 100 ° C.) in advance, and is horizontal (sheared) with respect to the adhesive surface from a position 50 ⁇ m high from the adherend. Direction) and measure the adhesive force between the test piece and the adherend.
- the adhesive strength of the cured product is preferably 110 N / 2 mm ⁇ or more at 23 ° C.
- the cured product is excellent in transparency by measuring light transmittance.
- the light transmittance of the cured product is preferably 80% or more, particularly preferably 84% or more for light having a wavelength of 400 nm, and preferably 87% or more for light having a wavelength of 450 nm.
- the cured product is excellent in heat resistance over a long period of time because the change in transparency is small even after the cured product is placed at a high temperature for a long time.
- the transmittance at a wavelength of 400 nm is preferably 70% or more of the initial transmittance, more preferably 80% or more.
- the third of the present invention is a method of using the curable composition of the present invention as an adhesive for optical element fixing materials or an encapsulant for optical element fixing materials.
- optical elements include light emitting elements such as LEDs and LDs, light receiving elements, composite optical elements, and optical integrated circuits.
- the curable composition of this invention can be used conveniently as an adhesive agent for optical element fixing materials.
- the composition is applied to one or both adhesive surfaces of a material to be bonded (such as an optical element and its substrate). After the pressure bonding, there is a method in which the material to be bonded is firmly bonded by heat curing.
- Main substrate materials for bonding optical elements include glass such as soda lime glass and heat-resistant hard glass; ceramics; iron, copper, aluminum, gold, silver, platinum, chromium, titanium, and alloys of these metals , Metals such as stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone , Synthetic resins such as polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, norbornene resin, cycloolefin resin, glass epoxy resin, etc. .
- the heating temperature at the time of heat curing is usually 100 to 200 ° C. although it depends on the curable composition used.
- the heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.
- the curable composition of this invention can be used suitably as a sealing agent of an optical element sealing body.
- the curable composition of the present invention As a method of using the curable composition of the present invention as a sealant for an optical element fixing material, for example, after molding the composition into a desired shape to obtain a molded body containing the optical element, the process itself And the like, and the like.
- the method for molding the curable composition of the present invention into a desired shape is not particularly limited, and a known molding method such as a normal transfer molding method or a casting method can be employed.
- the heating temperature at the time of heat curing is usually 100 to 200 ° C. although it depends on the curable composition used.
- the heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.
- the obtained optical element sealing body uses the curable composition of the present invention, an optical element having a short peak wavelength of 400 to 490 nm such as white or blue light emitting LED is used. However, it is excellent in transparency and heat resistance that does not deteriorate due to heat or light.
- the weight average molecular weight (Mw) of the silane compound copolymer obtained in the production example was a standard polystyrene equivalent value, and was measured using the following apparatus and conditions.
- the obtained precipitate was dissolved and recovered in methyl ethyl ketone, and the solvent was distilled off under reduced pressure with an evaporator, followed by vacuum drying to obtain 14.7 g of a silane compound copolymer (A1).
- the weight average molecular weight (Mw) of the silane compound copolymer (A1) was 2,700, and the molecular weight distribution (Mw / Mn) was 1.53.
- IR spectrum (Fourier transform infrared spectrophotometer (FT-IR)) data of the silane compound copolymer (A1) is shown below. Si—Ph: 699 cm ⁇ 1 , 741 cm ⁇ 1 , Si—O: 1132 cm ⁇ 1 , —CO: 1738 cm ⁇ 1
- the weight average molecular weight (Mw) of the silane compound copolymer (A4) was 2,800, and the molecular weight distribution (Mw / Mn) was 1.56. Further, IR spectrum (Fourier transform infrared spectrophotometer (FT-IR)) data of the silane compound copolymer (A4) is shown below. Si-Ph: 700cm -1, 742cm -1, Si-O: 1132cm -1, epoxy group: 1254cm -1
- the weight average molecular weight (Mw) of the silane compound copolymer (A5) was 3,000, and the molecular weight distribution (Mw / Mn) was 1.59.
- IR spectrum data of the silane compound copolymer (A5) is shown below.
- the weight average molecular weight (Mw) of the silane compound copolymer (A6) was 3,300, and the molecular weight distribution (Mw / Mn) was 1.59.
- IR spectrum data of the silane compound copolymer (A6) is shown below. Si-Ph: 700cm -1, 742cm -1, Si-O: 1133cm -1, -Cl: 648cm -1
- the weight average molecular weight (Mw) of the silane compound copolymer (A7) was 3,400, and the molecular weight distribution (Mw / Mn) was 1.61.
- IR spectrum data of the silane compound copolymer (A7) is shown below. Si—Ph: 699 cm ⁇ 1 , 741 cm ⁇ 1 , Si—O: 1132 cm ⁇ 1 , —Cl: 648 cm ⁇ 1
- Production Example 8 In Production Example 5, the same procedure as in Production Example 5 was conducted, except that the amount of phenyltrimethoxysilane used was 11.9 g (60 mmol) and the amount of 3-chloropropyltrimethoxysilane used was 11.9 g (60 mmol). 12.9 g of silane compound copolymer (A8) was obtained.
- the weight average molecular weight (Mw) of the silane compound copolymer (A8) was 3,600, and the molecular weight distribution (Mw / Mn) was 1.63.
- IR spectrum data of the silane compound copolymer (A8) is shown below. Si-Ph: 700cm -1, 741cm -1, Si-O: 1133cm -1, -Cl: 648cm -1
- the weight average molecular weight (Mw) of the silane compound copolymer (A9) was 2,900, and the molecular weight distribution (Mw / Mn) was 1.58.
- IR spectrum data of the silane compound copolymer (A9) is shown below. Si-Ph: 700cm -1, 741cm -1, Si-O: 1131cm -1, -CN: 2252cm -1
- the weight average molecular weight (Mw) of the silane compound copolymer (A10) was 3,200, and the molecular weight distribution (Mw / Mn) was 1.64.
- IR spectrum data of the silane compound copolymer (A10) is shown below. Si—Ph: 699 cm ⁇ 1 , 742 cm ⁇ 1 , Si—O: 1131 cm ⁇ 1 , —CN: 2253 cm ⁇ 1
- the weight average molecular weight (Mw) of the silane compound copolymer (A11) was 3,300, and the molecular weight distribution (Mw / Mn) was 1.62.
- IR spectrum data of the silane compound copolymer (A11) is shown below. Si—Ph: 699 cm ⁇ 1 , 742 cm ⁇ 1 , Si—O: 1131 cm ⁇ 1 , —CN: 2253 cm ⁇ 1
- the weight average molecular weight (Mw) of the silane compound copolymer (A12) was 3,500, and the molecular weight distribution (Mw / Mn) was 1.61.
- IR spectrum data of the silane compound copolymer (A12) is shown below. Si-Ph: 700cm -1, 742cm -1, Si-O: 1133cm -1, -CN: 2252cm -1
- Example 1 10 g of the silane compound copolymer (A1) obtained in Production Example 1 was added to an epoxy compound having an isocyanurate skeleton as an epoxy compound (B) (TEPIC-PAS B26, Nissan Chemical Industries, Ltd., epoxy equivalent 137 g / eq) (the following In Table 1 and Table 1-2, it is described as “B1”.) 1.5 g, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) as the curing agent (C) (Described as “C1” in Tables 1 and 1 below) 0.375 g and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd.) ) (An alicyclic acid anhydride having a carboxyl group) (described as “C2” in Table 1 and Table 1 below) 0.75 g, and as a silane coupling agent (D)
- Example 2 Curable compositions (2) to (7) were obtained in the same manner as in Example 1 using a silane compound copolymer, an epoxy compound, a curing agent, and a silane coupling agent according to Table 1 below.
- B2 represents an epoxy compound having an isocyanurate skeleton (TEPIC-PAS B22, Nissan Chemical Industries, Ltd., epoxy equivalent 179 g / eq).
- Curable compositions (8) and (9) were obtained in the same manner as in Example 1 using a silane compound copolymer, an epoxy compound, a curing agent, and a silane coupling agent according to Table 1 below.
- Example 3 (Comparative Example 3) In Example 1, instead of the epoxy compound (B), 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl (manufactured by Sigma-Aldrich) (in Table 1 and Table 2 below) It is described as “BF1.”) A curable composition (10) was obtained in the same manner as in Example 1 except that 1.5 g was used.
- Example 4 (Comparative Example 4) In Example 1, instead of the silane compound copolymer (A1) obtained in Production Example 1, the silane compound copolymer (A4) obtained in Production Example 4 was used. A curable composition (11) was obtained.
- Example 5 Comparative Example 5
- silane coupling agent (D1) 3-glycidoxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (in Table 1 and Table 2 below, “DF1”)
- DF1 3-glycidoxypropyltrimethoxysilane
- Example 8 10 g of the silane compound copolymer (A5) obtained in Production Example 5 and 1.5 g of an epoxy compound having an isocyanurate skeleton as an epoxy compound (B) (TEPIC-PAS B26 manufactured by Nissan Chemical Industries, epoxy equivalent: 137 g / eq)
- B epoxy compound having an isocyanurate skeleton
- B epoxy compound having an isocyanurate skeleton
- C curing agent
- 0.38 g of 4-methylcyclohexane-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi) By adding 0.75 g of Gas Chemical Co., Ltd.) and 0.38 g of 3-triethoxysilylpropyl succinic anhydride (manufactured by Amax Co.) as the silane coupling agent (D), thoroughly mixing and degassing the whole volume
- Curable compositions (15) to (31) were obtained in the same manner as in Example 8 using a silane compound copolymer, an epoxy compound, a curing agent, and a silane coupling agent according to Table 1 below.
- Each of the curable compositions 1 to 31 was applied to a mirror surface of a 2 mm square silicon chip to a thickness of about 2 ⁇ m, and the coated surface was placed on an adherend (silver-plated copper plate) and pressure-bonded. Then, it heat-processed at 180 degreeC for 2 hours, it was made to harden
- the test piece-attached adherend is left for 30 seconds on a measurement stage of a bond tester (series 4000, manufactured by Daisy) heated in advance to a predetermined temperature (23 ° C., 100 ° C.), and has a height of 50 ⁇ m from the adherend.
- each of the curable compositions 1 to 31 was poured into a mold so as to have a length of 25 mm, a width of 20 mm, and a thickness of 1 mm, and cured by heating at 140 ° C. for 6 hours to prepare test pieces. With respect to the obtained test piece, the initial transmittance (%) at wavelengths of 400 nm and 450 nm was measured with a spectrophotometer (MPC-3100, manufactured by Shimadzu Corporation).
- the transmittance at 400 nm was evaluated as “ ⁇ ” when 80% or more, “ ⁇ ” when 70% or more and less than 80%, and “ ⁇ ” when less than 70%.
- the cured products of the curable compositions of Examples 1 to 15 (1 to 7 and 14 to 21) have a high adhesive strength of 134 N / 2 mm ⁇ or more at 23 ° C. Even at high temperature (100 ° C.), it maintained an adhesive strength of 58% or more of the adhesive strength at 23 ° C., and was excellent in adhesion heat resistance. Moreover, initial transmittance at wavelengths of 400 nm and 450 nm and transmittance after heating were both high, and excellent initial transparency and heat resistance (transparency after heating).
- the cured products of the curable compositions (8, 12, 13, 22, 25 to 27, 30, 31) of Comparative Examples 1, 5 to 7, 10 to 12, 15, and 16 were inferior in initial transparency.
- the cured products of the curable compositions (9, 23, 28) of Comparative Examples 2, 8, 13 are inferior in both adhesive strength and adhesive heat resistance, and the curable compositions of Comparative Examples 3, 4, 9, 14 (10, 11). 24, 29) was extremely inferior in heat resistance (transparency after heating).
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Abstract
Description
また、近年、硬化性組成物は、光素子封止体を製造する際に、光素子固定材用接着剤や光素子固定材用封止剤等の光素子固定材用組成物としても利用されてきている。 Conventionally, curable compositions have been improved in various ways depending on the application, and have been widely used in industry as raw materials for optical parts and molded articles, adhesives, coating agents, and the like. For example, a curable composition that forms a cured product having excellent transparency is used as a raw material for optical components and a coating agent thereof, and a curable composition that forms a cured product having a high adhesive force is used as an adhesive or coating. Often used preferably as an agent.
In recent years, curable compositions have also been used as compositions for optical element fixing materials, such as adhesives for optical element fixing materials and sealing agents for optical element fixing materials, when producing optical element sealing bodies. It is coming.
しかしながら、特許文献1~3に記載されたポリシルセスキオキサン化合物を主成分とする光素子固定材用組成物の硬化物であっても、十分な接着力を保ちつつ、耐熱性及び透明性を得るのは困難な場合があった。 In order to solve this problem, Patent Documents 1 to 3 propose compositions for optical element fixing materials containing a polysilsesquioxane compound as a main component.
However, even a cured product of a composition for optical element fixing materials mainly composed of a polysilsesquioxane compound described in Patent Documents 1 to 3, heat resistance and transparency can be maintained while maintaining sufficient adhesive force. It was sometimes difficult to get.
しかしながら、これらの組成物を用いる場合であっても、経時変化に伴う十分な耐光劣化性を満足することができなかったり、接着力が低下する場合があった。 Moreover, as a composition used for optical element sealing, Patent Document 4 proposes an epoxy resin composition using an alicyclic epoxy resin, and Patent Document 5 proposes an epoxy resin composition containing a polythiol compound. ing.
However, even when these compositions are used, there is a case where sufficient light deterioration resistance accompanying a change with time cannot be satisfied or the adhesive force is lowered.
かくして本発明の第1によれば、下記〔1〕~〔9〕の硬化性組成物が提供される。
〔1〕(A)分子内に、下記式(i)、(ii)及び(iii) As a result of intensive studies to solve the above problems, the present inventors have (A) a specific silane compound copolymer, (B) an epoxy compound having an isocyanurate skeleton, and (C) an alicyclic group having a carboxyl group. The cured product of the composition containing the acid anhydride-containing curing agent and (D) the silane coupling agent having an acid anhydride structure has excellent transparency and heat resistance over a long period of time, and at a high temperature. Has been found to be a cured product having a high adhesive force, and the present invention has been completed.
Thus, according to the first aspect of the present invention, the following curable compositions [1] to [9] are provided.
[1] (A) In the molecule, the following formulas (i), (ii) and (iii)
で表される繰り返し単位のうち、(i)及び(ii)、(i)及び(iii)、(ii)及び(iii)、又は(i)、(ii)及び(iii)の繰り返し単位を有し、重量平均分子量が、1,000~30,000であるシラン化合物共重合体、
(B)イソシアヌレート骨格を有するエポキシ化合物、
(C)カルボキシル基を有する脂環式酸無水物を含有する硬化剤、並びに
(D)酸無水物構造を有するシランカップリング剤
を含有する硬化性組成物。 [Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X 0 represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group for a hydroxyl group) D) represents a single bond or a linking group. R 2 represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted phenyl group. ]
(I) and (ii), (i) and (iii), (ii) and (iii), or (i), (ii) and (iii) having repeating units A silane compound copolymer having a weight average molecular weight of 1,000 to 30,000,
(B) an epoxy compound having an isocyanurate skeleton,
(C) A curable composition containing a curing agent containing an alicyclic acid anhydride having a carboxyl group, and (D) a silane coupling agent having an acid anhydride structure.
〔3〕前記(A)、(B)、(C)及び(D)成分の含有割合が、(A)と〔(B)+(C)+(D)〕の質量比で、(A):〔(B)+(C)+(D)〕=90:10~50:50であることを特徴とする〔1〕又は〔2〕に記載の硬化性組成物。 [2] The silane compound copolymer of the above (A) is an abundance of a group represented by the formula: R 1 —CH (X 0 ) —D— ([R 1 —CH (X 0 ) —D]) Is a silane compound copolymer of [R 1 -CH (X 0 ) -D]: [R 2 ] = 60: 40 to 5:95 in a molar ratio of the abundance of R 2 and R 2 ([R 2 ]). [1] The curable composition according to [1].
[3] The content ratio of the components (A), (B), (C), and (D) is a mass ratio of (A) and [(B) + (C) + (D)]. The curable composition according to [1] or [2], wherein [(B) + (C) + (D)] = 90:10 to 50:50.
〔式中、R1は水素原子又は炭素数1~6のアルキル基を表し、X0はハロゲン原子、シアノ基又は式:OGで表される基(式中、Gは水酸基の保護基を表す。)を表し、Dは単結合又は連結基を表す。R3は炭素数1~6のアルキル基を表し、X1はハロゲン原子を表し、pは0~3の整数を表す。〕
で表されるシラン化合物(1)の少なくとも一種、及び
式(2):R2Si(OR4)q(X2)3-q
(式中、R2は、炭素数1~20のアルキル基又は置換基を有していてもよいフェニル基を表し、R4は炭素数1~6のアルキル基を表し、X2はハロゲン原子を表し、qは0~3の整数を表す。)
で表されるシラン化合物(2)の少なくとも一種を含むシラン化合物の混合物を縮合させて得られる、重量平均分子量が1,000~30,000であるシラン化合物共重合体、
(B)イソシアヌレート骨格を有するエポキシ化合物、
(C)カルボキシル基を有する脂環式酸無水物を含有する硬化剤、並びに
(D)酸無水物構造を有するシランカップリング剤
を含有する硬化性組成物。 [4] (A ′) Formula (1): R 1 —CH (X 0 ) —D—Si (OR 3 ) p (X 1 ) 3-p
[Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X 0 represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group for a hydroxyl group) D) represents a single bond or a linking group. R 3 represents an alkyl group having 1 to 6 carbon atoms, X 1 represents a halogen atom, and p represents an integer of 0 to 3. ]
And at least one silane compound (1) represented by formula (2): R 2 Si (OR 4 ) q (X 2 ) 3-q
(In the formula, R 2 represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted phenyl group, R 4 represents an alkyl group having 1 to 6 carbon atoms, and X 2 represents a halogen atom. Q represents an integer of 0 to 3.)
A silane compound copolymer having a weight average molecular weight of 1,000 to 30,000, obtained by condensing a mixture of silane compounds containing at least one of the silane compounds (2) represented by:
(B) an epoxy compound having an isocyanurate skeleton,
(C) A curable composition containing a curing agent containing an alicyclic acid anhydride having a carboxyl group, and (D) a silane coupling agent having an acid anhydride structure.
〔6〕前記(A’)、(B)、(C)及び(D)成分の含有割合が、(A’)と〔(B)+(C)+(D)〕の質量比で、(A’):〔(B)+(C)+(D)〕=90:10~50:50であることを特徴とする〔4〕又は〔5〕に記載の硬化性組成物。 [5] The silane compound copolymer of (A ′) described above has a molar ratio of silane compound (1) and silane compound (2): [silane compound (1)]: [silane compound (2)] = The curable composition according to [4], which is obtained by condensation at a ratio of 60:40 to 5:95.
[6] The content ratio of the components (A ′), (B), (C) and (D) is a mass ratio of (A ′) and [(B) + (C) + (D)]. A ′): [(B) + (C) + (D)] = 90:10 to 50:50 The curable composition as described in [4] or [5].
〔8〕前記(C)の硬化剤が、カルボキシル基を有する脂環式酸無水物及びその他の脂環式酸無水物から選ばれる一種又は二種以上からなり、その質量比が、(カルボキシル基を有する脂環式酸無水物):(その他の脂環式酸無水物)=100:0~10:90である〔1〕又は〔4〕に記載の硬化性組成物。
〔9〕光素子固定材用組成物である〔1〕又は〔4〕に記載の硬化性組成物。 [7] The content ratio of the components (B), (C) and (D) is a mass ratio of [(B) + (C)] and (D), and [(B) + (C)] :( D) = 90: 10 to 10:90, The curable composition according to [1] or [4].
[8] The curing agent (C) is composed of one or more selected from alicyclic acid anhydrides having a carboxyl group and other alicyclic acid anhydrides, and the mass ratio thereof is (carboxyl group The curable composition according to [1] or [4], wherein: (an alicyclic acid anhydride): (other alicyclic acid anhydride) = 100: 0 to 10:90.
[9] The curable composition according to [1] or [4], which is a composition for an optical element fixing material.
〔10〕〔1〕又は〔4〕に記載の硬化性組成物を硬化してなる硬化物。
〔11〕光素子固定材である〔10〕に記載の硬化物。 According to the second aspect of the present invention, the following [10] and [11] cured products are provided.
[10] A cured product obtained by curing the curable composition according to [1] or [4].
[11] The cured product according to [10], which is an optical element fixing material.
〔12〕〔1〕又は〔4〕に記載の硬化性組成物を、光素子固定材用接着剤として使用する方法。
〔13〕〔1〕又は〔4〕に記載の硬化性組成物を、光素子固定材用封止剤として使用する方法。 According to a third aspect of the present invention, there is provided a method of using the curable composition of the present invention of the following [12] and [13].
[12] A method of using the curable composition according to [1] or [4] as an adhesive for an optical element fixing material.
[13] A method of using the curable composition according to [1] or [4] as a sealant for an optical element fixing material.
本発明の硬化性組成物は、光素子固定材を形成する際に使用することができ、特に、光素子固定材用接着剤、及び光素子固定材用封止剤として好適に使用することができる。 According to the curable composition of the present invention, even when irradiated with high energy light or in a high temperature state, it does not color and does not deteriorate transparency, and has excellent transparency over a long period of time. In addition, a cured product having a high adhesive force even at a high temperature can be obtained.
The curable composition of the present invention can be used when forming an optical element fixing material, and particularly preferably used as an adhesive for an optical element fixing material and an encapsulant for an optical element fixing material. it can.
1)硬化性組成物
本発明の硬化性組成物は、
(A)分子内に、下記式(i)、(ii)及び(iii) Hereinafter, the present invention will be described in detail by dividing it into 1) a curable composition, 2) a cured product, and 3) a method of using the curable composition.
1) Curable composition The curable composition of the present invention comprises:
(A) In the molecule, the following formulas (i), (ii) and (iii)
で表される繰り返し単位のうち、(i)及び(ii)、(i)及び(iii)、(ii)及び(iii)、又は(i)、(ii)及び(iii)の繰り返し単位を有し、重量平均分子量が、1,000~30,000であるシラン化合物共重合体、(B)イソシアヌレート骨格を有するエポキシ化合物、(C)カルボキシル基を有する脂環式酸無水物を含有する硬化剤、並びに(D)酸無水物構造を有するシランカップリング剤を含有することを特徴とする。 [Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X 0 represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group for a hydroxyl group) D) represents a single bond or a linking group. R 2 represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted phenyl group. ]
(I) and (ii), (i) and (iii), (ii) and (iii), or (i), (ii) and (iii) having repeating units And a silane compound copolymer having a weight average molecular weight of 1,000 to 30,000, (B) an epoxy compound having an isocyanurate skeleton, and (C) an alicyclic acid anhydride having a carboxyl group. And (D) a silane coupling agent having an acid anhydride structure.
本発明の硬化性組成物は、(A)成分として、前記式(i),(ii)及び(iii)で表される繰り返し単位のうち、(i)及び(ii)、(i)及び(iii)、(ii)及び(iii)、又は(i)、(ii)及び(iii)の繰り返し単位を有し、重量平均分子量が、1,000~30,000であるシラン化合物共重合体(以下、「シラン化合物共重合体(A)」ということがある。)を含有する。
シラン化合物共重合体(A)は、(i)、(ii)、(iii)で表される繰り返し単位をそれぞれ一種有していてもよく、二種以上有していてもよい。 (A) Silane compound copolymer The curable composition of the present invention comprises (i) and (i) of the repeating units represented by the formulas (i), (ii) and (iii) as the component (A). having a repeating unit of ii), (i) and (iii), (ii) and (iii), or (i), (ii) and (iii), and having a weight average molecular weight of 1,000 to 30,000 A silane compound copolymer (hereinafter sometimes referred to as “silane compound copolymer (A)”).
The silane compound copolymer (A) may have one type of repeating unit represented by (i), (ii), or (iii), or may have two or more types.
R1で表される炭素数1~6のアルキル基としては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、t-ブチル基、i-ブチル基、s-ブチル基、n-ペンチル基、n-ヘキシル基等が挙げられる。 In the formulas (i) to (iii), R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R 1 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, s- Examples thereof include a butyl group, an n-pentyl group, and an n-hexyl group.
連結基としては置換基を有していてもよい2価の有機基が挙げられる。当該有機基の炭素数は1~20が好ましく、1~10がより好ましい。
置換基を有していてもよい2価の有機基としては、例えば、置換基を有していてもよいアルキレン基、置換基を有していてもよいアルケニレン基、置換基を有していてもよいアルキニレン基、置換基を有していてもよいアリーレン基、置換基を有していてもよい(アルキレン基、アルケニレン基、又はアルキニレン基)と置換基を有していてもよいアリーレン基との組み合わせからなる2価の基等が挙げられる。 D represents a single bond or a linking group.
Examples of the linking group include a divalent organic group that may have a substituent. The organic group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
Examples of the divalent organic group that may have a substituent include an alkylene group that may have a substituent, an alkenylene group that may have a substituent, and a substituent. An alkynylene group which may have a substituent, an arylene group which may have a substituent, an arylene group which may have a substituent (an alkylene group, an alkenylene group or an alkynylene group) and an arylene group which may have a substituent; And a divalent group consisting of the above-mentioned combinations.
置換基を有していてもよいアルケニレン基のアルケニレン基としては、ビニレン基、プロペニレン基、ブテニレン基、ペンテニレン基等の炭素数2~20のアルケニレン基、好ましくは、炭素数2~10のアルケニレン基が挙げられる。
置換基を有していてもよいアルキニレン基のアルキニレン基としては、エチニレン基、プロピニレン基等の炭素数2~20のアルキニレン基、好ましくは炭素数2~10のアルキニレン基が挙げられる。
置換基を有していてもよいアリーレン基のアリーレン基としては、o-フェニレン基、m-フェニレン基、p-フェニレン基、2,6-ナフチレン基等の炭素数6~20のアリーレン基、好ましくは炭素数6~10のアリーレン基が挙げられる。 As the alkylene group of the alkylene group which may have a substituent, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc., having 1 to 20 carbon atoms, preferably And an alkylene group having 1 to 10 carbon atoms.
The alkenylene group of the alkenylene group which may have a substituent is an alkenylene group having 2 to 20 carbon atoms such as vinylene group, propenylene group, butenylene group or pentenylene group, preferably an alkenylene group having 2 to 10 carbon atoms. Is mentioned.
Examples of the alkynylene group which may have a substituent include alkynylene groups having 2 to 20 carbon atoms such as ethynylene group and propynylene group, preferably alkynylene groups having 2 to 10 carbon atoms.
The arylene group of the arylene group which may have a substituent is preferably an arylene group having 6 to 20 carbon atoms such as an o-phenylene group, an m-phenylene group, a p-phenylene group, or a 2,6-naphthylene group, Includes an arylene group having 6 to 10 carbon atoms.
これらの置換基は、アルキレン基、アルケニレン基、アルキニレン基及びアリーレン基等の基において任意の位置に結合していてよく、同一若しくは相異なって複数個が結合していてもよい。 Examples of the substituent for the arylene group include: a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; And alkylthio groups such as ethylthio group; and the like.
These substituents may be bonded at arbitrary positions in groups such as an alkylene group, an alkenylene group, an alkynylene group, and an arylene group, and a plurality of them may be bonded in the same or different manner.
R2で表される炭素数1~20のアルキル基としては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、s-ブチル基、i-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基、n-オクチル基、i-オクチル基、n-ノニル基、n-デシル基、n-ドデシル基等が挙げられる。 In formulas (i) to (iii), R 2 represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted phenyl group.
Examples of the alkyl group having 1 to 20 carbon atoms represented by R 2 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t- Examples include a butyl group, n-pentyl group, n-hexyl group, n-octyl group, i-octyl group, n-nonyl group, n-decyl group, n-dodecyl group and the like.
式:R1-CH(X0)-D-で表される基及びR2の存在量は、例えば、シラン化合物共重合体(A)のNMRスペクトルを測定して定量することができる。 In the silane compound copolymer (A), the amount of the group represented by the formula: R 1 —CH (X 0 ) —D— ([R 1 —CH (X 0 ) —D]) and R 2 The molar ratio of the abundance ([R 2 ]) is preferably [R 1 —CH (X 0 ) —D]: [R 2 ] = 60: 40 to 5:95, more preferably 50:50 to 5:95. 50:50 to 10:90 are particularly preferable. By being in such a range, the cured | curing material which is excellent in transparency and adhesiveness, and excellent in heat resistance is obtained.
The amount of the group represented by the formula: R 1 —CH (X 0 ) —D— and R 2 can be quantified by, for example, measuring the NMR spectrum of the silane compound copolymer (A).
シラン化合物共重合体がラダー型構造を有していることは、例えば、反応生成物の赤外線吸収スペクトル測定、X線回折測定、NMR測定を行うことによって確認することができる。 The silane compound copolymer (A) is a polysilsesquioxane compound having a ladder structure.
The fact that the silane compound copolymer has a ladder structure can be confirmed, for example, by performing infrared absorption spectrum measurement, X-ray diffraction measurement, and NMR measurement of the reaction product.
(A’)式(1):R1-CH(X0)-D-Si(OR3)p(X1)3-p
〔式中、R1は水素原子又は炭素数1~6のアルキル基を表し、X0はハロゲン原子、シアノ基又は式:OGで表される基(式中、Gは水酸基の保護基を表す。)を表し、Dは単結合又は連結基を表す。R3は炭素数1~6のアルキル基を表し、X1はハロゲン原子を表し、pは0~3の整数を表す。〕
で表されるシラン化合物(1)の少なくとも一種、及び
式(2):R2Si(OR4)q(X2)3-q
(式中、R2は、炭素数1~20のアルキル基又は置換基を有していてもよいフェニル基を表し、R4は炭素数1~6のアルキル基を表し、X2はハロゲン原子を表し、qは0~3の整数を表す。)
で表されるシラン化合物(2)の少なくとも一種を含むシラン化合物の混合物を縮合させて得られる、重量平均分子量が1,000~30,000であるシラン化合物共重合体(以下、「シラン化合物共重合体(A’)」ということがある。)であってもよく、シラン化合物共重合体(A)が、シラン化合物共重合体(A’)であることが好ましい。 In the curable composition of the present invention, the component (A) is
(A ′) Formula (1): R 1 —CH (X 0 ) —D—Si (OR 3 ) p (X 1 ) 3-p
[Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X 0 represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group for a hydroxyl group) D) represents a single bond or a linking group. R 3 represents an alkyl group having 1 to 6 carbon atoms, X 1 represents a halogen atom, and p represents an integer of 0 to 3. ]
And at least one silane compound (1) represented by formula (2): R 2 Si (OR 4 ) q (X 2 ) 3-q
(In the formula, R 2 represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted phenyl group, R 4 represents an alkyl group having 1 to 6 carbon atoms, and X 2 represents a halogen atom. Q represents an integer of 0 to 3.)
A silane compound copolymer having a weight average molecular weight of 1,000 to 30,000 (hereinafter referred to as “silane compound copolymer”) obtained by condensing a mixture of silane compounds containing at least one silane compound (2) represented by Polymer (A ′) ”), and the silane compound copolymer (A) is preferably a silane compound copolymer (A ′).
シラン化合物(1)は、式(1):R1-CH(X0)-D-Si(OR3)p(X1)3-pで表される化合物である。シラン化合物(1)を用いることにより、硬化後においても透明性、接着力が良好なシラン化合物共重合体を得ることができる。 [Silane compound (1)]
The silane compound (1) is a compound represented by the formula (1): R 1 —CH (X 0 ) —D—Si (OR 3 ) p (X 1 ) 3-p . By using the silane compound (1), it is possible to obtain a silane compound copolymer having excellent transparency and adhesion even after curing.
式(1)中、X0はフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、シアノ基又は式:OGで表される基(式中、Gは水酸基の保護基を表す。)を表し、Dは単結合又は連結基を表す。X0とDで表されるものの具体例としては、それぞれ、シラン化合物共重合体(A)におけるX0とDとして例示したものが挙げられる。 In the formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom. Specific examples include those exemplified as R 1 in the silane compound copolymer (A).
In the formula (1), X 0 is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a cyano group, or a group represented by the formula: OG (wherein, G represents a protecting group for a hydroxyl group). D represents a single bond or a linking group. Specific examples of those represented by X 0 and D, respectively, those exemplified as X 0 and D in the silane compound copolymer (A).
X1はフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子を表す。
pは0~3の整数を表す。
pが2以上のとき、OR3同士は同一であっても相異なっていてもよい。また、(3-p)が2以上のとき、X1同士は同一であっても相異なっていてもよい。 R 3 is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. Represents an alkyl group having 1 to 6 carbon atoms.
X 1 represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
p represents an integer of 0 to 3.
When p is 2 or more, the ORs 3 may be the same or different. When (3-p) is 2 or more, X 1 may be the same or different.
これらのシラン化合物(1)は一種単独で、或いは二種以上を組み合わせて用いることができる。 3-acetoxypropyltrichlorosilane, 3-acetoxypropyltribromosilane, 3-acetoxypropyldichloromethoxysilane, 3-acetoxypropyldichloroethoxysilane, 3-acetoxypropylchlorodimethoxysilane, 3-acetoxypropylchlorodiethoxysilane, 3- Benzoyloxypropyltrichlorosilane, 3-trimethylsilyloxypropylchlorodimethoxysilane, 3-triethylsilyloxypropyldichloromethoxysilane, 3- (2-tetrahydropyranyloxy) propylchlorodiethoxysilane, 3- (2-tetrahydrofuranyloxy) Propyldichloroethoxysilane, 3-methoxymethyloxypropyltribromosilane, 3-methoxyethoxymethyloxypropyltrichloro Lan, 3- (1-ethoxyethyloxy) propylchlorodimethoxysilane, 3-t-butoxycarbonyloxypropyldichloromethoxysilane, 3-t-butoxypropylchlorodiethoxysilane, 3-triphenylmethoxypropyldichloroethoxysilane, 3 -Halogenosilane compounds in which X 0 is a group represented by the formula: OG such as benzyloxypropyltribromosilane;
These silane compounds (1) can be used singly or in combination of two or more.
シラン化合物(2)は、式(2):R2Si(OR4)q(X2)3-qで表される化合物である。
式(2)中、R2は、炭素数1~20のアルキル基又は置換基を有していてもよいフェニル基を表す。具体例としては、シラン化合物共重合体(A)におけるR2として例示したものが挙げられる。 [Silane compound (2)]
The silane compound (2) is a compound represented by the formula (2): R 2 Si (OR 4 ) q (X 2 ) 3-q .
In formula (2), R 2 represents an alkyl group having 1 to 20 carbon atoms or a phenyl group which may have a substituent. Specific examples include those exemplified as R 2 in the silane compound copolymer (A).
X2は、前記X1と同様のハロゲン原子を表す。
qは0~3のいずれかの整数を表す。
qが2以上のとき、OR4同士は同一であっても相異なっていてもよい。また、(3-q)が2以上のとき、X2同士は同一であっても相異なっていてもよい。 R 4 represents the same alkyl group having 1 to 6 carbon atoms as R 3 .
X 2 represents the same halogen atom as X 1 .
q represents an integer of 0 to 3.
When q is 2 or more, OR 4 may be the same or different. When (3-q) is 2 or more, X 2 may be the same or different.
メチルクロロジメトキシシラン、メチルジクロロメトキシシラン、メチルクロロジエトキシシラン、エチルクロロジメトキシシラン、エチルジクロロメトキシシラン、n-プロピルクロロジメトキシシラン、n-プロピルジクロロメトキシシラン等のアルキルハロゲノアルコキシシラン化合物類;
メチルトリクロロシラン、メチルトリブロモシラン、エチルトリクロロシラン、エチルトリブロモシラン、n-プロピルトリクロロシラン等のアルキルトリハロゲノシラン化合物類; Specific examples of the silane compound (2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, i-butyltrimethoxy. Alkyltrialkoxysilane compounds such as silane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, i-octyltriethoxysilane, dodecyltrimethoxysilane, methyldimethoxyethoxysilane, methyldiethoxymethoxysilane;
Alkylhalogenoalkoxysilane compounds such as methylchlorodimethoxysilane, methyldichloromethoxysilane, methylchlorodiethoxysilane, ethylchlorodimethoxysilane, ethyldichloromethoxysilane, n-propylchlorodimethoxysilane, n-propyldichloromethoxysilane;
Alkyltrihalogenosilane compounds such as methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, ethyltribromosilane, n-propyltrichlorosilane;
フェニルクロロジメトキシシラン、フェニルジクロロメトキシシラン、フェニルクロロメトキシエトキシシラン、フェニルクロロジエトキシシラン、フェニルジクロロエトキシシラン等の置換基を有していてもよいフェニルハロゲノアルコキシシラン化合物類;
フェニルトリクロロシラン、フェニルトリブロモシラン、4-メトキシフェニルトリクロロシラン、2-クロロフェニルトリクロロシラン、2-エトキシフェニルトリクロロシラン等の置換基を有していてもよいフェニルトリハロゲノシラン化合物;が挙げられる。
これらのシラン化合物(2)は一種単独で、或いは二種以上を組み合わせて用いることができる。 Has substituents such as phenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 2-chlorophenyltrimethoxysilane, phenyltriethoxysilane, 2-methoxyphenyltriethoxysilane, phenyldimethoxyethoxysilane, phenyldiethoxymethoxysilane Optionally phenyltrialkoxysilane compounds;
Phenylhalogenoalkoxysilane compounds which may have a substituent such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, phenylchloromethoxyethoxysilane, phenylchlorodiethoxysilane, phenyldichloroethoxysilane;
And phenyltrihalogenosilane compounds which may have a substituent such as phenyltrichlorosilane, phenyltribromosilane, 4-methoxyphenyltrichlorosilane, 2-chlorophenyltrichlorosilane, and 2-ethoxyphenyltrichlorosilane.
These silane compounds (2) can be used singly or in combination of two or more.
シラン化合物共重合体(A’)を製造する際に用いられるシラン化合物の混合物としては、シラン化合物(1)及びシラン化合物(2)からなる混合物であっても、さらに、本発明の目的を阻害しない範囲でその他のシラン化合物を含む混合物であってもよいが、シラン化合物(1)及びシラン化合物(2)からなる混合物が好ましい。 [A mixture of silane compounds]
Even if the mixture of the silane compound (1) and the silane compound (2) is used as the mixture of the silane compound used for producing the silane compound copolymer (A ′), the object of the present invention is further inhibited. Although it may be a mixture containing other silane compounds as long as it is not, a mixture comprising the silane compound (1) and the silane compound (2) is preferred.
酸触媒としては、塩酸、硫酸、硝酸、リン酸等の無機酸;メタンスルホン酸、トリフルロロメタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸、酢酸、トリフルオロ酢酸等の有機酸;等が挙げられる。 The catalyst used may be either an acid catalyst or a base catalyst.
Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid and trifluoroacetic acid; Can be mentioned.
本発明の硬化性組成物は、(B)成分として、イソシアヌレート骨格を有するエポキシ化合物(以下、「エポキシ化合物(B)」ということがある。)を含有する。
本発明の硬化性組成物は、エポキシ化合物(B)を含有するため、熱履歴後においても、耐熱性、透明性に優れる硬化物を得ることができる。 (B) Epoxy Compound Having Isocyanurate Skeleton The curable composition of the present invention contains an epoxy compound having an isocyanurate skeleton (hereinafter sometimes referred to as “epoxy compound (B)”) as the component (B). To do.
Since the curable composition of the present invention contains the epoxy compound (B), a cured product having excellent heat resistance and transparency can be obtained even after heat history.
前記エポキシ環を有する基(E)としては、例えば、下記式 (In the above formula, E represents a group having an epoxy ring, and R represents an arbitrary group other than a group having an epoxy ring such as a hydrogen atom or an organic group.)
As the group (E) having an epoxy ring, for example, the following formula
本発明の硬化性組成物は、(C)成分として、カルボキシル基を有する脂環式酸無水物を含有する硬化剤(以下、「硬化剤(C)」ということがある。)を含む。本発明の硬化性組成物は、硬化剤(C)を含有するため、耐熱性に優れる硬化物を得ることができる。 (C) Curing Agent The curable composition of the present invention may be referred to as a curing agent (hereinafter referred to as “curing agent (C)”) containing an alicyclic acid anhydride having a carboxyl group as the component (C). )including. Since the curable composition of this invention contains a hardening | curing agent (C), the hardened | cured material excellent in heat resistance can be obtained.
カルボキシル基は、脂環式酸無水物の脂環式構造の任意の位置で置換してよく、置換位置や置換するカルボキシル基の数は特に限定されない。 The alicyclic acid anhydrides include 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, 3- Methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, Examples include methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride, and the like.
The carboxyl group may be substituted at any position of the alicyclic structure of the alicyclic acid anhydride, and the position of substitution and the number of carboxyl groups to be substituted are not particularly limited.
カルボキシル基を有する脂環式酸無水物は、一種単独で、或いは二種以上を組み合わせて用いることができる。 Among these, cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride and cyclohexane-1,2,3-tricarboxylic acid-1,2 anhydride in which a carboxyl group is substituted with hexahydrophthalic anhydride are preferable. Cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride is particularly preferable. This compound may exist as a stereoisomer, but may be any isomer.
The alicyclic acid anhydride having a carboxyl group can be used alone or in combination of two or more.
他の硬化剤としては、カルボキシル基を有しない脂環式酸無水物(以下、「その他の脂環式酸無水物」という。)、ポリアゼライン酸無水物等の脂肪族酸無水物、脂肪族アミン系硬化剤、脂環式アミン系硬化剤、第2級もしくは第3級アミン系硬化剤、芳香族アミン系硬化剤、ジシアンジアミド、三フッ化ホウ素アミン錯塩、イミダゾール化合物等が挙げられる。
他の硬化剤は、一種単独で、或いは二種以上を組み合わせて用いることができる。 The curing agent (C) may further contain another curing agent.
Other curing agents include alicyclic acid anhydrides having no carboxyl group (hereinafter referred to as “other alicyclic acid anhydrides”), polyazeline acid anhydrides and other aliphatic acid anhydrides, aliphatic Examples include amine curing agents, alicyclic amine curing agents, secondary or tertiary amine curing agents, aromatic amine curing agents, dicyandiamide, boron trifluoride amine complex salts, and imidazole compounds.
Another hardening | curing agent can be used individually by 1 type or in combination of 2 or more types.
本発明の硬化性組成物は、(D)成分として、酸無水物構造を有するシランカップリング剤(以下、「シランカップリング剤(D)」ということがある。)を含む。本発明の硬化性組成物は、シランカップリング剤(D)を含有するため、相分離(白濁)することなく、透明性に優れ、高い接着力を有する硬化物を得ることができる。 (D) Silane Coupling Agent The curable composition of the present invention has a silane coupling agent having an acid anhydride structure as the component (D) (hereinafter sometimes referred to as “silane coupling agent (D)”). including. Since the curable composition of this invention contains a silane coupling agent (D), it can obtain the hardened | cured material which is excellent in transparency and has high adhesive force, without carrying out phase separation (white turbidity).
Yとしては、下記式 In the formula, Y represents an acid anhydride structure, R a represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group, and R b represents an alkyl group having 1 to 6 carbon atoms. I represents an integer of 1 to 3, j represents an integer of 0 to 2, k represents an integer of 1 to 3, and i + j + k = 4.
As Y, the following formula
式(d)中、Ra、Rbで表される炭素数1~6のアルキル基としては、前記R1で表される炭素数1~6のアルキル基として先に例示したのと同様の基が挙げられ、前記Raで表される置換基を有していてもよいフェニル基としては、前記R2で表される置換基を有していてもよいフェニル基として先に例示したのと同様の基が挙げられる。
なかでも、式(d)で表される化合物としては、下記式(d-1) (Wherein, h represents an integer of 0 to 10) and the like, and the group represented by (Y1) is particularly preferable.
In the formula (d), the alkyl group having 1 to 6 carbon atoms represented by R a and R b is the same as that exemplified above as the alkyl group having 1 to 6 carbon atoms represented by R 1 . The phenyl group which may have a substituent represented by R a is exemplified above as the phenyl group which may have a substituent represented by R 2 . The same group is mentioned.
Among these, as the compound represented by the formula (d), the following formula (d-1)
で表される化合物が好ましい。式中、hは2~8であるのが好ましい。 (In the formula, R b , h, i, j and k represent the same meaning as described above.)
The compound represented by these is preferable. In the formula, h is preferably 2 to 8.
シランカップリング剤(D)は一種単独で、或いは二種以上を組み合わせて用いることができる。 Specific examples of the silane coupling agent represented by the formula (d-1) include 2-trimethoxysilylethyl succinic anhydride and 3-triethoxysilylpropyl succinic anhydride.
A silane coupling agent (D) can be used individually by 1 type or in combination of 2 or more types.
さらに、前記(B)、(C)及び(D)成分の含有割合が、〔(B)+(C)〕と(D)の質量比で、〔(B)+(C)〕:(D)=90:10~10:90であることが好ましい。
このような割合で各成分を用いることにより、長期にわたって透明性、耐熱性に優れ、高温においても高い接着力を有する硬化物が得られる硬化性組成物を得ることができる。 In the curable composition of the present invention, the content ratio of the components (A), (B), (C) and (D) is (A) and [(B) + (C) + (D)]. The mass ratio is preferably (A): [(B) + (C) + (D)] = 90:10 to 50:50. Further, the content ratio of the components (A ′), (B), (C) and (D) is a mass ratio of (A ′) and [(B) + (C) + (D)] (A '): [(B) + (C) + (D)] = 90:10 to 50:50 is preferable.
Further, the content ratio of the components (B), (C) and (D) is the mass ratio of [(B) + (C)] and (D), [(B) + (C)] :( D ) = 90: 10 to 10:90 is preferable.
By using each component in such a ratio, it is possible to obtain a curable composition capable of obtaining a cured product having excellent transparency and heat resistance over a long period of time and having a high adhesive force even at high temperatures.
他の成分としては、硬化触媒、酸化防止剤、紫外線吸収剤、光安定剤、希釈剤等が挙げられる。 The curable composition of the present invention may further contain other components as long as the object of the present invention is not impaired.
Examples of other components include a curing catalyst, an antioxidant, an ultraviolet absorber, a light stabilizer, and a diluent.
紫外線吸収剤としては、例えば、フェニルサリシレート、p-t-ブチルフェニルサリシレート、p-オクチルフェニルサリシレート等のサリチル酸類;2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノン、2-ヒドロキシ-4-ドデシルオキシベンゾフェノン、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2-ヒドロキシ-4-メトキシ-5-スルホベンゾフェノン等のベンゾフェノン類;2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-t-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-t-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-3’-t-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-t-ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-t-アミルフェニル)ベンゾトリアゾール、2-{(2’-ヒドロキシ-3’,3’’,4’’,5’’,6’’-テトラヒドロフタルイミドメチル)-5’-メチルフェニル}ベンゾトリアゾール等のベンゾトリアゾール類;ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)[{3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル}メチル]ブチルマロネート等のヒンダードアミン類;等が挙げられる。 The ultraviolet absorber is added for the purpose of improving the light resistance of the resulting cured product.
Examples of the ultraviolet absorber include salicylic acids such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy- Benzophenones such as 5-sulfobenzophenone; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-3 ', 5'-di-t -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di -T-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2-{(2'-hydroxy-3', 3 Benzotriazoles such as '', 4 '', 5 '', 6 ''-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole; bis (2,2,6,6-tetramethyl-4-piperidyl ) Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1 , 1-Dimethyle ) -4- hydroxyphenyl} methyl] hindered amines, such as butyl malonate; and the like.
紫外線吸収剤の使用量は、シラン化合物共重合体(A)又は(A’)100質量部に対して、通常0.01~10質量部である。 These ultraviolet absorbers can be used alone or in combination of two or more.
The amount of the ultraviolet absorber used is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the silane compound copolymer (A) or (A ′).
光安定剤としては、例えば、ポリ[{6-(1,1,3,3,-テトラメチルブチル)アミノ-1,3,5-トリアジン-2,4-ジイル}{(2,2,6,6-テトラメチル-4-ピペリジン)イミノ}ヘキサメチレン{(2,2,6,6-テトラメチル-4-ピペリジン)イミノ}]等のヒンダードアミン類等が挙げられる。 The light stabilizer is added for the purpose of improving the light resistance of the resulting cured product.
Examples of the light stabilizer include poly [{6- (1,1,3,3, -tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6 , 6-tetramethyl-4-piperidine) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidine) imino}] and the like.
光安定剤の使用量は、シラン化合物共重合体(A)又は(A’)100質量部に対して、通常0.01~10質量部である。 These light stabilizers can be used alone or in combination of two or more.
The amount of the light stabilizer used is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the silane compound copolymer (A) or (A ′).
希釈剤としては、例えば、グリセリンジグリシジルエーテル、ブタンジオールジグリシジルエーテル、ジグリシジルアニリン、ネオペンチルグリコールグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテル、アルキレンジグリシジルエーテル、ポリグリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、グリセリントリグリシジルエーテル、4-ビニルシクロヘキセンモノオキサイド、ビニルシクロヘキセンジオキサイド、メチル化ビニルシクロヘキセンジオキサイド等が挙げられる。
これらの希釈剤は一種単独で、或いは二種以上を組み合わせて用いることができる。 A diluent is added in order to adjust the viscosity of the curable composition.
Examples of the diluent include glycerin diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cyclohexane dimethanol diglycidyl ether, alkylene diglycidyl ether, polyglycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Examples include ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, and the like.
These diluents can be used alone or in combination of two or more.
したがって、本発明の硬化性組成物は、光学部品や成形体の原料、接着剤、コーティング剤等として好適に使用される。特に、光素子の高輝度化に伴う、光素子固定材の劣化に関する問題を解決することができることから、本発明の硬化性組成物は、光素子固定材用組成物として好適に使用することができる。 According to the curable composition of the present invention obtained as described above, even when irradiated with high energy light or in a high temperature state, it is not colored and the transparency is not lowered, and it is long-term. It is possible to obtain a cured product having excellent transparency and high adhesive strength.
Therefore, the curable composition of the present invention is suitably used as a raw material for optical parts and molded articles, an adhesive, a coating agent, and the like. In particular, since the problem relating to deterioration of the optical element fixing material accompanying the increase in luminance of the optical element can be solved, the curable composition of the present invention can be suitably used as a composition for optical element fixing material. it can.
本発明の第2は、本発明の硬化性組成物を硬化してなる硬化物である。
本発明の硬化性組成物を硬化する方法としては加熱硬化が挙げられる。硬化するときの加熱温度は、通常、100~200℃であり、加熱時間は、通常10分から20時間、好ましくは30分から10時間である。 2) Cured product The second of the present invention is a cured product obtained by curing the curable composition of the present invention.
Heat curing is mentioned as a method of hardening the curable composition of this invention. The heating temperature for curing is usually 100 to 200 ° C., and the heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.
したがって、本発明の硬化物は、光学部品や成形体、接着層、コーティング層等として好適に使用される。特に、光素子の高輝度化に伴う、光素子固定材の劣化に関する問題を解決することができることから、本発明の硬化物は、光素子固定材として好適に使用することができる。 The cured product of the present invention has excellent transparency over a long period of time, even when irradiated with high energy light or in a high temperature state, without being colored and having a reduced transparency, and High adhesive strength.
Therefore, the hardened | cured material of this invention is used suitably as an optical component, a molded object, an adhesive layer, a coating layer, etc. In particular, since the problem relating to the deterioration of the optical element fixing material accompanying the increase in luminance of the optical element can be solved, the cured product of the present invention can be suitably used as the optical element fixing material.
硬化物の接着力は、23℃において110N/2mm□以上であることが好ましい。 It can be confirmed that the cured product of the present invention has a high adhesive force, for example, by measuring the adhesive force as follows. That is, the curable composition is applied to the mirror surface of the silicon chip, and the coated surface is placed on the adherend and pressure-bonded, and then heated and cured. This is left for 30 seconds on a measurement stage of a bond tester that has been heated to a predetermined temperature (for example, 23 ° C., 100 ° C.) in advance, and is horizontal (sheared) with respect to the adhesive surface from a position 50 μm high from the adherend. Direction) and measure the adhesive force between the test piece and the adherend.
The adhesive strength of the cured product is preferably 110 N / 2 mm □ or more at 23 ° C.
本発明の第3は、本発明の硬化性組成物を、光素子固定材用接着剤又は光素子固定材用封止剤として使用する方法である。
光素子としては、LED、LD等の発光素子、受光素子、複合光素子、光集積回路等が挙げられる。 3) Method of using curable composition The third of the present invention is a method of using the curable composition of the present invention as an adhesive for optical element fixing materials or an encapsulant for optical element fixing materials.
Examples of optical elements include light emitting elements such as LEDs and LDs, light receiving elements, composite optical elements, and optical integrated circuits.
本発明の硬化性組成物は、光素子固定材用接着剤として好適に使用することができる。 <Adhesive for optical element fixing material>
The curable composition of this invention can be used conveniently as an adhesive agent for optical element fixing materials.
本発明の硬化性組成物は、光素子封止体の封止剤として好適に用いることができる。 <Sealant for optical element fixing material>
The curable composition of this invention can be used suitably as a sealing agent of an optical element sealing body.
本発明の硬化性組成物を所望の形状に成形する方法としては、特に限定されるものではなく、通常のトランスファー成形法や、注型法等の公知のモールド法を採用できる。 As a method of using the curable composition of the present invention as a sealant for an optical element fixing material, for example, after molding the composition into a desired shape to obtain a molded body containing the optical element, the process itself And the like, and the like.
The method for molding the curable composition of the present invention into a desired shape is not particularly limited, and a known molding method such as a normal transfer molding method or a casting method can be employed.
製造例で得たシラン化合物共重合体の重量平均分子量(Mw)は標準ポリスチレン換算値とし、以下の装置、及び条件にて測定した。
装置名:HLC-8220GPC、東ソー社製
カラム:TSKgelGMHXL、TSKgelGMHXL、およびTSKgel2000HXLを順次連結したもの
溶媒:テトラヒドロフラン
注入量:80μl
測定温度:40℃
流速:1ml/分
検出器:示差屈折計 (Weight average molecular weight measurement)
The weight average molecular weight (Mw) of the silane compound copolymer obtained in the production example was a standard polystyrene equivalent value, and was measured using the following apparatus and conditions.
Apparatus name: HLC-8220GPC, manufactured by Tosoh Corporation Column: TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL sequentially connected Solvent: Tetrahydrofuran Injection volume: 80 μl
Measurement temperature: 40 ° C
Flow rate: 1 ml / min Detector: Differential refractometer
製造例で得たシラン化合物共重合体のIRスペクトルは以下の装置を使用して測定した。
フーリエ変換赤外分光光度計(Spectrum100、パーキンエルマー社製) (Measurement of IR spectrum)
The IR spectrum of the silane compound copolymer obtained in Production Example was measured using the following apparatus.
Fourier transform infrared spectrophotometer (Spectrum 100, manufactured by PerkinElmer)
300mlのナス型フラスコに、シラン化合物(2)としてフェニルトリメトキシシラン(東京化成工業社製)16.7g(84mmol)と、シラン化合物(1)として3-アセトキシプロピルトリメトキシシラン(アヅマックス社製)8.0g(36mmol)、溶媒としてトルエン60ml、及び蒸留水30mlを仕込んだ後、攪拌しながら、触媒としてリン酸(関東化学社製)0.15g(1.5mmol)を加え、室温でさらに16時間攪拌を継続した。 (Production Example 1)
In a 300 ml eggplant-shaped flask, 16.7 g (84 mmol) of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as the silane compound (2) and 3-acetoxypropyltrimethoxysilane (manufactured by Amax Co.) as the silane compound (1) After charging 8.0 g (36 mmol), 60 ml of toluene as a solvent, and 30 ml of distilled water, 0.15 g (1.5 mmol) of phosphoric acid (manufactured by Kanto Chemical Co., Inc.) was added as a catalyst while stirring, and further 16 at room temperature. Stirring was continued for an hour.
シラン化合物共重合体(A1)の重量平均分子量(Mw)は2,700、分子量分布(Mw/Mn)は1.53であった。
また、シラン化合物共重合体(A1)のIRスペクトル(フーリエ変換赤外分光光度計(FT-IR))データを以下に示す。
Si-Ph:699cm-1、741cm-1、Si-O:1132cm-1、-CO:1738cm-1 After completion of the reaction, 100 ml of ethyl acetate was added to the reaction mixture and neutralized with a saturated aqueous sodium hydrogen carbonate solution. After leaving still for a while, the organic layer was fractionated. Next, the organic layer was washed twice with distilled water and then dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered off, the filtrate was concentrated to 50 ml with an evaporator, dropped into a large amount of n-hexane to precipitate, and the precipitate was separated by decantation. The obtained precipitate was dissolved and recovered in methyl ethyl ketone, and the solvent was distilled off under reduced pressure with an evaporator, followed by vacuum drying to obtain 14.7 g of a silane compound copolymer (A1).
The weight average molecular weight (Mw) of the silane compound copolymer (A1) was 2,700, and the molecular weight distribution (Mw / Mn) was 1.53.
Further, IR spectrum (Fourier transform infrared spectrophotometer (FT-IR)) data of the silane compound copolymer (A1) is shown below.
Si—Ph: 699 cm −1 , 741 cm −1 , Si—O: 1132 cm −1 , —CO: 1738 cm −1
製造例1において、フェニルトリメトキシシランの使用量を14.3g(72mmol)とし、3-アセトキシプロピルトリメトキシシランの使用量を10.7g(48mmol)とした以外は製造例1と同様にして、シラン化合物共重合体(A2)15.9gを得た。
シラン化合物共重合体(A2)の重量平均分子量(Mw)は2,600、分子量分布(Mw/Mn)は1.50であった。
また、シラン化合物共重合体(A2)のIRスペクトル(フーリエ変換赤外分光光度計(FT-IR))データを以下に示す。
Si-Ph:699cm-1、741cm-1、Si-O:1132cm-1、-CO:1738cm-1 (Production Example 2)
In the same manner as in Production Example 1, except that the amount of phenyltrimethoxysilane used was 14.3 g (72 mmol) and the amount of 3-acetoxypropyltrimethoxysilane used was 10.7 g (48 mmol). 15.9 g of silane compound copolymer (A2) was obtained.
The weight average molecular weight (Mw) of the silane compound copolymer (A2) was 2,600, and the molecular weight distribution (Mw / Mn) was 1.50.
Further, IR spectrum (Fourier transform infrared spectrophotometer (FT-IR)) data of the silane compound copolymer (A2) is shown below.
Si—Ph: 699 cm −1 , 741 cm −1 , Si—O: 1132 cm −1 , —CO: 1738 cm −1
製造例1において、フェニルトリメトキシシランの使用量を19.0g(96mmol)とし、3-アセトキシプロピルトリメトキシシランの使用量を5.3g(24mmol)とした以外は製造例1と同様にして、シラン化合物共重合体(A3)14.9gを得た。
シラン化合物共重合体(A3)の重量平均分子量(Mw)は2,500、分子量分布(Mw/Mn)は1.59であった。
また、シラン化合物共重合体(A3)のIRスペクトル(フーリエ変換赤外分光光度計(FT-IR))データを以下に示す。
Si-Ph:700cm-1、742cm-1、Si-O:1132cm-1、-CO:1738cm-1 (Production Example 3)
In the same manner as in Production Example 1, except that the amount of phenyltrimethoxysilane used was 19.0 g (96 mmol) and the amount of 3-acetoxypropyltrimethoxysilane used was 5.3 g (24 mmol). 14.9 g of a silane compound copolymer (A3) was obtained.
The weight average molecular weight (Mw) of the silane compound copolymer (A3) was 2500, and the molecular weight distribution (Mw / Mn) was 1.59.
Further, IR spectrum (Fourier transform infrared spectrophotometer (FT-IR)) data of the silane compound copolymer (A3) is shown below.
Si-Ph: 700cm -1, 742cm -1, Si-O: 1132cm -1, -CO: 1738cm -1
製造例1において、フェニルトリメトキシシラン16.7g(84mmol)と3-アセトキシプロピルトリメトキシシラン8.0g(36mmol)を用いる代わりに、フェニルトリメトキシシラン(東京化成工業社製)11.9g(60mmol)と3-グリシドキシプロピルトリメトキシシラン(東京化成工業社製)(下記第1表-1、第1表-2中、「GlyTMS」と記載する。)14.2g(60mmol)を用いる以外は、製造例1と同様にして、シラン化合物共重合体(A4)16.3gを得た。
シラン化合物共重合体(A4)の重量平均分子量(Mw)は2,800、分子量分布(Mw/Mn)は1.56であった。
また、シラン化合物共重合体(A4)のIRスペクトル(フーリエ変換赤外分光光度計(FT-IR))データを以下に示す。
Si-Ph:700cm-1、742cm-1、Si-O:1132cm-1、エポキシ基:1254cm-1 (Production Example 4)
In Production Example 1, instead of using 16.7 g (84 mmol) of phenyltrimethoxysilane and 8.0 g (36 mmol) of 3-acetoxypropyltrimethoxysilane, 11.9 g (60 mmol) of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) ) And 3-glycidoxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (denoted as “GlyTMS” in Tables 1 and 1 below) 14.2 g (60 mmol) In the same manner as in Production Example 1, 16.3 g of a silane compound copolymer (A4) was obtained.
The weight average molecular weight (Mw) of the silane compound copolymer (A4) was 2,800, and the molecular weight distribution (Mw / Mn) was 1.56.
Further, IR spectrum (Fourier transform infrared spectrophotometer (FT-IR)) data of the silane compound copolymer (A4) is shown below.
Si-Ph: 700cm -1, 742cm -1, Si-O: 1132cm -1, epoxy group: 1254cm -1
300mlのナス型フラスコにシラン化合物(2)としてフェニルトリメトキシシラン(東京化成工業社製)19.0g(96mmol)と、シラン化合物(1)として3-クロロプロピルトリメトキシシラン(東京化成工業社製)4.77g(24mmol)、溶媒としてトルエン60ml、蒸留水30mlを仕込んだ後、攪拌しながら、触媒としてリン酸(関東化学社製)0.15g(1.5mmol)を加え、室温でさらに16時間攪拌を継続した。 (Production Example 5)
In a 300 ml eggplant type flask, 19.0 g (96 mmol) of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as the silane compound (2) and 3-chloropropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as the silane compound (1) ) 4.77 g (24 mmol), 60 ml of toluene as a solvent and 30 ml of distilled water were added, and then 0.15 g (1.5 mmol) of phosphoric acid (manufactured by Kanto Chemical Co., Inc.) was added as a catalyst while stirring. Stirring was continued for an hour.
また、シラン化合物共重合体(A5)のIRスペクトルデータを以下に示す。
Si-Ph:700cm-1,741cm-1,Si-O:1132cm-1,-Cl:648cm-1 The weight average molecular weight (Mw) of the silane compound copolymer (A5) was 3,000, and the molecular weight distribution (Mw / Mn) was 1.59.
In addition, IR spectrum data of the silane compound copolymer (A5) is shown below.
Si-Ph: 700cm -1, 741cm -1, Si-O: 1132cm -1, -Cl: 648cm -1
製造例5において、フェニルトリメトキシシランの使用量を16.7g(84mmol)とし、3-クロロプロピルトリメトキシシランの使用量を7.15g(36mmol)とした以外は製造例5と同様にして、シラン化合物共重合体(A6)13.4gを得た。 (Production Example 6)
In the same manner as in Production Example 5, except that the amount of phenyltrimethoxysilane used was 16.7 g (84 mmol) and the amount of 3-chloropropyltrimethoxysilane used was 7.15 g (36 mmol), 13.4 g of silane compound copolymer (A6) was obtained.
また、シラン化合物共重合体(A6)のIRスペクトルデータを以下に示す。
Si-Ph:700cm-1,742cm-1,Si-O:1133cm-1,-Cl:648cm-1 The weight average molecular weight (Mw) of the silane compound copolymer (A6) was 3,300, and the molecular weight distribution (Mw / Mn) was 1.59.
In addition, IR spectrum data of the silane compound copolymer (A6) is shown below.
Si-Ph: 700cm -1, 742cm -1, Si-O: 1133cm -1, -Cl: 648cm -1
製造例5において、フェニルトリメトキシシランの使用量を14.3g(72mmol)とし、3-クロロプロピルトリメトキシシランの使用量を9.54g(48mmol)とした以外は製造例5と同様にして、シラン化合物共重合体(A7)13.0gを得た。 (Production Example 7)
In the same manner as in Production Example 5, except that the amount of phenyltrimethoxysilane used was 14.3 g (72 mmol) and the amount of 3-chloropropyltrimethoxysilane used was 9.54 g (48 mmol), 13.0 g of a silane compound copolymer (A7) was obtained.
また、シラン化合物共重合体(A7)のIRスペクトルデータを以下に示す。
Si-Ph:699cm-1,741cm-1,Si-O:1132cm-1,-Cl:648cm-1 The weight average molecular weight (Mw) of the silane compound copolymer (A7) was 3,400, and the molecular weight distribution (Mw / Mn) was 1.61.
In addition, IR spectrum data of the silane compound copolymer (A7) is shown below.
Si—Ph: 699 cm −1 , 741 cm −1 , Si—O: 1132 cm −1 , —Cl: 648 cm −1
製造例5において、フェニルトリメトキシシランの使用量を11.9g(60mmol)とし、3-クロロプロピルトリメトキシシランの使用量を11.9g(60mmol)とした以外は製造例5と同様にして、シラン化合物共重合体(A8)12.9gを得た。 (Production Example 8)
In Production Example 5, the same procedure as in Production Example 5 was conducted, except that the amount of phenyltrimethoxysilane used was 11.9 g (60 mmol) and the amount of 3-chloropropyltrimethoxysilane used was 11.9 g (60 mmol). 12.9 g of silane compound copolymer (A8) was obtained.
また、シラン化合物共重合体(A8)のIRスペクトルデータを以下に示す。
Si-Ph:700cm-1,741cm-1,Si-O:1133cm-1,-Cl:648cm-1 The weight average molecular weight (Mw) of the silane compound copolymer (A8) was 3,600, and the molecular weight distribution (Mw / Mn) was 1.63.
In addition, IR spectrum data of the silane compound copolymer (A8) is shown below.
Si-Ph: 700cm -1, 741cm -1, Si-O: 1133cm -1, -Cl: 648cm -1
製造例5において、3-クロロプロピルトリメトキシシラン4.77gに代えて、2-シアノエチルトリメトキシシラン(アヅマックス社製)4.21g(24mmol)を使用したこと以外は製造例5と同様にして、シラン化合物共重合体(A9)13.5gを得た。 (Production Example 9)
In Production Example 5, instead of 4.77 g of 3-chloropropyltrimethoxysilane, 4.21 g (24 mmol) of 2-cyanoethyltrimethoxysilane (manufactured by AMAX Co.) was used, in the same manner as in Production Example 5, 13.5 g of a silane compound copolymer (A9) was obtained.
また、シラン化合物共重合体(A9)のIRスペクトルデータを以下に示す。
Si-Ph:700cm-1,741cm-1,Si-O:1131cm-1,-CN:2252cm-1 The weight average molecular weight (Mw) of the silane compound copolymer (A9) was 2,900, and the molecular weight distribution (Mw / Mn) was 1.58.
In addition, IR spectrum data of the silane compound copolymer (A9) is shown below.
Si-Ph: 700cm -1, 741cm -1, Si-O: 1131cm -1, -CN: 2252cm -1
製造例9において、フェニルトリメトキシシランの使用量を16.7g(84mmol)とし、2-シアノエチルトリメトキシシランの使用量を6.31g(36mmol)とした以外は製造例9と同様にして、シラン化合物共重合体(A10)13.3gを得た。 (Production Example 10)
In the same manner as in Production Example 9, except that the amount of phenyltrimethoxysilane used was 16.7 g (84 mmol) and the amount of 2-cyanoethyltrimethoxysilane used was 6.31 g (36 mmol), 13.3 g of compound copolymer (A10) was obtained.
また、シラン化合物共重合体(A10)のIRスペクトルデータを以下に示す。
Si-Ph:699cm-1,742cm-1,Si-O:1131cm-1,-CN:2253cm-1 The weight average molecular weight (Mw) of the silane compound copolymer (A10) was 3,200, and the molecular weight distribution (Mw / Mn) was 1.64.
In addition, IR spectrum data of the silane compound copolymer (A10) is shown below.
Si—Ph: 699 cm −1 , 742 cm −1 , Si—O: 1131 cm −1 , —CN: 2253 cm −1
製造例9において、フェニルトリメトキシシランの使用量を14.3g(72mmol)として、2-シアノエチルトリメトキシシランの使用量を8.41g(48mmol)とした以外は製造例9と同様にして、シラン化合物共重合体(A11)12.8gを得た。 (Production Example 11)
In Production Example 9, the amount of phenyltrimethoxysilane used was 14.3 g (72 mmol), and the amount of 2-cyanoethyltrimethoxysilane used was 8.41 g (48 mmol). 12.8 g of compound copolymer (A11) was obtained.
また、シラン化合物共重合体(A11)のIRスペクトルデータを以下に示す。
Si-Ph:699cm-1,742cm-1,Si-O:1131cm-1,-CN:2253cm-1 The weight average molecular weight (Mw) of the silane compound copolymer (A11) was 3,300, and the molecular weight distribution (Mw / Mn) was 1.62.
In addition, IR spectrum data of the silane compound copolymer (A11) is shown below.
Si—Ph: 699 cm −1 , 742 cm −1 , Si—O: 1131 cm −1 , —CN: 2253 cm −1
製造例9において、フェニルトリメトキシシランの使用量を11.9g(60mmol)として、2-シアノエチルトリメトキシシランの使用量を10.5g(60mmol)とした以外は製造例9と同様にして、シラン化合物共重合体(A12)12.3gを得た。 (Production Example 12)
In Production Example 9, the amount of phenyltrimethoxysilane used was 11.9 g (60 mmol), and the amount of 2-cyanoethyltrimethoxysilane used was 10.5 g (60 mmol). 12.3 g of compound copolymer (A12) was obtained.
また、シラン化合物共重合体(A12)のIRスペクトルデータを以下に示す。
Si-Ph:700cm-1,742cm-1,Si-O:1133cm-1,-CN:2252cm-1 The weight average molecular weight (Mw) of the silane compound copolymer (A12) was 3,500, and the molecular weight distribution (Mw / Mn) was 1.61.
In addition, IR spectrum data of the silane compound copolymer (A12) is shown below.
Si-Ph: 700cm -1, 742cm -1, Si-O: 1133cm -1, -CN: 2252cm -1
製造例1で得たシラン化合物共重合体(A1)10gに、エポキシ化合物(B)としてイソシアヌレート骨格を有するエポキシ化合物(日産化学工業社製 TEPIC-PAS B26、エポキシ当量 137g/eq)(下記第1表-1、第1表-2中、「B1」と記載する。)1.5g、硬化剤(C)として4-メチルシクロヘキサン-1,2-ジカルボン酸無水物(東京化成工業社製)(下記第1表-1、第1表-2中、「C1」と記載する。)0.375gおよびシクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物(三菱ガス化学社製)(カルボキシル基を有する脂環式酸無水物)(下記第1表-1、第1表-2中、「C2」と記載する。)0.75g、並びに、シランカップリング剤(D)として3-トリエトキシシリルプロピル無水コハク酸(アヅマックス社製)(下記第1表-1、第1表-2中、「D1」と記載する。)0.375gを加え、全容を十分に混合、脱泡することにより、硬化性組成物(1)を得た。 Example 1
10 g of the silane compound copolymer (A1) obtained in Production Example 1 was added to an epoxy compound having an isocyanurate skeleton as an epoxy compound (B) (TEPIC-PAS B26, Nissan Chemical Industries, Ltd., epoxy equivalent 137 g / eq) (the following In Table 1 and Table 1-2, it is described as “B1”.) 1.5 g, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) as the curing agent (C) (Described as “C1” in Tables 1 and 1 below) 0.375 g and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd.) ) (An alicyclic acid anhydride having a carboxyl group) (described as “C2” in Table 1 and Table 1 below) 0.75 g, and as a silane coupling agent (D) 3-Triethoxysilyl By adding 0.375 g of propyl succinic anhydride (manufactured by Amax Co.) (described as “D1” in Table 1 and Table 1 below), thoroughly mixing and degassing the whole volume, A curable composition (1) was obtained.
下記第1表-1に従い、シラン化合物共重合体、エポキシ化合物、硬化剤及びシランカップリング剤を用い、実施例1と同様にして、硬化性組成物(2)~(7)を得た。
なお、下記第1表-1、第1表-2中、「B2」は、イソシアヌレート骨格を有するエポキシ化合物(日産化学工業社製 TEPIC-PAS B22、エポキシ当量 179g/eq)を表す。 (Examples 2 to 7)
Curable compositions (2) to (7) were obtained in the same manner as in Example 1 using a silane compound copolymer, an epoxy compound, a curing agent, and a silane coupling agent according to Table 1 below.
In Table 1 and Table 1 below, “B2” represents an epoxy compound having an isocyanurate skeleton (TEPIC-PAS B22, Nissan Chemical Industries, Ltd., epoxy equivalent 179 g / eq).
下記第1表-1に従い、シラン化合物共重合体、エポキシ化合物、硬化剤及びシランカップリング剤を用い、実施例1と同様にして、硬化性組成物(8)、(9)を得た。 (Comparative Examples 1 and 2)
Curable compositions (8) and (9) were obtained in the same manner as in Example 1 using a silane compound copolymer, an epoxy compound, a curing agent, and a silane coupling agent according to Table 1 below.
実施例1において、エポキシ化合物(B)の代わりに、3,4-エポキシシクロヘキサンカルボン酸3,4-エポキシシクロヘキシルメチル(シグマアルドリッチ社製)(下記第1表-1、第1表-2中、「BF1」と記載する。)1.5gを用いた以外は、実施例1と同様にして、硬化性組成物(10)を得た。 (Comparative Example 3)
In Example 1, instead of the epoxy compound (B), 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl (manufactured by Sigma-Aldrich) (in Table 1 and Table 2 below) It is described as “BF1.”) A curable composition (10) was obtained in the same manner as in Example 1 except that 1.5 g was used.
実施例1において、製造例1で得たシラン化合物共重合体(A1)の代わりに、製造例4で得たシラン化合物共重合体(A4)を用いた以外は、実施例1と同様にして、硬化性組成物(11)を得た。 (Comparative Example 4)
In Example 1, instead of the silane compound copolymer (A1) obtained in Production Example 1, the silane compound copolymer (A4) obtained in Production Example 4 was used. A curable composition (11) was obtained.
実施例1において、シランカップリング剤(D1)の代わりに、3-グリシドキシプロピルトリメトキシシラン(東京化成工業社製)(下記第1表-1、第1表-2中、「DF1」と記載する。)0.375gを用いた以外は、実施例1と同様にして、硬化性組成物(12)を得た。 (Comparative Example 5)
In Example 1, instead of the silane coupling agent (D1), 3-glycidoxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (in Table 1 and Table 2 below, “DF1”) The curable composition (12) was obtained in the same manner as in Example 1 except that 0.375 g was used.
実施例1のシランカップリング剤(D1)として、オルトケイ酸テトラメチル(東京化成工業社製)(下記第1表-1、第1表-2中、「DF2」と記載する。)0.375gを用いた以外は、実施例1と同様にして、硬化性組成物(13)を得た。 (Comparative Example 6)
As the silane coupling agent (D1) of Example 1, tetramethyl orthosilicate (manufactured by Tokyo Chemical Industry Co., Ltd.) (denoted as “DF2” in Tables 1 and 1 below) 0.375 g A curable composition (13) was obtained in the same manner as in Example 1 except that was used.
製造例5で得たシラン化合物共重合体(A5)10gに、エポキシ化合物(B)としてイソシアヌレート骨格を有するエポキシ化合物(日産化学工業社製 TEPIC-PAS B26、エポキシ当量 137g/eq)1.5g、硬化剤(C)として4-メチルシクロヘキサン-1,2-ジカルボン酸無水物(東京化成工業社製)0.38gおよびシクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物(三菱ガス化学社製)0.75g、並びに、シランカップリング剤(D)として3-トリエトキシシリルプロピル無水コハク酸(アヅマックス社製)0.38gを加え、全容を十分に混合、脱泡することにより、硬化性組成物(14)を得た。 (Example 8)
10 g of the silane compound copolymer (A5) obtained in Production Example 5 and 1.5 g of an epoxy compound having an isocyanurate skeleton as an epoxy compound (B) (TEPIC-PAS B26 manufactured by Nissan Chemical Industries, epoxy equivalent: 137 g / eq) As a curing agent (C), 0.38 g of 4-methylcyclohexane-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi) By adding 0.75 g of Gas Chemical Co., Ltd.) and 0.38 g of 3-triethoxysilylpropyl succinic anhydride (manufactured by Amax Co.) as the silane coupling agent (D), thoroughly mixing and degassing the whole volume A curable composition (14) was obtained.
下記第1表-2に従い、シラン化合物共重合体、エポキシ化合物、硬化剤及びシランカップリング剤を用い、実施例8と同様にして、硬化性組成物(15)~(31)を得た。 (Examples 9 to 15, Comparative Examples 7 to 16)
Curable compositions (15) to (31) were obtained in the same manner as in Example 8 using a silane compound copolymer, an epoxy compound, a curing agent, and a silane coupling agent according to Table 1 below.
測定結果を下記第2表-1、第2表-2に示す。 The cured products of the curable compositions 1 to 31 obtained in Examples 1 to 15 and Comparative Examples 1 to 16 were measured for adhesive strength, initial transmittance, and transmittance after heating as follows.
The measurement results are shown in Table 2 and Table 2 below.
2mm角のシリコンチップのミラー面に、硬化性組成物1~31のそれぞれを厚さが約2μmになるよう塗布し、塗布面を被着体(銀メッキ銅板)の上に載せ圧着した。その後、180℃で2時間加熱処理して硬化させて試験片付被着体を得た。この試験片付被着体を、予め所定温度(23℃、100℃)に加熱したボンドテスター(シリーズ4000、デイジ社製)の測定ステージ上に30秒間放置し、被着体から50μmの高さの位置より、スピード200μm/sで接着面に対し水平方向(せん断方向)に応力をかけ、23℃及び100℃における、試験片と被着体との接着力(N/2mm□)を測定した。 (Adhesion test)
Each of the curable compositions 1 to 31 was applied to a mirror surface of a 2 mm square silicon chip to a thickness of about 2 μm, and the coated surface was placed on an adherend (silver-plated copper plate) and pressure-bonded. Then, it heat-processed at 180 degreeC for 2 hours, it was made to harden | cure, and the adherend with a test piece was obtained. The test piece-attached adherend is left for 30 seconds on a measurement stage of a bond tester (series 4000, manufactured by Daisy) heated in advance to a predetermined temperature (23 ° C., 100 ° C.), and has a height of 50 μm from the adherend. From the position, stress was applied in the horizontal direction (shear direction) to the bonding surface at a speed of 200 μm / s, and the adhesive force (N / 2 mm □) between the test piece and the adherend at 23 ° C. and 100 ° C. was measured. .
接着力試験において、100℃における接着力が、23℃における接着力の50%以上である場合を「○」、50%未満である場合を「×」と評価した。 (Adhesive heat resistance)
In the adhesive strength test, the case where the adhesive strength at 100 ° C. was 50% or more of the adhesive strength at 23 ° C. was evaluated as “◯”, and the case where it was less than 50% was evaluated as “X”.
硬化性組成物1~31のそれぞれを、長さ25mm、幅20mm、厚さ1mmとなるように鋳型に流し込み、140℃で6時間加熱して硬化させ、試験片をそれぞれ作製した。得られた試験片につき、分光光度計(MPC-3100、島津製作所社製)にて、波長400nm、450nmの初期透過率(%)を測定した。 (Measurement of initial transmittance)
Each of the curable compositions 1 to 31 was poured into a mold so as to have a length of 25 mm, a width of 20 mm, and a thickness of 1 mm, and cured by heating at 140 ° C. for 6 hours to prepare test pieces. With respect to the obtained test piece, the initial transmittance (%) at wavelengths of 400 nm and 450 nm was measured with a spectrophotometer (MPC-3100, manufactured by Shimadzu Corporation).
初期透過率測定において、400nmの透過率が80%以上を「○」、70%以上80%未満を「△」、70%未満を「×」と評価した。 (Initial transparency)
In the initial transmittance measurement, the transmittance at 400 nm was evaluated as “◯” when 80% or more, “Δ” when 70% or more and less than 80%, and “×” when less than 70%.
初期透過率を測定した各試験片を150℃のオーブンに500時間投入し、再度、波長400nm、450nmの透過率(%)を測定した。これを加熱後透過率とした。 (Measurement of transmittance after heating)
Each test piece whose initial transmittance was measured was placed in an oven at 150 ° C. for 500 hours, and the transmittance (%) at wavelengths of 400 nm and 450 nm was measured again. This was defined as the transmittance after heating.
加熱後透過率測定において、400nmの透過率が、初期透過率の80%以上であれば「○」、70%以上80%未満であれば「△」、70%未満であれば「×」と評価した。 [Heat resistance (transparency after heating)]
In the transmittance measurement after heating, if the transmittance at 400 nm is 80% or more of the initial transmittance, “◯”, if it is 70% or more and less than 80%, “Δ”, if it is less than 70%, “×”. evaluated.
Claims (13)
- (A)分子内に、下記式(i)、(ii)及び(iii)
〔式中、R1は水素原子又は炭素数1~6のアルキル基を表し、X0はハロゲン原子、シアノ基又は式:OGで表される基(式中、Gは水酸基の保護基を表す。)を表し、Dは単結合又は連結基を表す。R2は炭素数1~20のアルキル基又は置換基を有していてもよいフェニル基を表す。〕
で表される繰り返し単位のうち、(i)及び(ii)、(i)及び(iii)、(ii)及び(iii)、又は(i)、(ii)及び(iii)の繰り返し単位を有し、重量平均分子量が1,000~30,000であるシラン化合物共重合体、
(B)イソシアヌレート骨格を有するエポキシ化合物、
(C)カルボキシル基を有する脂環式酸無水物を含有する硬化剤、並びに
(D)酸無水物構造を有するシランカップリング剤
を含有する硬化性組成物。 (A) In the molecule, the following formulas (i), (ii) and (iii)
[Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X 0 represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group for a hydroxyl group) D) represents a single bond or a linking group. R 2 represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted phenyl group. ]
(I) and (ii), (i) and (iii), (ii) and (iii), or (i), (ii) and (iii) having repeating units A silane compound copolymer having a weight average molecular weight of 1,000 to 30,000,
(B) an epoxy compound having an isocyanurate skeleton,
(C) A curable composition containing a curing agent containing an alicyclic acid anhydride having a carboxyl group, and (D) a silane coupling agent having an acid anhydride structure. - 前記(A)のシラン化合物共重合体が、式:R1-CH(X0)-D-で表される基の存在量(〔R1-CH(X0)-D〕)とR2の存在量(〔R2〕)のモル比で、〔R1-CH(X0)-D〕:〔R2〕=60:40~5:95のシラン化合物共重合体である請求項1に記載の硬化性組成物。 The silane compound copolymer (A) described above has an abundance of a group represented by the formula: R 1 —CH (X 0 ) —D— ([R 1 —CH (X 0 ) —D]) and R 2 A silane compound copolymer of [R 1 —CH (X 0 ) —D]: [R 2 ] = 60: 40 to 5:95 in a molar ratio of the abundance ([R 2 ]). The curable composition according to 1.
- 前記(A)、(B)、(C)及び(D)成分の含有割合が、(A)と〔(B)+(C)+(D)〕の質量比で、(A):〔(B)+(C)+(D)〕=90:10~50:50であることを特徴とする請求項1又は2に記載の硬化性組成物。 The content ratio of the components (A), (B), (C) and (D) is a mass ratio of (A) and [(B) + (C) + (D)], and (A): [( The curable composition according to claim 1 or 2, wherein B) + (C) + (D)] = 90:10 to 50:50.
- (A’)式(1):R1-CH(X0)-D-Si(OR3)p(X1)3-p
〔式中、R1は水素原子又は炭素数1~6のアルキル基を表し、X0はハロゲン原子、シアノ基又は式:OGで表される基(式中、Gは水酸基の保護基を表す。)を表し、Dは単結合又は連結基を表す。R3は炭素数1~6のアルキル基を表し、X1はハロゲン原子を表し、pは0~3の整数を表す。〕
で表されるシラン化合物(1)の少なくとも一種、及び
式(2):R2Si(OR4)q(X2)3-q
(式中、R2は、炭素数1~20のアルキル基又は置換基を有していてもよいフェニル基を表し、R4は炭素数1~6のアルキル基を表し、X2はハロゲン原子を表し、qは0~3の整数を表す。)
で表されるシラン化合物(2)の少なくとも一種を含むシラン化合物の混合物を縮合させて得られる、重量平均分子量が1,000~30,000であるシラン化合物共重合体、
(B)イソシアヌレート骨格を有するエポキシ化合物、
(C)カルボキシル基を有する脂環式酸無水物を含有する硬化剤、並びに
(D)酸無水物構造を有するシランカップリング剤
を含有する硬化性組成物。 (A ′) Formula (1): R 1 —CH (X 0 ) —D—Si (OR 3 ) p (X 1 ) 3-p
[Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X 0 represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group for a hydroxyl group) D) represents a single bond or a linking group. R 3 represents an alkyl group having 1 to 6 carbon atoms, X 1 represents a halogen atom, and p represents an integer of 0 to 3. ]
And at least one silane compound (1) represented by formula (2): R 2 Si (OR 4 ) q (X 2 ) 3-q
(Wherein R 2 represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted phenyl group, R 4 represents an alkyl group having 1 to 6 carbon atoms, and X 2 represents a halogen atom. Q represents an integer of 0 to 3.)
A silane compound copolymer having a weight average molecular weight of 1,000 to 30,000, obtained by condensing a mixture of silane compounds containing at least one of the silane compounds (2) represented by:
(B) an epoxy compound having an isocyanurate skeleton,
(C) A curable composition containing a curing agent containing an alicyclic acid anhydride having a carboxyl group, and (D) a silane coupling agent having an acid anhydride structure. - 前記(A’)のシラン化合物共重合体が、シラン化合物(1)とシラン化合物(2)とを、モル比で、〔シラン化合物(1)〕:〔シラン化合物(2)〕=60:40~5:95の割合で縮合させて得られるものである請求項4に記載の硬化性組成物。 The silane compound copolymer (A ′) described above has a molar ratio of [silane compound (1)]: [silane compound (2)] = 60:40 between the silane compound (1) and the silane compound (2). The curable composition according to claim 4, which is obtained by condensation at a ratio of -5: 95.
- 前記(A’)、(B)、(C)及び(D)成分の含有割合が、(A’)と〔(B)+(C)+(D)〕の質量比で、(A’):〔(B)+(C)+(D)〕=90:10~50:50であることを特徴とする請求項4又は5に記載の硬化性組成物。 The content ratio of the components (A ′), (B), (C) and (D) is a mass ratio of (A ′) to [(B) + (C) + (D)], and (A ′) 6. The curable composition according to claim 4 or 5, wherein [(B) + (C) + (D)] = 90:10 to 50:50.
- 前記(B)、(C)及び(D)成分の含有割合が、〔(B)+(C)〕と(D)の質量比で、〔(B)+(C)〕:(D)=90:10~10:90であることを特徴とする請求項1又は4に記載の硬化性組成物。 The content ratio of the components (B), (C) and (D) is the mass ratio of [(B) + (C)] and (D), [(B) + (C)]: (D) = 5. The curable composition according to claim 1, wherein the curable composition is 90:10 to 10:90.
- 前記(C)の硬化剤が、カルボキシル基を有する脂環式酸無水物及びその他の脂環式酸無水物から選ばれる一種又は二種以上からなり、その質量比が、(カルボキシル基を有する脂環式酸無水物):(その他の脂環式酸無水物)=100:0~10:90である請求項1又は4に記載の硬化性組成物。 The curing agent (C) is composed of one or two or more kinds selected from alicyclic acid anhydrides having a carboxyl group and other alicyclic acid anhydrides, and the mass ratio thereof is (fatty acid having a carboxyl group). The curable composition according to claim 1 or 4, wherein cyclic acid anhydride): (other alicyclic acid anhydride) = 100: 0 to 10:90.
- 光素子固定材用組成物である請求項1又は4に記載の硬化性組成物。 The curable composition according to claim 1, wherein the curable composition is an optical element fixing material composition.
- 請求項1又は4に記載の硬化性組成物を硬化してなる硬化物。 Hardened | cured material formed by hardening | curing the curable composition of Claim 1 or 4.
- 光素子固定材である請求項10に記載の硬化物。 The cured product according to claim 10, which is an optical element fixing material.
- 請求項1又は4に記載の硬化性組成物を、光素子固定材用接着剤として使用する方法。 A method of using the curable composition according to claim 1 or 4 as an adhesive for an optical element fixing material.
- 請求項1又は4に記載の硬化性組成物を、光素子固定材用封止剤として使用する方法。 A method of using the curable composition according to claim 1 or 4 as a sealant for an optical element fixing material.
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Also Published As
Publication number | Publication date |
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KR20130034005A (en) | 2013-04-04 |
TWI504681B (en) | 2015-10-21 |
CN102906198B (en) | 2014-10-29 |
KR101768246B1 (en) | 2017-08-14 |
JP5725479B2 (en) | 2015-05-27 |
CN102906198A (en) | 2013-01-30 |
JPWO2011111667A1 (en) | 2013-06-27 |
TW201141952A (en) | 2011-12-01 |
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