JP2012111895A - Thermosetting resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that produces a cured coating film having excellent heat resistance, mechanical properties and dimensional stability.SOLUTION: The composition comprises a polyamide-imide obtained by using trimellitic anhydride/3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride/3,3',4,4'-biphenyl tetracarboxylic acid dianhydride or 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride=70-90/5-25/5-25 (mol%) as an acid and 3,3'-dimethyl-4,4'-biphenyl diamine as an amine or 3,3'-dimethyl-4,4'-biphenyl diisocyanate as an isocyanate when the amount of the acid, the amine or the isocyanate is 100 mol%, respectively, and an aromatic boron compound represented by general formula (b1) (wherein Rs are each independently a hydrogen atom, 1-4C alkyl or 1-4C alkoxy) or another aromatic boron compound.

Description

  The present invention relates to a liquid thermosetting resin composition containing an imide resin that can be applied or cast. Specifically, when this composition is coated and cured, the heat resistance, flame retardancy, and mechanical properties, which are the original properties of polyimide resin, are further improved, and thermosetting properties are also excellent in dimensional stability. The present invention relates to a resin composition.

  In the heat-resistant coating materials field, electrical insulation materials such as interlayer insulation materials for printed wiring boards and semiconductor insulation materials, build-up materials, prepreg resins, heat-resistant adhesives, etc., the toughness, heat resistance, There has been a demand for a resin composition capable of obtaining a cured product excellent in halogen-free flame retardancy. In particular, there is a strong demand for downsizing such as ultra-thin flexible film substrates and rigid substrates in the field of electronic equipment such as computers. To meet this demand, flexibility in the protective layer, adhesive layer, and insulating layer of the substrate is required. It is essential to improve heat resistance, dimensional stability, halogen-free flame retardancy, and heat-resistant decomposition at high temperatures.

  The polyimide resin has excellent heat resistance and mechanical strength, and is preferably used in the electric and electronics industry. A polyimide resin having a hardened cured film is disclosed as an imide resin mainly composed of a tetracarboxylic acid anhydride having a structure connected to both ends of an alkylene by an ester bond as an acid anhydride and a diamine compound having an oxyalkylene structure. (For example, refer to Patent Document 1). However, since the imide resin described in Patent Document 1 contains an ester bond and an aliphatic ether structure, there is a problem that sufficient heat resistance, dimensional stability, flame retardancy, and heat decomposition resistance at high temperatures cannot be obtained. Have.

  Moreover, the polyimide resin which improved the solvent solubility using aliphatic and / or alicyclic components, such as sebacic acid and a cyclohexane dimethanol, is also disclosed as a structural component (for example, refer patent document 2). However, since the polyimide resin described in Patent Document 2 contains an aliphatic structure or an alicyclic structure, the polyimide resin also requires solvent solubility, so that sufficient heat resistance, dimensional stability, flame retardancy, high temperature The thermal decomposition resistance at is not obtained.

  Furthermore, a polyimide resin having a carboxyl group, a linear hydrocarbon structure, a urethane bond, and an isocyanurate structure is disclosed as a general-purpose organic solvent-soluble polyimide resin (see, for example, Patent Document 3). Although the polyimide resin disclosed in Patent Document 3 is soluble in a solvent other than N-methylpyrrolidone, the polyimide resin alone has poor film-forming properties, and the combined use of an epoxy resin is indispensable. Although a cured coating film obtained by using an epoxy resin in combination has heat resistance, this polyimide resin also has insufficient mechanical properties such as dimensional stability and toughness, and thermal decomposition resistance at high temperatures.

  As described above, in recent years, a polyimide resin excellent in dimensional stability has not been obtained due to much efforts to improve solvent solubility.

JP 2006-22302 A JP 2007-138000 A JP 2003-292575 A

  The present invention provides a thermosetting resin composition having excellent dimensional stability in addition to heat resistance and mechanical properties, which are inherent characteristics of a polyimide resin, and a cured product obtained by curing the composition when cured. Is to provide.

  As a result of intensive studies, the present inventors have found that a resin composition containing a specific imide resin and a specific boron compound is excellent in flame retardancy, heat resistance and mechanical properties, high temperature thermal decomposition resistance and dimensional stability. The inventors have found that a film can be obtained and have completed the present invention.

  That is, the present invention provides trimellitic anhydride / 3,3 ′, 4,4′-benzophenonetetracarboxylic acid as the acid component when each of the acid component, amine component or isocyanate component of the polyamideimide resin is 100 mol%. Acid dianhydride / 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride or 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride = 70 to 90/5 to 25/5 To 25 (mol%) and 3,3′-dimethyl-4,4′-biphenyldiamine as the diamine component or 3,3′-dimethyl-4,4′-biphenyl diisocyanate as the diisocyanate component. Containing one or more boron compounds (B) selected from the group consisting of the following general formulas (b1) to (b3) There is provided a thermosetting resin composition that features Rukoto.

（式中Ｒ_１はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基または炭素原子数１〜４のアルコキシ基を表す。）

(In the formula, each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.)

（式中Ｒ_２は、それぞれ独立して水素、炭素原子数１〜４のアルキル基または炭素原子数１〜４のアルコキシ基を表す。Ｙは含窒素複素環化合物を表す。）

(In the formula, each R ₂ independently represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Y represents a nitrogen-containing heterocyclic compound.)

（式中Ｒ_３はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基または炭素原子数１〜４のアルコキシ基を表す。Ｚは含窒素複素環化合物を表す。）

(In the formula, each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Z represents a nitrogen-containing heterocyclic compound.)

  Moreover, this invention provides the hardened | cured material characterized by hardening the said thermosetting resin composition.

  When the thermosetting resin composition of the present invention is formed into a coating film, the coating film is excellent in flame retardancy, flexibility, heat resistance, thermal decomposition resistance at high temperatures, and dimensional stability, and is a coating agent and wiring interlayer insulation. It is useful for films, flexible metal-clad laminates, flexible printed wiring boards, adhesives and the like.

Hereinafter, the present invention will be described in detail.
The polyamideimide resin (A) used in the present invention is trimellitic anhydride / 3,3 ′, 4, as the acid component when each of the acid component, amine component or isocyanate component of the polyamideimide resin is 100 mol%. 4′-benzophenone tetracarboxylic dianhydride / 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride or 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride = 70 to 90 / 5 to 25/5 to 25 (mol%) and 3,3′-dimethyl-4,4′-biphenyldiamine as a diamine component or 3,3′-dimethyl-4,4′- as a diisocyanate component It is obtained using biphenyl diisocyanate.

  The polyamide-imide resin (A) can be produced by an ordinary method such as an isocyanate method, an acid chloride method, a low temperature solution polymerization method, or a room temperature solution polymerization method. Among these, from the viewpoint of reducing production costs and unreacted functional groups (carboxyl groups), a particularly preferred production method is an isocyanate method in which a polymer is obtained by a decarboxylation reaction.

  Trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride used in the production of polyamideimide (A) Examples of other acid components include terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, and 4,4′-benzophenone dicarboxylic acid. Acid, pyromellitic acid, trimellitic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, dimer acid, stilbene dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid Polycarboxylic acid such as acid, acid chloride of polyhydric carboxylic acid, pyromellitic anhydride, benzoic acid Non-tetracarboxylic anhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic anhydride, 3,3', 4,4'-diphenyltetracarboxylic anhydride, 4,4'-oxydiphthalic anhydride Thing etc. are mentioned.

  Examples of amine components other than 3,3′-dimethyl-4,4′-biphenyldiamine used in the production of polyamideimide (A) include p-phenylenediamine, m-phenylenediamine, and 3,4 ′ as amine components. -Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3, 3'-diaminobenzanilide, 4,4'-diaminobenzanilide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 2,6- Tolylenediamine, 2,4-Tolylenediamine, 4,4'-Diaminodiphenyl sulfide, 3,3'-diamino Phenyl sulfide, 4,4′-diaminodiphenylpropane, 3,3′-diaminodiphenylpropane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, P-xylenediamine, m-xylenediamine, 1,4 -Naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, 2,2'-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] Sulfone, bis [4- (3-aminophenoxy) phenyl] propane, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl and the like.

  Examples of amine components other than 3,3′-dimethyl-4,4′-biphenyl diisocyanate used in the production of polyamideimide (A) include, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m -Xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate, p- Xylene diisocyanate, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene, tetramethylxylylene diisocyanate, diphenylene ether-4,4′-diisocyanate and naphthalene diisocyanate Hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate and nor Bonu diisocyanate and the like.

  The polyamideimide resin of the present invention can be polymerized either in solution or in the solid phase, but solution polymerization is preferred from the viewpoint of versatility. Solvents used for synthesizing the polyamideimide of the present invention are dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylurea, dimethylsulfoxide, γ-butyrolactone, dimethylimidazolyl dinone and other high-boiling polar solvents alone or in mixed solvents However, it is not limited to these.

  The polyamide-imide resin of the present invention is synthesized by stirring at 50 to 250 ° C., preferably 80 to 230 ° C. in the above solvent, but amines such as triethylamine, lutidine, picoline, triethylenediamine, etc. are used to promote the reaction. , Lithium methylate, sodium methylate, lithium ethylate, sodium ethylate, magnesium ethylate, potassium butoxide, potassium fluoride, sodium fluoride, and other alkali metals, alkaline earth metal compounds, or cobalt, titanium, The reaction may be performed in the presence of a catalyst such as a metal such as tin or zinc, or a metalloid compound.

  The polyamideimide resin of the present invention has a logarithmic viscosity (measured in an N-methylpyrrolidone solution at 25 ° C. and a polymer concentration of 0.5 g / 100 ml) of 0.30 to 0.90 dl / g. This range is preferable from the viewpoint of fluidity and physical property balance during melt molding. If it is less than 0.30 dl / g, the obtained molded product is fragile and its use as an industrial part may be restricted. On the other hand, if it exceeds 0.90 dl / g, the fluidity of the melt is insufficient, so that the moldability is lowered, and there is a possibility that the thinning of the part which is one of the objects of the present invention is limited. Examples of means for adjusting the logarithmic viscosity of the polyamideimide resin include, but are not limited to, methods for controlling the equivalent ratio of reaction components, the order of addition, reaction time, reaction temperature, and the like.

  The polyamide-imide resin of the present invention needs to be taken out as a solid resin after the above solution polymerization. For example, the solvent may be evaporated and dried as it is, but in consideration of stability during subsequent molding, the solution is poured into a poor solvent such as water to solidify, and the solid resin is removed by filtration and dried. It is preferable to use a technique. The polyamideimide resin after drying may be pulverized to form a powder, or may be pelletized by melt kneading. As the poor solvent, water, glycols, cellosolves, alcohols and the like can be used.

  The polyimide resin (A) used in the present invention is preferably one that dissolves in an organic solvent. As the organic solvent to be used, for example, a conventionally used polar solvent organic solvent having a large dissolving power such as N-methylpyrrolidone, dimethylacetamide, and methylformamide can be used. However, nitrogen-containing polarities such as N-methylpyrrolidone can be used. Imide resins that are soluble only in solvents and the like have problems such as whitening due to hygroscopicity, and storage stability is insufficient. For this reason, the problem that the coating film (film) obtained using this resin cannot obtain the tough coating film and excellent electrical properties of the original imide resin arises. Therefore, an imide resin that is soluble in an organic solvent having a relatively weak solubility such as gamma butyrolactone (γ-butyrolactone) is more preferable.

  In addition, as the polyimide resin (A) used in the present invention, a polyimide resin that dissolves at around room temperature, for example, 10 to 30 ° C. is preferable, but an imide resin having crystallinity that dissolves at warming, for example, 100 to 150 ° C. It is possible to use. Especially, since the workability | operativity which forms a coating film becomes favorable, the imide resin which is soluble at 10-120 degreeC is more preferable.

  In the present invention, whether or not the polyimide resin (A) used in the present invention is dissolved in an organic solvent is determined by adding the polyimide resin concentration of the present invention to 10% by mass in an organic solvent and adding 7% at 25 ° C. After standing for days and hours, the appearance can be visually observed.

  The polyimide resin (A) used in the present invention is preferable because the polyimide resin dissolved in gamma butyrolactone is a polyimide resin having excellent storage stability, and when dissolved in gamma butyrolactone so that it becomes 10% by mass at 25 ° C. A polyimide resin that is soluble in water is preferred. In order to obtain a polyimide resin that dissolves in gamma butyrolactone, it can be obtained, for example, by a method for producing a polyimide resin described later.

  The polyimide resin (A) used in the present invention may be a polyimide resin having a linear structure or a polyimide resin having a branched structure. Further, the copolymer component may have a polyester-modified polyesterimide or urethane-modified polyurethaneimide structure.

  Examples of the terminal structure of the polyimide resin (A) used in the present invention include structures such as carboxylic acid, carboxylic acid anhydride, isocyanate group, and amine group. As the terminal structure, the structure of the carboxylic acid or its anhydride is preferable because the stability of the polyimide resin itself of the present invention and the stability after blending with an organic solvent or another resin are good. When the terminal structure is a carboxylic acid or its anhydride structure, the acid value is a polyimide resin with a solid content acid value of 1 to 50 that is easy to handle, and a film or molded product having excellent mechanical strength and dimensional stability can be obtained. To preferred.

  The molecular weight of the polyimide resin (A) used in the present invention is preferably from 1,000 to 200,000, and more preferably from 2,000 to 100,000, since a polyimide resin (A) that is easy to handle and a film or a molded product having excellent mechanical strength and dimensional stability can be obtained. The molecular weight can be measured by GPC or quantitative determination of the terminal functional group.

  The boron compound (B) used in the present invention is one or more boron compounds selected from the group consisting of the following general formulas (b1) to (b3). By selecting a boron compound having such a structure, it is possible to obtain a cured product having particularly excellent dimensional stability, flame retardancy, thermal decomposition resistance at high temperature, dimensional stability, and mechanical properties. The inventor of the present invention considers that the reason why a cured product having such characteristics is obtained is that an imide moiety or an amide moiety is complexed with a boron moiety.

（式中Ｒ_１はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基または炭素原子数１〜４のアルコキシ基を表す。）

(In the formula, each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.)

（式中Ｒ_２は、それぞれ独立して水素、炭素原子数１〜４のアルキル基または炭素原子数１〜４のアルコキシ基を表す。Yは含窒素複素環化合物を表す。）

(In the formula, each R ₂ independently represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Y represents a nitrogen-containing heterocyclic compound.)

（式中Ｒ_３はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基または炭素原子数１〜４のアルコキシ基を表す。Ｚは含窒素複素環化合物を表す。）

(In the formula, each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Z represents a nitrogen-containing heterocyclic compound.)

  Examples of the nitrogen-containing heterocyclic compound include various imidazole compounds represented by pyridine, pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridazine, pyrazine, piperazine, morpholine, pyricidine and the like. It is.

  In the compound represented by (b2), Y is preferably pyridine. In the compound represented by (b3), (Z) is preferably an imidazolium salt.

  The compound represented by (b1) is, for example, a cyclic boron compound in which R1 is represented by a hydrogen atom, a methyl group, an ethyl group, etc., for example, tris (phenylboric acid) anhydride or tris (methylphenylboric acid). ) Anhydride and the like.

  Examples of the compound represented by (b2) include pyridine salt of triphenylboron, pyridine salt of tri (monomethylphenyl) boron, pyrazole salt of triphenylboron, and the like.

  Examples of the compound represented by (b3) include tetraethyl boron 2-ethyl-4-methyl-imidazole salt as tetraphenyl boron imidazole salt, 2-ethyl-4-methyl-imidazole salt as tetramethyl phenyl boron, and the like. Is mentioned.

  Among the boron compounds (B), the boron compounds represented by the formulas (b2) and (b3) are preferable because a resin composition having excellent solubility is obtained and a cured product having excellent mechanical properties is obtained. Among the boron compounds represented by the formula (b2), a pyridine salt of triphenylboron is more preferable, and among the boron compounds represented by the formula (b3), a 2-ethyl-4-methyl-imidazole salt of tetraphenylboron is more preferable. .

  As a composition mixture ratio of the said polyimide resin (A) and a boron compound (B), 0.5-30 mass parts is preferable with respect to 100 mass parts of polyimide resin (A) solid content total. Especially, 0.5-20 mass parts is preferable, and 1-15 mass parts is more preferable.

  In order to prepare the thermosetting resin composition of the present invention, for example, the polyimide resin (A) and the boron compound (B) may be simply mixed or may be dissolved by heating after mixing. As the thermosetting resin composition of the present invention, it is preferable that the boron compound (B) is dissolved. In order to dissolve the boron compound (B), for example, after mixing the polyimide resin (A) and boric acid and / or boron compound (B), 50 to 200 ° C., preferably 80 to 180 ° C. for 1 minute to 60 Stir for minutes.

  In addition to the boron compound (B), a boron compound such as boric acid and / or a boric acid ester can be used in combination with the thermosetting resin composition of the present invention. Examples of such compounds include boric acid; trialkyl such as trimethyl borate, triethyl borate, tributyl borate, tri-n-octyl borate, tri (triethylene glycol methyl ether) borate ester, tricyclohexyl borate, and trimenthyl borate. Linear aliphatic borate esters typified by borate esters; aromatic borate esters such as tri-o-cresyl borate, tri-m-cresyl borate, tri-p-cresyl borate, triphenyl borate, tri Boric acid esters containing two or more boron atoms such as (1,3-butanediol) biborate, tri (2-methyl-2,4-pentanediol) biborate, trioctylene glycol diborate, etc. and containing a cyclic structure ; Polyvinyl alcohol borate ester Xylene glycol anhydrous boric acid to.

  When a compound other than the boron compound (B) is added to the thermosetting resin composition of the present invention, a thermosetting resin composition having good storage stability is obtained, and a cured coating film having excellent dimensional stability is obtained. Therefore, boric acid and linear aliphatic borate esters are preferable. Among the linear aliphatic borate esters, trialkyl borate esters having 4 to 20 carbon atoms are preferable, and tributyl borate (tributyl borate) is particularly preferable.

  Other thermosetting resin components can be further added to the thermosetting resin composition of the present invention. Specifically, an epoxy resin (D), an isocyanate compound, a silicate, an alkoxysilane compound, a melamine resin, etc. are mentioned, for example.

  The epoxy resin preferably has two or more epoxy groups in the molecule. Examples of such an epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin; Epoxy resins; epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols; biphenyl type epoxy resins such as epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol; Epoxy resin having naphthalene skeleton; aromatic epoxy resin such as epoxy resin having fluorene skeleton and hydrogenated product of these aromatic epoxy resins; neopentyl glycol diglycidyl Aliphatic epoxy resins such as ether and 1,6-hexanediol diglycidyl ether; fats such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate Cyclic epoxy resins; and heterocyclic ring-containing epoxy resins such as triglycidyl isocyanurate. Among these, an aromatic epoxy resin is preferable because a thermosetting polyimide resin composition excellent in opportunity physical properties of a cured coating film is obtained, and a novolac type epoxy resin is more preferable.

  The blending amount of the polyimide resin (A) and the epoxy resin (D) used in the present invention is such that (A) / (D) is used at a ratio of 1/50 to 50/1 as a mass ratio of the resin. More preferably, it is 1/10 to 10/1.

  Examples of the isocyanate compound include aromatic isocyanate compounds, aliphatic isocyanate compounds, and alicyclic isocyanate compounds. Preferably, a polyisocyanate compound having two or more isocyanate groups in one molecule is preferable. A blocked isocyanate compound can also be used.

  Examples of the alkylalkoxysilane include alkyltrialkoxysilane and dialkyldialkoxysilane.

  Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, Examples thereof include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, and phenyltributoxysilane.

  Examples of the dialkyl dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, and diphenyldimethoxy. Silane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldipropoxysilane, methylethyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane , Methylphenyldipropoxysilane, methylphenyldibutoxysilane, trimethylmethoxysilane, trimethyl ether Kishishiran, triethyl silane, triethyl silane, triphenyl methoxy silane, triphenyl ethoxy silane, and the like.

  Moreover, the condensate of alkyl alkoxysilane can also be used, for example, the condensate of the above-mentioned alkyl trialkoxysilane, the condensate of dialkyl dialkoxysilane, etc. are mentioned.

  As the melamine resin, for example, an alkoxylated melamine resin obtained by reacting a part or all of a methylol product obtained by reaction of a triazine ring-containing amino compound such as melamine or benzoguanamine with formaldehyde is used with an alcohol compound. be able to. As the alcohol compound used here, a lower alcohol having about 1 to 4 carbon atoms can be used. Specifically, a methoxymethylolated melamine resin, a butylated methylolated melamine resin, or the like can be used. The molecular structure may be completely alkoxylated, a methylol group may remain, or an imino group may remain.

  This alkoxylated melamine resin, in the thermosetting resin composition of the present invention, has the effect of preventing precipitation with time when boric acid and / or boric acid esters are added in addition to the improvement of heat resistance and physical properties as a crosslinking component. Yes, it improves the stability as a thermosetting resin composition.

  As the resin structure of the alkoxylated melamine resin, the methoxymethylolated melamine resin is preferable because of compatibility with the polyimide resin and good curability at the time of curing, and more preferably, a methoxymethylol having a methoxylation rate of 80% or more. A melamine resin is more preferable.

  The resin structure may be a polynuclear body by self-condensation. The degree of polymerization at this time is preferably about 1 to 5 in terms of compatibility and stability, and more preferably about 1.2 to 3.

  As the number average molecular weight of the alkoxylated melamine resin, those having a molecular weight of 100 to 10,000 can be used. Preferably, 300 to 2000 is preferable in terms of compatibility with the polyimide resin and curability at the time of curing, and more preferably 400 to 1000.

  As the alkoxylated melamine resin, even if melamine, benzoguanamine, formalin and alcohol are simultaneously charged and reacted, melamine or benzoguanamine and formalin are reacted in advance to obtain a methylolated melamine compound and then alkoxylated with the alcohol compound. May be.

  Specific examples of commercially available alkoxylated melamine resins include, for example, product Cymel 300, 301, 303, and 305 manufactured by Nippon Cytec Industries, as methoxymethylolated melamine resins. Examples of the methylol group-containing methoxymethylolated melamine resin include product Cymel 370 and 771 manufactured by Nippon Cytec Industries. Examples of the imino group-containing methoxylated melamine resin include commercial Cymel 325, 327, 701, 703, and 712 manufactured by Mitsui Cytec Co., Ltd. Examples of the methoxylated butoxylated melamine resin include product Cymel 232, 235, 236, 238, 266, 267, 285 manufactured by Nippon Cytec Industries. Examples of the butoxylated melamine resin include product Uban 20SE60 manufactured by Nippon Cytec Industries.

  The amount of the alkoxylated melamine resin used is 1 to 80 parts by mass, preferably 1 to 50, based on the total 100 masses of the polyimide resin (A) and the boron compound (B) because of excellent mechanical properties and high TG. A mass part and 1-30 mass parts are preferable.

  Further, the thermosetting resin composition of the present invention includes a binder resin such as polyester, phenoxy resin, PPS resin, PPE resin, polyarylene resin, phenol resin, melamine resin, alkoxysilane curing agent, polybasic acid anhydride, cyanate compound. Curing such as curing agents or reactive compounds such as melamine, dicyandiamide, guanamine and derivatives thereof, imidazoles, amines, phenols having one hydroxyl group, organic phosphines, phosphonium salts, quaternary ammonium salts, photocationic catalysts, etc. It is also possible to add a defoaming agent, leveling agent, slip agent, wetting improver, anti-settling agent, flame retardant, antioxidant, ultraviolet absorber, etc. as a catalyst, curing accelerator, further filler, and other additives .

  In addition, various fillers, organic pigments, inorganic pigments, extender pigments, rust inhibitors and the like can be added to the thermosetting resin composition of the present invention as necessary. These may be used alone or in combination of two or more.

  Examples of the filler include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, and alumina. Is mentioned.

  As the filler, those having various particle sizes can be used, and can be added to such an extent that the physical properties of the present resin and its composition are not impaired. Such an appropriate amount is in the range of about 5 to 80% by mass, and preferably used after being uniformly dispersed. As a dispersion method, it is possible to carry out dispersion by a known roll, bead mill, high-speed dispersion or the like, and the surface of the particles may be modified in advance with a dispersion treatment agent.

  Examples of the organic pigment include azo pigments; copper phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, and quinacridone pigments.

  Examples of the inorganic pigment include chromates such as chrome lead, zinc chromate and molybdate orange; ferrocyanides such as bitumen, titanium oxide, zinc white, bengara, iron oxide; metal oxides such as chromium carbide green, Cadmium yellow, cadmium red; metal sulfides such as mercury sulfide; selenides; sulfates such as lead sulfate; silicates such as ultramarine; carbonates, cobalt biored; phosphates such as manganese purple; aluminum powder, zinc dust Metal powders such as brass powder, magnesium powder, iron powder, copper powder and nickel powder; carbon black and the like.

  In addition, any of other coloring, rust prevention, and extender pigments can be used. These may be used alone or in combination of two or more.

  The thermosetting resin composition of the present invention can be dried or cured by heating at 100 to 300 ° C. after coating or molding.

  The substrate used in the method for forming the coating film can be used without any particular limitation. Examples of the substrate include plastic, metal, wood, glass, inorganic material, and composite materials thereof.

  The thermosetting resin composition of the present invention is a film (adhesive film) comprising a resin and a composition layer (A layer) and a support film (B layer), which is a suitable form for producing a flexible circuit board. ).

  The adhesive film is prepared according to various methods, for example, by preparing a resin varnish obtained by dissolving the thermosetting resin composition of the present invention in an organic solvent, applying the resin varnish to a support film, and heating or blowing hot air. It can manufacture by drying an organic solvent and forming a resin composition layer.

  The support film (B layer) serves as a support when the adhesive film is produced, and is finally peeled off or removed in the production of the flexible circuit board. Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, and release paper and copper foil. The metal foil etc. can be mentioned. In addition, when using copper foil as a support body film, it can remove by etching with etching liquid, such as ferric chloride and cupric chloride. The support film may be subjected to a release treatment in addition to a mat treatment and a corona treatment, but it is more preferable that the release treatment is performed in consideration of releasability. Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers.

  Organic solvents for preparing the varnish include, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, cellosolve, butyl Examples thereof include carbitols such as carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and gamma butyrolactone. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition is usually 5% by mass or less, preferably 3% by mass or less. The specific drying conditions vary depending on the curability of the resin composition and the amount of the organic solvent in the varnish. It can be dried to some extent. Those skilled in the art can appropriately set suitable drying conditions by simple experiments.

  The thickness of the resin composition layer (A layer) can usually be in the range of 5 to 500 μm. The preferred range of the thickness of the A layer varies depending on the use of the adhesive film, and when used for manufacturing a multilayer flexible circuit board by the build-up method, the thickness of the conductor layer forming the circuit is usually 5 to 70 μm. The thickness of the A layer corresponding to the layer is preferably in the range of 10 to 100 μm.

  The A layer may be protected with a protective film. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The protective film is peeled off during lamination. As the protective film, the same material as the support film can be used. Although the thickness of a protective film is not specifically limited, Preferably it is the range of 1-40 micrometers.

  The adhesive film obtained using the thermosetting resin composition of the present invention can be suitably used particularly for the production of multilayer flexible circuit boards. Below, the method to manufacture a multilayer flexible circuit board is demonstrated. The adhesive film obtained using the thermosetting resin composition of the present invention can be suitably laminated on a flexible circuit board by a vacuum laminator. The flexible circuit board used here is mainly composed of a conductive layer (circuit) patterned on one or both sides of a substrate such as a polyester substrate, a polyimide substrate, a polyamideimide substrate, or a liquid crystal polymer substrate, as well as alternating circuits and insulating layers. It is also possible to use a multilayer flexible circuit board that is layered and has a circuit formed on one or both sides for further multilayering. In addition, from the viewpoint of adhesion of the insulating layer to the circuit board, the surface of the circuit should have been previously roughened with a surface treatment agent such as hydrogen peroxide / sulfuric acid or MEC Etch Bond (MEC Co., Ltd.). preferable.

  Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo Morton, a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Techno Engineering Co., Ltd., Hitachi AIC ( A vacuum laminator manufactured by Co., Ltd. can be mentioned.

In the lamination, when the adhesive film has a protective film, the protective film is removed, and then the adhesive film is pressure-bonded to the circuit board while being pressurized and heated. The laminating conditions include pre-heating the adhesive film and the circuit board as required, laminating at a pressure of preferably 70 to 140 ° C., a pressure of pressure of preferably 1 to 11 kgf / cm ² and laminating under a reduced pressure of an air pressure of 20 mmHg or less. preferable. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the adhesive film on the circuit board, it is cooled to around room temperature and the support film is peeled off. Next, the thermosetting resin composition laminated on the circuit board is cured by heating. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes. When the support film has a release layer or a release layer such as silicon, the support film can be peeled after the thermosetting resin composition is heat-cured or after heat-curing and punching.

  After the insulating layer, which is a cured product of the thermosetting resin composition, is formed, the via holes and through holes are formed by drilling the circuit board as necessary using a method such as drilling, laser, plasma, or a combination thereof. May be. In particular, drilling with a laser such as a carbon dioxide laser or a YAG laser is generally used.

  Next, surface treatment of the insulating layer (cured product of the thermosetting resin composition) is performed. The surface treatment can employ a method used in a desmear process, and can be performed in a form that also serves as a desmear process. As a chemical used in the desmear process, an oxidizing agent is generally used. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, and the like. Preferably, an alkaline permanganate solution (for example, potassium permanganate, sodium hydroxide aqueous solution of sodium permanganate), which is an oxidizer widely used for roughening the insulating layer in the production of multilayer printed wiring boards by the build-up method. It is preferable to carry out the treatment using A treatment with a swelling agent can also be performed before the treatment with the oxidizing agent. Further, after the treatment with an oxidizing agent, neutralization treatment with a reducing agent is usually performed.

  After the surface treatment, a conductor layer is formed by plating on the surface of the insulating layer. The conductor layer can be formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

  As a method for forming a circuit by patterning the conductor layer, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. In the case of the subtractive method, the thickness of the electroless copper plating layer is 0.1 to 3 μm, preferably 0.3 to 2 μm. An electroplating layer (panel plating layer) is formed thereon with a thickness of 3 to 35 μm, preferably 5 to 20 μm, an etching resist is formed, and etching is performed with an etching solution such as ferric chloride or cupric chloride. After forming a conductor pattern by this, a circuit board can be obtained by peeling an etching resist. In the case of the semi-additive method, after forming the electroless copper plating layer with an electroless copper plating layer thickness of 0.1 to 3 μm, preferably 0.3 to 2 μm, a pattern resist is formed, and then the electrolytic copper A circuit board can be obtained by peeling after plating.

  A film in which the support film is replaced with a heat-resistant resin layer (heat-resistant resin film), that is, a film comprising the thermosetting composition layer (A layer) and the heat-resistant resin layer (C layer) of the present invention is a flexible circuit board. Can be used as a base film. A film comprising the thermosetting resin composition layer (A layer), the heat-resistant resin layer (C layer) and the copper foil (D layer) of the present invention can be used as a base film of a flexible circuit board as well. In this case, the base film has a layer structure in the order of A layer, C layer, and D layer. In the base film as described above, the heat-resistant resin layer is not peeled off and constitutes a part of the flexible circuit board.

  A film in which an insulating layer (A ′ layer) made of a cured product of the thermosetting resin composition of the present invention is formed on a heat-resistant resin layer (C layer) can be used as a base film for a single-sided flexible circuit board. Moreover, it consists of the film which has the layer structure of the order of A 'layer, C layer, and A' layer, and A 'layer, C layer, and copper foil (D layer), and the order of A' layer, C layer, and D layer. Similarly, a film having a layer structure can be used as a base film for a double-sided flexible circuit board.

  Examples of the heat-resistant resin used for the heat-resistant resin layer include a polyimide resin, an aramid resin, a polyamideimide resin, and a liquid crystal polymer. In particular, a polyimide resin and a polyamideimide resin are preferable. Moreover, on the characteristic used for a flexible circuit board, the breaking strength is 100 MPa or more, the breaking elongation is 5% or more, the thermal expansion coefficient between 20 and 150 ° C. is 40 ppm or less, and the glass transition temperature is 200 ° C. or more or the decomposition temperature is 300 ° C. It is preferable to use the above heat resistant resin.

  As the heat-resistant resin satisfying such characteristics, a heat-resistant resin that is commercially available in the form of a film can be suitably used. For example, a polyimide film “Upilex-S” manufactured by Ube Industries, Ltd., Toray DuPont Co., Ltd. ) Polyimide film "Kapton", Kaneka Chemical Co., Ltd. polyimide film "Apical", Teijin Advanced Films Ltd. "Aramika", Kuraray Co., Ltd. liquid crystal polymer film "Bexstar", Sumitomo Bakelite Co., Ltd. A polyether ether ketone film “Sumilite FS-1100C” and the like are known.

  The thickness of the heat-resistant resin layer is usually 2 to 150 μm, preferably 10 to 50 μm. As the heat-resistant resin layer (C layer), a surface-treated layer may be used. Examples of the surface treatment include dry treatment such as mat treatment, corona discharge treatment and plasma treatment, chemical treatment such as solvent treatment, acid treatment and alkali treatment, sand blast treatment and mechanical polishing treatment. In particular, from the viewpoint of adhesion to the A layer, it is preferable that plasma treatment is performed.

  A base film for a single-sided flexible circuit board comprising an insulating layer (A ′) and a heat-resistant resin layer (C) can be produced as follows. First, similarly to the adhesive film described above, a resin varnish prepared by dissolving the thermosetting resin composition of the present invention in an organic solvent is prepared, and this resin varnish is applied on a heat-resistant resin film, and heated or blown with hot air, etc. The organic solvent is dried to form a thermosetting resin composition layer. Conditions such as the organic solvent and drying conditions are the same as those for the adhesive film. The thickness of the resin composition layer is preferably in the range of 5 to 15 μm.

  Next, the thermosetting resin composition layer is dried by heating to form an insulating layer of the thermosetting resin composition. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes.

  The production of a base film of a double-sided flexible circuit board film consisting of three layers of an insulating layer (A ′ layer), a heat-resistant resin layer (C) layer and a copper foil (D layer) is made of a heat-resistant resin layer (C layer) and a copper foil. A resin composition may be formed on a copper-clad laminated film made of (D layer) and manufactured in the same manner as described above. Examples of the copper-clad laminated film include a cast method two-layer CCL (Copper-clad laminate), a sputtering method two-layer CCL, a laminate method two-layer CCL, and a three-layer CCL. The thickness of the copper foil is preferably 12 μm or 18 μm.

  Commercially available two-layer CCL includes Espanex SC (manufactured by Nippon Steel Chemical Co., Ltd.), Neoprex I <CM>, Neoprex I <LM> (Mitsui Chemicals), S'PERFLEX (Sumitomo Metal Mining Co., Ltd.) Nikaflex F-50VC1 (manufactured by Nikkan Kogyo Co., Ltd.) and the like are mentioned as the commercially available three-layer CCL.

  The production of a base film for a double-sided flexible circuit board film comprising three layers of an insulating layer (A ′ layer), a heat-resistant resin layer (C layer) and an insulating layer (A ′ layer) can be carried out as follows. First, in the same manner as the adhesive film described above, a resin varnish prepared by dissolving the thermosetting resin composition of the present invention in an organic solvent is prepared, and this resin varnish is applied onto a support film, and organic by heating or hot air blowing, etc. The solvent is dried to form a resin composition layer. Conditions such as the organic solvent and drying conditions are the same as those for the adhesive film. The thickness of the resin composition layer is preferably in the range of 5 to 15 μm.

  Next, this adhesive film is laminated on both surfaces of the heat resistant resin film. Lamination conditions are the same as described above. Moreover, if the resin composition layer is previously provided on one side of the heat-resistant film, the lamination may be only on one side. Next, the resin composition layer is cured by heating to form an insulating layer that is a layer of the resin composition. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes.

  A method for producing a flexible circuit board from the base film for the flexible circuit board will be described. In the case of a base film composed of an A ′ layer, a C layer, and an A ′ layer, first, after heat curing, a circuit board is drilled by a method such as drilling, laser, or plasma to form a through hole for conduction on both sides. . In the case of a base film composed of an A ′ layer, a C layer, and a D layer, holes are formed by the same method to form via holes. In particular, drilling with a laser such as a carbon dioxide laser or a YAG laser is generally used.

  Next, a surface treatment of the insulating layer (resin composition layer) is performed. About surface treatment, it is the same as that of the case of the adhesive film mentioned above. After the surface treatment, a conductor layer is formed by plating on the surface of the insulating layer. The formation of the conductor layer by plating is the same as in the case of the adhesive film described above. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

  Next, the conductor layer is patterned to form a circuit to obtain a flexible circuit board. When a base film composed of an A layer, a C layer, and a D layer is used, a circuit is also formed on the copper foil that is the D layer. As a circuit formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. Details are the same as in the case of the adhesive film described above.

  The single-sided or double-sided flexible circuit board obtained in this way can be produced as a multilayer flexible circuit board by using the adhesive film of the present invention, for example, as described above.

  The resin composition of the present invention is also useful as a material for forming a stress relaxation layer between a semiconductor and a substrate substrate. For example, in the same manner as described above, all or part of the uppermost insulating layer of the substrate substrate is formed by the adhesive film obtained by using the resin composition of the present invention, and the resin is connected by connecting the semiconductor. A semiconductor device in which a semiconductor and a substrate substrate are bonded via a cured product of the composition can be manufactured. In this case, the thickness of the resin composition layer of the adhesive film is appropriately selected within a range of 10 to 1000 μm. With the resin composition of the present invention, a conductor layer can be formed by plating, and a circuit pattern can also be produced by simply forming a conductor layer by plating on an insulating layer for stress relaxation provided on a substrate substrate. Is possible.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, all parts and “%” are based on mass unless otherwise specified.

Synthesis Example 1 [Preparation of polyamideimide resin (A)]
Trimellitic anhydride (hereinafter abbreviated as TMA; 150 ° C., 1 Torr sublimation purification; purity 99.9 mol%, trimellitic acid content 0.1 mol%), 172.9 g (90 mol%), 3 3 ', 4, 4'-diphenyl ether tetracarboxylic dianhydride (hereinafter ODPA; purity 99%) 31.0 g (10 mol%), 3, 3'-dimethyl-4, 4'-biphenyl diisocyanate (hereinafter TODI) Purity 99%) 264.3 g (100 mol%), N-methyl-2-pyrrolidone (hereinafter referred to as NMP; purity 99.9% or more) 2155 g, triethylenediamine 2.5 g were added, up to 100 ° C. under a nitrogen stream. The temperature was raised and reacted at 100 ° C. for 3 hours. Subsequently, it was made to react at 160 degreeC for 2 hours, and 180 degreeC for 2 hours, NMP630g (polymer concentration 12 weight%) was added, and it cooled to room temperature, and obtained the solution of the polyamidoimide resin (A1).

Synthesis example 2 (same as above)
In a reaction vessel, 153.7 g (80 mol%) of TMA, 15.5 g (5 mol%) of ODPA, 38.3 ′, 4′-benzophenone tetracarboxylic dianhydride (hereinafter referred to as BTDA; purity 99%) 48.3 g ( 15 mol%), TODI 264.3 g (100 mol%), diazabicyclo [5.4.0] undecene-7 (hereinafter DBU) 1.5 g, and NMP 2230 g were added, and the temperature was raised to 100 ° C. under a nitrogen stream. The reaction was carried out at 2 ° C. for 2 hours. Subsequently, after making it react at 160 degreeC for 3 hours, 658g (polymer concentration 12 weight%) of NMP was added, and it cooled to room temperature, and obtained the solution of the polyamideimide resin (A2).

Synthesis example 3 (same as above)
In a reaction vessel, 153.7 g (80 mol%) of TMA, 48.3 g (15 mol%) of BTDA, 14.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA; purity 99%) 5 mol%), TODI 264.3 g (100 mol%), DBU 1.5 g, and NMP (purity 99.9%) 2230 g were added, the temperature was raised to 100 ° C. under a nitrogen stream, and the reaction was carried out at 100 ° C. for 2 hours. . Subsequently, after making it react at 150 degreeC for 1 hour, NMP1307g (polymer concentration 10 weight%) was added, it cooled to room temperature, and the solution of the polyamideimide resin (A3) was obtained.

Synthesis example 4 (same as above)
In a reaction vessel, 153.7 g (80 mol%) of TMA, 48.3 g (15 mol%) of BTDA, 20.5 g (5 mol%) of ethylene glycol bis (anhydrotrimellitate) (TMEG; purity 99%), 264.3 g of TODI (100 mol%), 1.5 g of DBU and 598 g of NMP were added, the temperature was raised to 100 ° C. under a nitrogen stream, and the reaction was carried out at 100 ° C. for 5 hours. Next, 997 g of NMP was added and reacted at 160 ° C. for 3 hours, 849 g of NMP (polymer concentration 14% by weight) was further added, and the mixture was cooled to room temperature to obtain a solution of polyamideimide resin (A4).

Synthesis example 5 (same as above)
In a reaction vessel, 153.7 g (80 mol%) of TMA, 32.2 g (10 mol%) of BTDA, 14.7 g (5 mol%) of BPDA, 15.5 g (5 mol%) of ODPA, 264.3 g (100 mol%) of TODI, DBU1. 5 g and 2220 g of NMP were added, the temperature was raised to 100 ° C. under a nitrogen stream, and the reaction was carried out at 100 ° C. for 2 hours. Subsequently, after making it react at 160 degreeC for 3 hours, it cooled to room temperature and obtained the solution of the polyamidoimide resin (A5).

Synthesis example 6 (same as above)
To the reaction vessel, 134.5 g (70 mol%) of TMA, 80.6 g (25 mol%) of BTDA, 14.7 g (5 mol%) of BPDA, 264.3 g (100 mol%) of TODI, 1.5 g of DBU, and 2500 g of NMP were added, and a nitrogen stream was added. Then, the temperature was raised to 100 ° C. and reacted at 100 ° C. for 2 hours. Subsequently, after making it react at 150 degreeC for 3 hours, it cooled to room temperature and obtained the solution of the polyamideimide resin (A6).

Example 1
The thermosetting resin composition 1 of the present invention was prepared with the formulation shown in Table 1. The composition was adjusted by mixing and stirring at room temperature. The heat resistance, flame retardancy, mechanical properties and dimensional stability of the obtained thermosetting resin composition 1 were evaluated according to the following methods. The results are shown in Table 4.

(1) Evaluation of heat resistance (1)
The thermosetting resin composition was coated on a glass epoxy substrate laminated with copper so that the film thickness after curing was 30 μm, dried for 60 minutes with a 200 ° C. dryer, cooled to room temperature, and a test piece. It was created. This test piece was immersed in a molten solder bath at 260 ° C. for 30 seconds and cooled to room temperature. This solder bath immersion operation was performed three times in total, and the appearance of the cured coating film was evaluated according to the following evaluation criteria. The heat resistance was also evaluated by measuring Tg described later. The higher the Tg, the better the heat resistance.

○: Appearance abnormality is not observed in the coating film.
Δ: Abnormalities such as swelling and peeling are slightly observed in the coating film.
X: Abnormalities such as swelling and peeling are observed on the entire surface of the coating film.

(2) Heat resistance evaluation (2)
Evaluation was performed by performing pyrolysis measurement.
<Preparation of test piece>
The coating film from which the thermosetting resin composition 1 was obtained was coated on a tin plate so that the film thickness was 30 μm. Next, this coated plate was dried with a dryer at 50 ° C. for 30 minutes, with a dryer at 100 ° C. for 30 minutes, and with a dryer at 200 ° C. for 60 minutes to form a coating film (film). After cooling to room temperature, the coating film (film) was isolated from the substrate and used as a measurement sample.

<Pyrolysis measurement method>
Thermal decomposition was measured by differential thermal-thermogravimetric simultaneous measurement (TG-DGA). Specifically, the thermal weight reduction rate at 500 ° C. was measured with TG / DTA6200 manufactured by SII Nano Technology. For the measurement, the sample was cut into a size that could be enclosed in a measurement aluminum container (70 μl), and the initial sample mass was adjusted between 5.5 and 5.8 mg. Measurement was carried out by heating in a nitrogen stream from room temperature to 500 ° C. at a rate of 10 ° C./min. The evaluation is performed by weight loss%, and the smaller the value, the better the heat resistance.

(3) Evaluation of mechanical properties Mechanical properties were evaluated by conducting a tensile test of a coating film (film) and obtaining an elastic modulus, breaking strength, and breaking elongation.
<Preparation of test piece>
The coating film from which the thermosetting resin composition was obtained was coated on the tinplate substrate so that the film thickness was 30 μm. Next, this coated plate was dried with a dryer at 50 ° C. for 30 minutes, with a dryer at 100 ° C. for 30 minutes, and with a dryer at 200 ° C. for 60 minutes to form a coating film (film). After cooling to room temperature, the coating film (film) was cut into a predetermined size, isolated from the substrate, and used as a measurement sample.

<Tensile test measurement method>
Five samples for measurement were prepared and subjected to a tensile test under the following conditions to determine the elastic modulus, breaking strength, and breaking elongation. It represents that it is a coating film which is excellent in a softness, so that the value of an elasticity modulus is low. It represents that it is a coating film which is excellent in a softness | flexibility, so that the value of breaking elongation is high. And it shows that it is a tough coating film, so that the value of breaking strength is high.
Measuring instrument: Tensilon manufactured by Toyo Baldwin, Inc. Sample shape: 10 mm x 70 mm
Between chucks: 20 mm
Tensile speed: 10 mm / min
Measurement atmosphere: 22 ° C., 45% RH

(4) Evaluation of dimensional stability
<Preparation of test specimen>
The thermosetting resin composition was coated on a tin plate so that the film thickness after curing was 30 μm, dried for 20 minutes with a dryer at 70 ° C., cured for 1 hour at 200 ° C., cooled, and then peeled off. The cured coating film was cut into a width of 5 mm and a length of 30 mm, and used as a measurement sample.

<TG and linear expansion coefficient measurement method>
Using a thermal analysis system TMA-SS6000 manufactured by Seiko Electronics Co., Ltd., measurement was performed by the TMA (Thermal Mechanical Analysis) method under the conditions of a sample length of 10 mm, a heating rate of 10 ° C./min, and a load of 30 mN. In addition, TG calculated | required the inflection point from the temperature-dimension change curve by TMA measurement, and made the temperature TG. Furthermore, the temperature range used for the linear expansion coefficient was determined from the displacement of the sample length at 50 to 60 ° C and 110 to 120 ° C. The smaller the linear expansion coefficient, the better the dimensional stability.

(5) Evaluation of flame retardancy
<Preparation of test specimen>
The thermosetting resin composition was coated on a tin plate so that the film thickness after curing was 30 μm, dried for 20 minutes with a dryer at 70 ° C., cured for 1 hour at 200 ° C., cooled, and then peeled off. The cured coating film was cut into a width of 10 mm and a length of 40 mm, and this film was bent in half in the longitudinal direction to obtain a sample for measurement.

<Flame retardancy evaluation method>
The folded film sample was held horizontally with a clamp, and the flame was slowly ignited with a lighter at the other edge, and the evaluation was performed according to the following criteria.
○: The film sample ignites but disappears immediately.
Δ: The film sample ignites but disappears before the clamp.
X: The film sample burns up to the clamp.

Examples 2-18 and Comparative Examples 1-7
Thermosetting resin compositions 2 to 18 and comparative thermosetting resin compositions 1 'to 7' were obtained in the same manner as in Example 1 except that the compositions shown in Table 1 to Table 2 were used. . The same evaluation as in Example 1 was performed, and the results are shown in Tables 4-6.

Comparative Example 8
In a reaction vessel equipped with a nitrogen introduction tube and a cooling device, 0.5 mol of trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.), 0.5 mol of sebacic acid (manufactured by Toyokuni Seiyaku), Millionate MT (manufactured by Nippon Polyurethane Industry) 0.46 Mole, 0.5 mol of Coronate T100 (manufactured by Nippon Polyurethane Industry), cyclohexanone (manufactured by Kanto Denka Kogyo Co., Ltd.) as a solvent, and reaction at 140 ° C. for 1 hour at a solid concentration of 50%, followed by 1,8-diazabicyclo [5 as a catalyst 4.0] -7-undecene 0.02 mol was slowly added and reacted at 140 ° C. for 3 hours. To adjust the molecular weight, 0.02 mol of Millionate MT was added and further reacted at 140 ° C. for 2 hours, and then cooled and diluted with cyclohexanone so that the solid content concentration was 25% by mass to obtain a polyamideimide resin varnish. . This resin composition is referred to as a comparative thermosetting resin composition 8 '.

  Evaluation similar to Example 1 was performed using the comparative thermosetting resin composition 8 ', and the results are shown in Table 7.

Comparative Example 9
In a 500 ml four-necked flask equipped with a nitrogen inlet tube, a stirrer, a distillation outlet, and a thermometer, 270 g of GBL, 30 g of xylene, (A) component, 1,2-ethylenebis (anhydrotrimellitate (TMEG) 20.9 g (0.051 mol) (a1) and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA) 18.2 g (0.051 mol) (a2), component (B) 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 24.6 g (0.060 mol) (b1), and “Jephamine D-400” (average molecular weight 400) manufactured by HUNTSMAN 16.0 g (0.040 mol) (b2) was charged, and the temperature was raised to 180 ° C. while stirring under a nitrogen stream. The de reaction subjected to 5 hours to obtain a reaction solution after the resin concentration of about 20 wt% of the polyimide reaction completion. To this resin composition comparative thermosetting resin composition 9 '.

  Evaluation similar to Example 1 was performed using the comparative thermosetting resin composition 9 ', and the results are shown in Table 7.

Footnotes in Tables 1 to 3 TEPBIZ: 2-ethyl-4-methylimidazolium tetraphenylborate TRBB: pyridine triphenylborane TBBP: phenylboric anhydride (trimer)
CNE: Cresol novolac type epoxy resin, epoxy equivalent 214, softening point 80 ° C.
2E4MZ: 2 methyl 4-ethylimidazole

Claims (7)

Trimellitic anhydride / 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride / 3 as the acid component when each of the acid component, amine component or isocyanate component of the polyamideimide resin is 100 mol% , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride or 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride = 70 to 90/5 to 25/5 to 25 (mol%) , And 3,3′-dimethyl-4,4′-biphenyldiamine as the diamine component or 3,3′-dimethyl-4,4′-biphenyl diisocyanate as the diisocyanate component (A ) And one or more boron compounds (B) selected from the group consisting of the following general formulas (b1) to (b3): Fat composition.

(In the formula, each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.)

(In the formula, each R ₂ independently represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Y represents a nitrogen-containing heterocyclic compound.)

(In the formula, each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Z represents a nitrogen-containing heterocyclic compound.) The thermosetting resin composition according to claim 1, wherein the boron compound (B) is a boron compound represented by the general formula (b2) or the general formula (b3). The thermosetting resin composition according to claim 1, wherein Y of the boron compound represented by the general formula (b2) is pyridine, and Z + of the boron compound represented by the general formula (b3) is an imidazolium salt. The thermosetting resin composition according to claim 1, wherein a content of the boron compound (B) is 0.5 to 30 parts by mass with respect to 100 parts by mass of the polyamideimide resin (A). The thermosetting resin composition according to claim 1, wherein the polyamide-imide resin (A) is a polyamide-imide resin that is soluble in gamma-butyrolactone when dissolved in gamma-butyrolactone so as to be 10% by mass at 25 ° C. Hardened | cured material formed by hardening | curing the thermosetting resin composition of any one of Claims 1-5. The cured product according to claim 6, wherein the cured product is a film-shaped cured product.