WO2011043400A1 - Composition d'acide polycarboxylique, son procédé de préparation, et compositions de résines durcissables la contenant - Google Patents

Composition d'acide polycarboxylique, son procédé de préparation, et compositions de résines durcissables la contenant Download PDF

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WO2011043400A1
WO2011043400A1 PCT/JP2010/067594 JP2010067594W WO2011043400A1 WO 2011043400 A1 WO2011043400 A1 WO 2011043400A1 JP 2010067594 W JP2010067594 W JP 2010067594W WO 2011043400 A1 WO2011043400 A1 WO 2011043400A1
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carboxylic acid
compound
anhydride
polyvalent carboxylic
acid composition
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PCT/JP2010/067594
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English (en)
Japanese (ja)
Inventor
政隆 中西
直房 宮川
静 青木
義浩 川田
智江 佐々木
健一 窪木
瑞観 鈴木
正人 鎗田
敬夫 小柳
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日本化薬株式会社
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Priority to CN201080055368.8A priority Critical patent/CN102648244B/zh
Priority to JP2011535440A priority patent/JP5574447B2/ja
Publication of WO2011043400A1 publication Critical patent/WO2011043400A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • the present invention relates to a polyvalent carboxylic acid composition suitable for use in electrical and electronic materials and a method for producing the same. Furthermore, the present invention relates to a curable resin composition containing the polyvalent carboxylic acid composition as a curable component.
  • Polyvalent carboxylic acid has excellent performance as a crosslinking agent, condensing agent, etc., such as high thermal stability, good electrical properties, chemical resistance, etc., as well as formation of condensates and good reactivity. As a molecular manufacturing raw material, it has attracted much attention and is widely used. It is also known that polyvalent carboxylic acids can be used as curing agents for epoxy resins.
  • a curable resin composition containing an epoxy resin is used as a resin having excellent heat resistance in the fields of architecture, civil engineering, automobiles, aircraft, and the like.
  • electronic devices such as mobile phones with cameras, ultra-thin liquid crystals, plasma TVs, and light-weight notebook computers have become key to light, thin, short, and small.
  • Very high characteristics have been demanded for packaging materials represented by resins.
  • the use in the optoelectronics related field has attracted attention.
  • a technique utilizing an optical signal has been developed instead of the conventional signal transmission using electric wiring. Accordingly, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of a resin composition that gives a cured product having excellent transparency is desired.
  • the epoxy resin curing agent used in such a field includes acid anhydride compounds.
  • acid anhydrides formed with saturated hydrocarbons are often used because cured products have excellent light resistance (see, for example, Patent Documents 1 and 2).
  • these acid anhydrides alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride are generally used. Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. are mainly used.
  • these curing agents have a high vapor pressure and tend to partially evaporate during curing.
  • the effect of the above volatilization on the cured product is prominent when an LED, particularly an LED used for a SMD (Surface Mount Device) is sealed with a cured product using a conventional acid anhydride as a curing agent. Since LED sealing uses a small amount of resin, there is a problem that dents are generated when acid anhydrides volatilize, and in severe cases, the wires are exposed. Furthermore, since cracks and peeling occur during solder reflow, or curing becomes insufficient, the obtained cured product has a problem that it is difficult to withstand long-term lighting.
  • a method using polyvalent carboxylic acid as a curing agent can be considered.
  • ordinary polyvalent carboxylic acids are often solidified, particularly crystallized due to their hydrogen bonds, and are very difficult to use as a liquid composition.
  • the inventors of the present invention have studied using a silicone-based polyvalent carboxylic acid as a curing agent.
  • desired properties were not obtained in terms of adhesion and corrosion gas permeability, and it was difficult to use as a cured product such as a sealing material.
  • the resulting cured product tends to be brittle, and there is a problem in toughness.
  • the present invention provides a polyvalent carboxylic acid composition that suppresses volatilization of a curing agent during curing, and further provides a cured product excellent in heat resistance, light resistance, corrosion resistance gas permeability, adhesion, toughness, and the like. It aims at providing the manufacturing method. Another object of the present invention is to provide a curable resin composition containing the polyvalent carboxylic acid composition.
  • R 1 represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond
  • R 2 represents a methyl group or a phenyl group
  • n represents a repeating unit
  • the weight average molecular weight of the compound represented by) is 500 to 5,000.
  • a carboxylic acid compound (J) obtained by subjecting a silicone oil (a) represented by the formula (b) to a compound (b) having one or more carboxylic anhydride groups in the molecule; Polyvalent carboxylic acid obtained by addition reaction of saturated aliphatic polyhydric alcohol (c) having a bifunctional or higher alcoholic hydroxyl group and compound (d) having one or more carboxylic anhydride groups in the molecule
  • Compound (K) Containing a polyvalent carboxylic acid composition
  • (2) The polyvalent carboxylic acid composition according to item (1), wherein the compounds (b) and (d) are acid anhydrides having a cyclic saturated hydrocarbon as a mother skeleton, (3)
  • the polyvalent carboxylic acid composition as described, (6) A method for producing the polyvalent carboxylic acid composition according to any one of (1) to (5) above, Compounds (b) and (d) having one or more carboxylic anhydride groups in the molecule are added to a mixture containing silicone oil (a) and a saturated aliphatic polyhydric alcohol (c) having a bifunctional or higher functional alcoholic hydroxyl group. And the addition reaction between the silicone oil (a) and the compound (b) and the addition reaction between the compound (c) and the compound (d) are performed simultaneously.
  • Method for producing polyvalent carboxylic acid composition (9) A curable resin composition comprising the polyvalent carboxylic acid composition according to any one of (1) to (5) above and an epoxy resin; (10) The curable resin composition as described in (9) above, wherein the epoxy resin is an alicyclic epoxy resin and / or an epoxy group-containing silicone resin, (11) The curable resin composition as described in (9) above, wherein the epoxy resin is an epoxy group-containing silicone resin, (12) A cured product obtained by curing the curable resin composition according to any one of (9) to (11), About.
  • the polyvalent carboxylic acid composition of the present invention is useful as a curing agent for an epoxy resin.
  • the curable resin composition of the present invention is used as a curing agent in a temperature range usually employed for curing an epoxy resin.
  • it is excellent in heat resistance, light resistance, adhesion, corrosion resistance gas permeability, toughness and the like.
  • the polyvalent carboxylic acid composition of the present invention includes paints, adhesives, molded articles, semiconductors, optical semiconductor encapsulant resins, optical semiconductor die bond material resins, polyimide resins and other raw materials and modifiers, plasticizers, It is useful as a raw material for lubricating oils, intermediates for pharmaceuticals and agricultural chemicals, resin for paints, and resin for toners. Especially, it has excellent curing ability for epoxy resins and transparency of cured products obtained from it. It is extremely useful as a curing agent for an epoxy resin for sealing a representative optical semiconductor.
  • the polyvalent carboxylic acid composition of the present invention has the following formula (1)
  • R 1 represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond
  • R 2 represents a methyl group or a phenyl group
  • n represents a repeating unit
  • the weight average molecular weight of the compound represented by is 500 to 5,000.
  • a carboxylic acid compound (J) obtained by subjecting a silicone oil (a) represented by the formula (b) to a compound (b) having one or more carboxylic anhydride groups in the molecule; Polyvalent carboxylic acid obtained by addition reaction of saturated aliphatic polyhydric alcohol (c) having a bifunctional or higher alcoholic hydroxyl group and compound (d) having one or more carboxylic anhydride groups in the molecule And a compound (K).
  • the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) used in the production of the polyvalent carboxylic acid composition of the present invention are prepared in accordance with the following, and each raw material is allowed to react sequentially even if they are individually adjusted and mixed. May be.
  • the silicone oil (a) is represented by the formula (1).
  • R 1 specific examples of R 1 include alkylene groups having 1 to 10 carbon atoms and no ether bond, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene; 3 H 6 —O—C 2 H 4 —, —C 2 H 4 —O—C 2 H 4 —, —C 3 H 6 —O—C 3 H 6 — etc. 10 alkylene groups are mentioned. Of these, a propylene group or —C 3 H 6 —O—C 2 H 4 — is preferable because of easy availability in the market.
  • a commercially available product includes a polyethylene oxide adduct, but this is not preferable in terms of heat resistance and light resistance.
  • the preferred molecular weight range of the silicone oil (a) is 500 to 5000, more preferably 600 to 4000, and particularly preferably 600 to 2500 in terms of weight average molecular weight. The most preferable range is 600 to 1500.
  • the molecular weight is less than 500, the intermolecular force of the obtained product is increased and the viscosity is likely to increase.
  • the molecular weight is greater than 5000, the compatibility with other components is poor and the system often becomes cloudy. That is not preferable.
  • Such a carbinol-modified silicone compound can be synthesized, for example, using a technique described in Japanese Patent Application Laid-Open No. 2007-508424.
  • the commercially available compounds include Dow Corning 5562 (manufactured by Dow Corning Toray), X22-160-AS, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical), XF42-B0970 (manufactured by Momentive ), Silaplane FM-4411, FM-4421, FM-4425 (manufactured by Chisso) and the like.
  • saturated aliphatic polyhydric alcohol (c) having a bifunctional or higher alcoholic hydroxyl group examples include conventionally known alcohols, and from the viewpoint of a balance between heat resistance, light resistance and toughness, particularly preferred is a functional group. It is preferably a polyhydric alcohol having 2 to 6 groups, and the total number of carbon atoms in one molecule is 5 to 20. More preferred are chain alkylene diols having a branched structure, diols having a cyclic structure, triols, tetraols, hexaols and the like.
  • chain alkylene diol having a branched structure examples include neopentyl glycol, 2-ethyl-2-butylpropylene-1,3-diol, 2,4-diethylpentane-1,5-diol and the like.
  • diol having a cyclic structure examples include tricyclodecane diol, pentacyclopentadecane diol, 1,4-cyclohexane diol, norbornane diol, dioxane glycol, spiro glycol and the like.
  • triol examples include glycerin and trimethylolpropane
  • examples of the tetraol include pentaerythritol and ditrimethylolpropane
  • examples of the hexaol include dipentaerythritol.
  • 2,4-diethylpentane-1,5-diol, tricyclodecanediol, or pentaerythritol it is not limited to these specific examples, Furthermore, you may use 1 type or in mixture of 2 or more types.
  • phthalic anhydride trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Examples include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, cyclobutanetetracarboxylic acid dihydrate, butanetetracarboxylic dianhydride, and the like.
  • a compound having a saturated hydrocarbon structure is particularly preferable.
  • those having a cyclic saturated hydrocarbon structure as a mother skeleton are particularly preferable.
  • methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4- Tricarboxylic acid-1,2-anhydride and bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride are particularly preferred.
  • methylhexahydrophthalic anhydride or cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is particularly preferable from the viewpoint of optical properties.
  • the reaction for adding an alcohol and an acid anhydride is generally an addition reaction using an acid or a base as a catalyst.
  • a catalyst-free reaction is preferred.
  • hydrochloric acid sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds
  • sodium hydroxide potassium hydroxide
  • calcium hydroxide water
  • Metal hydroxides such as magnesium oxide, amine compounds such as triethylamine, tripropylamine, tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, imidazole, triazole, Heterocyclic compounds such as tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide Trimethyl
  • catalysts may be used alone or in combination of two or more. Of these, triethylamine, pyridine, and dimethylaminopyridine are preferred.
  • the amount of the catalyst used is not particularly limited, but is usually 0.001 to 5 parts by weight with respect to 100 parts by weight of the total weight of the raw materials.
  • a reaction without a solvent is preferable, but an organic solvent may be used.
  • the organic solvent is used in a weight ratio of 0.005 to 1, preferably 0.005 to 0.7, more preferably 0.005 to 0.5 (that is, outside) with respect to a total amount of reaction substrate of 1. 50% by weight or less). When the weight ratio exceeds 1, the progress of the reaction is extremely slow, which is not preferable.
  • organic solvents that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, diethyl ether , Ethers such as tetrahydrofuran and dioxane, and ester compounds such as ethyl acetate, butyl acetate and methyl formate.
  • alkanes such as hexane, cyclohexane and heptane
  • aromatic hydrocarbon compounds such as toluene and xylene
  • ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone
  • diethyl ether Ethers such as tetrahydrofuran and dioxane
  • the reaction temperature is preferably 40 to 200 ° C, particularly preferably 40 to 150 ° C.
  • the reaction at 100 ° C. or lower is preferred, and a reaction at 40 to 100 ° C., particularly 40 to 80 ° C. is preferred because of the volatilization of acid anhydride.
  • a compound having high crystallinity at room temperature such as cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride
  • the reaction is performed at 100 to 150 ° C. in order to sufficiently dissolve the crystal. It is preferable.
  • the acid anhydride which is easy to volatilize, and the acid anhydride with high crystallinity it is also possible to prevent volatilization of an acid anhydride by raising temperature in steps.
  • the reaction ratio of the compounds (a) and (b), (c) and (d) in the reaction for obtaining the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) is theoretically equivalent. Is preferable, but can be changed as necessary. That is, as will be described later, in the curing agent composition of the present invention, when the acid anhydride used in combination with the acid anhydride used here is the same as necessary, the reaction is carried out in an excess of acid anhydride at the time of production. When the reaction for obtaining the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) is completed, a mixture of the acid anhydride and the polyvalent carboxylic acid composition of the present invention can be used.
  • the functional group equivalent is compared.
  • the molar ratio (a) (or (c)) is 0.001 to 1. 0, more preferably 0.01 to 1.0, still more preferably 0.1 to 1.0.
  • the ratio is preferably in the range of 0.01 to 0.7, preferably 0.01 to 0.4. .
  • reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long reaction time is not preferable because it consumes a great deal of energy.
  • An excessively short reaction time means that the reaction is abrupt and is not preferable from the viewpoint of safety.
  • a preferred range is 1 to 48 hours, preferably 1 to 36 hours, and more preferably 1 to 24 hours.
  • the desired polycarboxylic acid (J) or (K) is obtained by removing the catalyst by neutralization, washing with water, adsorption, etc., and distilling off the solvent. .
  • the solvent is distilled off, and in the case of no solvent and without a catalyst, the polycarboxylic acid (J) or the polyvalent carboxylic acid (K) can be obtained by taking it out as it is. .
  • the most preferred production method is a method of reacting at 40 to 150 ° C. under the conditions of no catalyst and no solvent, and taking it out as it is after the reaction is completed.
  • the target polyvalent carboxylic acid composition can be obtained by mixing the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) thus obtained.
  • the ratio of (J) / (K) is particularly preferably 99/1 to 80/20, and more preferably 99/1 to 85/15.
  • the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) can also be produced simultaneously.
  • Specific methods include (i) Compounds (b) and (d) having one or more carboxylic acid anhydride groups in the molecule are charged into a mixture of silicone oil (a) and polyhydric alcohol (c) and reacted simultaneously. (Ii) The following steps (A) and (B) are sequentially reacted in one pot.
  • the compounds to be used in step (B) (or step (A)) are sequentially added, and reaction and mixing are performed in the system.
  • the polycarboxylic acid composition of the present invention thus obtained is usually a colorless liquid to semi-solid substance.
  • the polyvalent carboxylic acid composition of the present invention has excellent transparency, a curing agent for a curable resin such as an epoxy resin, a paint, an adhesive, a molded product, a semiconductor, a resin for an optical semiconductor encapsulant, and an optical semiconductor die bond material
  • a curing agent for a curable resin such as an epoxy resin, a paint, an adhesive, a molded product, a semiconductor, a resin for an optical semiconductor encapsulant, and an optical semiconductor die bond material
  • the polyvalent carboxylic acid composition of the present invention When used as a curing agent for an epoxy resin, the polyvalent carboxylic acid composition of the present invention exhibits excellent curability and the transparency of the cured product is excellent. It is extremely useful as a curing agent for epoxy resins used for sealing of other white semiconductor LEDs and other optical semiconductors.
  • the polyvalent carboxylic acid composition of the present invention is used as a curing agent for a curable resin such as an epoxy resin, particularly as a liquid composition
  • the polyvalent carboxylic acid composition of the present invention and another acid anhydride are mixed. It is preferably used in the form of a curing agent composition.
  • the acid anhydride that can be used a compound (e) having one or more carboxylic acid anhydride groups in the molecule is preferable, and an acid anhydride having no aromatic ring in its structure is particularly preferable.
  • the compound (e) having one or more carboxylic anhydride groups in the molecule include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1 ] Heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, etc. Is mentioned.
  • the proportion of the polyvalent carboxylic acid composition of the present invention is the total weight of the other acid anhydride and the polyvalent carboxylic acid composition of the present invention. On the other hand, it is 0.1 to 50% by weight, preferably 0.1 to 30% by weight. By using together in such a range, there is an effect in terms of fluidity of the composition and heat resistant mechanical strength of the cured product.
  • the curable resin composition of the present invention including the polyvalent carboxylic acid composition of the present invention will be described.
  • the curable resin composition of the present invention contains an epoxy resin as an essential component.
  • Examples of the epoxy resin that can be used in the curable resin composition of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins.
  • bisphenol A bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxy
  • an alicyclic epoxy resin and / or an epoxy-group containing silicone resin are preferable, and the epoxy resin of a silsesquioxane structure is more preferable.
  • an alicyclic epoxy resin a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is more preferable.
  • These alicyclic epoxy resins include esterification reaction of cyclohexene carboxylic acid with alcohols or esterification reaction of cyclohexene methanol with carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) ), Or Tyschenco reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and transesterification of cyclohexene carboxylic acid ester Examples thereof include an oxidized product of a compound that can be produced by a reaction (a method described in Japanese Patent Application Laid-Open No.
  • the alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane.
  • carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.
  • an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol is exemplified.
  • a reaction method it can be produced by applying a general acetalization reaction.
  • a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium US Pat. No. 2,945,008
  • concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the mixture and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No.
  • epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel) (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited thereto (Reference: Review Epoxy Resin Basic Edition I p76-85). These may be used alone or in combination of two or more.
  • the polyvalent carboxylic acid composition (or the curing agent composition) of the present invention may be used in combination with other curing agents.
  • the proportion of the polyvalent carboxylic acid of the present invention in the total curing agent is preferably 20% by weight or more, and particularly preferably 30% by weight or more.
  • other curing agents that can be used in combination include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds.
  • the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, Bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclo
  • the ratio of the total curing agent to the epoxy resin is 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups of the epoxy resin (note that acid anhydride groups are considered to be monofunctional).
  • the amount is particularly preferably 0.5 to 1.2 equivalents. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
  • a curing accelerator may be used in combination with a curing agent.
  • the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole.
  • the zinc salt and / or the zinc complex contributes as a curing accelerator between the epoxy resin and the curing agent.
  • the zinc salt and / or zinc complex is a salt and / or complex having a zinc ion as a central element, preferably a carboxylic acid having an alkyl group having 1 to 30 carbon atoms as a counter ion and / or a ligand. , Phosphoric acid ester, and phosphoric acid.
  • alkyl group having 1 to 30 carbon atoms examples include methyl group, isopropyl group, butyl group, 2-ethylhexyl group, octyl group, isodecyl group, isostearyl group, decanyl group, cetyl group and the like.
  • a zinc carboxylate and a zinc phosphate ester are particularly preferable. By using a zinc carboxylate body or a zinc phosphate ester body, corrosion resistance and gas permeability can be improved.
  • the particularly preferred zinc carboxylate in the present invention preferably has an alkyl group having a chain-branched structure or an alkyl group having a functional group such as an olefin in the compound, and among them, those having 3 to 30 carbon atoms are preferred. In particular, those having 5 to 20 carbon atoms are preferred. These are preferable in terms of compatibility, and when the number of carbon atoms is too large (when the number of carbon atoms exceeds 30), or when they do not have a structure such as a branched structure or a functional group, the compatibility with the resin is poor, which is not preferable. Specific examples include zinc 2-ethylhexylate, zinc isostearate and zinc undecylenate.
  • a zinc salt and / or a zinc complex of phosphoric acid, phosphoric acid ester (monoalkyl ester body, dialkyl ester body, trialkyl ester body, or a mixture thereof) is preferable.
  • the amount of the monoalkyl ester compound is 50 area% or more at the stage of the trimethylsilylation treatment.
  • Such zinc salt and / or zinc complex of zinc phosphate ester can be obtained, for example, by reacting a phosphate ester with, for example, zinc carbonate, zinc hydroxide, etc. (Patent Document EP 699708).
  • the ratio of phosphorus atom to zinc atom is preferably 1.2 to 2.3, more preferably 1.3 to 2.0. . Particularly preferred is 1.4 to 1.9. That is, in a particularly preferred form, the amount of phosphate ester (or phosphate derived from phosphate ester) is 2.0 mol or less per mol of zinc ion, and not a simple ionic structure, some molecules are ion-bonded (or arranged). Those having a structure related by coordinate bond) are preferred.
  • Such a zinc salt and / or zinc complex can also be obtained, for example, by the technique described in Japanese Patent Publication No. 2003-51495.
  • Examples of the phosphate ester and / or zinc phosphate include LBT-2000B (manufactured by SC Organic Chemical) and XC-9206 (manufactured by King Industry).
  • the curing accelerator is usually used in an amount of 0.001 to 15 parts by weight, more preferably 0.01 to 5 parts by weight, and particularly preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the epoxy resin.
  • curing is possible without using a curing accelerator, but from the viewpoint of coloring during curing, addition of a curing accelerator is preferred.
  • the use of zinc salts and / or zinc complexes is preferred in order to prevent coloring and to obtain corrosion-resistant gas permeability characteristics.
  • the curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component.
  • the phosphorus-containing compound may be a reactive type or an additive type.
  • Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-pho
  • Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
  • antioxidant to the curable resin composition of this invention as needed.
  • Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more.
  • the amount of the antioxidant used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the resin component in the curable resin composition of the present invention. It is.
  • antioxidants examples include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.
  • phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl- ⁇ - (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl
  • sulfur antioxidant examples include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyll-3,3′-thiodipropionate, and the like. .
  • phosphorus antioxidants include 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2 , 4-Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpenta Erythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert
  • a commercial item can also be used for the said phosphorus compound.
  • the amount of the phosphorus compound used is 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight with respect to the epoxy resin.
  • antioxidants can be used alone, but two or more kinds may be used in combination.
  • a phosphorus-based antioxidant is particularly preferable.
  • a light stabilizer it is preferable to contain a hindered amine compound especially, and it is preferable to contain a phosphorus compound as needed.
  • the amine compound that is the light stabilizer can be used as the amine compound that is the light stabilizer.
  • the light stabilizer is used in an amount of 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight with respect to the epoxy resin.
  • the amount is less than 0.005% by weight, the effect is insufficient, and when the amount exceeds 5% by weight, an influence on the heat-resistant coloring property appears, which is not preferable.
  • a binder resin can be blended with the curable resin composition of the present invention as required.
  • the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins.
  • the blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.
  • An inorganic filler can be added to the curable resin composition of the present invention as necessary.
  • inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like.
  • the present invention is not limited to these. These may be used alone or in combination of two or more.
  • the content of these inorganic fillers is used in an amount of 0 to 95% by weight in the curable resin composition of the present invention.
  • the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers.
  • agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers.
  • a compounding agent and various thermosetting resins can be added.
  • a fluorescent substance can be added as needed.
  • the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed.
  • fluorescent substance A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated.
  • phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO 3 : Ce, Y 3 Al 5 O 12 : Ce, Y 4 Al 2 O 9 : Ce, Y 2 O 2 S: Eu, Sr 5 (PO 4 ) 3 Cl: Eu, (SrEu) O.Al 2 O 3 and the like are exemplified.
  • the particle size of the phosphor those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 ⁇ m, particularly preferably 2 to 50 ⁇ m. When these phosphors are used, the addition amount thereof is 1 to 80 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the resin component.
  • silica fine powder also called Aerosil or Aerosol
  • a thixotropic agent can be added.
  • silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, AerosilR202, AerosilR202, AerosilR202 Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.
  • the curable resin composition of the present invention can be obtained by uniformly mixing each component.
  • the curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are thoroughly mixed using an extruder, kneader, roll, etc. as necessary until uniform.
  • the curable resin composition is in liquid form, potting or casting, impregnating the base material, pouring the curable resin composition into a mold, casting, curing by heating, or solid
  • the curing temperature and time are 80 to 200 ° C. and 2 to 10 hours.
  • a curing method it can be hardened at a high temperature at a stretch, but it is preferable to increase the temperature stepwise to advance the curing reaction. Specifically, initial curing is performed at 80 to 150 ° C., and post-curing is performed at 100 to 200 ° C.
  • the temperature is preferably increased in 2 to 8 stages, more preferably 2 to 4 stages.
  • the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, glass fiber,
  • a prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heat-dried is subjected to hot press molding to obtain a cured product of the curable resin composition of the present invention. can do.
  • the solvent is used in an amount usually accounting for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent.
  • cured material containing a carbon fiber can also be obtained with a RTM (Resin * Transfer * Molding) system with a liquid composition.
  • the curable resin composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used to improve flexibility in the B-stage.
  • a method for obtaining such a film-type resin composition first, the curable resin composition of the present invention is used as the curable resin composition varnish as described above, and this is applied onto a release film and heated under a solvent.
  • a method of forming a B-stage after removing the film is mentioned, whereby a film-type sealing composition can be obtained as a sheet-like adhesive.
  • This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
  • curable resin composition of the present invention is used as an optical semiconductor sealing material or die bond material.
  • a curing agent (curing agent composition) containing the polyvalent carboxylic acid of the present invention
  • a curable resin composition is prepared by sufficiently mixing additives such as a curing accelerator, a coupling material, an antioxidant, and a light stabilizer.
  • a mixing method a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, or the like may be used at room temperature or with heating.
  • the obtained curable resin composition can be used for a sealing material, or both a die-bonding material and a sealing material.
  • Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like.
  • Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material).
  • a wire such as a gold wire is connected to pass an electric current.
  • the periphery of such a semiconductor chip is sealed with a sealing material such as an epoxy resin.
  • the sealing material is used to protect the semiconductor chip from heat and moisture and to play a role of a lens function.
  • the curable resin composition of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the curable resin composition of the present invention for both the die bond material and the sealing material.
  • the curable resin composition of the present invention is applied on the substrate by dispenser, potting or screen printing, and then the curable resin is used.
  • a semiconductor chip is placed on the composition and heat-cured.
  • the semiconductor chip can be bonded to the substrate.
  • methods such as hot air circulation, infrared rays and high frequency can be used.
  • the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours.
  • post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
  • an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and then molded, and the sealing material on the mold A compression molding method is used in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from the mold.
  • the injection method include dispenser, transfer molding, injection molding and the like.
  • methods such as hot air circulation, infrared rays and high frequency can be used.
  • the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours.
  • post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
  • the application of the curable resin composition of the present invention is not limited to the above application, and can be applied to general applications in which a thermosetting resin such as an epoxy resin is used.
  • a thermosetting resin such as an epoxy resin
  • cyanate resin composition for resist and additives for other resins such as an acrylic ester resin as a curing agent for resist.
  • adhesives examples include civil engineering, architectural, automotive, general office, and medical adhesives, as well as electronic material adhesives.
  • adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).
  • sealing materials potting, dipping and transfer mold sealing used for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, potting sealings used for COB, COF, TAB, etc. of ICs and LSIs, flip Examples include underfill used for chips and the like, and sealing (including reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.
  • the cured product of the present invention obtained by curing the curable resin composition of the present invention can be used for various applications including optical component materials.
  • the optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field.
  • color PDP plasma display
  • antireflection films antireflection films
  • optical correction films housing materials
  • front glass protective films front glass replacement materials
  • adhesives and LED displays that are expected as next-generation flat panel displays
  • LED molding materials LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate
  • PLC plasma addressed liquid crystal
  • VD video disc
  • CD / CD-ROM CD-R / RW
  • DVD-R / DVD-RAM MO / MD
  • PD phase change disc
  • disc substrate materials for optical cards Pickup lenses, protective films, sealing materials, adhesives and the like.
  • optical equipment field they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor parts. It is also a photographic lens and viewfinder for video cameras.
  • optical components they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems.
  • optical passive components and optical circuit components there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like.
  • OEIC optoelectronic integrated circuit
  • automotive lamp reflectors In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, and automotive defenses Rusted steel plate, interior panel, interior material, wire harness for protection / bundling, fuel hose, automobile lamp, glass substitute.
  • it is a multilayer glass for railway vehicles.
  • they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wire harnesses, and corrosion-resistant coatings.
  • it In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film.
  • optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.
  • Synthesis example 2 A flask equipped with a stirrer, reflux condenser, and stirrer was charged with 98 parts of tricyclodecanediol, HTMan (1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, Mitsubishi Gas Chemical ( 99 parts), MH-700 (mixture of hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride, manufactured by Nippon Nippon Chemical Co., Ltd.), 84 parts, and 10 parts of toluene were charged in a reaction vessel at 100 ° C. for 1 hour. The reaction was carried out at 2 ° C. for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure to obtain 280 parts of a colorless solid resin carboxylic acid compound (K-1).
  • K-1 colorless solid resin carboxylic acid compound
  • Example 1 A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 68.3 parts of the carboxylic acid compound (J-1) while purging with nitrogen, and the mixture was stirred at 100 ° C., and the carboxylic acid compound (K -1) 28.1 parts were added, and the mixture was stirred as it was for 1 hour to be compatible with each other to obtain a polyvalent carboxylic acid composition (MA-1) of the present invention as a colorless transparent liquid.
  • Example 2 and Comparative Example 1 The polyvalent carboxylic acid composition (MA-1) of the present invention obtained in Example 1 and, as a comparative example, MH-700 (a mixture of hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) (Hereinafter referred to as H1) as a curing agent, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate as epoxy resin (UVR-6105 manufactured by Dow Chemical) (hereinafter referred to as epoxy resin (EP1)), curing Hexadecyltrimethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd., 25% methanol solution, hereinafter referred to as C1) is used as an accelerator, blended at the blending ratio (parts by weight) shown in Table 1 below, and desorbed for 20 minutes. Foaming was performed to obtain a curable resin composition of the present
  • LED sealing test Surface mount type (SMD) in which the curable resin compositions obtained in the examples and comparative examples were vacuum degassed for 20 minutes, filled in a syringe and mounted with a light emitting element having an emission wavelength of 465 nm using a precision discharge device.
  • Evaluation item Volatility The presence or absence of dents on the surface of the cured product after sealing was visually evaluated. In the table, ⁇ : no dent is observed, ⁇ : some dent is observed, x: many dents are observed (there is an exposed wire).
  • Example 2 shows that the curable resin composition of the present invention has a small amount of volatilization and does not cause problems such as wire exposure even when the LED is sealed. Furthermore, it can be seen that there is a tendency to reduce cracks during reflow. From the above results, it can be seen that the polyvalent carboxylic acid of the present invention and the curing agent composition containing the polyvalent carboxylic acid can give a curable resin composition effective for volatility.
  • Synthesis example 4 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (59.1 parts), polydimethyldiphenylsiloxane having a silanol group having a molecular weight of 1700 (measured by GPC) 130.6 parts, 0.5 wt% KOH methanol solution 10.0 The portion was charged into a reaction vessel and heated to 75 ° C. After raising the temperature, the mixture was reacted at 75 ° C. under reflux for 8 hours. After the reaction, 135 parts of methanol was added, 25.9 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted at 75 ° C. for 8 hours under reflux.
  • reaction mixture was neutralized with a 5 wt% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 170 parts of methyl isobutyl ketone (MIBK) was added for washing, and washing with water was repeated three times. Subsequently, 162 parts of epoxy resins (EP2) were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic layer.
  • the epoxy equivalent of the obtained compound was 707 g / eq, the weight average molecular weight was 2680, and the appearance was colorless and transparent.
  • Example 3 A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 500 parts of both ends carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) while purging with nitrogen, MH (methylhexahydrophthalic anhydride, 168 parts (manufactured by Nippon Nippon Chemical Co., Ltd.) and reacted at 70 ° C.
  • carbinol-modified silicone X22-160AS manufactured by Shin-Etsu Chemical Co., Ltd.
  • MH methylhexahydrophthalic anhydride
  • polycarboxylic acid (J) derived from carbinol-modified silicone at both ends is about 70% by weight
  • polycarboxylic acid derived from 2,4-diethylpentane-1,5-diol (K) is about 30% by weight
  • Example 4 A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while carrying both ends of the carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) 500 parts, MH (methylcyclohexanedicarboxylic anhydride, 168 parts by Nippon Nippon Chemical Co., Ltd., 80 parts by Kyowadiol PD9 (2,4-diethylpentane-1,5-diol manufactured by Kyowa Hakko Chemical), HTAn (1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride) 198 parts by Mitsubishi Gas Chemical Co., Ltd.), reacted at 70 ° C.
  • MH methylcyclohexanedicarboxylic anhydride, 168 parts by Nippon Nippon Chemical Co., Ltd., 80 parts by Kyowadiol
  • polyvalent carboxylic acid composition (MA-3) of the present invention.
  • the obtained polyvalent carboxylic acid composition was a colorless and transparent liquid.
  • polycarboxylic acid (J) derived from carbinol-modified silicone at both ends is about 70% by weight
  • polycarboxylic acid derived from 2,4-diethylpentane-1,5-diol (K) About 27% by weight and about 3% by weight of acid anhydride
  • Corrosion gas 20% by weight aqueous solution of ammonium sulfide (turns black when sulfur component reacts with silver)
  • Contact method A container of an ammonium sulfide aqueous solution and the LED package were mixed in a wide-mouth glass bottle, and the wide-mouth glass bottle was covered to bring the volatilized ammonium sulfide gas into contact with the LED package in a sealed state.
  • Judgment of corrosion The time when the lead frame inside the LED package was discolored black (referred to as blackening) was observed, and the longer the discoloration time, the better the corrosion resistance gas permeability.
  • the epoxy resin composition of the present invention has a dent and is excellent not only in reflow resistance but also in a cured product excellent in corrosion resistance and gas permeability.
  • SI-1 Chisso FM-4411
  • SI-2 Shin-Etsu Chemical X22-160AS
  • AL-1 Kyowa Hakko Chemical Kyowajiru PD-9
  • AL-2 OXEA TCDAlchol-DM
  • H1 Rikacid MH-700, manufactured by Shin Nippon Rika
  • H2 Rikacid MH, manufactured by Shin Nippon Rika
  • H3 H-TMAn, manufactured by Mitsubishi Gas Chemical.
  • Synthesis example 8 A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 100 parts of acid anhydride (H2) and saturated aliphatic polyhydric alcohol (AL-1) while purging with nitrogen, and at 70 ° C. for 3 hours. Stirring at 30 ° C. for 30 minutes gave 120 parts of a mixture of a colorless and transparent carboxylic acid compound and an acid anhydride. The ratio of the obtained carboxylic acid to acid anhydride was approximately 52:48 as a result of measurement by gel permeation chromatography.
  • Synthesis Example 10 375 parts of ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1900 (measured by GPC) (silanol equivalent 950, half of the weight average molecular weight measured using GPC) 40 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into a reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
  • Examples 16 to 19 and Comparative Example 4 The polyvalent carboxylic acid composition of the present invention (MA-4, MA-5, MA-6, MA-10), as a comparative example, a polyvalent carboxylic acid resin (J-3) is used as a curing agent, and an epoxy resin Using the epoxy resin (EP-4) obtained in Synthesis Example 10, zinc octylate (18% Octopus Zn, hereinafter referred to as C2) manufactured by Hope Pharmaceutical, and light stabilizer (LA-81 or less, manufactured by ADEKA) were added as a curing accelerator. And an antioxidant (made by ADEKA, ADEKA 260, called additive AD-2)), and blended at the blending ratio (parts by weight) shown in Table 4 below, and removed for 20 minutes.
  • an antioxidant made by ADEKA, ADEKA 260, called additive AD-2
  • Foaming was performed to obtain a curable resin composition of the present invention and a comparative curable resin composition. Using the obtained curable resin composition, a test was conducted in the following manner, and the results are shown in Table 4. The curing conditions are 150 ° C. ⁇ 5 hours after preliminary curing at 120 ° C. ⁇ 2 hours, unless otherwise specified.
  • Examples 20-22, Comparative Example 5 The polyvalent carboxylic acid composition of the present invention (MA-7, MA-8, MA-9), as a comparative example, the polyvalent carboxylic acid resin (J-3) was used as a curing agent, and the epoxy resin was synthesized in Synthesis Example 9, 10 using the epoxy resins (EP-3, EP-4) obtained in No. 10, using the curing accelerator (C2) and additives (AD-1, AD-2), and the mixing ratios (weights) shown in Table 5 below. Part) and defoaming for 20 minutes to obtain a curable resin composition of the present invention and a comparative curable resin composition. Using the obtained curable resin composition, a test was conducted in the following manner, and the results are shown in Table 5. The curing conditions are 150 ° C.
  • the curable resin composition of the present invention is excellent in adhesion, toughness, and heat durability.
  • Corrosive gas 20% aqueous solution of ammonium sulfide (discolors black when sulfur component reacts with silver)
  • Contact method A container of an ammonium sulfide aqueous solution and the LED package were mixed in a wide-mouth glass bottle, and the wide-mouth glass bottle was covered to bring the volatilized ammonium sulfide gas into contact with the LED package in a sealed state.
  • Judgment of corrosion The time when the lead frame inside the LED package was blackened (referred to as blackening) was observed every hour, and it was judged that the longer the color changing time, the better the corrosion resistance gas resistance.
  • Example 26 Comparative Example 7
  • the polyvalent carboxylic acid composition (MA-13) of the present invention as a comparative example, the polycarboxylic acid resin (J-3) was used as a curing agent, and the epoxy resin obtained in Synthesis Examples 9 and 10 as an epoxy resin ( EP-3, EP-4), using curing accelerator (C2) and additives (AD-1, AD-2), and blending ratios (parts by weight) shown in Table 7 below, for 20 minutes Defoaming was performed to obtain a curable resin composition of the present invention and a comparative curable resin composition. Using the obtained curable resin composition, a test was conducted in the following manner, and the results are shown in Table 7. The curing conditions are 150 ° C. ⁇ 5 hours after preliminary curing at 120 ° C.
  • LED for lighting test is obtained by making it harden
  • the lighting test was performed at 210 mA, which is 7 times the specified current, for the acceleration test. Detailed conditions are shown below.
  • the illuminance before and after lighting for 40 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated.
  • Light emission wavelength 465nm Drive method: constant current method, 210 mA (light emitting element specified current is 30 mA)
  • Driving environment 25 ° C, 65% RH (4) Gas permeation resistance test (corrosion gas permeability test); The package of the LED prepared with the obtained curable resin composition was left in a corrosive gas under the following conditions, and the change in the color of the silver-plated lead frame inside the seal was observed.
  • Corrosive gas 20% aqueous solution of ammonium sulfide (discolors black when sulfur component reacts with silver)
  • Contact method A container of an ammonium sulfide aqueous solution and the LED package were mixed in a wide-mouth glass bottle, and the wide-mouth glass bottle was covered to bring the volatilized ammonium sulfide gas into contact with the LED package in a sealed state.
  • Judgment of corrosion The time during which the lead frame inside the LED package was blackened (referred to as blackening) was observed every hour, and it was judged that the longer the color changing time, the better the corrosion resistance.
  • the epoxy resin composition of the present invention is not only excellent in heat resistance and light resistance, but also in a cured product excellent in adhesion, toughness, and corrosion resistance gas permeability. I know you give it.

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  • Silicon Polymers (AREA)

Abstract

Cette invention concerne une composition d'acide polycarboxylique qui permet de réduire la volatilisation d'un durcisseur lors du durcissage et qui peut donner des produits durcis ayant une excellente résistance à la chaleur, résistance à la lumière, résistance à la perméation de gaz corrosifs, une propriété de forte adhérence et une excellente ténacité. La composition d'acide polycarboxylique selon l'invention est caractérisée en ce qu'elle comprend à la fois (J) un composé acide carboxylique obtenu par une réaction d'addition de (a) une huile silicone représentée par la formule générale (1) et de (b) un composé qui contient au moins un groupe anhydride carboxylique dans la molécule et (K) un composé acide polycarboxylique obtenu par une réaction d'addition de (c) un polyol aliphatique saturé contenant deux groupes hydroxyle alcooliques ou plus et de (d) un composé qui contient au moins un groupe anhydride carboxylique dans la molécule. Dans la formule générale (1), R1 est un groupe alkylène qui contient de 1 à 10 atomes de carbone au total et qui peut être interrompu par une liaison éther ; R2 est un méthyle ou un phényle ; et n représente le nombre de motifs de répétition, le composé de formule générale (1) ayant une masse moléculaire moyenne en poids de 500 à 5000.
PCT/JP2010/067594 2009-10-06 2010-10-06 Composition d'acide polycarboxylique, son procédé de préparation, et compositions de résines durcissables la contenant WO2011043400A1 (fr)

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JP2011256326A (ja) * 2010-06-11 2011-12-22 Nippon Kayaku Co Ltd 硬化性樹脂組成物およびその硬化物
JP2012001570A (ja) * 2010-06-14 2012-01-05 Nippon Steel Chem Co Ltd エポキシシリコーン樹脂含有硬化性樹脂組成物
WO2012137837A1 (fr) * 2011-04-07 2012-10-11 日本化薬株式会社 Résine d'acide polycarboxylique et sa composition
CN102746790A (zh) * 2012-07-23 2012-10-24 尹利勋 一种用于制作背投屏的成像材料
WO2013035740A1 (fr) * 2011-09-09 2013-03-14 日本化薬株式会社 Composition de résine durcissable pour le scellement étanche d'un élément semi-conducteur optique et produit durci à base de celle-ci
WO2013047620A1 (fr) * 2011-09-27 2013-04-04 日本化薬株式会社 Composition de résine durcissable destinée à sceller un élément semi-conducteur optique, et matériau durci obtenu à partir de celle-ci
WO2013180148A1 (fr) * 2012-05-31 2013-12-05 日本化薬株式会社 Composition d'acide polycarboxylique, procédé de fabrication d'une composition d'acide polycarboxylique, composition de durcisseur pour résine époxy, composition de résine époxy et produit durci
JP2014095053A (ja) * 2012-11-12 2014-05-22 Nippon Kayaku Co Ltd 硬化性樹脂組成物およびその硬化物
WO2014136693A1 (fr) * 2013-03-05 2014-09-12 日本化薬株式会社 Composition d'acide polycarboxylique, composition de durcisseur pour résines époxy, et composition de résine époxy et produit durci à base de celle-ci
WO2014157552A1 (fr) * 2013-03-28 2014-10-02 日本化薬株式会社 Composition de résine époxyde d'encapsulation de semi-conducteur en optique, produit durci correspondant et dispositif optique à semi-conducteur
JP2016045243A (ja) * 2014-08-20 2016-04-04 日本化薬株式会社 近赤外線吸収色素を含む熱硬化性樹脂組成物及び近赤外線カットフィルタ
JPWO2014050978A1 (ja) * 2012-09-27 2016-08-22 日本化薬株式会社 多価カルボン酸樹脂およびエポキシ樹脂組成物

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FR3006493A1 (fr) * 2013-06-04 2014-12-05 Nexans Cable electrique a moyenne ou haute tension
JP7236817B2 (ja) * 2017-06-19 2023-03-10 日本化薬株式会社 反応性ポリカルボン酸化合物、それを用いた活性エネルギー線硬化型樹脂組成物、その硬化物及びその用途

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JP2011102337A (ja) * 2009-11-10 2011-05-26 Nippon Kayaku Co Ltd エポキシ樹脂組成物
JP2011256326A (ja) * 2010-06-11 2011-12-22 Nippon Kayaku Co Ltd 硬化性樹脂組成物およびその硬化物
JP2012001570A (ja) * 2010-06-14 2012-01-05 Nippon Steel Chem Co Ltd エポキシシリコーン樹脂含有硬化性樹脂組成物
WO2012137837A1 (fr) * 2011-04-07 2012-10-11 日本化薬株式会社 Résine d'acide polycarboxylique et sa composition
JP5948317B2 (ja) * 2011-04-07 2016-07-06 日本化薬株式会社 多価カルボン酸樹脂およびその組成物
JPWO2013035740A1 (ja) * 2011-09-09 2015-03-23 日本化薬株式会社 光半導体素子封止用硬化性樹脂組成物およびその硬化物
WO2013035740A1 (fr) * 2011-09-09 2013-03-14 日本化薬株式会社 Composition de résine durcissable pour le scellement étanche d'un élément semi-conducteur optique et produit durci à base de celle-ci
CN103781815A (zh) * 2011-09-09 2014-05-07 日本化药株式会社 光半导体元件密封用固化性树脂组合物及其固化物
WO2013047620A1 (fr) * 2011-09-27 2013-04-04 日本化薬株式会社 Composition de résine durcissable destinée à sceller un élément semi-conducteur optique, et matériau durci obtenu à partir de celle-ci
JP2013071950A (ja) * 2011-09-27 2013-04-22 Nippon Kayaku Co Ltd 硬化性樹脂組成物およびその硬化物
WO2013180148A1 (fr) * 2012-05-31 2013-12-05 日本化薬株式会社 Composition d'acide polycarboxylique, procédé de fabrication d'une composition d'acide polycarboxylique, composition de durcisseur pour résine époxy, composition de résine époxy et produit durci
JPWO2013180148A1 (ja) * 2012-05-31 2016-01-21 日本化薬株式会社 多価カルボン酸組成物、多価カルボン酸組成物の製造方法、エポキシ樹脂用硬化剤組成物、エポキシ樹脂組成物および硬化物
CN102746790A (zh) * 2012-07-23 2012-10-24 尹利勋 一种用于制作背投屏的成像材料
JPWO2014050978A1 (ja) * 2012-09-27 2016-08-22 日本化薬株式会社 多価カルボン酸樹脂およびエポキシ樹脂組成物
JP2014095053A (ja) * 2012-11-12 2014-05-22 Nippon Kayaku Co Ltd 硬化性樹脂組成物およびその硬化物
WO2014136693A1 (fr) * 2013-03-05 2014-09-12 日本化薬株式会社 Composition d'acide polycarboxylique, composition de durcisseur pour résines époxy, et composition de résine époxy et produit durci à base de celle-ci
JPWO2014136693A1 (ja) * 2013-03-05 2017-02-09 日本化薬株式会社 多価カルボン酸組成物、エポキシ樹脂用硬化剤組成物、エポキシ樹脂組成物およびその硬化物
WO2014157552A1 (fr) * 2013-03-28 2014-10-02 日本化薬株式会社 Composition de résine époxyde d'encapsulation de semi-conducteur en optique, produit durci correspondant et dispositif optique à semi-conducteur
JP2016045243A (ja) * 2014-08-20 2016-04-04 日本化薬株式会社 近赤外線吸収色素を含む熱硬化性樹脂組成物及び近赤外線カットフィルタ

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