CN108291009A - Epoxy resin component, prepreg, epoxy resin component formed body and its hardening thing - Google Patents
Epoxy resin component, prepreg, epoxy resin component formed body and its hardening thing Download PDFInfo
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- CN108291009A CN108291009A CN201680071262.4A CN201680071262A CN108291009A CN 108291009 A CN108291009 A CN 108291009A CN 201680071262 A CN201680071262 A CN 201680071262A CN 108291009 A CN108291009 A CN 108291009A
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- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract 16
- 229920000647 polyepoxide Polymers 0.000 title claims abstract 16
- 239000007848 Bronsted acid Substances 0.000 claims abstract 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract 4
- 235000010290 biphenyl Nutrition 0.000 claims abstract 2
- 239000004305 biphenyl Substances 0.000 claims abstract 2
- 229920003986 novolac Polymers 0.000 claims abstract 2
- 229920005989 resin Polymers 0.000 claims abstract 2
- 239000011347 resin Substances 0.000 claims abstract 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 claims 1
- 239000009719 polyimide resin Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- 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
- C08G59/50—Amines
-
- 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
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
A kind of hardenability ensured under low temperature is provided, and can be formed with excellent heat resistance, water absorption rate, modulus of elasticity, mechanical strength, electric reliability hardening thing epoxy resin component；Use its prepreg, formed body, these hardening thing.Epoxy resin that epoxy resin component contains difunctionality or more, with the anline resin and Bronsted acid hardening accelerator for stretching biphenyl novolac structure, the content of above-mentioned Bronsted acid hardening accelerator is 0.01~10.0 parts by weight relative to 100 parts by weight of above-mentioned epoxy resin.
Description
Technical field
The present invention relates to a kind of epoxy resin component of suitable electric and electronic material applications etc., prepreg, epoxy resin
Constituent formed body and its hardening thing.
Background technology
Epoxy resin is because of workability and its excellent electrical characteristics of hardening thing, heat resistance, adherence, moisture-proof (water resistance)
Deng and be widely used in the fields such as electrical, electronic component, structure material material, solid, coating.Especially it is widely used as
Electrically, the matrix resin of the composite material in electronic field.
In recent years, in electrical, electronic field, with its development, encapsulating semiconductor, substrate (substrate itself or its
Periphery material) in field, with the transition of semiconductor, thin layer, stacking, systematization, high density structure dress technology become complicated,
The resin of the heat resistance (high Tg and low linear expansion rate) for very high grade is needed, and is needed certainly in response to Reflow Soldering, simultaneously
It is required that reducing or maintaining water absorption rate.Furthermore the expansion with plastic-packaged to vehicular applications, the raising of heat resistance require to become
It is tightened up.Specifically, the rising of the driving temperature because of semiconductor, and the heat resistance for starting 150 DEG C of requirement or more.In turn, exist
High density structure fills in the world of technology, is used in the hardening of resin temperature of semiconductor smears or interlayer dielectric, conductive paste
It is very high, so can cause the problems such as following in its cure step, that is, if expansion when heating is big, Silicon Wafer can occur
Generate warpage or cracking etc. (patent document 1).
Also, shaped epoxy resin as the composite material of matrix resin by heat hardening, it is adjoint when by shaping
The contraction of sclerous reaction and the convergent force caused by thermal contraction of the forming temperature into the cooling procedure of room temperature are to becoming matrix
Epoxy resin work, will produce residual stress in its situation hindered, and it becomes and keeps the machinery of formed products strong
Spend the factor reduced.In turn, since the coefficient of thermal expansion of the metals such as copper foil is far smaller than organic matter, so in thermosetting resin
Substrate forming step in, the thermal contraction from forming temperature copper foil and thermosetting resin into the cooling procedure of room temperature is usual
Residual stress can be generated because of difference, so as to cause the generation of reduction, the cracking of the intensity of formed products caused by this, resin
Stripping.However, in order to obtain the mechanical properties of resin itself, the hardening thing of excellent heat resistance, it is necessary in the high temperature more than 100 DEG C
It is heated for a long time.The energy-saving of step can not be carried out in 100 DEG C or more of hardening, cost can increase, so require profit
The saving of the energy is realized with hardening at subcritical temerature.Also, the mould of cheap FRP resins also can be used in hardening at subcritical temerature system in the presence of expectation
The technology of tool.Also, there are the equipment such as the hardening furnace deficiency that can be for a long time heated in high temperature in large-scale formed products, therefore
If completing also to seek to solve the problem of the workability if the heat-resisting stiffening system of hardening at subcritical temerature, for this aspect, to low
The exploitation of warm hardening requires also strong (patent document 2).
As the means solved these problems, industry requires to develop in 100 DEG C of hardening at subcritical temerature manufacturing methods below
It can be hardened, and the resin combination with heat resistance, low water absorption character, mechanical strength, electric reliability together.
Patent document 1：Japanese Patent Laid-Open 2006-188622 bulletins
Patent document 2：Japanese Patent Laid-Open 2007-031476 bulletins.
Invention content
[the problem of invention is to be solved]
Consider the curing agent for being using polyfunctional amine to assign heat resistance.However, in the situation, due to its crosslinking
Density is high, so the hydroxyl of the appearance when glycidyl carries out open loop, electrical characteristics due to it is influenced can be largely generated in system
Or water absorption character deteriorates as problem.Also, when using the situation of the aromatic amine of solid, even if not carrying out multiple functionalized also may be used
Heat resistance, mechanical strength are improved by importing rigid backbone, and then can largely be mixed in advance.However, because alkalinity it is weak and
The steric hindrance of aromatic rings, thus harden at low temperature it is slack-off, so need the hardening of high temperature.
On the other hand, when curing shrinkage when reducing thermosetting resin forming, exist the methods of following：(1) it uses
The low resin combination of hardening temperature, (2) resin combination for hardening formed products low using can get glass transition temperature,
(3) by using being blended with the resin combination of ingredient expanded in hardening, and increase the free volume of hardening thing,
(4) by using the resin for being imported with rigid backbone, and increase the free volume of hardening formed products, (5) use and are largely blended with
Inanimate matter fills the resin combination of the non-thermal contractions substances such as material.
However, about the method using above-mentioned (1) and (2), the heat resistance of the hardening formed products obtained is insufficient to.Also,
Utilize (3) and (4) although method can get the effect of certain degree, there is no at present and fully play its effect person, and
There are the limit in terms of the mechanical property or heat resistance of hardening formed products.And then utilize (5) although method in IC sealing material etc.
With being able to functionization on the way, if but largely fill material using inanimate matter certainly, the then characteristic of thermosetting resin can reduce,
Stripping with copper foil can be problem.
In particular, the thermal shrinkage stress when hardening of thermosetting resin depends on hardening of resin temperature and is obtained hard
Change the glass transition temperature of formed products, so industry expects that hardening temperature is low, and can get the glass transition temperature of hardening thing
The resin combination of high, mechanical strength hardening formed products.
Therefore, the present invention provides a kind of epoxy resin component, has the various characteristics needed for matrix resin, and hard
Change that temperature is low, thermal shrinkage force when hardening is small, and can get that glass transition temperature is high and the hardening formed products of mechanical strength.
[technical means to solve problem]
The inventors of the present invention carry out effort research in view of actual conditions as described above, as a result complete the present invention.That is, this hair
It is bright to be related to
[1] a kind of epoxy resin component, containing it is more than difunctionality epoxy resin, have stretch biphenyl novolac structure
Anline resin and Bronsted acid hardening accelerator, the content of above-mentioned Bronsted acid hardening accelerator is relative to above-mentioned epoxy resin 100
Parts by weight are 0.01~10.0 parts by weight；
[2] such as epoxy resin component recorded in preceding paragraph [1], wherein above-mentioned anline resin is recorded for following formula (1)
Structure,
[chemical formula 1]
(in formula, there are the alkyl that multiple R separately indicates hydrogen atom, carbon number 1~15；N is integer, and n's is averaged
It is worth (A) and indicates 1≤A≤5)；
[3] such as epoxy resin component recorded in preceding paragraph [1] to [2], contain selected from incombustible agent, filler, addition
It is more than any one of agent；
[4] a kind of prepreg is that the epoxy resin component recorded in any one of preceding paragraph [1] to [3] is made to be impregnated in
Sheet-like fiber base material forms；
[5] a kind of epoxy resin component formed body is the asphalt mixtures modified by epoxy resin made recorded in any one of preceding paragraph [1] to [3]
Fat composition is more than room temperature and 100 DEG C or less are molded with；
[6] a kind of hardening thing is to make epoxy resin component recorded in any one of preceding paragraph [1] to [3], preceding paragraph
[4] recorded epoxy resin component formed body hardens in the prepreg or preceding paragraph [5] recorded in.
[The effect of invention]
For the epoxy resin component of the present invention since the hardenability in low temperature is excellent, hardening thing has heat resistance, water suction
Characteristic, electric reliability and mechanical strength, so to electrical/electronic part insulating materials and laminated plates (printing distributing board, increasing layer
Substrate etc.) or it is useful as the various composite materials of representative, solid, coating etc. using CFRP.
Specific implementation mode
The present invention epoxy resin component contain difunctionality or more epoxy resin, have stretch biphenyl novolac structure
Anline resin and Bronsted acid hardening accelerator.
In the EMC (Epoxy Molding Compounds, epoxy molding plastic) using Bronsted acid as catalyst, logical
When the situation of normal EMC, since the addition of Bronsted acid can bring harmful effect to corrosion, so be difficult with, but if amine system,
Then due to being alkalinity in system, so the corrosion of metal wire etc. can be prevented.It in turn, also can be low in addition to being alkalinity in system
It is hardened under temperature, is captured so can inhibit chlorine contained in resin, therefore can provide a kind of electric reliability superior ring
Oxygen resin combination.
Hereinafter, being illustrated to the epoxy resin more than difunctionality used in epoxy resin component of the invention.
As the epoxy resin more than difunctionality used in the present invention, such as can enumerate：Bisphenol-type epoxy resin is (double
Phenol A, Bisphenol F, bisphenol-c, bis-phenol E, bis-phenol TMC, bisphenol Z etc.), biphenyl type epoxy resin (tetramethyl biphenyl bisglycidyl ethers,
Bis-epoxy propoxyl group biphenyl etc.), by phenols (phenol, alkyl substituted phenol, aromatic series fortified phenol, naphthols, alkyl-substituted naphthaline
Phenol, dihydroxy benzenes, alkyl substitution dihydroxy benzenes, dihydroxy naphthlene etc.) and various aldehyde (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl
Substituted benzaldehyde, hydroxy benzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnaldehydrum etc.) condensation polymer, phenols with
Various diolefin compound (bicyclopentadiene, terpenes, vinylcyclohexene, drop camphane diene (ノ Le ボ Le Na ジ エ Application), ethylene
Base norcamphene, tetrahydroindene, divinylbenzene, divinyl biphenyls, diisopropenyl biphenyl, butadiene, isoprene etc.) it is poly-
Close object, phenols and ketone (acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetophenone, benzophenone, Fluorene ketone etc.) condensation polymer,
Phenols and double halogenated methyl benzene classes, the condensation polymer of double halogenated methyl biphenyl classes, bisphenols and condensation polymer, the alcohols of various aldehyde etc. into
Glycidyl ethers made of row glycidyl are epoxy resin, with 4- vinyl -1- cyclohexene dicyclic oxide or 3,4- rings
Oxygen cyclohexyl methyl -3,4'- epoxycyclohexane carboxylates etc. are the alicyclic epoxy resin of representative, with four glycidyl diamines bases
Diphenyl methane (TGDDM) or three glycidyl-mutual-amino phenol etc. are that the epoxy propylamine of representative is epoxy resin, polyglycidyl
It is epoxy resin etc., is not limited to however, as long as commonly used epoxy resin such.These can be used alone, and also may be used
Use two or more.
In the present invention, most preferably at least include the connection such as tetramethyl biphenyl bisglycidyl ethers, bis-epoxy propoxyl group biphenyl
Benzene-type epoxy resin, tetramethyl bisphenol f type epoxy resin, crystal type bisphenol A type epoxy resin, tetrahydrochysene anthracene type epoxy resin, two
Hydroxyl naphthalene type epoxy resin, phenolphthalein type epoxy resin, phenol phthalimide type epoxy resin, bis-phenol Fluorene type epoxy resin
Deng the epoxy resin and Zylock for epoxy resin, phenol bicyclopentadiene condensation product bifunctional and with solid shape person
Type, phenol stretch biphenyl aralkyl-type, dihydroxy benzenes (resorcinol, hydroquinone, catechol)-phenol stretches biphenyl aralkyl-type
Etc. the phenolic resin varnish such as phenol aralkyl type epoxy resins, cresol novolak, phenol novolacs (softening point is molten
Point is 50 DEG C or more and not up to 200 DEG C, especially for being hardened at low temperature, is suitable for as in a low temperature of 100 DEG C or less
The softening point or fusing point of hardening process are 50 DEG C to not up to 100 DEG C of epoxy resin.
Usually heat resistance improves bys importing alicyclic epoxy resin etc., but in the present invention, due to the use of amine system
Curing agent, so it is preferable to use poor with alicyclic epoxy resin reactivity, and preferred difunctionality or more officials are thought among the above
The glycidyl ethers epoxy resin of energy.
And then in epoxy resin as used in the present invention, total chlorine amount/water-disintegrable chlorine is preferably 1000ppm or less.
Using a variety of epoxy resin situation when, the total amount of total chlorine/water-disintegrable chlorine in mixture is preferably shorter than 1000ppm.It is optimal
It is selected as 700ppm or less.
The compound of amine system as described above is possible to that chlorine can be captured in hardening, preferably used epoxy resin
Total chlorine is low as possible, if can at most lead to the deterioration of electric reliability, so it is not good enough.
Secondly, to used in the present invention there is the anline resin for stretching biphenyl novolac structure to illustrate.
The so-called of the present invention has that stretch the anline resin of biphenyl novolac structure be to connect benzene using double alkyl biphenyls of stretching
Amine (aromatic amine) class has the resin of molecular weight distribution with novolaks shape.
As workable phenyl amines, can enumerate：Aniline, 2-aminotoluene, 3- methylanilines, 4- methylanilines, 2- second
Base aniline, 3- ethyl aniline, 4- ethyl aniline, 23 dimethyl aniline, 2,4- dimethylanilines, 2,5- dimethylanilines, 2,
6- dimethylanilines, 3,4- dimethylanilines, 3,5- dimethylanilines, 2- propyl aniline, 3- propyl aniline, 4- propyl aniline,
2- isopropyl anilines, 3- isopropyl anilines, 4- isopropyl anilines, 2- ethyl -6- methylanilines, 2- secondary butyls aniline, 2- tri-
Grade butylaniline, 4- butylanilines, 4- secondary butyls aniline, 4- three-levels butylaniline, 2,3- diethylanilines, 2,4- diethyl
Aniline, 2,5- diethylanilines, 2,6- diethylanilines, 2- isopropyl -6- methylanilines, 4- amido biphenyl etc..These can be single
It solely uses, can also be used in combination of two or more.
Also, as epoxy resin component, so that it may obtain the superior hardening object space of heat resistance, impact resistance, flame retardancy
For face, preferably aniline, 2-aminotoluene, 2,6- dimethylanilines, most preferably aniline.
As the anti-of disubstituted methyl biphenyl class and above-mentioned phenyl amines using double methods for stretching alkyl biphenyl connection, can be enumerated
It answers.
As workable disubstituted methyl biphenyl, can enumerate：Bis- (chloromethyl) biphenyl of 4,4'-, 4,4'- dimethoxy first
Bis- (phenyl aminomethyl) biphenyl of base biphenyl, 4,4'- dimethoxy-methyls biphenyl, 4,4'-.It is described to can be used alone, it also can be simultaneously
Use two or more.
1 mole relative to used phenyl amines of the usage amount of disubstituted methyl biphenyl class is usually 0.05~0.8 mole,
Preferably 0.1~0.6 mole.
In above-mentioned reaction, acidic catalyst optionally can be used.As workable acidic catalyst, such as can arrange
It lifts：Hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric trichloride, aluminium chloride, p-methyl benzenesulfonic acid, methanesulfonic acid etc..These can be independent
Use, also can and with two or more.
The usage amount of catalyst is 0.1~0.8 mole relative to 1 mole of used phenyl amines, preferably 0.5~0.7
Mole, the case where being difficult to stir if the viscosity that at most there is reaction solution excessively is excessively high, if excessively few in the presence of reaction become
Slow situation.
As reaction method, by acid condition to phenyl amines, disubstituted methyl biphenyl, catalyst optionally,
Solvent (the preferably hydro carbons of the aromatic series such as toluene, dimethylbenzene, hexamethylene or ester ring type) carries out heating stirring and is obtained, and makees
For specific method, such as when the situation of above-mentioned 4,4'- dichloride methyls biphenyl, the sequence can be listed below.
After adding acidic catalyst into the mixed solution of anil and solvent, in the aqueous situation of catalyst
When, water is removed from system by azeotropic.Then 1~5 hour is lasted (preferably at 40~100 DEG C (preferably 50~80 DEG C)
It is 2~4 hours) addition 4,4'- dichloride methyl biphenyl, then heat up when removing solvent from system, and in 180~
240 DEG C (preferably 190~220 DEG C) carry out reaction 5~30 hours (preferably 10~20 hours).After reaction, it is utilizing
After alkaline aqueous solution neutralizes acidic catalyst, water-insoluble organic solvent is added into oil reservoir, and washing is repeated until useless
Water becomes neutrality, and in the case where heating is depressurized thus excessive anil or organic solvent distillation removal can get aniline
Resin.
It is the benzene recorded such as following formula (1) as the structural formula of the specific anline resin obtained by the above method
Polyimide resin.
[chemical formula 2]
(in formula, there are the alkyl that multiple R separately indicates hydrogen atom, carbon number 1~15；N is integer, and n's is averaged
It is worth (A) and indicates 1≤A≤5.)
In formula, among the alkyl of the carbon number 1~15 of R, preferably carbon number 1~10, most preferably carbon number 1~5.
The amine equivalent of such anline resin (aromatic amine resin) is preferably 180~300g/eq., most preferably 190~
250g/eq.。
The problem of softening point of anline resin (aromatic amine resin) used in the present invention is because of its formability, preferably
50 DEG C or more and not up to 180 DEG C, more preferably 150 DEG C or less.Also, melt viscosity is preferably 0.005~1.5Pas, most preferably
For 0.01~1.0Pas.
Furthermore especially in the situation of the compound using 4,4'- dichloride methyl biphenyl etc, remaining it may remain
Chlorine brings the worry seriously affected since chlorion has to electric reliability, so chlorion preferably by extraction be 10ppm,
Preferably 5ppm or less.
Secondly, the Bronsted acid hardening accelerator used in the present invention is illustrated.
As the Bronsted acid hardening accelerator used in the present invention, there are Bronsted acid and its salt, can especially enumerate with 1~
The aliphatic or aromatic list or polycarboxylic acids, sulfonic acid and phosphonic acids of 20 (preferably 2~12) carbon atoms.With carboxyl bond
Aliphatic and aromatic residue hetero atom and group containing O, S ,-N=,-NH- and-N (C1~C4 alkyl)-etc.As
Bronsted acid hardening accelerator and preferred concrete example can be enumerated：It is acetic acid, salicylic acid, propionic acid, butyric acid, octanoic acid, dodecanoic acid, pungent
Acid, maleic acid, succinic acid, nonyl or dodecyl succinate, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,
Benzoic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA) and naphthalenedicarboxylic acid, pyrovinic acid, trifluoromethane sulfonic acid, phenyl
Sulfonic acid, toluyl groups sulfonic acid, methylphosphonic acid and phenyl-phosphonic acid, phenol, cresols, dimethlbenzene, resorcinol, catechol,
The aphthols such as the phenols such as bisphenol-A, Bisphenol F, phenylphenol, amino-phenol and/or alpha-Naphthol, betanaphthol, dihydroxy naphthlene and its salt.
By the present invention in that using Bronsted acid as hardening accelerator, 100 DEG C of hardening below can be carried out.As its mechanism,
Speculate since the Hydrogen Proton disengaged from accelerating agent acts on the epoxy oxide of epoxy resin, promotes its cracking, so can carry out
Hardening under low temperature.
If using Bronsted acid as catalyst EMC (Epoxy Molding Compounds) and common EMC, then matter
The addition of sub- acid can bring harmful effect to corrosion, so be difficult with, but if amine system, then due to being alkalinity in system, therefore
And it can prevent from corroding.In turn, in addition to system is alkalinity, under low temperature chlorine contained in resin capture it is also suppressed, so can
Carry the superior material of power supply reliability.Also, organic carboxyl acid can carry out epoxy reaction, corresponding hardening can be in the netted knot of epoxy resin
Group enters hardening accelerator in structure, can prevent by the pollution caused by hardening accelerator.By the present invention epoxy resin component
When situation for liquid crystal sealing agent etc., it is believed that can improve by the liquid crystal pollution caused by hardening accelerator.Proton acid hardening promotees
Into agent relative to 100 parts by weight of epoxy resin, 0.01~10.0 parts by weight optionally can be used.And then preferably 0.1~5.0 weight
Measure part.
In the epoxy resin component of the present invention, so also can and with other hardening accelerators.
It is cationic polymerization initiator as concrete example, specifically, for by SbF6 -、BF4 -、AsF6 -、PF6 -、CF3SO3 -、
B(C6F5)4 -Equal anion components and the compound constituted comprising iodine, sulphur, nitrogen, the equiatomic aromatic series cation constituent of phosphorus.
As basic polymerization catalyst, specifically, can enumerate：Pyridine, dimethylaminopyridine, 1,8- diazabicyclos [5.4.0]-
7- hendecenes, imidazoles, triazole, tetrazolium, 2-methylimidazole, 2- phenylimidazoles, 2- undecyl imidazoles, 2- heptadecyl imidazoles,
2- phenyl -4-methylimidazole, 1- benzyl -2- phenylimidazoles, 1 benzyl 2 methyl imidazole, 1- 1-cyanoethyl-2-methylimidazoles, 1-
Cyanoethyl -2- phenylimidazoles, 1- cyanoethyl -2- undecyl imidazoles, 2,4- bis- amido -6 (2'- methylimidazoles are (1')) ethyl -
Symmetrical three mouthfuls of wells, the symmetrical three mouthfuls of wells of 2,4- bis- amido -6 (2'- undecyl imidazoles are (1')) ethyl -, -6 (2'- of bis- amidos of 2,4-
Ethyl -4-methylimidazole is (1')) the symmetrical three mouthfuls of wells of ethyl -, 2,4- bis- amido -6 (2'- methylimidazoles are (1')) ethyl-symmetrical three
The 2 of mouth well-fulminuric acid addition product, 2-methylimidazole fulminuric acid：3 addition products, 2- phenylimidazole fulminuric acids add
At object, 2- phenyl -3,5- bishydroxymethyls imidazoles, 2- phenyl -4- hydroxymethyl -5- methylimidazoles, 1- cyanoethyl -2- phenyl -
Hetero ring type compounds class and these hetero ring type compound classes and dicyandiamide etc. such as various of 3,5- dicyano ethoxyl methyl imidazoles
Phenodiazines heterocompound and the tetraphenyl borate salts, the phenol systems such as amides, 1,8- diazas-bicyclic (5.4.0) -7- hendecenes
Salt, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, the hydrogen of the salts such as novolaks, above-mentioned polybasic carboxylic acid class or phosphonic acid
Aoxidize tetrapropyl ammonium, tetrabutylammonium, hydroxide ethyl ammonium, hydroxide propyl ammonium, hydroxide front three
Base butyl ammonium, hydroxide cetyl ammonium, hydroxide tricaprylmethylammonium, tetramethyl ammonium chloride, tetramethylammonium bromide, iodine
Change ammonium salts, triphenylphosphine, three (toluyl groups) phosphines, the brominations such as tetramethyl-ammonium, acetic acid tetramethyl-ammonium, acetic acid tricaprylmethylammonium
Phenols, the amine addition such as the phosphines such as tetraphenylphosphoniphenolate, tetraphenylboronic acid tetraphenylphosphoniphenolate or phosphonium compounds, tri- aminomethyl phenol of 2,4,6-
Object, carboxylic metallic salt (zinc salt, pink salt, zirconates of 2 ethyl hexanoic acid, stearic acid, twenty diacid, myristic acid etc.) or phosphate gold
Belong to salt (zinc salt of octylphosphonic acid, stearyl phosphoric acid etc.), metal alkoxides salt (tri-butyl aluminum, tetrapropyl zirconium etc.), acetylacetone,2,4-pentanedione
Metallic compounds such as salt (acetylacetone,2,4-pentanedione zirconium chelate, acetylacetone titanium chelate etc.) etc..In the present invention, Qi Shi phosphonium salts of You or
The aspect of the coloring or its variation of ammonium salt, metal compound species when hardening is preferred.Also, when using the situation of level Four salt, with
The salt of halogen can in its hardening thing residual halogens, it is not good enough for the viewpoint of electric reliability and environmental problem.
In the epoxy resin component of the present invention, so also can and with other curing agents.Other are hard as workable
Agent, for the viewpoint of electric reliability, preferably phenol resin.Specifically, as phenol resin, can enumerate：Bisphenol-A, bis-phenol
F, bisphenol S, Fluorene bis-phenols, terpene diphenol, 4,4'- xenols, 2,2'- xenols, 3,3', 5,5'- tetramethyls-[1,1'- xenyls]-
4,4'- diphenol, hydroquinone, resorcinol, naphthalenediol, three-(4- hydroxy phenyls) methane, 1,1,2,2- tetra- (4- hydroxy phenyls)
Ethane, phenols (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy benzenes, dihydroxy naphthlene etc.) and formaldehyde, second
Aldehyde, benzaldehyde, parahydroxyben-zaldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, bicyclopentadiene, chaff
Bis- (the chloromethyl) -1,1'- biphenyl of aldehyde, 4,4'-, bis- (the methoxy) -1,1'- biphenyl of 4,4'-, bis- (chloromethyl) benzene of 1,4'-
Or the condensation polymer and the halogenated bisphenols class such as these modification object, tetrabromobisphenol A of bis- (methoxy) benzene of 1,4'- etc., terpenes with
The phenol resin such as the condensation product of phenols；The compound etc. of imidazoles, trifluoroboranes-amine misfit object, guanidine derivatives, but it is not limited to this
A bit.These can be used alone, two or more also can be used.
In turn, in the epoxy resin component of the present invention, times in incombustible agent and filler, additive can optionally be blended
More than one.
It as filler, is not particularly limited, can enumerate selected from bimetallic salt complex, activated carbon, layered clay mineral, metal oxygen
Filler etc. in compound.As bimetallic salt complex, preferably houghite compound.So-called houghite compound is logical
Formula [M2+ 1-XM3+ X(OH)2][An- X/n·mH2O] represented by compound, M2+With M3+Indicate divalent and trivalent metal ion, An-X/n
Indicate interlayer anion.Specifically, representative hydrotalcite system such as Mg6Al2(OH)16CO3·4H2The compound indicated as O.
Product キ ョ ー ワ ー De series as commercially available product, chemistry of coordinating is effective.It can enumerate：キョーワード500、キョー
ワ ー De 1000, キ ョ ー ワ ー De 700, キ ョ ー ワ ー De 600, キ ョ ー ワ ー De 200, キ ョ ー ワ ー De 2000 etc..
In the present invention, it is preferred to be oxygen in terms of for the amount ratio of magnesia, aluminium oxide, silica in especially contained ingredient
Change magnesium ＞ aluminium oxide, and the structure of magnesia ＞ silica.Specifically, preferably キ ョ ー ワ ー De 500 or キ ョ ー ワ
ー De 1000 etc..
As workable activated carbon, preferably chemical activation carbon.As chemical activation carbon, as long as such as to utilize chlorination
Zinc, phosphoric acid etc. implement processor, then there is no particular restriction, have the worry being directed into chlorine in product through zinc chloride activation person,
So most preferably phosphoric acid activation carbon.Furthermore the physics of porous materialization is carried out by using vapor or air, carbon dioxide etc.
Method and the activated carbon that obtains can be also used in combination, about its ratio, preferably according to the condition handled with chemical activation activated carbon
At least chemical activation carbon phase is more than the ratio of 50 weight % for the amount of gross activity carbon.
As raw material, can enumerate：Wooden (sawdust etc.), coal (lignite, mud coal, coal etc.), coconut husk, phenol resin etc., but
In the present invention, most preferably wooden system.As commercially available product, can enumerate：Off タ system ラ chemistry manufacture too collaboration row (CG, CW, G,
The series such as QW, S, ACF)；Hide ホ Network エ Star series (SD, BA, F, ZN, Y-180C, H- of plain Off ァ イ Application テ Network ノ manufactures
The series such as 10CL, H-8CL, G-10F, CL-K)；White hawk (C, LGK-400, G system of Japanese エ Application バ イ ロ ケ ミ カ Le ズ manufactures
Row, DO series, Wc, Sx, WHA etc.), カ Le ボ ラ Off ィ Application etc.；NORIT manufacture PK series, PKDA series, ELORIT, AZO,
DARCO series, HYDRODARCO series, PETRODARCO, GAC series, GCN, CGRAN, ROW, ROY, ROX, RO, RB, R,
R.EXTRA, SORBNORIT, GF series, CNR, ROZ, RBAA, RBHG, RZN, RGM, SX, SA, D 10, VETERINAIR, PN,
ZN, S Α-SW, W, GL, SAM, HB PLUS, EUR, USP, CA, CG, GB, CAP SUPER, CGP SUPER, S-51 series, HDB,
HDC, HDR, HDW, GR O SAFE, FM-1, PAC series etc.；RP-20, YP-17D etc. of Kuraray manufacture.
As clay mineral, the preferably layered clay mineral of montmorillonite system, can enumerate：Bentonite, montmorillonite, aluminium swelling
Stone, nontronite, saponite, lithium montmorillonite, synthetic swelling stone etc..As commercially available product, can enumerate：The ス メ of Network ニ ミ ネ industry manufacture
Network ト Application (synthetic swelling stone), bentonite (sodium-salt type, calcium salt type), the Network ニ ピ ア F (ベ of montmorillonite), ホ ー ジ ュ Application manufacture
Application ゲ Le series, ベ Application ゲ Le W series, ベ Application ゲ Le Block ラ イ ト series, ベ Application ゲ Le SH, ベ Application ゲ Le A, コ ー Off ケ ミ カ
Le manufactures ル ー セ Application タ イ ト series.
As metal oxide, can enumerate：Silica, calcium carbonate, silica flour, aluminium powder, graphite, talcum, glues aluminium oxide
The inorganic fills material such as soil, iron oxide, titanium oxide, aluminium nitride, asbestos, mica, glass powder.
And then in the epoxy resin component of the present invention, it can optionally blend well known additive.As workable
The concrete example of additive can be enumerated：The fluorine tree such as hardener for epoxy resin, polyamide, polysilicone, polytetrafluoroethylene (PTFE)
The cross-linking agent of the acrylic resins such as fat, polymethyl methacrylate, benzoguanamine or melamine and formaldehyde, polybutadiene and
It modifies object, the modification object of acrylonitrile copolymer, polyphenylene oxide, polystyrene, polyethylene, polyimides, fluororesin, maleic two
Imide series compound, cyanate ester based compound, poly- silica gel, silicone and silane coupling agent etc it is inorganic
Fill the colorants such as surface conditioning agent, releasing agent, carbon black, phthalocyanine blue, the phthalocyanine green of material.The blended amount of these additives relative to
100 parts by weight of hardening resin composition, preferably 1,000 parts by weight are hereinafter, more preferably 700 parts by weight range below.
The preparation method of the epoxy resin component of the present invention is not particularly limited, and only can equably be mixed each ingredient,
Or pre-polymerization materialization can be carried out.For example, by by poly- maleimide resin and epoxy resin in the presence of a catalyst or
In the absence of, in the presence of the solvent or in the absence of heated and carry out pre-polymerization materialization.It similarly, also can be to poly- maleic
Imidodicarbonic diamide resin and epoxy resin optionally add amine compounds, maleimide based compound, cyanate esterification conjunction
The curing agents such as object, phenol resin, anhydride compound and other additives and carry out pre-polymerization materialization.The mixing or pre-polymerization materialization of each ingredient
It ties up in the absence of solvent such as using extruder, kneader, roller, in the presence of the solvent using with agitating device
Reaction kettle etc..
It is in the range of room temperature~100 DEG C (preferably 50~100 DEG C) as the method equably mixed
At a temperature of mixed using the mode that the devices such as kneader, roller, planetary stirring machine are kneaded, and uniform epoxy is made
Resin combination.
The epoxy resin component obtained is shaped to the ingot shape of cylinder using molding machines such as tablet press machines after crushing,
The formed body of granular powder or powdery is either made or melts these constituents on the support of surface
Type is the sheet of 0.05mm~10mm thickness, to which the epoxy resin component formed body of the present invention be made.The molding obtained
Body becomes in 0~20 DEG C of inviscid formed body, and i.e. convenient for -25~0 DEG C of keeping 1 week flowing above property, hardenability also almost
It will not reduce.The epoxy resin component formed body of the present invention is preferably to add pigment or carbon black in the stage of constituent, excellent
It is selected as being coloured through the molding stage.
Hardening thing is shaped to using transfer formation machine, compacting shape machine to the formed body obtained.Hardening temperature is preferred
It is 100 or less.
The hardening thing being so molded with 100 DEG C of display or more in terms of heat resistance (Tg).Most preferably 150 DEG C or more.
The present invention epoxy resin component or its formed body can be used as semiconductor element sealing material (silicon, silicon carbide,
Hardened and protected the semiconductor sealing material of semiconductor in the semiconductor elements such as gallium nitride periphery).In setting on/within mold
Mold, package substrate (substrate, submount), surface support (film etc.) semiconductor element on carry out 100~300 DEG C it is molten
Melt, harden, thus can get the semiconductor device containing semiconductor element.
Organic solvent can be added into the epoxy resin component of the present invention and the constituent of varnish shape is made (hereinafter, letter
Referred to as varnish).The epoxy resin component of the present invention is optionally dissolved in toluene, dimethylbenzene, acetone, methyl ethyl ketone, first
In base isobutyl ketone, dimethylformamide, dimethylacetylamide, N- methylpyrrole pyridine ketone equal solvents, epoxy resin composition is made
Object varnish is allowed to be impregnated in the base materials such as glass fibre, carbon fiber, polyester fiber, Fypro, alumina fibre, paper, go forward side by side
Row heat drying and obtain prepreg, the preimpregnation body heat press molding that will be obtained, thus can be made into the present invention epoxy resin
The hardening thing of constituent.Solvent at this time is usually used in mixture of the epoxy resin component with the solvent of the present invention to be accounted for
The amount of 10~70 weight % (preferably 15~70 weight %).Also, if liquid constituent, then it also can be directly for example with the side RTM
Formula obtains the epoxy cure object containing carbon fiber.
Also, modification agent of the epoxy resin component of the present invention as membranous type constituent also can be used.Specifically, can be
It is used when the situation for improving the flexibility in B- stages etc..The resin combination of such membranous type can be by the epoxy resin component of the present invention
Above-mentioned epoxy resin component varnish is made and is coated on stripping film, after removing solvent under heating, carries out B-stage, by
This and in the form of the solid of sheet obtain.The sheet solid can be used as the interlayer insulating film in multilager base plate etc..
The epoxy resin component of the present invention is heated into melting, carries out lowering viscousity, and be allowed to be impregnated in glass fibre, carbon
Thus the reinforcing fibers such as fiber, polyester fiber, Fypro, alumina fibre can get prepreg.
Also, also prepreg can be obtained by so that above-mentioned varnish is impregnated in reinforcing fiber and being thermally dried.
Above-mentioned prepreg is cut into desired shape, optionally with after the laminations such as copper foil, passes through press molding method on one side
Or autoclave forming process, sheet material winding shaping method etc. apply pressure to laminate, on one side by laminated plates epoxy resin component
Thus heat hardening can get laminated plates.
In turn, so that copper foil is overlapped in surface and manufactured laminated plates formation circuit, prepreg or copper foil etc. is made to be overlapped in
Thereon, and aforesaid operations are repeated, and can get the circuit board of multilayer.
The hardening thing of the present invention can be used in the various uses such as moulding material, solid, composite material, coating.In particular, by
Excellent flame retardancy is shown in the epoxy cure object of the present invention, so in IC sealing materials, laminated material, electric insulation
The electric and electronics such as material field is useful.
[embodiment]
Secondly, the present invention is further illustrated by embodiment, is then parts by weight as long as following part is not specified.
Furthermore the present invention is not limited to these embodiments.
The various analysis methods used in embodiment are recorded below.
Epoxide equivalent：According to JIS K 7236 (ISO 3001)
Amine equivalent：According to method recorded in JIS K-7236 appendix As
Diphenylamine content：It is measured by gas chromatography
ICI melting viscosities：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)
Iron：ICP ICP Atomic Emission Spectrophotometers
·GPC：
Analysis condition
Tubing string (Shodex KF-603, KF-602 × 2, KF-601 × 2)
Connection eluat is tetrahydrofuran
Flow velocity is 0.5ml/min.
Tubing string temperature is 40 DEG C
Detection：RI (differential refractive detector)
Hardening fever：The hardening initial temperature carried out, hardening fever peak temperature and fever are measured using MDSC to terminate
The measurement of temperature
Analysis condition
Analytical model：MDSC is measured
Analyzer：Q2000TA-instruments companies manufacture
Heating rate：3℃/min
Condition 1：Transfer forming (100 DEG C of press temperature)+baking oven (100 DEG C × 2h)
Condition 2：Transfer forming (175 DEG C of press temperature)+baking oven (160 DEG C × 2h+180 DEG C × 6h)
Formability in transfer forming：Shape the appearance of sample.
·Tg：The peak dot (tan δ MAX) of Tan δ during DMA is measured is set as Tg.
Analysis condition
Measurement of Dynamic Viscoelasticity device：TA-instruments is manufactured, Q-800
Measuring temperature range：30 DEG C~280 DEG C
Heating rate：2℃/min
Specimen size：Using being cut into 5mm × 50mm person (thickness is about 800 μm).
Bending strength：It is measured in 30 DEG C according to JIS-6481 (bending strength).
Water absorption rate：With 100 DEG C × for 24 hours impregnate after hardening thing weight increase %
·Td10：10% thermogravimetric amount of the hardening thing through crushing reduces temperature
Measurement device：TG/DTA-6200
Sample particle diameter：100~200 μm
Measuring temperature：30~580 DEG C
Heating rate：10℃/min
Measure atmosphere：Air
(synthesis example 1)
Benzene is added to being equipped in the flask of thermometer, condenser pipe, Dean-Stark azeotropic distillation separator, blender
146 parts of 35% hydrochloric acid was added dropwise with 1 hour at room temperature in 200 parts of 372 parts of amine and toluene.It is heated and will be total to after completion of dropwise addition
The water of boiling and toluene cooling, liquid separation, then only make the toluene as organic layer be back in system and are dehydrated.Then, by 4,
Bis- 125 parts of (chloromethyl) biphenyl of 4'- last 1 hour when remaining 60~70 DEG C and are added, and then mutually synthermal
Under carry out reaction 2 hours.After reaction, toluene distillation is removed when heating up, 195~200 DEG C will be set as in system,
And reaction 15 hours is carried out at such a temperature.Then, while cooling in a manner of it will not tempestuously be flowed back in system
330 parts of 30% sodium hydrate aqueous solution is slowly added dropwise, the toluene of distillation removal is back in system when making to heat up at 80 DEG C or less,
In 70 DEG C~80 DEG C standings.The water layer of separated lower layer is removed, the washing of reaction solution is repeated until detergent remover becomes
It is neutral.Then, using rotary evaporator from oil reservoir in the case where heating is depressurized (200 DEG C, 0.6KPa) by excessive aniline and toluene
Distillation removal, thus to obtain 173 parts of aromatic amine resin (A).The resin obtained is being heated using rotary evaporator again
(200 DEG C, 4KPa) a small amount of water that is gradually added dropwise replaces being blown into vapor under decompression.As a result, obtaining aromatic amine resin 166
Part.The softening point of the aromatic amine resin obtained be 56 DEG C, melt viscosity 0.035Pas, diphenylamine be 0.1% with
Under.Also, amine equivalent is 195g/eq..
(embodiment 1)
Blending epoxy resin 1, (57.5 DEG C of the NC-3000 epoxide equivalent 277g/eq. softening points of Japanese chemical drug manufacture are hereinafter referred to as
For " EP1 ") 73 parts, aromatic amine resin (hereinafter referred to as " H1 ", amine equivalent obtained in the synthesis example 1 as curing agent
195g/eq.) 26 parts by weight and salicylic acid (the pure chemical reagent of C1) 1 weight as Bronsted acid hardening accelerator (catalyst)
Part, it equably mixed, be kneaded using mixing mill, and hardening fever is measured.Show the result in table 1.
(embodiment 2)
Blending epoxy resin 1, (57.5 DEG C of the NC-3000 epoxide equivalent 277g/eq. softening points of Japanese chemical drug manufacture are hereinafter referred to as
For " EP1 ") 73 parts, aromatic amine resin (hereinafter referred to as " H1 ", amine equivalent obtained in the synthesis example 1 as curing agent
195g/eq.) 26 parts by weight and 1 parts by weight of octanoic acid as Bronsted acid hardening accelerator (catalyst), use mixing mill (C2
Supelco companies manufacture) it equably mixed, be kneaded, and hardening fever is measured.Show the result in table 1.
(embodiment 3)
Blending epoxy resin 1, (57.5 DEG C of the NC-3000 epoxide equivalent 277g/eq. softening points of Japanese chemical drug manufacture are hereinafter referred to as
For " EP1 ") 73 parts, aromatic amine resin (hereinafter referred to as " H1 ", amine equivalent obtained in the synthesis example 1 as curing agent
195g/eq.) 26 parts by weight and amino-phenol (C3, SIGMA-ALDRICH examination as Bronsted acid hardening accelerator (catalyst)
Agent) 1 parts by weight, it equably mixed, be kneaded using mixing mill, and hardening fever is measured.Show the result in table 1.
(comparative example 1)
Blending epoxy resin 1, (57.5 DEG C of the NC-3000 epoxide equivalent 277g/eq. softening points of Japanese chemical drug manufacture are hereinafter referred to as
For " EP1 ") 74 parts, aromatic amine resin (hereinafter referred to as " H1 ", amine equivalent obtained in the synthesis example 1 as curing agent
195g/eq.) 26 parts by weight are equably mixed using mixing mill, are kneaded, and are measured to hardening fever.Result is shown
In table 1.
(comparative example 2)
Blending epoxy resin 1, (57.5 DEG C of the NC-3000 epoxide equivalent 277g/eq. softening points of Japanese chemical drug manufacture are hereinafter referred to as
For " EP1 ") 72 parts, aromatic amine resin (hereinafter referred to as " H1 ", amine equivalent obtained in the synthesis example 1 as curing agent
195g/eq.) 26 parts by weight and triphenylphosphine (the emerging chemical industry manufacture in the north C-4) 2 weight as hardening accelerator (catalyst)
Part, it equably mixed, be kneaded using mixing mill, and hardening fever is measured.Show the result in table 1.
(comparative example 3)
Blending epoxy resin 1, (57.5 DEG C of the NC-3000 epoxide equivalent 277g/eq. softening points of Japanese chemical drug manufacture are hereinafter referred to as
For " EP1 ") 57 parts, as (the KAYAHARD GPH-65 hydroxyl equivalents 199g/ of Japanese chemical drug manufacture of curing agent 2 of curing agent
Eq. 65 DEG C of softening point hereinafter referred to as " H2 ") 41 parts by weight and (north C-4 is emerging as the triphenylphosphine of hardening accelerator (catalyst)
Chemical industry manufactures) 2 parts by weight, it equably mixed, be kneaded using mixing mill, and hardening fever is measured.It will knot
Fruit is shown in table 1.
(comparative example 4)
Blending epoxy resin 1, (57.5 DEG C of the NC-3000 epoxide equivalent 277g/eq. softening points of Japanese chemical drug manufacture are hereinafter referred to as
For " EP1 ") 58 parts, as (the KAYAHARD GPH-65 hydroxyl equivalents 199g/ of Japanese chemical drug manufacture of curing agent 2 of curing agent
Eq. 65 DEG C of softening point hereinafter referred to as " H2 ") 41 parts by weight and (C1 is pure as the salicylic acid of Bronsted acid hardening accelerator (catalyst)
Positive chemical reagent) 1 parts by weight, it equably mixed, be kneaded using mixing mill, and hardening fever is measured.By result
It is shown in table 1.
Table 1
According to the above results it is found that the epoxy resin component of the present invention shows excellent hardenability (hardening at subcritical temerature
Property), especially in using salicylic system, the system phase with the phenol system curing agent used as common aromatic hardener
Than showing excellent hardenability (hardening at subcritical temerature).
(embodiment 4)
Blending epoxy resin 1, (57.5 DEG C of the NC-3000 epoxide equivalent 277g/eq. softening points of Japanese chemical drug manufacture are hereinafter referred to as
For " EP1 ") 72 parts, aromatic amine resin (hereinafter referred to as " H1 ", amine equivalent obtained in the synthesis example 1 as curing agent
195g/eq.) 25 parts by weight and salicylic acid (the pure chemical reagent of C1) 3 weight as Bronsted acid hardening accelerator (catalyst)
Part, it in 80 DEG C of roll temperature, equably mixed, be kneaded using mixing mill, after carrying out tabletting, hardened under condition 1.
The physical property of hardening thing for project below to being obtained in the above described manner is measured.Show the result in table 2.
(comparative example 5)
Blending epoxy resin 1, (57.5 DEG C of the NC-3000 epoxide equivalent 277g/eq. softening points of Japanese chemical drug manufacture are hereinafter referred to as
For " EP1 ") 72 parts, phenol system novolaks (bright and chemical conversion manufacture H-3, hydroxyl equivalent 106g/eq.) 27 parts by weight and as hard
Triphenylphosphine (the pure chemical reagent of C4) 1 parts by weight for changing accelerating agent (catalyst), are equably mixed using mixing mill, are mixed
Practice, after carrying out tabletting, by translating into shape for resin molded body, and is hardened under condition 2.For project below
The physical property of hardening thing to being obtained in the above described manner is measured.Show the result in table 2.
(reference example 1)
Blending epoxy resin 1, (57.5 DEG C of the NC-3000 epoxide equivalent 277g/eq. softening points of Japanese chemical drug manufacture are hereinafter referred to as
For " EP1 ") 73 parts, aromatic amine resin (hereinafter referred to as " H1 ", amine equivalent obtained in the synthesis example 1 as curing agent
195g/eq.) 26 parts by weight and salicylic acid (the pure chemical reagent of C1) 1 weight as Bronsted acid hardening accelerator (catalyst)
Part, it in 80 DEG C of roll temperature, equably mixed, be kneaded using mixing mill, after carrying out tabletting, hardened under condition 2.
The physical property of hardening thing for project below to being obtained in the above described manner is measured, and the result of gained is shown in table 2.
Table 2
According to the above results it is found that 100 DEG C of epoxy resin component of the present invention or less formed body and 180 DEG C of forming
The hardening thing of body is compared, and heat resistance, thermal decomposition characteristic, mechanical strength, the reduction of low water absorption character are few, even if so display exists
It can be also formed under 100 DEG C of forming temperatures below, with the phenol system novolaks used as common phenol system curing agent
Situation is compared, and shows excellent heat resistance, mechanical strength, water resistance.The mobile reduction of the higher then ion of water resistance, and in low
In warm hardening chlorine contained in resin capture it is suppressed, so the superior material of power supply reliability can be carried.
Even if the multifunctional phenol resin of the epoxy resin component skeleton similar with using of the present invention is as curing agent person's phase
Than, also there is excellent hardenability, higher heat resistance, mechanical strength, agent of low hygroscopicity and electric reliability, so it is suitble to semiconductor
Sealing, substrate (substrate itself or its periphery material) field.
With reference to specific embodiment, the present invention is described in detail, but be illustrated can be by those skilled in the art
It makes various changes and corrects in the case of without departing from spirit and scope of the invention.
Furthermore the application is Japanese patent application (the Japan Patent Patent filed an application based on December 11st, 2015
2015-242469), it is quoted entirely through reference.Also, cited herein with reference to being compiled in the form of whole
Enter.
Claims (6)
1. a kind of epoxy resin component, containing it is more than difunctionality epoxy resin, with the benzene for stretching biphenyl novolac structure
The content of polyimide resin and Bronsted acid hardening accelerator, the Bronsted acid hardening accelerator is relative to 100 parts by weight of epoxy resin
0.01~10.0 parts by weight.
2. epoxy resin component according to claim 1, wherein the anline resin is the structure that following formula (1) is recorded,
[chemical formula 1]
(in formula, there are the alkyl that multiple R separately indicates hydrogen atom, carbon number 1~15；N is integer, the average value of n
(A) 1≤A≤5 are indicated).
3. epoxy resin component according to claim 1 or 2 contains in incombustible agent, filler and additive
More than any.
4. a kind of prepreg is that the epoxy resin component described in any one of claims 1 to 3 is made to be impregnated in sheet-like fiber
Base material forms.
5. a kind of epoxy resin component formed body is the epoxy resin component made described in any one of claims 1 to 3
More than room temperature and 100 DEG C or less are molded with.
6. a kind of hardening thing, made described in epoxy resin component described in any one of claims 1 to 3, claim 4
Prepreg or claim 5 described in epoxy resin component formed body harden.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015242469 | 2015-12-11 | ||
| JP2015-242469 | 2015-12-11 | ||
| PCT/JP2016/086628 WO2017099194A1 (en) | 2015-12-11 | 2016-12-08 | Epoxy resin composition, prepreg, epoxy resin composition molded body, and cured product thereof |
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| Publication Number | Publication Date |
|---|---|
| CN108291009A true CN108291009A (en) | 2018-07-17 |
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| CN201680071262.4A Pending CN108291009A (en) | 2015-12-11 | 2016-12-08 | Epoxy resin component, prepreg, epoxy resin component formed body and its hardening thing |
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| Country | Link |
|---|---|
| JP (1) | JPWO2017099194A1 (en) |
| KR (1) | KR20180092934A (en) |
| CN (1) | CN108291009A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114929773A (en) * | 2019-11-21 | 2022-08-19 | Swimc有限公司 | Two-part epoxy composition for adhesive coating of storage articles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2990181T3 (en) * | 2017-12-01 | 2024-11-29 | Teijin Ltd | Prepreg, method for producing the same and method for producing fiber-reinforced composite material |
| JP7027382B2 (en) * | 2019-09-30 | 2022-03-01 | 積水化学工業株式会社 | Resin film and multi-layer printed wiring board |
| CN117691199B (en) * | 2024-01-31 | 2024-05-10 | 帕瓦(长沙)新能源科技有限公司 | Glass fiber-based composite material and preparation method and application thereof |
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| JPH02222413A (en) * | 1989-02-23 | 1990-09-05 | Three Bond Co Ltd | Curing agent composition for epoxy resin and curing of epoxy resin using the composition |
| CN102617981A (en) * | 2004-11-30 | 2012-08-01 | 住友电木株式会社 | Epoxy resin composition and semiconductor device |
| CN102630233A (en) * | 2009-12-01 | 2012-08-08 | 长濑化成株式会社 | Epoxy resin composition |
| WO2015152007A1 (en) * | 2014-04-02 | 2015-10-08 | 日本化薬株式会社 | Aromatic amine resin, maleimide resin, and curable resin composition and cured product thereof |
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| JP2007031476A (en) | 2005-07-22 | 2007-02-08 | Dainippon Ink & Chem Inc | Epoxy resin composition for molding material, molded cured product thereof and method for producing molded cured product |
| JP5019585B2 (en) * | 2007-02-26 | 2012-09-05 | 日本化薬株式会社 | Epoxy resin composition, cured product thereof, and fiber-reinforced composite material |
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2016
- 2016-12-08 CN CN201680071262.4A patent/CN108291009A/en active Pending
- 2016-12-08 JP JP2017555142A patent/JPWO2017099194A1/en active Pending
- 2016-12-08 KR KR1020187009714A patent/KR20180092934A/en not_active Withdrawn
- 2016-12-08 WO PCT/JP2016/086628 patent/WO2017099194A1/en active Application Filing
- 2016-12-09 TW TW105141128A patent/TW201731949A/en unknown
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| JPS62232429A (en) * | 1986-04-03 | 1987-10-12 | Nippon Kayaku Co Ltd | Curing agent composition |
| JPH02222413A (en) * | 1989-02-23 | 1990-09-05 | Three Bond Co Ltd | Curing agent composition for epoxy resin and curing of epoxy resin using the composition |
| CN102617981A (en) * | 2004-11-30 | 2012-08-01 | 住友电木株式会社 | Epoxy resin composition and semiconductor device |
| CN102630233A (en) * | 2009-12-01 | 2012-08-08 | 长濑化成株式会社 | Epoxy resin composition |
| WO2015152007A1 (en) * | 2014-04-02 | 2015-10-08 | 日本化薬株式会社 | Aromatic amine resin, maleimide resin, and curable resin composition and cured product thereof |
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| CN114929773A (en) * | 2019-11-21 | 2022-08-19 | Swimc有限公司 | Two-part epoxy composition for adhesive coating of storage articles |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201731949A (en) | 2017-09-16 |
| KR20180092934A (en) | 2018-08-20 |
| WO2017099194A1 (en) | 2017-06-15 |
| JPWO2017099194A1 (en) | 2018-09-27 |
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