JP2008179751A - Novel thermosetting resin composition, cured film and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which can be suitably used as an electronic material, particularly as a film-forming material for coating a conductor circuit pattern and excels in the balance of properties (flexibility, a high elongation, high flexural property, adhesion to a substrate, high insulation property, and environmental stability). <P>SOLUTION: The thermosetting resin composition comprises (A) a polyamide resin having a specific structure, (B) a thermosetting resin, (C) inorganic or organic fine particles, and (D) an organic solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition, and relates to a thermosetting resin composition that can be suitably used as a material for covering a circuit surface in an electronic material (printed wiring board or the like).

  2. Description of the Related Art In recent years, electronic devices with high performance, high functionality, and miniaturization are rapidly progressing, and there is an increasing demand for miniaturization and weight reduction of electronic components used in electronic devices. Accordingly, various physical properties such as heat resistance, mechanical strength, electrical characteristics, and fine molding have been demanded more strongly than ever for materials for electronic components.

  In particular, with respect to a printed wiring board, high characteristics are required not only for a substrate for holding wiring but also for a surface protective material used as a wiring protective material. Furthermore, for the purpose of preventing oxidation of the conductor circuit pattern and maintaining insulation, it is necessary to use solder resist ink etc. on the formed conductor circuit pattern by screen printing method, spray method, photo development method, ink jet method, etc. In many cases, it is applied as an insulating pattern to form an insulating film. This insulating film is also required to have high insulation, environmental stability, adhesion to a substrate, high heat resistance, and mechanical strength. In particular, the printed wiring board has been changed from a hard substrate as a base material to a printed wiring board using a flexible substrate such as a polyimide film, and the material coated on the surface has high bending performance and stress on the base material. It is desired to be a low-stress material that is not applied.

  In addition, technological innovation related to COF (chip on film) that mounts recent IC chips on printed wiring boards is remarkable. The wiring width of the inner lead portion and the outer lead portion is now L / S and a product with a pitch of 25 μm is about to be commercialized. With the miniaturization of the wiring interval, a material that covers and insulates the wiring is desired to have high insulation and environmental stability.

  Conventionally, epoxy resin compositions that have been widely used for wiring coating materials have a problem that they are not flexible and cannot be used as protective materials for flexible printed wiring boards that require flexibility. For example, a resin composition using an epoxy-based resin has poor flexibility and has a problem of having only a few bending resistances (see, for example, Patent Document 1).

  Furthermore, there is an example of using polyimide siloxane as a polyimide resin whose resin is flexible and reduced in elastic modulus. However, these polyimide siloxanes use diamine having a dimethylsiloxane bond as a starting material for reducing the elastic modulus. Although it is used, there is a problem that adhesion with a sealing material, solvent resistance, and chemical resistance (solder flux resistance) decrease with an increase in the amount of siloxane modification (see, for example, Patent Document 2 or 3). .)

In addition, there is an example in which a polyimide resin having a urethane skeleton is used as a resin that has overcome the above-mentioned problems, but the resistance to an acidic solution is low. For example, a metal is laminated on the copper wiring surface of the printed wiring board surface by plating. At this time, there was a problem that the acidic solution was likely to permeate the metal / resin interface of the coating film (for example, see Patent Document 4).
JP 2002-40647 A JP 7-304950 A JP-A-8-333455 JP 2002-145981 A

  An object of the present invention is to obtain a thermosetting resin composition having improved adhesion to an encapsulant, solvent resistance, chemical resistance (solder flux resistance) and improved resistance to an acidic solution. Furthermore, in addition to the said characteristic, it is providing the thermosetting resin composition excellent in the softness | flexibility, adhesiveness with a base material, high insulation reliability, and moisture-proof adhesiveness at the time of low temperature hardening.

As a result of diligent research to solve the above-mentioned problems, the present inventors have conducted various studies on chemical resistance, which is a problem with the urethane imide, in particular, chemical resistance against acidic solutions. It has been found that the above-mentioned problems can be solved by using the urethane curable resin composition of the present invention containing a urethane urea imide resin into which a urea bond is introduced and a thermosetting resin.
That is, the present invention provides at least (A) the general formula (1).

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基を示し、複数個のＸ、Ｙ、Ｗは、それぞれ独立にアルキレン基、及び/又はアリーレン基を示し、ｌ、ｍ、ｎは１〜２０の整数であり、ｏは１以上、ｐは０以上の整数である。Ｚは一般式群（１）

(Wherein a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, and a plurality of X, Y, and W each independently represent an alkylene group and / or an arylene group; m and n are integers of 1 to 20, o is 1 or more, and p is an integer of 0 or more, Z is the general formula group (1)

に示される２価の有機基である。）
で表される繰り返し単位を有するポリイミド樹脂、
（Ｂ）熱硬化性樹脂、
（Ｃ）無機及び／又は有機の微粒子、及び
（Ｄ）有機溶剤
を含有することを特徴とする熱硬化性樹脂組成物である。
更に、前記（Ａ）ポリイミド樹脂が、
（ａ）一般式（２）

Is a divalent organic group. )
A polyimide resin having a repeating unit represented by:
(B) thermosetting resin,
A thermosetting resin composition comprising (C) inorganic and / or organic fine particles and (D) an organic solvent.
Further, the (A) polyimide resin is
(A) General formula (2)

（式中Ｚは一般式群（１）

(Wherein Z represents the general formula group (1)

より選ばれる２価の有機基を示す）
で表されるテトラカルボン酸二無水物、及び
（ｂ）一般式（３）

A divalent organic group selected from
A tetracarboxylic dianhydride represented by formula (b), and (b) a general formula (3)

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基を示し、複数個のＸ、Ｙは、それぞれ独立にアルキレン基、及び/又はアリーレン基を示し、ｌ、ｍ、ｎは１〜２０の整数である。）
で表されるウレタンウレアジアミン化合物を必須成分として反応させて得られることを特徴とする熱硬化性樹脂組成物である。
更に、前記（Ａ）ポリイミド樹脂が、
前記（ａ）のテトラカルボン酸二無水物、及び
前記（ｂ）のウレタンウレアジアミンに加えて、
さらに（ｃ）一般式（４）

(Wherein a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, a plurality of X's and Y's each independently represents an alkylene group and / or an arylene group; n is an integer of 1 to 20.)
It is obtained by making the urethane ureadiamine compound represented by these react as an essential component, It is a thermosetting resin composition characterized by the above-mentioned.
Further, the (A) polyimide resin is
In addition to the (a) tetracarboxylic dianhydride and the (b) urethane ureadiamine,
Furthermore, (c) general formula (4)

（式中、Ｗは一般式群（２）

Wherein W is the general formula group (2)

に示される２価の有機基を示す。）
で表されるジアミン化合物を追加のジアミン成分として反応させて得られるものであることを特徴とする熱硬化性樹脂組成物である。
更に、前記ウレタンウレアジアミン化合物が、
（ｄ）一般式（５）

The bivalent organic group shown by these is shown. )
It is obtained by making the diamine compound represented by these react as an additional diamine component, It is a thermosetting resin composition characterized by the above-mentioned.
Further, the urethane ureadiamine compound is
(D) General formula (5)

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基を示し、複数個のＸは、それぞれ独立にアルキレン基、及び/又はアリーレン基を示し、ｌ、ｍは１〜２０の整数である。）
で表されるポリジイソシアネート化合物と、
（ｅ）一般式（６）

(Wherein a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, a plurality of X's each independently represents an alkylene group and / or an arylene group; (It is an integer of 20.)
A polydiisocyanate compound represented by:
(E) General formula (6)

（式中、Ｙは一般式群（２）

(Where Y is the general formula group (2)

に示される２価の有機基を示す。）
で表されるジアミン化合物を反応成分として反応させて得られるウレタンウレアジアミン化合物であることを特徴とする熱硬化性樹脂組成物である。
更に、前記ポリジイソシアネート化合物が、一般式（７）

The bivalent organic group shown by these is shown. )
It is a urethane urea diamine compound obtained by making the diamine compound represented by these react as a reaction component, It is a thermosetting resin composition characterized by the above-mentioned.
Further, the polydiisocyanate compound has the general formula (7)

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基を示し、ｌは、１〜２０の整数である。）
で表されるポリカーボネートジオールと、一般式（８）

(In the formula, a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, and l is an integer of 1 to 20).
A polycarbonate diol represented by the general formula (8)

（式中、Ｘは、アルキレン基、及び/又はアリーレン基を示す。）
で表されるジイソシアネートとを反応させることにより得られるポリジイソシアネート化合物であることを特徴とする熱硬化性樹脂組成物である。

(In the formula, X represents an alkylene group and / or an arylene group.)
It is a polydiisocyanate compound obtained by making it react with the diisocyanate represented by These are thermosetting resin compositions characterized by the above-mentioned.

  Particularly, with respect to 100 parts by weight of the component (A), the component (B) is 0.1 to 50 parts by weight, the component (C) is 1 to 90 parts by weight, and the component (D) is 100 to 300 parts by weight, It is a thermosetting resin composition characterized by containing.

  Furthermore, the component (B) is an epoxy resin, and is a thermosetting resin composition.

  Further, the component (C) is a thermosetting resin composition comprising at least one kind of inorganic fine particles selected from mica, silica, mica, barium sulfate, and talc.

  Another invention of the present invention is a cured film formed by curing a thermosetting resin composition, and further a printed wiring board formed by coating the thermosetting resin composition.

  The thermosetting resin composition of the present invention is a thermosetting resin composition having an excellent balance of physical properties required for electronic material applications, and even when blended with various thermosetting components, The composition can be suitably used as a coating forming material for coating a conductor circuit pattern without impairing the characteristics of the thermosetting component.

The present invention will be described below. The present invention includes at least (A) the general formula (1)

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基を示し、複数個のＸ、Ｙ、Ｗは、それぞれ独立にアルキレン基、及び/又はアリーレン基を示し、ｌ、ｍ、ｎは１〜２０の整数であり、ｏは１以上、ｐは０以上の整数である。Ｚは一般式群（１）

(Wherein a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, and a plurality of X, Y, and W each independently represent an alkylene group and / or an arylene group; m and n are integers of 1 to 20, o is 1 or more, and p is an integer of 0 or more, Z is the general formula group (1)

に示される２価の有機基である。）
で表される繰り返し単位を有するポリイミド樹脂、
（Ｂ）熱硬化性樹脂、
（Ｃ）無機又は有機の微粒子、及び
（Ｄ）有機溶剤
を含有することを特徴とする熱硬化性樹脂組成物である。

Is a divalent organic group. )
A polyimide resin having a repeating unit represented by:
(B) thermosetting resin,
A thermosetting resin composition containing (C) inorganic or organic fine particles and (D) an organic solvent.

The polyimide resin is
(A) tetracarboxylic dianhydride represented by the following general formula (2),

（式中Ｚは一般式群（１）より選ばれる２価の有機基を示す。）

(In the formula, Z represents a divalent organic group selected from the general formula group (1).)

及び、
下記一般式（３）で表される（ｂ）ウレタンウレアジアミン

as well as,
(B) Urethane ureadiamine represented by the following general formula (3)

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基を示し、複数個のＸ、Ｙは、それぞれ独立に炭素数１〜１８のアルキレン基又はアリーレン基を示し、ｌ、ｍ、ｎは１〜２０の整数である。）
を必須成分として反応させることにより得られる。
下記のそれぞれの構成原料についての説明を行う。

(In the formula, a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, and a plurality of X and Y each independently represents an alkylene group or arylene group having 1 to 18 carbon atoms; , M and n are integers of 1 to 20.)
Can be obtained by reacting as an essential component.
Each of the following constituent materials will be described.

<Acid dianhydride>
As the (a) tetracarboxylic dianhydride described in the general formula (2), in the present invention, in particular, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 2,2′-hexafluoropropylidenediphthalic dianhydride, 2,2-bis (4- Hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid It is preferable to use a dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, or 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride. Use of these tetracarboxylic dianhydrides is preferable for imparting toughness, heat resistance and solubility in organic solvents to the polyimide resin. Among these, the use of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is particularly preferable because the acid resistance of the thermosetting resin can be improved.

<Method for producing urethane ureadiamine>
In the present invention, (b) the urethane ureadiamine represented by the general formula (3) is (d) the general formula (5).

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基を示し、複数個のＸは、それぞれ独立に炭素数１〜１８のアルキレン基又はアリーレン基を示し、ｌ、ｍは１〜２０の整数である）
で表されるポリジイソシアネート化合物と、
（ｅ）一般式（６）

(Wherein a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, and a plurality of X's each independently represents an alkylene group or arylene group having 1 to 18 carbon atoms; Is an integer from 1 to 20)
A polydiisocyanate compound represented by:
(E) General formula (6)

（式中、Ｙは一般式群（２）

(Where Y is the general formula group (2)

に示される２価の有機基を示す。）
で表されるジアミン化合物を反応成分として反応させて得られる。
上記一般式（５）で表されるポリジイソシアネート化合物は、一般式（７）

The bivalent organic group shown by these is shown. )
It is obtained by reacting a diamine compound represented by
The polydiisocyanate compound represented by the general formula (5) is represented by the general formula (7).

（式中、複数個のＲはそれぞれ独立に炭素数１〜１８のアルキレン基を示し、ｌは、１〜２０の整数である。）
で表されるポリカーボネートジオールと、
下記一般式（８）

(In the formula, a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, and l is an integer of 1 to 20).
Polycarbonate diol represented by
The following general formula (8)

（式中、Ｘは、アルキレン基、及び/又はアリーレン基を示す。）
で表されるジイソシアネートとを無溶媒あるいは有機溶媒中で反応させることにより得られる。
ポリカーボネートジオールとしては、
下記一般式（７）の構造を有するポリカーボネートジオールであって、

(In the formula, X represents an alkylene group and / or an arylene group.)
It can be obtained by reacting with a diisocyanate represented by the formula in the absence of a solvent or in an organic solvent.
As polycarbonate diol,
A polycarbonate diol having the structure of the following general formula (7),

特に、式中のＲは、−（ＣＨ_２）_４−、−（ＣＨ_２）_５−、−（ＣＨ_２）_６−、−ＣＨ_２Ｃ（ＣＨ_３）_２ＣＨ２−、−ＣＨ_２ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ₃）ＣＨ_２ＣＨ_２−、から選ばれる少なくとも１種であることが好ましい。このような好適な構造を有するポリカーボネートジオール化合物としては、例えば、ダイセル化学（株）製の商品名ＰＬＡＣＣＥＬ、ＣＤ−２０５、２０５ＰＬ、２０５ＨＬ、２１０、２１０ＰＬ、２１０ＨＬ、２２０、２２０ＰＬ、２２０ＨＬ、旭化成（株）製の商品名ＰＣＤＬ、Ｔ６００２、Ｔ６００１、Ｔ５６５２、Ｔ５６５１、Ｔ５６５０Ｊ、Ｔ４６７２、Ｔ４６７１、Ｔ４６９２、Ｔ４６９１として市販されているのものが挙げられ、これらを単独で又は２種類以上を組み合わせて使用できる。

In particular, R in the _{formula, - (CH 2) 4 -} , - (CH 2) 5 -, - (CH 2) 6 -, - CH 2 C (CH 3) 2 CH2 -, - CH 2 CH (CH _{3) CH 2 -, - CH} 2 CH (CH 3) CH 2 CH 2 -, is preferably at least one selected from the. As the polycarbonate diol compound having such a suitable structure, for example, trade names PLACEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL, manufactured by Daicel Chemical Co., Ltd., Asahi Kasei Corporation ) Manufactured product names PCDL, T6002, T6001, T5652, T5651, T5650J, T4672, T4671, T4692, and T4691 can be used, and these can be used alone or in combination of two or more.

  Examples of the diisocyanates represented by the general formula (8) include diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'-, 4,2'-, or 4,3'-. Or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2 ' -Or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3 '-Or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane- 4,4'-diisocyanate, diphenylmethane-3 3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, Such as tolylene-2,6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate Preference is given to using aromatic polyisocyanates. These can be used alone or in combination of two or more. In addition, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, lysine diisocyanate, etc. Aliphatic or alicyclic isocyanates and tri- or higher functional polyisocyanates may be used, and those stabilized with a blocking agent may be used. Examples of the blocking agent include alcohol, phenol and oxime, but there is no particular limitation.

  Isocyanates that can be used particularly preferably include benzophenone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, and tolylene-2,6-diisocyanate to improve acid resistance and improve adhesion to metals. This is preferable.

  The blending amount of the polycarbonate diol represented by the general formula (7) and the diisocyanate represented by the general formula (8) is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is isocyanate group / hydroxyl group = 2.00 or more. The polydiisocyanate compound represented by the general formula (5) is synthesized by reacting without solvent or in an organic solvent.

  The reaction temperature at this time is preferably 60 to 250 ° C., and the reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and the like.

  The reaction can be carried out without a solvent, but in order to arrange isocyanate groups at both ends, it is preferable to carry out the reaction at a reduced concentration in a solvent system, for example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, Formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-vinyl- Pyrrolidone solvents such as 2-pyrrolidone, phenol solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol, catechol, hexamethylphosphoramide, γ-butyrolactone, methyl monoglyme (1, 2-dimethoxyethane), methyldi Glyme (bis (2-methoxyethoxy) ether), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl Symmetrical glycol diethers such as monoglyme (1,2-diethoxyethane), ethyl diglyme (bis (2-ethoxyethyl) ether), butyl diglyme (bis (2-butoxyethyl) ether), methyl acetate, Ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate, acetic acid 2- (2-butoxyethoxy) ) Ethyl)), diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, etc. Acetates, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n- Propyl ether, propylene glycol phenyl ether, dipropy Glycol dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, can be used diethylene glycol monobutyl ether, ethers such as ethyl ether also ethylene glycol.

  The amount of the solvent used in the reaction is preferably such that the solute weight concentration of the solute (polycarbonate diol and diisocyanate) in the reaction solution is 5% by weight or more and 90% by weight or less. More preferably, it is 10 to 80% by weight. When the solution concentration is 5% or less, the polymerization reaction is difficult to occur, the reaction rate is lowered, and a desired structural substance may not be obtained.

  The reaction temperature is preferably 60 to 200 ° C, more preferably 80 to 150 ° C. If it is less than 60 ° C., the reaction time becomes too long, and if it exceeds 200 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed. If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound. In addition, the isocyanate group at the end of the resin can be blocked with a blocking agent such as alcohols, lactams, or oximes after completion of the synthesis.

<Diamines used for urethane ureadiamine>
It is preferable to use (c) a diamine represented by the following general formula (6) used as a raw material for urethane urea diamine.
(E) General formula (6)

（式中、Ｙは一般式群（２）

(Where Y is the general formula group (2)

に示される２価の有機基を示す。）
上記一般式（４）のジアミンとしては、ｍ−フェニレンジアミン、ｏ−フェニレンジアミン、ｐ−フェニレンジアミン、ｍ−アミノベンジルアミン、ｐ−アミノベンジルアミン、ビス（３−アミノフェニル）スルフィド、（３−アミノフェニル）（４−アミノフェニル）スルフィド、ビス（４−アミノフェニル）スルフィド、ビス（３−アミノフェニル）スルホキシド、（３−アミノフェニル）（４−アミノフェニル）スルホキシド、ビス（４−アミノフェニル）スルホキシド、ビス（３−アミノフェニル）スルホン、（３−アミノフェニル）（４−アミノフェニル）スルホン、ビス（４−アミノフェニル）スルホン、３，４’−ジアミノベンゾフェノン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノン、３，３’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、ビス［４−（３−アミノフェノキシ）フェニル］スルホキシド、ビス［４−（アミノフェノキシ）フェニル］スルホキシド、（４−アミノフェノキシフェニル）（３−アミノフェノキシフェニル）フェニル］スルホキシド、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ビス［４−（アミノフェノキシ）フェニル］スルホン、（４−アミノフェノキシフェニル）（３−アミノフェノキシフェニル）フェニル］スルホン、ビス［４−（３−アミノフェノキシ）フェニル］スルフィド、ビス［４−（アミノフェノキシ）フェニル］スルフィド、（４−アミノフェノキシフェニル）（３−アミノフェノキシフェニル）フェニル］スルフィド、３，３’−ジアミノベンズアニリド、３，４’−ジアミノベンズアニリド、４，４’−ジアミノベンズアニリド、ビス［４−（３−アミノフェノキシ）フェニル］メタン、ビス［４−（４−アミノフェノキシ）フェニル］メタン、[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）]メタン、１，１−ビス［４−（３−アミノフェノキシ）フェニル］エタン、１，１−ビス［４−（４−アミノフェノキシ）フェニル］エタン、１，１−[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）]エタン、１，２−ビス［４−（３−アミノフェノキシ）フェニル］エタン、１，２−ビス［４−（４−アミノフェノキシ）フェニル］エタン、１，２−[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）]エタン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）] プロパン、２，２−ビス［３−（３−アミノフェノキシ）フェニル］−１，１，１，３，３，３−ヘキサフルオロプロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］−１，１，１，３，３，３−ヘキサフルオロプロパン、２，２−[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）] −１，１，１，３，３，３−ヘキサフルオロプロパン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，４−ビス（３−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、４，４’−ビス（３−アミノフェノキシ）ビフェニル、ビス［４−（３−アミノフェノキシ）フェニル］ケトン、ビス［４−（４−アミノフェノキシ）フェニル］ケトン、ビス［４−（３−アミノフェノキシ）フェニル］エーテル、ビス［４−（４−アミノフェノキシ）フェニル］エーテル、ポリテトラメチレンオキシド−ジ−Ｐ−アミノベンゾエート、ポリ（テトラメチレン／３−メチルテトラメチレンエーテル）グリコールビス（４−アミノベンゾエート）、トリメチレン―ビス（４−アミノベンゾエート）、ｐ-フェニレン−ビス（４−アミノベンゾエート）、ｍ−フェニレン−ビス（４−アミノベンゾエート）、ビスフェノールＡ−ビス（４−アミノベンゾエート）、２，４−ジアミノ安息香酸、２，５−ジアミノ安息香酸、３，５−ジアミノ安息香酸、３，３’−ジアミノ−４，４’−ジカルボキシビフェニル、４，４’−ジアミノ−３，３’−ジカルボキシビフェニル、４，４’−ジアミノ−２，２’−ジカルボキシビフェニル、[ビス(４-アミノ-２-カルボキシ)フェニル]メタン、 [ビス(４-アミノ-３-カルボキシ)フェニル]メタン、[ビス(３-アミノ-４-カルボキシ)フェニル]メタン、 [ビス(３-アミノ-５-カルボキシ)フェニル]メタン、２，２−ビス[３−アミノ−４−カルボキシフェニル]プロパン、２，２−ビス[４−アミノ−３−カルボキシフェニル]プロパン、２，２−ビス[３−アミノ−４−カルボキシフェニル]ヘキサフルオロプロパン、２，２−ビス[４−アミノ−３−カルボキシフェニル]ヘキサフルオロプロパン、３，３’−ジアミノ−４，４’−ジカルボキシジフェニルエーテル、４，４‘−ジアミノ−３，３’−ジカルボキシジフェニルエーテル、４，４’−ジアミノ−２，２’−ジカルボキシジフェニルエーテル、３，３’−ジアミノ−４，４‘−ジカルボキシジフェニルスルフォン、４，４’−ジアミノ−３，３’−ジカルボキシジフェニルスルフォン、４，４’−ジアミノ−２，２’−ジカルボキシジフェニルスルフォンをあげることができる。
さらには、２，３−ジアミノフェノール、２，４−ジアミノフェノール、２，５−ジアミノフェノール、３，５−ジアミノフェノール等のジアミノフェノール類、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、４，４’−ジアミノ−３，３’−ジヒドロキシビフェニル、４，４’−ジアミノ−２，２’−ジヒドロキシビフェニル、４，４’−ジアミノ−２，２’，５，５’−テトラヒドロキシビフェニル等のヒドロキシビフェニル化合物類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルメタン、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルメタン、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルメタン等のジヒドロキシジフェニルメタン類、２，２−ビス[３−アミノ−４−ヒドロキシフェニル]プロパン、２，２−ビス[４−アミノ−３−ヒドロキシフェニル]プロパン等のビス[ヒドロキシフェニル]プロパン類、２，２−ビス[３−アミノ−４−ヒドロキシフェニル]ヘキサフルオロプロパン、２，２−ビス[３−アミノ−４−ヒドロキシフェニル]ヘキサフルオロプロパン等のビス[ヒヒドロキシフェニル]ヘキサフルオロプロパン類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルエーテル、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルエーテル等のヒドロキシジフェニルエーテル類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルフォン、４，４’−ジアミノ−３，３‘−ジヒドロキシジフェニルスルフォン、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルスルフォン等のジヒドロキシジフェニルスルフォン類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジアミノ−３，３‘−ジヒドロキシジフェニルスルフィド、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルスルフィド等のジヒドロキシジフェニルスルフィド類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルホキシド、４，４’−ジアミノ−３，３‘−ジヒドロキシジフェニルスルホキシド、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルスルホキシド等のジヒドロキシジフェニルスルホキシド類、２，２−ビス[４−（４−アミノ−３−ヒドロキシフェノキシ）フェニル]プロパン等のビス［（ヒドロキシフェニル）フェニル］アルカン化合物類、４，４’−ビス（４−アミノ−３−ヒドキシフェノキシ）ビフェニル等のビス（ヒドキシフェノキシ）ビフェニル化合物類、２，２−ビス[４−（４−アミノ−３−ヒドロキシフェノキシ）フェニル]スルフォン等のビス[（ヒドロキシフェノキシ）フェニル]スルフォン化合物、４，４’−ジアミノ−３，３’−ジハイドロキシジフェニルメタン、４，４’−ジアミノ−２，２’−ジハイドロキシジフェニルメタン、２，２−ビス[３−アミノ−４−カルボキシフェニル]プロパン、４，４’−ビス（４−アミノ−３−ヒドキシフェノキシ）ビフェニル等のビス（ヒドキシフェノキシ）ビフェニル化合物類をあげることができる。

The bivalent organic group shown by these is shown. )
Examples of the diamine of the general formula (4) include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide, (3- Aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4-aminophenyl) Sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,3′-dia Minodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis [4- (3- Aminophenoxy) phenyl] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone Bis [4- (aminophenoxy) phenyl] sulfone, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- ( Aminoph Noxy) phenyl] sulfide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfide, 3,3′-diaminobenzanilide, 3,4′-diaminobenzanilide, 4,4′-diaminobenzanilide Bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl) ] Methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1- [4- (4-amino) Phenoxyphenyl)] [4- (3-aminophenoxyphenyl)] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2- [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] ethane, 2, 2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- [4- (4-aminophenoxyphenyl)] [ 4- (3-aminophenoxyphenyl)] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2- [4- (4-aminophenoxyphenyl)] [4- (3-amino Phenoxyphenyl)]-1, 1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) ) Benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3 -Aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, Polytetramethylene oxide-di-P-aminobenzoate, poly (tetramethylene / 3-methyltetramethylene ether) glycol bis ( -Aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-aminobenzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis (4-aminobenzoate), 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3 '-Dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, [bis (4-amino-2-carboxy) phenyl] methane, [bis (4-amino-3-carboxy) phenyl] Methane, [bis (3-amino-4-carboxy) phenyl] methane, [bis (3-amino-5-carboxy) phenyl] methane, 2,2-bis [3-amino-4-carboxy Enyl] propane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 2,2-bis [4-amino- 3-carboxyphenyl] hexafluoropropane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxydiphenyl ether, 4,4′-diamino-2, 2'-dicarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3'-dicarboxydiphenyl sulfone, 4,4'-diamino-2, 2'-dicarboxydiphenyl sulfone can be mentioned.
Further, 2,3-diaminophenol, 2,4-diaminophenol, 2,5-diaminophenol, diaminophenols such as 3,5-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-2,2′-dihydroxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxy Hydroxybiphenyl compounds such as biphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′- Dihydroxydiphenylmethanes such as dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2 Bis [hydroxyphenyl] propanes such as bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2-bis [3-amino Bis [hyhydroxyphenyl] hexafluoropropanes such as -4-hydroxyphenyl] hexafluoropropane, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxy Hydroxy diphenyl ethers such as diphenyl ether, 4,4′-diamino-2,2′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 4,4′-diamino-3,3′- Dihydroxydiphenylsulfone, 4,4′-diamino-2,2′-dihydroxydipheny Dihydroxydiphenyl sulfones such as sulfone, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfide, 4,4′-diamino-2,2 Dihydroxydiphenyl sulfides such as' -dihydroxydiphenyl sulfide, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfoxide, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfoxide, 4,4'-diamino Dihydroxydiphenyl sulfoxides such as -2,2'-dihydroxydiphenyl sulfoxide, and bis [(hydroxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane 4,4′-bis (4-amino-3- Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as bis (hydroxyphenoxy) biphenyl compounds such as (hydroxyphenoxy) biphenyl and 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, Bis (hydroxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl can be exemplified.

  Among them, diamines that can be particularly preferably used are 3,5-diaminobenzoic acid, [bis (4-amino-3-carboxy) phenyl] methane, 3,5-diaminophenol, 4,4′-diamino-2, 2′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3- Aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4′- Bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethyl) Benzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′-dihydroxy-4,4′-diaminobiphenyl is preferably used. The diamine compound of component (c) constituting the urethane urea diamine is preferably an aromatic diamine, and considering the balance of heat resistance, solubility, mechanical properties, cost, etc., 3,3′-diamino Particularly preferred are diphenylsulfone, 4,4′-diaminodiphenylsulfone, and 3,4′-diaminodiphenylsulfone.

<Method for synthesizing urethane ureadiamine>
The urethane urea diamine of the present invention is obtained by reacting a polydiisocyanate compound represented by (d) general formula (5) and a diamine compound represented by (e) general formula (6) to obtain urethane urea diamine. Can do.

  The blending amount of the diamine compound represented by the general formula (6) and the polydiisocyanate compound represented by the general formula (5) is such that the ratio of the number of diamine groups to the number of isocyanate groups is diamine group / isocyanate group = 2.00 or more. The urethane ureadiamine represented by the general formula (3) is synthesized by reacting without solvent or in an organic solvent.

  The reaction temperature at this time is preferably -20 to 150 ° C., and the reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and the like. Since this reaction is a competitive reaction with the synthesis reaction of the urea resin, it is desirable that the reaction be carried out at a low reaction temperature, −20 to 150 ° C. or less, preferably −20 to 100 ° C. or less, more preferably −20 to It is desirable to make it react at 60 degrees C or less.

  Although this reaction can be carried out with a useless agent, in order to arrange a diamine group at both ends, it is desirable to carry out the reaction in a solvent system. As the solvent used, the above polydiisocyanate compound is synthesized. It may be the same as or different from the solvent used in the above. The solvent which can be preferably used is the same as the solvent used for the synthesis of the polydiisocyanate compound.

  The amount of the solvent used in the reaction is preferably such that the solute weight concentration of the solute (polyisocyanate compound and diamine compound) in the reaction solution is 5 wt% or more and 90 wt% or less. More preferably, it is 10 to 80% by weight. When the solution concentration is 5% or less, the polymerization reaction is difficult to occur and the reaction rate is lowered, and a desired structural substance may not be obtained.

<Additional diamine>
In the present invention, in addition to the urethane urea diamine, the diamine compound of the above general formula (4) can be used in combination as an additional diamine. Use of an additional diamine component in combination is preferable for imparting heat resistance and adjusting physical properties. As such a diamine compound, it is desirable to use one or more diamine compounds represented by the general formula (4).

  Examples of the diamine represented by the general formula (4) include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, and bis (3-aminophenyl). ) Sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4, 4'-diaminobenzophenone, 3,3'-diaminobenzo Enone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, Bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfoxide, bis [4- (3 -Aminophenoxy) phenyl] sulfone, bis [4- (aminophenoxy) phenyl] sulfone, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] The Fido, bis [4- (aminophenoxy) phenyl] sulfide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfide, 3,3′-diaminobenzanilide, 3,4′-diaminobenzanilide, 4,4′-diaminobenzanilide, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, [4- (4-aminophenoxyphenyl)] [4 -(3-aminophenoxyphenyl)] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1 -[4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] ethane, 1,2-bis [4- ( -Aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2- [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl) )] Ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- [4- (4- Aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2- [4- (4-aminophenoxyphenyl)] [ 4- (3 Aminophenoxyphenyl)]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) Biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4 -Aminophenoxy) phenyl] ether, polytetramethylene oxide-di-P-aminobenzoate, poly (tetramethylene / 3-methylteto Methylene ether) glycol bis (4-aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-aminobenzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis (4-aminobenzoate), 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4 '-Diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, [bis (4-amino-2-carboxy) phenyl] methane, [bis (4-amino -3-carboxy) phenyl] methane, [bis (3-amino-4-carboxy) phenyl] methane, [bis (3-amino-5-carboxy) phenyl] 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] ] Hexafluoropropane, 2,2-bis [4-amino-3-carboxyphenyl] hexafluoropropane, 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3 '-Dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3' -Dicarboxydiphenyl sulfone and 4,4'-diamino-2,2'-dicarboxydiphenyl sulfone can be mentioned.

  Further, 2,3-diaminophenol, 2,4-diaminophenol, 2,5-diaminophenol, diaminophenols such as 3,5-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-2,2′-dihydroxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxy Hydroxybiphenyl compounds such as biphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′- Dihydroxydiphenylmethanes such as dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxypheny Bis [hydroxyphenyl] propanes such as 2, 2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, , 2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, etc., bis [hyhydroxyphenyl] hexafluoropropanes, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′- Hydroxydiphenyl ethers such as diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 4,4 ′ -Diamino-3,3'-dihydroxydiphenylsulfone, 4,4'-dia Di-2,2′-dihydroxydiphenylsulfone, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfide, 4 , 4'-diamino-2,2'-dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfides, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfoxide, 4,4'-diamino-3,3'-dihydroxy Dihydroxy sulfoxide, dihydroxydiphenyl sulfoxides such as 4,4′-diamino-2,2′-dihydroxydiphenyl sulfoxide, bis [2, such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane (Hydroxyphenyl) pheny ] Alkane compounds, bis (hydroxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, 2,2-bis [4- (4-amino-3- Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as hydroxyphenoxy) phenyl] sulfone, 34,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane Bis (hydroxyphenoxy) biphenyl compounds such as 2,2-bis [3-amino-4-carboxyphenyl] propane and 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl Can do.

  Among them, diamines that can be particularly preferably used are 3,5-diaminobenzoic acid, [bis (4-amino-3-carboxy) phenyl] methane, 3,5-diaminophenol, 4,4′-diamino-2, 2′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3- Aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4′- Bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethyl) Benzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′-dihydroxy-4,4′-diaminobiphenyl is preferably used.

  As the diamine compound as the component (c), 50 to 100% by weight of the total amount is preferably aromatic diamine, and considering the balance of heat resistance, solubility, mechanical properties, cost, etc., 3, 3 Particularly preferred are '-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, and 3,4'-diaminodiphenylsulfone.

<Relationship between the amount of each raw material used>
In the present invention, the blending ratio of the urethane urea diamine represented by the general formula (3) of the component (b) and the additional diamine compound of the component (c) is 0.00 by the equivalent ratio of the component (b) / (c) component. 1 / 0.9 to 1.0 / 0.0 is preferable, 0.2 / 0.8 to 1.0 / 0.0 is more preferable, and 0.3 / 0.7 to 1 Particularly preferred is 0.0 / 0.0. If the equivalent ratio is less than 0.1 / 0.9, the elastic modulus cannot be reduced, and the warpage and adhesion tend to be lowered.

  The ratio of the tetracarboxylic dianhydride of the component (a) is such that the ratio of the total number of acid anhydride groups of the component (a) to the total number of diamine groups in the components (b) and (c) is 0.00. It is preferably 6 to 1.4, more preferably 0.7 to 1.3, and particularly preferably 0.8 to 1.2. When this ratio is less than 0.6 or exceeds 1.4, it tends to be difficult to increase the molecular weight of the polyimide resin.

<Polymerization method>
The polyimide resin of the present invention is obtained by dehydrating and ring-closing the corresponding precursor polyamic acid polymer. The polyamic acid polymer comprises (a) a tetracarboxylic dianhydride represented by the general formula (2) and (b) a diamine component represented by the general formula (3) and (c) the general formula (4). It can be obtained by a substantially equimolar reaction.

  A typical procedure for the reaction is a method in which one or more diamine components are dissolved or dispersed in an organic polar solvent, and then one or more acid dianhydride components are added to obtain a polyamic acid solution. Moreover, there is no problem even if the polyimide resin solution is synthesized without going through the polyamic acid solution. Specifically, the following method is mentioned. The reaction time and reaction temperature are not particularly limited.

1) A method of adding a urethane urea diamine (general formula (3)) and a diamine (general formula (4)), which have been synthesized in advance by adding an acid dianhydride component to an organic polar solvent in advance.
2) A method in which, after synthesizing urethane ureadiamine, a diamine component is additionally added and reacted with an acid dianhydride component.
3) After synthesizing urethane ureadiamine, a method of adding an acid dianhydride component and reacting it can be adopted.

<Polymerization solvent>
Examples of the organic polar solvent used for the polyamic acid polymerization reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N- Acetamide solvents such as dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, Phenolic solvents such as halogenated phenol and catechol, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ether), methyltriglyme (1,2-bis (2-methoxy) Ethoxy) ethane), methyltetragly (Bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyl diglyme (bis (2-ethoxyethyl) ether), butyl diglyme (bis (2 Symmetric glycol diethers such as -butoxyethyl) ether), γ-butyrolactone, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate (aka carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate)), diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol mono Acetates such as methyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene Glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n-propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane , Ethylene glycol monobutyl ether, diethylene glycol monoe Ether, diethylene glycol monobutyl ether, a solvent may be used ethers such as ethyl ether also ethylene glycol.

  It describes about the imidation method of the polyamic acid of this invention. As a method for imidizing a polyamic acid solution, there are a thermal imidization method in which heating and dehydration are carried out without using a catalyst or a dehydrating agent, and a chemical imidation method in which a dehydrating agent and a catalyst are mixed and heated.

  Examples of the dehydrating agent used in the chemical imidization method include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides. Preferably, acetic anhydride is used for the polyimide resin extraction step. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, isoquinoline, β-picoline, γ-picoline, and lutidine. And the like. However, depending on the catalyst used, the reaction time may be long or imidization may not proceed sufficiently, and it is preferable to select a suitable catalyst for the polyimide resin as appropriate. In particular, catalysts that can be suitably used in the present invention are pyridine, isoquinoline, and β-picoline.

  The amount of the dehydrating agent and the catalyst added to the polyamic acid depends on the chemical structural formula constituting the polyamic acid, but is preferably the dehydrating agent mole number / the amide group mole number in the polyamic acid = 10 to 0.01. The number of moles of medium amide group is preferably 10 to 0.01. More preferably, the number of moles of dehydrating agent / the number of amide groups in the polyamic acid is preferably 5 to 0.5, and the number of moles of amide groups in the catalyst / polyamic acid is preferably 5 to 0.5.

  In the chemical imidization method, in order to accelerate the imidization reaction, it is preferable to heat the stirring solution by adding a dehydrating agent and a catalyst to the polyamic acid solution at 200 ° C. or less, more preferably 150 ° C. or less. It is preferable that the heating is carried out in order to advance the imidization reaction. The heating temperature is preferably selected in consideration of the catalyst used, the boiling point of the dehydrating agent, and the like. The heating time is preferably appropriately selected according to the type of polyimide resin, the catalyst, and the type of dehydrating agent, but is preferably 1 hour or longer and 10 hours or shorter, more preferably 1 hour or longer and 5 hours or shorter. Since imidation reaction can be advanced, it is preferable. The imidation reaction is desirably performed in a solvent in which the polyamic acid solution is dissolved.

  In addition, a method of directly heating a polyamic acid solution to thermally imidize is also known. As an azeotropic solvent in the polyamic acid solution, aromatic hydrocarbons such as toluene, xylene, solvent naphtha, cyclohexane, methylcyclohexane , Cycloidic hydrocarbons such as dimethylcyclohexane, etc. are mixed in the range of 1 to 30% by weight, preferably 5 to 20% by weight in the total organic solvent, and azeotropically distilled while distilling off the water to heat imidization. Is used. The heating temperature is desirably equal to or higher than the glass transition temperature of the finally obtained polyimide resin.

  It describes about the extraction method of imide resin from the said solution. As a method of extracting a polyimide resin from a polyimide resin solution produced by the above polyimide resin production method, a polyimide resin solution containing a polyimide resin, an imidization dehydrating agent, and an imidization catalyst is contained in a poor solvent for the polyimide resin. , Or a method of extracting a polyimide resin into a solid state by introducing a poor solvent. The poor solvent for the polyimide resin used in the present invention is a poor solvent for the corresponding polyimide, such as water, methyl alcohol, ethyl alcohol, ethylene glycol, triethylene glycol, isopropyl alcohol, and the like, as a dissolving solvent for the polyamic acid and the polyimide resin. Those miscible with the organic solvent used are used, and the above-mentioned alcohols are preferably used.

  When injecting the polyimide resin solution into the poor solvent, the diameter immediately before the addition of the polyimide resin solution is preferably 1 mm or less, and more preferably, the diameter is 0.5 mm in the drying process. Preferred for removing the solvent. The amount of the poor solvent is preferably extracted in an amount of 3 times or more of the polyimide resin solution (amount including all the catalyst and dehydrating agent).

  In the present invention, since the resin is in the form of a thread immediately after the resin is charged, it is preferable to stir at a high speed rotation of 100 rotations / minute or more in order to form a flaky polyimide resin as fine as possible. .

  The solid polyimide resin is taken out and cleaned in a cleaning device equivalent to a Soxhlet cleaning device. The solvent to be used is preferably a volatile solvent, and a solvent such as methanol, ethanol or isopropanol is preferred.

  The drying method of the resin solid material solidified and formed into flakes in the present invention may be vacuum drying or hot air drying. Although the drying temperature depends on the imide resin, it is desirable to dry at a temperature lower than the glass transition temperature, and it is desirable to dry at a temperature higher than the boiling points of various solvents, catalysts, and dehydrating agents.

  In addition to the above extraction method, a method of extracting the resin by heating and drying the polyimide resin solution directly at a temperature higher than the boiling point of the solvent component contained in the system is also used.

  As the thermal imidization method, it is desirable to perform imidization while volatilizing the solvent in a heat-dryable apparatus equipped with a vacuum apparatus. In particular, the heating temperature is desirably higher than the glass transition temperature of the polyimide resin and higher than the boiling point of the substance that volatilizes from the system by 10 ° C. or more for 1 hour or more, and the degree of vacuum is desirably 10 Torr or less. In this way, the solvent content in the polyimide resin is completely volatilized by raising the temperature above the glass transition temperature of the polyimide resin after the solvent is volatilized, and at the same time, water generated by the imidization reaction is promoted by imidizing the polyimide resin. This is preferable because it can be removed.

(B) Thermosetting resin The thermosetting resin used in the resin composition of the present invention is epoxy resin, isocyanate resin, bismaleimide resin, bisallyl nadiimide resin, acrylic resin, methacrylic resin, hydrosilyl cured resin, allyl cured. Resin, thermosetting resin such as unsaturated polyester resin, and side chain having a reactive group such as glycidyl group, isocyanate group, allyl group, vinyl group, alkoxysilyl group, hydrosilyl group at the side chain or terminal of polymer chain A reactive group type thermosetting polymer or the like can be used. The thermosetting component may be used alone or in combination of two or more.

  Among these, it is preferable to use an epoxy resin. By containing an epoxy resin component or an isocyanate resin, heat resistance can be imparted to a cured resin obtained by curing a thermosetting resin composition, and adhesion to a conductor such as a metal foil or a circuit board is imparted. be able to.

  The epoxy resin contains at least two epoxy groups in the molecule, and is bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolac type epoxy resin. , Water added bisphenol A type epoxy resin, ethylene oxide adduct bisphenol A type epoxy resin, propylene oxide adduct bisphenol A type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, Alkylphenol novolac type epoxy resin, polyglycol type epoxy resin, cycloaliphatic epoxy resin, cyclopentadiene type epoxy resin, dicyclopentadiene Type epoxy resins, cresol novolak type epoxy resins, glycidyl amine type epoxy resins, naphthalene type epoxy resins, urethane modified epoxy resins, rubber-modified epoxy resin, an epoxy resin such as epoxy-modified polysiloxane. These epoxy resins may be used alone or in combination of two or more at any ratio.

  Examples of the epoxy resin include, for example, the product name Epicron HP-4700 of the naphthalene type tetrafunctional epoxy resin manufactured by Dainippon Ink Chemical Co., Ltd., the product name Epicron HP-7200 of the cyclopentadiene type epoxy resin, and the product of phenol novolac type epoxy resin The name Epicron N-740, Epicron EXA-7240, which is a highly heat-resistant epoxy resin, Epicron N-660, N-665, N-670, N-680, N-665, which is a cresol novolac type polyfunctional epoxy resin EXP, trade name of phenol novolac type epoxy resin Epicron N-740, trade name of tetraphenylethane type epoxy resin, Epicron ETePE, trade name of triphenylmethane type epoxy resin, Epicron ETrPM, trade name of Japan Epoxy Resin Co., Ltd. Bisphenol A type epoxy resin such as Tote Kasei Co., Ltd., Bisphenol F type epoxy resin such as YDF-170, manufactured by Toto Kasei Co., Ltd., Epicoat 152, 154 manufactured by Japan Epoxy Resin Co., Ltd., Nippon Kayaku ( Phenol novolac type epoxy resin such as trade name EPPN-201 manufactured by Dow Chemical Co., Ltd., and trade name EOCN-125S, 103S, 104S manufactured by Nippon Kayaku Co., Ltd. Novolac type epoxy resin, trade name Epon 1031S manufactured by Japan Epoxy Resins Co., Ltd., trade name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., trade names Denacol EX-611, EX-614 manufactured by Nagase Chemical Co., Ltd. EX-614B, EX-622, EX-512, EX-521, EX 421, EX-411, EX-321 and other polyfunctional epoxy resins, Japan Epoxy Resin Co., Ltd. trade name Epicoat 604, Toto Kasei Co., Ltd. trade name YH434, Mitsubishi Gas Chemical Co., Ltd. trade name TETRAD-X, TERRAD-C, Nippon Kayaku Co., Ltd. trade name GAN, Sumitomo Chemical Co., Ltd. trade name ELM-120, etc. Amine type epoxy resin, Ciba Specialty Chemicals Co., Ltd. Heterocycle-containing epoxy resins such as the name Araldite PT810, and alicyclic epoxy resins such as ERL4234, 4299, 4221, and 4206 manufactured by UCC, and the like can be used alone or in combination of two or more.

  Among these epoxy resins, an epoxy resin having two or more epoxy groups in one molecule is particularly preferable in terms of improving heat resistance, solvent resistance, chemical resistance, and moisture resistance of the thermosetting resin composition.

  The amount of the (B) component epoxy resin used in the present invention is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, more preferably 100 parts by weight of the (A) component polyimide resin. Preferably it is 0.5-20 weight part. Solvent resistance, chemical resistance, moisture resistance, and heat resistance can be imparted by setting the compounding amount of the epoxy resin to 0.1 parts by weight or more, and if it exceeds 100 parts by weight, the thermosetting resin composition. Tend to lose its flexibility.

  The epoxy resin (B) used in the resin composition of the present invention may contain an epoxy compound having only one epoxy group in one molecule. Such an epoxy compound is preferably used in the range of 0 to 20% by weight based on the total amount of the polyimide resin. Examples of such epoxy compounds include n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, and dibromocresyl glycidyl ether. In addition, alicyclic epoxy compounds such as 3,4-epoxycyclohexyl and methyl (3,4-epoxycyclohexane) carboxylate can be used.

(C) Inorganic or organic fine particles (C) Inorganic and / or organic fine particles used in the present invention can be dispersed in the above-described polyimide resin solution to form a paste, and can impart thixotropic properties to the paste. If so, there is no problem. In particular, it is preferable to use inorganic fine particles because of excellent thermal stability, and it is particularly preferable to include at least one kind of inorganic fine particles selected from mica, silica, mica, barium sulfate, and talc.

  In addition to the above inorganic fine particles, for example, mica, alumina (Al 2 O 3), titania (TiO 2), tantalum oxide (Ta 2 O 5), zirconia (ZrO 2), silicon nitride (Si 3 N 4), barium titanate (BaO · TiO 2), barium carbonate (BaCO3), lead titanate (PbO.TiO2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO.Al2O3), mullite (3Al2O3.2SiO2) ), Cordierite (2MgO · 2Al2O3 / 5SiO2), talc (3MgO · 4SiO2 · H2O), aluminum titanate (TiO2-Al2O3), yttria-containing zirconia (Y2O3-ZrO2), barium silicate (BaO · 8SiO2), boron nitride (BN), calcium carbonate (CaCO3), calcium sulfate (CaSO4), zinc oxide (ZnO), magnesium titanate (MgO · TiO2), barium sulfate (BaSO4). Organic bentonite, carbon (C), etc. can be used. Furthermore, the organic fine particles used in the present invention are preferably heat-resistant resin fine particles having an amide bond, an imide bond, an ester bond or an ether bond. As the heat-resistant resin, polyimide fine particles and polyamide fine particles are preferably used from the viewpoint of heat resistance and mechanical properties.

  As the inorganic and / or organic fine particles in the present invention, those having an average particle size of 50 μm or less and a maximum particle size of 100 μm or less are preferably used. If the average particle diameter exceeds 50 μm, it will be difficult to sufficiently impart thixotropy described later, and if the maximum particle diameter exceeds 100 μm, the appearance and adhesion of the coating film tend to be insufficient. It is preferable to use inorganic fine particles as the fine particles.

  The amount of inorganic and / or organic fine particles used in the present invention is in the range of 1 to 90 parts by weight with respect to 100 parts by weight of the polyimide resin. If it is less than 1 part by weight, the thixotropic property is not sufficient, and if it exceeds 90 parts by weight, the fluidity of the paste is impaired and the surface smoothness of the film tends to be lowered. In particular, the amount is preferably 2 to 50 parts by weight.

  As a method for dispersing inorganic and / or organic fine particles in a polyimide resin solution, roll kneading, mixer mixing, bead dispersion, homogenizer dispersion, etc., which are usually performed in the paint field, are applied, and sufficient dispersion is achieved. There is no particular limitation as long as it is performed. A plurality of kneading operations with three rolls is most preferable.

(D) Organic solvent As the organic solvent used in the present invention, any solvent can be used as long as the polyimide resin and the thermosetting resin are dissolved therein. For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide , Pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol and catechol, or hexamethyl Phosphoramide, γ-butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ether), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane ), Methyltetra Glyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyl diglyme (bis (2-ethoxyethyl) ether), butyl diglyme (bis ( 2-butoxyethyl) ether), symmetric glycol diethers, γ-butyrolactone, N-methyl-2-pyrrolidone, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate , Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate), diethylene glycol monobutyl ether acetate, Acetates such as 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, and dipropylene glycol methyl ether , Tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n-propyl ether, propylene glycol phenyl ether, dipropylene Glycol dimethyl ether, 1,3-dioxolane, ethylene glycol Over mono-butyl ether, it may be mentioned diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, a solvent of ethers such as ethyl ether also ethylene glycol. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

  The (D) organic solvent in the present invention contains 100 to 300 parts by weight of the component (D) with respect to 100 parts by weight of the component (A), so that the solution viscosity of the thermosetting resin does not become too high. Therefore, it is preferable.

(E) Other components In the thermosetting resin composition of the present invention, an interface such as an antifoaming agent and a leveling agent is added to the thermosetting resin composition of the present invention, if necessary, in order to improve the workability during coating and the film properties before and after film formation. To impart activators, coloring agents such as dyes or pigments for coloring, curing accelerators for improving thermosetting properties, thermal stabilizers for preventing heat deterioration, antioxidants, flame retardancy It is preferable to use various additives such as a flame retardant and a lubricant for imparting slipperiness of the thermosetting resin film.

For example, the epoxy curing agent is not particularly limited, but phenol phenolic resins such as phenol novolac phenol resin, cresol novolac phenol resin, naphthalene phenol resin; dodecyl succinic anhydride, polyadipic anhydride, Aliphatic acid anhydrides such as polyazeline acid anhydride; alicyclic acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic acid; phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid, ethylene glycol bis trimelli Aromatic acid anhydrides such as tate and glycerol trislimitate; amino resins, urea resins, melamine resins, dicyandiamide, dihydrazine compounds, imidazole compounds, Lewis acids, and Bronsted acid salts, polymercaptan compounds S, isocyanate and blocked isocyanate compounds, and the like can be exemplified.
The said hardening | curing agent should just be used combining 1 type (s) or 2 or more types, and it is preferable to use within the range of 1 weight part-100 weight part with respect to 100 weight part of all the epoxy resins.

  In addition, the curing accelerator for the epoxy resin is not particularly limited. For example, a phosphine compound such as triphenylphosphine; an amine compound such as tertiary amine, trimethanolamine, triethanolamine, and tetraethanolamine; 1 Borate compounds such as 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazoles such as 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole; 2-methylimidazoline , 2-ethyli Imidazolines such as dazoline, 2-isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; 2,4-diamino-6- [2′- Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 Examples include azine-based imidazoles such as-[2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine. When the imide resin contains an amino group, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-diamino-6- [ It is preferable to use imidazoles such as 2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine.

  The said hardening accelerator should just be used combining 1 type (s) or 2 or more types, and it is used within the range of 0.01 weight part-10 weight part with respect to 100 weight part of all thermosetting resin group compositions. preferable.

  The thermosetting resin composition of the present invention includes, for example, an interlayer insulating film, a surface protective film, a solder resist layer, an adhesive layer, and the like in the field of overcoat materials for semiconductor elements and various electronic parts, rigid or flexible substrates, and liquid sealing. It can be used for a varnish for a sheet, a varnish for an MCL laminate, and a varnish for a friction material in combination with a base material such as a stopper, an enameled wire varnish, an impregnation varnish for electrical insulation, a casting varnish, mica, and a glass cloth.

  In particular, since the thermosetting resin composition of the present invention is excellent in flexibility and excellent in electrical insulation reliability, it can be suitably used as a coating material for printed wiring boards such as semiconductor elements, flexible circuit boards, and laminates. it can.

  The thermosetting resin composition in the Example of this invention evaluated the physical-property value by the method shown below.

(Adhesion evaluation)
An organic solvent solution of the thermosetting resin composition is applied to a 25 μm polyimide film (manufactured by Kaneka Corporation, Apical 25 NPI), dried at 120 ° C. for 90 minutes and 160 ° C. for 30 minutes, and the polyimide film surface has a thickness of 20 μm. A film was formed. The adhesive strength of this coating film was evaluated by a cross-cut tape method according to JIS K-5400.
○ The one that does not peel off by the cross-cut tape method
△, if more than half of the cells remain
The case where the residual amount of the squares was less than half was marked with x.

(Flexibility evaluation)
An organic solvent solution of the thermosetting resin composition was applied to a 25 μm polyimide film (manufactured by Kaneka Corporation, Apical 25 NPI) and dried at 120 ° C. for 90 minutes and 160 ° C. for 30 minutes to obtain a polyimide film laminate. This polyimide film laminate was cut into 30 mm × 10 mm strips, bent 10 times at 180 ° at 15 mm, and the coating film was visually confirmed to check for cracks.
○: The cured film has no cracks Δ: The cured film has some cracks ×: The cured film has cracks (warping amount)
A thermosetting resin composition is applied to the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) so that the final coating thickness is 25 μm, and heated and dried at 120 ° C. for 90 minutes and 160 ° C. for 30 minutes. Thus, a polyimide film laminate was obtained. A 50 mm × 50 mm square film was cut out from this polyimide film laminate, placed on a surface plate with the coated surface down, and the warp height was evaluated. In addition, what a film completely curls and becomes cylindrical is described as curl.

(Acid resistance)
A thermosetting resin composition was applied to the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) and a 18 μm-thick copper foil (Nihon Denki Co., Ltd. USLPSE-18) so that the final coating thickness was 20 μm. Then, it was heated and dried at 120 ° C. for 90 minutes and 160 ° C. for 30 minutes to obtain a polyimide film laminate. The state of the film after immersing this polyimide film and copper foil in a 10% hydrochloric acid solution (30 ° C.) for 10 minutes was observed.
◯: No penetration at the edge of the coating film ×: Permeation at the edge of the coating film Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is limited only to these examples. It is not a thing.

(Formulation example 1)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane (hereinafter abbreviated as methyltriglyme) as a solvent for polymerization was adjusted to a solid content concentration of 50% by weight of the polyimide resin solution. Tolylene diisocyanate (a mixture of 80% tolylene-2,4-diisocyanate and 20% tolylene-2,6-diisocyanate) (0.100 mol), trade name PCDLT6002 manufactured by Asahi Kasei Co., Ltd. (R in the general formula (7) was — (CH ₂ ) ₆ — and the average molecular weight was 2000, 0.050 mol), heated to 80 ° C. and reacted for 5 hours to obtain diisocyanate. The reaction solution was cooled to 20 ° C., 3,3′-diaminodiphenylsulfone (0.100 mol) was added, and the mixture was stirred uniformly for 5 hours to sufficiently react in the solution to synthesize urethane ureadiamine. BPADA (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride) (0.050 mol) was added to this solution, and the solution was charged at 80 ° C. for 1 hour and at 140 ° C. for 3 hours. The resulting solution was heated to reflux at 180 ° C. for 5 hours to obtain a polyimide resin solution. To 100 parts by weight of this polyimide resin solution, 2.0 parts by weight of silica (manufactured by Nippon Aerosil Co., Ltd., R-974), 2.0 parts by weight of talc (Fuji talc industry, LMS-200), barium sulfate (Sakai Chemical Industry) Co., B-34) 19 parts by weight was added to obtain a thermosetting resin composition.

(Formulation example 2)
In a separable flask pressurized with nitrogen, methyltriglyme as a solvent for polymerization was charged so that the solid content concentration of the polyimide resin solution was 50% by weight, and tolylene diisocyanate (toluene-2,4- (Mixture of 80% diisocyanate and 20% toluene-2,6-diisocyanate) (0.100 mol), trade name PCDLT5652 manufactured by Asahi Kasei Co., Ltd. (R of general formula (7) (CH ₂ ) ₅ -,- (CH ₂ ) ₆ — with an average molecular weight of 2000, 0.050 mol) was charged, heated to 80 ° C. and reacted for 5 hours to obtain diisocyanate. The reaction solution was cooled to 20 ° C., 3,3′-diaminodiphenylsulfone (0.100 mol) was added, and the mixture was stirred uniformly for 5 hours to sufficiently react in the solution to synthesize urethane ureadiamine. BPADA (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride) (0.050 mol) was added into the above homogeneously stirred solution of urethane urea diamine at 80 ° C. For 1 hour, 140 ° C. for 3 hours, and 180 ° C. for 5 hours to obtain a polyimide resin solution. To 100 parts by weight of this polyimide resin solution, 2.0 parts by weight of silica (manufactured by Nippon Aerosil Co., Ltd., R-974), 2.0 parts by weight of talc (Fuji talc industry, LMS-200), barium sulfate (Sakai Chemical Industry) Co., B-34) 19 parts by weight was added to obtain a thermosetting resin composition.

(Formulation example 3)
In a separable flask pressurized with nitrogen, methyltriglyme as a solvent for polymerization was charged so that the solid content concentration of the polyimide resin solution was 50% by weight, and diphenylmethane-4,4′-diisocyanate (0 100 mol), trade name PCDLT5652 manufactured by Asahi Kasei Corporation (R in the general formula (7) is — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —), and the average molecular weight is 2000, 0.050. Mole) was heated to 140 ° C. and reacted for 5 hours to obtain diisocyanate. The reaction solution was cooled to 20 ° C., 3,3′-diaminodiphenylsulfone (0.100 mol) was added, and the mixture was stirred uniformly for 5 hours to sufficiently react in the solution to synthesize urethane ureadiamine. BPADA (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride) (0.050 mol) was added into the above homogeneously stirred solution of urethane urea diamine at 80 ° C. For 1 hour, 140 ° C. for 3 hours, and 180 ° C. for 5 hours to obtain a polyimide resin solution. To 100 parts by weight of this polyimide resin solution, 2.0 parts by weight of silica (manufactured by Nippon Aerosil Co., Ltd., R-974), 2.0 parts by weight of talc (Fuji talc industry, LMS-200), barium sulfate (Sakai Chemical Industry) Co., B-34) 19 parts by weight was added to obtain a thermosetting resin composition.

(Formulation example 4)
In a separable flask pressurized with nitrogen, methyltriglyme as a solvent for polymerization was charged so that the solid content concentration of the polyimide resin solution was 50% by weight, and diphenylmethane-4,4′-diisocyanate (0 100 mol), trade name PCDLT4672 manufactured by Asahi Kasei Co., Ltd. (R in the general formula (7) is — (CH ₂ ) ₄ —, — (CH ₂ ) ₆ —), and the average molecular weight is 2000, 0.050. Mole) was heated to 140 ° C. and reacted for 5 hours to obtain diisocyanate. The reaction solution was cooled to 20 ° C., 3,3′-diaminodiphenylsulfone (0.100 mol) was added, and the mixture was stirred uniformly for 5 hours to sufficiently react in the solution to synthesize urethane ureadiamine. BPADA (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride) (0.050 mol) was added into the above homogeneously stirred solution of urethane urea diamine at 80 ° C. For 1 hour, 140 ° C. for 3 hours, and 180 ° C. for 5 hours to obtain a polyimide resin solution. To 100 parts by weight of this polyimide resin solution, 2.0 parts by weight of silica (manufactured by Nippon Aerosil Co., Ltd., R-974), 2.0 parts by weight of talc (Fuji talc industry, LMS-200), barium sulfate (Sakai Chemical Industry) Co., B-34) 19 parts by weight was added to obtain a thermosetting resin composition.

(Formulation example 5)
In a separable flask pressurized with nitrogen, methyltriglyme as a solvent for polymerization was charged so that the solid content concentration of the polyimide resin solution was 50% by weight, and diphenylmethane-4,4′-diisocyanate (0 100 mol), trade name PCDLT6002 manufactured by Asahi Kasei Co., Ltd. (R in the general formula (7) is — (CH ₂ ) ₆ — and the average molecular weight is 2000, 0.050 mol) is added to 140 ° C. Diisocyanate was obtained by heating and reacting for 5 hours. This reaction solution was cooled to 20 ° C., charged with bis [4- (3-aminophenoxy) phenyl] sulfone (0.100 mol), stirred uniformly for 5 hours and allowed to react sufficiently in the solution to obtain urethane ureadiamine. Was synthesized. After adding bis [4- (3-aminophenoxy) phenyl] sulfone (0.050 mol) in the homogeneously stirred solution of urethane ureadiamine and dissolving it, BPADA (2,2-bis [4 -(3,4-dicarboxyphenoxy) phenyl] propane dianhydride) (0.100 mol) was added and heated to reflux at 80 ° C for 1 hour, 140 ° C for 3 hours, and 180 ° C for 5 hours. A polyimide resin solution was obtained. To 100 parts by weight of this polyimide resin solution, 2.0 parts by weight of silica (manufactured by Nippon Aerosil Co., Ltd., R-974), 2.0 parts by weight of talc (Fuji talc industry, LMS-200), barium sulfate (Sakai Chemical Industry) Co., B-34) 19 parts by weight was added to obtain a thermosetting resin composition.

(Formulation example 6)
In a separable flask pressurized with nitrogen, methyltriglyme as a solvent for polymerization was charged so that the solid content concentration of the polyimide resin solution was 50% by weight, and diphenylmethane-4,4′-diisocyanate (0 100 mol), trade name PCDLT6002 manufactured by Asahi Kasei Co., Ltd. (R is — (CH ₂ ) ₆ — in the general formula (7), and the average molecular weight is 2000. 050 mol) was added, heated to 140 ° C. and reacted for 5 hours to obtain diisocyanate. The reaction solution was cooled to 10 ° C. or lower, and BPADA (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride) (0.050 mol) was added thereto. A polyimide resin solution was obtained by heating at reflux for 1 hour at 140 ° C., 3 hours at 140 ° C., and 5 hours at 180 ° C. To 100 parts by weight of this polyimide resin solution, 2.0 parts by weight of silica (manufactured by Nippon Aerosil Co., Ltd., R-974), 2.0 parts by weight of talc (Fuji talc industry, LMS-200), barium sulfate (Sakai Chemical Industry) Co., B-34) 19 parts by weight was added to obtain a thermosetting resin composition.

(Examples 1-5)
(Adjustment of thermosetting resin composition)
Epoxy resin solution prepared by dissolving epoxy resin (Dainippon Ink Co., Ltd., product number N-655-EXP) in methyltriglyme with a solid content concentration of 50% in 95 parts by weight of the thermosetting resin composition of Formulation Examples 1-5 Was added to prepare an epoxy resin-containing thermosetting resin composition. Evaluation of physical properties of the epoxy resin-containing thermosetting resin composition was performed. The evaluation results are summarized in Table 1.

(Examples 6 to 10)
5 parts of an epoxy resin solution prepared by dissolving an epoxy resin (Dainippon Ink Co., Ltd., product number N-540) in methyltriglyme at a solid content concentration of 50% is added to 95 parts by weight of the thermosetting resin composition of Formulation Examples 1 to 5. An epoxy resin-containing thermosetting resin composition was prepared by adding parts by weight. Evaluation of physical properties of the epoxy resin-containing thermosetting resin composition was performed. The evaluation results are summarized in Table 2.

(Examples 11 to 13)
An epoxy resin solution in which the thermosetting resin composition of Formulation Example 1 and an epoxy resin (Dainippon Ink Co., Ltd., product number N-760) are dissolved in methyltriglyme at a solid content concentration of 50% are shown in Table 3. Addition and mixing were performed to prepare an epoxy resin-containing thermosetting resin composition. Evaluation of physical properties of the epoxy resin-containing thermosetting resin composition was performed. The evaluation results are summarized in Table 3.

(Reference Example 1)
An epoxy resin-containing epoxy resin solution prepared by mixing an epoxy resin (Dainippon Ink Co., Ltd., product number N-760) in methyl triglyme with a solid content concentration of 50% was mixed with the thermosetting resin composition of Formulation Example 6. The thermosetting resin composition was prepared and the physical property value evaluation was implemented. The evaluation results are summarized in Table 4.

(Comparative Example 1)
In a 5-liter four-necked flask equipped with a stirrer, a cooling pipe with an oil / water separator, a nitrogen inlet pipe and a thermometer, PLACECELCD-220 (trade name of 1,6-hexanediol-based polycarbonate diol manufactured by Daicel Chemical Industries, Ltd.) 100.0 g (0.050 mol) and 25.03 g (0.100 mol) of 4,4′-diphenylmethane diisocyanate and 114.8 g of γ-butyrolactone were charged, heated to 140 ° C., and reacted for 5 hours. Furthermore, 35.83 g (1.00 mol) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and 12.51 g (0.50 mol) of 4,4′-diphenylmethane diisocyanate were added to this reaction solution. And 58.50 g of γ-butyrolactone were charged and the temperature was raised to 160 ° C., followed by reaction for 5 hours to obtain a polyimide resin solution. YH-434 (trade name of amine type epoxy resin manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 120, 4 epoxy groups / molecule) in γ-butyrolactone based on 95 parts by weight of the resin content of this polyimide resin solution 5 parts by weight of a solution dissolved at a concentration of 50% was added to obtain a thermosetting resin composition. The evaluation results are summarized in Table 4.

Claims (10)

At least (A) general formula (1)

(Wherein a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, and a plurality of X, Y, and W each independently represent an alkylene group and / or an arylene group; m and n are integers of 1 to 20, o is 1 or more, and p is an integer of 0 or more, Z is the general formula group (1)

Is a divalent organic group. )
A polyimide resin having a repeating unit represented by:
(B) thermosetting resin,
A thermosetting resin composition comprising (C) inorganic and / or organic fine particles and (D) an organic solvent. The (A) polyimide resin is
(A) General formula (2)

(Wherein Z represents the general formula group (1)

A divalent organic group selected from
A tetracarboxylic dianhydride represented by formula (b), and (b) a general formula (3)

(Wherein a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, a plurality of X's and Y's each independently represents an alkylene group and / or an arylene group; n is an integer of 1 to 20.)
The thermosetting resin composition according to claim 1, which is obtained by reacting a urethane ureadiamine compound represented by the formula as an essential component. The (A) polyimide resin is
In addition to the (a) tetracarboxylic dianhydride and the (b) urethane ureadiamine,
Furthermore, (c) general formula (4)

Wherein W is the general formula group (2)

The bivalent organic group shown by these is shown. )
The thermosetting resin composition according to claim 2, wherein the thermosetting resin composition is obtained by reacting a diamine compound represented by the formula: The urethane ureadiamine compound is
(D) General formula (5)

(Wherein a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, a plurality of X's each independently represents an alkylene group and / or an arylene group; (It is an integer of 20.)
A polydiisocyanate compound represented by:
(E) General formula (6)

(Where Y is the general formula group (2)

The bivalent organic group shown by these is shown. )
The thermosetting resin composition according to claim 2, which is a urethane urea diamine compound obtained by reacting a diamine compound represented by the formula: The polydiisocyanate compound has the general formula (7)

(In the formula, a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, and l is an integer of 1 to 20).
A polycarbonate diol represented by the general formula (8)

(In the formula, X represents an alkylene group and / or an arylene group.)
The thermosetting resin composition according to claim 4, which is a polydiisocyanate compound obtained by reacting with a diisocyanate represented by the formula:   0.1 to 50 parts by weight of component (B), 1 to 90 parts by weight of component (C), and 100 to 300 parts by weight of component (D) with respect to 100 parts by weight of component (A). The thermosetting resin composition according to any one of claims 1 to 5, wherein   The said (B) component is an epoxy resin, The thermosetting resin composition of any one of Claims 1-6 characterized by the above-mentioned.   The thermosetting according to any one of claims 1 to 7, wherein the component (C) contains at least one kind of inorganic fine particles selected from mica, silica, mica, barium sulfate, and talc. Resin composition. The cured film formed by hardening | curing the thermosetting resin composition of any one of Claims 1-8. The printed wiring board formed by coat | covering the thermosetting resin composition of any one of Claims 1-8.