JP2008094927A - Novel thermosetting resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermosetting resin composition excellent in adhesive properties, flexing properties and HAST resistance. <P>SOLUTION: The thermosetting resin composition comprises (A) a polyimide resin obtained by a reaction of three kinds of aromatic diamines of diaminodiphenyl sulfones, diaminobenzoates and aromatic diamines containing a carboxy group or a hydroxy group with an aromatic acid dianhydride of a specific structure, (B) a thermosetting resin, (C) an inorganic or organic fine particle and (D) an organic solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition, and more preferably, thermosetting that can be suitably used as a material for coating a circuit surface in an electronic material such as a coating forming material for coating a printed wiring board substrate. The present invention relates to a functional resin composition.

  Conventionally, the use of polyimide resin, epoxy resin, etc. as a coating film for circuits is known, for example, in applications such as insulation coatings for solid elements, passivation films, semiconductor integrated circuits, flexible wiring boards, etc. ing. In general, the insulating coating agent needs to be used in combination with a curing agent, and there are various problems such as storage stability related to the curing agent, workability for two-component preparation, and the insulating coating agent is used as the above-mentioned insulating coating agent. In some cases, the insulating film formed by thermosetting is rigid, lacks flexibility, and has poor flexibility.

  Also, since polyimide resin is difficult to dissolve in organic solvents, it is used as a polyimide resin precursor (polyamic acid) solution to form a coating film, followed by drying and imidization at high temperatures for a long time. By processing, it was necessary to form a protective film of polyimide resin, and there was a problem that the electrical or electronic member itself to be protected was thermally deteriorated.

On the other hand, as a coating material using a polyimide resin soluble in an organic solvent, for example, an aromatic obtained by polymerizing and imidizing biphenyltetracarboxylic acid and a diamine compound in an organic polar solvent as described in Patent Document 1. Group polyimides are known, but the polyimide resin is not sufficiently adhesive (adhesive) with substrates and circuits such as silicon wafers, glass plates, flexible substrates, copper foils, etc., so that adhesion of substrates etc. is promoted in advance A method such as treatment with an agent was required.
Japanese Patent Publication No.57-41491

  An object of the present invention is to provide a thermosetting resin composition having an excellent balance of physical properties, which can be suitably used as a coating forming material for coating an electronic material, particularly a conductor circuit pattern.

The present invention can solve the above problems by the following novel configuration.
1) (A) General formula (1)

（式中Ｒ₁、Ｒ₂、Ｒ₃は一般式群（１）より選ばれる２価の有機基を示す。同一であってもよいし、異なっていてもよい。R₄は、一般式群（２）より選ばれる有機基である。Ｒ₅は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ３）２−，−ＣＨ２−，−ＳＯ２−，−Ｏ−，−Ｃ（ＣＦ３）２−，−ＣＨ（ＣＨ３）−，−Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）−，シクロヘキシルのいずれかから選ばれる基である。Ｒ₆は-ＯＨ、−ＣＯＯＨのいずれかの基である。ｌ、ｍ、ｎ、ｐは０以上の整数であって、０．０５≦ｌ/（ｌ＋ｍ＋ｎ）≦０．８０、０.３５≦ｍ/（ｌ＋ｍ＋ｎ）≦０．７０、０．０１≦ｎ/（ｌ＋ｍ＋ｎ）≦０．５０である。）で表される繰り返し単位を有することを特徴とするポリイミド樹脂。

(Wherein R ₁ , R ₂ and R ₃ represent a divalent organic group selected from general formula group (1). They may be the same or different. R ₄ is a general formula group. R ₅ is —, — (C═O) —, —C (CH 3) 2 —, —CH 2 —, —SO 2 —, —O—, —C (CF 3) 2. -, - CH (CH3) - , - C (CH3) (CH2CH3) -, a group selected from any of cyclohexyl .R ₆ is -OH, is any group of -COOH .l, m, n and p are integers of 0 or more, 0.05 ≦ l / (l + m + n) ≦ 0.80, 0.35 ≦ m / (l + m + n) ≦ 0.70, 0.01 ≦ n / (l + m + n) ≦ 0.50.) A polyimide resin having a repeating unit represented by:

（式中のｘ、ｙ、ｚ、ｗは１以上の整数である）、及び
（Ｂ）熱硬化性樹脂、
（Ｃ）無機又は有機の微粒子、
（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。
２）
（Ａ）１）記載のポリイミド樹脂が、
（ａ）一般式（２）

(Wherein x, y, z and w are integers of 1 or more), and (B) a thermosetting resin,
(C) inorganic or organic fine particles,
(D) an organic solvent,
A thermosetting resin composition comprising:
2)
(A) The polyimide resin described in 1) is
(A) General formula (2)

（式中Ｒ₇は一般式群（１）より選ばれる２価の有機基を示す）

(Wherein R ₇ represents a divalent organic group selected from general formula group (1))

で表される芳香族酸二無水物及び
（ｂ）一般式（３）

And (b) the general formula (3)

で表されるジアミン及び
（ｃ）一般式（４）

(C) General formula (4)

（式中Ｒ₈は一般式群（２）から選ばれる１種以上の基である。）

(Wherein R ₈ is one or more groups selected from general formula group (2).)

（式中のｘ、ｙ、ｚ、ｗは１以上の整数である）
であらわされる両末端にｐ−アミノ安息香酸エステル基を持つビス−ｐ−アミノベンゾエート類及び、
（ｄ）一般式（５）

(Where x, y, z and w are integers of 1 or more)
Bis-p-aminobenzoates having a p-aminobenzoic acid ester group at both ends represented by:
(D) General formula (5)

（式中Ｒ₉は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ３）２−，−ＣＨ２−，−ＳＯ２−，−Ｏ−，−Ｃ（ＣＦ３）２−，−ＣＨ（ＣＨ３）−，−Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）−，シクロヘキシルのいずれかから選ばれる基である。Ｒ₁₀は-ＯＨ、−ＣＯＯＨのいずれかである。ｐは０以上である。）を必須成分として反応させて得られるポリイミド樹脂、及び
（Ｂ）熱硬化性樹脂
（Ｃ）無機又は有機の微粒子、
（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。
３）前記（Ａ）成分１００重量部に対して、（Ｂ）成分を０.５〜１００重量部含有することを特徴とする１）〜２）記載の熱硬化性樹脂組成物。
４）前記（Ｂ）成分が、エポキシ樹脂であることを特徴とする請求項２記載の熱硬化性樹脂組成物。
５）さらに、マイカ、シリカ、雲母、タルクの無機フィラーを含有してなる１）〜４）のいずれか一項に記載の熱硬化性樹脂組成物。

(Wherein R ₉ is-,-(C = O)-, -C (CH3) 2-, -CH2-, -SO2-, -O-, -C (CF3) 2-, -CH (CH3)- , -C (CH3) (CH2CH3) -., the .R ₁₀ is a group selected from any of cyclohexyl -OH, .p is either -COOH is 0 or more) is reacted as essential components And (B) thermosetting resin (C) inorganic or organic fine particles,
(D) an organic solvent,
A thermosetting resin composition comprising:
3) The thermosetting resin composition according to 1) to 2), wherein the component (B) is contained in an amount of 0.5 to 100 parts by weight with respect to 100 parts by weight of the component (A).
4) The thermosetting resin composition according to claim 2, wherein the component (B) is an epoxy resin.
5) The thermosetting resin composition according to any one of 1) to 4), further comprising an inorganic filler of mica, silica, mica, and talc.

  The thermosetting resin composition of the present invention is a polyimide resin having an excellent balance of physical properties necessary for electronic material applications, and even when blended with various thermosetting components, the thermosetting component and blending characteristics are impaired. It becomes possible to use for the covering formation material for covering a conductor circuit pattern, without.

  The thermosetting resin composition of the present invention has the following general formula (1).

（式中Ｒ₁、Ｒ₂、Ｒ₃は一般式群（１）より選ばれる２価の有機基を示す。同一であってもよいし、異なっていてもよい。R₄は、一般式群（２）より選ばれる有機基である。Ｒ₅は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ３）２−，−ＣＨ２−，−ＳＯ２−，−Ｏ−，−Ｃ（ＣＦ３）２−，−ＣＨ（ＣＨ３）−，−Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）−，シクロヘキシルのいずれかから選ばれる基である。Ｒ₆は―ＯＨ、−ＣＯＯＨのいずれかの基である。ｌ、ｍ、ｎ、ｐは０以上の整数であって、０．０５≦ｌ/（ｌ＋ｍ＋ｎ）≦０．８０、０.３５≦ｍ/（ｌ＋ｍ＋ｎ）≦０．７０、０．０１≦ｎ/（ｌ＋ｍ＋ｎ）≦０．５０である。）で表される繰り返し単位を有することを特徴とするポリイミド樹脂、および、

(Wherein R ₁ , R ₂ and R ₃ represent a divalent organic group selected from general formula group (1). They may be the same or different. R ₄ is a general formula group. R ₅ is —, — (C═O) —, —C (CH 3) 2 —, —CH 2 —, —SO 2 —, —O—, —C (CF 3) 2. -, - CH (CH3) - , - C (CH3) (CH2CH3) -, a group selected from any of cyclohexyl .R ₆ is -OH, is any group of -COOH .l, m, n and p are integers of 0 or more, 0.05 ≦ l / (l + m + n) ≦ 0.80, 0.35 ≦ m / (l + m + n) ≦ 0.70, 0.01 ≦ n / (l + m + n) ≦ 0.50.) A polyimide resin characterized by having a repeating unit represented by:

（式中のｘ、ｙ、ｚ、ｗは１以上の整数である）
（Ｂ）熱硬化性樹脂を含む樹脂組成物である。
特に物性バランス（柔軟性、高い屈曲性、基材との接着性、高い絶縁性、耐環境安定性）に優れた特性を発現するためには、一般式（１）のｌ、ｍ、ｎの比率は０．０５≦ｌ/（ｌ＋ｍ＋ｎ）≦０．８０、０.３５≦ｍ/（ｌ＋ｍ＋ｎ）≦０．７０、０．０１≦ｎ/（ｌ＋ｍ＋ｎ）≦０．５０であり、特に好ましくは０．１０≦ｌ/（ｌ＋ｍ＋ｎ）≦０．６０、０.４０≦ｍ/（ｌ＋ｍ＋ｎ）≦０．６０、０．０１≦ｎ/（ｌ＋ｍ＋ｎ）≦０．４０である。ｌ、ｍ、ｎを上記範囲とすることで、ポリイミド樹脂組成物に柔軟性、屈曲性及び耐熱性を付与しながら耐熱性及び有機溶剤への溶解性も付与することができるので望ましい。特に、ｍ/（ｌ＋ｍ＋ｎ）が０.３５より小さい場合には、ポリイミド樹脂組成物を基材に被覆した際に、応力が残り易くフィルムがカールする場合がある。また、ｍ/（ｌ＋ｍ＋ｎ）が０.７０より大きい場合には、ポリイミド樹脂組成物の耐熱性が低下するので望ましくない。また、ｎ/（ｌ＋ｍ＋ｎ）の値が０.０１未満だと熱硬化性樹脂との併用において、耐熱性付与の効果が薄れて耐熱性が低下する場合がある。

(Where x, y, z and w are integers of 1 or more)
(B) A resin composition containing a thermosetting resin.
In particular, in order to express properties excellent in physical property balance (flexibility, high flexibility, adhesion to a substrate, high insulation, environmental stability), l, m, and n of general formula (1) The ratios are 0.05 ≦ l / (l + m + n) ≦ 0.80, 0.35 ≦ m / (l + m + n) ≦ 0.70, 0.01 ≦ n / (l + m + n) ≦ 0.50, particularly preferably 0. 10 ≦ l / (l + m + n) ≦ 0.60, 0.40 ≦ m / (l + m + n) ≦ 0.60, 0.01 ≦ n / (l + m + n) ≦ 0.40. By setting l, m, and n in the above ranges, heat resistance and solubility in an organic solvent can be imparted to the polyimide resin composition while imparting flexibility, flexibility, and heat resistance. In particular, when m / (l + m + n) is smaller than 0.35, when the substrate is coated with the polyimide resin composition, stress may easily remain and the film may curl. Moreover, when m / (l + m + n) is larger than 0.70, the heat resistance of the polyimide resin composition is lowered, which is not desirable. On the other hand, if the value of n / (l + m + n) is less than 0.01, the effect of imparting heat resistance may be diminished and the heat resistance may be lowered in combination with the thermosetting resin.

In addition, although the polyimide resin of this invention may have a block structure which consists of a polyimide unit of the said General formula (1), the characteristics of the polyimide resin of this invention are the following acid dianhydride components and diamine. The component is used as an essential component and may not have a block structure. (A) General formula (2)

（式中Ｒ₇は一般式群（１）より選ばれる２価の有機基を示す）

(Wherein R ₇ represents a divalent organic group selected from general formula group (1))

で表される芳香族酸二無水物及び
（ｂ）一般式（３）

And (b) the general formula (3)

で表されるジアミン及び
（ｃ）一般式（４）

(C) General formula (4)

（式中Ｒ₈は一般式群（２）から選ばれる１種以上の基である。）

(Wherein R ₈ is one or more groups selected from general formula group (2).)

（式中のｘ、ｙ、ｚ、ｗは１以上の整数である）
であらわされる両末端にｐ−アミノ安息香酸エステル基を持つビス−ｐ−アミノベンゾエート類及び、
（ｄ）一般式（５）

(Where x, y, z and w are integers of 1 or more)
Bis-p-aminobenzoates having a p-aminobenzoic acid ester group at both ends represented by:
(D) General formula (5)

（式中Ｒ₉は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ３）２−，−ＣＨ２−，−ＳＯ２−，−Ｏ−，−Ｃ（ＣＦ３）２−，−ＣＨ（ＣＨ３）−，−Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）−，シクロヘキシルのいずれかから選ばれる基である。Ｒ₁₀は-ＯＨ、−ＣＯＯＨのいずれかである。ｐは０以上である。）を必須成分として反応させて得られるポリイミド樹脂であればよい。

(Wherein R ₉ is-,-(C = O)-, -C (CH3) 2-, -CH2-, -SO2-, -O-, -C (CF3) 2-, -CH (CH3)- , -C (CH3) (CH2CH3) -., the .R ₁₀ is a group selected from any of cyclohexyl -OH, .p is either -COOH is 0 or more) is reacted as essential components Any polyimide resin may be used.

  A polyimide resin using such an acid dianhydride component and a diamine can provide a polyimide resin excellent in a balance of properties such as heat resistance, long-term stability, and insulation as physical properties of a film formed using the dianhydride component and diamine.

  Furthermore, the thermosetting resin of this invention should just be a resin composition containing the said (A) polyimide resin and (B) thermosetting resin.

  By containing the component (A), the thermosetting resin composition is provided with excellent heat resistance, flex resistance, solvent resistance, environmental stability, solder heat resistance, and the like. By containing a component, it becomes possible to provide excellent processability, curing characteristics, and high adhesiveness.

  Each component which comprises the thermosetting resin composition of this invention is demonstrated.

(A) Polyimide resin component The polyimide resin of the present invention has the following general formula (1).

（式中Ｒ₁、Ｒ₂、Ｒ₃は一般式群（１）より選ばれる２価の有機基を示す。同一であってもよいし、異なっていてもよい。R₄は、一般式群（２）より選ばれる有機基である。Ｒ₅は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ３）２−，−ＣＨ２−，−ＳＯ２−，−Ｏ−，−Ｃ（ＣＦ３）２−，−ＣＨ（ＣＨ３）−，−Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）−，シクロヘキシルのいずれかから選ばれる基である。Ｒ₆は−ＯＨ、−ＣＯＯＨのいずれかの基である。ｌ、ｍ、ｎ、ｐは０以上の整数であって、０．０５≦ｌ/（ｌ＋ｍ＋ｎ）≦０．８０、０.３５≦ｍ/（ｌ＋ｍ＋ｎ）≦０．７０、０．０１≦ｎ/（ｌ＋ｍ＋ｎ）≦０．５０である。）で表される繰り返し単位を有することを特徴とするポリイミド樹脂である。

(Wherein R ₁ , R ₂ and R ₃ represent a divalent organic group selected from general formula group (1). They may be the same or different. R ₄ is a general formula group. R ₅ is —, — (C═O) —, —C (CH 3) 2 —, —CH 2 —, —SO 2 —, —O—, —C (CF 3) 2. -, - CH (CH3) - , - C (CH3) (CH2CH3) -, a group selected from any of cyclohexyl .R ₆ is -OH, is any group of -COOH .l, m, n and p are integers of 0 or more, 0.05 ≦ l / (l + m + n) ≦ 0.80, 0.35 ≦ m / (l + m + n) ≦ 0.70, 0.01 ≦ n / (l + m + n) ≦ 0.50.) Is a polyimide resin having a repeating unit represented by the following formula.

（式中のｘ、ｙ、ｚ、ｗは１以上の整数である）
特に物性バランス（柔軟性、高い屈曲性、基材との接着性、高い絶縁性、耐環境安定性）に優れた特性を発現するためには、一般式（１）のｌ、ｍ、ｎの比率は０．０５≦ｌ/（ｌ＋ｍ＋ｎ）≦０．８０、０.３５≦ｍ/（ｌ＋ｍ＋ｎ）≦０．７０、０．０１≦ｎ/（ｌ＋ｍ＋ｎ）≦０．５０であり、特に好ましくは０．１０≦ｌ/（ｌ＋ｍ＋ｎ）≦０．６０、０.４０≦ｍ/（ｌ＋ｍ＋ｎ）≦０．６０、０．０１≦ｎ/（ｌ＋ｍ＋ｎ）≦０．４０である。ｌ、ｍ、ｎを上記範囲とすることで、ポリイミド樹脂組成物に柔軟性、屈曲性及び耐熱性を付与しながら耐熱性及び有機溶剤への溶解性も付与することができるので望ましい。特に、ｍ/（ｌ＋ｍ＋ｎ）が０.３５より小さい場合には、ポリイミド樹脂組成物を基材に被覆した際に、応力が残り易くフィルムがカールする場合がある。また、ｍ/（ｌ＋ｍ＋ｎ）が０.７０より大きい場合には、ポリイミド樹脂組成物の耐熱性が低下するので望ましくない。また、ｎ/（ｌ＋ｍ＋ｎ）の値が０.０１未満だと熱硬化性樹脂との併用において、耐熱性付与の効果が薄れて耐熱性が低下する場合がある。

(Where x, y, z and w are integers of 1 or more)
In particular, in order to express properties excellent in physical property balance (flexibility, high flexibility, adhesion to a substrate, high insulation, environmental stability), l, m, and n of general formula (1) The ratios are 0.05 ≦ l / (l + m + n) ≦ 0.80, 0.35 ≦ m / (l + m + n) ≦ 0.70, 0.01 ≦ n / (l + m + n) ≦ 0.50, particularly preferably 0. 10 ≦ l / (l + m + n) ≦ 0.60, 0.40 ≦ m / (l + m + n) ≦ 0.60, 0.01 ≦ n / (l + m + n) ≦ 0.40. By setting l, m, and n in the above ranges, heat resistance and solubility in an organic solvent can be imparted to the polyimide resin composition while imparting flexibility, flexibility, and heat resistance. In particular, when m / (l + m + n) is smaller than 0.35, when the substrate is coated with the polyimide resin composition, stress may easily remain and the film may curl. Moreover, when m / (l + m + n) is larger than 0.70, the heat resistance of the polyimide resin composition is lowered, which is not desirable. On the other hand, if the value of n / (l + m + n) is less than 0.01, the effect of imparting heat resistance may be diminished and the heat resistance may be lowered in combination with the thermosetting resin.

In addition, although the polyimide resin of this invention may have a block structure which consists of a polyimide unit of the said General formula (1), the characteristics of the polyimide resin of this invention are the following acid dianhydride components and diamine. The component is used as an essential component and may not have a block structure. (A) General formula (2)

（式中Ｒ₇は一般式群（１）より選ばれる２価の有機基を示す）

(Wherein R ₇ represents a divalent organic group selected from general formula group (1))

で表される芳香族酸二無水物及び
（ｂ）一般式（３）

And (b) the general formula (3)

で表されるジアミン及び
（ｃ）一般式（４）

(C) General formula (4)

（式中Ｒ₈は一般式群（２）から選ばれる１種以上の基である。）

(Wherein R ₈ is one or more groups selected from general formula group (2).)

（式中のｘ、ｙ、ｚ、ｗは１以上の整数である）
であらわされる両末端にｐ−アミノ安息香酸エステル基を持つビス−ｐ−アミノベンゾエート類及び、
（ｄ）一般式（５）

(Where x, y, z and w are integers of 1 or more)
Bis-p-aminobenzoates having a p-aminobenzoic acid ester group at both ends represented by:
(D) General formula (5)

（式中Ｒ₉は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ３）２−，−ＣＨ２−，−ＳＯ２−，−Ｏ−，−Ｃ（ＣＦ３）２−，−ＣＨ（ＣＨ３）−，−Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）−，シクロヘキシルのいずれかから選ばれる基である。Ｒ₁₀は−ＯＨ、−ＣＯＯＨのいずれかである。ｐは０以上である。）を必須成分として反応させて得られるポリイミド樹脂であればよい。
このような酸二無水物成分およびジアミンを用いたポリイミド樹脂は、これを用いて形成した被膜物性として、耐熱性、長期安定性、絶縁性などの特性バランスに優れたポリイミド樹脂が得られる。

(Wherein R ₉ is-,-(C = O)-, -C (CH3) 2-, -CH2-, -SO2-, -O-, -C (CF3) 2-, -CH (CH3)- , -C (CH3) (CH2CH3) -., the .R ₁₀ is a group selected from any of cyclohexyl -OH, .p is either -COOH is 0 or more) is reacted as essential components Any polyimide resin may be used.
A polyimide resin using such an acid dianhydride component and a diamine can provide a polyimide resin excellent in a balance of properties such as heat resistance, long-term stability, and insulation as physical properties of a film formed using the dianhydride component and diamine.

  Among the acid dianhydrides described in the general formula (2), 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] is used to develop the solubility and mechanical properties of the present invention. 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'- The use of diphenylsulfonetetracarboxylic dianhydride is preferable for imparting toughness, heat resistance and solubility in organic solvents to the polyimide resin. It is desirable to select and use one or more kinds of acid dianhydrides among the above acid dianhydrides. It is particularly preferable to use 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride from the viewpoint of solubility of the polyimide resin in a solvent.

  As the diamine represented by the general formula (3), 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, and 3,4′-diaminodiphenyl sulfone are used to convert the polyimide resin into an organic solvent. This is desirable because the heat resistance can be improved while increasing the solubility.

  As the diamine represented by the general formula (4), poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate) (Porea SL-100A, trade name of diamine manufactured by Ihara Chemical Co., Ltd.), Poly (tetramethylene / 3,3-dimethyltetramethylene ether) glycol bis (4-aminobenzoate), poly (3-methyltetramethylene ether) glycol bis (4-aminobenzoate), poly (3,3′-dimethyltetra Methylene ether) glycol bis (4-aminobenzoate) is preferably used. Among them, (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate) (Porea SL-100A, trade name of diamine manufactured by Ihara Chemical Co., Ltd.) Preferably used.

  Examples of diamines represented by the general formula (5) include benzoic acids such as 2,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, and 3,5-diaminobenzoic acid. 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, 4, , 4′-diamino-2,2 ′, 5,5′-tetracarboxybiphenyl and the like, 3,3′-diamino-4,4′-dicarboxydiphenylmethane, [bis (4-amino-3 -Carboxy) phenyl] methane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-a No-4-carboxyphenyl] hexafluoropropane, carboxydiphenylmethane such as 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenylmethane, carboxydiphenylalkanes such as carboxyphenylpropane, 3,3 ′ -Diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-diamino Carboxydiphenyl ether compounds such as -2,2 ', 5,5'-tetracarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3'-di Carboxydiphenyl sulfone, 4,4′-diamino-2,2 ′ Diphenylsulfone compounds such as dicarboxydiphenylsulfone, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenylsulfone, 2,2-bis [4- (4-amino-3-carboxyphenoxy) Bis [(carboxyphenyl) phenyl] alkane compounds such as phenyl] propane, bis [(carboxyphenoxy) phenyl] sulfone compounds such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone Can give.

  Further, 2,5-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 ′ -Dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4- Mino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane, etc. Hydroxydiphenylalkanes such as hydroxydiphenylmethane, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2 ′ -Hydroxydiphenyl ether compounds such as dihydroxydiphenyl ether, 4,4'-diamino-2,2 ', 5,5'-tetrahydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4' -Diamino-3,3'-dihydroxydiphenyl Diphenylsulfone compounds such as ruphone, 4,4′-diamino-2,2′-dihydroxydiphenylsulfone, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylsulfone, 2,2-bis Bis [(hydroxyphenyl) phenyl] alkane compounds such as [4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, etc. Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as bis (hydroxyphenoxy) biphenyl compounds, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone, 34,4′-diamino -3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydro Bis (hydroxyphenoxy) biphenyl compounds such as xydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane and 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl I can give you.

  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 and 4,4′-diamino-3,3′-dihydroxybiphenyl are desirable for stably proceeding from the polyamide resin to the polyimide resin when synthesizing the polyimide resin.

  In addition, by using a diamine having a carboxylic acid group or a hydroxyl group as an essential component in combination with such a chain, heat resistance can be imparted to a polyimide resin composition mixed and thermoset with a thermosetting resin. It is desirable to use a diamine having such a side chain group in combination.

  The polyimide resin of the present invention is obtained by dehydrating and ring-closing the corresponding precursor polyamic acid polymer. The polyamic acid polymer is obtained by reacting an acid dianhydride component and a diamine component in substantially equimolar amounts. However, the amount of acid dianhydride and diamine may be adjusted in order to control the molecular weight for the purpose of adjusting the viscosity of the organic solvent solution in which the polyimide resin is dissolved. More specifically, the molar amount of the acid dianhydride / the molar amount of the diamine is controlled to 0.80 to 0.99 as a molar ratio, and the terminal group of the polyimide resin is changed to an amine group. Alternatively, it may be controlled to 1.01 to 1.25 to form an acid anhydride group. In particular, in order to improve the environmental stability of the polyimide resin, the end group of the polyimide resin is preferably an amine group. In the synthesis reaction of polyimide, if the purity of acid dianhydride is reduced, the molecular weight may not increase, so it may not be possible to set the target molecular weight even if it is set in the above range It is desirable to change the molar ratio as appropriate.

  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. The order of addition of each monomer is not particularly limited, and the acid dianhydride component may be added to the organic polar solvent in advance, and the diamine component may be added to form a polyamic acid polymer solution, or the diamine component may be added to the organic polar solvent. A suitable amount of the acid dianhydride component may be added first, and then an excess amount of the dianhydride component may be added, and a diamine component corresponding to the excess amount may be added to form a polyamic acid polymer solution. There are various other addition methods known to those skilled in the art. Specifically, the following method is mentioned.

  As used herein, “dissolution” refers to the case where the solute is uniformly dispersed in the solvent and substantially dissolved in addition to the case where the solvent completely dissolves the solute. Including. The reaction time and reaction temperature are not particularly limited.

  1) A method in which a diamine component is dissolved in an organic polar solvent, and this is reacted with a substantially equimolar acid dianhydride component for polymerization.

  2) An acid dianhydride component and a small molar amount of the diamine component are reacted with each other in an organic polar solvent to obtain a prepolymer having acid anhydride groups at both ends. Then, the method of superposing | polymerizing using a diamine component so that an acid dianhydride component and a diamine component may become substantially equimolar in all the processes.

  3) The acid dianhydride component is reacted with an excess molar amount of the diamine component in an organic polar solvent to obtain a prepolymer having amino groups at both ends. Subsequently, after the diamine component is additionally added, polymerization is performed using the acid dianhydride component so that the acid dianhydride component and the diamine component are substantially equimolar in all steps.

  4) A method in which an acid dianhydride component is dissolved in an organic polar solvent and then polymerized using a diamine compound component so as to be substantially equimolar.

  5) A method of polymerizing by reacting a substantially equimolar mixture of an acid dianhydride component and a diamine component in an organic polar solvent is used.

  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, Examples thereof include phenol solvents such as halogenated phenols and catechols, hexamethylphosphoramide, and γ-butyrolactone. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

  Further, for example, methyl monoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ether), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (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, 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, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Acetates such as 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, di Lopylene 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 monoethyl ether, diethylene glycol monobutyl ether, ethyl ether of ethylene glycol, etc. These ether solvents can also be used.

  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 trimethylamine, triethylamine and tributylamine, aromatic tertiary amines such as dimethylaniline and diethylaniline, pyridine, isoquinoline, β-picoline, γ-picoline and lutidine. And heterocyclic tertiary amines. 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. Further, as a thermal imidization method, there is a method in which imidization is advanced while reacting in a high boiling point solvent and heating to a temperature higher than the boiling point of water (100 ° C. or higher). The heating temperature is desirably equal to or higher than the glass transition temperature of the finally obtained polyimide resin. The obtained polyimide resin solution may be used as it is, or the polyimide resin can be taken out by the following method. In addition, when taking out with powder, since it melt | dissolves in the optimal solvent suitably and a polyimide resin composition can be created, it is desirable.

  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 desirable because it can be removed.

  The polyimide resin thus obtained may be used by blending with various thermosetting components.

  Moreover, you may add various additives, such as an organic or inorganic filler, an antifoamer, a leveling material, a stabilizer, and antioxidant, as needed.

(B) Thermosetting resin The thermosetting resin used in the resin composition of the present invention is epoxy resin, bismaleimide resin, bisallyl nadiimide resin, acrylic resin, methacrylic resin, hydrosilyl cured resin, allyl cured resin, non-curable resin. Thermosetting resin such as saturated polyester resin; side chain reactive group type thermosetting polymer having reactive groups such as allyl group, vinyl group, alkoxysilyl group, hydrosilyl group, etc. at the side chain or terminal of the polymer chain Etc. 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, 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 can be imparted. .

  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 polyimide resin composition.

  The amount of the (B) component epoxy resin used in the present invention is preferably 0.5 to 100 parts by weight, more preferably 1 to 50 parts by weight, still more preferably 100 parts by weight of the (A) component polyimide resin. 2 to 40 parts by weight. If the amount of the epoxy resin is less than 0.5 parts by weight, the solvent resistance, chemical resistance, moisture resistance, and heat resistance tend to decrease, and if it exceeds 100 parts by weight, the flexibility of the polyimide resin tends to be impaired. It is in.

  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.

Preferred blending ratio of component (A) and component (B) The curing agent, curing accelerator, and thermosetting component are within a range that does not impair the properties of the cured resin obtained by curing the thermosetting resin composition. It is preferable to make it contain in a polyimide resin. Therefore, with respect to 100 parts by weight of component (A), component (B) is preferably 0.5 to 100 parts by weight, particularly preferably 1 to 50 parts by weight. When the blending amount of the epoxy resin is less than 1 part by weight, the workability and the adhesiveness tend to be lowered, and when it exceeds 100 parts by weight, the balance such as heat resistance and flexibility may be lost.

  As a method for adding the epoxy resin, the epoxy resin to be added may be added after dissolving in advance in the same solvent as that contained in the polyimide resin, or may be added directly to the polyimide resin.

(C) Inorganic or organic fine particles (C) Inorganic or organic fine particles used in the present invention are those that can be dispersed in the polyimide resin solution described above to form a paste and impart thixotropic properties to the paste. There is no particular problem.

  Examples of such inorganic fine particles include mica, mica, silica (SiO2), alumina (Al2O3), titania (TiO2), tantalum oxide (Ta2O5), zirconia (ZrO2), silicon nitride (Si3N4), and barium titanate. (BaO · TiO2), 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), silicate barium (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), and the like can be used, and one or more of these can also 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.

  The polyimide resin composition of the present invention has an interface such as an organic or inorganic filler, antifoaming agent, leveling agent, etc., if necessary, in order to improve workability during coating and film properties before and after film formation. Activators, colorants such as dyes or pigments, curing accelerators, heat stabilizers, antioxidants, flame retardants, and lubricants can be added.

(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 ( Symmetric glycol diethers such as 2-butoxyethyl) ether), 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, 3 -Acetates such as 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, 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 Mono butyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, may be mentioned solvents 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.

(E) Other components In the thermosetting resin composition of the present invention, various additives such as an antifoaming material, a leveling material, a stabilizer and an antioxidant, a curing agent for an epoxy resin component, an epoxy, as necessary. A thermosetting component such as a curing accelerator for accelerating the reaction between the resin component and the curing agent may be included.

  The epoxy curing agent is not particularly limited, but phenolic resins such as phenol novolac type phenol resin, cresol novolac type phenol resin, naphthalene type phenol resin; dodecyl succinic anhydride, polyadipic anhydride, polyazeline Aliphatic acid anhydrides such as acid anhydrides; alicyclic acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic acid; phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid, ethylene glycol bistrimellitate, Aromatic acid anhydrides such as glycerol trislimitate; amino resins, urea resins, melamine resins, dicyandiamide, dihydrazine compounds, imidazole compounds, Lewis acids and Bronsted acid salts, polymercaptan compounds, I Cyanate and blocked isocyanate compounds, etc. can be mentioned.

  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.

  Further, the curing accelerator is not particularly limited, but for example, phosphine compounds such as triphenylphosphine; amine compounds such as tertiary amine, trimethanolamine, triethanolamine and tetraethanolamine; 1,8- Borate compounds such as diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-un Imidazoles such as decylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole; 2-methylimidazoline, 2- Ethyl imidazoline, 2 Imidazolines such as 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- [2 ′ And azine-based imidazoles such as -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.

(Usage mode of the resin composition of the present invention)
Next, although the usage aspect of the thermosetting resin composition of this invention is demonstrated, it is not limited to the following description.

  The thermosetting resin composition of the present invention is combined with a base material such as an overcoat material for electronic parts, a liquid sealing material, a varnish for enameled wire, an impregnating varnish for electrical insulation, a casting varnish, mica, glass cloth, etc. Sheet varnishes, MCL laminated varnishes, friction material varnishes, interlayer insulation films, surface protective films, solder resist layers, adhesive layers, etc. in the printed circuit board field, and other electronic components such as semiconductor elements. It is suitably used as a forming material.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.

  In the examples, the acid dianhydride and diamine used are described by the following abbreviations.

BPADA: 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride 6FDA: 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane Anhydride 4,4′-DDS: 4,4′-Diaminodiphenylsulfone 3,3′-DDS: 3,3′-Diaminodiphenylsulfone Pore SL100A: Poly (tetramethylene / 3-methyltetramethylene ether) glycol bis ( 4-aminobenzoate) (trade name of diamine manufactured by Ihara Chemical Co., Ltd., average molecular weight: 1238 (theoretical amount))
Elastomer 1000: Polytetramethylene oxide-di-P-aminobenzoate (trade name of diamine manufactured by Ihara Chemical Co., Ltd., average molecular weight: 1238 (theoretical amount))
MBAA: [bis (4-amino-3-carboxy) phenyl] methane HAB: 4,4′-diamino-3,3′-dihydroxybiphenyl 3,5-DABA: 3,5-diaminobenzoic acid (Example 1)
(Polyimide resin adjustment)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration would be 50% by weight. 0.050 mol), 4,4′-DDS (0.045 mol) and MBAA (0.005 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

(Adhesion evaluation)
The polyimide resin composition was applied to a 25 μm polyimide film (manufactured by Kaneka Corporation, Apical 25NPI) and dried at 120 ° C. for 90 minutes to form a 20 μm thick film on the polyimide film surface. The adhesive strength of this coating film was evaluated by a cross-cut tape method according to JIS K-5400. It is desired that it is at least Δ or more.

○ 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.

(Evaluation of elongation of polyimide resin composition)
The polyimide resin composition was applied to an aluminum foil having a thickness of 30 μm (manufactured by Tokai Aluminum Co., Ltd.) and dried at 120 ° C. for 90 minutes to obtain a coating film on the aluminum foil. This coating film was immersed in an etching solution of ferric chloride solution (manufactured by Sanhayato Co., Ltd.) for etching to obtain a polyimide film having a thickness of 20 μm. This polyimide film was measured according to ASTM-D882 using a tensile tester (Autograph S-100-C) manufactured by Shimadzu Corporation. When the elongation percentage of the polyimide resin composition is 30% or more, it is preferable that cracks are not easily generated on the surface of the polyimide resin composition when it is used as a wiring coating material in which bending occurs.

(Flexibility evaluation)
A polyimide resin composition was applied to the surface of a 25 μm thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) so that the final film thickness was 20 μm, and dried at 120 ° C. for 90 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. If the cured film has some cracks, it cannot be used at the bent part, so it is desirable that it is ◯.

○: The cured film has no cracks Δ: The cured film has some cracks ×: The cured film has cracks (HAST resistance)
A polyimide resin composition was applied to the surface of a 25 μm thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) so that the final film thickness was 20 μm, and dried at 120 ° C. for 90 minutes to obtain a polyimide film laminate.

  This polyimide film laminate was cut into 2 cm × 5 cm, left in an environmental test apparatus at 121 ° C./2 atm for 50 hours, and the change in appearance of the coating film was evaluated according to the following criteria.

  As HAST resistance, when the appearance of the entire surface is changed, and when used as an electrical wiring coating material, it causes a short circuit, and thus it is desirable that the HAST resistance is Δ or more.

○: No change in appearance △: Partial change in appearance ×: Change in overall appearance (warpage)
A polyimide resin composition is applied to the surface of a 25 μm-thick polyimide film (Akane 25NPI manufactured by Kaneka Corporation) so that the final coating thickness is 20 μm, and heated and dried at 120 ° C. for 90 minutes to obtain a polyimide film laminate. It was. 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. When the warp height is 20 mm or less, it is desirable because stress is unlikely to occur when applied to the polyimide resin wiring board surface and dried.

  The above evaluation results are summarized in Table 1.

(Example 2)
In the adjustment method of the polyimide resin composition, a polyimide resin composition was prepared and evaluated in the same manner as in Example 1 except that the product name Epicron HP-4700 of Naphthalene type tetrafunctional epoxy resin manufactured by Dainippon Ink Co., Ltd. was used. Went. The evaluation results are shown in Table 1.

(Example 3)
In the adjustment method of the polyimide resin composition, a polyimide resin composition was prepared and evaluated in the same manner as in Example 1 except that Dainippon Ink, Inc. cyclopentadiene type epoxy resin trade name Epicron HP-7200 was used. It was. The evaluation results are shown in Table 1.

Example 4
In the adjustment method of a polyimide resin composition, a polyimide resin composition was prepared and evaluated in the same manner as in Example 1 except that Dainippon Ink Co., Ltd. phenol novolac type epoxy resin trade name Epicron N-740 was used. It was. The evaluation results are shown in Table 1.

(Example 5)
In the adjustment method of a polyimide resin composition, the polyimide resin composition was prepared and evaluated by the same method as Example 1 except having used the trade name YH-434 of the amine type epoxy resin by Tohto Kasei Co., Ltd. The evaluation results are shown in Table 1.

(Example 6)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol), 4,4′-DDS (0.045 mol) and HAB (0.005 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
2.5 parts by weight of cresol novolac type polyfunctional epoxy resin (manufactured by Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665 EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. Dilution with 1,2-bis (2-methoxyethoxy) ethane gave a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 7)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol), 4,4′-DDS (0.045 mol) and 3,5-DABA (0.005 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
2.5 parts by weight of cresol novolac type polyfunctional epoxy resin (manufactured by Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665 EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. Dilution with 1,2-bis (2-methoxyethoxy) ethane gave a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 8)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol), 4,4′-DDS (0.040 mol) and MBAA (0.010 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

Example 9
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol), 4,4′-DDS (0.030 mol) and MBAA (0.020 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 10)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid concentration would be 50% by weight. Mol) and 4,4′-DDS (0.030 mol) and HAB (0.010 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 11)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol) and 3,3′-DDS (0.047 mol) and MBAA (0.003 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 12)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol), 3,3′-DDS (0.045 mol) and MBAA (0.005 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 13)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.0475) was added. Mol), 3,3′-DDS (0.0475 mol) and MBAA (0.0050 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 14)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol), 3,3′-DDS (0.045 mol) and HAB (0.005 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 15)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol), 3,3′-DDS (0.045 mol) and 3,5-DABA (0.005 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 16)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol), 3,3′-DDS (0.040 mol) and MBAA (0.010 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 17)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol), 3,3′-DDS (0.030 mol) and MBAA (0.020 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 18)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol), 3,3′-DDS (0.010 mol) and MBAA (0.040 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Example 19)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid content concentration was 50% by weight, and Porea SL100A (0.050 Mol) and 3,3′-DDS (0.045 mol) and MBAA (0.005 mol) were added and completely dissolved. In this solution, 6FDA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1.

(Comparative Example 1)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid concentration was 50% by weight, and elastomer 1000 (0.030) was added. Mol) and 4,4′-DDS (0.070 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the solution temperature was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1. In the case where a diamine having a carboxylic acid group or a hydroxyl group in the side chain is not used in the polyimide resin, it has been clarified that even if a thermosetting resin is used in combination, the heat resistance is low and the HAST resistance is not present. It has also been found that desirable properties cannot be achieved without an optimal structure.

(Comparative Example 2)
In a separable flask pressurized with nitrogen, 1,2-bis (2-methoxyethoxy) ethane as a solvent for polymerization was charged so that the final solid concentration would be 50% by weight, and elastomer 1000 (0.080 Mol) and 4,4′-DDS (0.020 mol) were added and completely dissolved. In this solution, BPADA (0.095 mol) was added and heated to 140 ° C. to conduct a polymerization reaction for 5 hours.

  After the above reaction, the temperature of the solution was raised to 180 ° C. to carry out an imidization reaction.

(Adjustment of polyimide resin composition)
5 parts by weight of a cresol novolac type polyfunctional epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-665-EXP) is added to 100 parts by weight of the resin content of the obtained polyimide resin solution. , 2-bis (2-methoxyethoxy) ethane was diluted to obtain a polyimide resin composition having a nonvolatile content of 50% by weight. To 100 parts by weight of the obtained polyimide resin composition, 2.8 parts by weight of silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 380) is added, first roughly kneaded, and then using a high speed three roll The kneading was repeated three times to perform the main kneading to obtain a polyimide resin composition in which silica fine particles were uniformly dispersed.

  Evaluation similar to Example 1 was performed about the polyimide resin composition. The evaluation results are shown in Table 1. In the case where a diamine having a carboxylic acid group or a hydroxyl group in the side chain is not used in the polyimide resin, it has been found that even when a thermosetting resin is used in combination, the heat resistance is low and there is no HAST resistance.

Evaluation results of physical properties of thermosetting resin composition

The thermosetting resin composition of the present invention is combined with a base material such as an overcoat material for electronic parts, a liquid sealing material, an varnish for enameled wire, an impregnating varnish for electrical insulation, a casting varnish, mica, glass cloth, Sheet varnishes, MCL laminated varnishes, friction material varnishes, interlayer insulation films, surface protective films, solder resist layers, adhesive layers, etc. in the printed circuit board field, and other electronic components such as semiconductor elements. It is suitably used as a forming material.

Claims (5)

(A) General formula (1)

(Wherein R ₁ , R ₂ and R ₃ represent a divalent organic group selected from the following general formula group (1) and may be the same or different. R ₄ is a general formula R ₅ is an organic group selected from the group (2) R ₅ is —, — (C═O) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —O—, —C. (CF ₃ ) ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₃ ) —, or cyclohexyl, R ₆ is either —OH or —COOH. L, m, n, and p are integers of 0 or more, and 0.05 ≦ l / (l + m + n) ≦ 0.80, 0.35 ≦ m / (l + m + n) ≦ 0.70, 0.01 ≦ n / (l + m + n) ≦ 0.50)), and a polyimide resin characterized by having a repeating unit represented by:

(Where x, y, z and w are integers of 1 or more)
(B) thermosetting resin,
(C) inorganic or organic fine particles,
(D) an organic solvent,
A thermosetting resin composition comprising: (A) The polyimide resin according to claim 1 is
(A) General formula (2)

(Wherein R ₇ represents a divalent organic group selected from general formula group (1))

And (b) the general formula (3)

(C) General formula (4)

(Wherein R ₈ is one or more groups selected from general formula group (2).)

(Where x, y, z and w are integers of 1 or more)
Bis-p-aminobenzoates having a p-aminobenzoic acid ester group at both ends represented by:
(D) General formula (5)

Wherein R ₉ is-,-(C = O)-, -C (CH ₃ ) _2- , -CH _2- , -SO _2- , -O-, -C (CF ₃ ) _2- , -CH. A group selected from (CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₃ ) —, and cyclohexyl, R ₁₀ is either —OH or —COOH, and p is 0 or more. A polyimide resin obtained by reacting as an essential component, and (B) a thermosetting resin,
(C) inorganic or organic fine particles,
(D) an organic solvent,
A thermosetting resin composition comprising: 0.5-100 parts by weight of component (B), 1-40 parts by weight of component (C), and 100-300 parts by weight of component (D) with respect to 100 parts by weight of component (A). The thermosetting resin composition according to claim 1 or 2. The thermosetting resin composition according to claim 2, wherein the component (B) is an epoxy resin. The thermosetting resin composition according to claim 1, wherein the component (C) is inorganic fine particles selected from mica, silica, mica, and talc.