WO2008081958A1 - 新規エポキシ樹脂、該エポキシ樹脂を必須成分とするエポキシ樹脂組成物及び該エポキシ樹脂を必須成分とする硬化物 - Google Patents
新規エポキシ樹脂、該エポキシ樹脂を必須成分とするエポキシ樹脂組成物及び該エポキシ樹脂を必須成分とする硬化物 Download PDFInfo
- Publication number
- WO2008081958A1 WO2008081958A1 PCT/JP2007/075346 JP2007075346W WO2008081958A1 WO 2008081958 A1 WO2008081958 A1 WO 2008081958A1 JP 2007075346 W JP2007075346 W JP 2007075346W WO 2008081958 A1 WO2008081958 A1 WO 2008081958A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- primary hydroxyl
- epoxy
- molecule
- group
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
- C08G59/186—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Definitions
- the present invention relates to an epoxy resin useful for photocuring, an epoxy resin composition, and an epoxy resin cured product.
- the novel epoxy resin, epoxy resin composition, and epoxy resin cured product of the present invention are paints, adhesives, stereolithography, Useful for encapsulants, casting materials, electro-optic and optical circuit materials.
- Epoxy resins are widely used in electronic parts, electrical equipment, automotive parts, FRP, sports equipment, etc. due to their excellent adhesiveness, heat resistance, and moldability. Epoxy resins can be cured by heating using a hardener. Examples of the curing agent used include amine curing agents and acid anhydride curing agents. However, epoxy resin compositions using these curing agents have a limited pot life because the reaction gradually proceeds and thickens even at room temperature.
- a photocuring system that cures an epoxy resin using a photopolymerization initiator does not cause a curing reaction unless it is irradiated with light energy. Therefore, it has much better storage stability than the above-mentioned amine curing agents and acid anhydride curing agents.
- An epoxy resin composition is obtained.
- Epoxy resin photo-curing systems are blended with a photopolymerization initiator, and are generally compositions with added flexibility and improved reactivity by blending polyols (Non-patent Document 1). . This is because the reaction between the epoxy group of the epoxy resin and the primary hydroxyl group of the polyol is faster than the epoxy groups, so that the reactivity is improved (Non-patent Document 2).
- the blended polyols have a low molecular weight, there is a problem that they volatilize during curing, and there is a problem that poor curing occurs due to moisture absorption.
- the polyols are high molecular weight, There were problems such as a decrease in heat resistance due to a decrease in density.
- Non-Patent Document 1 The Dow Chemi cal Company “CYRACURE Cycloaliphatic Epoxides Cationic UV Cure J
- Non-Patent Document 2 “Optical Application Technology ⁇ Material Dictionary” Editorial Committee “Optical Application Technology ⁇ Material Dictionary” Industrial Technology Service Center Co., Ltd. (2 0 0 6) Disclosure of Invention
- a novel epoxy resin useful for a photocuring system has been intensively studied, and a novel epoxy resin having one or more primary hydroxyl groups and one or more epoxy groups in one molecule having a specific general formula. Resin not only improves reactivity and gives flexibility of cured products, but also improves volatility, high hygroscopicity, and low heat resistance problems that were problematic in conventional polyol compounding systems. It has been found that an epoxy resin composition and a cured epoxy resin can be obtained, and the present invention has been completed. The problem of volatilization, the problem of moisture absorption, and the heat resistance, which have been problems by mixing polyols in the past.
- the present invention provides an epoxy resin, an epoxy resin composition, and a cured epoxy resin that can solve the above problems.
- the above problem could be solved by using a novel epoxy resin having one or more primary hydroxyl groups and one or more epoxy groups in one molecule represented by the general formula 1. [Chemical 1]
- (Ep) is the reaction residue of the epoxy resin, and is specifically expressed by the general formulas 2 and 3.
- (E) is: ⁇ ⁇ Reaction residue of Poxy resin, specifically represented by general formulas 4 and 5.
- (X) is a carbon alone or a hydrocarbon group and may contain nitrogen, phosphorus, oxygen, or sulfur atoms.
- ( ⁇ ) is a hydrocarbon group of an acid anhydride residue and may contain nitrogen, phosphorus, oxygen, or sulfur atoms.
- R is hydrogen or a hydrocarbon group and may contain nitrogen, phosphorus, oxygen, or sulfur atoms.
- ⁇ is a hydrocarbon group and may contain nitrogen, phosphorus, oxygen, and sulfur atoms.
- the structure may be linear, branched, cyclic, aromatic, or complex.
- Q is a hydrocarbon group and may contain nitrogen, phosphorus, oxygen, or sulfur atoms.
- the structure may be linear, branched, cyclic, aromatic, or heterocyclic.
- Y ′ is a hydrocarbon group and may contain nitrogen, phosphorus, oxygen, or sulfur atoms.
- the structure may be linear, branched, cyclic, aromatic, or heterocyclic.
- Q ' is a hydrocarbon group and may contain nitrogen, phosphorus, oxygen, or sulfur atoms.
- the structure may be linear, branched, cyclic, aromatic, or heterocyclic.
- FIG. 1 shows the molecular distribution of the epoxy resin obtained in Example 1 by GPC.
- FIG. 2 shows the measurement results of FTIR of the epoxy resin obtained in Example 1.
- FIG. 3 shows the molecular distribution of the epoxy resin obtained in Example 5 by GPC.
- FIG. 4 shows the measurement results of FTIR of the epoxy resin obtained in Example 5.
- FIG. 5 shows the molecular distribution of the epoxy resin obtained in Example 6 by GPC.
- FIG. 6 shows the measurement results of FTIR of the epoxy resin obtained in Example 6.
- the novel epoxy resin in the present invention is represented by the general formula 1 and is an epoxy resin having one or more primary hydroxyl groups and one or more epoxy groups in one molecule.
- the compound having one or more primary hydroxyl groups and one or more carboxyl groups in one molecule include glycolic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. It can also be obtained by reacting alcohols having two or more primary hydroxyl groups in one molecule with carboxylic acids containing acid anhydrides, but is not limited to these and used in combination of two or more. You may do it.
- epoxy resins that react with compounds having one or more primary hydroxyl groups and one or more carboxyl graves in one molecule
- known epoxy resins can be used. Specifically, Epototo YD manufactured by Toto Kasei Co., Ltd. — 1 2 8, Epototo YD— 8 1 2 5, Epototo YD— 1 2 7, Epototo YD— 8 2 5 GS, Epotot YD_ 1 34, Epototo YD— 0 1 1, Epototo YD— 0 1 2, Epototo YD— 0 1 3, Epototo YD— 9 0 1, Epototo YD—90, BPA type epoxy resin such as Epototo YD—90, Epototo YD F—1 70, Epotot YDF—8 1 7 0, Epototo YDF 8 7 0 GS, Epototo YDF—2 0 0 1, BPF type epoxy resin such as Epototo Y
- Type epoxy resins aralkyl novolac type epoxy resins such as E SN— 1 75, ESN— 3 75, ESN— 4 85, amine type epoxy resins such as Epototo YH— 4 34, YH-4 34, etc.
- glycidyl ester type epoxy resin Epototo YH— 3 0 0, Epototo ZX— 1 54 2, Epototo P G_ 2 0 7, Epototo PG— 20 7 GS, etc.
- Aliphatic epoxy resin epototo ST— 3 0 0 0, epototo ZX— 1 6 5 8, Epototo ZX— 1 6 5 8 GS, epototo ZX— 1 7 1 5, HB PA_DGE, DC PD_E P, TC PD—EP, manufactured by Maruzen Petrochemical Co., Ltd., YX 8 00, YX 8 0, manufactured by Japan Epoxy Resin Co., Ltd. 34, Celoxide manufactured by Daicel Chemical Industries, Ltd.
- Aliphatic ring such as epoxy resin of hydrogenated dimer acid Epoxy resins and the like are listed, but the resin is not limited to these, and two or more types may be used in combination.
- the reaction is carried out by blending such that the epoxy group is 1.1 mol or more, preferably 2.0 mol or more, more preferably 3.0 mol or more with respect to 1.0 mol of the carboxyl group.
- reaction of a compound having one or more primary hydroxyl groups and one or more carboxyl groups in one molecule with epoxy resins can be carried out by a known synthesis method. That is, in one molecule
- a compound having at least one primary hydroxyl group and at least one carboxyl group and an epoxy resin can be blended and reacted by heating. If necessary, an inert solvent or a catalyst may be used.
- the reaction temperature is 50 ° C to 200 ° C, more preferably 80 ° to 180 ° C.
- the end point of the reaction can be determined by confirming the disappearance of the carboxyl group by instrumental analysis or by confirming the acid value by chemical analysis. Reaction time is 1 to 6 hours.
- the inert solvent that can be used, a solvent having no hydroxyl group is preferable. Specific examples include benzene, toluene, xylene, and the like. However, the present invention is not limited to these, and a mixture of two or more types may be used. good.
- Usable catalysts include 2-methylimidazole, 2-ethylimidazole, imidazoles such as 4-methylimidazole, phosphines such as triphenylphosphine, tritylphosphine, and tris (2,6-dimethoxyphenyl) phosphine.
- Phosphonium salts such as tetrabutyl phosphonium bromide, tetrabutyl phosphonium bromide, ethyl rifuenil phosphophosphonium bromide, ethinoretri fenenore phosphonium bromide, etc. However, these are not limited to these, and two or more kinds may be mixed and used.
- a compound that has one or more primary hydroxyl groups in one molecule and one or more carboxyl groups reacts with carboxylic acids containing two or more primary hydroxyl groups in one molecule and acid anhydrides. Can also be obtained.
- the compound has 1 or more primary hydroxyl groups and 1 or more carboxyl groups in one molecule by reacting so that the equivalent of acid anhydride is less than 1 equivalent to 1 equivalent of primary hydroxyl group. Can be obtained.
- 1 equivalent of acid anhydride is equivalent to 1 equivalent of primary hydroxyl group
- the epoxy resin of the present invention cannot be obtained because the primary hydroxyl group does not remain.
- the acid anhydride equivalent is greater than 1 equivalent relative to 1 equivalent of the primary hydroxyl group, the acid anhydride remains, which may cause gelation during the reaction with the epoxy resin.
- the acid anhydride equivalent is preferably less than 1 and up to 0.5 equivalents per equivalent of primary hydroxyl group.
- the primary hydroxyl group can be arbitrarily adjusted by adjusting the equivalent of the primary hydroxyl group and the acid anhydride equivalent.
- alcohols having two or more primary hydroxyl groups in one molecule include ethylene glycol, diethylene glycolol, propylene dallicol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol , 1,8-octanediol, cyclohexanedimethanol, spiroglycone, etc.
- Trihydric alcohols such as Kisantori ol trimethylol propane to, sorbitol, shea user closed, Pentaerisuri toe Le, ditrimethylol Rogue les ethane, Jitorimechiro one Norepuroha 0 down, such Jipentaerisuri Tozore Examples include polyhydric alcohols and alkylene oxide adducts of these alcohols, but the present invention is not limited to these, and two or more types may be used in combination.
- Acid anhydrides include itaconic anhydride, citraconic anhydride, 2-carboxyethyl-methyl-phosphinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexaphthalophthalic acid Anhydride, Methyltetrahydrophthalic acid anhydride, Methyl nadic acid anhydride, Dodecyl succinic acid anhydride, Pyromeric acid anhydride, Benzophenone tetracarboxylic acid anhydride, Ethylenedaricolbis (anhydrotrimate), Methylcycl Examples include, but are not limited to, oral hexene tetracarboxylic acid anhydride, trimellitic acid anhydride, naphthalic acid anhydride, and acid anhydrides described in JP-A-6-08056. Instead, two or more types may be used in combination.
- the reaction of carboxylic acids including alcohols and acid anhydrides proceeds by charging a predetermined amount and heating. At this time, an inert solvent or catalyst may be used as necessary.
- the reaction temperature is from 50 ° C to 180 ° C, more preferably from 80 ° C to 150 ° C.
- the end point of the reaction can be determined by confirming the disappearance of the acid anhydride by instrumental analysis or by confirming the acid value by chemical analysis.
- the reaction time is 1 to 6 hours.
- an inert solvent that can be used in the reaction it is necessary that the reaction product dissolves, but a nonpolar solvent is preferable, and examples thereof include benzene, toluene, xylene, and methylisoptyl ketone.
- the present invention is not limited to these, and two or more kinds may be mixed and used.
- a compound having two or more carboxyl groups in one molecule can be reacted with an epoxy resin having one or more primary hydroxyl groups and two or more epoxy groups in one molecule.
- a new epoxy resin having one or more primary hydroxyl groups and one or more epoxy groups can be synthesized.
- Examples of compounds having two or more carboxyl groups in one molecule include oxalic acid, malonic acid, fumaric acid, succinic acid, gnoretoleic acid, adipic acid, phthalanolic acid, maleic acid, sebacic acid, itaconic acid, citraconic acid, Examples include cyclohexanetricarboxylic acid and naphthalenedicarboxylic acid.
- a compound having two or more carboxyl groups in one molecule may be synthesized by reacting the alcohol having two or more primary hydroxyl groups in one molecule with a carboxylic acid containing acid anhydrides. . At that time, the primary hydroxyl group may remain.
- Epoxy resins with one or more primary hydroxyl groups in one molecule can be adjusted by adjusting the amount of alcohol, amount of catalyst, reaction temperature and reaction time when epoxidizing a compound with two or more primary hydroxyl groups. It can be obtained by adding an epoxy group while leaving a primary hydroxyl group by synthesis.
- a compound having two or more carboxyl groups in one molecule and an epoxy resin having one or more primary hydroxyl groups and two or more epoxy groups in one molecule can be reacted by a known method. That is, it can react by mixing a predetermined amount and heating. You may use an inert solvent, a catalyst, etc. as needed.
- the reaction temperature is from 50 ° C. to 200 ° C., more preferably from 80 ° C. to 180 ° C.
- the end point of the reaction can be determined by confirming the disappearance of the carboxyl group by instrumental analysis or by confirming the acid value by chemical analysis.
- the reaction time is 1 to 6 hours.
- the epoxy resin composition of the present invention is blended with the novel epoxy resin of the present invention and / or other epoxy resins so that the epoxy group is in the range of 5 to 50 equivalents per equivalent of primary hydroxyl group. Adjust to. Thus, high reactivity and high heat resistance of the cured product, which are the objects of the present invention, are exhibited.
- the heat resistance decreases when the epoxy group is less than 5 equivalents or more than 50 equivalents per equivalent of primary hydroxyl group.
- Examples of the curing agent used in the epoxy resin composition of the present invention include a photopolymerization initiator.
- photopolymerization initiators include Lewis acid, prensted acid, sulfonium salt, and iodine.
- Various sodium salts such as salts and diazonium salts. Of these, a sulfonium salt is preferable, and an aromatic sulfonium salt is more preferable among the sulfonium salts.
- the blending amount of the photopolymerization initiator varies depending on the light irradiation conditions, the type and amount of the epoxy resin, the type of the photopolymerization initiator, the thickness and the shape of the cured product, etc., but is 100 parts by weight of the epoxy resin. 0.01 to 10 parts by weight.
- the epoxy resin composition of the present invention includes a sensitizer, an antioxidant, a stabilizer, a plasticizer, a wax, a leveling agent, a filler, a pigment, a dye, a flame retardant, a foaming agent, and a charge. Inhibitors, fungicides, viscosity modifiers, solvents, etc. may be added. Moreover, it is also possible to mix
- the cured epoxy resin of the present invention can be obtained by irradiating and / or heating the epoxy resin composition of the present invention.
- the light to be irradiated when the epoxy resin composition of the present invention is cured is not particularly limited as long as it can be cured by the photopolymerization initiator, and any light is used depending on the type of the photopolymerization initiator. be able to.
- the light source is not particularly limited, and for example, a general light source such as a fluorescent lamp or a high-pressure mercury lamp can be used. Further, as the light source, for example, a low-pressure mercury lamp, a xenon lamp, a metal halide lamp, a germicidal lamp, laser light, LED light, or the like may be used.
- the illuminance of light, irradiation amount, and irradiation time are the type and amount of photopolymerization initiator, and the epoxy of the present invention. Although it varies depending on the resin skeleton, additives, thickness, etc., it can be appropriately adjusted depending on the physical properties of the cured product.
- heat curing can be performed before and after light irradiation, and curing can proceed further.
- pentaerythritol number-average functional group number of primary hydroxyl group in one molecule is 4, manufactured by Mitsubishi Gas Chemical Co., Ltd.
- Drophthalic anhydride manufactured by Shin Nippon Rika Co., Ltd. 1 34.3 parts and 30.0 parts of toluene were charged, and the temperature was raised while stirring in a nitrogen gas atmosphere. At this time, the acid anhydride group with respect to the primary hydroxyl group was 0.79.
- HB PA—DGE hydrogenated BPA type epoxy resin, manufactured by Maruzen Petrochemical Co., Ltd.
- TPP-BB n-ptyltriphenyl phosphonium bromide, manufactured by Hokuko Chemical Co., Ltd.
- the epoxy equivalent of the obtained epoxy resin was 4 2 0.8 g / eq, and the primary hydroxyl equivalent was 3 2 6 1 g Z eq.
- the molar ratio of epoxy groups to primary hydroxyl groups was 9.3.
- Fig. 1 shows the molecular weight distribution by GPC
- Fig. 2 shows the FT IR measurement results.
- Example 2 The same operation as in Example 1 was carried out except that the MH—700 was changed to 1 5 1.0 and HB PA—DGE was changed to 7 5 3.1.
- the acid anhydride group for the primary hydroxyl group was 0.89.
- the epoxy equivalent of the obtained epoxy resin was 3 8 1.9 g / e q, and the primary hydroxyl group equivalent was 2 160 gZe q.
- the molar ratio of epoxy groups to primary hydroxyl groups was 24.28.
- Example 2 The same operation as in Example 1 was carried out except that the MH-7700 was changed to 15.6.6 and the HBPA-DGE was 66.7.0.
- the acid anhydride group for the primary hydroxyl group was 0.950.
- the epoxy equivalent of the obtained epoxy resin was 40 8.9 g / e q, and the primary hydroxyl group equivalent was 1 7 2 1 2 e q.
- the molar ratio of epoxy group to primary hydroxyl group was 4 2. 09.
- Acid anhydride Jamaicacid HN A_ 1 0 0 (Methyl nadic acid anhydride, Shin Nippon Chemical Co., Ltd.) 1 6 5. 7 parts, epoxy resin ceroxide 20 2 1 4 9 1. 5 parts, ZX— 1 6 5 8 (epoxidation product of cyclohexane dimethanol, primary hydroxyl group equivalent 1 1 0 5 g / eq, manufactured by Tohto Kasei Co., Ltd.) 2 1 6. 1 Operations were performed in the same manner as in Example 1 except that 1 part was used. The acid anhydride group for the primary hydroxyl group was 0.900.1.
- the epoxy equivalent of the obtained epoxy resin was 4 9 1.5 g / eq, and the primary hydroxyl equivalent was 1 7 3 4 geq.
- the molar ratio of epoxy group to primary hydroxyl group was 13 ⁇ 11.
- Figure 3 shows GPC minutes
- Fig. 4 shows the FT IR measurement results.
- Example 2 The same operation as in Example 1 was carried out except that 7 parts by weight of MH—70 0 1 0 0. 7 as an acid anhydride and 99.0 parts of HB P A —DGE as an epoxy resin.
- the epoxy resin thus obtained had an epoxy equivalent of 450.07 g / eq and a primary hydroxyl group equivalent of 144.82 g / eq.
- the molar ratio of epoxy group to primary hydroxyl group was 3.29.
- Example 2 The same operation as in Example 1 was conducted except that MH—70 0 1 1 5.4 parts as an acid anhydride and 58.8 parts of HB P A —DGE 5 as an epoxy resin were used.
- the epoxy equivalent of the obtained epoxy resin was 4 3 5.
- l g / e q, and the primary hydroxyl equivalent was 2 1 6 6 g / e q.
- the molar ratio of epoxy group to primary hydroxyl group was 4.98.
- Example 2 The same operation as in Example 1 was carried out except that MH—70 0 1 6 8.0 parts as an acid anhydride and 89.8 parts of HB PA as an epoxy resin were used.
- the epoxy resin obtained has an epoxy equivalent of 4 18.2 g / eq and no primary hydroxyl equivalent. 100 parts of epoxy resin was dissolved in cyclohexanone, and 0.5 part of Silica UV I-6 976 (manufactured by Dow Chemical Company) was blended as a photopolymerization initiator. Was applied at Pas Kota release film, the solvent is removed for 30 minutes at 5 0, Ushio Denki Co.
- the cured product was peeled off from the release film, and the glass transition temperature was measured with XS TAR 6200 DSC manufactured by SII Nano Technology Co., Ltd.
- the measurement conditions were that the temperature was raised from room temperature to 200 ° C at 10 ° C / min, and the first inflection point in the second cycle data was taken as the glass transition temperature. The results are shown in the table.
- Infrared absorption spectrum was measured with 1760 X manufactured by Perkin Elma Ichi Japan.
- the molecular weight distribution was measured with a liquid guchimatography HLC-8120 manufactured by Tosoh Corporation.
- Example 6 It can be seen that the use of an epoxy resin having a primary hydroxyl group improves the heat resistance even when a new epoxy resin having a primary hydroxyl group and an epoxy group is synthesized. Industrial applicability
- the novel epoxy resin according to the present invention does not need to be newly blended with polyols, compatibility problems such as separation and clouding in the blending of the epoxy resin and the polyol are eliminated.
- the epoxy resin composition the polyol blended near the liquid surface moves and does not adsorb moisture in the air, eliminating the problem of high hygroscopicity.
- the monomer since the monomer is not present as when the polyol is blended, the problem of volatility is eliminated.
- heat resistance the presence of primary hydroxyl groups and epoxy groups in one molecule increases the crosslink density, and the heat resistance is higher than when polyol is added.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2007800487792A CN101611067B (zh) | 2006-12-28 | 2007-12-21 | 环氧树脂、以该环氧树脂为必须成分的环氧树脂组合物以及以该环氧树脂为必须成分的固化物 |
US12/223,793 US7906562B2 (en) | 2006-12-28 | 2007-12-21 | Epoxy resin, epoxy resin composition containing the epoxy resin as an essential component and a cured product containing the epoxy resin as an essential component |
KR1020097013210A KR101443406B1 (ko) | 2006-12-28 | 2007-12-21 | 신규 에폭시 수지, 이 에폭시 수지를 필수성분으로 하는 에폭시 수지 조성물 및 그 에폭시 수지를 필수성분으로 하는 경화물 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006353732A JP5344789B2 (ja) | 2006-12-28 | 2006-12-28 | 新規エポキシ樹脂、該エポキシ樹脂を必須成分とするエポキシ樹脂組成物及び該エポキシ樹脂を必須成分とする硬化物 |
JP2006-353732 | 2006-12-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008081958A1 true WO2008081958A1 (ja) | 2008-07-10 |
Family
ID=39588635
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2007/075346 WO2008081958A1 (ja) | 2006-12-28 | 2007-12-21 | 新規エポキシ樹脂、該エポキシ樹脂を必須成分とするエポキシ樹脂組成物及び該エポキシ樹脂を必須成分とする硬化物 |
Country Status (5)
Country | Link |
---|---|
US (1) | US7906562B2 (ja) |
JP (1) | JP5344789B2 (ja) |
KR (1) | KR101443406B1 (ja) |
CN (1) | CN101611067B (ja) |
WO (1) | WO2008081958A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011058962A1 (ja) * | 2009-11-10 | 2011-05-19 | 日本化薬株式会社 | エポキシ樹脂組成物 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5669289B2 (ja) * | 2008-05-23 | 2015-02-12 | 新日鉄住金化学株式会社 | 新規エポキシ樹脂及びその製造方法、該エポキシ樹脂を必須成分とするエポキシ樹脂組成物及び該エポキシ樹脂を必須成分とする硬化物 |
JP5357629B2 (ja) * | 2008-07-01 | 2013-12-04 | 新日鉄住金化学株式会社 | 光導波路用樹脂組成物およびそれを用いた光導波路 |
JP5101425B2 (ja) * | 2008-07-28 | 2012-12-19 | 日東電工株式会社 | 光半導体素子封止用エポキシ樹脂組成物およびそれを用いた光半導体装置 |
CN104797622A (zh) * | 2012-11-16 | 2015-07-22 | 陶氏环球技术有限公司 | 环氧树脂组合物 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2539333A1 (de) * | 1975-09-04 | 1977-03-17 | Hoechst Ag | Verfahren zur herstellung von epoxidfestharzen |
JPH0570559A (ja) * | 1991-09-13 | 1993-03-23 | Toyo Ink Mfg Co Ltd | 硬化性樹脂組成物 |
JPH10130367A (ja) * | 1996-10-28 | 1998-05-19 | Toyo Ink Mfg Co Ltd | カチオン硬化性プレポリマーおよびそれを用いた活性エネルギー線硬化型塗料組成物 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4284574A (en) * | 1979-06-15 | 1981-08-18 | Ciba-Geigy Corporation | Diglycidyl ethers of di-secondary alcohols, their preparation, and curable compositions containing them |
US4818776A (en) * | 1983-02-07 | 1989-04-04 | Union Carbide Corporation | Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials having primary hydroxyl content |
US4874798A (en) * | 1983-02-07 | 1989-10-17 | Union Carbide Corporation | Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials and substituted cycloaliphatic monoepoxide reactive diluents |
DE3518732A1 (de) * | 1985-05-24 | 1986-11-27 | BASF Lacke + Farben AG, 4400 Münster | Wasserverduennbare bindemittel fuer kationische elektrotauchlacke und verfahren zu ihrer herstellung |
ES2020299B3 (es) * | 1986-12-19 | 1991-08-01 | Ciba-Geigy Ag | Resinas epoxidicas con contenido de poliester sobre base de polialquilenglicol. |
BE1010656A4 (fr) * | 1996-09-30 | 1998-11-03 | Ucb Sa | Monomeres, oligomeres et polymeres a groupes oxirannes terminaux, leur procede de preparation et leur polymerisation cationique sous irradiation. |
US6451929B1 (en) * | 1999-10-29 | 2002-09-17 | Resolution Performance Products, Llc | Glycidyl ester by reacting COOH polyester with epihalohydrin |
-
2006
- 2006-12-28 JP JP2006353732A patent/JP5344789B2/ja not_active Expired - Fee Related
-
2007
- 2007-12-21 CN CN2007800487792A patent/CN101611067B/zh not_active Expired - Fee Related
- 2007-12-21 KR KR1020097013210A patent/KR101443406B1/ko not_active IP Right Cessation
- 2007-12-21 US US12/223,793 patent/US7906562B2/en not_active Expired - Fee Related
- 2007-12-21 WO PCT/JP2007/075346 patent/WO2008081958A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2539333A1 (de) * | 1975-09-04 | 1977-03-17 | Hoechst Ag | Verfahren zur herstellung von epoxidfestharzen |
JPH0570559A (ja) * | 1991-09-13 | 1993-03-23 | Toyo Ink Mfg Co Ltd | 硬化性樹脂組成物 |
JPH10130367A (ja) * | 1996-10-28 | 1998-05-19 | Toyo Ink Mfg Co Ltd | カチオン硬化性プレポリマーおよびそれを用いた活性エネルギー線硬化型塗料組成物 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011058962A1 (ja) * | 2009-11-10 | 2011-05-19 | 日本化薬株式会社 | エポキシ樹脂組成物 |
JP2011102337A (ja) * | 2009-11-10 | 2011-05-26 | Nippon Kayaku Co Ltd | エポキシ樹脂組成物 |
Also Published As
Publication number | Publication date |
---|---|
CN101611067B (zh) | 2012-11-28 |
JP5344789B2 (ja) | 2013-11-20 |
KR101443406B1 (ko) | 2014-09-24 |
KR20090103891A (ko) | 2009-10-01 |
JP2008163169A (ja) | 2008-07-17 |
US20100168268A1 (en) | 2010-07-01 |
CN101611067A (zh) | 2009-12-23 |
US7906562B2 (en) | 2011-03-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5057016B2 (ja) | 活性エネルギー線の照射により活性化するアミンイミド化合物、それを用いた組成物およびその硬化方法 | |
JP4555995B2 (ja) | 光塩基発生剤並びにそれを用いた硬化性組成物及び硬化方法 | |
JP6964981B2 (ja) | 光硬化性エポキシ樹脂系 | |
EP2421907B1 (en) | Thermosettable composition containing a half ester of a cycloaliphatic diol and a thermoset product therefrom | |
JP2004204228A (ja) | 硬化性エポキシ樹脂組成物および硬化物 | |
KR20050076687A (ko) | 비-에스테르형 에폭시 수지 및 수지 조성물 | |
WO2008081958A1 (ja) | 新規エポキシ樹脂、該エポキシ樹脂を必須成分とするエポキシ樹脂組成物及び該エポキシ樹脂を必須成分とする硬化物 | |
KR101540831B1 (ko) | 신규 에폭시 수지 및 그의 제조방법, 그 에폭시 수지를 필수성분으로 하는 에폭시 수지 조성물 및 그 에폭시 수지를 필수성분으로 하는 경화물 | |
JP6295048B2 (ja) | 高分子量エポキシ樹脂、エポキシ樹脂組成物及び硬化物 | |
TW200306339A (en) | Unsaturated polybranched compounds, curable compositions containing the same and cured articles thereof | |
JP4701846B2 (ja) | 硬化性組成物 | |
JP4841529B2 (ja) | 変性ポリシロキサン | |
JP4089562B2 (ja) | 熱硬化性組成物 | |
WO2020202777A1 (ja) | エポキシ硬化用化合物及びエポキシ樹脂組成物 | |
JPWO2006115011A1 (ja) | エポキシ化合物の製造方法および硬化性エポキシ樹脂組成物 | |
TW201006859A (en) | Epoxy compound having protection group and curable resin composition containing the same | |
JP2007321120A (ja) | 硬化性組成物 | |
JP3896119B2 (ja) | 表示素子用光硬化性樹脂組成物及び表示素子 | |
JP5268233B2 (ja) | エポキシ樹脂、エポキシ樹脂組成物、並びにその硬化物 | |
JPH05287055A (ja) | 光硬化性エポキシ樹脂組成物 | |
JP2018016726A (ja) | 組成物 | |
JP2011080012A (ja) | エポキシ基を有するポリオキシアルキレン系重合体および、その硬化性組成物 | |
JP2006342274A (ja) | 硬化性組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200780048779.2 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12223793 Country of ref document: US |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07860543 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020097013210 Country of ref document: KR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 07860543 Country of ref document: EP Kind code of ref document: A1 |