KR20150082181A - Polyvalent phenylene ether novolac resin, epoxy resin composition, and cured product thereof - Google Patents
Polyvalent phenylene ether novolac resin, epoxy resin composition, and cured product thereof Download PDFInfo
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- KR20150082181A KR20150082181A KR1020157007946A KR20157007946A KR20150082181A KR 20150082181 A KR20150082181 A KR 20150082181A KR 1020157007946 A KR1020157007946 A KR 1020157007946A KR 20157007946 A KR20157007946 A KR 20157007946A KR 20150082181 A KR20150082181 A KR 20150082181A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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Abstract
An object of the present invention is to provide a polyphenylene ether novolak resin which provides a cured product having high heat resistance and excellent dielectric properties and an epoxy resin composition containing the same. The polyvalent phenylene ether novolak resin of the present invention has a molecular weight of 400 to 8000 (weight average molecular weight in terms of polystyrene) poly (phenylene ether) resin connected by an organic group.
Description
The present invention relates to a novolac resin, an epoxy resin composition, and a cured product thereof, which are preferable for use in electric and electronic materials requiring heat resistance and electric characteristics (dielectric properties, etc.).
BACKGROUND ART Epoxy resin compositions have been extensively used in fields such as electric and electronic parts, structural materials, adhesives, paints and the like due to workability and cured products thereof with excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance)
In recent years, however, in the field of electric and electronic devices, there has been a tendency to increase the viscosity of the resin composition, such as high purity, humidity resistance, adhesion, dielectric properties, low viscosity for high filling of fillers (inorganic or organic fillers) Improvement of various properties such as increase in reactivity is further demanded. In addition, as a structural material, a lightweight material having excellent mechanical properties is required for use in aerospace materials, leisure and sports apparatuses, and the like.
In the field of semiconductor encapsulation and the substrate (the substrate itself or the peripheral material thereof), it is complicated by thinning, stacking, systemization, and three-dimensionalization depending on the transition of the semiconductor, . In order to realize high-speed communication, excellent dielectric properties are required for semiconductor peripheral materials. It is difficult to increase the speed of the electric signal due to the occurrence of the delay and noise of the electric signal having poor dielectric characteristics.
In this field, especially in a network substrate such as a server, a dielectric property in a high frequency is required. In particular, low-dielectric-constant tangency becomes important in the evolutionary network environment. Poly (phenylene ether) resins can be mainly used for such applications, and various investigations have been made.
The poly (phenylene ether) resin is characterized by its excellent dielectric properties, but in order to realize its dielectric properties, the number of functional groups is extremely small and its heat resistance is low.
According to recent reports, studies such as (a) a method of inserting a functional group or (b) a bifunctionality have been conducted with respect to such a problem. However, in (a), since introduction of a functional group is difficult, In (b), there is some improvement but still insufficient level.
Faced with this problem, we have reached the present invention.
That is, an object of the present invention is to provide a polyphenylene ether novolak resin capable of providing a cured product having excellent heat resistance while maintaining excellent dielectric properties, an epoxy resin composition containing the same, and a cured product thereof.
Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-described facts and have completed the present invention.
That is,
(1) A poly (phenylene ether) novolak resin characterized by having a poly (phenylene ether) resin having a molecular weight of 400 to 8000 (weight average molecular weight in terms of polystyrene) connected by an organic group,
(2) The polyphenylene ether novolac resin according to (1), wherein the organic group is represented by at least one of the following formula (1)
Wherein * moiety is bonded to the benzene skeleton of the poly (phenylene ether) resin,
(3) The polyphenylene ether novolac resin according to (1) or (2), wherein the poly (phenylene ether) resin is an oxidized polymer of a phenol compound or a bisphenol compound and a phenol compound,
(4) An epoxy resin composition comprising at least one polyvalent phenylene ether novolac resin according to any one of (1) to (3) above,
(5) A cured product obtained by curing the epoxy resin composition according to (4) above.
(Effects of the Invention)
The cured product of the epoxy resin composition using the polyvalent phenylene ether novolak resin of the present invention not only has a high dielectric property but also exhibits excellent heat resistance and can be used as an insulating material for electrical and electronic parts and a laminated board Etc.) and various composite materials including CFRP, adhesives, and paints. In particular, it is very useful for a semiconductor sealing material for protecting semiconductor devices.
The polyvalent phenylene ether novolak resin of the present invention has a structure in which a resin having a poly (phenylene ether) structure is bonded through an organic group such as an alkylene group (hereinafter referred to as a bonding group or a linking group). That is, the polyvalent phenylene ether novolak resin of the present invention is a resin having a poly (phenylene ether) structure and a novolac resin structure.
Specific examples of the resin having a poly (phenylene ether) structure are the resins described in Patent Documents 1 and 2 mentioned above, and oxides of xylenol or trimethylphenol are generally used. However, as resins described in Patent Document 2, And oxidation polymers of bisphenols and phenol compounds such as 2,6-xylenol and the like.
As the bisphenols, for example, bisphenols such as bisphenol A, bisphenol F, bisphenol S, and bisphenol I can be used. Commercially available products include PPO (registered trademark) produced by SABIC, and SA120 and SA90-100 are particularly preferable in the molecular weight range. In particular, it is preferable to use a bifunctional compound such as SA90-100 at the degree of multi-functionalization. Examples of the non-phenol include compounds represented by the following formulas.
[Wherein, R 1 each represent independently a substituent of a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 3, an aralkyl group, an aryl group, an alkoxy group, t represents an integer of 1 to 4;
Examples of the phenol compounds include o-cresol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-ethylphenol, 2- Propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2- -Propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, Phenylphenol, 2-phenylphenol, 2,6-diphenylphenol, 2,6-bis- (4-fluorophenyl) phenol, 2-methyl-6-tolylphenol and 2,6-ditolylphenol And monovalent phenol compounds.
The molecular weight of the poly (phenylene ether) resin to be used is 400 to 8000 (weight average molecular weight measured by gel permeation chromatography in terms of polystyrene), preferably 500 to 4,000.
When the molecular weight of the resin to be used is too high, compatibility with a solvent and compatibility with other resins are impaired, and when the resin is blown into a cured product, it is not preferable because it causes separation of properties and unevenness of properties. When the molecular weight is small, particularly about 200, it is not preferable because a difference in dielectric properties can not be obtained as compared with a general novolac resin.
These molecular weights can be controlled not only by linking molecules but also by molecular weight control by depolymerization by radicals.
The polyvalent phenylene ether novolak resin of the present invention is novolak or a similar type (expressed as novolak for convenience) by connecting a phenylene structure to a bonding group.
The bonding group is preferably a hydrocarbon group having 1 to 20 carbon atoms. Specific examples thereof include methylene, ethylene, propylene, cyclohexane-diyl, phenylmethylene, phenylenebismethylene, bienylenebismethylene, phenylenebisethylene and phenylenebispropylene.
As the bonding group in the present invention, a structure represented by the following formula (1) is particularly preferable.
Wherein * moiety is bonded to the benzene skeleton of the poly (phenylene ether) resin,
As a bonding method of these linking groups, there can be used a bonding forming compound such as a raw poly (phenylene ether) resin and various aldehydes, ketones, benzylmethylene compounds, and compounds having a vinylbenzene structure, and heating under acidic or basic conditions in the presence of a solvent Can be synthesized.
Specific examples of the bond forming compound include aldehydes such as formaldehyde, acetaldehyde, glyoxal, propylaldehyde, isobaldealdehyde, octylaldehyde, furfural, benzaldehyde and pyridinecarboxyaldehyde, acetone, methyl ethyl ketone, cyclopentanone, Xylene, etc.), ketones such as cyclohexanone, xylylene glycol, xylylene dihalide (including halogen: chlorine, bromine and the like), bisalkoxymethylbenzene (xylylenebisalkylether, specifically bismethoxymethylbenzene, And alkoxymethyl compounds having 1 to 6 carbon atoms, such as bisethoxymethylbenzene, bispropoxymethylbenzene, bisbutoxymethylbenzene, bisphenoxymethylbenzene, bisaryloxymethylbenzene etc. In this synthesis reaction, in particular, xylyl Xylylene dichloride, and bismethoxymethylbenzene are preferable. The arrangement of the substituent may be any one of ortho, meta and para Biphenyl dimethanol, bis-halogenmethylbiphenyl (including halogen: chlorine, bromine and the like), bisalkoxy (meth) acrylates, and the like may be used, Methyl biphenyl (specifically, bismethoxymethylbiphenyl, bisethoxymethylbiphenyl, bispropoxymethylbiphenyl, bisbutoxymethylbiphenyl, bisphenoxymethylbiphenyl, bisaryloxymethylbiphenyl, etc.) , An alkoxymethyl compound having 1 to 6 carbon atoms, etc.), and a compound having a vinylbenzene structure such as divinylbenzene.
In the synthesis reaction, biphenyl dimethanol, bischloromethylbiphenyl, and bismethoxymethylbiphenyl are particularly preferable.
The polyvalent phenylene ether novolak resin of the present invention can be obtained by heating a mixture of a raw poly (phenylene ether) resin and a coupling-forming compound with a solvent by adding a catalyst as required.
In addition, a bond forming compound may be gradually added to a solution obtained by dissolving a raw poly (phenylene ether) resin and, if necessary, a catalyst. The reaction time is usually 3 to 150 hours, and the reaction temperature is usually 40 to 150 ° C. The polyhydric phenylene ether novolac resin thus obtained may be used without purification according to the application. Usually, after completion of the reaction, the reaction mixture is subjected to treatment such as neutralization if necessary, and then the solvent is removed under crystallization or heating and decompression Purified and used for various purposes. In addition, the average molecular weight of the obtained polyphenylene ether novolak resin is increased due to the reaction, so that the softening point of the resin becomes very high and it becomes difficult to take out the polyphenylene ether novolac resin from the reaction vessel, so that the following methods (a) to (d) can be used.
(a) a method obtained by diluting in a water-soluble solvent and then mixing with water and re-precipitating.
(b) is obtained by diluting with alcohols having 1 to 4 carbon atoms (methanol, ethanol, propanol, butanol, etc.) and re-precipitating.
(c) removing only the water contained in the solvent after the completion of the reaction and purification (heating decompression, etc.), and then removing the solvent from the reaction vessel as a solvent-cut varnish. (Resin concentration is preferably 10 to 90% by weight, more preferably 10 to 80% by weight, and particularly preferably 30 to 80% by weight). In particular, viscosity is important in many cases. ° C is preferably 1000 Pa · s or less, more preferably 100 Pa · s or less. When the viscosity is too high, there is no fluidity at the time of use, so that it may be difficult to take out and mix with other resins. Usable solvents will be described later (solvents described in the item of the curable resin composition varnish).
(d) mixing with another resin (a resin described in the item of the curing agent for a curable resin composition described later) to take out from the reaction vessel as a curing agent composition. (The mixing ratio is preferably 90:10 to 30:70, more preferably 80:20 to 30:70, by weight of the other resin and the resin of the present invention.) When the blending amount of the resin of the present invention is small, There is no major improvement of.
The reaction molar ratio (hydroxyl equivalent ratio) of the raw poly (phenylene ether) resin to the bond forming compound is preferably 1.2: 1 to 20: 1, more preferably 1.5: 1 to 15: 1, : 1 to 10: 1. When the reaction molar ratio is less than 1.2: 1, that is, when the raw poly (phenylene ether) resin is less than 1.2 based on the bond forming compound 1, the molecular weight of the resulting multibranched phenylene ether novolac resin becomes too large, , And compatibility with other resins may be poor. In addition, when the raw material poly (phenylene ether) resin exceeds 20: 1, that is, the raw material poly (phenylene ether) resin exceeds 20, the heat resistance may be poor.
Examples of the solvent that can be used in the synthesis of the polyvalent phenylene ether novolak resin of the present invention include toluene, xylene, methyl isobutyl ketone, anion, cyclopentanone, methyl ethyl ketone, Or two or more of them may be used in combination. Examples of the solvent which can be used in combination include alcohols such as methanol, ethanol, isopropanol and butanol, ketones such as acetone, esters such as ethyl acetate, butyl acetate, carbitol acetate and propylene glycol monomethyl ether acetate, Ethers such as tetrahydrofuran and dioxane, and nitrogen-containing solvents such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. The amount of the solvent to be used is generally in the range of 5 to 500 parts by weight, preferably 10 to 400 parts by weight, based on 100 parts by weight of the total amount of the raw poly (phenylene ether) resin and the bond forming compound.
As the catalyst, it is preferable to use an acidic catalyst basically. When the coupling-forming compound is a benzyl halide, the reaction can proceed smoothly even without addition of a catalyst, and from the viewpoint of easy purification afterwards, it is preferable not to use the catalyst or little use thereof. When a catalyst is used, specific examples of the acid catalyst include minerals such as hydrochloric acid, sulfuric acid, and phosphoric acid; Organic acids such as oxalic acid, toluenesulfonic acid and acetic acid; Acidic catalysts commonly used for the production of novolak resins such as organic acids and inorganic acid salts exhibiting other acidic properties such as activated carbon, inorganic acids, stannic chloride, zinc chloride, ferric chloride and the like, . These catalysts are not limited to the above-mentioned materials, and they may be used singly or in combination of two or more. The amount of the catalyst to be used is preferably in the range of 0.005 to 2.0 times by mole, preferably 0.01 to 1.1 times by mole, or 0.1 to 50 g per 100 g of the starting poly (phenylene ether) resin And more preferably 0.3 to 20 parts by weight. When the amount of the catalyst is small, the progress of the reaction is delayed. In addition, problems such as a reaction at a high temperature and a reaction not progressing to the end are generated, which is not preferable. When the amount of the catalyst is too large, a great labor may be required in the post-treatment such as neutralization and refining.
In the case where a corrosive gas is generated by the reaction, it is preferable to discharge by suction pressure or an inert gas such as nitrogen, thereby discharging the gas from the system.
The polyvalent phenylene ether novolak resin thus obtained is represented by a structural formula shown by the following formula (A), and specific examples of this representative structural formula will be described below.
The obtained polyhydric phenylene ether novolac resin is bonded to the benzene skeleton of the poly (phenylene ether) resin exemplarily described in B below by a linking group exemplarily shown in the following A, Benzene skeleton in the same molecule of two or more poly (phenylene ether) resins, or between benzene skeletons of two or more molecules of poly (phenylene ether) resin.
Then, the partial structure around the connector becomes, for example, the following structure (A). In addition, the following benzene skeleton represents a benzene skeleton in a poly (phenylene ether) resin molecule.
Wherein R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, * is a hydrogen atom, or a group represented by the formula (1) X, and n represents an integer of 1 to 2,
Here, the residue of the poly (phenylene ether) resin can also be connected to the benzene skeleton in the poly (phenylene ether) resin molecule through X in a separate benzene skeleton.
The polyvalent phenylene ether novolak resin of the present invention thus obtained is a brown resinous (or powdery) resin soluble in an organic solvent and can be handled as a varnish.
The hydroxyl group equivalent of the polyvalent phenylene ether novolak resin of the present invention thus obtained is preferably from 400 to 6000, and particularly preferably from 500 to 5,000.
The weight average molecular weight is preferably 600 to 50,000, and particularly preferably 700 to 25,000.
The polyvalent phenylene ether novolac resin of the present invention may be used as it is as it is, or may be used as a raw material for an epoxy resin or as a curing agent thereof, by mixing with thermoplastic plastics.
Hereinafter, an epoxy resin composition (hereinafter referred to as a curable resin composition) of the present invention containing the polyvalent phenylene ether novolak resin of the present invention will be described. In the curable resin composition of the present invention, an epoxy resin is used as an essential component.
In the curable resin composition of the present invention, a composition comprising an epoxy resin-curing agent as an essential component and a polyphenylene ether novolak resin are necessarily contained as a curing agent for an epoxy resin. It also contains a curing accelerator, if necessary.
Specific examples of the epoxy resin that can be used in the curable resin composition of the present invention include novolak type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins and phenol aralkyl type epoxy resins have. Specific examples thereof include bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpenediphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'- (1,1'-biphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis Hydroxyphenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p- hydroxybenzaldehyde, Benzoyl peroxide, benzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'- (Methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene and 1,4-bis (methoxymethyl) benzene, and their modified products, tetrabromobisphenol A , Halogenated bisphenols such as (Linear, cyclic, ladder-type, or at least one of them) derived from a silsesquioxane-based epoxy resin, an alicyclic epoxy resin, a glycidylamine-based epoxy resin and a glycidyl ester- Or an epoxy resin having a glycidyl group and / or an epoxy cyclohexane structure in a siloxane structure having at least two mixed structures), but the present invention is not limited thereto.
As the curing agent contained in the curable resin composition of the present invention, other curing agents other than the polyvalent phenylene ether novolak resin of the present invention may be used in combination. When used in combination, the polyvalent phenylene ether novolak resin of the present invention can be used as a curing agent composition for the other curing agent. When used in combination, the proportion of the polyvalent polyphenylene ether novolac resin of the present invention in the total epoxy resin composition is preferably 30% by weight or more, more preferably 40% by weight or more.
Examples of the curing agent that can be used in combination include a phenol resin, a phenol compound, an amine compound, an acid anhydride compound, an amide compound, and a carboxylic acid compound.
Specific examples of the curing agent that can be used are as follows.
Phenolic resins, phenolic compounds; Bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1 (4-hydroxyphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalene diol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis Ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene and the like) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, Bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) biphenyl, dihydroxyacetophenone, dicyclopentadiene, furfural, Polycondensates such as 1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene and 1,4'-bis (methoxymethyl) benzene, and modified products thereof, tetrabromobisphenol A Halogenated bisphenols, axes of terpenes and phenols Polyphenols such as polyphenylene sulfide, polyphenol such as polyphenylene sulfide, polyphenylene sulfide, and polyphenol. These may be used alone, or two or more of them may be used.
A preferable phenol resin is a phenol aralkyl resin (a resin having an aromatic alkylene structure) from the viewpoint of the dielectric constant, particularly preferably a structure having at least one kind selected from phenol, naphthol and cresol, Wherein the resin is at least one selected from the group consisting of an alkylene-addition-benzene structure, a biphenyl structure, and a naphthalene structure (specifically, a resin selected from the group consisting of xylyl, naphthol xylox, phenol biphenylene novolak resin, cresol- , Phenol-naphthalene novolak resin, and the like).
Amine-based compounds, amide-based compounds; Nitrogen-containing compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a dimer of linoleic acid, and a polyamide resin synthesized by ethylenediamine But are not limited to these. These may be used alone, or two or more of them may be used.
Acid anhydride-based compounds, and carboxylic acid-based compounds; Examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, anhydrous nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Carboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane Acid anhydrides such as 1,3,4-tricarboxylic acid-3,4-anhydride; Various alcohols, and carboxylic acid resins obtained by addition reaction of carbinol-modified silicone with the acid anhydrides described above, but are not limited thereto. These may be used alone, or two or more of them may be used.
Other examples of curing agents that can be used in combination include imidazole, trifluoroborane-amine complexes, and compounds of guanidine derivatives, but are not limited thereto. These may be used alone, or two or more of them may be used.
In the curable resin composition of the present invention, the curing agent is preferably used in an amount of 0.7 to 1.2 equivalents based on 1 equivalent of the epoxy group of the whole epoxy resin in terms of its functional group (hydroxyl group) equivalent. When the equivalent of 0.7 equivalents or more than 1.2 equivalents with respect to one equivalent of the epoxy group is exceeded, the curing becomes incomplete in all cases, and good curing properties can not be obtained.
In the curable resin composition of the present invention, a curing accelerator may be used in combination with a curing agent. Specific examples of the curing accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) Tertiary amines such as diazabicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecanylammonium salts, cetyltrimethyl And quaternary phosphonium salts such as quaternary ammonium salts such as ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts and tetrabutylphosphonium salts. (A counter ion of a quaternary salt is not particularly specified, such as a halogen, an organic acid ion, or a hydroxide ion, but an organic acid ion or a hydroxide ion is particularly preferable), and metal compounds such as tin octylate. When a curing accelerator is used, 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin is used as needed.
The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be of reaction type or of addition type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dicresyl phosphate, Cresyl phosphate), 1,4-phenylenebis (dicresyl phosphate), and 4,4'-biphenyl (dicresyl phosphate); 10-dihydroxy-10-phosphapenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) Phosphates such as oxides; Phosphorus-containing epoxy compounds obtained by reacting an epoxy resin with active hydrogens of the above-mentioned phosphates, and red phosphorus. Phosphoric acid esters, phosphates or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylene bis Silane phosphate), 1,4-phenylenebis (dicresylphosphate), 4,4'-biphenyl (dicresylphosphate) or phosphorus-containing epoxy compounds are particularly preferable. The content of the phosphorus-containing compound is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is less than 0.1, flame retardancy may be insufficient, and when it is more than 0.6, hygroscopicity and dielectric properties of the cured product may be lowered.
An antioxidant may be added to the curable resin composition of the present invention if necessary. Examples of the antioxidant that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. The antioxidant may be used alone or in combination of two or more. The amount of the antioxidant to be 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.
Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6- Di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5- Bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butyl anilino) -1,3,5-triazine, 2,4- ] -o-cresol; (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl- Butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2-thio-diethylenebis [3- Dihydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2 - {? - (3 (3,5-di-t-butyl) -4-hydroxyphenyl] 4-hydroxybenzylsulfonic acid ethyl) calcium; Methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3' (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,6-di (tert- butylphenyl) butyric acid] glycol ester, (1H, 3H, 5H) trione, tocopherol, and the like Of polymeric phenols.
Specific examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate And the like.
Specific examples of the phosphorus antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris (2,4- (2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbis Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl- 4- {2- (octadecyloxycarbonyl) ethyl} phenyl] Phosphites; 10,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5- Oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene- And the like.
These antioxidants may be used alone, but two or more antioxidants may be used in combination. Particularly, in the present invention, an antioxidant of phosphorus is preferable.
Further, a light stabilizer may be added to the curable resin composition of the present invention if necessary.
As light stabilizers, hindered amine light stabilizers, particularly HALS, are preferred. The HALS is not particularly limited, but typical examples thereof include dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl- A polycondensation product of 6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl succinate-1- (2-hydroxyethyl) -4- 2,2,6,6-tetramethylpiperidine polycondensate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl } {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino} (2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4- hydroxyphenyl] methyl] butyl malonate, bis 2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis -2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) (1,2,2,6,6-pentamethyl-4-piperidyl), etc. The HALS may be used alone or in combination of two or more.
In the curable resin composition of the present invention, a binder resin may be blended if necessary. As the binder resin, a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy -NBR resin, a polyamide resin, a polyimide resin, But are not limited thereto. 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 by weight, based on 100 parts by weight of the resin component.
An inorganic filler may be added to the curable resin composition of the present invention, if necessary. Examples of the inorganic filler include powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, titania, talc, , But are not limited to these. These may be used alone, or two or more of them may be used. The content of these inorganic fillers in the curable resin composition of the present invention is 0 to 95% by weight. Further, various curing agents such as silane coupling agent, stearic acid, palmitic acid, zinc stearate, calcium stearate, surfactants, dyes, pigments, ultraviolet absorbers, and various thermosetting resins are added to the curable resin composition of the present invention .
The curable resin composition of the present invention is obtained by uniformly mixing each component. The curable resin composition of the present invention can be easily made into the cured product by the same method as a conventionally known method. For example, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent may be added to the polyphenylene ether novolak resin of the present invention and an epoxy resin arrangement, if necessary, using an extruder, a kneader, And then the mixture is sufficiently mixed until homogeneous to obtain a curable resin composition. The curable resin composition is molded by using a mold or a transfer molding machine after potting and melting (melting in the case of a liquid phase) and molding at 80 to 200 ° C for 2 to 10 hours The cured product of the present invention can be obtained by heating.
The curable resin composition of the present invention may be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethylacetamide or N-methylpyrrolidone, A prepreg obtained by impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper or the like with a composition varnish by heating and drying is hot-pressed to obtain a cured product of the curable resin composition A . The amount of the solvent used in the mixture of the curable resin composition of the present invention and the solvent is usually from 10 to 70% by weight, preferably from 15 to 70% by weight. Further, it is also possible to obtain a cured product of an epoxy resin containing a carbon fiber by the RTM method, for example, in the liquid composition.
The curable resin composition of the present invention can also be used as a modifier for film-like compositions. More specifically, it can be used in the case of improving the flexibility in the B-stage. Such a film-like resin composition is obtained as a sheet-like adhesive by applying the curable resin composition of the present invention onto a release film as the curable resin composition varnish, removing the solvent under heating, and then carrying out B staging. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
The curable resin composition of the present invention can be used in general applications in which an epoxy resin is used. Examples of the curable resin composition include adhesives, paints, coating agents, molding materials (including sheets, films, FRP and the like) Etc.), additives to other resins other than the sealing agent, and the like. Examples of the adhesive include adhesives for electronic materials, as well as adhesives for civil engineering, construction, automobile, general office, and medical applications. Of these, examples of the adhesive for electronic materials include an interlayer adhesive of a multilayer substrate such as a build-up substrate, an adhesive for semiconductor such as a die bonding agent and an underfill, an underfill for BGA reinforcement, an anisotropic conductive film (ACF), an anisotropic conductive paste And an adhesive for mounting of the adhesive layer.
Porting, dipping, transfer mold sealing for ICs, LSIs, ICs, LSIs, pottings for COB, COF, TAB, and underfills for flip chips, QFPs for capacitors, transistors, diodes, , Sealing (including underfill for reinforcement) and package substrates when installing IC packages such as BGA and CSP. It is also preferable for a substrate which requires a function as a network substrate or a module substrate.
(Example)
Next, the present invention will be described in more detail with reference to examples, but parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
Various analytical methods used in the examples are described below.
Epoxy equivalent: according to JIS K 7236 (ISO 3001)
ICI melt viscosity: according to JIS K 7117-2 (ISO 3219)
Softening point: according to JIS K 7234
Total chlorine: According to JIS K 7243-3 (ISO 21672-3)
GPC:
Columns (Shodex KF-603, KF-602.5, KF-602, KF-601x2)
The connecting eluent was tetrahydrofuran
The flow rate was 0.5 ml / min
The column temperature was 40 [
Detection: RI (differential refraction detector)
Hereinafter, the present invention will be described in detail with reference to examples and comparative examples.
(Example 1)
175 parts of a polyphenylene ether resin (MX90-100 manufactured by SABIC, Mn = 2066, Mw = 3553, Mz = 5951 in a GPC chart) was added to a flask equipped with a stirrer, a reflux condenser, 9.6 parts of p-xylylene glycol (production reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 300 parts of toluene (manufactured by Junsei Chemical Co., Ltd.), paratoluenesulfonic acid monohydrate , 2 parts of a polymerization initiator and 2 parts of a polymerization initiator were added, and the mixture was reacted at 100 ° C for 2 hours, then refluxed at 110-120 ° C and reacted for 7 hours.
After completion of the reaction, 200 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Thereafter, the solvent was distilled off from the oil layer using a rotary evaporator to obtain a polyphenylene ether- Thereby obtaining 179 parts of a boric acid resin (P-1). (Also, in the GPC chart of the polyphenylene ether resin as the raw material, Mn = 2091, Mw = 4215, Mz = 7774)
(Example 2)
75 parts of a polyphenylene ether resin (MX90-100, manufactured by SABIC), p-xylylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a flask equipped with a stirrer, , 130 parts of toluene (manufactured by Junsei Chemical Co., Ltd.) and 1 part of para-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and reacted at 100 ° C for 2 hours. Thereafter, the mixture was refluxed at 110-120 占 폚, and the reaction was continued for 10 hours.
After the completion of the reaction, 100 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Thereafter, the solvent was slowly removed from the oil layer using a rotary evaporator to confirm that the water did not leak, Methyl isobutyl ketone was added to adjust the resin concentration to 50%. Thus, 143 parts of the polyvalent phenylene ether novolak resin varnish (V-1) of the present invention was obtained. In the GPC chart, Mn = 2111, Mw = 4345, and Mz = 7932.
(Example 3)
87.5 parts of a polyphenylene ether resin (MX90-100, manufactured by SABIC), p-xylylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a flask equipped with a stirrer, 138 parts of methyl isobutyl ketone (manufactured by Junsei Chemical Co., Ltd.) and 1 part of para-toluenesulfonic acid monohydrate (produced by Tokyo Chemical Industry Co., Ltd.) were added and reacted at 100 ° C for 2 hours After that, the reaction was carried out at reflux at 110-120 ° C for 7 hours.
After the completion of the reaction, 100 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Thereafter, the solvent was slowly removed from the oil layer using a rotary evaporator to confirm that the water did not leak, Methyl isobutyl ketone was added to adjust the resin concentration to 60%.
50 parts of the obtained polyvalent phenylene ether novolak resin varnish (V-2) of the present invention and 70 parts of phenol biphenylene novolac (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) were added and dissolved, The solvent was distilled off under reduced pressure in a pouring machine to obtain a curing agent composition (H-1) containing 30% of the polyvalent phenylene ether novolak resin of the present invention. The softening point was 121 占 폚.
(Example 4)
(H-2) of the present invention was obtained in the same manner as in Example 3 except that 30 parts of phenol biphenylene novolac (KAYAHARD GPH-65, manufactured by Nippon Kayaku Co., Ltd.) was changed to 30 parts .
(Example 5)
In the same manner as in Example 3, except that 70 parts of phenol biphenylene novolac (KAYAHARD GPH-65, manufactured by Nippon Kayaku Co., Ltd.) was changed to 20 parts, the same procedure was repeated to obtain a polyvalent phenylene ether novolac resin % Of a curing agent composition (H-3). The softening point was 130 ° C.
(Example 6)
A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 100 parts of a polyphenylene ether resin (SABIC manufactured SA120-100, Mn = 2960, Mw = 6863, Mz = 11851 in GPC measurement) , 10 parts of p-xylylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 140 parts of toluene (manufactured by Junsei Chemical Co., Ltd.), 10 parts of paratoluenesulfonic acid monohydrate , 2.0 parts of a polymerization initiator) and reacted at 100 DEG C for 2 hours, and then at 110-120 DEG C under reflux for 7 hours.
After completion of the reaction, 100 parts of methyl ethyl ketone was added, and the mixture was slowly added dropwise to a vessel containing 1000 parts of methanol to perform reprecipitation. The obtained resin powder was filtered, washed with methanol: water = 1: 1100 parts, and washed with 100 parts of water five times. Thus, 89 parts of the polyvalent phenylene ether novolak resin (P-3) of the present invention was obtained. In the GPC chart, Mn = 3683, Mw = 7356 and Mz = 11860. After 20 parts of KAYAHARD GPH-65 and 30 parts of toluene were mixed with 30 parts of the resultant (P-3), the curing agent composition (H-4) was obtained by distilling off the solvents under reduced pressure using a rotary evaporator .
(Comparative Example 1)
, 30 parts of polyphenylene ether resin (MX90-100 manufactured by SABIC) and 70 parts of phenol biphenylene novolac (KAYAHARD GPH-65, manufactured by Nippon Kayaku Co., Ltd.) were added and dissolved in methyl isobutyl ketone. The solvents were distilled off under reduced pressure in a pourer to obtain a comparative curing agent composition (H'-1).
(Comparative Example 2)
30 parts of a polyphenylene ether resin (MX90-100 manufactured by SABIC) and 20 parts of phenol biphenylene novolac (KAYAHARD GPH-65, manufactured by Nippon Kayaku Co., Ltd.) were added and dissolved in methyl isobutyl ketone. The solvents were distilled off under reduced pressure in a purger to obtain a comparative curing agent composition (H'-2).
Examples 7 to 8 and Comparative Example 3
<Permittivity and dielectric tangent test>
The curing agent composition and the epoxy resin obtained as described above were compounded in the ratio (parts by weight) shown in Table 1, and were uniformly mixed and kneaded using a mixing roll to obtain a sealing epoxy resin composition. This epoxy resin composition was pulverized with a mixer, and tableted by a tablet machine. The tableted epoxy resin composition was transferred (175 DEG C for 60 seconds), and after the demolding, test pieces for curing and evaluation were obtained under conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours.
The physical properties of the cured product were measured in the following manner.
· Dielectric constant · dielectric tangent: cavity resonance technique
Application Kanto Electric Application Development Joint Resonator 1GHz
Reference Teflon (registered trademark)
Example 9 and Comparative Example 4
<Dielectric characteristics test and heat resistance test>
The curing agent composition and the epoxy resin obtained as described above were compounded in the ratio (parts by weight) shown in Table 2 and uniformly mixed and kneaded using a mixing roll to obtain a sealing epoxy resin composition. This epoxy resin composition was pulverized with a mixer, and tabletted by a tablet machine. The tableted epoxy resin composition was transferred (175 DEG C for 60 seconds) and after demolding, test pieces for curing and evaluation were obtained under conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours.
The physical properties of the cured product were measured in the following manner.
· Dielectric constant · dielectric tangent: cavity resonance technique
Application Kanto Electric Application Development Joint Resonator 1GHz
Reference Teflon (registered trademark)
Heat Resistance (TMA): Measured according to JIS K 7244.
Example 10 and Comparative Example 5
<Heat resistance test and dielectric property test>
The curing agent composition and the epoxy resin obtained as described above were compounded in the ratio (parts by weight) shown in Table 3 and uniformly mixed and kneaded using a mixing roll to obtain a sealing epoxy resin composition. This epoxy resin composition was pulverized with a mixer, and tabletted by a tablet machine. The tableted epoxy resin composition was transferred (175 DEG C for 60 seconds), and after the demolding, test pieces for curing and evaluation were obtained under conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours.
The physical properties of the cured product were measured in the following manner.
· Dielectric constant · dielectric tangent: cavity resonance technique
Application Kanto Electric Application Development Joint Resonator 1GHz
Reference Teflon (registered trademark)
Heat resistance (DMA)
Dynamic viscoelasticity measuring instrument: TA-instruments, DMA-2980
Measuring temperature range: -30 ~ 280 ℃
Heating rate: 2 캜 / min
Test piece size: 5 mm × 50 mm was used to cut out the water (about 800 μm in thickness)
And the peak point of Tg: Tan- delta was defined as Tg
Heat Resistance (TMA): Measured according to JIS K 7244.
From the above results, it is apparent that the curable resin composition of the present invention is superior in heat resistance to H'-1 and H'-2 having similar structures as the curing agent (composition), and has a dielectric constant · It was confirmed that the dielectric loss tangent was good and that it had excellent dielectric properties.
Although the present invention has been described in detail with reference to specific embodiments thereof, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.
The present application is based on Japanese patent application (patent application 2012-244309) filed on November 6, 2012, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated by reference in their entirety.
The polyphenylene ether novolac resin of the present invention is useful as a curing agent for an epoxy resin and the like. The epoxy resin composition containing the polyphenylene ether novolak resin as a curing agent is useful as an insulating material for electrical and electronic parts and a laminate (printed wiring board, Etc.), CFRP, and various other composite materials, adhesives, and paints.
Claims (5)
Wherein the organic group is represented by at least one of the following formula (1).
Wherein * moiety is bonded to the benzene skeleton of the poly (phenylene ether) resin,
Wherein the poly (phenylene ether) resin is an oxidized polymer of a non-phenol or a bisphenol and a phenol compound.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012244309 | 2012-11-06 | ||
| JPJP-P-2012-244309 | 2012-11-06 | ||
| PCT/JP2013/079920 WO2014073536A1 (en) | 2012-11-06 | 2013-11-05 | Polyvalent phenylene ether novolac resin, epoxy resin composition, and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20150082181A true KR20150082181A (en) | 2015-07-15 |
| KR102047681B1 KR102047681B1 (en) | 2019-11-22 |
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| KR1020157007946A KR102047681B1 (en) | 2012-11-06 | 2013-11-05 | Polyvalent phenylene ether novolac resin, epoxy resin composition, and cured product thereof |
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| Country | Link |
|---|---|
| JP (1) | JP6240613B2 (en) |
| KR (1) | KR102047681B1 (en) |
| CN (1) | CN104781307B (en) |
| TW (1) | TW201431901A (en) |
| WO (1) | WO2014073536A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04183707A (en) * | 1990-11-19 | 1992-06-30 | Mitsubishi Petrochem Co Ltd | Production of polyphenylene ether crosslinked molded product |
| JP2003012796A (en) | 2001-06-28 | 2003-01-15 | Mitsubishi Gas Chem Co Inc | Oligomer of bifunctional phenylene ether and method for manufacturing the same |
| JP2006291178A (en) | 2005-03-14 | 2006-10-26 | Asahi Kasei Chemicals Corp | Process for production of polyfunctional polyphenylene ether |
| JP2011084626A (en) * | 2009-10-14 | 2011-04-28 | Jsr Corp | Resin composition and its application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1914239B (en) * | 2004-01-30 | 2010-05-05 | 新日铁化学株式会社 | Curable resin composition |
| KR100660182B1 (en) * | 2005-03-25 | 2006-12-21 | 한국화학연구원 | Aromatic polyether resins crosslinked by amic acid or imide side chain |
| EP1988112A4 (en) * | 2006-02-21 | 2012-02-01 | Asahi Kasei Chemicals Corp | Process for producing low-molecular polyphenylene ether |
| JP5104507B2 (en) * | 2007-04-26 | 2012-12-19 | 日立化成工業株式会社 | Process for producing resin varnish containing thermosetting resin of semi-IPN type composite, and resin varnish for printed wiring board, prepreg and metal-clad laminate using the same |
| JP2011074123A (en) * | 2009-09-29 | 2011-04-14 | Panasonic Electric Works Co Ltd | Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board |
-
2013
- 2013-11-05 KR KR1020157007946A patent/KR102047681B1/en active IP Right Grant
- 2013-11-05 JP JP2014545711A patent/JP6240613B2/en active Active
- 2013-11-05 WO PCT/JP2013/079920 patent/WO2014073536A1/en active Application Filing
- 2013-11-05 CN CN201380058014.2A patent/CN104781307B/en not_active Expired - Fee Related
- 2013-11-06 TW TW102140254A patent/TW201431901A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04183707A (en) * | 1990-11-19 | 1992-06-30 | Mitsubishi Petrochem Co Ltd | Production of polyphenylene ether crosslinked molded product |
| JP2003012796A (en) | 2001-06-28 | 2003-01-15 | Mitsubishi Gas Chem Co Inc | Oligomer of bifunctional phenylene ether and method for manufacturing the same |
| JP2006291178A (en) | 2005-03-14 | 2006-10-26 | Asahi Kasei Chemicals Corp | Process for production of polyfunctional polyphenylene ether |
| JP2011084626A (en) * | 2009-10-14 | 2011-04-28 | Jsr Corp | Resin composition and its application |
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| Publication number | Publication date |
|---|---|
| KR102047681B1 (en) | 2019-11-22 |
| CN104781307B (en) | 2017-04-12 |
| TW201431901A (en) | 2014-08-16 |
| CN104781307A (en) | 2015-07-15 |
| JPWO2014073536A1 (en) | 2016-09-08 |
| JP6240613B2 (en) | 2017-11-29 |
| WO2014073536A1 (en) | 2014-05-15 |
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