WO2006013989A1 - Curable triazine composition for electronic components, production method therefor and cured product thereof - Google Patents

Curable triazine composition for electronic components, production method therefor and cured product thereof Download PDF

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WO2006013989A1
WO2006013989A1 PCT/JP2005/014460 JP2005014460W WO2006013989A1 WO 2006013989 A1 WO2006013989 A1 WO 2006013989A1 JP 2005014460 W JP2005014460 W JP 2005014460W WO 2006013989 A1 WO2006013989 A1 WO 2006013989A1
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group
compound
curable
triazine
formula
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PCT/JP2005/014460
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French (fr)
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Hiroshi Uchida
Kentaro Seki
Yuko Sakata
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Showa Denko K.K.
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Publication of WO2006013989A1 publication Critical patent/WO2006013989A1/en

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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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions

Definitions

  • Section 111 (a) with claiming the benefit of U.S. provisional application Serial No. 60/599,882 filed August 10, 2004 under the provision of35U.S.C. Ill (b) , pursuant to 35 U.S.C. Section
  • the present invention relates to a curable triazine composition containing a triazine compound which can be cured with heat or light, which is used for sealing material and varnish for electronic components, a production method therefor and a cured product thereof.
  • a curable resin composition obtained by blending a photo-polymerization initiator, a heat-curable resin, a diluent and the like with a photo-sensitive polymer such as urethane (meth) acrylate compound is disclosed as an example of material to make up for deficiency in the properties of conventional epoxy (meth) acrylate resins and melamine resins (in JP-A-2004-062057) , however, its low resistance to tin-plating is disadvantageous.
  • triazine resins such as a polycyanurate resin, a polythiocyanurate resin and a polyguanamine resin each having a triazine skeleton in the structure thereof are known as resin excellent in heat resistance and flame retardance.
  • polycyanurate resin and polyguanamine resin are described in JP-A-10-287745
  • polythiocyanurate resin is described in JP-A-2002-47345.
  • these triazine resins do not have a curable group as is used in the present invention.
  • a triazine compound and a triazine composition, curable with heat or light, used for sealing material and varnish for electronic components which can give a cured product excellent in heat resistance, electric properties, flame retardance and resistance against tin plating, especially excellent in heat resistance and resistance against tin plating, and a production method therefor.
  • a curable triazine composition comprising (A) a triazine compound represented by formula (1) :
  • R 1 each independently represents a divalent organic group
  • X 1 each independently represents a monovalent organic group
  • X 2 represents an oxygen atom, a sulfur atom or a group represented by formula (2) :
  • R 2 represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an aryl group or an aralkyl group; and n represents an integer of from 2 to 100, wherein part or all of n X lf s in the triazine compound have curable groups capable of being cured with heat or light, and comprising (B) a curing agent.
  • X 1 represents a monovalent organic group including a curable group capable of being cured with heat or light
  • X 3 represents a halogen atom
  • X 1 represents a monovalent organic group including a curable group capable of being cured with heat or light:
  • R 1 represents a divalent organic group
  • X 4 represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group.
  • X 1 represents a monovalent organic group including a curable group capable of being cured with heat or light. 5.
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having from 1 to 12 carbon atoms, an aralkyl group, a perfluoroalkyl group, a cyclohexyl group or a phenyl group;
  • R 7 's each independently represent a hydrogen atom or a methyl group
  • R 30 ' s each independently represent a hydrogen atom or a methyl group
  • R 31 ' s each independently represent a hydrogen atom or a methyl group
  • R 32 's each independently represent a hydrogen atom or a methyl group. 6.
  • curable triazine composition as described in 1, wherein part or all of the X 1 ' s have a (meth) acryloyl group, and wherein the curing agent is an azo compound.
  • curable triazine composition as described in 1, wherein part or all of the X 1 ' s have an epoxy group, and wherein the curing agent comprises a polyfunctional compound of an amine, a carboxylic acid or an acid anhydride.
  • [A] h+ represents an onium ion
  • [X] h" represents an anion
  • h represents an integer
  • curable triazine composition as described in 1, wherein part or all of the X 1 ' s have a carboxyl group or an acid anhydride, and wherein the curing agent comprises a polyfunctional compound of an epoxy compound, an oxetane compound, an amine compound or an isocyanate compound.
  • curable triazine composition as described in 1, wherein part or all of the X 1 ' s have an amino group, and wherein the curing agent comprises a polyfunctional compound of an epoxy compound, an isocyanate compound, an acid anhydride or an ⁇ , ⁇ -unsaturated carbonyl compound.
  • curable triazine composition as described in 1, wherein part or all of the X 1 ' s have a thiol group, and wherein the curing agent comprises a polyene compound.
  • curable triazine composition as described in 1, wherein part or all of the X 1 ' s have an isocyanate group which may be blocked, and wherein the curing agent comprises a polyfunctional compound of an amine compound or a carboxylic compound or an acid anhydride.
  • the organic or inorganic particulate substance is at least one kind selected from the group consisting of silica (SiO 2 ), alumina (AI2O3) , titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), silicon nitride (Si 3 N 4 ), barium titanate (BaO-TiO 2 ) , barium carbonate (BaCO 3 ) , lead titanate (PbO-TiO 2 ) , lead zirconate titanate (PZT) , lead lanthanum zirconate titanate (PLZT) , gallium oxide (Ga 2 O 3 ) , spinel (MgO-Al 2 O 3 ) , mullite (3Al 2 O 3 -2SiO 2 )
  • a method for producing a curable triazine composition wherein a curing agent is blended in a triazine compound obtained by reacting one or more types of dihalotriazine compounds represented by formula (3) with one or more types selected from compounds each having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups or phenolic hydroxyl groups in one molecule:
  • X 1 represents a monovalent organic group including a curable group capable of being cured with heat or light
  • X 3 represents a halogen atom.
  • X 1 represents a monovalent organic group including a curable group capable of being cured with heat or light:
  • R 1 represents a divalent organic group
  • X 4 represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group.
  • a method for producing a curable triazine composition wherein a curing agent is blended in a triazine compound obtained by reacting one or more types of triazine dithiol compounds represented by formula (4) with one or more types of bifinctional ⁇ , ⁇ -unsaturated carbonyl compounds: X 1
  • X 1 represents a monovalent organic group including a curable group capable of being cured with heat or light.
  • X 1 represents a monovalent organic group including a curable group capable of being cured with heat or light.
  • R 1 each independently represents a divalent organic group
  • X 1 each independently represents a monovalent organic group
  • X 2 represents an oxygen atom, a sulfur atom or a group represented by formula (2)
  • R 2 represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an aryl group or an aralkyl group; and n represents an integer of from 2 to 100, in which part or all of n X 1 ' s present in the triazine compound have groups curable with heat or light, the divalent organic group represented by R 1 is an organic group represented by formula (58), (59) or (60),
  • the monovalent organic group represented by X 1 is an organic group having an ethylenic carbon-carbon double bond, and X 2 is an oxygen atom or a sulfur atom.
  • 26. A cured product obtained by curing the curable triazine composition as described in any one of 1 to 21.
  • 27. A sealing material for electronic component comprising the curable triazine composition as described in any one of 1 to 21.
  • 28. A varnish for electronic component comprising the curable triazine composition as described in any one of 1 to 21.
  • the curable triazine composition according to the present invention provides a cured product excellent in heat resistance, electric properties, flame retardance, resistance against tin plating and the like and can favorably be used as sealing material or varnish for electronic components.
  • the triazine composition according to the present invention contains (A) a triazine compound represented by formula (1) and (B) a curing agent.
  • R 1 represents a divalent organic group.
  • R lf s include an alkylene group having from 1 to 12 carbon atoms, an alkenylene group having from 1 to 12 carbon atoms, an alkynylene group having from 1 to 12 carbon atoms, a cycloalkylene group, an arylene group, an aralkylene group and groups represented by formulae (6) to (46) :
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having from 1 to 12 carbon atoms, an aralkyl group, a perfluoroalkyl group, a cyclohexyl group or a phenyl group.
  • R 7 represents a hydrogen atom or a methyl group, the R 7 ' s may be the same with or different from one another;
  • R 8 and R 9 each independently represent a hydrogen atom or a methyl group
  • k and m each independently represent 0 or an integer and the relationship of k and m is l ⁇ k+m ⁇ 18.
  • p represents an integer of from 1 to 50;
  • r represents an integer of from 1 to 50 ;
  • R 10 represents a divalent organic group
  • R 10 ' s include an alkylene group having from 1 to 12 carbon atoms, a cycloalkylene group, an alkenylene group, an arylene group, an aralkylene group or groups represented by (10) to (17) and s represents an integer of from 1 to 50;
  • R 11 and R 12 each independently represent a divalent organic group, wherein preferred examples of R u 's and R 12 's include an alkylene group having from 1 to 12 carbon atoms, a cycloalkylene group, an alkenylene group, an arylene group, an aralkylene group or groups represented by the above-described formulae (10) to (17) and t represents an integer of from 1 to 50;
  • u represents an integer of from 1 to 50; wherein v represents an integer of from 1 to 50;
  • w and x each independently represent 0 or an integer and the relationship of x and x is l ⁇ w+x ⁇ 50;
  • y represents an integer of 1 to 50
  • z represents an integer of from 1 to 50;
  • R 13 represents a hydrogen atom or a methyl group, the R 13 ' s may be the same with or different from each other;
  • R 14 represents a hydrogen atom or a methyl group, the R 14 ' s may be the same with or different from each other;
  • R 15 represents a hydrogen atom or a methyl group, the R 15 ' s may be the same with or different from each other;
  • R 16 represents a hydrogen atom or a methyl group, the R 16 ' s may be the same with or different from each other;
  • R 17 represents a hydrogen atom or a methyl group, the R 17 ' s may be the same with or different from each other;
  • R 18 , R 19 and R 20 each independently represent a hydrogen atom or a methyl group, b and c each independently represent 0 or an integer and the relationship of b and c is 2 ⁇ b+c ⁇ 20;
  • R 21 represents a hydrogen atom or a methyl group
  • the R 21 ' s may be the same with or different from each other and d represents an integer of from 1 to 50;
  • R 22 represents a hydrogen atom or a methyl group
  • the R 22 ' s may be the same with or different from each other and e represents an integer of from 1 to 50;
  • R 23 represents a hydrogen atom or a methyl group
  • the R 23 ' s may be the same with or different from each other and f represents an integer of from 1 to 50;
  • R 24 represents a hydrogen atom or a methyl group
  • the R 24 ' s may be the same with or different from each other
  • R 25 represents an alkylene group having from 1 to 12 carbon atoms, an alkenylene group, an alkynylene group, a cycloalkylene group, an aralkylene group or a group represented by any one of the above-described formulae (10) to (17), and g represents an integer of from 1 to 50;
  • R > 26 represents a hydrogen atom or a methyl group
  • R ,26,'s may be the same with or different from each other, and u represents an integer of from 1 to 50;
  • R 27 represents a hydrogen atom or a methyl group, the R 27 's may be the same with or different from each other, and v represents an integer of from 1 to 50;
  • R 28 represents a hydrogen atom or a methyl group
  • the R 28 's may be the same with or different from each other and w and x each independently represent 0 or an integer and the relationship of w and x is l ⁇ w+x ⁇ 50;
  • R 29 represents a divalent organic group and preferably represents an alkylene group having from 1 to 12 carbon atoms, an arylene group, an aralkylene group or a group represented by any one of the above-described (10) to (33) .
  • n number of substituents (specific examples of R 1 ) in formula (1) may be one type or a combination of two or more types.
  • X 1 represents a monovalent organic group and a part or all of such X lf s are groups each containing a curable group capable of being cured with heat or light.
  • curable group include an allyl group, a vinyl group, a (meth)acryloyl group, an epoxy group, an oxetanyl group, a carboxyl group, an acid anhydride group, an amino group, a thiol group and an isocyanate group which may be blocked.
  • Specific preferred examples of X 1 containing an allyl group include an allyloxy group, an allylamino group, a diallylamino group and an allyloxyalkyl group.
  • X 1 containing a vinyl group examples include (2-vinyloxy) ethyloxy group and (4-vinyloxy) cyclohexyloxy group.
  • Specific preferred examples of X 1 containing a (meth) acryloyl group include 2- (meth) acryloyl ethyloxy group.
  • Specific preferred examples of X 1 containing an epoxy group include a glycidyloxy group.
  • Specific preferred examples of X 1 ' containing an oxetanyl group include
  • X 1 containing a carboxyl group examples include l-carboxy-3-methylpropylamino group, 1-carboxyethylamino group, 2-carboxyethylamino group, 1, 2-dicarboxyethylamino group,
  • X 1 containing an acid anhydride group examples include 2- [2, 4, 5-tricarboxy-4, 5-anhydrobenzoyloxy] ethyloxy group.
  • X 1 containing an amino group examples include (2-aminoethyl) amino group,
  • X 1 containing a thiol group examples include (2-mercaptoethyl) thio group.
  • Specific preferred examples of X 1 containing an isocyante group which may be blocked include isocyanate compound as represented by formula (47) and blocked compounds thereof.
  • One of these compounds as X 1 may be used singly or two or more types may be used in combination.
  • a part of X ⁇ s may be a group which does not contain a curable group.
  • Preferred examples of such an X 1 include an alkoxy group having from 1 to 6 carbon atoms, a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2-methoxyphenoxy group, a 4-methoxyphenoxy group, a benzyloxy group, a diethylamino group, a diisopropylamino group, diphenylamino group, a benzylamino group and a thiophenoxy group.
  • One of these groups can be used singly or two or more kinds of them may be used in combination.
  • the amount of X 1 having a curable group is 5 % by mol or more in the total amount of X ⁇ s contained in the triazine compound as represented by formula (1) .
  • X 1 is less than 5 % by mol, curability is deteriorated.
  • X 2 represents an oxygen atom, a sulfur atom or a group represented formula (2) :
  • R 2 represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an aryl group or an aralkyl group.
  • Preferred examples of R 2 include a methyl group, an ethyl group, a phenyl group and a benzyl group.
  • One of these groups may be used singly or two or more types may be used in combination.
  • n represents an integer of from 2 to 100, preferably 2 to 50, and more preferably 5 to 30.
  • n represents an integer of from 2 to 100, preferably 2 to 50, and more preferably 5 to 30.
  • the triazine compound as represented by formula (1) can be obtained, for example, by reacting a dihalotriazine compound as represented by formula (3) with a compound having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups or phenolic hydroxyl groups in one molecule, such as at least one type selected from a group of compounds consisting of a diol compound, a dithiol compound, a diamine compound, a bifunctional phenolic compound and a bifunctional thiophenolic compound (hereinafter simply referred to as "diol compound (s) and the like".
  • X 1 represents the same groups as defined in formula (1) .
  • X 3 represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom is preferred from the standpoint of easy availability of a raw material thereof.
  • the dihalotriazine compound as represented by formula (3) can be obtained, for example, by reacting a cyanuric halide such as cyanuric chloride with at least one compound selected from a group of compounds consisting of an alcoholic compound, a thiol compound, an amine compound, a phenolic compound and a thiophenolic compound (hereinafter, simply referred to as "alcoholic compound(s) and the like”) .
  • a cyanuric halide such as cyanuric chloride
  • a compound selected from a group of compounds consisting of an alcoholic compound, a thiol compound, an amine compound, a phenolic compound and a thiophenolic compound hereinafter, simply referred to as "alcoholic compound(s) and the like
  • alcoholic compound usable for the reaction with cyanuric halide include methanol, ethanol, isopropanol, allyl alcohol, glycidol, ethylene glycol, ethylene glycol monovinyl ether, 1, 4-butanediol monovinyl ether, cyclohexane dimethanol monovinyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 3-ethyl-3-hydroxymethyl oxetane.
  • Preferred examples of thiol compounds usable for the reaction with the cyanuric halide include 1, 2-propanedithiol .
  • amine compounds usable for the reaction with the cyanuric halide include diethylamine, diisopropylamine, diallylamine, allyl-methyl-amine,
  • phenolic compounds usable for the reaction with the cyanuric halide include phenol, o-cresol, m-cresol, p-cresol, p-methoxyphenol, ⁇ -naphthol, ⁇ -naphthol, 4-hydroxybiphenyl and 2-hydroxybiphenyl.
  • thiophenolic compounds usable for the reaction with the cyanuric halide include thiophenol.
  • the reaction of the cyanuric halide with the alcoholic compound and the like can efficiently be performed using bases .
  • the use amount of the alcoholic compound and the like be 1.0 to 20 mol based on 1 mol of cyanuric halide, from the standpoint of reaction yield, economical efficiency or the like.
  • Preferred examples of base usable in the reaction include inorganic bases such as alkali hydroxide, alkali carbonate, alkali hydrogen carbonate, alkali fluoride, alkali hydride and alkali metal, and organic bases such as pyridine, derivatives thereof and aliphatic tertiary amine.
  • alkali hydroxide include sodium hydroxide and potassium hydroxide.
  • alkali carbonate include sodium carbonate and potassium carbonate.
  • Examples of alkali hydride include sodium hydride.
  • Examples of alkali metal include metallic sodium.
  • Examples of aliphatic tertiary amine include triethylamine and tri-n-propylamine.
  • the use amount be from 0.5 to 30 mol and, more preferably, from 1.0 to 20 mol based on 1 mol of cyanuric halide, and when a divalent base is used, it is preferable that the use amount be from 0.25 to 15 mol and, more preferably, from 0.5 to 10 mol based on 1 mol of cyanuric halide.
  • the alkali hydroxide or the alkali carbonate may be added to the reaction system as an aqueous solution. On this occasion, it is preferable that the concentration of the alkali hydroxide or the alkali carbonate in the solution be in the range of from 10 to 70 % by mass.
  • the reaction temperature of the reaction is preferably from -20 to 150 0 C from the standpoint of the reaction rate and prevention of a side reaction and, when a base is added, it is preferable to add the base at such a speed that the above-described temperature range can be maintained.
  • the reaction pressure is not particularly limited and any of normal pressure, an increased pressure or a reduced pressure may be used.
  • the reaction time is ordinarily from 1 to 30 hours. Further, the whole amount of the cyanuric halide may be added at a time, or the amount may be divided into several portions so that the cyanuric halide may be added portionwise to the reaction mixture. On this occasion, it is also preferable to add the cyanuric halide in such a manner that the above-described reaction temperature range may be maintained.
  • reaction solvents include aromatic hydrocarbons such as toluene and xylene, ethers such as tetrahydrofuran, dibutyl ether and 1, 4-dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbon solvents such as chloroform and dichloromethane, and aprotic polar solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidone and dimethyl sulfoxide.
  • aromatic hydrocarbons such as toluene and xylene
  • ethers such as tetrahydrofuran, dibutyl ether and 1, 4-dioxane
  • ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • halogenated hydrocarbon solvents such as chloroform and dichlorome
  • an amount (entire amount) thereof to be used is preferably from 300 mL to 10 L based on 1 mol of cyanuric halide.
  • a phase-transfer catalyst for the purpose of promoting the reaction.
  • phase-transfer catalyst usable in the reaction include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetramethylammoniuiu sulfate, benzyltriethylammonium chloride, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide and cetyltributylammonium bromide; quaternary phophonium salts such as tetrabutylphosphonium bromide and cetyltributylphosphonium bromide; crown ethers such as 15-crown-5, 18-crown-6, benzo-18-crown-6, di
  • polymerization inhibitors include monophenolic compounds such as hydroquinone, 2, 6-di-t-butyl-p-cresol, butylated hydroxyanisole and 2, 6-di-t-butyl-4-ethylphenol stearyl- ⁇ - (3, 5-di-t-butyl-4-hydroxyphenyl)propionate; bisphenolic compounds such as
  • the thus-obtained dihalotriazine compounds may be used as they are or after optionally subjected to any one of an acid anhydride modification, an acid chloride modification, a diisocyanate modification, an epichlorohydrin modification and a subsequent dehydrochloric acid reaction, oxidation-epoxidation of an olefin and the like.
  • acid anhydrides to be used in the above treatments include dicarboxylic anhydrides such as succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride and phthalic anhydride; tricarboxylic anhydrides such as trimellitic anhydride; and tetracarboxylic acid dianhydrides such as pyromellitic acid dianhydride, 3, 3' , 4, 4' -biphenyl tetracarboxylic acid dianhydride, 2, 2' , 3, 3' -bisphenyl tetracarboxylic acid dianhydride, 2, 2' , 3, 3' -biphenyl tetracarboxylic acid dianhydride, 2, 3, 3' 4' -biphenyl tetracarboxylic acid dianhydride, 2, 2-bis (3, 4-dicarboxyphenyl)propane dianhydride, 1, 1-bis (3, 4-dicarboxyphenyl) e
  • R 8 and R 9 each independently represent a hydrogen atom or a methyl group and, k and m each independently represent 0 or an integer and the relationship of k and m is 2 ⁇ k+m ⁇ 20;and high molecular weight diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate diol and (hydrogenated) polybutadiene diol.
  • dithiol compound which can be used in the reaction with the dihalotriazine compound
  • 1,2-ethane dithiol and the like can be mentioned.
  • diamine compounds which can be used in the reaction with the dihalotriazine compound include aliphatic diamine such as ethylene diamine, tetramethylene diamine, hexamethylene diamine and anN,N' -dimethyl form, a diethyl form, a diphenyl form and dibenzyl form of these diamines; xylylene diamines such as m-xylylene diamine, p-xylylene diamine, and an N,N' -dimethyl form, a diethyl form, a diphenyl form and a dibenzyl form of these diamines; piperazines such as piperazine, 2,5-dimethyl piperazine and
  • aromatic diamines such as o-phenylene diamine, m-phenylene diamine, p-phenylene-diamine, 3, 3' -diamino-diphenyl ether, 4, 4' -diaminodiphenyl ether, 3, 4-diamino-diphenyl ether,
  • a compound which simultaneously contains a hydroxyl group and an amino group such as monoethanol amine or m-aminophenol can also be used.
  • the total amount of the diol compound and the like be in the range of 0.5 to 1.5 mol based on 1 mol of the dihalotriazine compound and, more preferably from 0.8 to 1.2 mol.
  • the total amount of the diol compound and the like is less than 0.5 mol or exceeds 1.5 mol, the molecular weight of the triazine compound thereby obtained is not increased and, then, characteristics such as flexibility of a curedproduct produced from the curable triazine composition by blending the triazine compound therein are deteriorated.
  • the reaction of the dihalotriazine compound with the diol compound and the like be performed in an organic solvent.
  • organic solvents include those as illustrated as usable in the reaction between the above-described cyanuric halide with the alcoholic compound and the like. From the standpoint of the reaction rate or the economical efficiency, it is preferable that the amount of the organic solvent to be used is from 0.1 to 10 L , based on 1 mol of the dihalotriazine compound and, more preferably 0.5 to 5 L.
  • the reaction of the dihalotriazine compound with the diol compound and the like be performed in the presence of a base as an acid acceptor.
  • acid acceptors include those bases as illustrated as usable in the reaction of the above-described cyanuric halide with the alcohol and the like and aqueous solutions thereof.
  • the amount of the acid acceptor be 2 to 20 mol based on 1 mol of the dihalotriazine and that when divalent acid acceptor is used, 1 to 10 mol.
  • phase-transfer catalyst In the reaction of the dihalotriazine compound with the diol compound and the like, when an aqueous alkaline solution is used as the acid acceptor, a phase-transfer catalyst may be added in the reaction system.
  • phase-transfer catalysts include those as illustrated as usable in the reaction between the above-described cyanuric halide with the alcohol and the like. From the standpoint of the reaction rate, economical efficiency and the like, it is preferable that the amount of each of the catalyst be 1 to 100 % by mol based on the dihalotriazine compound.
  • the reaction of the dihalotriazine compound with the diol compound and the like be performed in the temperature range of 0 to 200 0 C and at the same time that at the temperature, the curable group present in the dihalotriazine compound be sufficiently stable.
  • the temperature is 0 °C or less, the reaction proceeds slowly, while, when the temperature exceeds 200°C, it might lead to hydrolysis of the triazine compound thus generated.
  • the temperature exceeds the temperature at which the curable group in the dihalotriazine compound can stay sufficiently stable, it may lead to gelation in the reaction system. Therefore, it is necessary to determine an upper limit of the temperature by taking into consideration the type of functional group to be used.
  • a polymerization inhibitor may optionally be added.
  • Preferred examples of polymerization inhibitors include those as illustrated as usable in the reaction of the above-described dihalotriazine compound with the alcohol and the like. One of these polymerization inhibitors may be used singly or two or more types may be used in combination.
  • the triazine compound as represented by formula (1) can also be obtained by the method as described below. Namely, after a cyanuric halide such as cyanuric chloride is allowed to react with at least one type of compound (hereinafter, referred to also as "diol compound and the like" for short) selected from among compounds having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups or phenolic hydroxide groups in one molecule such as diol compound, dithiol compound, diamine compound, bifunctional phenolic compound and bifunctional thiophenolic compound, the resultant reaction product is allowed to react with at least one type of compounds (hereinafter, referred to also as "alcoholic compound and the like” for short) selected from among alcoholic compound, thiol compound, amine compound, phenolic compound and thiophenolic compound, to thereby obtain the triazine compound.
  • diol compound and the like which can be used in this reaction include those as illustrated
  • the entire amount of the diol compound and the like be in the range of from 0.8 to 1.2 mol based on 1 mol of the dihalotriazine compound.
  • the molecular weight of the triazine compound thereby obtained is not increased and, then, characteristics such as flexibility of a cured product produced from the curable triazine composition obtained by blending the triazine compound therein may sometimes be deteriorated.
  • the reaction of the above-described cyanuric halide with the diol compound and the like be performed in an organic solvent.
  • organic solvents include those as illustrated as usable in the reaction of the above-described cyanuric halide with the alcoholic compound and the like. From the standpoint of the reaction rate or the economical efficiency, it is preferable that the amount of the organic solvent to be used be 0.5 to 10 L based on 1 mol of the cyanuric halide.
  • the reaction of the cyanuric halide with the diol compound anf the like be performed in the presence of an acid acceptor.
  • acid acceptors include those as illustrated as usable in the reaction of the cyanuric halide with the alcohol and the like and aqueous solutions thereof. From the standpoint of the reaction rate, economical efficiency and the like, it is preferable that, when the acid acceptor is monovalent, the amount of the acid acceptor to be used be 2 to 20 mol based on 1 mol of the cyanuric halide and that when the acid acceptor is divalent, the amount be 1 to 10 mol.
  • phase-transfer catalyst in the reaction of the above-described cyanuric halide with the diol compound and the like, when an aqueous alkaline solution is used as the acid acceptor, a phase-transfer catalyst can be added in the reaction system.
  • phase-transfer catalysts include those as illustrated as usable in the reaction of the above-described cyanuric halide with the alcohol and the like. From the standpoint of the reaction rate, economical efficiency and the like, it is preferable that the amount of the catalyst to be used be 1 to 100 % by mol based on the dihalotriazine compound. It is preferable that the reaction of the cyanuric halide with the diol compound and the like be performed in the temperature range of 0 to 150 0 C. When the temperature is 0 °C or less, the reaction proceeds slowly, while, when the temperature exceeds 150 °C, it might lead to hydrolysis or gelation of the triazine compound thus generated.
  • a polymerization inhibitor may optionallybe added.
  • Preferred examples of polymerization inhibitors include those as illustrated as usable in the reaction of the cyanuric halide with the alcohol and the like. One of these polymerization inhibitors may be used singly or two or more of them may be used in combination.
  • Preferred examples of alcoholic compounds and the like to react with the product obtained by the above reaction of cyanuric halide with the diol compound and the like include those as illustrated as usable for producing the dihalotriazine compound as represented by formula (3) by reacting with the cyanuric halide.
  • the alcoholic compound and the like may directly be added to the reaction system where the cyanuric halide is reacted with the diol compound and the like, or after the reaction product is once taken out of the reaction system, the alcoholic compound and the like may be allowed to react therewith.
  • the total amount of the alcoholic compound and the like be from 1 to 5 mol based on 1 mol of the cyanuric halide.
  • the reaction using the alcoholic compound and the like be performed in an organic solvent.
  • organic solvents include those as illustrated as usable in the previously-mentioned reaction of the cyanuric halide and the alcoholic compound and the like. From the standpoint of the reaction rate or the economical efficiency, it is preferable that the amount of the organic solvent to be used be from 0.2 to 10 L based on 1 mol of the cyanuric halide.
  • the reaction be performed in the presence of an acid acceptor.
  • acid acceptors include those as illustrated as usable in the previously-mentioned reaction of the cyanuric halide with the alcohol and the like and aqueous solutions thereof.
  • the amount of acid acceptor to be used be 1 to 20 mol based on 1 mol of the dihalotriazine, and that when the acid acceptor is divalent, the amount be 0.5 to 10 mol .
  • phase-transfer catalyst When the alcoholic compound and the like are reacted with the reaction product of the reaction of the cyanuric halide with the diol compound and the like, in a case where an aqueous alkaline solution is used as the acid acceptor, a phase-transfer catalyst may be added in the reaction system.
  • phase-transfer catalysts include those as illustrated as usable in the previously-mentioned reaction of the cyanuric halide with the alcohol and the like. From the standpoint of the reaction rate, economical efficiency and the like, it is preferable that the amount of the catalyst to be used be 1 to 100 % by mol based on the cyanuric halide.
  • the reaction in the temperature range of from 0 to 200 °C.
  • the temperature is 0 0 C or less, the reaction proceeds slowly, while, when the temperature exceeds 200 °C, it might lead to hydrolysis of the triazine compound thus generated. Further, when the temperature exceeds the temperature at which the curable group present in the dihalotriazine compound can stay sufficiently stable, it might cause gelation in the reaction system.
  • a polymerization inhibitor may optionally be added.
  • Preferred examples of polymerization inhibitors include those as illustrated as usable in the previously-mentioned reaction of the dihalotriazine compound with the alcohol and the like.
  • One of these polymerization inhibitors may be used singly or two or more of them may be used in combination.
  • the triazine compound as represented by formula (1) can also be obtained by a method as described below. Namely, the triazine compound can be obtained by reacting a triazine dithiol compound as represented by formula (4) with a compound as represented by formula (5) or a bifunctional ⁇ , ⁇ -unsaturated carbonyl compound.
  • X 1 in formula (4) represents the same group as in X 1 in formula (1) .
  • the triazine dithiol compound as represented by formula (4) can be obtained, for example, by reacting dihalotriazine compound as represented by formula (3) with an alkaline hydrosulfide or an alkaline sulfide.
  • the reaction between the dihalotriazine compound and the alkaline hydrosulfide or the alkaline sulfide be performed in an organic solvent.
  • organic solvents which can be used on this occasion include alcohols such as methanol, ethanol and isopropyl alcohol and amide-type solvents such as N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone and 1, 3-dimethyl-2-imidazolidone.
  • One of these organic solvents may be used singly or two or more types may be used in combination. It is preferable that the use amount of the organic solvent be 0.1 to 5 L based on 1 mol of the dihalotriazine compound.
  • the use amount of alkaline hydrosulfide or alkaline sulfide be of from 2 to 10 mol based on 1 mol of the dihalotriazine compound. Further, from the standpoint of the reaction efficiency, it is preferable that the alkaline hydrosulfide or alkaline sulfide be added after being dissolved in water. On this occasion, it is preferable that the concentration of the alkaline hydrosulfide or alkaline sulfide be from 10 to 70 % by mass.
  • reaction temperature be from -20 to 50 °C.
  • a polymerization inhibitor may optionally be added.
  • Preferred examples of polymerization inhibitors include those as illustrated as usable in the previously-mentioned reaction of the dihalotriazine compound with the alcoholic compound and the like.
  • R 1 represents the same group as in R 1 in formula ( 1 ) .
  • X 4 represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a methane sulfonyloxy group, a trifluoromethane sulfonyloxy group or a p-toluene sulfonyloxy group and, preferably, represents a bromine atom, a methane sulfonyloxy group or a p-toluene sulfonyloxy group.
  • Preferred examples of compounds as represented by formula (5) include 1, 2-dibromoethane, 1, 2-dibromopropane, 1, 3-dibromopropane, 1, 3-dibromobutane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, 1, 10-dibromodecane, 1, 4-dichlorobenzene, p,p' -dibromobiphenyl and, further, a methane sulfonyl acid ester and a p-toluene sulfonic acid ester of the compounds as illustrated as preferred examples of diol compounds which can be used for producing triazine compound as represented by formula (1) by allowing any one of them to react with the dihalotriazine compound.
  • bifunctional ⁇ , ⁇ -unsaturated carbonyl compounds to react with the triazine ditiol compound as represented by formula (4) include bismaleimide and, further, a (meth) acrylic acid ester of the compounds as illustrated as preferred examples of diol which can be used for producing the triazine compound as represented by formula (1) by allowing them to react with the dihalotriazine compound.
  • One of these compounds may be used singly or two or more types may be used in combination.
  • the amount of the compound as represented by formula (5) or the ⁇ , ⁇ -unsaturated carbonyl compound be from 0.5 to 1.5 mol based on 1 mol of the triazine dithiol compound.
  • the entire amount of the compound as represented by formula (5) or the ⁇ , ⁇ -unsaturated carbonyl compound is less than 0.5 mol or more than 1.5 mol, the molecular weight of the triazine compound thereby obtained is not increased and, then, characteristics such as flexibility of a curedproduct produced from the curable triazine composition obtained by blending the triazine compound therein are deteriorated.
  • organic solvents include aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene and benzonitrile; halogen-type solvents such as chloroform, dichloromethane, 1, 2-dichloroethane, 1, 1, 2, 2-tetrachloroethane and dichlorobenzene; and ether-type solvents such as tetrahydrofuran and dioxane.
  • the amount of the organic solvent to be used be from 0.5 to 10 L based on 1 mol of the triazine dithiol compound as represented by formula (4) . It is preferable that the reaction between the tirazine dithiol compound and the compound as represented by formula (5) or the bifunctional ⁇ , ⁇ -unsaturated carbonyl compound be performed in the presence of a base catalyst.
  • base catalysts include those as illustrated as usable in the previously-mentioned reaction of the cyanuric halide with the alcohol or the like.
  • the amount of the base catalyst to be used be from 1 mmol to 5 mol and that when the base is monovalent the amount be 0.5 mmol to 2.5 mol, based on 1 mol of triazine dithiol.
  • phase-transfer catalyst When the reaction between the triazine dithiol compound and the compound as represented by formula (5) or the bifunctional ⁇ , ⁇ -unsaturated carbonyl compound is performed in two-phase system of organic solvent and water, a phase-transfer catalyst may be added in the reaction system.
  • phase-transfer catalysts include those as illustrated as usable in the previously-mentioned reaction of the dihalotriazine compound with the diol compound and the like. It is preferable that the reaction between the triazine dithiol compound and the compound as represented by formula
  • the ⁇ , ⁇ -unsaturated carbonyl compound be performed in the temperature range of 0 to 200 °C and at a temperature at which the curable group present in the triazine dithiol compound can be sufficiently stable.
  • the temperature is less than 0 °C, the reaction proceeds slowly, while, when the temperature exceeds 200 0 C, it might cause hydrolysis of a triazine resin. Further, when the temperature exceeds the temperature at which the curable group in the triazine dithiol compound can stay sufficiently stable, it might lead to gelation in the reaction system.
  • the reaction be performed at the reaction temperature of 200 0 C or less, while, when the curable group is an acryloyl group, it is preferable that the reaction be performed at the reaction temperature of 150 °C or less.
  • a polymerization inhibitor may optionally be added. Preferred examples of polymerization inhibitors include those as illustrated as usable in the previously-mentioned reaction of the cyanuric halide and the alcohol or the like.
  • the triazine compound as represented by formula (1) obtained by reacting the dihalotriazine compound as represented by formula (3) with the diol compound and the like or by reacting the triazine dithiol compound as represented by formula (4) with the compound as represented by formula (5) or the ⁇ , ⁇ -unsaturated compound, may be used after optionally subjected to any one of an acid anhydride modification, an acid chloride modification, a diisocyanate modification, an epichlorohydrin modification accompanied by subsequent dehydrochloric acid reaction, oxidation-epoxidation of an olefin and the like.
  • Examples of acid anhydrides, acid chlorides and diisocyanates to be used on this occasion include those as previously illustrated as usable in the modification of the dihalotriazine compound.
  • one of the triazine compounds which can be represented by formula (1) and each contain groups curable with heat or light as a part or all of n X ⁇ s may be used singly or two or more types of the compounds may be used in combination.
  • examples of curing agent serving as component (B) and preferable use amount thereof are described below.
  • heat radical polymerization initiators include organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetate peroxide, acetyl acetate peroxide, 1, 1-bis (t-butylperoxy)butane, 1, 1-bis (t-butylperoxy) cyclohexane,
  • One of these compounds may be used singly or two or more of them may be used in combination. It is preferable that the use amount of heat radical polymerization initiator be from 0.1 to 10 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • the curing group is a vinyl group or a (meth) acryloyl group It is preferable to use a heat radical polymerization initiator or a light radical polymerization initiator as a curing agent.
  • heat radical polymerization initiators include such organic peroxides as illustrated in the above (a) and azo compounds such as
  • One of these compounds may be used singly or two or more of them may be used in combination. It is preferable that the use amount of heat radical polymerization initiator be from
  • light radical polymerization initiators include acetophenone type initiators such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone,
  • 2-chlorothioxanthone 2-methylthioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2, 4-diisopropyl thioxanthone, isopropyl thioxanthone, l-chloro-4-propoxy thioxanthone and 2, 4-dichlorothioxanthone; ketone type initiators such as ⁇ -acyloxime ester, methyl phenyl glyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone and
  • the use amount of the light polymerization initiator be from 0.01 to 20 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • Preferred examples of amines include not only such diamine compounds as illustrated as usable for producing the triazine compound as represented by formula (1) by allowing reacting with the dihalotriazine compound as represented by formula (3) but also triamine compounds such as diethylene triamine, tetramine compounds such as triethylene tetramine, and melamines such as melamine, acetoguanamine and benzoguanamine .
  • triamine compounds such as diethylene triamine, tetramine compounds such as triethylene tetramine, and melamines such as melamine, acetoguanamine and benzoguanamine .
  • One of these compounds may be used singly or two or more of them may be used in combination.
  • carboxylic acids include dicarboxylic acids such as succinic acid, maleic acid, fumaric acid, adipic acid, tetrahydrophthalic acid, 1, 4-cyclohexane dicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid; tricarboxylic acids such as trimellitic acid and trimesic acid; tetracarboxylic acids such as pyromellitic acid,
  • the use amount of the curing agent be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • the acid anhydride is used as a curing agent, it is preferable to add a curing accelerator.
  • curing accelerators include amine type compounds such as benzyldimethylamine (BDMA) , l-benzyl-2-phenylimidazole, 2-heptadecylimidazole, 2-phenyl-4, 5-dihydroxyimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 4-diamino-6- [2-methylimidazolyl- (1) ] -ethy1-s-triazine, l-cyanoethyl-2-undecylimidazole, 2-ethyl-4-methylimidazole, 1, 8-diazabicyclo [5.4.0]undecene-7 and salts of these compounds; phosphine type compounds such as triphenyl phosphine, tris (2, 6-dimethoxyphenyl)phosphine and of these compounds; and organic metallic salts.
  • BDMA benzyldimethylamine
  • an onium salt as represented by formula (49) is preferably used. [A] h+ [X] h ⁇ (49)
  • [A] h+ represents an onium ion such as diphenyliodonium, 4-methoxydiphenyliodonium, bis(4-methyl phenyl) iodonium, bis (4-tert-butyl phenyl) iodonium, bis (dodecylphenyl) iodonium, triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl)phenyl) sulfonio) -phenyl] sulfid e or ⁇ 5-2, 4- (cyclopentadienyl) [1, 2, 3, 4, 5, 6- ⁇ - (methyl ethyl)benzene-iron (1+) ; and [X] h ⁇ represents a halogenated complex such as dipheny
  • One of these light cationic polymerization initiators may be used singly or two or more of them may be used in combination and, it is preferable that the use amount of the light cationic polymerization initiator be from 0.1 to 10 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • heat cationic polymerization initiator include metal chelate compounds such as aluminum trisacetylacetonate and sulfonium-salt compounds such as dialkyl benzyl sulfonium, benzyl-4-hydroxyphenyl methyl sulfonium, hexafluoroantimonate, benzyl-4-hydroxyphenyl-methyl-sulfonium, hexafluoroantimonate, benzyl-4-methoxyphenyl-methy1-sulfonium, hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenyl-methyl-sulfonium, hexafluoroantimonate and benzyl-3-chloro-4-hydroxyphenylmethyl-sulfonium.
  • metal chelate compounds such as aluminum trisacetylacetonate and sulfonium-salt compounds
  • dialkyl benzyl sulfonium such as aluminum tri
  • a compound having a functional group which can be added to the oxetane ring such as a carboxylic acid, an acid anhydride or the like may be used.
  • carboxylic acids and acid anhydrides include those as illustrated in the above (c) .
  • the use amount of the carboxylic acid or the acid anhydride be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • curing accelerators include onium salts such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide and triphenylbenzylphosphonium chloride; amines such as triethylamine, tributylamine,
  • One of these compounds may be used singly or two or more types may be used in combination.
  • the use amount of the curing accelerator be from 0.1 to 20 parts by mass based on 100 parts by mass of the triazine compound which is the resin (A) .
  • a compound having a functional group reactive with a carboxyl group or an acid anhydride group such as a multi-functional epoxy compound, an oxetane compound, an amine compound or an isocyanate compound.
  • epoxy resins include polyglycidyl ethers such as ethylene glycol diglycidyl ether, trimethyrol propane polyglycidyl ether and neopentyl glycol glycidyl ether; epoxy resins each having a triazine ring such as triglycidyl cyanurate and triglycidyl isocyanurate; a bisphenol A type epoxy resin; a bisphenol F type epoxy resin; an epoxy novolac resin; a phenol novolac type epoxy resin; and an ortho-cresol novolac type epoxy resin.
  • polyglycidyl ethers such as ethylene glycol diglycidyl ether, trimethyrol propane polyglycidyl ether and neopentyl glycol glycidyl ether
  • epoxy resins each having a triazine ring such as triglycidyl cyanurate and triglycidyl isocyanurate
  • One of these epoxy resins may be used singly or two or more types thereofmaybe used in combination. It is preferable that the use amount of the epoxy resin be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • any one of the compounds illustrated in the above (c) as examples of curing accelerators in an amount of from 0.1 to 20 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • i represents an integer of from 1 to 3
  • One of these oxetane compounds may be used singly or two or more types may be used in combination and it is preferable that the use amount of the oxetane compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • a curing accelerator be used.
  • Preferred examples of curing accelerators include those as illustrated as the curing accelerators in the above (d) and it is preferable that the use amount of the oxetane compound be from 0.1 to 20 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • Examples of amine compounds include those as illustrated as amine compounds usable in the above (c) .
  • One of these amine compounds may be used singly or two or more types thereof may be used in combination and it is preferable that the use amount of the amine compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • isocyanate compounds include such diisocyanate compounds as illustrated as usable for modifying the dihalotriazine compound as represented by formula (3) .
  • One of these isocyanate compounds may be used singly or two or more types of them may be used in combination and it is preferable that the use amount of the isocyanate compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • a compound having a functional group reactive with an amino group such as a multi-functional epoxy compound, an isocyanate compound, an acid anhydride or an ⁇ , ⁇ -unsaturated carbonyl compound.
  • epoxy compounds include those as illustrated as usable in above (d) .
  • One of these epoxy compounds may be used singly or two or more types thereof may be used in combination and it is preferable that the use amount of the epoxy resin compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • isocyanate compounds include those as illustrated as usable for modifying the dihalotriazine compound as represented by formula (3) .
  • One of these isocyanate compounds may be used singly or two or more types thereof may be used in combination. It is preferable that the use amount of the isocyanate compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • Examples of acid anhydrides include those as illustrated as usable in above (c) . One of these acid anhydrides may be used singly or two or more types thereof may be used in combination. It is preferable that the use amount of the acid anhydride be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • Examples of ⁇ , ⁇ -unsaturated carbonyl compounds include not only those as illustrated as usable for producing the triazine compound as represented by the above-descried general formula (1) by reacting with the triazine diol compound as represented by formula (4) but also poly(meth) acrylates such as (meth) acrylate of alkyl-modified dipentaerythritol,
  • ⁇ , ⁇ -unsaturated carbonyl compounds may be used singly or two or more types thereof may be used in combination. It is preferable that the use amount of the ⁇ , ⁇ -unsaturated carbonyl compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound, (g) In a case where the curing group is a thiol group It is preferable to use a polyene compound such as polybutadiene, polyisoprene or natural rubber as a curing agent . One of these polyene compounds may be used singly or two or more of them may be used in combination. It is preferable that the use amount of the polyene compound be from 5 to 200 parts bymass based on 100 parts bymass of the (A) triazine compound.
  • a compound having an active proton such as a multi-functional amine compound or a carboxylic acid compound or an acid anhydride.
  • Preferred examples of amine compounds include those as illustrated as usable in above (c) .
  • One of these amine compounds may be used singly or two or more types of them may be used in combination. It is preferable that the use amount of the amine compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • Examples of carboxylic acid compounds and acid anhydrides include those as illustrated as usable in above (c) .
  • One of these carboxylic acid compounds or acid anhydrides may be used singly or two or more of them may be used in combination. It is preferable that the use amount of the compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
  • the curable triazine composition according to the present invention not only the (A) triazine compound as represented by formula (1) and the -(B) curing agent but also, optionally, components such as a flame retardant and a reactive diluent may be blended.
  • flame retardant examples include non-halogen type flame retardants such as a phosphorous type flame retardant, a triazine compound such as melamine and an inorganic type flame retardant such as aluminum hydroxide.
  • a solvent is further blended therein to prepare the varnish thereof.
  • solvents for preparing varnish include amide type solvents such as N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone and
  • ether type solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether
  • sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone and sulfolane
  • ester type solvents such as ⁇ - butyrolactone, cellosolve acetate, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate
  • ketone type solvents such as cyclohexanone and methyl ethyl ketone
  • aromatic hydrocarbon type solvents such as toluene and xylene.
  • Particularly preferred among them are ether type solvents, sulfur-containing solvents, ester type solvents, ketone type solvents and aromatic hydrocarbon type solvents.
  • the use amount of the solvent be from 20 to 400 parts by mass based on 100 parts by mass of the sum total of the (A) triazine compound curing agent and the other components optionally added, such as flame retardant andreactive diluent.
  • Inorganic and/or organic fine particles to be used as the (D) component in the present invention are not particularly limited so long as they can be dispersed in the above-described composition which has been made into varnish as (C) component, to thereby form a paste.
  • inorganic fine particles examples include silica (SiO 2 ) , alumina (Al 2 Oj) , titania (TiO 2 ), tantalum oxide (Ta 2 Os) , zirconia (ZrO 2 ), silicon nitride (Si 3 N 4 ), barium titanate (BaO-TiO 2 ), barium carbonate (BaCOj) , lead titanate (PbO-TiO 2 ), lead zirconate titanate (PZT), leadlanthanum zirconate titanate (PLZT), gallium oxide (Ga 2 O 3 ) , spinel (MgO-Al 2 O 3 ) , mullite (3Al 2 O 3 -2SiO 2 ) / cordierite (2MgO-2Al 2 O 3 /5SiO 2 ) , talc ⁇ 3MgO-4SiO 2 -H 2 O) , aluminum titanate (TiO 2 -Al 2
  • Organic fine particles to be used according to the present invention is not particularly limited so long as they can be dispersed in the composition which has been made into varnish, to thereby form a paste.
  • Preferred examples of such organic fine particles are fine particles of heat resistant resins having an amide bond, an iraide bond, an ester bond or an ether bond.
  • heat resistant resins from the viewpoint of heat resistance and mechanical properties, polyimide resins or precursors thereof, polyamidoiiaide resins or precursors thereof and fine particles of polyamide resins are preferably used.
  • Organic fine particles to be used in the curable triazine resin composition having thixotropic properties according to the present invention are insoluble in solvent.
  • (B) curing agent according to the present invention may form a uniform layer containing the above-described curable triazine compound and the organic fine particles after cured with heat.
  • inorganic and/or organic fine particles having an average particle diameter of 50 ⁇ m or less and a maximum diameter of 100 ⁇ m or less are preferably used.
  • the average particle diameter exceeds 50 ⁇ m, it is difficult to obtain a paste having a thixotropic coefficient of 1.1 ormore which is describedbelow, while, when themaximum particle diameter exceeds 100 ⁇ m, appearance and adhesiveness of coated film obtained by using such particles tend to be insufficient.
  • the present invention as method for dispersing the inorganic and/or organic fine particles in varnish, roll kneading, mixer blending or the like as is conventionally employed in the technical field of coating may be used, and any dispersion method may be employed so long as the particles can be dispersed sufficiently.
  • viscosity at.25°C of the resin composition for electronic components having thixotropic properties be from 0.5 to 500 Pa-s when measured by a rotational viscometer and that the thixotropic coefficient be 1.1 or more.
  • the viscosity of the paste is expressed in terms of a viscosity at 5 rpm measured by using an E-type viscometer (EHD-R; Rotor N: 0.7; manufactured by Tokimec Inc.) .
  • the thixotropic coefficient (TI value) of the paste is expressed in terms of a ratio of an apparent viscosity ⁇ .5 at rotation of 0.5 rpm to an apparent viscosity ⁇ 5 at rotation of 5 rpm, namely, ⁇ .5/ ⁇ 5, as measured in the same manner as in the above.
  • the amount of the inorganic and/or organic fine particles to be blended as (D) component be in the range of from 1 to 90 parts by mass based on 100 parts by mass of the varnish as the (C) component.
  • the amount is less than the above-described range, the viscosity and the thixotropic coefficient of the resin composition become low and, further, the composition becomes threadier and more of the composition tends to flow out after printing, which causes the film to be thinner.
  • the amount is more than the above-described range, since theviscosity and the thixotropic coefficient become high, the transcriptability to the basematerial is deteriorated and, at the same time, the number of voids andpinholes in the printed film tend to be increased.
  • Fig.1 is a chart showing 1 H-NMR analysis ⁇ solvent : heavy chloroform) results of the powdery resin obtained in Example 2.
  • Fig.2 is a chart showing 13 C-NMRanalysis (solvent : heavy chloroform) results of the powdery resin obtained in Example 2.
  • the substrate having a cured film thereon obtained in (1-3) was rinsedwith ion-exchangedwater, subjected to an acid degreasing treatment with an ICP Clean 91 (available fromOkuno Chemical Industries Co., Ltd.) for 1 minute at 30 0 C, rinsed with ion-exchangedwater, subjected to pickling treatment with a 10% sulfuric acid for 1 minute at 30 °c and, then rinsed with ion-exchanged water.
  • ICP Clean 91 available fromOkuno Chemical Industries Co., Ltd.
  • the resultant substrate was dipped for 3 minutes in a beaker which contained TINPOSIT LT-34 (tin plating solution; available from Rohiii & Haas) heated at 70 0 C and then, dipped in ion-exchanged water for 3 minutes at 70 "C. Subsequently, the substrate was subjected to thermal treatment in a box oven for 100 minutes at 120 0 C. In the resultant plated substrate, slight creeping of plating was observed, however, no discoloration of the cured film or the copper foil was observed.
  • TINPOSIT LT-34 titanium plating solution
  • the powdery resin was subjected to thermogravimetric analysis (TGAmethod) and the temperature for 5% weight loss was 315 0 C.
  • the powdery resin was subje6 ' ted to thermogravimetric analysis (TGA method) and- ' the temperature for 5% weight loss was 289 0 C.
  • the mixture was heated while stirring and the heating was stopped when the temperature was enhanced to 60 °C. Then, 0.16 g of dibutyl tin laurate was added thereto. When the temperature inside the reaction container began decreasing, the heating was resumed and stirring was continued while maintaining the temperature to be 80 °C. The reaction was terminated when disappearance of the absorption of isocyanate group at 2280 cm "1 was confirmed in the infrared absorption spectrum, to thereby obtain a viscous liquid urethane acrylate compound.
  • the number average molecular weight of the urethane acrylate was 250,000, the acid value was 40 mgKOH/g, and the solid content was 50 % by mass.
  • the urethane acrylate and an epoxy resin PRODUCT
  • NAMErEPIKOTE 828 manufactured by JAPAN EPOXY RESINS, CO., LTD.
  • melamine NAMErEPIKOTE 828, manufactured by JAPAN EPOXY RESINS, CO., LTD.
  • NAMErEPIKOTE 828 were blended together so that the blending ratio of epoxy group against carboxy group was 1.1 equivalent, and further melamine (NISSAN CHEMICAL INDUCTRIES, LTD.) was added thereto at an amount of 8 parts by mass based on 100 parts by mass of the epoxy resin, to thereby obtain a curable resin composition.
  • the curable triazine composition obtained according to the present invention gives cured products excellent in thermal resistance, resistance to the tin-plating and the like and can favorablybe used as sealingmaterial for electronic components and/or varnish for electronic components.

Abstract

The invention relates to a curable triazine composition used as sealing material or varnish for electronic components, comprising a triazine compound represented by formula (1): (the symbols have the same meaning as defined in the Description), wherein part or all of the n X1’s have a group curable by heat or light, production method thereof and a cured product thereof excellent in heat resistance and resistance against tin plating.

Description

DESCRIPTION
CURABLE TRIAZINE COMPOSITION FOR ELECTRONIC COMPONENTS, PRODUCTION METHOD THEREFOR AND CURED PRODUCT THEREOF
CROSS-REFERENCE TO THE RELATED APPLICATIONS
This is an application filed pursuant to 35 U.S.C.
Section 111 (a) with claiming the benefit of U.S. provisional application Serial No. 60/599,882 filed August 10, 2004 under the provision of35U.S.C. Ill (b) , pursuant to 35 U.S.C. Section
119(e) (1) .
TECHNICAL FIELD
The present invention relates to a curable triazine composition containing a triazine compound which can be cured with heat or light, which is used for sealing material and varnish for electronic components, a production method therefor and a cured product thereof.
BACKGROUND ART
In recent years, in the field of electronic components, there is an increasing demand for a material having not only properties such as heat resistance and electric properties which have conventionally been considered as essential, but also resistance to lead-free soldering or tin-plating.
With respect to sealing material for electronic components such as insulating protective film, a curable resin composition obtained by blending a photo-polymerization initiator, a heat-curable resin, a diluent and the like with a photo-sensitive polymer such as urethane (meth) acrylate compound is disclosed as an example of material to make up for deficiency in the properties of conventional epoxy (meth) acrylate resins and melamine resins (in JP-A-2004-062057) , however, its low resistance to tin-plating is disadvantageous. On the other hand, triazine resins such as a polycyanurate resin, a polythiocyanurate resin and a polyguanamine resin each having a triazine skeleton in the structure thereof are known as resin excellent in heat resistance and flame retardance. As examples of such resins, polycyanurate resin and polyguanamine resin are described in JP-A-10-287745, and polythiocyanurate resin is described in JP-A-2002-47345. However, these triazine resins do not have a curable group as is used in the present invention.
Further, although a triazine resin having an allyl group as a curable group is described and a composition curable with electron beam is disclosed in JP-A-S60-91349, a curable triazine composition containing a triazine compound curable with heat or light, used for sealing material for electronic components and varnish for electronic components as in the present invention, is not described.
DISCLOSURE OF THE INVENTION
According to the present invention, there are provided a triazine compound and a triazine composition, curable with heat or light, used for sealing material and varnish for electronic components, which can give a cured product excellent in heat resistance, electric properties, flame retardance and resistance against tin plating, especially excellent in heat resistance and resistance against tin plating, and a production method therefor.
According to the present invention, the following are provided.
1. A curable triazine composition, comprising (A) a triazine compound represented by formula (1) :
Figure imgf000004_0001
wherein R1 each independently represents a divalent organic group, X1 each independently represents a monovalent organic group, X2 represents an oxygen atom, a sulfur atom or a group represented by formula (2) :
Figure imgf000004_0002
wherein R2 represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an aryl group or an aralkyl group; and n represents an integer of from 2 to 100, wherein part or all of n Xlfs in the triazine compound have curable groups capable of being cured with heat or light, and comprising (B) a curing agent.
2. The curable triazine composition as described in 1, which is obtained by blending a curing agent in a triazine compound obtained by reacting one or more types of dihalotriazine compounds represented by formula (3) with one or more types selected from compounds each having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups or phenolic hydroxyl groups in one molecule: X1 N^N (3)
X3 ^N"^X3
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light, and X3 represents a halogen atom.
3. The curable triazine composition as described in 1, which is obtained by blending a curing agent in a triazine compound obtained by reacting one or more types of triazine dithiol compounds represented by formula (4) with one or more types of compounds represented by formula (5) :
Figure imgf000005_0001
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light:
X4^-X4 (5) wherein R1 represents a divalent organic group, and X4 represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group.
4. The curable triazine composition as described in 1, which is obtained by blending a curing agent in a triazine compound obtained by reacting one or more types of triazine dithiol compounds represented by formula (4) with one or more types of bifunctional α, β-unsaturated carbonyl compounds:
X1
(4)
HS N ^SH
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light. 5. The curable triazine composition as described in 1, wherein the n Rlfs in formula (1) represent at least one group selected from those represented by formulae (6) to (9) and (55) to (57) :
Figure imgf000006_0001
wherein R3, R4, R5 and R6 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having from 1 to 12 carbon atoms, an aralkyl group, a perfluoroalkyl group, a cyclohexyl group or a phenyl group;
Figure imgf000007_0001
wherein the four R7's each independently represent a hydrogen atom or a methyl group,
Figure imgf000007_0002
wherein the four R30' s each independently represent a hydrogen atom or a methyl group,
Figure imgf000007_0003
wherein the four R31 ' s each independently represent a hydrogen atom or a methyl group,
Figure imgf000007_0004
wherein the four R32's each independently represent a hydrogen atom or a methyl group. 6. The curable triazine composition as described in 1, wherein the n R1' s in formula (1) represent at least one group selected from those represented by formulae (58) to (60) .
Figure imgf000008_0001
7. The curable triazine composition as described in 1, wherein part or all of the X1' s represent a monovalent organic group having at least one group selected from among allyl group, vinyl group, (meth) acryloyl group, epoxy group, oxetanyl group, carboxyl group, acid anhydride group, amino group, thiol group and isocyanate group which may be blocked.
8. The curable triazine composition as described in 1, wherein part or all of the X1' s have an allyl group, and wherein the curing agent comprises an organic peroxide.
9. The curable triazine composition as described in 1, wherein part or all of the X1' s have a (meth) acryloyl group, and wherein the curing agent is an azo compound.
10. The curable triazine composition as described in 1, wherein part or all of the X1' s have an epoxy group, and wherein the curing agent comprises a polyfunctional compound of an amine, a carboxylic acid or an acid anhydride.
11. The curable triazine composition as described in 1, wherein part or all of the X1' s have an oxetanyl compound, and wherein the curing agent comprises an onium salt represented by formula (49) , [A]h+[X]h~ (49)
wherein [A]h+ represents an onium ion, [X]h" represents an anion, and h represents an integer.
12. The curable triazine composition as described in 1, wherein part or all of the X1' s have a carboxyl group or an acid anhydride, and wherein the curing agent comprises a polyfunctional compound of an epoxy compound, an oxetane compound, an amine compound or an isocyanate compound.
13. The curable triazine composition as described in 1, wherein part or all of the X1' s have an amino group, and wherein the curing agent comprises a polyfunctional compound of an epoxy compound, an isocyanate compound, an acid anhydride or an α, β-unsaturated carbonyl compound.
14. The curable triazine composition as described in 1, wherein part or all of the X1' s have a thiol group, and wherein the curing agent comprises a polyene compound.
15. The curable triazine composition as described in 1, wherein part or all of the X1' s have an isocyanate group which may be blocked, and wherein the curing agent comprises a polyfunctional compound of an amine compound or a carboxylic compound or an acid anhydride.
16. The curable triazine composition as described in 1, further containing a solvent.
17. The curable triazine composition as described in 16, wherein the solvent is at least one kind selected from the group consisting of ether solvent, sulfur-containing solvent, ester solvent, ketone solvent and aromatic hydrocarbon solvent.
18. The curable triazine composition as described in 16, wherein organic or inorganic fine particles are blended in. 19. The curable triazine composition as described in 18, wherein the organic or inorganic particulate substance is at least one kind selected from the group consisting of silica (SiO2), alumina (AI2O3) , titania (TiO2), tantalum oxide (Ta2O5), zirconia (ZrO2), silicon nitride (Si3N4), barium titanate (BaO-TiO2) , barium carbonate (BaCO3) , lead titanate (PbO-TiO2) , lead zirconate titanate (PZT) , lead lanthanum zirconate titanate (PLZT) , gallium oxide (Ga2O3) , spinel (MgO-Al2O3) , mullite (3Al2O3-2SiO2) , cordierite (2MgO-2Al2O3/5SiO2) , talc -(3MgO-4SiO2-H2O) , aluminum titanate (TiO2-Al2O3), zirconia containing yttria (Y2O3-ZrO2) , barium silicate (BaO-8SiO2) , boron nitride (BN), calcium carbonate (CaCO3), calcium sulfate (CaSO4) , zinc oxide (ZnO), magnesium titanate (MgO-TiO2), barium sulfate (BaSO4), organic bentonite, carbon (C), polyimide resin or its precursor, polyamideimide resin or its precursor and polyamide resin.
20. The curable triazine composition as described in 19, wherein the average particle size of the organic or inorganic particulate substance is 50 μm or less.
21. The curable triazine composition as described in any one of 18 to 20, having a viscosity of 0.5 to 500 Pa-s at 25 0C and a thixotropic coefficient of 1.1 or more.
22. A method for producing a curable triazine composition, wherein a curing agent is blended in a triazine compound obtained by reacting one or more types of dihalotriazine compounds represented by formula (3) with one or more types selected from compounds each having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups or phenolic hydroxyl groups in one molecule:
Figure imgf000011_0001
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light, and X3 represents a halogen atom. 23. A method for producing a curable triazine composition, wherein a curing agent is blended in a triazine compound obtained by reacting one or more types of triazine dithiol compounds represented by formula (4) with one or more types of compounds represented by formula (5) :
X1
N^N (4) HS N^SH
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light:
X'-R'-X4 (5) wherein R1 represents a divalent organic group, and X4 represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group.
24. A method for producing a curable triazine composition, wherein a curing agent is blended in a triazine compound obtained by reacting one or more types of triazine dithiol compounds represented by formula (4) with one or more types of bifinctional α,β-unsaturated carbonyl compounds: X1
N^N (4)
HS N^SH
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light. 25. A triazine compound represented by formula (1),
Figure imgf000012_0001
wherein R1 each independently represents a divalent organic group, X1 each independently represents a monovalent organic group, X2 represents an oxygen atom, a sulfur atom or a group represented by formula (2),
Figure imgf000012_0002
wherein R2 represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an aryl group or an aralkyl group; and n represents an integer of from 2 to 100, in which part or all of n X1' s present in the triazine compound have groups curable with heat or light, the divalent organic group represented by R1 is an organic group represented by formula (58), (59) or (60),
Figure imgf000013_0001
the monovalent organic group represented by X1 is an organic group having an ethylenic carbon-carbon double bond, and X2 is an oxygen atom or a sulfur atom. 26. A cured product obtained by curing the curable triazine composition as described in any one of 1 to 21. 27. A sealing material for electronic component comprising the curable triazine composition as described in any one of 1 to 21. 28. A varnish for electronic component comprising the curable triazine composition as described in any one of 1 to 21.
EFFECTS OF THE INVENTION The curable triazine composition according to the present invention provides a cured product excellent in heat resistance, electric properties, flame retardance, resistance against tin plating and the like and can favorably be used as sealing material or varnish for electronic components.
DETAILED DESCRIPTION OF THE INVENTION
The triazine composition according to the present invention contains (A) a triazine compound represented by formula (1) and (B) a curing agent.
Figure imgf000014_0001
In formula (1), R1 represents a divalent organic group. Preferred examples of Rlfs include an alkylene group having from 1 to 12 carbon atoms, an alkenylene group having from 1 to 12 carbon atoms, an alkynylene group having from 1 to 12 carbon atoms, a cycloalkylene group, an arylene group, an aralkylene group and groups represented by formulae (6) to (46) :
Figure imgf000014_0002
wherein R3, R4, R5 and R6 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having from 1 to 12 carbon atoms, an aralkyl group, a perfluoroalkyl group, a cyclohexyl group or a phenyl group.
Figure imgf000015_0001
wherein R7 represents a hydrogen atom or a methyl group, the R7' s may be the same with or different from one another;
Figure imgf000015_0002
wherein R8 and R9 each independently represent a hydrogen atom or a methyl group, k and m each independently represent 0 or an integer and the relationship of k and m is l≤k+m<18. -(CH2CH2O)PCH2CH2- (15) wherein p represents an integer of from 1 to 50;
-(CH2CH2CH2θ)qCH2CH2CH2- (16) wherein q represents an integer of from 1 to 50 ;
-(CH2CH2CH2CH2O)rCH2CH2CH2- (17) wherein r represents an integer of from 1 to 50 ;
-R10-O-(CO-O-R10-O)s-CO-O-R10- (18) wherein R10 represents a divalent organic group, wherein Preferred examples of R10' s include an alkylene group having from 1 to 12 carbon atoms, a cycloalkylene group, an alkenylene group, an arylene group, an aralkylene group or groups represented by (10) to (17) and s represents an integer of from 1 to 50;
-R11-O-(CO-R12-COO-R11-O),-CO-R12-COO-R11- (19) wherein R11 and R12 each independently represent a divalent organic group, wherein preferred examples of Ru's and R12's include an alkylene group having from 1 to 12 carbon atoms, a cycloalkylene group, an alkenylene group, an arylene group, an aralkylene group or groups represented by the above-described formulae (10) to (17) and t represents an integer of from 1 to 50;
Figure imgf000016_0001
wherein u represents an integer of from 1 to 50;
Figure imgf000017_0001
wherein v represents an integer of from 1 to 50;
Figure imgf000017_0002
wherein w and x each independently represent 0 or an integer and the relationship of x and x is l<w+x<50;
Figure imgf000017_0003
wherein y represents an integer of 1 to 50;
Figure imgf000017_0004
wherein z represents an integer of from 1 to 50;
Figure imgf000018_0001
Figure imgf000018_0002
wherein R13 represents a hydrogen atom or a methyl group, the R13' s may be the same with or different from each other;
Figure imgf000018_0003
« ^-0-(CHz)8-O-Vv # (33) wherein a represents an integer of from 1 to 5 ;
Figure imgf000019_0001
wherein R14 represents a hydrogen atom or a methyl group, the R14' s may be the same with or different from each other;
Figure imgf000019_0002
wherein R15 represents a hydrogen atom or a methyl group, the R15' s may be the same with or different from each other;
Figure imgf000019_0003
wherein R16 represents a hydrogen atom or a methyl group, the R16' s may be the same with or different from each other;
Figure imgf000019_0004
wherein R17 represents a hydrogen atom or a methyl group, the R17' s may be the same with or different from each other;
Figure imgf000020_0001
wherein R18, R19 and R20 each independently represent a hydrogen atom or a methyl group, b and c each independently represent 0 or an integer and the relationship of b and c is 2<b+c≤20;
Figure imgf000020_0002
wherein R21 represents a hydrogen atom or a methyl group, the R21' s may be the same with or different from each other and d represents an integer of from 1 to 50;
Figure imgf000020_0003
wherein R22 represents a hydrogen atom or a methyl group, the R22' s may be the same with or different from each other and e represents an integer of from 1 to 50;
Figure imgf000020_0004
wherein R23 represents a hydrogen atom or a methyl group, the R23' s may be the same with or different from each other and f represents an integer of from 1 to 50;
Figure imgf000021_0001
wherein R24 represents a hydrogen atom or a methyl group, the R24' s may be the same with or different from each other, R25 represents an alkylene group having from 1 to 12 carbon atoms, an alkenylene group, an alkynylene group, a cycloalkylene group, an aralkylene group or a group represented by any one of the above-described formulae (10) to (17), and g represents an integer of from 1 to 50;
Figure imgf000021_0002
wherein R >26 represents a hydrogen atom or a methyl group, the
R ,26,'s may be the same with or different from each other, and u represents an integer of from 1 to 50;
Figure imgf000021_0003
wherein R27 represents a hydrogen atom or a methyl group, the R27's may be the same with or different from each other, and v represents an integer of from 1 to 50;
Figure imgf000022_0001
wherein R28 represents a hydrogen atom or a methyl group, the R28's may be the same with or different from each other and w and x each independently represent 0 or an integer and the relationship of w and x is l≤w+x≤50;
Figure imgf000022_0002
wherein R29 represents a divalent organic group and preferably represents an alkylene group having from 1 to 12 carbon atoms, an arylene group, an aralkylene group or a group represented by any one of the above-described (10) to (33) .
These "n" number of substituents (specific examples of R1) in formula (1) may be one type or a combination of two or more types.
In formula (1) , X1 represents a monovalent organic group and a part or all of such Xlfs are groups each containing a curable group capable of being cured with heat or light. Preferred examples of curable group include an allyl group, a vinyl group, a (meth)acryloyl group, an epoxy group, an oxetanyl group, a carboxyl group, an acid anhydride group, an amino group, a thiol group and an isocyanate group which may be blocked. Specific preferred examples of X1 containing an allyl group include an allyloxy group, an allylamino group, a diallylamino group and an allyloxyalkyl group. Specific preferred examples of X1 containing a vinyl group include (2-vinyloxy) ethyloxy group and (4-vinyloxy) cyclohexyloxy group. Specific preferred examples of X1 containing a (meth) acryloyl group include 2- (meth) acryloyl ethyloxy group. Specific preferred examples of X1 containing an epoxy group include a glycidyloxy group. Specific preferred examples of X1' containing an oxetanyl group include
(3-ethyl-3-oxetanyl)methyloxy group. Specific preferred examples of X1 containing a carboxyl group include l-carboxy-3-methylpropylamino group, 1-carboxyethylamino group, 2-carboxyethylamino group, 1, 2-dicarboxyethylamino group,
[1-carboxy- (4-hydroxyphenyl) ethyl] amino group,
(carboxymethyl) amino group,
2- (3-carboxypropanoyloxy) ethyloxy group,
2- (3-carboxy-2-propenoyloxy) ethyloxy group, 2- (2-carboxybenzoyloxy) ethyloxy group,
2- (2, 4-dicarboxybenzoyloxy) ethyloxy group and 2- (2, 5-dicarboxybenzoyloxy) ethyloxy group. Specific preferred examples of X1 containing an acid anhydride group include 2- [2, 4, 5-tricarboxy-4, 5-anhydrobenzoyloxy] ethyloxy group. Specific preferred examples of X1 containing an amino group include (2-aminoethyl) amino group,
(4-aminophenyl) amino group and (3-aminophenyl) amino group. Specific preferred examples of X1 containing a thiol group include (2-mercaptoethyl) thio group. Specific preferred examples of X1 containing an isocyante group which may be blocked include isocyanate compound as represented by formula (47) and blocked compounds thereof.
Figure imgf000024_0001
One of these compounds as X1 may be used singly or two or more types may be used in combination.
Further, a part of X^s may be a group which does not contain a curable group. Preferred examples of such an X1 include an alkoxy group having from 1 to 6 carbon atoms, a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2-methoxyphenoxy group, a 4-methoxyphenoxy group, a benzyloxy group, a diethylamino group, a diisopropylamino group, diphenylamino group, a benzylamino group and a thiophenoxy group. One of these groups can be used singly or two or more kinds of them may be used in combination.
In the curable triazine composition according to the present invention, it is preferable that the amount of X1 having a curable group is 5 % by mol or more in the total amount of X^s contained in the triazine compound as represented by formula (1) . When X1 is less than 5 % by mol, curability is deteriorated.
In formula (1), X2 represents an oxygen atom, a sulfur atom or a group represented formula (2) :
Figure imgf000024_0002
In formula (2) , R2 represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an aryl group or an aralkyl group. Preferred examples of R2 include a methyl group, an ethyl group, a phenyl group and a benzyl group. One of these groups may be used singly or two or more types may be used in combination.
In formula (1) , n represents an integer of from 2 to 100, preferably 2 to 50, and more preferably 5 to 30. When n is 1, cross-linking density of an cured product obtained by curing the triazine compound as represented by formula (1) is low and characteristics such as heat resistance are deteriorated, while it is difficult to produce a compound in which n is more than 100.
The triazine compound as represented by formula (1) can be obtained, for example, by reacting a dihalotriazine compound as represented by formula (3) with a compound having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups or phenolic hydroxyl groups in one molecule, such as at least one type selected from a group of compounds consisting of a diol compound, a dithiol compound, a diamine compound, a bifunctional phenolic compound and a bifunctional thiophenolic compound (hereinafter simply referred to as "diol compound (s) and the like".
Figure imgf000025_0001
In formula (3), X1 represents the same groups as defined in formula (1) . Further, X3 represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom is preferred from the standpoint of easy availability of a raw material thereof.
The dihalotriazine compound as represented by formula (3) can be obtained, for example, by reacting a cyanuric halide such as cyanuric chloride with at least one compound selected from a group of compounds consisting of an alcoholic compound, a thiol compound, an amine compound, a phenolic compound and a thiophenolic compound (hereinafter, simply referred to as "alcoholic compound(s) and the like") .
Preferred examples of alcoholic compound usable for the reaction with cyanuric halide include methanol, ethanol, isopropanol, allyl alcohol, glycidol, ethylene glycol, ethylene glycol monovinyl ether, 1, 4-butanediol monovinyl ether, cyclohexane dimethanol monovinyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 3-ethyl-3-hydroxymethyl oxetane.
Preferred examples of thiol compounds usable for the reaction with the cyanuric halide include 1, 2-propanedithiol .
Preferred examples of amine compounds usable for the reaction with the cyanuric halide include diethylamine, diisopropylamine, diallylamine, allyl-methyl-amine,
N-methylaniline, valine, alanine, β-alanine, aspartic acid and glycine.
Preferred examples of phenolic compounds usable for the reaction with the cyanuric halide include phenol, o-cresol, m-cresol, p-cresol, p-methoxyphenol, α-naphthol, β-naphthol, 4-hydroxybiphenyl and 2-hydroxybiphenyl.
Preferred examples of thiophenolic compounds usable for the reaction with the cyanuric halide include thiophenol.
The reaction of the cyanuric halide with the alcoholic compound and the like can efficiently be performed using bases .
On this occasion, it is preferable that the use amount of the alcoholic compound and the like be 1.0 to 20 mol based on 1 mol of cyanuric halide, from the standpoint of reaction yield, economical efficiency or the like.
Preferred examples of base usable in the reaction include inorganic bases such as alkali hydroxide, alkali carbonate, alkali hydrogen carbonate, alkali fluoride, alkali hydride and alkali metal, and organic bases such as pyridine, derivatives thereof and aliphatic tertiary amine. Examples of alkali hydroxide include sodium hydroxide and potassium hydroxide. Examples of alkali carbonate include sodium carbonate and potassium carbonate. Examples of alkali hydride include sodium hydride. Examples of alkali metal include metallic sodium. Examples of aliphatic tertiary amine include triethylamine and tri-n-propylamine. As for the bases, from the standpoint of the reaction rate and the economical efficiency, when a monovalent base is used, it is preferable that the use amount be from 0.5 to 30 mol and, more preferably, from 1.0 to 20 mol based on 1 mol of cyanuric halide, and when a divalent base is used, it is preferable that the use amount be from 0.25 to 15 mol and, more preferably, from 0.5 to 10 mol based on 1 mol of cyanuric halide. Further, the alkali hydroxide or the alkali carbonate may be added to the reaction system as an aqueous solution. On this occasion, it is preferable that the concentration of the alkali hydroxide or the alkali carbonate in the solution be in the range of from 10 to 70 % by mass.
The reaction temperature of the reaction is preferably from -20 to 150 0C from the standpoint of the reaction rate and prevention of a side reaction and, when a base is added, it is preferable to add the base at such a speed that the above-described temperature range can be maintained. The reaction pressure is not particularly limited and any of normal pressure, an increased pressure or a reduced pressure may be used. The reaction time is ordinarily from 1 to 30 hours. Further, the whole amount of the cyanuric halide may be added at a time, or the amount may be divided into several portions so that the cyanuric halide may be added portionwise to the reaction mixture. On this occasion, it is also preferable to add the cyanuric halide in such a manner that the above-described reaction temperature range may be maintained. Although the reaction can be performedwithout a solvent, it is preferable to perform the reaction in an appropriate reaction solvent. Preferred examples of reaction solvents include aromatic hydrocarbons such as toluene and xylene, ethers such as tetrahydrofuran, dibutyl ether and 1, 4-dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbon solvents such as chloroform and dichloromethane, and aprotic polar solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidone and dimethyl sulfoxide. One of these solvents may be used singly or two or more of them may be used in combination. From the reaction efficiency, economical efficiency and the like, an amount (entire amount) thereof to be used is preferably from 300 mL to 10 L based on 1 mol of cyanuric halide. In the reaction, when an aqueous solution of an inorganic base is used as a base and an reaction solvent immiscible with this aqueous solution of the inorganic base is used, it is also preferable to use a phase-transfer catalyst for the purpose of promoting the reaction. Preferred examples of phase-transfer catalyst usable in the reaction include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetramethylammoniuiu sulfate, benzyltriethylammonium chloride, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide and cetyltributylammonium bromide; quaternary phophonium salts such as tetrabutylphosphonium bromide and cetyltributylphosphonium bromide; crown ethers such as 15-crown-5, 18-crown-6, benzo-18-crown-6, dibenzo-18-crown-6 and dibenzo-24-crown-8; and cryptands such as cryρtand[2, 2, 2] . One of these phase-transfer catalysts may be used singly or two or more of them may be used in combination.
When the reaction is performed, a polymerization inhibitor may optionally be added. Preferred examples of polymerization inhibitors include monophenolic compounds such as hydroquinone, 2, 6-di-t-butyl-p-cresol, butylated hydroxyanisole and 2, 6-di-t-butyl-4-ethylphenol stearyl-β- (3, 5-di-t-butyl-4-hydroxyphenyl)propionate; bisphenolic compounds such as
2,2' -methylenebis (4-methyl-6-t-butylphenol) , 4,4' -thiobis (3-methyl-6-t-butylphenol) and 4,4' -butylidenebis (3-methyl-6-t-butyl phenol) ; macromolecular phenolic compounds such as 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5, -di-t-butyl-4-hydroxybenzyl ) -benzene, tetrakis [methylene-3- (3' ,5' -di-t-butyl-4' -hydroxyphenyl) pr opionate]methane, tris (3' , 5' -di-t-butyl-4' -hydroxybenzyl) -s-triazine-2, 4, 6- ( IH, 3H, 5H) trione and tocopherol; sulfur compounds such as phenothiazine, dilauryl 3, 3' -thiodipropionate, dimyristyl 3, 3' -thiodipropionate and distearyl 3, 3' -thiodipropionate; and phosphorous compounds such as triphenyl phosphite, diphenyl isodecyl phosphite and phenyl diisodecyl phosphite. One of these polymerization inhibitors may be used singly or two or more of them may be used in combination.
The thus-obtained dihalotriazine compounds may be used as they are or after optionally subjected to any one of an acid anhydride modification, an acid chloride modification, a diisocyanate modification, an epichlorohydrin modification and a subsequent dehydrochloric acid reaction, oxidation-epoxidation of an olefin and the like.
Preferred examples of acid anhydrides to be used in the above treatments include dicarboxylic anhydrides such as succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride and phthalic anhydride; tricarboxylic anhydrides such as trimellitic anhydride; and tetracarboxylic acid dianhydrides such as pyromellitic acid dianhydride, 3, 3' , 4, 4' -biphenyl tetracarboxylic acid dianhydride, 2, 2' , 3, 3' -bisphenyl tetracarboxylic acid dianhydride, 2, 2' , 3, 3' -biphenyl tetracarboxylic acid dianhydride, 2, 3, 3' 4' -biphenyl tetracarboxylic acid dianhydride, 2, 2-bis (3, 4-dicarboxyphenyl)propane dianhydride, 1, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl)methane dianhydride, bis (3, 4-dicarboxyphenyl)methane dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 3, 4, 9, 10-perylene tetracarboxylic acid dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, benzene-1, 2, 3, 4-tetracarboxylic acid dianhydride, 3, 4, 3' , 4' -benzophenone tetracarboxylic acid dianhydride, 2, 3, 2' , 3' -benzophenone tetracarboxylic acid dianhydride, 2, 3, 3' , 4' -benzophenone tetracarboxylic acid dianhydride, 1, 2, 5, 6-naphthalene tetracarboxylic acid dianhydride, 2, 3, 6, 7-naphthalene tetracarboxylic acid dianhydride, 1, 2, 4, 5-naphthalene tetracarboxylic acid dianhydride, 1, 4, 5, 8-naphthalene tetracarboxylic acid dianhydride, 2, 6-dichloronaphthalene-l, 4, 5, 8-tetracarboxylic acid dianhydride, 2, 7-dichloronaphthalene-l, 4, 5, 8-tetracarboxylic acid dianhydride,
2,3,6, 7-tetrachlornaphthalene-l, 4, 5, 8-tetracarboxylic acid dianhydride, phenanthrene-1, 8, 9, 10-tetracarboxylic acid dianhydride, bis (3, 4-dicarboxyphenyl) -dimethyl-silane dianhydride, bis (3, 4-dicarboxyphenyl)methyl phenyl silane dianhydride, bis (3, 4-dicarboxyphenyl) diphenyl silane dianhydride, 1, 4-bis (3, 4-dicarboxyphenyl (dimethyl) silyl)benzene dianhydride, 1, 3-bis (3, 4-dicarboxyphenyl) -1,1,3, 3-tetramethyl dicyclohexane dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2, 2-bis{4- (3, 4-dicarboxypheno) phenyl}hexafluoropropane dianhydride,
2,2-bis{4-(3, 4-dicarboxypheno)phenyl}propane dianhydride, 4, 4-bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1, 4-bis (2-hydroxyhexafluoroisopropyl)benzenebis (trimellita te anhydride) , 1, 3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellita te anhydride) , 1, 2- (ethylene) bis (trimellitate anhydride) , 1, 3- (trimethylene)bis (trimellitate anhydride) , 1, 4- (tetramethylene)bis (trimellitate anhydride) , 1, 5- (pentamethylene)bis (trimellitate anhydride) , 1, 6- (hexamethylene)bis (trimellitate anhydride), 1, 7- (heptamethylene)bis (trimellitate anhydride) , 1, 8- (octamethylene)bis (trimellitate anhydride) , 1,9- (nonamethylene)bis (trimellitate anhydride) , 1,10- (decamethylene)bis (trimellitate anhydride) , 1, 12- (dodecamethylene)bis (trimellitate anhydride),
1,16- (hexadecamethylene)bis (trimellitate anhydride) , 1,18- (octadecamethylene)bis (trimellitate anhydride) , ethylene tetracarboxylic dianhydride, 1,2,3, 4-butane-tetracarboxylic dianhydride, pyrazine-2, 3, 5, 6-tetracarboxylic dianhydride, thiophene-2, 3, 4, 5-tetracarboxylic dianhydride, decahydronaphthalene-1, 4, 5, 8-tetracarboxylic dianhydride, 4, 8-dimethyl-l, 2,3,5, 6, 7-hexahydronaphthalene-l, 2, 5, 6-tetr acarboxylic dianhydride, cyclopentane-1, 2, 3, 4-tetracarboxylic dianhydride, pyrrolidine-2, 3, 4, 5-tetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, bis{exo-bicyclo- [2.2. l]heptane-2, 3-dicarboxylic anhydride}sulfone, bicyclo- [2.2.2]oct (7) -ene-2, 3, 5, 6-tetracarboxylic dianhydride,
5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane-l, 2-di carboxylic anhydride and tetrahydrofuran-2, 3, 4, 5-tetracarboxylic dianhydride. Further, as for preferable examples of acid chlorides, trimellitic anhydride chloride can be mentioned. Preferred examples of diisocyanates include aromatic diisocyanate compounds such as diphenyl methane-2, 4' -diisocyanate,
3,2'-, 3,3'-, 4,2'-, 4,3'-, 5,2'-, 5,3'-, 6,2'- or 6, 3' -dimethyl diphenyl methane-2, 4' -diisocyanate,
3,2'-, 3,3'-, 4,2'-, 4,3'-, 5,2'-, 5,3'-, 6, 2' - or 6, 3' -diethyl diphenyl methane-2, 4' -diisocyanate,
3,2'-, 3,3'-, 4,2'-, 4,3'-, 5,2'-, 5,3'-, 6,2'- or
6, 3' -dimethoxydiphenyl methane-2, 4' -diisocyanate, diphenyl methane-4, 4' -diisocyanate, diphenyl methane-3, 3' -diisocyanate, diphenyl methane-3, 4' -diisocyanate, diphenyl ether-4, 4' -diisocyanate, benzophenone-4, 4' -diisocyanate, diphenyl sulfone-4, 4' -diisocyanate, tolylene-2, 4-diisocyanate, tolylene-2, 6-diisocyanate, naphthylene-2, 6-diisocyanate and
4,4'-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate; aliphatic diisocyanates such as tetramethylene-1, 4-diisocyanate, hexamethylene-1, 6-diisocyanate,
2,2, 4-trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate,
4, 4 '-dicyclohexylmethane diisocyanate, transcyclohexane-1, 4-diisocyanate and hydrogenerated m-xylylene diisocyanate; m-xylylene diisocyanate; and p-xylylene diisocyanate.
Examples of diol compounds which can be used for the reaction with the dihalotriazine compounds include alkylenediols such as ethylene glycol, propylene glycol, trimethylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2-methyl-l, 3-propanediol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, 2, 2-dimethyl-l, 3-propanediol, neopentyl glycol, 2-methyl-l, 3-butanediol, 3-methyl-l, 3-butanediol, 3-methyl-l, 5-pentanediol and 1, 6-hexanediol; alicyclic diols such as 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexane dimethanol, 1, 3-cyclohexane dimethanol, 1, 4-cyclohexane dimethanol, 1,2-benzene dimethanol, 1,3-benzene dimethanol, 1,4-benzene dimethanol, 2, 3-dihydroxynorbornan, 2, 5-dihydroxynorbornan, 2, 6-dihydroxynorbornan, 2, 7-dihydroxynorbornan, dihydroxydicyclopentadiene and hydrogenated bisphenol A; aliphatic glycol ethers such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and 2, 2-bis [4- (2-hydroxyethyloxy) cyclohexyl]propane; aromatic glycol ethers such as
1, 4-bis (2-hydroxyethyloxy)benzene and compounds represented by formula (48) :
Figure imgf000034_0001
wherein R8 and R9 each independently represent a hydrogen atom or a methyl group and, k and m each independently represent 0 or an integer and the relationship of k and m is 2<k+m<20;and high molecular weight diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate diol and (hydrogenated) polybutadiene diol.
As for examples of the dithiol compound which can be used in the reaction with the dihalotriazine compound, 1,2-ethane dithiol and the like can be mentioned.
Examples of diamine compounds which can be used in the reaction with the dihalotriazine compound include aliphatic diamine such as ethylene diamine, tetramethylene diamine, hexamethylene diamine and anN,N' -dimethyl form, a diethyl form, a diphenyl form and dibenzyl form of these diamines; xylylene diamines such as m-xylylene diamine, p-xylylene diamine, and an N,N' -dimethyl form, a diethyl form, a diphenyl form and a dibenzyl form of these diamines; piperazines such as piperazine, 2,5-dimethyl piperazine and
1, 3-di (4-piperidyl)propane; and aromatic diamines such as o-phenylene diamine, m-phenylene diamine, p-phenylene-diamine, 3, 3' -diamino-diphenyl ether, 4, 4' -diaminodiphenyl ether, 3, 4-diamino-diphenyl ether,
3, 3' -diamino-diphenyl methane, 3,4' -diamino-diphenyl methane,
4, 4' -diamino-diphenyl methane, 3, 3' -diamino-diphenyl fluoromethane, 4, 4' -diamino-diphenyl difluoromethane,
3, 3' -diamino-diphenyl sulfone, 3, 4' -diamino-diphenyl sulfone, 4, 4' -diamino-diphenyl sulfone, 3, 3' -diamino-diphenyl sulfide,
2, 2-bis (3-aminophenyl)propane,
2, 2-bis (3,4' -diaminophenyl)propane,
2, 2-bis (4-aminophenyl)propane,
2, 2-bis (3-aminophenyl) hexafluoropropane, 2, 2-bis (3,4' -diaminophenyl) hexafluoropropane,
2, 2-bis (4-aminophenyl) hexafluoropropane,
1, 3-bis (3-aminophenyl)benzene,
1, 4-bis (4-aminophenyl)benzene,
3, 3' - [1, 4-phenylenebis (1-methylethylidene) ]bisaniline, 3, 4' - [1, 4-phenylenebis (1-methylethylidene) Jbisaniline,
4, 4' - [1, 4-phenylenebis (1-methylethylidene) Jbisaniline, 2, 2-bis [4- (3-aminophenoxy)phenyl]propane,
2, 2-bis [4- (4-aminophenoxy)phenyl]propane,
2, 2-bis [4- (3-aminophenoxy) phenyl]hexafluoropropane,
2, 2-bis [4- (4-aminophenoxy)phenyl]hexafluoropropane, bis [4- (3-aminophenoxy)phenyl] sulfide, bis [4- (4-aminophenoxy)phenyl] sulfide, bis [4- (3-aminophenoxy)phenyl] sulfone, bis [4- (4-aminophenoxy)phenyl] sulfone,
9, 9-bis (4-aminophenyl) fluorene, and an N,N' -dimethyl form, a diethyl form, a diphenyl form and a dibenzyl form of these diamines.
Preferred examples of bifunctional phenolic compounds which can react with the dihalotriazine compound include hydroquinone, catechol, resorcinol, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene,
1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene,
1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene,
2, 2' -biphenol, 4, 4' -biphenol, bis (4-hydroxyphenyl)methane,
1, 1-bis (4-hydroxyphenyl) ethane, 2, 2-bis (4-hydroxyphenyl)propane,
2, 2-bis (4-hydroxyphenyl) -4-methylbutane,
1, 1-bis (4-hydroxyphenyl) decane,
2, 2-bis [ (4-hydroxy-3-phenyl)phenyl]propane,
2-phenyl-2, 2-bis (4-hydroxyphenyl) ethane, 1, 1-bis (4-hydroxyphenyl) cyclopentane,
1, 1-bis (4-hydroxyphenyl) cyclohexane,
9, 9-bis (4-hydroxyphenyl) fluorene,
3, 3' , 5, 5' -tetramethyl-4, 4' -biphenol, bis (4-hydroxy-3, 5-dimethyl phenyl)methane, 1, 1-bis (4-hydroxy-3, 5-dimethyl phenyl) ethane,
2, 2-bis (4-hydroxy-3, 5-dimethyl phenyl)propane, bis (4-hydroxy-3, 5-dimethylphenyl) phenylmethane, 1, 1-bis (4-hydroxy-3, 5-dimethylphenyl) cyclopentane, 1, 1-bis (4-hydroxy-3, 5-dimethylphenyl) cyclohexane and 9, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene. Preferred examples of bifunctional thiophenols which can react with the dihalotriazine compound include 4-t-butyl-l, 2-dimercaptobenzene and 4, 4' -thiodibenzene thiol.
Further, a compound which simultaneously contains a hydroxyl group and an amino group such as monoethanol amine or m-aminophenol can also be used.
In performing the reaction of the dihalotriazine compound with the diol compound and the like, it is preferable that the total amount of the diol compound and the like be in the range of 0.5 to 1.5 mol based on 1 mol of the dihalotriazine compound and, more preferably from 0.8 to 1.2 mol. When the total amount of the diol compound and the like is less than 0.5 mol or exceeds 1.5 mol, the molecular weight of the triazine compound thereby obtained is not increased and, then, characteristics such as flexibility of a curedproduct produced from the curable triazine composition by blending the triazine compound therein are deteriorated.
It is preferable that the reaction of the dihalotriazine compound with the diol compound and the like be performed in an organic solvent. Preferred examples of organic solvents include those as illustrated as usable in the reaction between the above-described cyanuric halide with the alcoholic compound and the like. From the standpoint of the reaction rate or the economical efficiency, it is preferable that the amount of the organic solvent to be used is from 0.1 to 10 L , based on 1 mol of the dihalotriazine compound and, more preferably 0.5 to 5 L.
It is preferable that the reaction of the dihalotriazine compound with the diol compound and the like be performed in the presence of a base as an acid acceptor. Preferred examples of acid acceptors include those bases as illustrated as usable in the reaction of the above-described cyanuric halide with the alcohol and the like and aqueous solutions thereof.
From the standpoint of the reaction rate, economical efficiency and the like, it is preferable that, when monovalent acid acceptor is used, the amount of the acid acceptor be 2 to 20 mol based on 1 mol of the dihalotriazine and that when divalent acid acceptor is used, 1 to 10 mol.
In the reaction of the dihalotriazine compound with the diol compound and the like, when an aqueous alkaline solution is used as the acid acceptor, a phase-transfer catalyst may be added in the reaction system. Preferred examples of phase-transfer catalysts include those as illustrated as usable in the reaction between the above-described cyanuric halide with the alcohol and the like. From the standpoint of the reaction rate, economical efficiency and the like, it is preferable that the amount of each of the catalyst be 1 to 100 % by mol based on the dihalotriazine compound.
It is preferable that the reaction of the dihalotriazine compound with the diol compound and the like be performed in the temperature range of 0 to 2000C and at the same time that at the temperature, the curable group present in the dihalotriazine compound be sufficiently stable. When the temperature is 0 °C or less, the reaction proceeds slowly, while, when the temperature exceeds 200°C, it might lead to hydrolysis of the triazine compound thus generated. Further, when the temperature exceeds the temperature at which the curable group in the dihalotriazine compound can stay sufficiently stable, it may lead to gelation in the reaction system. Therefore, it is necessary to determine an upper limit of the temperature by taking into consideration the type of functional group to be used.
When the reaction between the dihalotriazine compound with the diol compound and the like is performed, a polymerization inhibitor may optionally be added. Preferred examples of polymerization inhibitors include those as illustrated as usable in the reaction of the above-described dihalotriazine compound with the alcohol and the like. One of these polymerization inhibitors may be used singly or two or more types may be used in combination.
Further, the triazine compound as represented by formula (1) can also be obtained by the method as described below. Namely, after a cyanuric halide such as cyanuric chloride is allowed to react with at least one type of compound (hereinafter, referred to also as "diol compound and the like" for short) selected from among compounds having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups or phenolic hydroxide groups in one molecule such as diol compound, dithiol compound, diamine compound, bifunctional phenolic compound and bifunctional thiophenolic compound, the resultant reaction product is allowed to react with at least one type of compounds (hereinafter, referred to also as "alcoholic compound and the like" for short) selected from among alcoholic compound, thiol compound, amine compound, phenolic compound and thiophenolic compound, to thereby obtain the triazine compound. Preferred examples of diol compound and the like which can be used in this reaction include those as illustrated as usable for obtaining the triazine compound represented by formula (1) by reacting with the above-described dihalotriazine compound.
In performing the reaction of the above-described cyanuric halide with the diol compound and the like, it is preferable that the entire amount of the diol compound and the like be in the range of from 0.8 to 1.2 mol based on 1 mol of the dihalotriazine compound. When the entire amount of the diol compound and the like is less than 0.8 mol or more than 1.2 mol, the molecular weight of the triazine compound thereby obtained is not increased and, then, characteristics such as flexibility of a cured product produced from the curable triazine composition obtained by blending the triazine compound therein may sometimes be deteriorated. It is preferable that the reaction of the above-described cyanuric halide with the diol compound and the like be performed in an organic solvent. Preferred examples of organic solvents include those as illustrated as usable in the reaction of the above-described cyanuric halide with the alcoholic compound and the like. From the standpoint of the reaction rate or the economical efficiency, it is preferable that the amount of the organic solvent to be used be 0.5 to 10 L based on 1 mol of the cyanuric halide.
It is preferable that the reaction of the cyanuric halide with the diol compound anf the like be performed in the presence of an acid acceptor. Preferred examples of acid acceptors include those as illustrated as usable in the reaction of the cyanuric halide with the alcohol and the like and aqueous solutions thereof. From the standpoint of the reaction rate, economical efficiency and the like, it is preferable that, when the acid acceptor is monovalent, the amount of the acid acceptor to be used be 2 to 20 mol based on 1 mol of the cyanuric halide and that when the acid acceptor is divalent, the amount be 1 to 10 mol. In the reaction of the above-described cyanuric halide with the diol compound and the like, when an aqueous alkaline solution is used as the acid acceptor, a phase-transfer catalyst can be added in the reaction system. Preferred examples of phase-transfer catalysts include those as illustrated as usable in the reaction of the above-described cyanuric halide with the alcohol and the like. From the standpoint of the reaction rate, economical efficiency and the like, it is preferable that the amount of the catalyst to be used be 1 to 100 % by mol based on the dihalotriazine compound. It is preferable that the reaction of the cyanuric halide with the diol compound and the like be performed in the temperature range of 0 to 150 0C. When the temperature is 0 °C or less, the reaction proceeds slowly, while, when the temperature exceeds 150 °C, it might lead to hydrolysis or gelation of the triazine compound thus generated.
When the reaction of the cyanuric halide with the diol compound and the like is performed, a polymerization inhibitor may optionallybe added. Preferred examples of polymerization inhibitors include those as illustrated as usable in the reaction of the cyanuric halide with the alcohol and the like. One of these polymerization inhibitors may be used singly or two or more of them may be used in combination.
Preferred examples of alcoholic compounds and the like to react with the product obtained by the above reaction of cyanuric halide with the diol compound and the like include those as illustrated as usable for producing the dihalotriazine compound as represented by formula (3) by reacting with the cyanuric halide. On this occasion, the alcoholic compound and the like may directly be added to the reaction system where the cyanuric halide is reacted with the diol compound and the like, or after the reaction product is once taken out of the reaction system, the alcoholic compound and the like may be allowed to react therewith. Further, from the standpoint of the reaction rate, economical efficiency and the like, it is preferable that when the reaction is performed, the total amount of the alcoholic compound and the like be from 1 to 5 mol based on 1 mol of the cyanuric halide.
When the alcoholic compound and the like are reacted with the reaction product of the reaction of the cyanuric halide with the diol compound and the like, it is preferable that the reaction using the alcoholic compound and the like be performed in an organic solvent. Preferred examples of organic solvents include those as illustrated as usable in the previously-mentioned reaction of the cyanuric halide and the alcoholic compound and the like. From the standpoint of the reaction rate or the economical efficiency, it is preferable that the amount of the organic solvent to be used be from 0.2 to 10 L based on 1 mol of the cyanuric halide.
When the alcoholic compound and the like are reacted with the reaction product of the reaction of the cyanuric halide with the diol compound and the like, it is preferable that the reaction be performed in the presence of an acid acceptor. Preferred examples of acid acceptors include those as illustrated as usable in the previously-mentioned reaction of the cyanuric halide with the alcohol and the like and aqueous solutions thereof.
From the standpoint of the reaction rate, economical efficiency and the like, it is preferable that when the acid acceptor is monovalent, the amount of acid acceptor to be used be 1 to 20 mol based on 1 mol of the dihalotriazine, and that when the acid acceptor is divalent, the amount be 0.5 to 10 mol .
When the alcoholic compound and the like are reacted with the reaction product of the reaction of the cyanuric halide with the diol compound and the like, in a case where an aqueous alkaline solution is used as the acid acceptor, a phase-transfer catalyst may be added in the reaction system. Preferred examples of phase-transfer catalysts include those as illustrated as usable in the previously-mentioned reaction of the cyanuric halide with the alcohol and the like. From the standpoint of the reaction rate, economical efficiency and the like, it is preferable that the amount of the catalyst to be used be 1 to 100 % by mol based on the cyanuric halide.
When the alcoholic compound and the like are reacted with the reaction product of the reaction of the cyanuric halide with the diol compound and the like, it is preferable to perform the reaction in the temperature range of from 0 to 200 °C. When the temperature is 00C or less, the reaction proceeds slowly, while, when the temperature exceeds 200 °C, it might lead to hydrolysis of the triazine compound thus generated. Further, when the temperature exceeds the temperature at which the curable group present in the dihalotriazine compound can stay sufficiently stable, it might cause gelation in the reaction system.
When the alcoholic compound and the like are reacted with the reaction product of the reaction of the cyanuric halide with the diol compound and the like, a polymerization inhibitor may optionally be added. Preferred examples of polymerization inhibitors include those as illustrated as usable in the previously-mentioned reaction of the dihalotriazine compound with the alcohol and the like. One of these polymerization inhibitors may be used singly or two or more of them may be used in combination.
The triazine compound as represented by formula (1) can also be obtained by a method as described below. Namely, the triazine compound can be obtained by reacting a triazine dithiol compound as represented by formula (4) with a compound as represented by formula (5) or a bifunctional α, β-unsaturated carbonyl compound.
X1 N^N (4)
HS NΓ --SH
X4^-X4 :5)
X1 in formula (4) represents the same group as in X1 in formula (1) .
The triazine dithiol compound as represented by formula (4) can be obtained, for example, by reacting dihalotriazine compound as represented by formula (3) with an alkaline hydrosulfide or an alkaline sulfide.
It is preferable that the reaction between the dihalotriazine compound and the alkaline hydrosulfide or the alkaline sulfide be performed in an organic solvent. Preferred examples of organic solvents which can be used on this occasion include alcohols such as methanol, ethanol and isopropyl alcohol and amide-type solvents such as N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone and 1, 3-dimethyl-2-imidazolidone. One of these organic solvents may be used singly or two or more types may be used in combination. It is preferable that the use amount of the organic solvent be 0.1 to 5 L based on 1 mol of the dihalotriazine compound. In the reaction between the halotriazine compound and the alkaline hydrosulfide or alkaline sulfide, from the standpoint of the reaction yield or the economical efficiency, it is preferable that the use amount of alkaline hydrosulfide or alkaline sulfide be of from 2 to 10 mol based on 1 mol of the dihalotriazine compound. Further, from the standpoint of the reaction efficiency, it is preferable that the alkaline hydrosulfide or alkaline sulfide be added after being dissolved in water. On this occasion, it is preferable that the concentration of the alkaline hydrosulfide or alkaline sulfide be from 10 to 70 % by mass.
In the reaction between the dihalotriazine compound and the alkaline hydrosulfide or alkaline sulfide, it is preferable that the reaction temperature be from -20 to 50 °C.
In the reaction between the dihalotriazine compound and the alkaline hydrosulfide or alkaline sulfide, a polymerization inhibitor may optionally be added. Preferred examples of polymerization inhibitors include those as illustrated as usable in the previously-mentioned reaction of the dihalotriazine compound with the alcoholic compound and the like.
In formula (5) , R1 represents the same group as in R1 in formula ( 1 ) .
In formula (5), X4 represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a methane sulfonyloxy group, a trifluoromethane sulfonyloxy group or a p-toluene sulfonyloxy group and, preferably, represents a bromine atom, a methane sulfonyloxy group or a p-toluene sulfonyloxy group.
Preferred examples of compounds as represented by formula (5) include 1, 2-dibromoethane, 1, 2-dibromopropane, 1, 3-dibromopropane, 1, 3-dibromobutane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, 1, 10-dibromodecane, 1, 4-dichlorobenzene, p,p' -dibromobiphenyl and, further, a methane sulfonyl acid ester and a p-toluene sulfonic acid ester of the compounds as illustrated as preferred examples of diol compounds which can be used for producing triazine compound as represented by formula (1) by allowing any one of them to react with the dihalotriazine compound. One of these compounds may be used singly or two or more types may be used in combination. Preferred examples of bifunctional α, β-unsaturated carbonyl compounds to react with the triazine ditiol compound as represented by formula (4) include bismaleimide and, further, a (meth) acrylic acid ester of the compounds as illustrated as preferred examples of diol which can be used for producing the triazine compound as represented by formula (1) by allowing them to react with the dihalotriazine compound. One of these compounds may be used singly or two or more types may be used in combination.
In the reaction between the triazine dithiol compound and the compound as represented by formula (5) or the α, β-unsaturated carbonyl compound, it is preferable that the amount of the compound as represented by formula (5) or the α, β-unsaturated carbonyl compound be from 0.5 to 1.5 mol based on 1 mol of the triazine dithiol compound. When the entire amount of the compound as represented by formula (5) or the α, β-unsaturated carbonyl compound is less than 0.5 mol or more than 1.5 mol, the molecular weight of the triazine compound thereby obtained is not increased and, then, characteristics such as flexibility of a curedproduct produced from the curable triazine composition obtained by blending the triazine compound therein are deteriorated.
It is preferable that the reaction between the triazine dithiol compound and the compound as represented by formula (5) or the bifunctoinal α,β-unsaturated carbonyl compound be performed in an organic solvent. Preferred examples of organic solvents include aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene and benzonitrile; halogen-type solvents such as chloroform, dichloromethane, 1, 2-dichloroethane, 1, 1, 2, 2-tetrachloroethane and dichlorobenzene; and ether-type solvents such as tetrahydrofuran and dioxane. From the standpoint of the reaction rate or the economical efficiency, it is preferable that the amount of the organic solvent to be used be from 0.5 to 10 L based on 1 mol of the triazine dithiol compound as represented by formula (4) . It is preferable that the reaction between the tirazine dithiol compound and the compound as represented by formula (5) or the bifunctional α, β-unsaturated carbonyl compound be performed in the presence of a base catalyst. Preferred examples of base catalysts include those as illustrated as usable in the previously-mentioned reaction of the cyanuric halide with the alcohol or the like. From the standpoint of the reaction rate, the economical efficiency or the like, it is preferable that when the base is monovalent, the amount of the base catalyst to be used be from 1 mmol to 5 mol and that when the base is monovalent the amount be 0.5 mmol to 2.5 mol, based on 1 mol of triazine dithiol.
When the reaction between the triazine dithiol compound and the compound as represented by formula (5) or the bifunctional α, β-unsaturated carbonyl compound is performed in two-phase system of organic solvent and water, a phase-transfer catalyst may be added in the reaction system. Preferred examples of phase-transfer catalysts include those as illustrated as usable in the previously-mentioned reaction of the dihalotriazine compound with the diol compound and the like. It is preferable that the reaction between the triazine dithiol compound and the compound as represented by formula
(5) or the α,β-unsaturated carbonyl compound be performed in the temperature range of 0 to 200 °C and at a temperature at which the curable group present in the triazine dithiol compound can be sufficiently stable. When the temperature is less than 0 °C, the reaction proceeds slowly, while, when the temperature exceeds 2000C, it might cause hydrolysis of a triazine resin. Further, when the temperature exceeds the temperature at which the curable group in the triazine dithiol compound can stay sufficiently stable, it might lead to gelation in the reaction system. For example, when the curable group is an allyl group, it is preferable that the reaction be performed at the reaction temperature of 200 0C or less, while, when the curable group is an acryloyl group, it is preferable that the reaction be performed at the reaction temperature of 150 °C or less. When the reaction between the tirazine dithiol compound and the compound as represented by formula (5) or the bifunctional α, β-unsaturated carbonyl compound is performed, a polymerization inhibitor may optionally be added. Preferred examples of polymerization inhibitors include those as illustrated as usable in the previously-mentioned reaction of the cyanuric halide and the alcohol or the like. One of these polymerization inhibitors may be used singly or two or more of them may be used in combination. According to the present invention, the triazine compound as represented by formula (1) obtained by reacting the dihalotriazine compound as represented by formula (3) with the diol compound and the like or by reacting the triazine dithiol compound as represented by formula (4) with the compound as represented by formula (5) or the α,β-unsaturated compound, may be used after optionally subjected to any one of an acid anhydride modification, an acid chloride modification, a diisocyanate modification, an epichlorohydrin modification accompanied by subsequent dehydrochloric acid reaction, oxidation-epoxidation of an olefin and the like.
Examples of acid anhydrides, acid chlorides and diisocyanates to be used on this occasion include those as previously illustrated as usable in the modification of the dihalotriazine compound. According to the present invention, one of the triazine compounds which can be represented by formula (1) and each contain groups curable with heat or light as a part or all of n X^s may be used singly or two or more types of the compounds may be used in combination. According to the present invention, examples of curing agent serving as component (B) and preferable use amount thereof are described below.
(a) In a case where the curing group is an allyl group It is preferable to use a heat radical polymerization initiator as a curing agent. Preferred examples of heat radical polymerization initiators include organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetate peroxide, acetyl acetate peroxide, 1, 1-bis (t-butylperoxy)butane, 1, 1-bis (t-butylperoxy) cyclohexane,
1, 1-bis (t-butylperoxy) -2-methylcyclohexane,
1, 1-bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane,
1, 1-bis (t-butylperoxy) cyclododecane,
1, 1-bis (t-hexylperoxy) cyclohexane, 1, 1-bis (t-hexylperoxy) -3, 3, 5-trimethyl cyclohexane, 2, 2-bis (4, 4-di-t-butylperoxycyclohexyl)propane, t-butyl hydroperoxide, t-hexyl hydroperoxide, 1, 1, 3, 3-tetramethyl butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, α,α' -bis (t-butylperoxy) diisopropylbenzene, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3, 3, 5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicabonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α,α' -bis (neodecanoylperoxy) diisopropylbenzene, t-butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate,
1, 1, 3, 3-tetramethylbutyl peroxyneodecanoate,
1-cyclohexy1-1-methylethyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethyl-hexanoate,
1,1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate,
2, 5-dimethyl-2, 5-bis (2-ethyl hexanoyl peroxy) hexane,
1-cyclohexyl-l-methyl ethyl peroxy-2-ethyl hexanoate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, t-butyl peroxyisopropylmonocarbonate, t-hexyl peroxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butyl peroxyallylmonocarbonate, t-butyl peroxyisobutyrate, t-butyl peroxymaleate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy-m-toluylbenzoate, t-butyl peroxylaurate, t-butyl peroxyacetate, bis (t-butylperoxy) isophthalate,
2, 5-dimethyl-2, 5-bis (m-toluylperoxy) hexane, 2, 5-dimethyl-2, 5-bis (benzoylperoxy)hexane, t-butyl trimethyl silyl peroxide,
3, 3' , 4, 4' -tetra (t-butyl peroxycarbonyl)benzophenone and
2, 3-dimethyl-2, 3-diphenyl butane.
One of these compounds may be used singly or two or more of them may be used in combination. It is preferable that the use amount of heat radical polymerization initiator be from 0.1 to 10 parts by mass based on 100 parts by mass of the (A) triazine compound.
(b) In a case where the curing group is a vinyl group or a (meth) acryloyl group It is preferable to use a heat radical polymerization initiator or a light radical polymerization initiator as a curing agent.
Preferred examples of heat radical polymerization initiators include such organic peroxides as illustrated in the above (a) and azo compounds such as
1- [ (1-cyano-l-methylethyl) azo] formamide,
1,1' -azobis (cyclohexane-1-carbonitrile) ,
2,2' -azobis (2-methylbutyronitrile) ,
2,2' -azobisisobutyronitrile, 2,2' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile) ,
2,2' -azobis (2, 4-dimethylvaleronitrile) ,
2-phenylazo-4-methoxy-2, 4-dimethylvaleronitrile,
2,2' -azobis (2-ruethylpropionamidine) dihydrochloride,
2,2' -azobis (2-methyl-N-phenylpropionamidine) dihydrochloride,
2,2'-azobis[N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride,
2, 2' -azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2' -azobis [2-methyl-N- (2-propenyl)propionamidine] dihydrochloride,
2,2' -azobis [N- (2-hydroxyethyl) -2-methyl propionamidine] dihydrochloride,
2, 2' -azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride,
2,2' -azobis [2- (2-imidazoline-2-yl)propane] , 2,2' -azobis [2- (2-imidazo1ine-2-yl)propane] dihydrochloride,
2, 2' -azobis [2- (5-methyl-2-imidazoline-2-yl)propane] dihydrochloride,
2,2' -azobis{2- [1- (2-hydroxyethyl) -2-imidazoline-2-yl]propa ne} dihydrochloride,
2, 2' -azobis [2- (4, 5, 6, 7-tetrahydro-lH-l, 3-diazepine-2-yl)pr opane] dihydrochloride,
2,2' -azobis [2- (3,4,5, 6-tetrahydropyrimidine-2-yl)propane] dihydrochloride, 2,2' -azobis [2- (5-hydroxy-3, 4, 5, 6-tetrahydropyrimidine-2-yl
)propane] dihydrochloride,
2,2' -azobis (2-methylpropionamide) ,
2,2' -azobis [2-methyl-N- (2-hydroxyethyl)propionaitiide] ,
2,2' -azobis{2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyet hyl]propionamide} ,
2,2' -azobis{2-methyl-N- [1, 1-bis (hydroxymethyl) ethyl]propio namide} , 2, 2' -azobis (2-methylpropane) ,
2,2' -azobis (2,4, 4-trimethylpentane) , dimethyl-2, 2' -azobis (2-methyl propionate) , 4, 4' -azobis (4-cyanopentanoic acid) and
2, 2' -azobis [2- (hydroxymethyl)propionitrile] . These compounds may be used singly or in combinations of two types or more.
One of these compounds may be used singly or two or more of them may be used in combination. It is preferable that the use amount of heat radical polymerization initiator be from
0.1 to 10 parts by mass based on 100 parts by mass of the (A) triazine compound.
Further, Preferred examples of light radical polymerization initiators include acetophenone type initiators such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone,
4-t-butyl-trichloroacetophenone, diethoxyacetophenone,
2-hydroxy-2-phenyl-l-phenylpropane-l-one,
1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-l-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-l-one,
4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone,
1-hydroxycyclohexyl phenyl ketone and
2-methyl-l- [4- (methylthio)phenyl] -2-morpholinopropane-l; benzoin type initiators such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzyl methyl ketal; benzophenone type initiators such as benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4' -methyldiphenyl sulfide,
3,3' -dimethyl-4-methoxybenzophenone,
4,4' -dimethylaminobenzophenone,
4, 4' -diethylaminobenzophenone and 3, 3' , 4, 4' -tetra (t-butyl peroxycarbonyl)benzophenone; thioxanthone type initiators such as thioxanthone,
2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2, 4-diisopropyl thioxanthone, isopropyl thioxanthone, l-chloro-4-propoxy thioxanthone and 2, 4-dichlorothioxanthone; ketone type initiators such as α-acyloxime ester, methyl phenyl glyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone and
4' , 4"-diethylisophthalophenone; imidazole type initiators such as 2,2' -bis (2-chlorophenyl) -4, 4' , 5, 5' -tetraphenyl-1, 2' -imidaz ole/ acylphosphine oxide type initiators such as 2, 4, 6-trimethyl benzoyldiphenyl phosphine oxide; carbazole type initiators; and onium salts of Lewis acids such as triphenylphosphonium hexafluoroantintonate, triphenylphosphonium hexafluorophosphate, [p- (phenylthio)phenyl]diphenylsulfonium hexafluoroantimonate, (4-chlorophenyl) diphenylsulfonium hexafluorophosphate and (2, 4-cyclopentadiene-l-yl) [ (1-methyl ethyl)benzene] -iron-hexafluorophosphate.
It is preferable that the use amount of the light polymerization initiator be from 0.01 to 20 parts by mass based on 100 parts by mass of the (A) triazine compound.
(c) In a case where the curing group is an epoxy group It is preferable to use as a curing agent, a compound such as a multi-functional amine, a carboxylic acid or an acid anhydride, having a functional group reactive with an epoxy group, and particularly preferred is the acid anhydride. Preferred examples of amines include not only such diamine compounds as illustrated as usable for producing the triazine compound as represented by formula (1) by allowing reacting with the dihalotriazine compound as represented by formula (3) but also triamine compounds such as diethylene triamine, tetramine compounds such as triethylene tetramine, and melamines such as melamine, acetoguanamine and benzoguanamine . One of these compounds may be used singly or two or more of them may be used in combination.
Further, examples of carboxylic acids include dicarboxylic acids such as succinic acid, maleic acid, fumaric acid, adipic acid, tetrahydrophthalic acid, 1, 4-cyclohexane dicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid; tricarboxylic acids such as trimellitic acid and trimesic acid; tetracarboxylic acids such as pyromellitic acid,
3, 3' , 4, 4' -biphenyl tetracarboxylic acid, 2, 2' , 3, 3' -bisphenyl tetracarboxylic acid,
2, 2' , 3, 3' -biphenyl tetracarboxylic acid,
2, 3, 3' , 4' -biphenyl tetracarboxylic acid,
2, 2-bis (3, 4-dicarboxyphenyl)propane,
1, 1-bis (3, 4-dicarboxyphenyl) ethane, bis (2, 3-dicarboxyphenyl)methane, bis (3, 4-dicarboxyphenyl)methane, bis (3, 4-dicarboxyphenyl) sulfone,
3, 4, 9, 10-perylene tetracarboxylic acid, bis (3, 4-dicarboxyphenyl) ether, benzene-1, 2, 3, 4-tetracarboxylic acid,
3, 4, 3' , 4' -benzophenone tetracarboxylic acid,
2, 3, 2' , 3' -benzophenone tetracarboxylic acid,
2, 3, 3' , 4' -benzophenone tetracarboxylic acid,
1, 2, 5, 6-naphthalene tetracarboxylic acid, 2, 3, 6, 7-naphthalene tetracarboxylic acid,
1, 2, 4, 5-naphthalene tetracarboxylic acid,
1, 4, 5, 8-naphthalene tetracarboxylic acid,
2, 6-dichlornaphthalene-l, 4, 5, 8-tetracarboxylic acid,
2, 7-dichloronaphthalene-l, 4, 5, 8-tetracarboxylic acid, 2, 3, 6, 7-tetrachlornaphthalene-l, 4, 5, 8-tetracarboxylic acid, phenanthrene-1, 8, 9, 10-tetracarboxylic acid, bis (3, 4-dicarboxyphenyl) dimethyl silane, bis (3, 4-dicarboxyphenyl)methyl phenyl silane, bis (3, 4-dicarboxyphenyl) diphenyl silane, 1, 4-bis (3, 4-dicarboxyphenyl dimethyl silyl)benzene,
1, 3-bis (3, 4-dicarboxyphenyl) -1,1,3, 3-tetramethyl dicyclohexane, p-phenylenebis (trimellitic acid monoester) ,
2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane,
2, 2-bis{4- (3, 4-dicarboxypheno)phenyl}hexafluoropropane, 2, 2-bis{4- (3, 4-dicarboxypheno)phenyl}propane,
4, 4-bis (3, 4-dicarboxyphenoxy) diphenyl sulfide,
1, 4-bis (2-hydroxyhexafluoroisopropyl)benzenebis (trimellita te),
1, 3-bis (2-hydroxyhexafluoroisopropyl)benzenebis (trimellita te),
1,2- (ethylene)bis (trimellitate) ,
1, 3- (trimethylene)bis (trimellitate) ,
1, 4- (tetramethylene)bis (trimellitate) ,
1, 5- (pentamethylene)bis (trimellitate) , 1, 6- (hexamethylene)bis (trimellitate) ,
1, 7- (heptamethylene)bis (trimellitate) ,
1, 8- (octamethylene)bis (trimellitate) ,
1, 9- (nonamethylene)bis (trimellitate) ,
1, 10- (decamethylene)bis (trimellitate) , 1, 12- (dodecamethylene)bis (trimellitate) ,
1, 16- (hexadecamethylene)bis (trimellitate) ,
1,18- (octadecamethylene)bis (trimellitate) , ethylene tetracarboxylic acid,
1, 2, 3, 4-butane tetracarboxylic acid, pyrazine-2, 3, 5, 6-tetracarboxylic acid, thiophene-2, 3, 4, 5-tetracarboxylic acid, decahydronaphthalene-1, 4,5, 8-tetracarboxylic aid,
4, 8-dimethyl-l, 2, 3, 5, 6, 7-hexahydronaphthalene-l, 2, 5, β-tetr acarboxylic acid, cyclopentane-1, 2, 3, 4-tetracarboxylic acid, pyrrolidine-2, 3, 4, 5-tetracarboxylic acid, 1, 2, 3, 4-cyclobutane tetracarboxylic acid, bis{exo-bicyclo- [2.2. l]heptane-2, 3-dicarboxylic acid}sulfone, bicyclo- [2.2.2] -oct (7) -ene-2, 3, 5, 6-tetracarboxylic acid, 5- (2, 5-dioxotetrahydrofuryl) -S-methyl-S-cyclohexane-l, 2-di carboxylic acid and tetrahydrofuran-2, 3, 4, 5-tetracarboxylic acid; and resins having two or more carboxyl groups such as polyacrylic acid. One of these compounds and resin may be used singly or two or more of them may be used in combination. Further, examples of acid anhydrides include those as illustrated as usable in modification of the dihalotriazine compound as represented by formula (3) . One of those may be used singly or two or more types may be used in combination.
It is preferable that the use amount of the curing agent be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
Further, when the acid anhydride is used as a curing agent, it is preferable to add a curing accelerator.
Preferred examples of curing accelerators include amine type compounds such as benzyldimethylamine (BDMA) , l-benzyl-2-phenylimidazole, 2-heptadecylimidazole, 2-phenyl-4, 5-dihydroxyimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 4-diamino-6- [2-methylimidazolyl- (1) ] -ethy1-s-triazine, l-cyanoethyl-2-undecylimidazole, 2-ethyl-4-methylimidazole, 1, 8-diazabicyclo [5.4.0]undecene-7 and salts of these compounds; phosphine type compounds such as triphenyl phosphine, tris (2, 6-dimethoxyphenyl)phosphine and of these compounds; and organic metallic salts. One of these curing accelerators may be used singly or two or more of them may be used in combination and, it is preferable that the use amount of the curing accelerator be from 0 to 20 parts by mass based on 100 parts by mass of the
(A) triazine compound.
(d) In a case where the curing group is an oxetanyl group It is preferable to use a light cationic polymerization initiator or a heat cationic polymerization initiator as a curing agent.
As for the light cationic polymerization initiator, an onium salt as represented by formula (49) is preferably used. [A]h+[X]h~ (49)
In formula (49), [A] h+ represents an onium ion such as diphenyliodonium, 4-methoxydiphenyliodonium, bis(4-methyl phenyl) iodonium, bis (4-tert-butyl phenyl) iodonium, bis (dodecylphenyl) iodonium, triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl)phenyl) sulfonio) -phenyl] sulfid e or η5-2, 4- (cyclopentadienyl) [1, 2, 3, 4, 5, 6-η- (methyl ethyl)benzene-iron (1+) ; and [X]h~ represents a halogenated complex such as tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate or hexachloroantimonate; an aromatic anion such as tetra (fluorophenyl)borate, tetra (difluorophenyl)borate, tetra (trifluorophenyl)borate, tetra (tetrafluorophenyl)borate, tetra (pentafluorophenyl)borate, tetra (perfluorophenyl)borate, tetra (trifluoromethylphenyl)borate or tetra (di (trifluoromethyl)phenyl)borate; or an anion such as a perchlorate ion, a trifluoromethanesulfonate ion, a toluene sulfonate ion or a trinitrotoluenesulfonate ion. One of these light cationic polymerization initiators may be used singly or two or more of them may be used in combination and, it is preferable that the use amount of the light cationic polymerization initiator be from 0.1 to 10 parts by mass based on 100 parts by mass of the (A) triazine compound.
Preferred examples of heat cationic polymerization initiator include metal chelate compounds such as aluminum trisacetylacetonate and sulfonium-salt compounds such as dialkyl benzyl sulfonium, benzyl-4-hydroxyphenyl methyl sulfonium, hexafluoroantimonate, benzyl-4-hydroxyphenyl-methyl-sulfonium, hexafluoroantimonate, benzyl-4-methoxyphenyl-methy1-sulfonium, hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenyl-methyl-sulfonium, hexafluoroantimonate and benzyl-3-chloro-4-hydroxyphenylmethyl-sulfonium.
Further, a compound having a functional group which can be added to the oxetane ring such as a carboxylic acid, an acid anhydride or the like may be used. Preferred examples of carboxylic acids and acid anhydrides include those as illustrated in the above (c) . Here, it is preferable that the use amount of the carboxylic acid or the acid anhydride be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
Further, in a case where the carboxylic acid or the acid anhydride is used as a curing agent, it is preferable to use a curing accelerator. Preferred examples of curing accelerators include onium salts such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide and triphenylbenzylphosphonium chloride; amines such as triethylamine, tributylamine,
1, 8-diazabicyclo [5.4.0]undecene-7; a crown ether complex; and triphenyl phosphine. One of these compounds may be used singly or two or more types may be used in combination. On this occasion, it is preferable that the use amount of the curing accelerator be from 0.1 to 20 parts by mass based on 100 parts by mass of the triazine compound which is the resin (A) .
(e) In a case where the curing group is a carboxyl group or an acid anhydride group
It is preferable to use as a curing agent, a compound having a functional group reactive with a carboxyl group or an acid anhydride group such as a multi-functional epoxy compound, an oxetane compound, an amine compound or an isocyanate compound.
As for epoxy compounds, various types of epoxy resins can be used. Specific examples of the epoxy resins include polyglycidyl ethers such as ethylene glycol diglycidyl ether, trimethyrol propane polyglycidyl ether and neopentyl glycol glycidyl ether; epoxy resins each having a triazine ring such as triglycidyl cyanurate and triglycidyl isocyanurate; a bisphenol A type epoxy resin; a bisphenol F type epoxy resin; an epoxy novolac resin; a phenol novolac type epoxy resin; and an ortho-cresol novolac type epoxy resin.
One of these epoxy resins may be used singly or two or more types thereofmaybe used in combination. It is preferable that the use amount of the epoxy resin be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
Further, when the epoxy compound is used as the curing agent, it is preferable to simultaneously use as a curing accelerator, any one of the compounds illustrated in the above (c) as examples of curing accelerators, in an amount of from 0.1 to 20 parts by mass based on 100 parts by mass of the (A) triazine compound.
As for examples of such oxetane compounds, compounds as represented by formulae (50) to (54) can be mentioned:
Figure imgf000062_0001
Figure imgf000062_0002
wherein i represents an integer of from 1 to 3
Figure imgf000062_0003
One of these oxetane compounds may be used singly or two or more types may be used in combination and it is preferable that the use amount of the oxetane compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
Further, when the oxetane compound is used as a curing agent, it is preferable that a curing accelerator be used. Preferred examples of curing accelerators include those as illustrated as the curing accelerators in the above (d) and it is preferable that the use amount of the oxetane compound be from 0.1 to 20 parts by mass based on 100 parts by mass of the (A) triazine compound.
Examples of amine compounds include those as illustrated as amine compounds usable in the above (c) . One of these amine compounds may be used singly or two or more types thereof may be used in combination and it is preferable that the use amount of the amine compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
Examples of isocyanate compounds include such diisocyanate compounds as illustrated as usable for modifying the dihalotriazine compound as represented by formula (3) .
One of these isocyanate compounds may be used singly or two or more types of them may be used in combination and it is preferable that the use amount of the isocyanate compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
(f) In a case where the curing group is an amino group
It is preferable to use as a curing agent, a compound having a functional group reactive with an amino group such as a multi-functional epoxy compound, an isocyanate compound, an acid anhydride or an α, β-unsaturated carbonyl compound. Examples of epoxy compounds include those as illustrated as usable in above (d) . One of these epoxy compounds may be used singly or two or more types thereof may be used in combination and it is preferable that the use amount of the epoxy resin compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
Examples of isocyanate compounds include those as illustrated as usable for modifying the dihalotriazine compound as represented by formula (3) . One of these isocyanate compounds may be used singly or two or more types thereof may be used in combination. It is preferable that the use amount of the isocyanate compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound.
Examples of acid anhydrides include those as illustrated as usable in above (c) . One of these acid anhydrides may be used singly or two or more types thereof may be used in combination. It is preferable that the use amount of the acid anhydride be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound. Examples of α,β-unsaturated carbonyl compounds include not only those as illustrated as usable for producing the triazine compound as represented by the above-descried general formula (1) by reacting with the triazine diol compound as represented by formula (4) but also poly(meth) acrylates such as (meth) acrylate of alkyl-modified dipentaerythritol,
(meth) acrylate of ε-caprolactone-modified dipentaerythritol, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethacrylate of EO-modified trimethyrolpropane, trimethylolpropane tri (meth) acrylate and pentaerythritol triacrylate.
One of these α,β-unsaturated carbonyl compounds may be used singly or two or more types thereof may be used in combination. It is preferable that the use amount of the α,β-unsaturated carbonyl compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound, (g) In a case where the curing group is a thiol group It is preferable to use a polyene compound such as polybutadiene, polyisoprene or natural rubber as a curing agent . One of these polyene compounds may be used singly or two or more of them may be used in combination. It is preferable that the use amount of the polyene compound be from 5 to 200 parts bymass based on 100 parts bymass of the (A) triazine compound.
(h) In a case where the curing group is a (blocked) isocyanate group
It is preferable to use a compound having an active proton such as a multi-functional amine compound or a carboxylic acid compound or an acid anhydride.
Preferred examples of amine compounds include those as illustrated as usable in above (c) . One of these amine compounds may be used singly or two or more types of them may be used in combination. It is preferable that the use amount of the amine compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound. Examples of carboxylic acid compounds and acid anhydrides include those as illustrated as usable in above (c) . One of these carboxylic acid compounds or acid anhydrides may be used singly or two or more of them may be used in combination. It is preferable that the use amount of the compound be from 5 to 200 parts by mass based on 100 parts by mass of the (A) triazine compound. In the curable triazine composition according to the present invention, not only the (A) triazine compound as represented by formula (1) and the -(B) curing agent but also, optionally, components such as a flame retardant and a reactive diluent may be blended.
Here, preferred examples of flame retardant include non-halogen type flame retardants such as a phosphorous type flame retardant, a triazine compound such as melamine and an inorganic type flame retardant such as aluminum hydroxide. In a case where the composition according to the present invention is to be used as varnish for electronic components, a solvent is further blended therein to prepare the varnish thereof. Preferred examples of solvents for preparing varnish include amide type solvents such as N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone and
1, 3-dimethyl-2-imidazolidinone; ether type solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether; sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone and sulfolane; ester type solvents such as γ- butyrolactone, cellosolve acetate, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate; ketone type solvents such as cyclohexanone and methyl ethyl ketone; and aromatic hydrocarbon type solvents such as toluene and xylene. Particularly preferred among them are ether type solvents, sulfur-containing solvents, ester type solvents, ketone type solvents and aromatic hydrocarbon type solvents.
One of these solvents may be used singly or two or more types of them may be used in combination. It is preferable that the use amount of the solvent be from 20 to 400 parts by mass based on 100 parts by mass of the sum total of the (A) triazine compound curing agent and the other components optionally added, such as flame retardant andreactive diluent. Inorganic and/or organic fine particles to be used as the (D) component in the present invention are not particularly limited so long as they can be dispersed in the above-described composition which has been made into varnish as (C) component, to thereby form a paste. Examples of such inorganic fine particles include silica (SiO2) , alumina (Al2Oj) , titania (TiO2), tantalum oxide (Ta2Os) , zirconia (ZrO2), silicon nitride (Si3N4), barium titanate (BaO-TiO2), barium carbonate (BaCOj) , lead titanate (PbO-TiO2), lead zirconate titanate (PZT), leadlanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3) , spinel (MgO-Al2O3) , mullite (3Al2O3-2SiO2) / cordierite (2MgO-2Al2O3/5SiO2) , talc <3MgO-4SiO2-H2O) , aluminum titanate (TiO2-Al2O3), zirconia containing yttria (Y2O3-ZrO2), barium silicate (BaOSSiO2) , boron nitride (BN) , calcium carbonate (CaCO3), calcium sulfate (CaSθ4) , zinc oxide (ZnO), magnesium titanate (MgO-TiO2), barium sulfate (BaSO^), organic bentonite and carbon (C) . One of these compounds may be used singly or two or more types of them may be used in combination.
Organic fine particles to be used according to the present invention is not particularly limited so long as they can be dispersed in the composition which has been made into varnish, to thereby form a paste. Preferred examples of such organic fine particles are fine particles of heat resistant resins having an amide bond, an iraide bond, an ester bond or an ether bond. As for such heat resistant resins, from the viewpoint of heat resistance and mechanical properties, polyimide resins or precursors thereof, polyamidoiiaide resins or precursors thereof and fine particles of polyamide resins are preferably used.
Organic fine particles to be used in the curable triazine resin composition having thixotropic properties according to the present invention, are insoluble in solvent. Generally, Organic fine particles having such a composition that the organic fine particles which, before drying by heating, are present as a heterogeneous layer in the varnish containing (A) curable triazine compound as represented by formula (1) and
(B) curing agent according to the present invention, may form a uniform layer containing the above-described curable triazine compound and the organic fine particles after cured with heat.
In the present invention, inorganic and/or organic fine particles having an average particle diameter of 50 μm or less and a maximum diameter of 100 μm or less are preferably used. When the average particle diameter exceeds 50 μm, it is difficult to obtain a paste having a thixotropic coefficient of 1.1 ormore which is describedbelow, while, when themaximum particle diameter exceeds 100 μm, appearance and adhesiveness of coated film obtained by using such particles tend to be insufficient.
According to the present invention, as method for dispersing the inorganic and/or organic fine particles in varnish, roll kneading, mixer blending or the like as is conventionally employed in the technical field of coating may be used, and any dispersion method may be employed so long as the particles can be dispersed sufficiently.
According to thepresent invention, it is preferable that viscosity at.25°C of the resin composition for electronic components having thixotropic properties be from 0.5 to 500 Pa-s when measured by a rotational viscometer and that the thixotropic coefficient be 1.1 or more.
Here, the viscosity of the paste is expressed in terms of a viscosity at 5 rpm measured by using an E-type viscometer (EHD-R; Rotor N: 0.7; manufactured by Tokimec Inc.) . Further, the thixotropic coefficient (TI value) of the paste is expressed in terms of a ratio of an apparent viscosity ηθ.5 at rotation of 0.5 rpm to an apparent viscosity η5 at rotation of 5 rpm, namely, ηθ.5/η5, as measured in the same manner as in the above. When the viscosity is less than 0.5 Pa-s, not only the paste tends to flow out considerably but also the film tends to be thinner. Whereas, when the viscosity exceeds 500 Pa-s, not only transcribability of the resin composition onto the base material is deteriorated, but also the number of voids and pinholes in the printed film tends to be increased.
Further, when the thixotropic coefficient is less than 1.1, not only the paste becomes threadier, but also more paste tends to flow after printing, which causes the film to be thinner. In the resin composition for electronic components according to the present invention, it is preferable that the amount of the inorganic and/or organic fine particles to be blended as (D) component be in the range of from 1 to 90 parts by mass based on 100 parts by mass of the varnish as the (C) component. When the amount is less than the above-described range, the viscosity and the thixotropic coefficient of the resin composition become low and, further, the composition becomes threadier and more of the composition tends to flow out after printing, which causes the film to be thinner. Further, when the amount is more than the above-described range, since theviscosity and the thixotropic coefficient become high, the transcriptability to the basematerial is deteriorated and, at the same time, the number of voids andpinholes in the printed film tend to be increased.
BRIEF DESCRIPTION OF DRAWINGS Fig.1 is a chart showing 1H-NMR analysis {solvent : heavy chloroform) results of the powdery resin obtained in Example 2. Fig.2 is a chart showing 13C-NMRanalysis (solvent : heavy chloroform) results of the powdery resin obtained in Example 2.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention is described in more detail with reference to examples but is not limited thereto.
Example 1
(1-1) Synthesis of a triazine compound
In a 200 mL four-necked flask equipped with a rotator, a condenser, a nitrogen introducing tube and a thermometer, 10.0- g (50-πmol) of Bisphenol F (o,m,p-substitutedmixture, available from Honshu Chemical Industry Co., Ltd.) and 100 mL of N-methyl pyrrolidone (available fromWako Pure Chemical Industries, Ltd. ) were placed and dissolved. 27.6 g (200 mmol) of potassium carbonate (available from Junsei Chemical Co., Ltd.) was added thereto at 25 0C and the resultant mixture was stirred for 30 minutes. Then, 10.3 g (50 miaol) of
2-allyloxy-4, 6-dichloro-l, 3,5-triazine was added dropwise at 0 °C and reaction was conducted for 48 hours at 250C. The reaction solution was added dropwise to 2 L of water, to thereby cause a precipitation. The precipitation was filtered out and stirred in water for 7 hours at 60 0C, to thereby remove the solvent incorporated therein. Further, the resultant was dried at 70 0C for 8 hours by using a vacuum dryer, to thereby obtain 15.5 g of a white powdery resin. The number average molecular weight of the resin measured by Gel Permeation chromatography (hereinafter, abbreviated as "GPC") was 4,700 in terms of polystyrene.
The powdery resin was subjected to thermogravimetric analysis (TGA method) and the temperature for 5% weight loss was 320 0C. (1-2) Preparation of a curable triazine composition
To 100 parts by mass of the powdery resin obtained in (1-1) , 2 parts by mass of
2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Product name: PERHEXA 25B, manufactured by NOF CORPORATION) was added, and the mixture was dissolved in γ-butyrolactone, to thereby obtain a triazine resin composition having a nonvolatile content of 25 % by mass.
(1-3) Coatingwith the curable triazine composition and curing The triazine resin composition obtained in (1-2) was applied by using a bar coater onto UPICEL N®(grade: SE1310; one-side copper-laminate plate; available fromUbe Industries, Ltd.) which had previously been immersed in an acidic degreasing agent (AC-401) for 1 minute at 25 *C , rinsed with ion-exchanged water and dried for 3 minutes at 70 0C. The resultant coated substrate was dried for 30 minutes at 80 βC and then cured by heating for 1 hour at 160 0C. (1-4) Evaluation of the cured product
The substrate having a cured film thereon obtained in (1-3) was rinsedwith ion-exchangedwater, subjected to an acid degreasing treatment with an ICP Clean 91 (available fromOkuno Chemical Industries Co., Ltd.) for 1 minute at 300C, rinsed with ion-exchangedwater, subjected to pickling treatment with a 10% sulfuric acid for 1 minute at 30 °c and, then rinsed with ion-exchanged water. After water was well removed off the substrate, the resultant substrate was dipped for 3 minutes in a beaker which contained TINPOSIT LT-34 (tin plating solution; available from Rohiii & Haas) heated at 700C and then, dipped in ion-exchanged water for 3 minutes at 70 "C. Subsequently, the substrate was subjected to thermal treatment in a box oven for 100 minutes at 1200C. In the resultant plated substrate, slight creeping of plating was observed, however, no discoloration of the cured film or the copper foil was observed.
Example 2
(2-1) Synthesis of a triazine compound
15.8 g of a white powdery resin was obtainedby conducting synthesis in the same manner as in (1-1) except that Bisphenol F (p,p'-compound, available fromHonshu Chemical Industry Co., Ltd.) was used in place of Bisphenol F (o,m,p-substituted mixture, available from Honshu Chemical Industry Co., Ltd.) . The number average molecular weight of the resin measured by Gel Permeation chromatography (hereinafter, abbreviated as "GPC") was 3,600 in terms of polystyrene. The 1H-NMR and 13C-NMR analysis results of the obtained powdery resin were shown in Figures 1 and 2 (the solvent used in both analysis methods was heavy chloroform and the measuring apparatus was AL-400 manufactured by JEOL) . From the analysis results, it was confirmed that the obtained compound was a compound represented by formula (1) wherein X1 was an allyloxy group, X2 was an oxygen atom, R1 was an organic group of formula
(59) , and n was 11.
Moreover, the powdery resin was subjected to thermogravimetric analysis (TGAmethod) and the temperature for 5% weight loss was 315 0C.
(2-2) Preparation of a curable triazine composition
By using the powdery resin obtained in (2-1) , a curable triazine resin composition having a nonvolatile content of 20 % by mass was obtained in the same manner as in (1-2) . (2-3) Coating with the curable triazine composition and curing By using the curable triazine composition obtained in
(2-2), coating and curing were conducted in the same manner as in (1-3) .
(2-4) Evaluation of the cured product Using the substrate having a cured film thereon curable triazine composition obtained in (2-3) , the cured product was evaluated in the same manner as in (1-4) . In the resultant plated substrate, slight creeping of plating was observed, however, no discoloration of the cured film or the copper foil was observed.
Example 3 (3-1) Synthesis of a triazine compound
15.8 g of a white powdery resin was obtained by conducting synthesis in the same manner as in (1-1) except that
4, 4' -dihydroxyphenylether (product name: SPECIANOL DPE-H, available from DAINIPPON INK AND CHEMICALS, INCORPORATED) was used in place of Bisphenol F (o,m,p-substituted mixture, available from Honshu Chemical Industry Co., Ltd.) . The number average molecular weight of the resin measured by gel permeation chromatography (hereinafter, abbreviated as "GPC") was 2,500 in terms of polystyrene.
Moreover, the powdery resin was subje6'ted to thermogravimetric analysis (TGA method) and-'the temperature for 5% weight loss was 289 0C.
(3-2) Preparation of a curable triazine composition
By using the powdery resin obtained in (3-1) , a curable triazine resin composition having a nonvolatile content of 20 % by mass was obtained in the same manner as in (1-2) . (3-3) Coating with the curable triazine composition and curing By using the curable triazine composition obtained in (3-2), coating and curing were conducted in the same manner as in (1-3) .
(3-4) Evaluation of the cured product Using the substrate having a cured film thereon curable triazine composition obtained in (3-3) , the cured product was evaluated in the same manner as in (1-4) . In the resultant plated substrate, only slight creeping of plating and slight discoloration of the cured film and the copper foil were observed.
Comparative Example
In a reaction container equipped with a stirrer, a thermometer and a condenser, 600 g of carbitol acetate as a synthesis solvent, 375.O g (=0.3 mol) of polycaprolactonediol (product name:PLACCEL212, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) as a polymerpolyol, 40.2 g (=0.3 mol) of dimethylolpropionic acid as a dihydroxyl compound having a carboxylic group, 155.4 g (=0.7 mol) of isophorone diisocyanate as a polyisocyanate, 23.8 g (=0.2 mol) of 2-hydroxyethyl acrylate as an acrylate having a hydroxyl group, and each 0.1 g of p-methoxyphenol and di-t-butyl-hydroxytoluene were placed. The mixture was heated while stirring and the heating was stopped when the temperature was enhanced to 60 °C. Then, 0.16 g of dibutyl tin laurate was added thereto. When the temperature inside the reaction container began decreasing, the heating was resumed and stirring was continued while maintaining the temperature to be 80 °C. The reaction was terminated when disappearance of the absorption of isocyanate group at 2280 cm"1 was confirmed in the infrared absorption spectrum, to thereby obtain a viscous liquid urethane acrylate compound. The number average molecular weight of the urethane acrylate was 250,000, the acid value was 40 mgKOH/g, and the solid content was 50 % by mass. The urethane acrylate and an epoxy resin (PRODUCT
NAMErEPIKOTE 828, manufactured by JAPAN EPOXY RESINS, CO., LTD. ) were blended together so that the blending ratio of epoxy group against carboxy group was 1.1 equivalent, and further melamine (NISSAN CHEMICAL INDUCTRIES, LTD.) was added thereto at an amount of 8 parts by mass based on 100 parts by mass of the epoxy resin, to thereby obtain a curable resin composition.
By using this curable resin composition, a substrate having a cured film thereon was obtained in the same manner as in (1-3) of Example 1, and evaluation on resistance against tin plating was made in the same manner as in (1-4) . As a result creeping of plating was clearly observed, and significant discoloration of the cured film was observed.
INDUSTRIAL APPLICABILITY The curable triazine composition obtained according to the present invention gives cured products excellent in thermal resistance, resistance to the tin-plating and the like and can favorablybe used as sealingmaterial for electronic components and/or varnish for electronic components.

Claims

1. A curable triazine composition, comprising (A) a triazine compound represented by formula (1) :
Figure imgf000077_0001
wherein R1 each independently represents a divalent organic group, X1 each independently represents a monovalent organic group, X2 represents an oxygen atom, a sulfur atom or a group represented by formula (2) :
Figure imgf000077_0002
wherein R2 represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an aryl group or an aralkyl group; and n represents an integer of from 2 to 100, wherein part or all of n X1' s in the triazine compound have curable groups capable of being cured with heat or light, and comprising (B) a curing agent.
2. The curable triazine composition as claimed in claim 1, which is obtained by blending a curing agent in a triazine compound obtained by reacting one or more types of dihalotriazine compounds represented by formula (3) with one or more types selected from compounds each having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups or phenolic hydroxyl groups in one molecule:
Figure imgf000078_0001
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light, and X3 represents a halogen atom.
3. The curable triazine composition as claimed in claim 1, which is obtained by blending a curing agent in a triazine compound obtained by reacting one or more types of triazine dithiol compounds represented by formula (4) with one or more types of compounds represented by formula (5) : ■
X1
N^N (4) HS NT^SH
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light:
X4-Rx-X4 (5) wherein R1 represents a divalent organic group, and
X4 represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group.
4. The curable triazine composition as claimed in claim 1, which is obtained by blending a curing agent in a triazine compound obtained by reacting one or more types of triazine dithiol compounds represented by formula (4) with one or more types of bifunctional α,β-unsaturated carbonyl compounds:
X1
N^N (4) HS NT ^SH
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light.
5. The curable triazine composition as claimed in claim 1, wherein the n Rlfs in formula (1) represent at least one group selected from those represented by formulae (6) to (9) and (55) to (57) :
Figure imgf000079_0001
wherein R3, R4, R5 andR6 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having from 1 to 12 carbon atoms, an aralkyl group, a perfluoroalkyl group, a cyclohexyl group or a phenyl group;
Figure imgf000080_0001
wherein the four R7's each independently represent a hydrogen atom or a methyl group,
Figure imgf000080_0002
wherein the four R30' s each independently represent a hydrogen atom or a methyl group,
Figure imgf000080_0003
wherein the four R31's each independently represent a hydrogen atom or a methyl group,
Figure imgf000080_0004
wherein the four R32's each independently represent a hydrogen atom or a methyl group.
6. The curable triazine composition as claimed in claim 1, wherein the n Rlfs in formula (1) represent at least one group selected from those represented by formulae (58) to (60) .
Figure imgf000081_0001
7. The curable triazine composition as claimed in claim 1, wherein part or all of the X1' s represent a monovalent organic grouphaving at least one group selected fromamong a'llyl group, vinyl group, (meth)acryloyl group, epoxy group, oxetanyl group, carboxyl group, acid anhydride group, amino group, thiol group and isocyanate group which may be blocked.
8. The curable triazine composition as claimed in claim 1, wherein part or all of the X1's have an allyl group, and wherein the curing agent comprises an organic peroxide.
9. The curable triazine composition as claimed in claim 1, wherein part or all of the X1' s have a (meth) acryloyl group, and wherein the curing agent comprises an azo compound.
10. The curable triazine composition as claimed in claim 1, wherein part or all of the X1' s have an epoxy group, and wherein the curing agent comprises a polyfunctional compound of an amine, a carboxylic acid or an acid anhydride.
11. The curable triazine composition as claimed in claim 1, wherein part or all of the Xlfs have an oxetanyl compound, and wherein the curing agent comprises an onium salt represented by formula (49) ,
[A]h+[X]h" (49)
wherein [A]h+ represents an onium ion, [X]h" represents an anion, and h represents an integer.
12. The curable triazine composition as claimed in claim 1, wherein part or all of the X1' s have a carboxyl group or an acid anhydride, and wherein the curing agent comprises a polyfunctional compound of an epoxy compound, an oxetane compound, an amine compound or an isocyanate compound.
13. The curable triazine composition as claimed in claim 1, wherein part or all of the X1' s have an amino group, and wherein the curing agent comprises a polyfunctional compound of an epoxy compound, an isocyanate compound, an acid anhydride or an a, β-unsaturated carbonyl compound.
14. The curable triazine composition as claimed in claim 1, wherein part or all of the Xlfs have a thiol group, and wherein the curing agent comprises a polyene compound.
15. The curable triazine composition as claimed in claim 1, wherein part or all of the X1' s have an isocyanate group which may be blocked, and wherein the curing agent comprises a polyfunctional compound of an amine compound or a carboxylic compound or an acid anhydride.
16. The curable triazine composition as claimed in claim 1, further containing a solvent.
17. The curable triazine composition as claimed in claim 16, wherein the solvent is at least one kind selected from the group consisting of ether solvent, sulfur-containing solvent, ester solvent, ketone solvent and aromatic hydrocarbon solvent.
18. The curable triazine composition as claimed in claim 16, wherein organic or inorganic fine particles are blended in.
19. The curable triazine composition as claimed in claim 18, wherein the organic or inorganic particulate substance is at least one kind selected from the group consisting of silica
(SiO2), alumina (Al2O3), titania (TiO2), tantalum oxide (Ta2O5), zirconia (ZrO2), silicon nitride (Si3N4), barium titanate (BaO-TiO2), barium carbonate (BaCO3), lead titanate (PbO-TiO2), lead zirconate titanate (PZT) , lead lanthanum zirconate titanate (PLZT) , gallium oxide (Ga2O3) , spinel (MgO-Al2O3) , mullite (3Al2O3-2SiO2) , cordierite (2MgO-2Al2O3/5SiO2) , talc (3MgO-4SiO2-H2O) , aluminum titanate (TiO2-Al2O3), zirconia containing yttria (Y2O3-ZrO2) , barium silicate (BaO-8SiO2) , boron nitride (BN) , calcium carbonate (CaCO3) , calcium sulfate (CaSO4) , zinc oxide (ZnO), magnesium titanate (MgO-TiO2), barium sulfate (BaSO4), organic bentonite, carbon (C), polyimide resin or its precursor, polyamideimide resin or its precursor and polyamide resin.
20. The curable triazine composition as claimed in claim 19, wherein the average particle size of the organic or inorganic particulate substance is 50 μm or less.
21. The curable triazine composition as claimed in claim any one of 18 to 20, having a viscosity of 0.5 to 500 Pa-s at 25 0C and a thixotropic coefficient of 1.1 or more.
22. A method for producing a curable triazine composition, wherein a curing agent is blended in a triazine compound obtained by reacting one or more types of dihalotriazine compounds represented by formula (3) with one or more types selected from compounds each having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups or phenolic hydroxyl groups in one molecule:
Figure imgf000084_0001
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light, and X3 represents a halogen atom.
23. A method for producing a curable triazine composition, wherein a curing agent is blended in a triazine compound obtained by reacting one or more types of triazine dithiol compounds represented by formula (4) with one or more types of compounds represented by formula (5) :
Figure imgf000085_0001
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light:
X4-Rx-X4 (5) wherein R1 represents a divalent organic group, and X4 represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group.
24. A method for producing a curable triazine composition, wherein a curing agent is blended in a triazine compound obtained by reacting one or more types of triazine dithiol compounds represented by formula (4) with one or more types of bifinctional α,β-unsaturated carbonyl compounds:
Figure imgf000085_0002
wherein X1 represents a monovalent organic group including a curable group capable of being cured with heat or light.
25. A triazine compound represented by formula (1),
Figure imgf000086_0001
wherein R1 each independently represents a divalent organic group, X1 each independently represents a monovalent organic group, X2 represents an oxygen atom, a sulfur atom or a group represented by formula (2),
N (2)
wherein R2 represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an aryl group or an aralkyl group; and n represents an integer of from 2 to 100, in which part or all of n X1' s present in the triazine compound have groups curable with heat or light, the divalent organic group represented by R1 is an organic group represented by formula (58), (59) or (60),
KJ V7 (58)
Figure imgf000086_0002
the monovalent organic group represented by X1 is an organic group having an ethylenic carbon-carbon double bond, and X2 is an oxygen atom or a sulfur atom.
26. A cured product obtained by curing the curable triazine composition as described in any one of claims 1 to 21.
27. A sealing material for electronic component comprising the curable triazine composition as described in any one of claims 1 to 21.
28. A varnish for electronic component comprising the curable triazine composition as described in any one of claims 1 to 21.
PCT/JP2005/014460 2004-08-02 2005-08-01 Curable triazine composition for electronic components, production method therefor and cured product thereof WO2006013989A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6091349A (en) * 1983-10-26 1985-05-22 Kanto Kagaku Kk Composition for negative type electron ray resist
EP0668529A2 (en) * 1994-02-14 1995-08-23 Hoechst Aktiengesellschaft Triazine polymers
DE19644930A1 (en) * 1996-09-16 1998-03-19 Bayer Ag Triazine polymers and their use in electroluminescent devices

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6091349A (en) * 1983-10-26 1985-05-22 Kanto Kagaku Kk Composition for negative type electron ray resist
EP0668529A2 (en) * 1994-02-14 1995-08-23 Hoechst Aktiengesellschaft Triazine polymers
DE19644930A1 (en) * 1996-09-16 1998-03-19 Bayer Ag Triazine polymers and their use in electroluminescent devices

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 009, no. 239 (P - 391) 25 September 1985 (1985-09-25) *

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