TW201026748A - Aromatic polyamide resin containing phenolic hydroxy group, and use thereof - Google Patents

Abstract

Disclosed is a resin which can be cured into a product having a low linear expansion coefficient and has excellent electrical properties, good adhesion to various base materials and fully satisfactory heat resistance and flame retardancy. Also disclosed is a composition containing the resin. Specifically disclosed is (A) a polyamide resin containing a phenolic hydroxy group. which is represented by formula (2) Wherein m and n independently represents a mean value which fulfill the requirement represented by the following formula 0≤m/(m+n)≤0.8 wherein the sum total of m and n (i.e., m+n) is a positive number of 2 to 200; Ar3 represents a bivalent aromatic group which is derived from at least one compound selected from para-phenylenediamine, meta-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 1,5-naphthalenediamine and 1,8-naphthalenediamine; and q represents a mean number of substituents and is an integer of 1 to 4].

Description

201026748 VI. Description of the Invention: [Technical Field] The present invention relates to a resin composition containing a phenolic hydroxyl group, an epoxy resin as a polyacetamide resin, a polyacetamide resin, and a use thereof. Flexible printed wiring board ^Inch and + conductor insulating film, the 3 phenolic bismuth-based fragrant polyamide tree ^ ^ φ ^ for low shrinkage, heat resistance, successor, electrical Insulation characteristics and ❹ * A sufficiently hardened material, and when it is formed into a film shape, it has sufficient flexibility. [Prior Art] The polyamine resin has been developed as an additive or a curing agent for modifying properties such as an epoxy resin, and is generally used as an epoxy component of a component, and can be generally It is widely used in the fields of adhesives, paints, laminates, molding materials, and injection materials, such as heat-resistant, mechanical properties, and chemical resistance. The main component of such an epoxy resin composition: an epoxy resin which is most commonly used, for example, a bisphenolphthalein type epoxy resin. In addition, in the field of electrical and electronic parts, a phenolic varnish-based resin excellent in electrical reliability is often used in the field of electrical and electronic parts. Patent Document 2, Patent Document 3 and Patent Document 4 disclose that a polyamine resin containing a phenolic hydroxyl group and an epoxy resin composition containing the same and an epoxy resin are excellent in heat resistance and flame retardancy, and are applicable. It is a material for a flexible printed wiring board or a fiber reinforcing agent. However, the resin disclosed in Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4, and the composition containing the same, have a high coefficient of linear expansion, 3 201026748 when it is combined with a general copper foil or a latent amine film. When combined, a large curl occurs due to the difference in shrinkage ratio, which causes a problem of connection reliability in the construction step. Patent Document 1: Japanese Patent Publication No. Hei 7-42359, Patent Document 2: Japanese Patent Publication No. 2000-273168, Patent Publication No. 2000-273168, Japanese Patent Publication; Patent Publication No. 9987 Patent Document 4 . International Publication No. WO04/048436 [Disclosed] An object of the present invention is to provide an epoxy resin composition containing a polyamide resin, which has a cured product due to low linear expansion. When the film is applied to a film-form substrate for curing, it does not cause curling, and the cured product is excellent in heat resistance, adhesion, and flame retardancy, and has sufficient flexibility even when formed into a sheet shape. Electrical reliability. The inventors of the present invention have diligently studied in order to solve the above problems, and have completed the present invention. The present invention is related to: (1) A polyamine resin (A) containing a phenolic hydroxyl group, which is represented by the following (2): 201026748) 111 and n-average values satisfying m/(m) +n) g 0.8 —, m+n is a positive number of 2 to 200. Ar3 represents a selected from the group consisting of p-phenylenediamine, fenpropanamine, 4,4-diaminodiphenyl ether, 4,4,diaminodiphenylmethane, I, naphthalene-amine, 1,8-naphthalene The number of the average substituents of the divalent aromatic group '1 derived from the above-mentioned compounds in the group consisting of diamines, and an integer of 4 1 to 4. (2) The phenolic hydroxyl group-containing polyamine resin (A) according to the above (1), wherein m and n' in the formula (7) satisfy the relationship of 〇$m/(m+n)g〇 5 ,

Further, the Aq is a divalent aromatic group derived from a compound of the above-mentioned compounds in the group consisting of p-phenylenediamine, m-phenylenediamine and 4,4,diaminobenzophenone. (3) The phenolic hydroxyl group-containing polyamine resin (A) according to the above (1) or (2), wherein the glass transition temperature is 3 〇 (rc or more, and 1 〇〇 2 〇〇 &lt; t The linear expansion coefficient is 40 ppm or less. (4) An epoxy resin composition containing the phenolic hydroxyl group-containing polyamine resin (A) according to any one of the above (1) to (3), And the epoxy resin (B). (5) A film obtained by processing the epoxy resin composition described in the above (4) into a sheet shape. (6) An adhesive sheet for a flexible printed wiring board, The epoxy resin composition according to the above (4), which is the epoxy resin composition described in the above (4), the film described in the above (5), or the above (6). (8) A reinforcing sheet for a flexible printed wiring board, comprising the epoxy resin composition described in the above (4) or a cured layer thereof. (9) A flexible sheet A cover film for a printed wiring board (C〇verlay), which has the epoxy resin composition described in the above (4) or a cured layer thereof. The double-sided metal-covered resin laminated board is characterized in that: one side or two sides of the film or the hardened layer of the five-loaded metal layer is connected with: one side of the metal falling layer or one side of the metal covering resin laminated board ( The flexible printed wiring board according to the above (7), the sheet according to the above (6), the reinforcing sheet according to the above (8), the cover film described in the above (9), and the above (10) (1) A semiconductor insulating film having the epoxy resin composition described in the above (4) or a cured layer thereof. (13) A phenolic hydroxyl group The method for producing a polyamine resin (Α), which is a polyphenol resin containing phenolic hydroxyl groups described in (1) above, wherein &lt;A&gt; is selected from p-phenylenediamine, One or more compounds of the group consisting of phenylenediamine, 4,4, diaminodiphenyl ether, A〆, · diaminodiphenylmethane, naphthalenediamine, anthracene, and 8-naphthalenediamine, and <B> Benzoic acid and phthalic acid as an optional component (of which 20 mol% or more of the two are less than 0/〇 is a hydroxy benzoic acid The acid is subjected to a condensation reaction. (14) A method for producing a phenolic hydroxyl group-containing polyamine resin, which is a polyphenol resin containing a phenolic hydroxyl group as described in the above (2), which is selected as &lt;A&gt; a compound of at least one of the group consisting of p-phenylenediamine, m-phenylenediamine, and 4,4'-diaminodiphenylmethane, and &lt;B&gt;hydroxyphthalic acid and benzoic acid as an optional component (Including, among the two 201026748, 50 mol% or more and 100 mol% or less of polyhydroxyphthalic acid), the condensation reaction is carried out. The polyhydroxylamine resin containing a hydroxy group of the present invention is excellent in heat resistance and is formed into a film. It also has a low coefficient of linear expansion. Moreover, the epoxy resin composition of the present invention containing the polyamide resin and the epoxy resin maintains the heat resistance and low characteristics of the polyamide resin even in the form of a film-like cured product. Since it has a linear expansion coefficient and excellent electrical reliability, it can be widely used in the manufacture of a printable substrate = substrate or a semiconductor insulating material, and is extremely suitable for use in electrical materials such as electric substrates and insulating films. [Embodiment] The phenolic hydroxyl group-containing aromatic polyamine resin of the present invention can be obtained by condensation reaction of the following compound group (a) with the compound group (b). The compound group (a) is selected from the group consisting of p-phenylenediamine, m-diphenylamine, 4,4,-diaminodiphenyl ether, M, _-amino group m, 1 &gt; 5-naphthyldiamine' - a group of above compounds (b)

Formic acid and benzoic acid as an optional component are highly crystalline acids due to the compound group (a) monoamine" (hereinafter, also referred to as "the solvent solubility is extremely precipitated, but by aromatic The condensation reaction of a diamine (hereinafter, simply referred to as "aromatic" with the aromatic di-supplemental aromatic dicarboxylic acid of the compound group (b)) reduces the amount of the condensation reaction as it is.曰^ Use a certain amount or more of aromatic dicarboxylic warmer 7 201026748 Hydroxyphthalic acid (preferably hydroxyisophthalic acid) having a phenolic hydroxyl group, can inhibit the precipitation of aromatic diamine in the condensation reaction, An aromatic polyamine resin containing a phenolic hydroxyl group having a high glass transition point and a low linear expansion coefficient is obtained. The phenolic hydroxyl group-containing polyamine resin (A) of the present invention preferably has a temperature of from 100 to 200 ° C. A linear expansion coefficient of 40 ppm or less. If the linear expansion coefficient in the temperature range exceeds 40 ppm', a film or a flexible printed wiring board having a phenolic hydroxyl group-containing polyamine resin is used, and various heat treatments such as reflowing are used. Steps to produce a large curl一般 The general copper box and polyimide film used in the flexible printed wiring board, the linear expansion coefficient between 100 and 2 〇〇 is about 2 〇 ppm, and the closer to this value, the less the curl is. Therefore, The polyamine resin (A) of the desired base (A) '1〇〇~2〇 (the linear expansion coefficient between TC is more preferably close to 2〇ppm. The phenolic hydroxyl group-containing polyamine resin of the present invention (A) The aromatic diamine can be prepared by a condensation reaction between an aromatic diamine and an aromatic dicarboxylic acid by, for example, a method such as the application of the patent No. 2,969,585, or the like. The amount of the aromatic diamine used in the condensation reaction is relatively In the aromatic dicapric acid (10) Mo, usually 5〇~2〇〇 Moel is preferably 8〇~125 Mo, more preferably 90~11 〇苴E i4. ^ U 耳,特佳为95 ～105 mol. The aromatic-&lt;mole ratio of amine to scented dicarboxylic acid used in the condensation reaction is closer to 1 / the molecular weight of the obtained phenolic hydroxyl group-containing polyamine resin (4) is larger. The condensation reaction between a group of amines and an aromatic dibasic acid is carried out in the presence of a bite-derivative derivative, using a phosphorus-based shrinkage in W Gu·mask and organic agents. A phosphorus-based condensing agent is preferably known as a phosphite. Further, if an inorganic salt such as vaporized lithium or vaporized calcium is added at the time of the reaction, (1) a phenolic hydroxyl group having a larger molecular weight is attached to 201026748. Polyamine resin (A). By the production method, even if the functional group, that is, the phenolic hydroxyl group, is not protected, the reaction of the phenolic hydroxyl group with other reactive groups (for example, a carboxyl group or an amine group) is not caused, and it can be easily produced. The aromatic polyamine resin having a phenolic hydroxyl group and a condensation reaction can be carried out at a low temperature of about 15 or less. Hereinafter, the synthesis of the phenolic hydroxyl group-containing polyamine resin (A) of the present invention will be described in more detail. Method for synthesizing the aromatic diamine used, preferably p-benzoic acid, m-p-monoamine, 4,4,-diaminodiphenyl or 4,4'-diaminodiphenyl fluorene, The aromatic polyamine resin (A) containing a phenolic hydroxyl group has a linear expansion coefficient which is better than that of p-phenylenediamine, m-phenylenediamine or 4,4,-diaminodipyridinium. Phenylenediamine is particularly preferred. Aroma used in synthesis

T 1 to 4 groups may be substituted, and examples thereof include 5-perylene phthalic acid, 4 hydroxy hydroxy meta-benzoic acid, and 2 hydroxyisophthalic acid ' 3 -hydroxyisophthalic acid and 2 - transbasic terephthalic acid. Among them, the solvent solubility and purity of the obtained aramid-containing aramid-tree (4), the electrical properties of the composition of the cyclic oxime resin, and the adhesion to the metal flute and the polyimine are considered. , 5-aminoisophthalic acid is the best. Further, among the aromatic dicarboxylic acids used in the synthesis, as the benzoic acid which is an optional component, phthalic acid, m-dicarboxylic acid, and benzoic acid may be used, but the dicarboxylic acid is used. good. If the content of the hydroxyphthalic acid in the component of the aromatic dicarboxylic acid is low, then the synthesis will precipitate. _ The phthalic acid of the diamine will be precipitated. θ (4) Fangxiangtongtong A 20 It is expected that the use of citric acid 1 'in the total aromatic two-rebel acid, usually 20 mol% or more 丨 莫 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ More preferably, it is 75 mol% or more and 1 mol% or less. 9 201026748 By using the amount of fresh dicarboxylic acid in the above range, the repeating unit m and n in the above formula (7) can be obtained to satisfy osn^m+n. a phenolic hydroxyl group-containing aromatic polyamine resin (A) having a relationship of + η) and 0.5, and a polyamine resin having a desired hydroxyl group is described in Japanese Patent No. 2969585. The amount of the acid retardant used in the carboxylic acid component is 5 mol% or more in the total carboxylic acid component, but the aromatic acid in the condensation reaction is suppressed by using a specific amount of the dicarboxylic acid having a phenolic hydroxyl group. The effect of precipitation of a diamine is not described. Specific examples of the phosphite used as a condensing agent at the time of synthesis include, for example, sub- Triphenyl phosphate, diphenyl phosphite, tri-o-tolyl phosphite, di-o-methyl phosphite, tri-tolyl phosphite, tri-p-tolyl phosphite, di-p-tolyl phosphite, two pairs of phosphite Benzene ester, tri-p-phenylene phosphite, di-p-chlorophenyl phosphite, etc., but not limited to these. Further, the pyridine derivative used together with the sub-disk acid ester can be exemplified by pyridine, 2- Methylpyridine, 3-methylpyridine, 4-pyridylpyridine and 2,4-dipyridinium. The above phosphite is generally used as a condensing agent in a mixture of a pyridine derivative and an organic solvent. The organic solvent is preferably a substance. It does not react with a phosphite, and has the property which can melt|dissolve the said aromatic diamine and this aromatic dicarboxylic acid, and the phenolic hydroxyl group-containing polyamine resin (A) of the reaction product is a good solvent. Such an organic solvent may, for example, be an amine-based solvent such as Ν·甲久0, benzophenone or N,N-dimercaptoacetamide, and a mixed solvent of the oxime, methyl ethyl ketone or the like. Among them, preferred is N methyl-2-° decyl ketone. The amount of pyridine derivative used In the mixture of the pyridine derivative and the organic solvent, it is usually 5 to 30 parts by weight of ruthenium. 201026748 Further, in order to obtain a phenolic hydroxyl group-containing polyamine resin (A) having a high degree of polymerization, in addition to the above phosphite and pyridine In addition to the derivative, an inorganic salt such as vaporized lithium or vaporized calcium is preferably added. The following describes in detail a preferred embodiment of the method for producing the phenolic hydroxyl group-containing polyamine resin (A) of the present invention. First, a phosphite and an inorganic salt are added to a mixed solvent composed of an organic solvent containing a pyridine derivative, and 5-hydroxyisophthalic acid is added thereto, and phthalic acid is added as appropriate. The dicarboxylic acid component is 1 〇〇 耳 5 〇 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 After the completion of the reaction, a poor solvent such as water, methanol or hexane is added to the reaction liquid, or the reaction liquid is introduced into a poor solvent to separate the produced polymer, and the by-product or inorganic salt is removed by reprecipitation. Thus, an aromatic polyamine resin containing a phenolic hydroxyl group represented by the above formula can be obtained. In the above production method, the amount of the phosphite added as the condensing agent is usually the same or more than the molar amount of the amine group, but the efficiency is not more than 3 Torr. ❽ When the phosphite triester is used, the phosphite diester of the by-product also acts as a condensing agent, so it is usually about 80% by mole. The amount of the bite derivative must be equal to or greater than the same amount as the amine group, but actually functions as a reaction solvent and is often used in a much excess. The above pyridine. The amount of the mixture of the derivative and the organic solvent is preferably such that the concentration of the theoretically obtained phenolic hydroxyl group-containing aromatic polyamide resin is in the range of 5 to 3 % by weight. The reaction temperature is usually from 6 Torr to 18 (rc, preferably from 8 Torr to 12 Torr). The reaction time is greatly affected by the reaction temperature, but in any case, the reaction is carried out until the highest viscosity at the highest polymerization degree is obtained. Preferably, 11 201026748 is usually from about several minutes to about 20 hours, preferably from about 5 to 12 hours. Under the above preferred reaction conditions, if the molar is 5-hydroxyisophthalic acid and optionally added In the case of isophthalic acid and p-phenylenediamine, a phenolic hydroxyl group-containing aromatic polyamine resin (A) having an optimum average degree of polymerization of about 2 to 200 may be obtained. The number average molecular weight of the aromatic polyamine resin (A) of the hydroxyl group is usually from about 3,000 to 60,000, preferably from about 10,000 to about 40,000, and the weight average molecular weight is usually from about 1 to about 00 to about 25 Torr, preferably about The calculated value of the active hydrogen equivalent is usually from 180 to 5,000 g/eq., preferably from 200 to l〇〇〇g/eq., more preferably from 200 to 500 g/eq., still more preferably from 200 to 200,000. 400g/eq., preferably 220~350g/eq·. Generally speaking, is it The preferred average degree of polymerization is determined by reference to the molecular weight. If the weight average molecular weight is less than 1 Å, the film formability or the properties of the aromatic polyamide resin cannot be sufficiently exhibited, which is not preferable. If it is more than 250,000, the degree of polymerization will be too high, and the solubility of the solvent will be deteriorated, and the formability will be deteriorated. Further, the number average molecular weight and the weight average molecular weight are converted by polystyrene according to gel permeation chromatography. The numerical value (the same applies hereinafter). A simple method of adjusting the degree of polymerization of the aromatic-containing polyamide resin (4), for example, a method of using either an aromatic diamine or an aromatic acid excessively. Next, the epoxy resin composition of the present invention will be described.

The epoxy resin composition # of this month is a composition containing a sulphur-containing amine resin (A) and an epoxy resin (B). The epoxy resin (8) used in the 12 201026748 epoxy resin composition of the present invention is added for the purpose of recording the desired base in the aromatic polyamine resin (4) containing the aged base group, and the end rebellion. The base or / and terminal amine groups are reacted. By reacting the heteropoly M-based aromatic polyamine resin (4) with the epoxy resin (B), the crosslinking density of the polyamidamide resin of the present invention is increased, and the cured epoxy resin composition of the present invention is cured. Increased financial performance and adhesion to substrates. The epoxy resin (b) to be used is not particularly limited as long as it is two or more epoxy groups per knife U. However, it is preferably a benzene ring, in view of mechanical strength and flame retardancy. An aromatic ring such as a biphenyl ring or a naphthalene ring, and a group having two or more ring gas groups in the molecule. Specifically, for example, a varnish-type epoxy resin, a varnish-type epoxy resin containing a phthalic acid (a varnish), a varnish-type epoxy resin containing a biphenyl skeleton, a double-presence A-type epoxy resin, and a double F Type epoxy resin, : A: biphenyl type epoxy resin, etc., considering the phase of the polyamidamide resin containing a dilute hydroxyl group, the epoxy tree wax having a biphenyl skeleton is particularly preferred. The epoxy resin in the epoxy resin composition = the oxy-resin composition contains a sulphur-containing aromatic sulphur-containing chlorine, and the equivalent amount is usually 12 equivalents, preferably * 垔 more preferably 0.05 to 〇 3 equivalents. The active hydrogen equivalent of the phenolic polyamine resin (Α) can be calculated from the total of the aromatic dicarboxylic acid of the hydroxyl group at the time of reaction, and the phenol contained therein. The remaining diamine component or diterpene component is The epoxy resin composition of the present invention may also be combined with a hardening agent, for example, two-part two stupid, = 伸乙可_: 13 201026748 amine-extension ethylene tetraamine-amine diphenyl dish, isophorone Diamine, dicyandiamide, dilinoleic acid dimer and polyamidamine resin synthesized from ethylenediamine, benzoic acid Anhydride, trimellitic anhydride, pyrochloric anhydride, maleic anhydride, tetrahydroxyphthalic anhydride, mercapto tetrahydroxy phthalic anhydride, quinone nadic anhydride, hexahydrodicarboxylic anhydride, fluorenyl six Hydrogen phthalic anhydride, a phenolic hydroxyl group-containing resin, tri-methane and such denatured substances, imidazole, BF3_amine complex, pulsed organism, etc., but are not limited thereto. When the curing agent is blended, the ratio of the aromatic epoxy resin (A) to the total hardener in the epoxy resin composition is usually 2% by weight or more, preferably 30%. More than weight%. Further, a curing accelerator may be used in combination when the above curing agent is used. Specific examples of the hardening accelerator to be used include, for example, 2·methylimidazole, 2-ethylisosole, 2-ethyl-4-indolyl saliva, and 2-phenyl-4-45-dihydroxymethylhydrazine. Mizozol, phenyl-4-methyl-5-ylaminomethyl sylvestine, etc., scorpion, 2_(dimethylaminomethyl), 1,8-anthracene bicyclic (5,4, 〇 a tertiary amine such as eleven_7-ene, a phosphine such as triphenylphosphine, or a metal compound such as tin octylate. The hardening accelerator is used in an amount of from 01 to 5 parts by weight, based on 100 parts by weight of the epoxy resin. The epoxy resin composition of the present invention optionally contains a base-free filler. Specific examples of the inorganic filler to be used include cerium oxide, aluminum hydroxide, oxyhydroxide, carbon _, oxygen oxol, slip S, and glass short fibers. The inorganic filler is used in an amount of 〇 to 90% by weight based on the epoxy resin composition of the present invention. Further, in the epoxy resin composition of the present invention, various compounding agents such as a decane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, and a pigment may be added. 201026748

环氧树脂 The epoxy resin composition of the present invention may also be dissolved in a solvent as needed. The solvent to be used may, for example, be r-butyrolactone, n-methylalkanone (NMP), N,N-dimethylformamide (DMF), n,n-dimethylamine, anthracene , hydrazine-based solvents such as hydrazine dimethyl oxazolidinone, sulfones such as cyclobutyl hydrazine: diethylene glycol dimethyl (tetra), diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl acetate Ethyl alcohol such as vinegar, propylene glycol monobutyl hydride, methyl ethyl hydrazine, methyl isobutyl ketone, cyclopentanone, cyclohexyl ketone, etc., aromatic solvents such as toluene and xylene, etc. The solid content of the solvent to be removed is usually from 1 to 7 % by weight, preferably from 30 to 70% by weight, as needed. The epoxy resin composition of the present invention has a characteristic of 100 to 20 in the cured product (the linear expansion coefficient between TC is 5 〇 ppm or less. If the linear expansion coefficient exceeds 50 Ppm, the coating film is formed. In the production of a film or a flexible printed wiring board, f is greatly curled by various heat treatment steps such as retracement. v. The flexible printed wiring board is used as usual, and the polyacrylamide film 200 C is used. The coefficient of linear expansion is about 2 〇ppm, and the closer to this value, the less the curling. The epoxy resin composition of the present invention is obtained by uniformly mixing the above components. The epoxy resin composition of the present invention, The cured product can be easily obtained by the same method as the conventional method. For example, the epoxy resin composition, and optionally the hardener, and optionally the hardening accelerator, the inorganic filler, and the compounding agent can be used. 'Using an extruder, a kneading machine' roll, etc., if necessary, mixing the slag σ uniformly'. The epoxy resin composition is formed by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like. 15 201026748 and 80~2〇 (TC heating 2 to 1 hour, whereby the cured product of the present invention can be obtained. The film or cured product obtained by processing the oxygen resin composition after the present invention can be obtained by dissolving the epoxy resin composition of the present invention in a solvent. The solvent to be used may, for example, be r-butyl vinegar, N-methyl (tetra)-pyrene (test), hydrazine, hydrazine-dimethylformamide (DMF), N,N-dimethylacetamide , N,N dimethylimidazolidone and other guanamine solvents, guanidines such as cyclohexane, diethylene glycol dimethyl ether, = ethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoterpene ether An ether solvent such as acetate or propylene glycol monobutyl ether; a ketone solvent such as methyl hydrazine, decyl isobutyl ketone, cyclopentanone or cyclohexanone; or an aromatic solvent such as toluene or xylene; The solid content in the obtained varnish is usually from 2 to 8 % by weight, preferably from 3 to 70% by weight. The film of the present invention is a gravure coating method known per se. Various coating methods such as screen printing, metal masking, and spin coating are applied to the planar support so that the film thickness after drying is A predetermined thickness (for example, 50 to 500 m) is applied and dried, and the coating method is appropriately selected depending on the type, shape, size, and film thickness of the substrate. For example, polyamine, polyimine, polyamidamine, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyetheretherketone, a film made of various polymers such as polyether phthalimide, polyether ketone 'polyketone, polyethylene, polypropylene, and/or a copolymer thereof, or a metal foil such as a copper pig, and a polyimine or a metal Preferably, the film is obtained by further heating to obtain a sheet-like cured product. For the preferred use of the present invention, for example, a back sheet for a flexible printed wiring board or a reinforcing sheet for a flexible printed wiring board, A cover layer for a flexible printed wiring board, a resin layer of a single-sided or double 16 201026748 surface metal-covered resin laminated board (hereinafter referred to as a material for a flexible printed wiring board), the present invention The epoxy resin composition is an adhesive for forming such a flexible printed wiring board or Billion for the resin layer to such material, the planar support most of the material has a function of peeling of the film. Further, the varnish obtained above is impregnated with a prepreg obtained by heating a substrate such as glass fiber, carbon fiber, polyester fiber, aromatic polyamine fiber, ZylOx fiber, alumina fiber, paper, etc., and heat it. Press forming can also produce a cured product. The solvent at this time is usually used in an amount of from 1 to 70% by weight, preferably from 15 to 70% by weight, based on the total of the epoxy resin composition of the present invention and the solvent. EXAMPLES Next, the present invention will be described more specifically by way of examples and comparative examples, but the invention is not limited to the examples. Synthetic Example A flask equipped with a thermometer, a cooling tube and a stirrer was flushed with nitrogen, and filled with 5-hydroxyisophthalic acid (2,6 g (〇.H mol) and p-phenylenediamine 12.51 g (0.12). Mohr), lithium chloride 〇.96g, N-methyl-2-° ratio of ca. ketone 120.98g and "bite bite 26.80g, after mixing and dissolving, adding triphenyl phosphite to 5 8.09g, The reaction was carried out at 95 ° C for 8 hours to obtain the following formula (4) 17 201026748 [Chemical 2]

The reaction liquid of the phenolic hydroxyl group-containing aromatic polyamine resin (A) of the present invention is shown. After cooling the reaction mixture to room temperature, 50 g of decyl alcohol and 2 g of water were added, and the precipitated resin was separated by filtration, washed with 2 g of methanol, and then purified by refluxing with methanol. Then, after cooling to room temperature, the mixture was filtered, and the filtrate was dried to obtain a resin powder (this resin was designated as Α_ι). The amount obtained was 27.8 g, and the yield was 95.6%. The resin powder had a molecular weight, a number average molecular weight of 37,900, and a weight average molecular weight of 169,000. The active hydrogen equivalent which can be reacted with the epoxy group is calculated to be 246.6 g/eq· (base equivalent is 256.4 g/eq·). Synthesis Example 2 A flask equipped with a thermometer, a cooling tube and a stirrer was flushed with nitrogen, and charged with 15.71 g (0.09 mol) of 5-hydroxyisophthalic acid and 4.78 g (0.03 mol) of isophthalic acid. ), p-phenylenediamine 12.69g (0_12 mol), lithium chloride 〇.955g, N-methyl-2-pyrrolidone 129.80g and pyridine 27.18g, after mixing and dissolving, add the sub-disc three stupid S 5,90g, reacted at 90 ° C for 8 hours to obtain the following formula (5) 18 201026748 am

Reaction solution. After cooling the reaction mixture to room temperature, 5 g of methanol and 200 g of water were added, and the precipitated resin was separated by filtration and washed with methanol 2, and then purified by refluxing with decyl alcohol. Then, after cooling to room temperature, a transition was made, and the resultant was dried to obtain a resin powder (the resin was designated as A_2). The amount obtained was 28.0 g, and the yield was 96.4. / (^ The molecular weight of the resin powder, the number average molecular weight is 39,000, the weight average molecular weight is 1394 〇〇〇. The active hydrogen equivalent which can be reacted with the epoxy group, the calculated value is 319.54 g / eq. (the hydroxyl equivalent is 336.58 g / Eq.) ° Synthesis Example 3 A flask equipped with a thermometer, a cooling tube and a stirrer was purged with nitrogen gas, and filled with 5-hydroxyisophthalic acid 20.66 g (〇.n mol), stupid 12.51 g (0.12 mol) of diamine, 96 g of vaporized lithium ruthenium, 100.98 g of N-methyl-2-pyrrolidone and 26.80 g of acridine. After stirring and dissolving, 58.09 g of triamyl phosphite was added to 95. The reaction was carried out at ° C for 8 hours to obtain the following formula (6) im

19 201026748 A reaction liquid of the phenolic hydroxyl group-containing aromatic polyamine resin (A) of the present invention. After the reaction solution was cooled to room temperature, 50 g of decyl alcohol and 200 g of water were added. The precipitated resin was separated by filtration, washed with 2 〇〇g of decyl alcohol, and then purified by refluxing with methanol. Then, after cooling to room temperature, the mixture was filtered, and the filtrate was dried to obtain a resin powder (the resin was designated as A-3). The amount obtained was 25.2 g, and the yield was 8 ό 6%. The resin powder had a molecular weight, a number average molecular weight of 19,300, and a weight average molecular weight of 972 Å. The active hydrogen equivalent which can be reacted with an epoxy group was calculated to be 246.6 g/eq. (hydroxy equivalent: 256.4 g/eq·). Synthesis Example 4 A flask equipped with a thermometer, a cooling tube, and a stirrer was flushed with nitrogen, and loaded with 5.72 g of 5-hydroxyisophthalic acid (4.〇9 mol), 4,4,-diamine. Base one benzophenone 17.45g (0.09 moles), gasification clock 〇 96g, N-methyl-2-» 嘻垸嗣l〇iJ8g and pyridine 2〇.39g, stir to dissolve, add subscale 44.20 g of acid vinegar and reacted at 95 C for 8 hours to obtain the following formula (7)

[chemical

A reaction liquid of the phenolic hydroxyl group-containing aromatic polyamine resin (A) of the present invention. After cooling the reaction mixture to room temperature, 5 〇g of methanol and water 20 201026748 2 〇〇g were charged, and the precipitated resin was separated by filtration and washed with methanol 2 ′ followed by refluxing with decyl alcohol. Then, after cooling to room temperature, the mixture was filtered, and the filtrate was dried to obtain a resin powder (the resin was designated as A_4). The obtained amount is 27.6 g, and the yield is 91.8%. The amount of the resin powder is 〇, and the weight average molecular weight is 12Q8: the active hydrogen equivalent and the calculated value are 335 〇g/eq·(hydroxy equivalent Is 348 4 g/eq.). Synthesis Example 5 A flask equipped with a thermometer, a cooling tube and a stirrer was flushed with nitrogen, and charged with 5-hydroxyisophthalic acid 15 64 g (〇〇9 mol), 4 4,-diamino group 17.94 g (0.09 mol) of ether, 96 g of lithium chloride, 1.62 g of N-methyl-2-pyrrolidone, and 2 g of pyridine. After stirring, the mixture was dissolved, and then 43.97 g of triphenyl phosphite was added to 951. The reaction was carried out for 8 hours to obtain the following formula (8) [Chemical 6]

The reaction liquid of the phenolic hydroxyl group-containing aromatic polyamine resin (A) of the present invention is shown. After the reaction solution was cooled to room temperature, 50 g of methanol and 200 g of water were added, and the precipitated resin was separated by filtration, washed with 2 g of methanol, and then purified by refluxing with methanol. Then, after cooling to room temperature, filtration was carried out, and the filter 21 201026748 was dried to obtain a resin powder (the resin was designated as A-5). The amount obtained was 28.4 g, and the yield was 94.4%. The resin powder had a molecular weight, a number average molecular weight of 40,000, and a weight average molecular weight of 164,200. The active hydrogen equivalent which can be reacted with an epoxy group, calculated as 336.8 g/eq. (hydroxyl equivalent is 35 〇 3 g/eq.) 〇Comparative Synthesis Example 1 A flask equipped with a thermometer, a cooling tube and a stirrer was used. Nitrogen flushing, filled with 0.44 g (0.002 mol) of 5-hydroxyisophthalic acid, 19.52 g (0.12 mol) of p-diphenyldicarboxylic acid, 13.22 g (0.12 mol) of p-phenylenediamine, and 0.96 of lithium niobate. g, N-methyl-2-pyrrolidone 76.16g and pyridine 28.32g, after mixing and dissolving, adding 61.38 g of triphenyl phosphite to 90. (: reaction, the following formula (9) is obtained [Chem. 7]

m:n=98:2

When the reaction liquid of the phenolic hydroxyl group-containing aromatic polyamine resin was used for comparison, the reaction product was precipitated, and it was confirmed that it was not dissolved in the solvent. Comparative Synthesis Example 2 A flask equipped with a thermometer, a cooling tube and a stirrer was flushed with nitrogen, and charged with 5-hydroxyisophthalic acid I 2.00 g (0.07 mol), 3, 3', 5, 5'. -tetraethyl-4,4'-diaminodiphenylmethane 20.86g (0.07 mole), 22 201026748 lithium chloride 2.88g, N-methyl-2-° 嘻 纲 114.98g and ° bite L5.56g, after mixing and adding, add 'sodium squarate II from day 33.73g' to react at 95C for 8 hours to obtain the following formula (10) [Chemical 8]

0〇) The reaction liquid for the phenolic hydroxyl group-containing aromatic polyamide resin used for comparison. After cooling the reaction mixture to room temperature, 50 g of methanol and 200 g of water were added. The precipitated resin was separated by hydrazine, washed with 2 〇〇g of methanol, and then purified by refluxing with methanol. Then, after cooling to room temperature, the mixture was filtered, and the filtrate was dried to obtain a resin powder (the resin was designated as R 2 ). The amount obtained was 28.0 g, and the yield was 91.9%. The molecular weight of the resin powder was 19,300 and the weight average molecular weight was 691 Å. The active hydrogen equivalent which can be reacted with an epoxy group is calculated to be 445 〇g/eq (hydroxy equivalent weight is 462 8 g/eq.). Comparative Synthesis Example 3 A flask equipped with a thermometer, a cooling tube and a stirrer was flushed with nitrogen gas to which 14 57 g of isophthalic acid (〇〇9 mol) and 5 g of interstitial benzoic acid (0.33 g) were charged. 〇2 Mohr), 34 diaminodiphenyl to i828g (〇〇9 23 201026748 Moer), gasified lithium ruthenium. 96g, N-methyl-2-pyrrolidone 98.90g and pyridine 21.15g, stirred to dissolve Thereafter, 45.83 g of triphenyl phosphite was added and reacted at 95 ° C for 8 hours to obtain the following formula (11) [Chem. 9]-seven. (10)

OH πι: η-98:2 The reaction liquid for the aromatic polyamine resin containing a heterogeneous group. After cooling the reaction mixture to room temperature, 50 g of methanol and 2 g of water were added, and the precipitated resin was separated by filtration, washed with 200 g of decyl alcohol, and then purified by refluxing with methanol. Then, after cooling to room temperature, filtration was carried out, and the filtrate was dried to obtain a resin powder (the resin was designated as R_3). The amount obtained was 27.7 g, and the yield was 92.5%. The resin powder had a molecular weight, a number average molecular weight of 44,000, and a weight average molecular weight of 1〇6〇〇〇. The calculated active hydrogen equivalent of the reaction with the epoxy group was calculated to be 5577 g/eq. (hydroxy equivalent weight was 16731 g/eq.). 13 Test Example The resin powders (Al, A-2 'A-3, A-4, A-5, R-2, R-3) obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 2 and 3 were synthesized. The N,N-dimercaptoacetamide was diluted to have a solid concentration of 20% by weight to prepare a phenolic hydroxyl group-containing aromatic polyamine resin solution. The resin solution was applied to a PET film so as to have a thickness of 2 μm after drying, and then dried at 14 ° C to remove the PET film, and then fixed in a mold frame and dried at 2 〇〇〇c. Minutes, 24 201026748 Thereby, a separate film of the phenolic hydroxyl group-containing polyamine resin of the present invention and comparative use is obtained. For the obtained film, the glass transition temperature (Tg) at a temperature of 5 ° C from 5 ° C to 400 ° C and the linear expansion between 1 〇〇 and 200 ° C were measured using a TMA apparatus (manufactured by Perkin Elmer). Coefficient (CTE), the measurement results are shown in the table. [Table 1]

Tg CTE A-1 400 C or more 23.3ppm

A] 400 C or more 24·6ρριη

Ad 305.8. . 33.9 ppm 313.8 C 36.1 ppm A·5 324 0〇C 38.5 ppm R-2 285.3 ° C 65.9 ppm R-3 246.1 ° C 55.0 ppm Examples 1, 2, 3, Comparative Example 1. Synthesis of Example 1 Aromatic polyamine resin (A-1) containing a divalent group, a phenolic hydroxyl group-containing aromatic polyamine resin (R-3) obtained by a comparative synthesis example, an epoxy resin, a hardener, and a hardening accelerator The solvent (Dmac; dimethylamino cinnamic acid) was combined at a ratio (parts by weight) shown in Table 2 to obtain an epoxy resin composition of the present invention and comparative use. 25 201026748 [Table 2] Example 1 Example 2 Example 3 Comparative Example 1 A-1 25.0 25.0 25.0 R-3 25.0 NC-3000 (*1) 28.05 5.61 2.81 2.25 GPH-65 (*2) 0.63 2PHZ (* 3) 1.25 0.25 0.25 0.10 DMAC 65.0 65.0 65.0 65.0 *ι: Epoxy resin manufactured by Nippon Kayaku Co., Ltd., biphenyl skeleton 环氧树脂 epoxy resin 'epoxy equivalent 280g/eq 2 · hardener' Co., Ltd., 3 phenolic hydroxyl resin of biphenyl skeleton, active hydrogen equivalent 2 〇 5 g / eq. * 3: hardening accelerator 'Siguo Chemical Co., Ltd., 2-phenyl-4,5- Examples 4, 5, and 6 and Comparative Example 2 The resin compositions of Examples 1, 2, and 3 and Comparative Example 1 were applied to a PET film so as to have a thickness of 20 μm after drying. On the other hand, the PET crucible was removed after drying for 1 knives with i4 〇 °c, thereby obtaining a film of the epoxy resin composition of the present invention and comparatively. Examples 7, 8, 9, and Comparative Example 3 The combs specified in IPC-SM-840 formed by the use of poly(imide) copper-clad laminates were made by Xilu D (trade name, manufactured by Ube Industries, Ltd.). ^'electrode (conductor/line spacing=50 // m/50 // m) is used as an evaluation circuit, and the invention and the comparative use 26 201026748 are bonded to the embodiments 4, 5, 6 and the comparative example 2 The film was heat-pressed at 200 ° C and 5 MPa for 60 minutes to prepare a sample for electrical reliability test (the present invention and a laminate for comparison). An ion migration plus 'speed tester was used to apply a direct current of 50 V at 121 ° C, l〇〇% RH. The electrode was pressed between the electrodes, and the continuous resistance (PCBT) of the insulation resistance value was measured at 1000 hours. The time when the insulation resistance value was 10 or less ohms of 10 was measured, and as a result, it was 1000 hours or more. Examples 10, 11, 12, and Comparative Example 4 The films obtained in Examples 4, 5, and 6 and Comparative Example 2 were cut into a square having a side length of 20 cm, and were sandwiched by a Teflon (registered trademark) plate using a hot plate. The press machine was heat-treated at 200 ° C and 5 MPa for 60 minutes to be cured, and the cured film of the present invention and the comparative film were obtained. Flame retardancy of the cured product, glass transition temperature (Tg) obtained by TMA measurement, coefficient of linear expansion (CTE) between 100 and 200 °C, glass transition temperature (Tg) obtained by DMA measurement, and elasticity at 30 °C The modulus is shown in Table 3. [Table 3] Example 10 Example 11 Example 12 Comparative Example 4 Flame retardancy V-0 V-0 V-0 V-1 TMA-Tg (°C) 326 400 ° C or more 400 ° C or more 255 TMA- CTE (ppm) 43.6 41.5 36.2 65.1 DMA-Tg (°C) 320 331 342 248 Elastic modulus (MPa) 3250 4330 52000 3210 Examples 13, 14, 15, Comparative Example 5 Examples 1, 2, 3 and comparison The resin composition of Example 1 was applied to a thickness of 25 &quot; 27 201026748 m by using an applicator so as to have a thickness of 20 / zm after drying (Ubi Rex 25SGA, Ube Industries Co., Ltd.) After the preparation of the company, the solvent was removed at 140 ° C for 10 minutes to obtain a bisexex film with an adhesive layer (Comparative Examples 16 , 17 , 18 of the present invention and comparative coating films) Example 6 The calendered copper box having a thickness of 18 νηι was attached to the subsequent layer of the Rex-Rex film of the adhesive layer obtained in Examples 13, 14, 15 and Comparative Example 5 (BHN foil manufactured by Nippon Mining Materials Co., Ltd.) The roughened surface was heated and crimped at 230 ° C and 5 MPa for 60 minutes using a hot plate press to obtain a single-sided copper-coated tree for use in the present invention. A laminated board was used to measure the peeling of the copper foil and the resin layer by the method of JIS C648 1 using a universal tensile tester (Tensilon) (manufactured by Toyo Paulo Co., Ltd.). The results were all 8 to 11 N/cm. Examples 19, 20, 21 and Comparative Example 7 The resin compositions of Examples 1, 2, 3 and Comparative Example 1 were coated with a roll coater so that the thickness after drying was 20, from the method of m, was applied to a roughened surface of a rolled copper foil (manufactured by Nippon Mining Materials Co., Ltd., bhn foil) having a thickness of igy m, and the solvent was removed under a drying condition of 14 (TC '10 minutes. Cutting 2 pieces of rolled copper foil with a backing layer of 20 cm and having the following layers were brought into contact with each other, and the same layer was brought into contact with each other by a hot plate press at 23 (TC, 5 MPa for 60 minutes by heating). And a double-sided copper-clad resin laminated board for comparison. The obtained double-sided copper-coated resin laminated board is subjected to a universal tensile testing machine (manufactured by Toyo Paro, Inc.) to measure copper foil and according to the method of JIS C6481. Peel strength of copper foil, the result is 1 〇~14N /cm. Example 22' 23, 24, Comparative Example 8 28 201026748 The film of Becker Examples 4, 5, 6 and Comparative Example 2 was used to make the imine (Ubi Rex 25SGA, Ube Industries Co., Ltd.) There is ^ company ^ clamping, heated at 230 C, 5MPa for 6 〇 minutes to obtain the laminate of epoxy resin and polyurethane. For the obtained laminate, a universal tensile tester (manufactured by Toyo Baladwin Co., Ltd.) was used to measure the peel strength of the both of the brewed imine and the polyimine according to the method of JISC6481, and the results were all 8 to 9 N/cm. . °#This' The aromatic polyamine resin of the present invention is melted in a versatile base; the optional 'epoxy resin composition containing the same' can reduce the properties of the composition or the cured product thereof, It also provides hardening with low coefficient of linear expansion and excellent electrical properties. Therefore, the phenol resin ' of the present invention can be sufficiently used for the adhesiveness, heat resistance and flame retardancy of various substrates, and is suitable for use in a sheet, a cover film, a reinforcing sheet, a resin laminate, and the like. The present invention has been described with reference to the specific embodiments thereof, and it is understood that various changes and modifications can be made without departing from the spirit and scope of the invention. ❹ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Moreover, all of the reference frames cited herein are used in the present invention as a whole. [Simple description of the diagram] None [Key component symbol description] None 29

Claims (1)

201026748 VII. Patent application scope: 1. A polyamine resin (A) containing a phenolic hydroxyl group, which is represented by the following formula (2): am (In the formula (2), m and n are average values, satisfying the relationship of 8, and m + η is a positive number of 2 to 200' Αγ3 is selected from p-phenylenediamine, m-phenylenediamine, 4,4,-di a divalent aromatic group derived from one or more compounds of the group consisting of amine diisopropyl ether, 4,4'-diaminodiphenyl decane, 1,5-naphthalene monoamine, and 1,8-naphthalenediamine , q is the average number of substituents, which is an integer from 1 to 4. 2. The phenolic hydroxyl group-containing polyamine resin (A) according to the scope of the patent application, wherein m and n in the formula (7) satisfy the relationship of $, and the Aq is selected from the group consisting of p-phenylenediamine and A divalent aromatic group derived from one or more compounds of the group consisting of phenylenediamine and 4,4, diamine.匕 3. For example, the phenolic hydroxyl group-containing polyamine resin (A) of the patent scope or the second item of the patent range is 30 (TC above TC, and 100~2 〇 (line expansion between rc) The coefficient is 40 ppm or less. The epoxy resin composition containing the phenolic hydroxyl group-containing polyamine resin (A) and the epoxy tree 30 201026748 4 of the scope of claims ii to 3 The epoxy resin group of the item has a patent application for 5 types of film, which is applied for a patent to be processed into a thin sheet. ' 6. A flexible printed wiring board with a favorable range 4 items of epoxy resin composition. 7· - Articles of the patents of the fourth paragraph of the patent application scope, the film of the patent application scope 5 or the film of the sixth day of the patent application range ❹ /· - A reinforcing plate for a flexible printed wiring board, which has an epoxy resin composition of the fourth application of the patent scope or a cured layer thereof. 9. Covering a flexible printed wiring board Membrane (—η#), which has the epoxy resin composition of claim 4 or its hardened layer 10, a single-sided or double-sided metal-covered resin laminated board characterized by a single-sided or double-sided film of the patent application scope 或其5 or a hardened layer thereof, bonded to a single side or a single layer of a metal layer The surface of the resin covers the resin surface of the resin laminate. 11. A flexible printed wiring board using a film selected from the fifth item of the patent application scope, and the patent scope of the patent application: One of the group consisting of the reinforced plate of the eight items, the cover film of the ninth patent of the patent application, and the laminated board of the tenth application of the patent application. 12. A semiconductor insulating film having the patent application scope 4 The epoxy resin composition or the cured layer thereof. 13 - A method for producing a phenolic hydroxyl group-containing polyamine resin, which is a polyphenol resin containing a phenolic hydroxyl group in the scope of the patent application ( A) 'System made &lt;A&gt; selected from the group consisting of p-diamine, m-phenylenediamine, 4,4,-diaminodiphenyl 31 201026748 鲢, 4,4 amine-based, abbreviated, 丨, 5-naphthyl One or more compounds of the group consisting of diamine and iota, 8-naphthalenediamine, and &lt;B&gt; A phthalic acid and a phthalic acid as an optional component (of which 20 mol% or more and 100 mol% or less of the two are hydroxy phthalic acid) are subjected to a condensation reaction. 14. A phenolic hydroxyl group-containing polyamine A method for producing a resin (A) which is a polyamine resin (A) containing a sulfhydryl group according to item 2 of the patent scope, wherein &lt;A&gt; is selected from the group consisting of p-diamine, m-phenylenediamine and a compound of one or more of the group consisting of 4,4'-diaminodimethane, and &lt;B&gt; adipic acid and phthalate as an optional component (of which 50% by mole of the two) The above condensation reaction is carried out by 100 mol% or less of hydroxybenzoic acid. Eight, schema · ,, -- no 32