WO2014034675A1 - シアヌル酸変性リン含有エポキシ樹脂の製造方法、該シアヌル酸変性リン含有エポキシ樹脂を含む樹脂組成物、及びその硬化物 - Google Patents
シアヌル酸変性リン含有エポキシ樹脂の製造方法、該シアヌル酸変性リン含有エポキシ樹脂を含む樹脂組成物、及びその硬化物 Download PDFInfo
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- WO2014034675A1 WO2014034675A1 PCT/JP2013/072894 JP2013072894W WO2014034675A1 WO 2014034675 A1 WO2014034675 A1 WO 2014034675A1 JP 2013072894 W JP2013072894 W JP 2013072894W WO 2014034675 A1 WO2014034675 A1 WO 2014034675A1
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- cyanuric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
Definitions
- the present invention relates to a method for producing a halogen-free flame-retardant epoxy resin containing a phosphorus atom and a nitrogen atom in the molecular skeleton, an epoxy resin composition containing an epoxy resin obtained from the production method and another epoxy resin, and the epoxy resin composition
- the present invention relates to a curable epoxy resin composition containing a product and a curing agent, and an epoxy resin cured product obtained by curing the curable epoxy resin composition.
- Cyanuric acid remaining in the reaction system reacts with the epoxy resin only at a very slow rate, and unreacted cyanuric acid has poor solubility in the solvent, and unreacted cyanuric acid has an adverse effect on the cured material properties. There was a further need for reduction.
- the present inventor made the residual of cyanuric acid by reacting with a certain proportion of a specific phosphorus compound with respect to cyanuric acid in the reaction of epoxy resin and cyanuric acid.
- the present invention was completed by finding that the reaction with the epoxy resin easily proceeds without requiring a very long reaction.
- the present invention (1) A method for producing a cyanuric acid-modified phosphorus-containing epoxy resin obtained by reacting a phosphorus compound, cyanuric acid and an epoxy resin as essential components, wherein the phosphorus compound is The following general formula (1): [Wherein n represents 0 or 1, and R 1 and R 2 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or cyclic with a phosphorus atom It may be. ]
- R 3 and R 4 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or cyclic with a phosphorus atom. It may be.
- a phosphorus compound containing both of them wherein 2.5 to 50 moles of the phosphorus compound is blended with 1 mole of cyanuric acid, and the epoxy resin is prepared in advance in the presence of the phosphorus compound and cyanuric acid.
- the reaction After mixing, the reaction is performed, the phosphorus content is 1.0 to 5.0 mass%, the nitrogen content is 0.1 to 2.0 mass%, and the total of the phosphorus content and nitrogen content is 2.5 to 5.5 mass%
- a method for producing a cyanuric acid-modified phosphorus-containing epoxy resin
- the cyanuric acid-modified phosphorus-containing epoxy resin obtained by the production method described in (1) above has a functional group ratio of 0.4 to 2.0 equivalents relative to 1 equivalent of the epoxy group of the cyanuric acid-modified phosphorus-containing epoxy resin.
- a curable epoxy resin composition containing a curing agent (4) A curable epoxy resin composition comprising the epoxy resin composition according to (2) above containing a curing agent having a functional group ratio of 0.4 to 2.0 equivalents with respect to 1 equivalent of epoxy groups of the epoxy resin composition.
- the present invention is a cyanuric acid-modified phosphorus-containing epoxy resin obtained by reacting with a specific phosphorus compound in a molar ratio of 2.5 to 50 moles per mole of cyanuric acid and then reacting with the epoxy resin. It is possible to produce an epoxy resin cured product having excellent physical properties, which can be produced by the above-mentioned method, and cyanuric acid remains very little.
- the phosphorus compound represented by the general formula (1) or (2) of the present invention specifically includes dimethylphosphine, diethylphosphine, diphenylphosphine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide (DOPO), dimethylphosphine oxide, diethylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide, 1,4-cyclooctylenephosphine oxide, 1,5-cyclooctylenephosphine oxide (CPHO, manufactured by Nippon Chemical Industry Co., Ltd.) Etc.
- DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide
- dimethylphosphine oxide diethylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide, 1,4-cyclooctylenephosphine oxide, 1,5-cyclooctylene
- cyanuric acid indicates s-triazine-2,4,6-triol and s-triazine-2,4,6-trione which are tautomers, and the ratio thereof is particularly specified. No.
- cyanuric acid is added as a nitrogen-based flame retardant
- it is difficult to obtain a uniform resin composition because of poor solubility in cyanuric acid solvent and poor compatibility with epoxy resin and curing agent, There were variations in flame retardancy.
- the cyanuric acid-modified phosphorus-containing epoxy resin obtained from the production method of the present invention becomes uniform in the resin composition by reacting cyanuric acid with the epoxy resin, stable flame retardancy is obtained.
- the resin composition of the present invention is used to include both an epoxy resin composition and a curable epoxy resin composition, unless otherwise specified. Show one.
- the epoxy resins used for producing the cyanuric acid-modified phosphorus-containing epoxy resin of the present invention are Epototo® YD-128, Epototo® YD-8125 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type epoxy resin), Epototo® YDF-170, Epototo® YDF-8170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol F type epoxy resin), YSLV-80XY (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., tetramethylbisphenol F type epoxy resin), Epototo® YDC-1312 (hydroquinone type epoxy resin), jER YX-4000H (Mitsubishi Chemical Corporation, biphenyl type epoxy resin), Epototo YDPN-638, Epototo N YDPN-63X (Shin Nippon Steel Co., Ltd.,
- epoxy resins may be used alone or in combination of two or more, and bisphenol type epoxy resins, phenol novolac type epoxy resins, and cresol novolac type epoxy resins can be suitably used.
- the reaction of the phosphorus compound represented by formula (1) or (2) with cyanuric acid and the epoxy resin is caused to react with the epoxy resin in the presence of the phosphorus compound and cyanuric acid.
- 50 mol of the phosphorus compound is required, and the preferred molar ratio of the phosphorus compound is 2.7 to 25 mol, preferably 3 to 10 mol, per mol of cyanuric acid. If the phosphorus compound is less than 2.5 moles per mole of cyanuric acid, the reaction between cyanuric acid and the epoxy resin will not proceed sufficiently, and the residual amount of cyanuric acid will increase.
- the reaction temperature for obtaining the cyanuric acid-modified phosphorus-containing epoxy resin of the present invention may be a temperature usually set for the synthesis of the epoxy resin, and is 100 to 250 ° C., preferably 120 to 200 ° C.
- a catalyst may be used for shortening the time and reducing the reaction temperature.
- the catalyst that can be used is not particularly limited, and those usually used for the synthesis of epoxy resins can be used.
- tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, ethyltriphenylphosphonium bromide, etc.
- catalysts such as phosphonium salts, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used, and these may be used alone or in combination of two or more. is not. Further, it may be divided and used in several times.
- the amount of catalyst used in the reaction is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less based on the epoxy resin used.
- the amount of the catalyst exceeds 5% by mass, the self-polymerization reaction of the epoxy group tends to proceed and the resin viscosity tends to increase, which is not preferable.
- an inert solvent may be used for the reaction.
- various hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethyl ether, isopropyl ether, butyl ether, diisoamyl ether, methylphenyl Ethers, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methyl furan, tetrahydrofuran, and other ethers, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether,
- the epoxy equivalent of the cyanuric acid-modified phosphorus-containing epoxy resin obtained in the present invention is preferably 100 to 700 g / eq, more preferably 200 to 600 g / eq. If the epoxy equivalent is less than 100 g / eq, the adhesiveness of the cured product tends to be inferior, and if it is more than 700 g / eq, the glass transition temperature (Tg) of the cured product is lowered, and the resin composition has a high viscosity and improves workability. It tends to be inferior.
- the phosphorus content of the cyanuric acid-modified phosphorus-containing epoxy resin obtained in the present invention is 1.0 to 5.0% by mass, preferably 1.5 to 4.0% by mass, and more preferably 2.0 to 3.5% by mass.
- the nitrogen content is 0.1 to 2.0% by mass, preferably 0.5 to 1.0% by mass.
- the total of the phosphorus content and the nitrogen content is 2.5 to 5.5% by mass, preferably 3.0 to 4.5% by mass, more preferably 3.0 to 4.0% by mass. Since the flame retardancy of the cyanuric acid-modified phosphorus-containing epoxy resin obtained in the present invention is exhibited by the synergistic effect of phosphorus and nitrogen, it is meaningless to define either range, phosphorus content and nitrogen content It is necessary to specify the range of the sum of rates.
- the flame retardancy may not be sufficiently exhibited depending on the resin composition. Further, if the total of the phosphorus content and the nitrogen content exceeds 5.5% by mass, the flame retardancy can be sufficiently exerted, but the resin composition has a high viscosity and may adversely affect the solvent solubility. Therefore, the total range of the phosphorus content and the nitrogen content is preferably 2.5 to 5.5% by mass.
- the same epoxy resin as the above epoxy resin can be used in combination with the cyanuric acid-modified phosphorus-containing epoxy resin as long as the characteristics of the present invention are not impaired.
- the cyanuric acid-modified phosphorus-containing epoxy resin or epoxy resin composition of the present invention can be made into a curable epoxy resin composition by blending a curing agent.
- a curing agent commonly used curing agents for epoxy resins such as various phenol compounds, acid anhydrides, amines, hydrazides, and acidic polyesters can be used, and only one of these curing agents is used. Or you may use together 2 or more types. Of these, dicyandiamide or a phenol compound is preferable as the curing agent contained in the curable epoxy resin composition of the present invention.
- the amount of the curing agent used is preferably 0.4 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents of the functional group of the curing agent with respect to 1 equivalent of the epoxy group that is a functional group of the epoxy resin. 0.5 to 1.0 equivalent is particularly preferred.
- the curing agent is less than 0.4 equivalent or 1 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
- phenols examples include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, and phenylphenol.
- naphthols examples include 1-naphthol and 2-naphthol. Can be mentioned.
- the aldehydes include formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, pimelin aldehyde. , Sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like.
- biphenyl condensing agent examples include bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, bis ( Chloromethyl) biphenyl and the like, but are not limited thereto.
- an organic solvent can also be used for viscosity adjustment.
- Organic solvents that can be used include amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, benzene, toluene and the like.
- Aromatic hydrocarbons etc. are mentioned.
- One of these solvents or a mixture of a plurality of them can be blended in the range of 25 to 250 parts by mass with respect to 100 parts by mass of the epoxy resin component in the resin composition.
- a curing accelerator can be used as necessary.
- curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo ( 5,4,0) tertiary amines such as undecene-7, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane phosphines, and metal compounds such as tin octylate.
- the amount of the curing accelerator used is preferably 0.02 to 5.0 parts by mass with respect to 100 parts by mass of the epoxy resin component in the resin composition of the present invention.
- a filler can be used in the curable epoxy resin composition of the present invention as necessary.
- specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, boehmite, and silica balloon, but pigments and the like may be blended.
- the reason for using a general inorganic filler is an improvement in impact resistance.
- metal hydroxides, such as aluminum hydroxide and magnesium hydroxide are used, it acts as a flame retardant aid, and flame retardancy can be ensured even if the phosphorus content in the resin composition is small.
- the blending amount is not more than 10 parts by mass with respect to 100 parts by mass of the epoxy resin component, the effect of impact resistance is small. However, if the blending amount exceeds 150 parts by mass, the adhesiveness, which is a necessary item for the use of laminates, is lowered.
- fiber fillers such as glass fibers, pulp fibers, synthetic fibers, and ceramic fibers, and organic fillers such as fine particle rubbers and thermoplastic elastomers can also be contained in the resin composition.
- a cured product of phosphorus and nitrogen-containing epoxy resin can be obtained by curing the curable epoxy resin composition of the present invention.
- a resin sheet, a copper foil with resin, a prepreg, and the like are laminated, and cured by heating and pressing to obtain a cured phosphorus-containing epoxy resin as a laminate.
- the epoxy equivalent of the epoxy resin measured in Examples and Comparative Examples was measured according to JIS K 7236.
- the nitrogen content was calculated as a percentage of the cyanuric acid-modified phosphorus-containing epoxy resin from the nitrogen content and the blending amount of cyanuric acid.
- the phosphorus content of the epoxy resins synthesized in the examples and comparative examples was measured by the following method. That is, 3 mL of sulfuric acid is added to 150 mg of sample and heated for 30 minutes. Return to room temperature, add 3.5 mL of nitric acid and 0.5 mL of perchloric acid and heat decompose until the contents are clear or yellow. Dilute this solution with pure water in a 100 mL volumetric flask.
- the obtained cyanuric acid-modified phosphorus-containing epoxy resin was checked for the presence or absence of residual cyanuric acid based on the appearance of turbidity. No turbidity was defined as no residual cyanuric acid (O), and turbidity was defined as residual cyanuric acid present (X).
- the glass transition temperature of the cured product was Exster 6000 manufactured by Seiko Instruments Inc., DSC used the first inflection point as the glass transition temperature, and TMA used the inflection point as the glass transition temperature.
- Copper foil peel strength was measured according to JIS C 6481 5.7
- interlayer adhesion was measured by peeling between one prepreg and the remaining three sheets according to JIS C 6481 5.7.
- Flame retardancy was measured according to UL (Underwriter Laboratorics) standards. Further, the afterflame time is the sum of the flammable combustion durations of five test pieces.
- the reaction rate of cyanuric acid was determined by the following equation using values of initial epoxy equivalent, theoretical epoxy equivalent and epoxy equivalent (final epoxy equivalent) of cyanuric acid-modified phosphorus-containing epoxy resin. [(Final epoxy equivalent ⁇ initial epoxy equivalent) / (theoretical epoxy equivalent ⁇ initial epoxy equivalent)] ⁇ 100 However, when the final epoxy equivalent was larger than the theoretical epoxy equivalent, the reaction rate was 100%.
- Example 1 Epototo YDPN-638 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., phenol novolac type epoxy resin: epoxy equivalent of 177 g / eq) with a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet ), 850 parts, HCA (manufactured by Sanko Co., Ltd., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus content 14.2%), 127 parts, cyanuric acid (Tokyo Chemical Industry Co., Ltd.) 23 parts) was added, stirred while introducing nitrogen gas, heated and heated to 130 ° C.
- HCA manufactured by Sanko Co., Ltd., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus content 14.2%
- cyanuric acid Tokyo Chemical Industry Co
- the initial epoxy equivalent in the mixed state was 207 g / eq.
- 0.14 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours.
- the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-1) had a phosphorus content of 1.8%, a theoretical epoxy equivalent of 270 g / eq, a final epoxy equivalent of 272 g / eq, and a reaction rate of cyanuric acid of 100%. .
- the results are shown in Table 1.
- Example 2 The same operation as in Example 1 was performed, except that Epototo YDPN-638 was changed to 758 parts, cyanuric acid was changed to 3 parts, and HCA was changed to 239 parts.
- the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-2) has a phosphorus content of 3.4%, an initial epoxy equivalent of 232 g / eq, a theoretical epoxy equivalent of 320 g / eq, a final epoxy equivalent of 332 g / eq, The reaction rate was 100%.
- Table 1 The results are shown in Table 1.
- Example 3 Epototo YDPN-63X (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., narrowly dispersed phenol novolac type epoxy resin: epoxy equivalent 176 g), equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device / eq) was charged with 692 parts, HCA with 250 parts, and cyanuric acid with 58 parts. The mixture was stirred while introducing nitrogen gas and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 254 g / eq. After measuring the initial epoxy equivalent, 0.33 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours.
- the obtained cyanuric acid-modified phosphorus-containing epoxy resin (A-3) had a phosphorus content of 3.6%, a theoretical epoxy equivalent of 701 g / eq, a final epoxy equivalent of 669 g / eq, and a reaction rate of cyanuric acid of 93%. .
- the results are shown in Table 1.
- Example 4 The same operation as in Example 3 was performed, except that Epototo YDPN-63X was changed to 640 parts, cyanuric acid was changed to 15 parts, and HCA was changed to 345 parts.
- the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-4) has a phosphorus content of 4.9%, an initial epoxy equivalent of 275 g / eq, a theoretical epoxy equivalent of 592 g / eq, a final epoxy equivalent of 594 g / eq, The reaction rate was 100%.
- Table 1 The results are shown in Table 1.
- FIG. A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device, 507 parts of Epototo YDPN-638, Epotot YD-128 (Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type) Liquid epoxy resin: 300 parts of epoxy equivalent (186 g / eq), 162 parts of HCA and 31 parts of cyanuric acid were added, stirred while introducing nitrogen gas, heated and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 223 g / eq.
- Example 6 A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, 433 parts of Epotot YDPN-638, Epotot YDCN-704 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., cresol novolak type) Epoxy resin: Epoxy equivalent: 209 g / eq) 300 parts, HCA 250 parts, cyanuric acid 17 parts were charged, stirred while introducing nitrogen gas, heated and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 258 g / eq.
- cyanuric acid-modified phosphorus-containing epoxy resin (A-6) had a phosphorus content of 3.6%, a theoretical epoxy equivalent of 429 g / eq, a final epoxy equivalent of 428 g / eq, and a reaction rate of cyanuric acid of 99%. .
- Table 1 The results are shown in Table 1.
- Example 7 A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, 442 parts of Epototo YDPN-638, YSLV-80XY (Nippon Steel & Sumikin Chemical Co., Ltd., Tetramethylbisphenol F)
- Type epoxy resin Epoxy equivalent 190g / eq 300 parts, HCA 250 parts, cyanuric acid 6 parts were charged, stirred while introducing nitrogen gas, heated and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 245 g / eq. After measuring the initial epoxy equivalent, 0.25 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C.
- the obtained cyanuric acid-modified phosphorus-containing epoxy resin (A-7) had a phosphorus content of 3.6%, a theoretical epoxy equivalent of 360 g / eq, a final epoxy equivalent of 360 / eq, and a reaction rate of cyanuric acid of 100%. .
- the results are shown in Table 1.
- Example 8 A four-necked glass separable flask equipped with a stirrer, thermometer, cooling pipe, and nitrogen gas introduction device, 860 parts of Epototo YDPN-638, CPHO (Nippon Chemical Industry Co., Ltd., 1,5-cyclooctyl) Lenphosphine oxide (phosphorus content 19.6%) (110 parts) and cyanuric acid (30 parts) were charged, stirred while introducing nitrogen gas, heated and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 206 g / eq. After measuring the initial epoxy equivalent, 0.14 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours.
- Epototo YDPN-638 860 parts of Epototo YDPN-638, CPHO (Nippon Chemical Industry Co., Ltd., 1,5-cyclooctyl) Lenphosphine oxide (phosphorus content 19.6%) (110 parts) and
- the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-8) had a phosphorus content of 2.2%, a theoretical epoxy equivalent of 289 g / eq, a final epoxy equivalent of 290 / eq, and a cyanuric acid reaction rate of 100%. .
- the results are shown in Table 1.
- Comparative Example 1 A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device was charged with 954 parts of Epototo YDPN-638 and 46 parts of cyanuric acid, and stirred while introducing nitrogen gas. And heated to raise the temperature. The temperature was raised to 130 ° C. The initial epoxy equivalent in the mixed state was 185 g / eq. After measuring the initial epoxy equivalent, 0.05 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours.
- the final epoxy equivalent of the obtained cyanuric acid-modified epoxy resin (A-9) was 194 g / eq, and the phosphorus content was 0%.
- the theoretical epoxy equivalent was 230 g / eq, and the reaction rate of cyanuric acid was 20%.
- the results are shown in Table 1.
- Comparative Example 2 The same operation as in Example 1 was performed, except that Epototo YDPN-638 was changed to 843 parts and cyanuric acid was changed to 31 parts.
- the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-10) has a phosphorus content of 1.8%, an initial epoxy equivalent of 209 g / eq, a theoretical epoxy equivalent of 287 g / eq, and a final epoxy equivalent of 263 g / eq.
- the reaction rate was 69%.
- Table 1 The results are shown in Table 1.
- Comparative Example 3 The same operation as in Example 1 was conducted except that Epototo YDPN-638 was changed to 882 parts, cyanuric acid was changed to 23 parts, and HCA was changed to 95 parts.
- the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-11) has a phosphorus content of 1.35%, initial epoxy equivalent of 200 g / eq, theoretical epoxy equivalent of 248 g / eq, final epoxy equivalent of 231 g / eq, cyanuric acid The reaction rate was 65%.
- Table 1 The results are shown in Table 1.
- Comparative Example 4 In a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, 788 parts of Epototo YDPN-638, 23 parts of cyanuric acid, HCA-HQ (manufactured by Sanko Co., Ltd., Charge 189 parts of 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus content 9.6%), stir while introducing nitrogen gas, and heat Went and warmed up. The temperature was raised to 130 ° C. The initial epoxy equivalent in the mixed state was 223 g / eq. After measuring the initial epoxy equivalent, 0.2 parts of triphenylphosphine was added as a catalyst and reacted at 160 ° C. for 4 hours. Resin was not obtained. Moreover, cyanuric acid remained solid in the gelled product.
- Comparative Example 5 The same operation as in Comparative Example 4 was performed except that epototo YDPN-638 was changed to 855 parts, cyanuric acid was changed to 15 parts, and HCA-HQ was changed to 130 parts.
- the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-12) has a phosphorus content of 1.2%, an initial epoxy equivalent of 206 g / eq, a theoretical epoxy equivalent of 271 g / eq, and a final epoxy equivalent of 224 g / eq. The reaction rate was 28%.
- Table 1 The results are shown in Table 1.
- Comparative Example 6 A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, 683 parts of Epototo YDPN-638, Epotot YDF-2001 (Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol F type) Solid epoxy resin: 190 parts of epoxy equivalent (469 g / eq) and 127 parts of HCA were charged, stirred while introducing nitrogen gas, heated and heated. The temperature was raised to 130 ° C. The initial epoxy equivalent in the mixed state was 235 g / eq.
- Examples 9-12 and 14-16, and Comparative Examples 7-11 The cyanuric acid-modified phosphorus-containing epoxy resins of Examples 1 to 5, Comparative Examples 1 to 3, and Comparative Example 5, and the phosphorus-containing epoxy resin of Comparative Example 6 and DICY as a curing agent (Dicyandiamide, manufactured by Nippon Carbide Corporation) was used to prepare a curable epoxy resin composition.
- Table 2 shows the formulation of the solid content.
- the epoxy resin was dissolved in methyl ethyl ketone and used.
- DICY was used by dissolving in methoxypropanol and N, N-dimethylformamide.
- 2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd., 2-ethyl-4-methylimidazole
- methoxypropanol was dissolved in methoxypropanol and used. After blending, the solution was adjusted with methyl ethyl ketone and methoxypropanol so that the non-volatile content was 50% to obtain a uniform resin varnish.
- the obtained resin varnish was impregnated into glass cloth WEA 7628 XS13 (manufactured by Nitto Boseki Co., Ltd., thickness 0.18 mm).
- the impregnated glass cloth was dried in a hot air circulating furnace at 150 ° C. for 8 minutes to obtain a prepreg. 4 sheets of prepreg obtained are stacked, and copper foil (Mitsui Metal Mining Co., Ltd., 3EC) is stacked on top and bottom, and heated and pressed at 130 ° C x 15 min and 170 ° C x 20 kg / cm 2 x 70 min. Got.
- Table 2 shows the physical properties of the obtained laminate.
- TX-1210-90 in the table represents Epototo TX-1210-90 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., substituted phenol type epoxy resin: epoxy equivalent 293 g / eq).
- An epoxy resin composition was prepared using the cyanuric acid-modified phosphorus-containing epoxy resin obtained in Examples 2 and 8 and BRG-557 (manufactured by Showa Denko KK, phenol novolac resin) as a curing agent. Table 2 shows the formulation of the solid content. At the time of blending, the epoxy resin and BRG-557 were dissolved in methyl ethyl ketone and used. 2E4MZ was used by dissolving in methoxypropanol. After blending, the solution was adjusted with methyl ethyl ketone and methoxypropanol so that the non-volatile content was 50% to obtain a uniform resin varnish.
- the obtained resin varnish was impregnated into glass cloth WEA 7628 XS13 (manufactured by Nitto Boseki Co., Ltd., thickness 0.18 mm).
- the impregnated glass cloth was dried in a hot air circulating furnace at 150 ° C. for 8 minutes to obtain a prepreg.
- Table 2 shows the physical properties of the obtained laminate.
- the present invention is a manufacturing method in which a specific phosphorus compound and cyanuric acid coexist in a specific molar ratio and react with an epoxy resin, and the cyanuric acid-modified phosphorus-containing epoxy resin obtained from the manufacturing method is flame retardant. It can be used as an epoxy resin for electronic circuit boards having excellent heat resistance and adhesiveness.
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Abstract
Description
(1)リン化合物、シアヌル酸及びエポキシ樹脂を必須成分として反応して得られるシアヌル酸変性リン含有エポキシ樹脂の製造方法であって、前記リン化合物が、
下記一般式(1):
で示されるリン化合物、または、その両者を含むリン化合物であり、シアヌル酸1モルに対して該リン化合物を2.5~50モル配合した、リン化合物及びシアヌル酸の共存下に、前記エポキシ樹脂を予め混合し、その後に反応を行い、リン含有率が1.0~5.0質量%、窒素含有率が0.1~2.0質量%、かつ、リン含有率と窒素含有率の総和が2.5~5.5質量%であることを特徴とするシアヌル酸変性リン含有エポキシ樹脂の製造方法、
(4)上記(2)に記載のエポキシ樹脂組成物に、該エポキシ樹脂組成物のエポキシ基1当量に対して、官能基比で0.4~2.0当量の硬化剤を含有した硬化性エポキシ樹脂組成物、
に関する。
窒素含有率はシアヌル酸の窒素含有率と配合量から、シアヌル酸変性リン含有エポキシ樹脂に対する百分率を算出した。
実施例及び比較例で合成されたエポキシ樹脂のリン含有率は以下の方法で測定を行った。すなわち、試料150mgに硫酸3mLを加え30分加熱する。室温に戻し、硝酸3.5 mL及び過塩素酸0.5 mLを加えて内容物が透明又は黄色になるまで加熱分解する。この液を100mLメスフラスコに純水で希釈する。この試料液10mLを50mLメスフラスコに入れ、フェノールフタレイン指示薬を1滴加え、2mol/Lアンモニア水を微赤色になるまで加える。50%硫酸液2mLを加え、純水を加える。2.5g/Lのメタバナジン酸アンモニウム水溶液を5mL及び50g/Lモリブデン酸アンモニウム水溶液5mLを加えた後、純水で定容とする。室温で40分放置した後、分光光度計を用いて波長440nmの条件で純水を対照として測定し、吸光度からリン含有率を求めた。
銅箔剥離強さはJIS C 6481 5.7に準じて、層間接着力はJIS C 6481 5.7に準じてプリプレグ1枚と残りの3枚の間で剥離を行い測定した。
難燃性はUL(Underwriter Laboratorics)規格に準じて測定を行った。また、残炎時間は試験片5本の有炎燃焼持続時間を合計して示した。
[(最終エポキシ当量-初期エポキシ当量)/(理論エポキシ当量-初期エポキシ当量)]×100
ただし、最終エポキシ当量が理論エポキシ当量より大きい場合は、反応率は100%とした。
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた4つ口のガラス製セパラブルフラスコに、エポトートYDPN-638(新日鉄住金化学株式会社製、フェノールノボラック型エポキシ樹脂:エポキシ当量177g/eq)を850部、HCA(三光株式会社製、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキサイド、リン含有率14.2%)を127部、シアヌル酸(東京化成工業株式会社製)を23部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は207g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.14部添加して160℃で4時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-1)のリン含有率は1.8%、理論エポキシ当量は270g/eq、最終エポキシ当量は272g/eq、シアヌル酸の反応率は100%であった。結果を表1に示した。
エポトートYDPN-638を758部に、シアヌル酸を3部にHCAを239部に変更した以外は実施例1と同様の操作を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-2)のリン含有率は3.4%、初期エポキシ当量は232g/eq、理論エポキシ当量は320g/eq、最終エポキシ当量は332g/eq、シアヌル酸の反応率は100%であった。結果を表1に示した。
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた4つ口のガラス製セパラブルフラスコに、エポトートYDPN-63X(新日鉄住金化学株式会社製、狭分散フェノールノボラック型エポキシ樹脂:エポキシ当量176g/eq)を692部、HCAを250部、シアヌル酸を58部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は254g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.33部添加して160℃で4時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-3)のリン含有率は3.6%、理論エポキシ当量は701g/eq、最終エポキシ当量は669g/eq、シアヌル酸の反応率は93%であった。結果を表1に示した。
エポトートYDPN-63Xを640部に、シアヌル酸を15部にHCAを345部に変更した以外は実施例3と同様の操作を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-4)のリン含有率は4.9%、初期エポキシ当量は275g/eq、理論エポキシ当量は592g/eq、最終エポキシ当量は594g/eq、シアヌル酸の反応率は100%であった。結果を表1に示した。
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた4つ口のガラス製セパラブルフラスコに、エポトートYDPN-638を507部、エポトート YD-128(新日鉄住金化学株式会社製、ビスフェノールA型液状エポキシ樹脂:エポキシ当量186g/eq)を300部、HCAを162部、シアヌル酸を31部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は223g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.25部添加して160℃で4時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-5)のリン含有率は2.3%、理論エポキシ当量は333g/eq、最終エポキシ当量は330g/eq、シアヌル酸の反応率は97%であった。結果を表1に示した。
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた4つ口のガラス製セパラブルフラスコに、エポトートYDPN-638を433部、エポトート YDCN-704(新日鉄住金化学株式会社製、クレゾールノボラック型エポキシ樹脂:エポキシ当量209g/eq)を300部、HCAを250部、シアヌル酸を17部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は258g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.25部添加して160℃で4時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-6)のリン含有率は3.6%、理論エポキシ当量は429g/eq、最終エポキシ当量は428g/eq、シアヌル酸の反応率は99%であった。結果を表1に示した。
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた4つ口のガラス製セパラブルフラスコに、エポトートYDPN-638を442部、YSLV-80XY(新日鉄住金化学株式会社製、テトラメチルビスフェノールF型エポキシ樹脂:エポキシ当量190g/eq)を300部、HCAを250部、シアヌル酸を6部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は245g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.25部添加して160℃で4時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-7)のリン含有率は3.6%、理論エポキシ当量は360g/eq、最終エポキシ当量は360/eq、シアヌル酸の反応率は100%であった。結果を表1に示した。
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた4つ口のガラス製セパラブルフラスコに、エポトートYDPN-638を860部、CPHO(日本化学工業株式会社製、1,5-シクロオクチレンホスフィンオキサイド、リン含有率19.6%)を110部、シアヌル酸を30部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は206g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.14部添加して160℃で4時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-8)のリン含有率は2.2%、理論エポキシ当量は289g/eq、最終エポキシ当量は290/eq、シアヌル酸の反応率は100%であった。結果を表1に示した。
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた4つ口のガラス製セパラブルフラスコに、エポトートYDPN-638を954部、シアヌル酸を46部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って昇温した。130℃まで昇温した。混合状態での初期エポキシ当量は185g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.05部を添加して160℃で4時間反応を行った。得られたシアヌル酸変性エポキシ樹脂(A-9)の最終エポキシ当量は194g/eq、リン含有率は0%であった。理論エポキシ当量は230g/eq、シアヌル酸の反応率は20%であった。結果を表1に示した。
エポトートYDPN-638を843部に、シアヌル酸を31部に変更した以外は実施例1と同様の操作を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-10)のリン含有率は1.8%、初期エポキシ当量は209g/eq、理論エポキシ当量は287g/eq、最終エポキシ当量は263g/eq、シアヌル酸の反応率は69%であった。結果を表1に示した。
エポトートYDPN-638を882部に、シアヌル酸を23部に、HCAを95部に変更した以外は実施例1と同様の操作を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-11)のリン含有率は1.35%、初期エポキシ当量は200g/eq、理論エポキシ当量は248g/eq、最終エポキシ当量は231g/eq、シアヌル酸の反応率は65%であった。結果を表1に示した。
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた4つ口のガラス製セパラブルフラスコに、エポトートYDPN-638を788部、シアヌル酸を23部、HCA-HQ(三光株式会社製、10-(2,5-ジヒドロキシフェニル)-10H-9-オキサ-10-ホスファフェナントレン-10-オキシド、リン含有率9.6%)を189部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って昇温した。130℃まで昇温した。混合状態での初期エポキシ当量を測定したら223g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.2部添加して160℃で4時間反応を行った所、ゲル化してしまいエポキシ樹脂は得られなかった。また、ゲル化物中にはシアヌル酸が固形で残存していた。
エポトートYDPN-638を855部に、シアヌル酸を15部に、HCA-HQを130部に変更した以外は比較例4と同様の操作を行った。得られたシアヌル酸変性リン含有エポキシ樹脂(A-12)のリン含有率は1.2%、初期エポキシ当量は206g/eq、理論エポキシ当量は271g/eq、最終エポキシ当量は224g/eq、シアヌル酸の反応率は28%であった。結果を表1に示した。
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた4つ口のガラス製セパラブルフラスコに、エポトートYDPN-638を683部、エポトート YDF-2001(新日鉄住金化学株式会社製、ビスフェノールF型固形エポキシ樹脂:エポキシ当量469g/eq)を190部、HCAを127部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って昇温した。130℃まで昇温した。混合状態での初期エポキシ当量は235g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.13部を添加して160℃で4時間反応を行った。得られたリン含有エポキシ樹脂(A-13)の最終エポキシ当量は272g/eq、リン含有率は1.8%であった。理論エポキシ当量は272g/eqであった。結果を表1に示した。
実施例1~5、比較例1~3、及び比較例5のシアヌル酸変性リン含有エポキシ樹脂、並びに比較例6のリン含有エポキシ樹脂と、硬化剤としてDICY(日本カーバイト株式会社製、ジシアンジアミド)を使用して硬化性エポキシ樹脂組成物を作成した。固形分での配合処方を表2に示した。配合の際にエポキシ樹脂はメチルエチルケトンに溶解して用いた。DICYはメトキシプロパノール、N,N-ジメチルホルムアミドに溶解して使用した。2E4MZ(四国化成工業株式会社製、2-エチル-4-メチルイミダゾール)はメトキシプロパノールに溶解して使用した。配合後、メチルエチルケトン、メトキシプロパノールにて不揮発分50 %となるように調整して、均一溶液な樹脂ワニスを得た。
なお、表中のTX-1210-90は、エポトートTX-1210-90(新日鉄住金化学株式会社製、置換フェノール型エポキシ樹脂:エポキシ当量293g/eq)を示す。
実施例2と8で得られたシアヌル酸変性リン含有エポキシ樹脂と、硬化剤としてBRG-557(昭和電工株式会社製、フェノールノボラック樹脂)を使用してエポキシ樹脂組成物を作成した。固形分での配合処方を表2に示した。配合の際にエポキシ樹脂及びBRG-557はメチルエチルケトンに溶解して用いた。2E4MZはメトキシプロパノールに溶解して使用した。配合後、メチルエチルケトン、メトキシプロパノールにて不揮発分50 %となるように調整して、均一溶液な樹脂ワニスを得た。
Claims (5)
- リン化合物、シアヌル酸、及びエポキシ樹脂を必須成分として反応して得られるシアヌル酸変性リン含有エポキシ樹脂の製造方法であって、前記リン化合物が、
下記一般式(1):
または、下記一般式(2):
で示されるリン化合物、または、その両者を含むリン化合物であり、シアヌル酸1モルに対して、該リン化合物を2.5~50モルにした、リン化合物及びシアヌル酸の共存下に、前記エポキシ樹脂を予め混合し、その後に反応を行い、リン含有率が1.0~5.0質量%、窒素含有率が0.1~2.0質量%、かつ、リン含有率と窒素含有率の総和が2.5~5.5質量%であることを特徴とするシアヌル酸変性リン含有エポキシ樹脂の製造方法。 - 請求項1に記載の製造方法により得られるシアヌル酸変性リン含有エポキシ樹脂に、他のエポキシ樹脂を配合したエポキシ樹脂組成物。
- 請求項1に記載の製造方法により得られるシアヌル酸変性リン含有エポキシ樹脂に、該シアヌル酸変性リン含有エポキシ樹脂のエポキシ基1当量に対して、官能基比で0.4~2.0当量の硬化剤を含有した硬化性エポキシ樹脂組成物。
- 請求項2に記載のエポキシ樹脂組成物に、該エポキシ樹脂組成物のエポキシ基1当量に対して、官能基比で0.4~2.0当量の硬化剤を含有した硬化性エポキシ樹脂組成物。
- 請求項3または4に記載の硬化性エポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物。
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WO2008143309A1 (ja) * | 2007-05-18 | 2008-11-27 | Tohto Kasei Co., Ltd. | 新規な難燃性エポキシ樹脂、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その硬化物 |
JP2010241872A (ja) * | 2009-04-01 | 2010-10-28 | Nippon Steel Chem Co Ltd | エポキシ樹脂、その製造方法、エポキシ樹脂組成物および硬化物 |
JP2012229364A (ja) * | 2011-04-27 | 2012-11-22 | Nippon Steel Chem Co Ltd | リン及び窒素含有エポキシ樹脂 |
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JP2010241872A (ja) * | 2009-04-01 | 2010-10-28 | Nippon Steel Chem Co Ltd | エポキシ樹脂、その製造方法、エポキシ樹脂組成物および硬化物 |
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JP6246126B2 (ja) | 2017-12-13 |
KR20150052011A (ko) | 2015-05-13 |
CN104583263B (zh) | 2018-02-13 |
TWI620762B (zh) | 2018-04-11 |
CN104583263A (zh) | 2015-04-29 |
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