JP2012180471A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in heat resistance and moldability, capable of sufficiently improving electric reliability (migration resistance) under high humidity and high voltage conditions and excellent in storage stability and printing properties.SOLUTION: This resin composition includes a polyimide resin (A) having a melt viscosity at 150°C of 30-3,000 Pa s and a temperature of 1% mass loss of not lower than 350°C and a solvent (B), and the solvent (B) is a mixture of an ether type organic solvent and a hydrocarbon organic solvent containing an aromatic ring, or an organic solvent containing both an ether bond and an aromatic ring, and has a boiling point of 180-220°C.

Description

  The present invention relates to a resin composition.

In recent years, electronic devices have been reduced in size and speeded up with advances in the electronics field. For this reason, even in packages directly mounting semiconductor elements such as ICs and LSIs, high density and high reliability due to fine patterns have been achieved. It has been demanded.
Conventionally, a thermosetting resin composition such as a novolac type epoxy resin is generally used as an underfill material or a sealing material for the purpose of protecting, damp-proofing, and insulating a semiconductor element in a package in which a semiconductor element such as IC or LSI is mounted. (For example, refer to Patent Document 1).
However, when the thermosetting resin composition is used as an underfill material or a sealing material, a crack or the like may occur in the underfill material or the sealing material due to a difference in thermal expansion coefficient between the semiconductor element and the mounting substrate. The electrical reliability tends to decrease.
In addition, for the purpose of improving yield and moisture resistance due to internal stress relaxation, an epoxy resin composition using a specific acid anhydride as a curing agent has been proposed (for example, see Patent Document 2). Reliability cannot be said to be sufficient, and further performance improvement is desired.
On the other hand, a thermoplastic resin is excellent in flexibility and has an advantage that stress is easily relieved because it is not accompanied by curing shrinkage due to thermosetting. Among such thermoplastic resins, polyolefin resins such as polypropylene have excellent electrical reliability (see, for example, Patent Document 3), but tend to have insufficient heat resistance.

JP 2000-103940 A JP 2002-080562 A International Publication No. 07/032406 Pamphlet

On the other hand, a polyimide resin is known as an insulating material excellent in electrical reliability and heat resistance.
However, a polyimide resin generally has a high melting point and requires a high curing temperature when processed from polyamic acid, so that a load is applied to the base material, and electrical reliability may be lowered.
For this reason, it is difficult to use polyimide resin as an electrical insulating material in fields where further improvement in electrical reliability under severe usage conditions such as high humidity and high voltage is desired.
Moreover, since the polyimide resin has poor solubility in a general organic solvent, there is a problem that the polyimide resin solution is inferior in printability.
The present invention has been made in view of the above circumstances, is excellent in heat resistance and workability, and can sufficiently improve electrical reliability (migration resistance) under high humidity and high voltage conditions. An object of the present invention is to provide a resin composition that is excellent in storage stability and printability.

In order to achieve the above object, the present invention comprises (A) a polyimide resin having a melt viscosity of 30 to 3000 Pa · s at 150 ° C. and a 1% mass reduction temperature of 350 ° C. or higher and (B) a solvent, The resin composition in which the solvent of the component (B) has a boiling point of 180 to 220 ° C. and is a mixture of an ether organic solvent and a hydrocarbon organic solvent containing an aromatic ring or an organic solvent containing both an ether bond and an aromatic ring I will provide a.
By providing the resin composition of the present invention with the above-described configuration, the resin composition is excellent in heat resistance and bondability, and sufficiently improves electrical reliability (migration resistance) under high humidity and high voltage conditions. And a resin composition having excellent storage stability and printability can be provided.
In the resin composition of the present invention, the polyimide resin preferably has a repeating unit represented by the following general formula (1).

ここで、一般式（１）中、Ａｒ^１は４価の有機基を示し、Ａｒ^２は２価の有機基を示し、Ａｒ^１及び／又はＡｒ^２は主鎖に炭素数５〜２０のアルキレン鎖を含む。
これにより、樹脂組成物は、可とう性が高くなり、加工性により一層優れるものとなる。
また、上記Ａｒ^１が、下記一般式（２）で表される基であることが好ましく、これにより樹脂組成物の可とう性をより一層向上することができる。

Here, in General Formula (1), Ar ¹ represents a tetravalent organic group, Ar ² represents a divalent organic group, and Ar ¹ and / or Ar ² are alkylene having 5 to 20 carbon atoms in the main chain. Contains chains.
Thereby, a resin composition becomes high in flexibility, and becomes more excellent in workability.
Further, the Ar ¹ is preferably a group represented by the following general formula (2), thereby making it possible to further improve the flexibility of the resin composition.

ここで、一般式（２）中、Ｘは炭素数５〜２０のアルキレン基を示し、Ｒ^１及びＲ^２はそれぞれ独立に水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｍ及びｎはそれぞれ独立に１〜３の整数を示す。ｍが２以上の場合、複数存在するＲ^１は同一でも異なっていてもよく、ｎが２以上の場合、複数存在するＲ^２は同一でも異なっていてもよい。
上記一般式（１）において、Ａｒ^２が下記一般式（３）で表される２価の基であると好ましく、可とう性に優れるため加工性を向上できるだけでなく、反りを低減することができる。

Here, in the general formula (2), X represents an alkylene group having 5 to 20 carbon atoms, ^{R 1} and ^{R 2} each independently represents a hydrogen atom and a alkyl group or 1 to 3 carbon atoms An alkoxy group, m and n each independently represent an integer of 1 to 3; When m is 2 or more, a plurality of R ¹ may be the same or different, and when n is 2 or more, a plurality of R ² may be the same or different.
In the general formula (1), Ar ² is preferably a divalent group represented by the following general formula (3), and is excellent in flexibility, not only improving workability but also reducing warpage. it can.

ここで、一般式（３）中、Ｚは単結合又は２価の有機基を示し、Ｙ^１及びＹ^２はそれぞれ独立に炭素数５〜２０のアルキレン基を示す。
耐熱性の観点から、上記Ｚが、下記一般式（４）、（５）及び（６）でそれぞれ表される２価の基からなる群より選ばれる少なくとも１種の基であることが好ましく、これにより、耐熱性が向上し、アウトガスをより一層低減できる。

Here, in the general formula (3), Z represents a single bond or a divalent organic group, an alkylene group having 5 to 20 carbon atoms in each Y ¹ and Y ² independently.
From the viewpoint of heat resistance, it is preferable that Z is at least one group selected from the group consisting of divalent groups represented by the following general formulas (4), (5) and (6), respectively. Thereby, heat resistance improves and outgas can be reduced further.

ここで、一般式（４）、（５）及び（６）中、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立に水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｑ、ｒ及びｓは、それぞれ独立に１〜４の整数を示す。ｑが２以上の場合、複数存在するＲ^８は同一でも異なっていてもよく、ｒが２以上の場合、複数存在するＲ^９は同一でも異なっていてもよく、ｓが２以上の場合、複数存在するＲ^１０は同一でも異なっていてもよい。
上記ポリイミド樹脂が、下記一般式（７）で表される繰り返し単位を更に有することが好ましい。
これにより、耐熱性及び電気的信頼性に優れるという本発明の効果をより一層有効かつ確実に発揮することができる。

In the general formula (4), (5) and ^(6), R 8, ^{R 9} and ^{R 10} each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, alkenyl of 1 to 10 carbon atoms A group or an alkoxy group having 1 to 3 carbon atoms, q, r and s each independently represent an integer of 1 to 4; When q is 2 or more, a plurality of R ⁸ may be the same or different. When r is 2 or more, a plurality of R ⁹ may be the same or different. When s is 2 or more, The existing R ¹⁰ may be the same or different.
It is preferable that the said polyimide resin further has a repeating unit represented by following General formula (7).
Thereby, the effect of the present invention that is excellent in heat resistance and electrical reliability can be more effectively and reliably exhibited.

ここで、一般式（７）中、Ａｒ^１は下記一般式（２）で表される４価の有機基を示し、Ａｒ^３は、芳香族炭化水素基を含む２価の有機基を示す。

Here, in General Formula (7), Ar ¹ represents a tetravalent organic group represented by the following General Formula (2), and Ar ³ represents a divalent organic group containing an aromatic hydrocarbon group.

ここで、一般式（２）中、Ｘは炭素数５〜２０のアルキレン基を示し、Ｒ^１及びＲ^２はそれぞれ独立に水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｍ及びｎはそれぞれ独立に１〜３の整数を示す。ｍが２以上の場合、複数存在するＲ^１は同一でも異なっていてもよく、ｎが２以上の場合、複数存在するＲ^２は同一でも異なっていてもよい。
また、上記一般式（７）において、Ａｒ^３が、置換基を有していてもよいアリーレン基、下記一般式（８）で表される基及び下記一般式（９）で表される基からなる群より選ばれる少なくとも１種の基であることが好ましい。
これにより、ポリイミド樹脂の１５０℃における溶融粘度を良好な範囲にすることができ、かつ、耐熱性を向上することができる。

Here, in the general formula (2), X represents an alkylene group having 5 to 20 carbon atoms, ^{R 1} and ^{R 2} each independently represents a hydrogen atom and a alkyl group or 1 to 3 carbon atoms An alkoxy group, m and n each independently represent an integer of 1 to 3; When m is 2 or more, a plurality of R ¹ may be the same or different, and when n is 2 or more, a plurality of R ² may be the same or different.
In the general formula (7), Ar ³ may be an arylene group which may have a substituent, a group represented by the following general formula (8), and a group represented by the following general formula (9). It is preferably at least one group selected from the group consisting of
Thereby, the melt viscosity at 150 ° C. of the polyimide resin can be in a favorable range, and the heat resistance can be improved.

ここで、一般式（８）及び（９）中、Ｄ及びＥはそれぞれ独立に単結合、エーテル結合、チオエーテル結合、カルボニル基、スルホニル基、メチレン基、エチレン基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基、下記式（ｉ）で表される基又は下記式（ｉｉ）で表される基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６はそれぞれ独立に水素原子、水酸基、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｔ１、ｔ２、ｔ３、ｔ４、ｔ５及びｔ６は、それぞれ独立に１〜４の整数を示す。
ｔ１が２以上の場合、複数存在するＲ^１１は同一でも異なっていてもよく、ｔ２が２以上の場合、複数存在するＲ^１２は同一でも異なっていてもよく、ｔ３が２以上の場合、複数存在するＲ^１３は同一でも異なっていてもよく、ｔ４が２以上の場合、複数存在するＲ^１４は同一でも異なっていてもよく、ｔ５が２以上の場合、複数存在するＲ^１５は同一でも異なっていてもよく、ｔ６が２以上の場合、複数存在するＲ^１６は同一でも異なっていてもよい。

In the general formulas (8) and (9), D and E are each independently a single bond, an ether bond, a thioether bond, a carbonyl group, a sulfonyl group, a methylene group, an ethylene group, an isopropylidene group, or a hexafluoroisopropylidene group. Group, a group represented by the following formula (i) or a group represented by the following formula (ii), wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, A hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is shown, and t1, t2, t3, t4, t5 and t6 each independently represent an integer of 1 to 4.
When t1 is 2 or more, a plurality of R ¹¹ may be the same or different. When t2 is 2 or more, a plurality of R ¹² may be the same or different. When t3 is 2 or more, a plurality of R ¹¹ are present. R ¹³ present may be the same or different. When t4 is 2 or more, a plurality of R ¹⁴ may be the same or different. When t5 is 2 or more, a plurality of R ¹⁵ are the same or different. even well, in the case of t6 is 2 or more, R ¹⁶ existing in plural numbers may be the same or different.

また、耐熱性及び電気的信頼性をより一層向上するためには、ポリイミド樹脂のイミド化率が８０％以上であることが好ましい。

In order to further improve the heat resistance and electrical reliability, it is preferable that the imidization ratio of the polyimide resin is 80% or more.

  According to the present invention, it is possible to provide a resin composition that is excellent in heat resistance and printability and can sufficiently improve migration resistance (electrical reliability) under high humidity and high voltage conditions. it can.

It is a model top view of the board | substrate for migration resistance evaluation.

The resin composition of the present invention comprises (A) a polyimide resin having a melt viscosity of 30 to 3000 Pa · s at 150 ° C. and a 1% mass reduction temperature of 350 ° C. or more and (B) a solvent, The solvent of the component contains a mixture of an ether organic solvent having a boiling point of 180 to 220 ° C. and a hydrocarbon organic solvent containing an aromatic ring, or both an ether bond and an aromatic ring.
Hereinafter, each component which comprises the resin composition of this invention is demonstrated in detail.

((A) Polyimide resin)
The polyimide resin used in the present invention is a polyimide resin having a melt viscosity at 150 ° C. of 30 to 3000 Pa · s and a 1% mass reduction temperature of 350 ° C. or more. The polyimide resin preferably has a repeating unit represented by the general formula (1).
In General Formula (1), Ar ¹ represents a tetravalent organic group, Ar ² represents a divalent organic group, and Ar ¹ and / or Ar ² includes an alkylene chain having 5 to 20 carbon atoms in the main chain. .
The polyimide resin is synthesized by a known method from a tetracarboxylic dianhydride component and a diamine component.
The tetracarboxylic dianhydride component and / or diamine component preferably contains an alkylene group having 5 to 20 carbon atoms in the main chain. By including an alkylene group having 5 to 20 carbon atoms, low temperature curability, flexibility, low water absorption and low warpage of the resin composition can be achieved.
In addition, when the tetracarboxylic dianhydride component and / or the diamine component has an aromatic group in the main chain, the heat resistance is improved, so that outgassing can be reduced.
On the other hand, the polyimide resin preferably does not contain an ether bond such as a polyalkyleneoxy group. The ether bond is easily broken at a high temperature, heat resistance is lowered, and outgas is easily generated. Moreover, when a polyimide resin has an ether bond, water absorption increases and it may influence an insulation characteristic.

The tetracarboxylic dianhydride component preferably has an alkylene group having 5 to 20 carbon atoms in the main chain, and more preferably has a group represented by the general formula (2).
Examples of such a tetracarboxylic dianhydride component include compounds represented by the following general formula (10).

ここで、一般式（１０）中、Ｘは炭素数５〜２０アルキレン基であり、８〜１５のアルキレン基であることが好ましい。
一般式（１０）で表される化合物としては、例えば、ペンタメチレンビストリメリテート二無水物、ヘキサメチレンビストリメリテート二無水物、ヘプタメチレンビストリメリテート二無水物、オクタメチレンビストリメリテート二無水物、ノナメチレンビストリメリテート二無水物、デカメチレンビストリメリテート二無水物、ドデカメチレンビストリメリテート二無水物等が挙げられる。
これらは、１種を単独で又は２種以上を組み合わせて使用することができる。

Here, in General formula (10), X is a C5-C20 alkylene group, and it is preferable that it is a C8-C15 alkylene group.
Examples of the compound represented by the general formula (10) include pentamethylene bis trimellitate dianhydride, hexamethylene bis trimellitate dianhydride, heptamethylene bis trimellitate dianhydride, octamethylene bis trimellitate dianhydride. Nonamethylene bis trimellitate dianhydride, decamethylene bis trimellitate dianhydride, dodecamethylene bis trimellitate dianhydride and the like.
These can be used alone or in combination of two or more.

Moreover, when synthesizing a polyimide resin, a tetracarboxylic dianhydride other than a tetracarboxylic dianhydride component having an alkylene group having 5 to 20 carbon atoms in the main chain may be used in combination.
Examples of such tetracarboxylic dianhydrides include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic anhydride. 1,2,4,5-cyclopentanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid anhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,3 ′ , 4,4′-bicyclohexyltetracarboxylic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Water, 3,3 ', 4,4'-biphenyl ether tetracarboxylic anhydride (4,4'-oxydiphthalic dianhydride), 2,3', 4,4'-diphenyl ether tetracarboxylic dianhydride 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfonetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic acid Dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis [4- (3,4-di Carboxybenzoyl Xyl) phenyl] nonane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] decane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyl) Oxy) phenyl] tridecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] tetradecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyl) Oxy) phenyl] pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-methyldecane dianhydride, 1,1-bis [4- (3,4- Dicarboxybenzoyloxy) phenyl] -2-methyloctane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-ethylpentade Candianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] dodecane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] decane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] tridecane dianhydride, 2, 2-bis [3,5-diethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] cyclohexane Dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] propylcyclohexane dianhydride, 1,1-bis [4- (3,4-dicarboxy) Nzoyloxy) phenyl] heptylcyclohexane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 4,4-bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride Can be mentioned.
These are used individually by 1 type or in combination of 2 or more types.

As a diamine component, it is preferable to have a C5-C20 alkylene chain in a principal chain, and it is more preferable to have a bivalent group represented by the said General formula (3).
In general formula (3), Y ¹ and Y ² are each independently an alkylene group having 5 to 20 carbon atoms, and preferably an alkylene group having 6 to 10 carbon atoms.
In the general formula (3), Z represents a single bond or a divalent organic group. When Z is a divalent organic group, each of the above general formulas (4), (5), and (6) It is preferably at least one group selected from the group consisting of represented divalent groups.

Examples of the diamine component having an alkylene group having 5 to 20 carbon atoms in the main chain include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, dodecamethylene diamine, and 2,11-diaminododecane. 1,12-diaminooctadecane, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 3 Examples thereof include aliphatic diamines such as methoxyhexamethylenediamine and compounds represented by the following general formulas (11), (12) and (13).
These are used individually by 1 type or in combination of 2 or more types.

ここで、一般式（１１）中、Ｙ^１及びＹ^２は、それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ^８は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｑは１〜４の整数を示す。なお、ｑが２以上の場合、複数存在するＲ^８は同一でも異なっていてもよい。
上記一般式（１１）で表される化合物を含有するジアミン成分として、例えば、１，４−ビス（１，１−ジメチル−５−アミノペンチル）ベンゼン、１，４−ビス（２−メトキシ−４−アミノペンチル）ベンゼン等が挙げられる。

Here, in General Formula (11), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms. 10 represents an alkenyl group or an alkoxy group having 1 to 3 carbon atoms, and q represents an integer of 1 to 4. When q is 2 or more, a plurality of R ⁸ may be the same or different.
Examples of the diamine component containing the compound represented by the general formula (11) include 1,4-bis (1,1-dimethyl-5-aminopentyl) benzene and 1,4-bis (2-methoxy-4). -Aminopentyl) benzene and the like.

ここで、一般式（１２）中、Ｙ^１及びＹ^２は、それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ^９は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｒは１〜４の整数を示す。なお、ｒが２以上の場合、複数存在するＲ^９は同一でも異なっていてもよい。

Here, in General Formula (12), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms. 10 represents an alkenyl group or an alkoxy group having 1 to 3 carbon atoms, and r represents an integer of 1 to 4. When r is 2 or more, a plurality of R ⁹ may be the same or different.

ここで、一般式（１３）中、Ｙ^１及びＹ^２は、それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ^１０は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｓは１〜４の整数を示す。なお、ｓが２以上の場合、複数存在するＲ^１０は同一でも異なっていてもよい。
上記一般式（１２）で表される化合物を含有するジアミン成分として、［３，４−ビス（１−アミノヘプチル）−６−ヘキシル−５−（１−オクテニル）］シクロヘキセン（コグニスジャパン社製、商品名「バーサミン５５１」）または（クローダ社製、商品名「プリアミン１０７４」）が市販品として入手可能である。

Here, in General Formula (13), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms. 10 represents an alkenyl group or an alkoxy group having 1 to 3 carbon atoms, and s represents an integer of 1 to 4. When s is 2 or more, a plurality of R ¹⁰ may be the same or different.
As a diamine component containing the compound represented by the general formula (12), [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene (manufactured by Cognis Japan, (Trade name “Versamin 551”) or (trade name “Puriamine 1074” manufactured by Croda) is available as a commercial product.

  Here, “versamin 551” and “priamine 1074” are diamine compounds including a compound represented by the following formula (21) and / or a compound in which an unsaturated portion of the compound represented by the following (21) is hydrogenated. It is.

Moreover, as a diamine component, from the viewpoint of improving heat resistance (1% mass reduction temperature), a diamine compound having an aromatic hydrocarbon group is used in combination with a diamine compound having an alkylene chain having 5 to 20 carbon atoms in the main chain. And preferably used.
The diamine compound having an aromatic hydrocarbon group is selected from the group consisting of an arylene group which may have a substituent, a group represented by the general formula (8) and a group represented by the general formula (9). More preferably, the diamine compound having at least one kind of group is used in combination with a diamine compound having an alkylene chain having 5 to 20 carbon atoms in the main chain.

  Examples of the diamine compound having a group represented by the general formula (8) include a diamine compound represented by the following general formula (14).

ここで、一般式（１４）中、Ｄは単結合、エーテル結合、チオエーテル結合、カルボニル基、スルホニル基、メチレン基、エチレン基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基、下記式（ｉ）で表される基又は下記式（ｉｉ）で表される基を示し、Ｒ^１１及びＲ^１２はそれぞれ独立に水素原子、水酸基、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｔ１及びｔ２はそれぞれ独立に１〜４の整数を示す。
ｔ１が２以上の場合、複数存在するＲ^１１は同一でも異なっていてもよく、ｔ２が２以上の場合、複数存在するＲ^１２は同一でも異なっていてもよい。

Here, in the general formula (14), D represents a single bond, an ether bond, a thioether bond, a carbonyl group, a sulfonyl group, a methylene group, an ethylene group, an isopropylidene group, a hexafluoroisopropylidene group, represented by the following formula (i). Or a group represented by the following formula (ii), R ¹¹ and R ¹² each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. , T1 and t2 each independently represents an integer of 1 to 4.
When t1 is 2 or more, a plurality of R ¹¹ may be the same or different, and when t2 is 2 or more, a plurality of R ¹² may be the same or different.

  Examples of the diamine compound having a group represented by the general formula (9) include a diamine compound represented by the following general formula (15).

ここで、一般式（１５）中、Ｅは単結合、エーテル結合、チオエーテル結合、カルボニル基、スルホニル基、メチレン基、エチレン基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基、上記式（ｉ）で表される基又は上記式（ｉｉ）で表される基を示し、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６はそれぞれ独立に水素原子、水酸基、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｔ３、ｔ４、ｔ５及びｔ６はそれぞれ独立に１〜４の整数を示す。ｔ３が２以上の場合、複数存在するＲ^１３は同一でも異なっていてもよく、ｔ４が２以上の場合、複数存在するＲ^１４は同一でも異なっていてもよく、ｔ５が２以上の場合、複数存在するＲ^１５は同一でも異なっていてもよく、ｔ６が２以上の場合、複数存在するＲ^１６は同一でも異なっていてもよい。

Here, in the general formula (15), E represents a single bond, an ether bond, a thioether bond, a carbonyl group, a sulfonyl group, a methylene group, an ethylene group, an isopropylidene group, a hexafluoroisopropylidene group, and the above formula (i). Or a group represented by the above formula (ii), wherein R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or 1 to 1 carbon atoms. 3 represents an alkoxy group, and t3, t4, t5 and t6 each independently represents an integer of 1 to 4. When t3 is 2 or more, the plurality of R ¹³ may be the same or different. When t4 is 2 or more, the plurality of R ¹⁴ may be the same or different. When t5 is 2 or more, The existing R ¹⁵ may be the same or different, and when t6 is 2 or more, the plurality of R ¹⁶ may be the same or different.

Examples of the diamine compound having an aromatic hydrocarbon group include 4,4′-diaminodibenzyl sulfoxide, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, and bis (4-amino). Phenyl) ethylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) -N-phenylamine, bis (4-aminophenyl) -N-methylamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 1 , 4-Diamino-2-methylnaphthalene, 1,5-diamy 2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,4 -Diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene, 1-methoxy-2,4-diaminobenzene, 1,3-diamino-4,6-dimethylbenzene, 1 , 4-diamino-2,5-dimethylbenzene, 1,4-diamino-2-methoxy-5-methylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, o-xylenediamine, m-xylenediamine, p-xylenediamine, 9,10-bis (4-aminophenyl) anthracene, 4-aminophenyl-3-aminobenzoe 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane, 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2 , 2,2-trifluoroethane, 1,3-bis (3-aminophenyl) decafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,4-bis (3 -Aminophenyl) but-1-ene-3-yne, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl- 4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diamino Diphenylmethane, 3,3′-dimethoxy-4,4′-diaminodiphenylmethane, 3,3′-diethoxy-4,4′-diaminodiphenylmethane, bis (3-aminophenyl) ether, bis (4-aminophenyl) ether, 3,4'-diaminodiphenyl ether, 3,3'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] Ether, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 3,3'-diethyl-4,4'-diaminodiphenyl sulfone, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfone, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl 4,4'-diaminodiphenylpropane, 3,3'-diethyl-4,4'-diaminodiphenylpropane, 3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,3'-diethoxy- 4,4'-diaminodiphenylpropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) Propane, 4,4'-diaminodiphenyl sulfide, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 3,3'-diethyl-4,4'-diaminodiphenyl sulfide, 3,3'-dimethoxy -4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 2,4'- Aminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (4-aminophenyl) ) Ethane, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (4-toluidine) sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3- Aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene, 4,4′-diaminobiphenyl, 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 9,9- Bis [4- (3-aminophenoxy) phenyl] fluorene, 3,3′-diaminobiphenyl, 3,3′-dimethyl Til-4,4'-diaminobiphenyl, 3,4'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-bis (4-amino Phenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2, 2-bis (3-aminophenyl) hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenyl) Hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (5-amino-4-methylphenyl) hexafluoropropane and the like.
These diamine components may be used alone or in combination of two or more.

Moreover, in the polyimide resin in the resin composition of this invention, diamine compounds other than the diamine compound represented by the said General Formula (11)-(15) can be used together.
Examples of diamine compounds other than the diamine compounds represented by the general formulas (11) to (15) include 4,4'-methylenebis (cyclohexylamine) and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane. 2,2'-diaminodiethyl sulfide.
These diamine components may be used alone or in combination of two or more.

In the present invention, from the viewpoint of improving the melt viscosity, heat resistance (1% mass reduction temperature), water absorption rate, and migration resistance, the tetracarboxylic dianhydride represented by the general formula (10) and the general formula ( 11) or a diamine compound represented by (12), a diamine compound having an arylene group which may have a substituent, and a diamine compound represented by formula (14) or (15). A polyimide resin is preferable.
The addition amount in the case of using the diamine compound having an aromatic hydrocarbon group is preferably 1 to 80 mol%, more preferably 5 to 50 mol%, more preferably 20 to 20 mol% based on the total amount of the diamine component. More preferably, it is 40 mol%.
If the addition amount of the diamine compound having an aromatic hydrocarbon group is less than 1 mol%, the heat resistance tends to be insufficient, and outgassing tends to occur. If the addition amount exceeds 80 mol%, the fluidity of the polyimide resin is insufficient. It tends to increase the melt viscosity at 0 ° C. and easily causes voids.
In addition, as a diamine component, diamine compounds other than the diamine compound mentioned above can be used together in the range which does not deviate from the range of the effect which this invention has.

The polyimide resin can be synthesized by selectively combining the tetracarboxylic dianhydride component and the diamine component and reacting them in an organic solvent.
Specifically, the polyimide resin is a polyamic acid obtained by addition polymerization of diamine component 0.92 to 0.94 in an organic solvent at 30 to 80 ° C. for 2 to 3 hours with respect to 1 mol of tetracarboxylic dianhydride component. After synthesizing the acid, it is obtained by dehydration condensation at 120 ° C. or higher, preferably 150 ° C. or higher for 1 to 5 hours, followed by ring closure and imidization.
From the viewpoint of improving heat resistance and storage stability, it is preferable that the ring is closed so that the imidization ratio is 80% or more, more preferably 90% or more, and still more preferably 95% or more. The imidization rate is a reaction rate of the imidization reaction, and can be performed using infrared spectroscopy as in the examples.
The combination of the tetracarboxylic dianhydride component and the diamine component is selected from the above-mentioned components in consideration of the heat resistance, mechanical properties, electrical properties, etc. of the cured film made of the polyimide resin to be finally formed. You can choose.

The melt viscosity at 150 ° C. of the polyimide resin used in the present invention is 30 to 3000 Pa · s, preferably 250 to 3000 Pa · s, and particularly preferably 1000 to 2500 Pa · s. When the melt viscosity is less than 30 Pa · s, it is difficult to form a resin layer having a target thickness, and when it exceeds 3000 Pa · s, the flexibility of the resin composition tends to be lowered and workability tends to be lowered.
Moreover, the 1% mass reduction | decrease temperature of the polyimide resin used by this invention is 350 degreeC or more, it is preferable that it is 360 degreeC or more, and it is more preferable that it is 370 degreeC or more.
When the 1% mass reduction temperature is less than 350 ° C., the heat resistance is lowered, so that outgas is easily generated.
The upper limit of the 1% mass reduction temperature of the polyimide resin is not particularly limited, but is usually about 400 ° C.
In addition, from the viewpoint of improving the flowability of the polyimide resin at 150 ° C. or less, the number average molecular weight of the polyimide resin is preferably 1000 to 30000, more preferably 1500 to 20000, and 2000 to 15000. Is more preferable, and it is especially preferable that it is 3000-10000.
If the number average molecular weight of the polyimide resin is less than 1000, the heat resistance and toughness tend to be insufficient, and if it exceeds 30000, the melt viscosity tends to increase and the workability tends to decrease.
In order to set the melt viscosity at 150 ° C. of the polyimide resin to 30 to 3000 Pa · s and the 1% mass reduction temperature to 350 ° C. or more, the average molecular weight per polyimide structure repeating unit in the polyimide resin is 800 to 1500. It is preferable to do it, it is more preferable to set it as 850-1200, and it is especially preferable to set it as 900-1100.
In addition, the average molecular weight per said polyimide structure repeating unit is computable from the mixture ratio (molar ratio) of the tetracarboxylic dianhydride component at the time of polyimide resin synthesis | combination and a diamine component.

((B) solvent)
As the solvent, the boiling point is 180 ° C. to 220 ° C., and an ether organic solvent (triglyme (boiling point 216 ° C.) etc.) and a hydrocarbon organic solvent containing an aromatic ring (tetralin (boiling point 207 ° C.) etc.) or An organic solvent containing both an ether bond and an aromatic ring (such as dimethoxybenzene (boiling point 217 ° C.)) can be used.
Nitrogen-containing solvents (N, N′-dimethylsulfoxide, N, N′-dimethylformamide, N, N′-diethylformamide, N, N′-dimethylacetamide, N, N′-diethylacetamide, N-methyl- 2-pyrrolidone, hexamethylenephosphoamide, N-methylpyrrolidone, etc.) are difficult to use as printing pastes from the viewpoint of water absorption, and ketones (cyclohexanone, isophorone, isobutyl ketone, etc.) undergo a dehydration condensation reaction with diamines. Is not preferable.
In addition, after synthesizing the polyamic acid, a solvent (for example, toluene) azeotropic with water may be added in order to promote imidization by a dehydration condensation reaction.

In the resin composition of the present invention, various additives may be blended in order to improve adhesion with various base materials and further improve migration resistance within a range that does not impair the properties of the resin composition. it can. Examples of the additive include a defoaming / leveling agent, a silane coupling agent, an antioxidant, an inorganic or organic filler, and a pigment.
Examples of the defoaming / leveling agent include “KS-602A”, “KS-603”, “KS-608”, “FA600” (above, trade names manufactured by Shin-Etsu Chemical Co., Ltd.), “BYK-A506”. , “BYK-A525”, “BYK-A530”, “BYK-A500”, “BYK-A500”, “BYK-A501”, “BYK-A515”, “BYK-A555”, “Byketol-OK” (and above) Commercially available products such as “trade name manufactured by Big Chemie Japan Co., Ltd.” and “ARUFON UP-1000” (trade name manufactured by Toagosei Co., Ltd.) can be suitably used. These antifoaming agents or leveling agents may be used alone or in combination of two or more.
The addition amount of the antifoaming agent and the leveling agent is preferably 0.2% to 5% by mass on the basis of the total solid content of the resin composition from the viewpoint of achieving both defoaming property and film forming property and shape retention. 0.5% to 2% by mass is more preferable

The resin composition can contain a thermoplastic resin other than the above. Examples of such thermoplastic resins include polyethylene, polypropylene, polyvinylidene fluoride, polyester, polyacrylonitrile, polystyrene, polyamide, polyamideimide, polyphenylene, and the like. These thermoplastic resins can be used individually by 1 type or in combination of 2 or more types, It is preferable to select according to use conditions (use temperature etc.).
The resin composition can be used in the form of a paste by adding a solvent as necessary to adjust the viscosity. The solvent that can be used is not particularly limited as long as it is not reactive with the polyimide resin and, if necessary, the thermoplastic resin and additives, and exhibits sufficient solubility.
The resin composition preferably has a low content of ionic impurities from the viewpoint of improving migration resistance.
Generally, it is known that polyimide resin has a low content of ionic impurities compared to epoxy resin, and the resin composition of the present invention has a low content of ionic impurities and migration due to ionic impurities. Can be suppressed. Examples of the ionic impurities include chlorine ions. The content of chlorine ions contained in the resin composition is preferably 5 ppm or less, more preferably less than 3 ppm, and even more preferably less than 1 ppm.

The elastic modulus of the resin film formed from the resin composition is preferably 10 to 3500 MPa, more preferably 10 to 3000 MPa, and more preferably 50 to 2800 MPa at a temperature of 10 to 30 ° C. More preferably, it is 50-1500 MPa, Most preferably, it is 100-1000 MPa.
The linear expansion coefficient of the resin film is preferably 300 ppm / ° C. or less, more preferably 200 ppm / ° C. or less, and further preferably 150 ppm / ° C. or less.
When the elastic modulus of the resin film exceeds 3500 MPa and the linear expansion coefficient exceeds 300 ppm / ° C., stress is generated between the materials, causing cracks or peeling, and tends to reduce migration resistance.
The water absorption of the resin composition is 2% by mass after being immersed in water at 25 ° C. for 24 hours from the viewpoint of improving insulating properties (migration resistance) when the thickness of the film formed from the resin composition is 20 μm. Is less than 1.5% by mass, more preferably less than 1.5% by mass, and even more preferably less than 0.5% by mass.

The resin composition of the present invention is a semiconductor represented by, for example, circuit connection materials, CSP (chip size package) elastomers, COF (chip on film) underfill materials, LOC tapes, die bond adhesives, and the like. It can be used as an element adhesive.
The resin composition of the present invention is particularly useful as an insulating resin used under severe conditions such as high humidity and high voltage.
Further, since the resin composition of the present invention has a low elastic modulus, it is particularly suitable as an underfill material for COF having no voids.
Here, the void is generated in the underfill material in the step of bonding the semiconductor element to the plated wiring substrate through the underfill material after forming the underfill material on the plated wiring substrate. It means a gap of 1 μm or more.
As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.
[Synthesis of polyimide resin]
Example 1
In a 500 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, decamethylene bistrimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd., as a tetracarboxylic dianhydride component) Trade name “DBTA-KU”) 77.25 g (148 mmol), diamine component “priamine 1074” (Dymerjamine, trade name, manufactured by Coda Japan Co., Ltd.) 42.27 g (77 mmol), solvent tetralin (boiling point 207 120 g) and 30 g of triglyme (boiling point 216 ° C.) were added and the reaction was carried out by stirring at 80 ° C. for 15 minutes. Next, 24.29 g (59 mmol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name “BAPP”) as a diamine component was added to the reaction solution. After adding for 30 minutes and stirring at 100 ° C. for 15 minutes, the temperature was raised to 150 ° C. and heated under reflux for 3 hours to carry out an imidization reaction while removing a part of the generated water and solvent.

(Example 2)
In a 500 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, decamethylene bistrimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd., as a tetracarboxylic dianhydride component) (Product name “DBTA-KU”) 77.25 g (148 mmol), “Priamine 1074” (trade name, produced by Croda Japan Co., Ltd.) 42.75 g (78 mmol) as a diamine component, tetralin 120 g and triglyme 30 g as a solvent are added. The reaction was carried out by stirring at 80 ° C. for 15 minutes. Next, 24.29 g (59 mmol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name “BAPP”) as a diamine component was added to the reaction solution. After adding for 30 minutes and stirring at 100 ° C. for 15 minutes, the temperature was raised to 150 ° C. and heated under reflux for 3 hours to carry out an imidization reaction while removing a part of the generated water and solvent.

(Example 3)
In a 500 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, decamethylene bistrimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd., as a tetracarboxylic dianhydride component) (Product name “DBTA-KU”) 77.25 g (148 mmol), “Priamine 1074” (trade name, produced by Croda Japan Co., Ltd.) 43.24 g (79 mmol) as a diamine component, tetralin 120 g and triglyme 30 g as a solvent are added. The reaction was carried out by stirring at 80 ° C. for 15 minutes. Next, 24.29 g (59 mmol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name “BAPP”) as a diamine component was added to the reaction solution. After adding for 30 minutes and stirring at 100 ° C. for 15 minutes, the temperature was raised to 150 ° C. and heated under reflux for 3 hours to carry out an imidization reaction while removing a part of the generated water and solvent.

Example 4
In a 500 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, decamethylene bistrimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd., as a tetracarboxylic dianhydride component) (Product name “DBTA-KU”) 77.25 g (148 mmol), “Priamine 1074” (trade name, produced by Croda Japan Co., Ltd.) 43.72 g (80 mmol) as a diamine component, tetralin 120 g and triglyme 30 g as a solvent are added. The reaction was carried out by stirring at 80 ° C. for 15 minutes. Next, 24.29 g (59 mmol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name “BAPP”) as a diamine component was added to the reaction solution. After adding for 30 minutes and stirring at 100 ° C. for 15 minutes, the temperature was raised to 150 ° C. and heated under reflux for 3 hours to carry out an imidization reaction while removing a part of the generated water and solvent.

(Example 5)
In a 500 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, decamethylene bistrimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd., as a tetracarboxylic dianhydride component) Trade name “DBTA-KU”) 77.25 g (148 mmol), diamine component “priamine 1074” (trade name, produced by Croda Japan Co., Ltd.) 43.72 g (80 mmol), solvent, dimethoxybenzene (boiling point 217 ° C.) 150 g was added, and the reaction was carried out by stirring at 80 ° C. for 15 minutes. Next, 24.29 g (59 mmol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name “BAPP”) as a diamine component was added to the reaction solution. After adding for 30 minutes and stirring at 100 ° C. for 15 minutes, the temperature was raised to 150 ° C. and heated under reflux for 3 hours to carry out an imidization reaction while removing a part of the generated water and solvent.

(Comparative Example 1)
In a 500 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, decamethylene bistrimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd., as a tetracarboxylic dianhydride component) (Product name “DBTA-KU”) 77.25 g (148 mmol), “Priamine 1074” (trade name, manufactured by Croda Japan Co., Ltd.) 45.17 g (83 mmol) as a diamine component, Tetralin 120 g and Triglyme 30 g as a solvent are added. The reaction was carried out by stirring at 80 ° C. for 15 minutes. Next, 24.29 g (59 mmol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name “BAPP”) as a diamine component was added to the reaction solution. After adding for 30 minutes and stirring at 100 ° C. for 15 minutes, the temperature was raised to 150 ° C. and heated under reflux for 3 hours to carry out an imidization reaction while removing a part of the generated water and solvent.

(Comparative Example 2)
In a 500 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, decamethylene bistrimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd., as a tetracarboxylic dianhydride component) Product name “DBTA-KU”) 77.25 g (148 mmol), diamine component as “priamine 1074” (trade name, produced by Croda Japan Co., Ltd.) 48.54 g (89 mmol), solvent as cyclohexanone (boiling point 156 ° C.) 225 g And stirred for 15 minutes at 80 ° C. to carry out the reaction. Next, 24.29 g (59 mmol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name “BAPP”) as a diamine component was added to the reaction solution. After the addition over 30 minutes, the temperature was raised to 150 ° C., heated under reflux for 3 hours, and an imidization reaction was carried out while removing a part of the generated water and solvent. The reaction solution is cooled to 40 ° C., 3.75 g (1% by mass) of “DISPARON 230” (trade name, manufactured by Enomoto Kasei Co., Ltd.) is added as an antifoaming agent, and stirred for 30 minutes to prepare a polyimide resin solution. did.

(Comparative Example 3)
In a 500 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, decamethylene bistrimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd., as a tetracarboxylic dianhydride component) Trade name “DBTA-KU”) 77.25 g (148 mmol), diamine component “priamine 1074” (trade name, produced by Croda Japan Co., Ltd.) 46.13 g (mm84 ol), solvent, isophorone (boiling point 215 ° C.) 225 g And stirred for 15 minutes at 80 ° C. to carry out the reaction. Next, 24.29 g (59 mmol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name “BAPP”) as a diamine component was added to the reaction solution. After adding for 30 minutes and stirring at 100 ° C. for 15 minutes, the temperature was raised to 150 ° C. and heated under reflux for 3 hours to carry out an imidization reaction while removing a part of the generated water and solvent.

(Comparative Example 4)
As a tetracarboxylic dianhydride component, 5- (2,5-dioxotetrahydro-3-furanyl) was added as a tetracarboxylic dianhydride component to a 300 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser. 18.4 g (70 mmol) of -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (manufactured by DIC Corporation, trade name “Epiclon B4400”), 11.68 g (21 mmol) of “priamine 1074” as the diamine component ), 164 g of cyclohexanone was added as a solvent, and the mixture was stirred at 40 ° C. for 15 minutes for reaction. Next, 11.49 g (28 mmol) of “BAPP” as a diamine component was added to the reaction solution over 15 minutes, and further, “APB-N; (1, -bis (3-aminophenoxy) benzene)” 6.13 g (21 mmol) was added over 15 minutes. After the addition, the temperature was raised to 150 ° C., heated under reflux for 3 hours, and an imidization reaction was performed while removing a part of the generated water and solvent to prepare a polyimide resin solution.

(Comparative Example 5)
In a 300 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, 53.43 g of a triblock polyetherdiamine compound (manufactured by Sun Techno Chemical Co., Ltd., trade name “XTJ-542”) (52.5 mol), 2.03 g (17.5 mmol) of hexamethylenediamine and 164 g of N-methylpyrrolidone were added and stirred at 40 ° C. for 15 minutes, and “Tepiclone B4400” was added as a tetracarboxylic dianhydride component there. 18.4 g (70 mmol) was added over 15 minutes. After completely dissolved, 50 g of toluene is added, heated to 150 ° C. and heated to reflux for 3 hours, heated to 200 ° C. and heated to reflux for 3 hours, while removing a part of the generated water and solvent. An imidization reaction was performed to prepare a polyimide resin solution.

(Comparative Example 6)
In a 500 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, decamethylene bistrimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd., as a tetracarboxylic dianhydride component) (Product name “DBTA-KU”) 77.25 g (148 mmol), “Priamine 1074” (trade name, manufactured by Croda Japan Co., Ltd.) 43.72 g (80 mmol) as the diamine component, 150 g of tetralin as the solvent, and 80 ° C. The reaction was carried out with stirring for 15 minutes. Next, 24.29 g (59 mmol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name “BAPP”) as a diamine component was added to the reaction solution. When added over 30 minutes and stirred at 100 ° C. for 15 minutes, a solid was precipitated.

(Comparative Example 7)
In a 500 mL separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dean-Stark reflux condenser, decamethylene bistrimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd., as a tetracarboxylic dianhydride component) (Product name “DBTA-KU”) 77.25 g (148 mmol), “Priamine 1074” (trade name, produced by Croda Japan Co., Ltd.) 43.72 g (80 mmol) as a diamine component, Triglyme 150 g as a solvent, and 80 ° C. The reaction was carried out with stirring for 15 minutes. Next, 24.29 g (59 mmol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name “BAPP”) as a diamine component was added to the reaction solution. After adding for 30 minutes and stirring at 100 ° C. for 15 minutes, the temperature was raised to 150 ° C. and heated under reflux for 3 hours to carry out an imidization reaction while removing a part of the generated water and solvent. When the reaction solution was cooled to 40 ° C., the resin precipitated and solidified.

  Using the resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 7, respectively, using a micro applicator on a polyethylene terephthalate (PET) film (trade name “Purex” manufactured by Teijin DuPont Films Ltd.) After coating, the film was dried at 120 ° C. for 3 hours, peeled from the PET film, and a film made of a polyimide resin having a thickness of 35 μm was obtained.

[Evaluation of various characteristics]
Various characteristics of the resin compositions prepared in Examples and Comparative Examples were evaluated by the following methods. The results are summarized in Table 1.

ＤＢＴＡ：デカメチレンビストリメリテート二無水物（黒金化成株式会社製）
Ｂ４４００：５−（２，５−ジオキソテトラヒドロ−３−フラニル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸無水物（ＤＩＣ株式会社製）
ＢＡＰＰ：２，２−ビス−［４−（４−アミノフェノキシ）フェニル］プロパン
プリアミン１０７４：ダイマージアミン（クローダジャパン株式会社製）
ＡＰＢ-Ｎ：１，３−ビス（３−アミノフェノキシ）ベンゼン
ＸＴＪ−５４２：トリブロックポリエーテルジアミン化合物（サンテクノケミカル株式会社製）
テトラリン：沸点２０７℃
トリグライム：沸点２１６℃
ジメトキシベンゼン：沸点２１７℃
シクロヘキサノン：沸点１５６℃
イソホロン：沸点２１５℃
Ｎ−メチルピロリドン：沸点２０２℃

DBTA: decamethylene bis trimellitate dianhydride (manufactured by Kurokin Kasei Co., Ltd.)
B4400: 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by DIC Corporation)
BAPP: 2,2-bis- [4- (4-aminophenoxy) phenyl] propanepriamine 1074: Dimer diamine (manufactured by Croda Japan Co., Ltd.)
APB-N: 1,3-bis (3-aminophenoxy) benzene XTJ-542: triblock polyether diamine compound (manufactured by Sun Techno Chemical Co., Ltd.)
Tetralin: boiling point 207 ° C
Triglyme: boiling point 216 ° C
Dimethoxybenzene: boiling point 217 ° C
Cyclohexanone: boiling point 156 ° C
Isophorone: boiling point 215 ° C
N-methylpyrrolidone: boiling point 202 ° C.

<Measurement of imidization ratio>
The films obtained in Examples and Comparative Examples, using an infrared measuring device (DIGILAB's trade name "EXCALIBUR SERIES"), measuring the infrared absorption spectrum (transmitted light) in a range of ^{4000cm -1 ~500cm} -1 The imidation ratio was determined from the absorbance ratio of the characteristic absorption of the imide group and the phenyl group. In addition, the absorption spectrum of the film after further heat-treating the film at 250 ° C. for 1 hour was theoretically assumed to be 100% imidation ratio, and the imidization ratio X (%) of the cured film was calculated by the following formula (a).

X (%) = [(K / L)-(M / N)] / [(O / P)-(M / N)] (a)

K: Absorbance of the maximum peak near 1780 cm ⁻¹ of the film L: Absorbance of the maximum peak near 1510 cm ⁻¹ of the film M: During the synthesis of the polyimide resin, a part of the resin was extracted before raising the temperature to 150 ° C. The absorbance of the maximum peak in the vicinity of 1780 cm ⁻¹ of the polyamic acid (0% imidization) after drying for 2 hours at N: During the synthesis of the polyimide resin, a part of the resin was extracted before the temperature was raised to 150 ° C. Absorbance of the maximum peak in the vicinity of 1510 cm ⁻¹ of the polyamic acid (imidation rate 0%) after drying at 120 ° C. for 2 hours O: of the film after heat treatment at 250 ° C. for 1 hour (imidation rate 100%) 1780 cm ^-1 vicinity of the maximum peak absorbance P: after 1 hour heat treatment at 250 ° C. the film (imidization ratio 100%) 1510 cm ^-1 vicinity of the maximum peak Absorbance of the click

<Measurement of melt viscosity>
Weigh 2 g as a test piece from each film and use a rheometer (trade name “EXTRADMS6000”, manufactured by Seiko Instruments Inc.) at a frequency of 5 Hz, a cooling rate of 5 ° C./min, and a measurement temperature of 23 to 200 ° C. The shear viscosity was measured, and the shear viscosity at 150 ° C. was defined as the melt viscosity of the polyimide resin.

<Measurement of 1% mass loss temperature>
0.5 mg is weighed as a test piece from each film, and the temperature rise rate is 10 ° C. by the TG-DTA method using a differential thermothermal gravimetric simultaneous measurement device (trade name “TG / DTA6300” manufactured by Seiko Instruments Inc.). / Min, a 1% mass reduction temperature of the polyimide resin under a nitrogen atmosphere (flow rate 20 mL / min) was measured.

<Joint evaluation test>
Flexible wiring board (trade name “JKIT COF TEG 25-B”, manufactured by Hitachi VLSI Systems, Inc., 2-layer casting material, 25 μm pitch, tin plating) and semiconductor chip (product name “JTEG, manufactured by Hitachi VLSI Systems, Inc.) PHASE6_25 ") was prepared. Next, the polyimide resin obtained on the test piece was applied so that the thickness after drying was 35 μm and dried at 120 ° C. for 3 hours. After drying, the semiconductor chip was thermocompression bonded at a stage temperature of 100 ° C., a tool temperature of 420 ° C., and a pressure of 60 N for 0.5 seconds using a bonding apparatus (trade name “FC-100M” manufactured by Toray Engineering Co., Ltd.). After metal bonding, it was heated at 150 ° C. for 3 hours and evaluated as “◯” when there was no void, and “X” when there was a void (remaining).

<Evaluation of outgas>
The film was thermocompression bonded under the same conditions as in the bonding evaluation test except that the flexible wiring board in the bonding evaluation test was replaced with a slide glass. After thermocompression bonding, the case where the deposits were not visible around the test piece on the slide glass was evaluated as “◯” and the case where the deposits were visible was evaluated as “X”.

<Evaluation of printability>
2 g of the obtained polyimide resin solution was collected in a metal dish and allowed to stand at 25 ° C. for 24 hours. When the rate of change in the solid content before and after standing was 110% or more, or “X” when the resin was precipitated due to water absorption, the transparency of the solution was maintained when the rate of change in the solid content was less than 110%. We evaluated what we have as “○”

<Migration resistance (HAST (unsaturated pressurized steam) resistance)>
FIG. 1 is a schematic plan view of a migration resistance evaluation substrate (25 μmP). Next, the polyimide resin obtained on the test piece was applied so that the thickness after drying was 35 μm and dried at 120 ° C. for 3 hours. Using an ion migration tester (trade name: MIG-8600, manufactured by IMV Corporation), migration resistance after treatment for 200 hours under the conditions of 105 ° C., 85% RH and 60 V was evaluated. Those having a resistance value of 1 × 10 ⁸ Ω or more were evaluated as “◯”, and those having a resistance value of less than 1 × 10 ⁸ Ω were evaluated as “×”.

<Polyamide acid solubility>
In the synthesis, the polyamic acid precipitated and solidified was evaluated as “×”, and the dissolved polyamic acid was evaluated as “◯”.

<Polyimide solubility (storage stability)>
Immediately after synthesis, polyimide is precipitated and solidified as “×”, stored for 1 month at room temperature (25 ° C.) and solidified as “△”, and solidified even after storage at room temperature for 1 month or more as “◯” As evaluated.

Each of the resin compositions obtained in Examples 1 to 5 has a melt viscosity of not more than 3000 Pa · s at 150 ° C., has sufficient flexibility and excellent bonding properties, and has a 1% mass reduction temperature. The heat resistance was high at 350 ° C. or higher, and generation of outgas could be sufficiently reduced.
On the other hand, when the melt viscosity exceeds 3000 Pa · s (Comparative Example 1), (1) a mixture of an ether organic solvent and a hydrocarbon organic solvent containing an aromatic ring, or (2) an ether bond and an aromatic ring. Comparative Examples 2-7 that do not use an organic solvent containing both are inferior to the properties evaluated above.
The resin compositions obtained in Comparative Examples 1 and 6 had a high melt viscosity, and the mountability as in Examples was not obtained. Since the 1% mass reduction temperature of Comparative Examples 4 and 5 was 270 ° C. and the heat resistance was low, generation of outgas was observed. Furthermore, in the resin compositions obtained in Comparative Examples 2 and 3, the molecular weight of the obtained resin varied depending on the solid content during synthesis due to the reaction between the amino group and the solvent. Further, Comparative Example 2 was poor in printability due to the volatilization of the solvent, and Comparative Example 3 was solidified by storage for 1 month at room temperature, resulting in poor storage stability. In Comparative Example 6, amic acid precipitated during synthesis, and in Comparative Example 7, the obtained resin composition solidified immediately.

DESCRIPTION OF SYMBOLS 1 ... Film-like base material 2 ... Tin plating copper wiring 3 ... Resin composition

Claims (8)

  (A) A polyimide resin having a melt viscosity at 150 ° C. of 30 to 3000 Pa · s and a 1% mass reduction temperature of 350 ° C. or more and (B) a solvent, wherein the solvent of the component (B) has a boiling point of 180 to A resin composition which is 220 ° C. and is an organic solvent containing a mixture of an ether organic solvent and a hydrocarbon organic solvent containing an aromatic ring, or an ether bond and an aromatic ring. (A) The resin composition of Claim 1 in which the polyimide resin of a component has a repeating unit represented by following General formula (1).

[In General Formula (1), Ar ¹ represents a tetravalent organic group, Ar ² represents a divalent organic group, and Ar ¹ and / or Ar ² represents an alkylene chain having 5 to 20 carbon atoms in the main chain. Including. ] The resin composition according to claim 2, wherein Ar ¹ is a group represented by the following general formula (2).

[In General Formula (2), X represents an alkylene group having 5 to 20 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. M and n each independently represent an integer of 1 to 3. When m is 2 or more, a plurality of R ¹ may be the same or different, and when n is 2 or more, a plurality of R ² may be the same or different. ] The resin composition according to claim 2 or 3, wherein the Ar ² is a divalent group represented by the following general formula (3).

[In General Formula (3), Z represents a single bond or a divalent organic group, and Y ¹ and Y ² each independently represents an alkylene group having 5 to 20 carbon atoms. ] The resin composition according to claim 4, wherein Z is at least one group selected from the group consisting of divalent groups represented by the following general formulas (4), (5) and (6), respectively. .

[In General Formulas (4), (5) and (6), R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or A C1-C3 alkoxy group is shown, q, r, and s show the integer of 1-4 each independently. When q is 2 or more, a plurality of R ⁸ may be the same or different. When r is 2 or more, a plurality of R ⁹ may be the same or different. When s is 2 or more, The existing R ¹⁰ may be the same or different. ] The resin composition as described in any one of Claims 2-5 in which the said polyimide resin further has a repeating unit represented by following General formula (7).

[In General Formula (7), Ar ¹ represents a tetravalent organic group represented by the following General Formula (2), and Ar ³ represents a divalent organic group containing an aromatic hydrocarbon group. ]

[In General Formula (2), X represents an alkylene group having 5 to 20 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. M and n each independently represent an integer of 1 to 3. When m is 2 or more, a plurality of R ¹ may be the same or different, and when n is 2 or more, a plurality of R ² may be the same or different. ] Ar ³ is at least one selected from the group consisting of an arylene group which may have a substituent, a group represented by the following general formula (8) and a group represented by the following general formula (9). The resin composition according to claim 6, which is a group.

[In General Formulas (8) and (9), D and E are each independently a single bond, an ether bond, a thioether bond, a carbonyl group, a sulfonyl group, a methylene group, an ethylene group, an isopropylidene group, or a hexafluoroisopropylidene group. , A group represented by the following formula (i) or a group represented by the following formula (ii), wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, A hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is shown, and t1, t2, t3, t4, t5 and t6 each independently represent an integer of 1 to 4.
When t1 is 2 or more, a plurality of R ¹¹ may be the same or different. When t2 is 2 or more, a plurality of R ¹² may be the same or different. When t3 is 2 or more, a plurality of R ¹¹ are present. R ¹³ present may be the same or different. When t4 is 2 or more, a plurality of R ¹⁴ may be the same or different. When t5 is 2 or more, a plurality of R ¹⁵ are the same or different. even well, in the case of t6 is 2 or more, R ¹⁶ existing in plural numbers may be the same or different. ]

  The resin composition as described in any one of Claims 1-7 whose imidation ratio of the said polyimide resin is 80% or more.

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