JP2005298568A - Polyimide composition and heat resistant resin composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a soluble polyimide having a reactive site without using a particular monomer, and to provide a heat resistant resin composition excellent in heat resistance and processability by a composition containing the soluble polyimide and a thermosetting compound. <P>SOLUTION: The soluble polyimide composition having imide and polyester acid structures in which the sites such as a carboxy group which react with a thermosetting compound is obtained from a tetracarboxylic dianhydride, an alcoholic diol and a diamine. The heat resistant resin composition is obtained by adding a thermosetting compound to the polyimide composition. The thermosetting compound to be added preferably includes a compound having a carbon-carbon double bond, an epoxy compound, an isocyanate compound and a cyanic acid ester compound. Moreover, the heat resistant resin composition may contain a flame retardant other than the polyimide composition and the thermosetting compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyimide composition and a heat resistant resin composition using the same.

  Polyimide is excellent in heat resistance among various organic polymers, and thus is widely used in the fields of space and aviation to electronic communication and OA equipment.

  In general, many polyimides are insoluble in a solution and have poor workability. Therefore, imidization is generally performed after processing into a film or other molded body in the state of polyamic acid as a precursor.

  Recent studies have reported soluble polyimides that are soluble in solvents. (Patent Document 1 and Patent Document 2) If soluble polyimide is used, an arbitrary part can be coated only by coating and drying with a solution. Further, since imidization has already been performed, heating at a high temperature of 250 ° C. or higher necessary for the conversion from ordinary polyamic acid to imide is not necessary.

  However, when this soluble polyimide is used as an adhesive, it must be bonded at a temperature higher than Tg, and must be exposed to a high temperature. Moreover, if Tg itself of soluble polyimide is made low, since the heat resistance of soluble polyimide falls, it is unpreferable.

As a method for achieving both workability and heat resistance, a heat resistant resin composition in which a soluble polyimide and a thermosetting compound are mixed has been reported. (Patent Document 3 and Patent Document 4) In particular, it has been reported that when soluble polyimide is provided with a site (carboxyl group or the like) that reacts with a thermosetting compound, it is further excellent in heat resistance. (Patent Document 5) However, in order to introduce a site that reacts with a thermosetting compound into soluble polyimide, a special diamine having a site (carboxyl group or the like) that is reacted with a diamine as a monomer is used. Therefore, the soluble polyimide is expensive.
JP 7-173287 A JP 7-166148 A Japanese Patent Laid-Open No. 7-242820 JP-A-8-027430 Japanese Patent Laid-Open No. 8-253676

  It is to provide a soluble polyimide having a reactive site without using a special monomer, and to provide a heat resistant resin composition containing the soluble polyimide and a thermosetting compound.

  The present invention provides the following novel polyimide composition and a heat-resistant resin composition using the same, thereby solving the above-mentioned problems.

  1st of this invention is a polyimide composition which has a structure of the following general formula (1) and general formula (2), and reacts a thermosetting compound with a soluble polyimide by making acid dianhydride and diol react. A site (carboxyl group or the like) can be introduced without using a special monomer.

（ただし、式中のＲ¹は芳香族テトラカルボン酸からテトラカルボン酸を除く４価の残基を示し、Ｒ²は２価の有機基、Ｒ³はジアミン化合物よりアミノ基を除く２価の残基を示す。）
本発明の第２は、請求項１記載のポリイミド組成物に加え、熱硬化性化合物を含有することを特徴とする耐熱性樹脂組成物であり、本発明のポリイミド組成物には熱硬化性化合物と反応する部位（カルボキシル基等）を有するため、熱硬化性化合物を混合することで加工性と耐熱性を高い次元で両立することが出来る。

(However, R ¹ in the formula represents a tetravalent residue excluding tetracarboxylic acid from aromatic tetracarboxylic acid, R ² is a divalent organic group, and R ³ is a divalent excluding amino group from the diamine compound. Indicates a residue.)
A second aspect of the present invention is a heat-resistant resin composition containing a thermosetting compound in addition to the polyimide composition according to claim 1, and the polyimide composition of the present invention includes a thermosetting compound. Since it has a site | part (carboxyl group etc.) which reacts with, a workability and heat resistance can be made compatible in a high dimension by mixing a thermosetting compound.

  A soluble polyimide having a reactive site can be provided without using a special monomer. Moreover, the heat resistant resin composition excellent in heat resistance and workability can be provided by the composition containing the soluble polyimide and the thermosetting compound.

The polyimide composition used in the present invention will be described.
The polyimide composition of this invention has the structure of the following general formula (1) and general formula (2).

（ただし、式中のＲ¹は芳香族テトラカルボン酸からテトラカルボン酸を除く４価の残基を示し、Ｒ²は２価の有機基、Ｒ³はジアミン化合物よりアミノ基を除く２価の残基を示す。）
一般式（１）の構造は、テトラカルボン酸二無水物とアルコール性ジオールと反応することにより得られる。例えば、下記スキーム１に示すように、テトラカルボン酸二無水物ｍモルとアルコール性ジオールｎモルを反応させれば、末端が酸無水物となる構造が得られる。（ｍ＞ｎ）
また、前述のスキーム１のようにテトラカルボン酸二無水物とアルコール性ジオールを反応させることにより、得られた前記末端が酸無水物となる構造中にカルボン酸基が生成する。

(However, R ¹ in the formula represents a tetravalent residue excluding tetracarboxylic acid from aromatic tetracarboxylic acid, R ² is a divalent organic group, and R ³ is a divalent excluding amino group from the diamine compound. Indicates a residue.)
The structure of the general formula (1) is obtained by reacting tetracarboxylic dianhydride with an alcoholic diol. For example, as shown in the following scheme 1, a structure in which the terminal is an acid anhydride can be obtained by reacting mmol of tetracarboxylic dianhydride and nmole of alcoholic diol. (M> n)
Further, by reacting tetracarboxylic dianhydride and alcoholic diol as in the above-described scheme 1, a carboxylic acid group is generated in the structure in which the obtained terminal is an acid anhydride.

次いで、スキーム１の反応の後に、スキーム２の様にジアミン化合物を反応させポリアミド酸としたあとに加熱するか脱水剤の存在下でイミド化させると、一般式（２）の構造（イミド構造）を得ることが出来る。

Next, after the reaction of Scheme 1, the diamine compound is reacted to form a polyamic acid as shown in Scheme 2, and then heated or imidized in the presence of a dehydrating agent to form the structure of formula (2) (imide structure) Can be obtained.

反応の順序は、テトラカルボン酸二無水物とアルコール性ジオールと反応させた後で、ジアミンと反応させてもよいし、逆にテトラカルボン酸二無水物とジアミンと反応させた後でアルコール性ジオールを反応させてもよい。反応の際に有機溶媒を用いてもよいし、
用いるモノマーが２００℃以下の温度で液化するのであれば、無溶媒で反応させることができる。 この時の反応温度は、−２０℃〜３００℃が望ましい。反応時間は３０分から２４時間程度である。

The reaction may be carried out by reacting a tetracarboxylic dianhydride and an alcoholic diol and then reacting with a diamine, or conversely reacting a tetracarboxylic dianhydride and a diamine and then reacting with an alcoholic diol. May be reacted. An organic solvent may be used in the reaction,
If the monomer to be used is liquefied at a temperature of 200 ° C. or lower, the reaction can be carried out without a solvent. The reaction temperature at this time is desirably -20 ° C to 300 ° C. The reaction time is about 30 minutes to 24 hours.

  The average molecular weight of the polyamic acid is desirably 2000 to 1000000. When the average molecular weight is less than 2000, the molecular weight of the finished polyimide composition is also low, and the resin tends to be brittle even if the polyimide composition is used as it is. On the other hand, if it exceeds 1,000,000, the viscosity of the polyamic acid becomes high and it becomes difficult to handle.

  Examples of the organic polar solvent used in the reaction for forming the polyamic acid and the polyimide composition include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N-dimethylformamide, and N, N-diethylformamide. Formamide solvents, N, N-dimethylacetamide, acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m -Or phenol solvents such as p-cresol, xylenol, halogenated phenol and catechol; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as methanol, ethanol and butanol; cellosolve such as butyl cellosolve Hexamethylphosphoramide, .gamma.-butyrolactone, etc. can be mentioned, although it is desirable to use them alone or as a mixture, further xylene, aromatic hydrocarbons such as toluene can be used. The solvent is not particularly limited as long as it dissolves the polyamic acid and the polyimide composition.

  The conditions for imidizing the polyamic acid may be heated to a temperature of 100 ° C. or higher, and water generated along with imidization may be pushed out of the system with an inert gas such as nitrogen, or an azeotropic solvent such as toluene or xylene. May be added to remove water produced by azeotropy. At this time, the water generated actively may be removed by reducing the pressure.

  As another imidization method, a chemical imidization method in which an aliphatic acid dianhydride such as acetic anhydride and a tertiary amine such as triethylamine, pyridine, picoline, and isoquinoline are added may be used.

The alcoholic diol used in this polyimide composition is not particularly limited as long as it has two alcoholic hydroxyl groups in the molecule. For example, HO—C _W H _2W —OH (w is an integer of 2 to 20). ) And xylylene glycols such as p-xylylene glycol, o-xylylene glycol, m-xylylene glycol, and the like. Moreover, if it is a part, you may use triols, such as glycerol.

  The acid dianhydride used in this polyimide composition is not particularly limited as long as it is an acid dianhydride. For example, 2,2′-hexafluoropropylidenediphthalic dianhydride, 2,2-bis (4- Hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3, 5,6-tricarboxynorbonane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuran ) -3-Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, etc. Aliphatic or cycloaliphatic tetracarboxylic dianhydrides; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl Sulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′- Biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1 , 2,3,4- Lantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4 '-Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride Bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylme Examples thereof include aromatic tetracarboxylic dianhydrides such as tan dianhydride. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

In particular, it is desirable to use at least one acid dianhydride selected from the structures represented by the following general formulas (3) and (4) in order to express heat resistance and mechanical properties at a high level. (R ⁴ represents an ester bond or an ether bond, R ⁵ is a divalent organic group, and is particularly selected from the group represented by the following general formulas (5), (6), (7) and (8)) One or more structures are desirable, and R ⁶ is a direct bond, —O—, —CH ₂ —, — (C═O) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, and — 1 or more types selected from SO _2- )

（式中、Ｒ⁷は、水素、ハロゲン、メトキシ、Ｃ₁〜Ｃ₁₆のアルキル基を、Ｒ⁸は−ＣＨ₂−，−Ｏ−，−ＳＯ₂−，−Ｃ（ＣＨ₃）₂−，−Ｃ（ＣＦ₃）₂−，−ＣＯ−を、ｒは０〜４の整数、ｓは０〜２の整数、ｔは０〜４の整数、ｕは１〜３の整数を示す。）
有機溶媒への溶解性の高いポリイミドを得るためには、一般式（３）または一般式（４）で示される酸二無水物として、２，２‘−ヘキサフルオロプロピリデンジフタル酸二無水物、２，３，３’，４‘−ビフェニルテトラカルボン酸二無水物、４，４−（４，４’−イソプロピリデンジフェノキシ）ビスフタル酸無水物、２，２−ビス（４−ヒドロキシフェニル）プロパンジベンゾエート−３，３‘，４，４’−テトラカルボン酸二無水物を一部用いることが望ましい。

(In the formula, R ⁷ is hydrogen, halogen, methoxy, a C _{1 to} C ₁₆ alkyl group, R ⁸ is —CH ₂ —, —O—, —SO ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —CO—, where r is an integer of 0 to 4, s is an integer of 0 to 2, t is an integer of 0 to 4, and u is an integer of 1 to 3.
In order to obtain a polyimide having high solubility in an organic solvent, 2,2′-hexafluoropropylidenediphthalic dianhydride is used as the acid dianhydride represented by the general formula (3) or the general formula (4). 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 4,4- (4,4′-isopropylidenediphenoxy) bisphthalic anhydride, 2,2-bis (4-hydroxyphenyl) It is desirable to partially use propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride.

Moreover, it is desirable to use a siloxane diamine represented by the following general formula (9) as the diamine compound used in Scheme 2, because a soluble imide having high flexibility and solubility can be obtained. (In the formula, R ⁹ is a C _{1 to} C ₁₂ alkyl group or phenyl group, x is an integer of 1 to 20, and y is an integer of 1 to 40.)

式中、Ｒ⁹の好ましい例としてメチル基、エチル基、及びフェニル基をあげることができ、さらに好ましくはメチル基である。またｘ＝２〜１０が好ましく、特に２〜５が好ましい。ｙ＝４〜３０が好ましく、さらに好ましくは５〜２０、特に８〜１５が好ましい。このなかでｙの値の範囲が物性に与える影響が大きく、ｙの値が小さいと、得られたポリイミドの可とう性が乏しくなり、また大きすぎるとポリイミド耐熱性が損なわれる傾向にある。

In the formula, preferred examples of R ⁹ include a methyl group, an ethyl group, and a phenyl group, and a methyl group is more preferred. X = 2 to 10 is preferable, and 2 to 5 is particularly preferable. y = 4-30 is preferable, More preferably, 5-20, Especially 8-15 are preferable. Among these, the range of the value of y has a great influence on the physical properties. When the value of y is small, the flexibility of the obtained polyimide is poor, and when it is too large, the heat resistance of the polyimide tends to be impaired.

  The siloxane diamine is preferably used in an amount of 5 to 70 mol%, more preferably 10 to 50 mol%, based on the total diamine component.

In addition, the diamine used in the polyimide composition is not particularly limited as long as it is a diamine. For example, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminophenylethane, 4,4′-diaminophenyl ether, 4,4′-didiaminophenyl sulfide, 4,4′-didiaminophenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 4,4 ′ -Diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoro Methylbenzanilide, 3,4'-diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2 , 2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4 , 4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) -biphenyl 1,3′-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m- Phenylene isopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-bis [4- (4-amino-2-tri) Aromatic diamines such as fluoromethyl) phenoxy] -octafluorobiphenyl; aromatic diamines having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and heteroatoms other than nitrogen atoms of the amino group; 1 , 1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, oct Methylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenediethylenediamine, tricyclo Mention may be made of aliphatic diamines and alicyclic diamines such as [6,2,1,0 ^2.7 ] -undecylenedimethyldiamine, 4,4′-methylenebis (cyclohexylamine). These diamine compounds can be used alone or in combination of two or more.

  When using an aromatic diamine, it is preferable to use a diamine having an amino group at the m-position (3-) because the solubility in a solvent tends to be improved.

  The COOH equivalent of the polyimide composition of the present invention is preferably 200 to 3000. This is realized by using the above-mentioned alcoholic diol as a raw material for the polyimide of the present invention. The sum of the general formula (1) and the terminal carboxylic anhydride is the amount of COOH present. That is, the presence ratio of the general formula (1) and the general formula (2) is adjusted so that the acid equivalent is in the range of 200 to 3000. General formula (1) / general formula (2) = 1/99 to 99/1, preferably 5/95 to 95/5, and more preferably 10/90 to 90/10. As a preferable COOH equivalent of a polyimide, it is 250-2500, More preferably, it is 350-2000. When the carboxylic acid equivalent is 200 or less, the electrical characteristics may be adversely affected.

  The monomer reaction ratio of the polyimide composition of the present invention is preferably in the range of acid dianhydride / (alcoholic diol + diamine) = 50/100 to 100/50. When the monomer reaction ratio is acid dianhydride> (alcoholic diol + diamine), it is an acid terminal, and when acid dianhydride <(alcoholic diol + diamine), it is an amine or alcoholic diol terminal. If it is in the range of the above-mentioned COOH equivalent, there is no problem even if the terminal is either.

  The heat resistant resin composition of the present invention contains a thermosetting compound in addition to polyimide. The thermosetting compound is a compound that undergoes a curing reaction when heated, and specifically includes a compound having a carbon-carbon double bond, an epoxy compound, an isocyanate compound, and a cyanate ester compound. .

  Examples of the compound having a carbon-carbon double bond include bisphenol F EO-modified (n = 2 to 50) diacrylate, bisphenol A EO-modified (n = 2 to 50) diacrelane, sphenol S EO modified (n = 2 to 2). 50) Diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane Tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate Relate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxy Ethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyl Oxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol di Methacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy 1,3 dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [ 4- (methacryloxy / diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy / polyethoxy) phenyl] propane, polyethylene glycol diacrylate, tripropylene glycol di Acrylate, polypropylene glycol diacrylate, 2,2-bis [4- (acryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (acryloxy-polyethoxy) phenyl] propane, 2-hydroxy 1-acryloxy 3-meta Cloxypropane, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, nonylphenoxypolyethylene glycol acrylate, nonylphenoxypolypropylene glycol acrylate, 1-acryloyl Oxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether Relate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-mexanediol dimethacrylate, 1 , 9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, 1,4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 2 , 2-hydrogenated bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) phenyl] propane, 2,4-diethyl-1,5-pentanediol diacrylate Ethoxylated tows Roll propane triacrylate, propoxylated tomethylol propane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxylated pentathritol tetraacrylate, propoxylated pentathritol tetraacrylate, ditrimethylolpropane tetreacrylate, di Pentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1,3,5-triacryloylhexahydro-s-triazine, triallyl 1,3,5-benzenecarboxylate, triallylamine, triallyl citrate , Triallyl phosphate, allobarbital, diallylamine, diallyldimethylsilane, diallyl disulfide, Diallyl ether, zalyl sialate, diallyl isophthalate, diallyl terephthalate, 1,3-dialyloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4'-isopropylidene diphenol dimethacrylate, 4,4'-isopropylidene Dendiphenol diacrylate and the like are preferable, but not limited thereto. In order to improve the crosslink density, it is particularly desirable to use a bifunctional or higher monomer.

  As other compounds having a carbon-carbon double bond, styrene, divinylbenzene, vinyl-4-t-butylbenzoate, vinyl n-butyl ether, vinyl isobutyl ether, vinyl n-butyrate, vinyl n-caprolate, vinyl n- Examples include vinyl compounds such as caprylate, and allyl compounds such as triallyl isocyanurate and diallyl phthalate.

  The compound having a carbon-carbon double bond is preferably blended in an amount of 1 to 200 parts by weight, more preferably 3 to 150 parts by weight, based on 100 parts by weight of the polyimide composition of the present invention. If it deviates from the range of 1 to 200 parts by weight, the intended effect may not be obtained. In addition, as a compound which has a carbon-carbon double bond, one type of compound may be used and several types may be mixed and used. Moreover, you may mix radical generators, such as a peroxide.

  The epoxy compound is not particularly limited as long as it has an epoxy group in the molecule, and can be exemplified as follows.

  For example, bisphenol resin such as Epicoat 828 (manufactured by Yuka Shell), orthocresol novolak resin such as 180S65 (manufactured by Yuka Shell), bisphenol A novolak resin such as 157S70 (manufactured by Yuka Shell), 1032H60 (oiled) Trishydroxyphenylmethane novolak resin such as ESN375, naphthalene aralkyl novolak resin such as ESN375, tetraphenylolethane 1031S (manufactured by Yuka Shell), YGD414S (Tohto Kasei), trishydroxyphenylmethane EPPN502H (Nippon Kayaku) And glycidylamine type resins such as special bisphenol VG3101L (Mitsui Chemicals), special naphthol NC7000 (Nippon Kayaku), TETRAD-X, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.

  Moreover, the compound which has an epoxy group and a double bond and a triple bond in a molecule | numerator can also be mixed. For example, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, propargyl glycidyl ether, glycidyl propiolate, and ethynyl glycidyl ether can be exemplified.

  In particular, among epoxy compounds, use of an epoxy compound having one epoxy group in the molecule is particularly desirable because it can suppress curing shrinkage during curing. As monofunctional epoxy compounds, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, alkyl monoglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, allyl glycidyl ether, pt-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, p -Sec-butylphenyl glycidyl ether, alkylphenol monoglycidyl ether, versatic acid monoglycidyl ester, linear alcohol monoglycidyl ether, glycerol monoglycidyl ether, polyglycol glycidyl ether, glycidyl methacrylate, etc. It is not a thing.

  Further preferred examples include pt-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, alkylphenol monoglycidyl ether, versatic acid monoglycidyl ester, linear alcohol monoglycidyl ether, glycerol monoglycidyl Ether, polyglycol glycidyl ether, 2-methylhexyl glycidyl ether, 3- (2-biphenyloxy) -1,2-epoxypropane, glycidyl 4-methoxyglycidyl ether, glycidyl mesityl ether, N- (2,3-epoxypropyl) ) Phthalimide, glycidyl hexadecyl ether, glycidyl nonyl phenyl ether, glycidyl lauryl ether, 3-dodecafluoroheproxy , 2-propoxide, Nippon Kayaku Co., Ltd. BR-250H, Nippon Kayaku Co., Ltd. BROC-Y, Nippon Kayaku Co., Ltd. BROC-C, Nippon Kayaku Co., Ltd. BROC, etc. can be illustrated. .

  The isocyanate compound used in the present invention may be any compound as long as it has two or more isocyanate groups in one molecule. Examples of such polyvalent isocyanates include aliphatic, alicyclic or aromatic diisocyanates such as 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate. Net, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl 3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate Net, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, etc. Rukoto can be.

  Further, the isocyanate compound is derived from an aliphatic, alicyclic or aromatic isocyanate, such as isocyanurate-modified isocyanate, burette-modified isocyanate, urethane-modified isocyanate, etc. May be. The isocyanate compound used in the present invention is preferably a blocked isocyanate obtained by blocking the isocyanate group of the isocyanate compound with a blocking agent.

  Examples of the blocking agent include alcohol, phenol, active methylene, mercaptan, acid amide, acid imide, imidazole, urea, oxime, amine, and imide. There are compounds, pyridine compounds, etc., and these may be used alone or in combination. Specific blocking agents include: methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexane as the alcohol system. For example, phenol, cresol, ethyl phenol, butyl phenol, nonyl phenol, dinonyl phenol, styrenated phenol, hydroxybenzoate, etc. As dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc., as mercaptans, butyl mercaptan, dodecyl mercaptan, etc., as acid amides, acetanilide, acetate amide, ε-caprolactam, δ-valerolactam Γ-Petitirolac As an acid imide system, succinimide, maleic imide, imidazole system, imidazole, 2-methylimidazole, urea system, urea, thiourea, ethylene urea, etc., as oxime system, Formaldehyde oxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc., amine type, diphenylamine, aniline, carbazole, etc., imine type, ethyleneimine, polyethyleneimine, etc., bisulfite, bisulfite soda Examples of pyridine-based compounds include 2-hydroxypyridine and 2-hydroxyquinoline.

  In particular, Elastron [trade name BN-P17, 4,4'-diphenylmethane diisocyanate blocker] manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Elastron [BN-04, BN-08, BN-44, BN] -45: 3 to 5 functional groups per molecule of urethane-modified isocyanate block. Any of them can be used after drying and isolation in a water emulsion product].

  This isocyanate compound is preferably blended in an amount of 1 to 200 parts by weight, more preferably 3 to 150 parts by weight, per 100 parts by weight of the polyimide composition of the present invention. If it deviates from the range of 1 to 200 parts by weight, the intended effect may not be obtained. As the isocyanate compound, one kind of compound may be used, or several kinds may be mixed and used. Good.

  The cyanate ester compound is not particularly limited as long as the cyanate ester is contained in the molecule, but can be exemplified as follows.

  As a specific chemical formula, one having a structure of the following general formula (10) can be exemplified.

一般式（１０）において、Ｒ¹⁰ は同一でも異なってもよく、水素かアルキル基、パーフルオロアルキル基、アリール基、またはハロゲンであり、Ａは単結合、未置換メチレン基、水素原子の１つまたは２つをアルキル基、パーフルオロアルキル基、および／またはアリール基で置換した置換メチレン基、５員もしくは６員の環状脂肪族基、スルホン基、２価の硫黄、酸素、２価のカルボニル基、メチレン基が置換又は未置換のキシリレン基、フェニル基である。ｗは４である。

In the general formula (10), R ¹⁰ may be the same or different and is hydrogen, an alkyl group, a perfluoroalkyl group, an aryl group, or a halogen, and A is one of a single bond, an unsubstituted methylene group, and a hydrogen atom. Or a substituted methylene group in which two are substituted with an alkyl group, a perfluoroalkyl group, and / or an aryl group, a 5- or 6-membered cyclic aliphatic group, a sulfone group, divalent sulfur, oxygen, or a divalent carbonyl group , A methylene group is a substituted or unsubstituted xylylene group or a phenyl group. w is 4.

  Examples of other cyanate esters include 1,3-dicyanate benzene, 1,4-dicyanate benzene, 1,3,5-tricyanate benzene 1,3-dicyanate naphthalene, 1,4-dicyanate naphthalene. 1,6-dicyanate naphthalene, 1,8-dicyanate naphthalene, 2,6-dicyanate naphthalene, 2,7-dicyanate naphthalene, 1,3,6-tricyanate naphthalene, 2,2-bis (3 , 5-dicyclo-4-cyanatephenyl) propane, tris (4-cyanatephenyl) phosphite, tris (4-cyanatephenyl) phosphate, and benzene polynuclear polycyanate obtained by reaction of phenolic resin with cyanogen halide Compounds and the like. Those obtained by oligomerizing the exemplified cyanate ester by heating can also be used.

  This cyanate ester compound is preferably blended in an amount of 1 to 200 parts by weight, more preferably 3 to 150 parts by weight, based on 100 parts by weight of the polyimide composition of the present invention. If it deviates from the range of 1 to 200 parts by weight, the intended effect may not be obtained. As the cyanate ester compound, one type of compound may be used, or several types may be mixed and used. Also good.

  The heat resistant resin composition of the present invention may contain a flame retardant in addition to the polyimide composition and the thermosetting compound.

  Next, the flame retardant used in the present invention will be described.

  When the flame retardant is a compound containing phosphorus, the phosphorus content is preferably 5.0% or more by weight, more preferably 7.0% or more from the viewpoint that flame retardancy can be effectively imparted. is there. When the flame retardant is a halogen-containing compound, the halogen content is preferably 15% or more, more preferably 20% or more from the viewpoint that flame retardancy can be effectively imparted. As halogen, those using chlorine or bromine are generally used. When the flame retardant is a compound containing a siloxane moiety, an organopolysiloxane compound containing an aromatic ring in a high ratio is preferable from the viewpoint of effectively imparting heat resistance and flame retardancy.

  When a phosphorus compound is used as a flame retardant, examples of the phosphorus compound include phosphazenes, phosphines, phosphine oxides, phosphoric acid esters (including condensed phosphoric acid esters), and phosphorous compounds such as phosphorous acid esters. From the aspect of compatibility with the polyimide composition of the present invention, phosphazene, phosphine oxide, or phosphate ester (including condensed phosphate ester) is preferable. The phosphorus content of the phosphorus compound used as a flame retardant is preferably 5.0% by weight, more preferably 7.0% or more.

  Furthermore, from the point that it can impart flame retardancy and has hydrolysis resistance, for example, SPE-100 (phosphazene compound manufactured by Otsuka Chemical), SPH-100 (phosphazene compound manufactured by Otsuka Chemical), TPP (triphenyl phosphate). ), TCP (tricresyl phosphate), TXP (trixylenyl phosphate), CDP (cresyl diphenyl phosphate), PX-110 (cresyl 2,6-xylenyl phosphate) (all manufactured by Daihachi Chemical) Non-halogen-based condensed phosphate esters such as phosphate ester, CR-733S (resinol diphosphate), CR-741, CR-747, PX-200 (all manufactured by Daihachi Chemical), Biscoat V3PA (Osaka Organic Chemical) Kogyo), MR-260 (manufactured by Daihachi Chemical), etc. And phosphites such as triphenyl phosphite.

When a halogen-containing compound is used as the flame retardant, the halogen content is preferably 30% by weight or more, more preferably 40% by weight or more, and most preferably 50% or more. From the standpoint of improving flame retardancy, the higher the halogen content, the better.
Examples of the halogen-containing compound include chlorine-containing organic compounds and bromine-containing organic compounds. From the viewpoint of imparting flame retardancy, bromine-containing compounds are preferred, and the following can be exemplified.

  For example, brominated monomers such as New Frontier BR-30, BR-30M, BR-31, BR-42M (Daiichi Kogyo Seiyaku), brominated aromatic triazines such as Piroguard SR-245 (Daiichi Kogyo Seiyaku), Examples thereof include brominated aromatic polymers such as Pyroguard SR-250 and SR-400A (Daiichi Kogyo Seiyaku), and brominated aromatic compounds such as Piroguard SR-990A (Daiichi Kogyo Seiyaku).

  The flame retardant may be a phosphorus compound having a halogen atom in one molecule. Examples of such a compound include CLP (tris (2-chloroethyl) phosphate), TMCPP (tris (chloropropyl) phosphate), And halogen-containing phosphates such as CRP (tris (dichloropropyl) phosphate) and CR-900 (tris (tribromoneopentyl) phosphate) (both manufactured by Daihachi Chemical).

  Furthermore, when a compound having a siloxane moiety is used as a flame retardant, it is preferably an organopolysiloxane compound containing a high proportion of aromatic rings because it imparts flame retardancy, and the phenyl group is selected from all organic substituents. It is preferably an organopolysiloxane compound containing 10% or more, more preferably 20% or more, more preferably 25% or more. The smaller the phenyl group content, the smaller the flame retardant effect, and the higher the phenyl group content, the higher the flame retardant effect.

  When an organopolysiloxane compound having a low phenyl group content is used as a flame retardant, the dispersibility and compatibility with the polyimide composition of the present invention and the compound having a carbon-carbon double bond tend to be poor, and heat resistance When a resin is formed into a film, there is a tendency that only a low-transparency film in which a plurality of components having different refractive indexes are phase-separated or an opaque film is obtained. In addition, when such an organopolysiloxane compound having a low phenyl group content is used, it is difficult to obtain a sufficient flame retardant effect unless the amount added is increased, but the heat resistant resin composition produced when the amount added is increased. There is a tendency that physical properties such as mechanical strength of the material are significantly lowered.

  Furthermore, when an organopolysiloxane compound is used, flame retarding of the resin can be realized without generating harmful gases during combustion. In the case of a resin composition containing a halogen-containing compound, although flame retardancy can be realized, there is a drawback that harmful halogen-based gas is generated during combustion.

  The structure of the organopolysiloxane compound is generally composed of a combination of a trifunctional siloxane unit (T unit), a bifunctional siloxane unit (D unit), and a tetrafunctional siloxane unit (Q unit). A good combination in the present invention is a system containing a D unit such as a T / D system, a T / D / Q system, a D / Q system, and the like, and thereby provides good flame retardancy. In any combination, the D unit needs to be contained in an amount of 10 to 80 mol%. When the D unit is less than 10 mol%, the flexibility imparted to the organopolysiloxane compound is poor, and as a result, sufficient flame retardancy cannot be obtained. Moreover, when it exceeds 80 mol%, the dispersibility and solubility with (A) component: soluble polyimide will fall, and the external appearance and optical transparency and intensity | strength of a heat resistant resin composition will worsen. More preferably, the content of the D unit is in the range of 10 to 70 mol%. Therefore, according to the good D unit content, in the case of the T / D system, the content of the T unit is in the range of 30 to 90 mol%, and in the case of the T / D / Q system or the D / Q system, The content of T units is 0 to 89.99 mol%, preferably 10 to 79.99 mol%, and the content of Q units is 0.01 to 50 mol%. As long as the degree of freedom of space is secured, it is more advantageous to contain a larger amount of highly oxidized Q units in order to reproduce the flame retardancy. However, Q units in the organopolysiloxane compound are more advantageous. When the content exceeds 60 mol%, the inorganic fine particle property becomes too strong, and the dispersibility in the soluble polyimide becomes poor. Therefore, the blending amount needs to be kept below this. From the above siloxane unit content range, in consideration of the balance of flame retardancy, workability, molded product performance, etc., select a region where T units account for 40-80% by weight of the total weight of phenylsiloxane. It is further desirable to do so.

Here, exemplifying preferable siloxane units, the trifunctional siloxane units (T units) are C6H5SiO3 / 2 and CH3SiO3 / 2, and the bifunctional siloxane units are (C6H5) 2SiO2 / 2, (CH3) C6H5SiO2 / 2. , (CH3) 2SiO2 / 2.
In this case, the dimethylsiloxane unit ((CH3) 2SiO2 / 2) as the D unit for imparting flexibility has the greatest effect of imparting flexibility to the silicone resin, but on the other hand, it is difficult if there are too many such sites. Since flame retardancy tends to decrease, it is difficult to improve flame retardancy, and it is not desirable to contain a large amount. Accordingly, the dimethylsiloxane unit is preferably suppressed to 60 mol% or less in the D unit. Methylphenylsiloxane units ((CH3) C6H5SiO2 / 2) are most preferred because they can provide flexibility and at the same time increase the phenyl group content. In addition, the diphenylsiloxane unit ((C6H5) 2SiO2 / 2) is excellent in maintaining high phenyl group content, but it has a structure in which bulky phenyl groups are concentrated on a single Si. Because of the large structure of the organopolysiloxane molecules, the spatial freedom of the siloxane skeleton is reduced, making it difficult for the aromatic rings to overlap each other, which is necessary for the flame-retarding mechanism due to the coupling between the aromatic rings. In some cases, the flame retardant effect may be reduced. Therefore, the D unit may be used by blending these three raw materials so as to satisfy the above-mentioned range, but it is preferable to mainly use a methylphenylsiloxane unit.

  The weight average molecular weight of the flame retardant phenylsiloxane is preferably in the range of 300 to 50,000. A weight average molecular weight of less than 300 is not preferable because the heat resistant resin composition may ooze out in the B-stage state. If it exceeds 50,000, the solubility in the developer is lowered, the development time is prolonged, and the workability may be lowered. More preferably, it is the range of 400-30,000.

  Such an organopolysiloxane compound can be produced by a known method. For example, organochlorosilane and / or organoalkoxysilane that can form the above siloxane units by hydrolysis condensation reaction, or partially hydrolyzed condensate thereof, hydrolyze all hydrolyzable groups (chlor groups, alkoxy groups, etc.) For this purpose, excess water, the raw material silane compound and the resulting organopolysiloxane compound are mixed into a mixed solution of a dissolvable organic solvent and subjected to a hydrolysis condensation reaction. An organopolysiloxa compound having a desired weight average molecular weight can be obtained by adjusting the reaction temperature and time, the amount of water and an organic solvent. When using, unnecessary organic solvent may be removed and powdered for use.

  For example, KF50-100S, KF54, KF56, HIVAC F4, HIVAC F5, X-22-1824B, KR211 and KR311 manufactured by Shin-Etsu Silicone Co., Ltd. can be mentioned. Also good.

  The flame retardant is preferably used in an amount of 5 to 50% by weight based on the total amount of the polyimide composition of the present invention and the compound having a carbon-carbon double bond. If it is less than 5%, it tends to be difficult to impart flame retardancy to the coverlay film after curing, and if it exceeds 50%, the mechanical properties of the coverlay film after curing tend to be poor.

  In addition, when halogen-containing compounds are used as flame retardants, antimony trioxide and / or antimony pentoxide are added, and the antimony oxide extracts halogen atoms from the flame retardant and is halogenated in the thermal decomposition start temperature range of the plastic. Since antimony is generated, the flame retardancy can be increased synergistically. The addition amount is preferably 0.1 to 10% by weight, more preferably 1 to 6% by weight based on the total weight of the polyimide composition of the present invention, the compound having a carbon-carbon double bond, and the flame retardant. % Is preferred.

  Since the antimony trioxide and antimony pentoxide white powders are not dissolved in an organic solvent, if the powder has a particle size of 100 μm or more, it becomes cloudy when mixed in the heat-resistant resin composition, making the resulting heat-resistant resin composition difficult. Although flame retardancy can be imparted, the transparency and developability tend to decrease, and therefore it is preferably 100 μm or less. Furthermore, in order to increase the flame retardancy without losing the transparency of the heat resistant resin composition, it is preferable to use antimony trioxide and / or antimony pentoxide having a powder particle size of 50 μm or less. More preferred is a powder having a particle size of 10 μm or less, and most preferred is a powder having a particle size of 5 μm or less.

  Examples of antimony pentoxide having a particle size of 50 μm or less include Sun Epoch NA-3181, NA-4800, NA-1030, NA-1070L (all manufactured by Nissan Chemical Industries).

  Antimony trioxide and / or antimony pentoxide may be mixed in the heat-resistant resin composition as a powder, or if the powder settles in the heat-resistant resin composition, the powder is dispersed in an organic solvent. Alternatively, it may be mixed after making into a sol form. As a specific method for forming a sol, a dispersant is added to an organic solvent together with antimony trioxide and / or antimony pentoxide powder to form a network to prevent the powder from settling. As this dispersing agent, a mixture of vapor phase silica (silicon dioxide) and alumina (aluminum trioxide) can be used. This dispersant is preferably added in an amount of 2 to 5 times the weight of antimony trioxide and / or antimony pentoxide.

  The polyimide composition and thermosetting compound of the present invention described above are dissolved in an organic solvent to obtain a solution of a heat resistant resin composition. Examples of the solvent used include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and the like. Acetamide solvents, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenols such as phenol, o-, m-, or p-cresol, xylenol, halogenated phenol and catechol Solvents, ether solvents such as tetrahydrofuran and dioxane, alcohol solvents such as methanol, ethanol and butanol, cellosolves such as butyl cellosolve or hexamethylphosphoramide, γ-butyrolactone, methyl ethyl ketone Acetone, it can be mentioned ketone solvents such as methyl isobutyl ketone, but it is desirable to use them alone or as a mixture, further xylene, aromatic hydrocarbons such as toluene can be used.

  The solution of the heat resistant resin composition can be directly applied to a ridged or flexible printed circuit board on which wiring is formed and dried to be used as a coverlay or a solder resist.

  Also, the solution of the heat resistant resin composition is applied to a film such as polyethylene terephthalate (PET) and dried, and then the film of the heat resistant resin composition is peeled off to form a single-layer adhesive sheet of the heat resistant resin composition. A single layer sheet may be laminated between the layers of the printed circuit board and used as an adhesive sheet for bonding the layers. Alternatively, a solution of the heat resistant resin composition may be applied and dried on a portion to be bonded to the ridged or flexible printed board, and used as an adhesive for bonding the layers.

  Examples are described below, but the present invention is not limited to these examples.

  The following materials were used as raw materials for polyimide.

  First, as tetracarboxylic dianhydride, 1,2-ethanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter referred to as TMEG), 3,3 ′, 4, 4'-benzophenone tetracarboxylic dianhydride (hereinafter referred to as BTDA) and 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as a-BPDA) were used.

  Next, bis [4- (3-aminophenoxy) phenyl] sulfone (hereinafter referred to as BAPS-M) and silicon diamine were used as the diamine compound.

  Further, N, N′-dimethylformamide (DMF) and dioxolane were used as organic polar solvents.

(Example 1)
(Synthesis of polyimide composition)
TMEG 41.0 g (100 mmol), ethylene glycol 1.86 g (30 mmol), silicon diamine KF-8010 (manufactured by Shin-Etsu Silicone) 49.8 g (60 mmol) were added to a 500 ml separable flask equipped with a stirrer, Was heated to 180 ° C. for 90 minutes to obtain 88 g of a polyimide composition.

(Evaluation of heat resistant resin composition)
The following components were mixed and dissolved in a methyl ethyl ketone solvent so as to have a solid content weight concentration of 40% to prepare a heat resistant resin composition solution.
(A) Polyimide composition synthesized by the above method 53 parts by weight (B) Compound having a carbon-carbon double bond: 15 parts by weight of Kyoeisha Chemical Co., Ltd. Light acrylate NP-4EA, and BR made by Daiichi Kogyo Seiyaku Co., Ltd. -42M 15 parts by weight (C) Epoxy compound: Epicoat 828 (Japan Epoxy Resin Co., Ltd.) 10 parts by weight (D) Curing agent: Perbutyl E (manufactured by NOF Corporation) 2 parts by weight (E) Others: Otsuka Chemical Co., Ltd. Manufactured phosphazene compound SP-100 5 parts by weight (adhesiveness)
The heat-resistant resin composition solution was applied to a polyimide film Apical 25NPI (manufactured by Kaneka Chemical Industry Co., Ltd.) so that the thickness after drying was 25 microns, dried at 90 ° C. for 5 minutes, and then electrolytic copper foil (Mitsui Metals 3EC The rough surface of -VLP (1 ounce) was aligned with the heat resistant resin composition side, laminated under conditions of 110 ° C. and 20000 Pa · m, and heated at 160 ° C. for 2 hours to obtain a laminate. This laminate was made according to the peel strength (90 degrees) of JIS C 6481. However, the width was measured at a width of 3 mm and converted to 1 cm. The adhesive strength was 11.8 N / cm.

(Solder heat resistance)
The heat-resistant resin composition solution was applied to the bright surface of electrolytic copper foil (Mitsui Metals 3EC-VLP 1 ounce) so that the thickness after drying was 25 microns, dried at 90 ° C. for 5 minutes, and subsequently 160 ° C. 2 The laminate was obtained by heating for a period of time. This laminate was conditioned at 40 ° C. and 95% RH for 24 hours, then immersed in a solder bath for 10 seconds, and the presence or absence of surface swelling and discoloration was observed. The maximum temperature without swelling or discoloration was defined as the solder heat resistance temperature. The solder heat resistance temperature was 280 ° C.

(Migration resistance)
Line / space = 50/50 μm shown in FIG. 1 on Nippon Steel Chemical's flexible copper-clad laminate (single-sided copper-clad laminate having a copper foil on one side of a polyimide resin: SC18-25-00FR) A comb pattern was formed. The heat-resistant resin composition solution was applied to a polyimide film Apical 25NPI (manufactured by Kaneka Chemical Industry Co., Ltd.) so that the thickness after drying was 25 microns, and the comb pattern was aligned with the heat-resistant resin composition side and pressed at 110 ° C. and 3 MPa. And heated at 160 ° C. for 2 hours to obtain a laminate. In an environment tester at 130 ° C. and 85% RH, a DC voltage of 60 V was applied to both terminals of the coated comb pattern, and changes in resistance value and presence / absence of migration were observed. The migration resistance showed a resistance value of 10 ⁻⁶ Ω or more for 75 hours or more, and no dendrite was observed.

(Example 2)
To a 500 ml separable flask equipped with a stirrer, 41.0 g (100 mmol) of TMEG, 4.15 g (30 mmol) of p-xylylene glycol, 49.8 g (60 mmol) of silicon diamine KF-8010 (manufactured by Shin-Etsu Silicone) were added, It heated for 90 minutes at 180 degreeC under nitrogen stream, and 91 g of polyimide compositions were obtained.

(Evaluation of heat resistant resin composition)
The following components were mixed and dissolved in a dioxolane solvent so as to have a solid content weight concentration of 40% to prepare a heat resistant resin composition solution.
(A) Polyimide composition synthesized by the above method 60 parts by weight (B) Epoxy compound: Epicoat YX4000H (Japan Epoxy Resin Co., Ltd.) 20 parts by weight, Epicoat 1032H60 (Japan Epoxy Resin Co., Ltd.) 20 parts by weight (C) Curing agent : None Evaluation was performed in the same manner as in Example 1, and the adhesive strength was 10.0 N / cm. The solder heat resistance temperature was 290 ° C. The migration resistance showed a resistance value of 10 ⁻⁶ Ω or more for 75 hours or more, and no dendrite was observed.

(Example 3)
In a 500 ml separable flask equipped with a stirrer, 32.2 g (100 mmol) of BTDA, 5.21 g (50 mmol) of 2,2-dimethyl-1,3-propanediol, and 60 g of dimethylformamide were taken at 80 ° C. for 1 hour. Heated. Next, 37.35 g (45 mmol) of silicon diamine KF-8010 (manufactured by Shin-Etsu Silicone) was added and heated to 180 ° C. for 90 minutes under reduced pressure to obtain 71 g of a polyimide composition.

(Evaluation of heat resistant resin composition)
The following components were mixed and dissolved in a solvent so as to have a solid content weight concentration of 40% to prepare a heat resistant resin composition solution.
(A) Polyimide composition synthesized by the above method 60 parts by weight (B) Bisphenol A-based cyanate ester compound; 2,2′-bis (4-phenylcyanato) propane (trade name: BADCY, manufactured by Lonza) 25 parts by weight (C) epoxy compound: glycidyl nonylphenyl ether 15 parts by weight (D) curing agent: none The evaluation was carried out in the same manner as in Example 1, and the adhesive strength was 12.0 N / cm. The solder heat resistance temperature was 285 ° C. The migration resistance showed a resistance value of 10 ⁻⁶ Ω or more for 75 hours or more, and no dendrite was observed.

Example 4
In a 500 ml separable flask equipped with a stirrer, 29.42 g (100 mmol) of a-BPDA, 3.12 g (30 mmol) of 2,2-dimethyl-1,3-propanediol and 60 g of dimethylformamide were taken at 80 ° C. Heated for 1 hour. Next, 33.2 g (40 mmol) of silicon diamine KF-8010 (manufactured by Shin-Etsu Silicone), 8.61 g (20 mmol) of BAPS-M and 30 g of DMF were added and heated to 180 ° C. for 90 minutes under reduced pressure to obtain 71 g of a polyimide composition.

(Evaluation of heat resistant resin composition)
The following components were mixed and dissolved in a dioxolane solvent so as to have a solid content weight concentration of 40% to prepare a heat resistant resin composition solution.
(A) Polyimide composition synthesized by the above method 70 parts by weight (B) Isocyanate compound: 4,4′-diphenylmethane diisocyanate 30 parts by weight (C) Curing agent: None Evaluation was performed in the same manner as in Example 1. The adhesive strength was 11.0 N / cm. The solder heat resistance temperature was 280 ° C. The migration resistance showed a resistance value of 10 ⁻⁶ Ω or more for 75 hours or more, and no dendrite was observed.
(Comparative Example 1)
To a 500 ml separable flask equipped with a stirrer, 32.2 g (100 mmol) of BTDA and 60 g of dimethylformamide were added, and then 83.0 g (100 mmol) of silicon diamine KF-8010 (manufactured by Shin-Etsu Silicone) was added. Heated to 90 ° C. for 90 minutes to obtain 109 g of a polyimide composition. The same procedure as in Example 4 was performed except that the polyimide composition was replaced with that synthesized in the comparative example.

  Evaluation was performed in the same manner as in Example 1, and the adhesive strength was 10.0 N / cm. Even when the solder heat resistance temperature was 250 ° C., swelling occurred. The migration resistance was short-circuited in 24 hours, and dendrite was observed.

Comb pattern (line / space = 50 / 50μm)

Claims (3)

The polyimide composition which has a structure of following General formula (1) and General formula (2).

(However, R ¹ in the formula represents a tetravalent residue excluding tetracarboxylic acid from aromatic tetracarboxylic acid, R ² is a divalent organic group, and R ³ is a divalent excluding amino group from the diamine compound. Indicates a residue.)   A heat-resistant resin composition comprising a thermosetting compound in addition to the polyimide composition according to claim 1.   The heat-resistant resin composition according to claim 2, further comprising a flame retardant.

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