JP2019172889A - Silicone-modified polyimide resin composition - Google Patents

Abstract

To provide a polyimide resin composition excellent in coating property, good in adhesiveness to various metal frames, and giving a cured product high in moisture-proof property, and exhibiting low elasticity and high heat resistance.SOLUTION: The silicone-modified polyimide resin includes: (A) a polyimide resin represented by Ee-Ff-Gg (1) where E is a group represented by formula (2), F is a group represented by formula (3): -Im-X-Im- (3) where Im is a group containing a cyclic imide structure at the terminal, and X is selected from a single bond, -O-, -S- and the like, G is a bivalent group derived from diamine, f+e+g=100 mol%, the mole ratio of f/(e+g) is 0.9-1.1, and e is 30-90 when the sum of e and g is 100; (B) a curing agent; and (C) a solvent.SELECTED DRAWING: None

Description

  The present invention relates to a silicone-modified polyimide resin composition.

In recent years, an epoxy resin sealant (Patent Document 1) has been widely used to avoid semiconductor elements from moisture and electromagnetic interference.
However, since epoxy resin has low moisture resistance and the cured product has high hardness, it may not adhere due to the difference in coefficient of linear expansion in the sealing process of the semiconductor element, and also peels off due to poor adhesion in the subsequent process. In many cases, there is a problem that the reliability of the package is lowered.

  In addition, there is an increasing demand for heat resistance in in-vehicle devices, and accordingly, adhesives and coating materials for in-vehicle devices are required to have stable high heat resistance over a longer period of time.

In this regard, polyimide resin has high heat resistance and excellent electrical insulation, so it is used as a material for printed circuit boards and heat-resistant adhesive tapes, and as a resin varnish for surface protection films and interlayers of electrical parts and semiconductor materials. It is also used as an insulating film.
However, since polyimide resin is soluble only in a limited solvent, in general, polyamic acid, which is a polyimide precursor that is relatively easy to dissolve in various organic solvents, is applied to a base material and dehydrated and cyclized by high-temperature treatment. A method for obtaining a cured product made of a polyimide resin is employed.

JP 2009-60146 A

  The present invention has been made in view of the above circumstances, and has excellent coatability, good adhesion to various metal frames, high moisture resistance, low-elasticity, high heat resistance, and a silicone that provides a cured product. It aims at providing the modified polyimide resin composition, the adhesive agent and coating agent which consist of this composition.

  As a result of intensive studies to solve the above problems, the present inventor obtained a silicone-modified polyimide resin having low elasticity and moisture resistance by introducing a silicone unit into the polyimide resin, and in the imide skeleton. By introducing an arylene alkyl moiety, it was found that a silicone-modified polyimide resin superior in heat resistance was obtained, and the present invention was completed.

（式（２）中、Ｒ^Aは、互いに独立して炭素原子数８〜１２のアリーレンアルキレン基を表し、Ｒ¹およびＲ²は、互いに独立して脂肪族不飽和結合を有しない置換または非置換の炭素原子数１〜１０の１価炭化水素基を表し、Ｒ³およびＲ⁴は、互いに独立して、置換または非置換の炭素原子数１〜１０の１価炭化水素基を表すが、Ｒ³およびＲ⁴の少なくとも一方は、脂肪族不飽和結合を有し、ｍは、０〜２０、ｎは、１〜２０、かつ、ｍ＋ｎ＝１〜４０を満たす整数を表す。なお、ｍ、ｎが付された括弧内のシロキサン単位の配列は、ランダム、交互またはブロックのいずれであってもよい。）
−Ｉｍ−Ｘ−Ｉｍ− （３）
〔式（３）中、Ｉｍは、環状イミド構造を端に含む環状の基を表し、Ｘは、単結合、−Ｏ−、−Ｓ−、−Ｓ（→Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｃ（＝Ｏ）−、−ＮＲ^N−（Ｒ^Nは、炭素原子数１〜１２の１価炭化水素基を表す。）、−ＣＲ^B ₂−（Ｒ^Bは、互いに独立して、水素原子またはハロゲン原子を含んでいてもよい炭素原子数１〜１２の１価炭化水素基を表す。）、−Ｒ^Ar _h−（Ｒ^Arは、炭素原子数６〜１２の２価のアリーレン基を表し、ｈは、１〜６の整数を表す。ｈが２以上のとき、Ｒ^Arは互いに同一でも異なっていてもよい。）、−Ｒ^Ar _h−（ＯＲ^Ar）_i−（Ｒ^Arおよびｈは、前記と同じ意味を表し、ｉは、１〜５の整数を表す。）、炭素原子数１〜１２の直鎖状または分岐状アルキレン基、炭素原子数５〜１２のシクロアルキレン基、および炭素原子数７〜１２のアリーレンアルキレン基から選択される２価の基を表す。〕｝
（Ｂ）硬化剤：０．１〜１０質量部、および
（Ｃ）溶剤：１００〜７００質量部
を含むことを特徴とするシリコーン変性ポリイミド樹脂組成物、
２． 前記Ｒ^Aが、下記の基から選ばれる１のシリコーン変性ポリイミド樹脂組成物、

（式中、Ｊは、炭素原子数２〜６のアルキレン基を表し、波線を付した線は結合手を表す。Ｊに結合している結合手はケイ素原子に結合し、他の結合手はＩｍに結合する。）
３． 前記Ｉｍが、下記の基から選ばれる１または２のシリコーン変性ポリイミド樹脂組成物、

（式中、波線を付した線は結合手を示す。窒素原子に結合している結合手はＥまたはＧに結合し、他の結合手はＸに結合する。）
４． 前記Ｇで表されるジアミン由来の２価の基において、ジアミンが、テトラメチレンジアミン、１，４−ジアミノシクロヘキサン、４，４’−ジアミノジシクロヘキシルメタン、ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルエーテル、２，２−ビス（４−アミノフェニル）プロパン、および２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパンから選ばれる１〜３のいずれかのシリコーン変性ポリイミド樹脂組成物、
５． 前記（Ａ）成分の式（１）で示されるシリコーン変性ポリイミド樹脂の重量平均分子量が、１０，０００〜１００，０００である１〜４のいずれかのシリコーン変性ポリイミド樹脂組成物、
６． 前記（Ｂ）成分の硬化剤が、熱分解性ラジカル開始剤である１〜５のいずれかのシリコーン変性ポリイミド樹脂組成物、
７． さらに、（Ｄ）嵩密度が１ｇ／ｍＬ未満、平均一次粒子径が１〜１００ｎｍ、かつ、ＢＥＴ比表面積が１００〜３００ｍ²／ｇである疎水性フュームドシリカを（Ａ）成分１００質量部に対して３〜５０質量部含む１〜６のいずれかのシリコーン変性ポリイミド樹脂組成物、
８． ２５℃における粘度が、１００〜１００，０００ｍＰａ・ｓである１〜７のいずれかのシリコーン変性ポリイミド樹脂組成物、
９． １〜８のいずれかのシリコーン変性ポリイミド樹脂組成物の硬化物、
１０． （α）２５℃における貯蔵弾性率が１００〜１，０００ＭＰａ、（β）ガラス転移点（Ｔｇ）が１００〜２００℃、（γ）４０℃での水蒸気透過度が２０ｇ／ｍ²・ｄａｙ以下、かつ、（δ）５％重量減少温度が４２０℃以上である９の硬化物、
１１． １〜８のいずれかのシリコーン変性ポリイミド樹脂組成物からなる接着剤、
１２． １〜８のいずれかのシリコーン変性ポリイミド樹脂組成物からなるコーティング剤、
１３． 下記（ｉ）〜（ｉｉｉ）の工程を含む下記式（４）

〔式中、Ｒ¹およびＲ²は、互いに独立して脂肪族不飽和結合を有しない置換または非置換の炭素原子数１〜１０の１価炭化水素基を表し、
Ｒ³およびＲ⁴は、互いに独立して、置換または非置換の炭素原子数１〜１０の１価炭化水素基を表すが、Ｒ³およびＲ⁴の少なくとも一方は、脂肪族不飽和結合を有し、
Ｒ^Cは、下記の基から選ばれる２価の基を表し、

（式中、Ｊは、炭素原子数２〜６のアルキレン基を表し、波線を付した線は結合手を表す。Ｊに結合している結合手はケイ素原子に結合し、他の結合手はＩｍに結合する。）
ｍは、０〜２０、ｎは１〜２０、かつ、ｍ＋ｎ＝１〜４０を満たす整数を表す。なお、ｍ、ｎが付された括弧内のシロキサン単位の配列は、ランダム、交互またはブロックのいずれであってもよい。〕
で示されるジアミノ変性シリコーンの製造方法、
（ｉ）（Ｅ）下記式（５）で示される化合物、

（式中、Ｒ¹およびＲ²は、前記と同じ意味を表し、Ｋは、末端に不飽和基を有する炭素原子数２〜６の１価の脂肪族不飽和炭化水素基である。）
（Ｆ）下記式（６）または下記式（７）で示される化合物：前記式（５）で示される化合物に対して２．０〜２．５モル当量、

（式中、ＬＧは、互いに独立して脱離基として機能する１価の官能基を表す。）
（Ｇ）遷移金属有機錯体触媒：前記式（５）で示される化合物に対して金属の含有量として０．０１〜５モル％、
（Ｈ）塩基：前記式（５）で示される化合物に対して２．０〜３．０モル当量、および
（Ｉ）溶剤：前記式（５）で示される化合物の濃度が０．１〜５．０モル／Ｌとなる量
の存在下で反応を行い、下記式（８）

（式中、Ｒ¹、Ｒ²およびＲ^Cは、前記と同じ意味を表す。）
で示される化合物を得る工程；
（ｉｉ）（Ｊ）前記工程（ｉ）で得られた前記式（８）で示される化合物、および
（Ｋ）遷移金属触媒：前記式（８）で示される化合物に対して金属の含有量として０．００１〜１モル％
の存在下で水素添加反応を行い、下記式（９）

（式中、Ｒ¹、Ｒ²、およびＲ^Cは、前記と同じ意味を表す。）
で示される化合物を得る工程；
（ｉｉｉ）（Ｎ）前記工程（ｉｉ）で得られた前記式（９）で示される化合物、
（Ｏ）−［Ｒ¹Ｒ²ＳｉＯ］−単位からなる環状シロキサン（式中、Ｒ¹およびＲ²は前記と同じ意味を表す。）：前記式（９）で示される化合物に対して−［Ｒ¹Ｒ²ＳｉＯ］−単位が０〜５モル当量となる量、
（Ｐ）−［Ｒ³Ｒ⁴ＳｉＯ］−単位からなる環状シロキサン（式中、Ｒ³およびＲ⁴は前記と同じ意味を表す。）：前記式（９）で示される化合物に対して−［Ｒ³Ｒ⁴ＳｉＯ］−単位が０．２５〜５モル当量となる量、および
（Ｑ）有機塩基触媒：前記式（９）で示される化合物に対して０．０１〜５質量％
の存在下で反応を行い、前記式（４）で示されるジアミノ変性シリコーンを得る工程
１４． 前記（ｉｉ）工程が、
（Ｊ）前記工程（ｉ）で得られた前記式（８）で示される化合物、
（Ｋ）遷移金属触媒：前記式（８）で示される化合物に対して金属の含有量として０．００１〜１モル％
（Ｌ）第３級アルキルミン化合物：前記式（８）で示される化合物に対して０モル当量より多く２モル当量未満、および
（Ｍ）ギ酸またはギ酸塩：反応混合液がｐＨ７以上となる量
の存在下で、大気圧において行われる１３のジアミノ変性シリコーンの製造方法
を提供する。 That is, the present invention
1. (A) Silicone-modified polyimide resin represented by the following formula (1): 100 parts by mass,
Ee-Ff-Gg (1)
{In Formula (1), E, F, and G are repeating units that are randomly bonded, E is a divalent group derived from diamino-modified silicone represented by Formula (2), and F is a formula ( 3) is a divalent group derived from a tetracarboxylic dianhydride, and G is a divalent group derived from a diamine. However, f + e + g = 100 mol%, the molar ratio of f / (e + g) is 0.9 to 1.1, and when the sum of e and g is 100, the e is 30 to 90.

(In the formula (2), R ^A independently represents an arylene alkylene group having 8 to 12 carbon atoms, and R ¹ and R ² independently represent a substituted or non-substituted group having no aliphatic unsaturated bond. A substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ and R ⁴ each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, At least one of R ³ and R ⁴ has an aliphatic unsaturated bond, m represents 0 to 20, n represents an integer satisfying 1 to 20, and m + n = 1 to 40. (The arrangement of siloxane units in parentheses to which n is attached may be random, alternating, or block.)
-Im-X-Im- (3)
[In the formula (3), Im represents a cyclic group including a cyclic imide structure at the end, and X represents a single bond, —O—, —S—, —S (→ O) —, —S (═O _{) 2 -, - C (=} O) -, - NR N - (R N represents a monovalent hydrocarbon group having 1 to 12 carbon _{^{atoms), -. CR B 2 -}} (R B are each independently And a monovalent hydrocarbon group having 1 to 12 carbon atoms which may contain a hydrogen atom or a halogen atom.), -R ^Ar _h- (R ^Ar is a divalent group having 6 to 12 carbon atoms). And h represents an integer of 1 to 6. When h is 2 or more, R ^Ar may be the same or different from each other.), —R ^Ar _h — (OR ^Ar ) _i — ( R ^Ar and h represent the same meaning as described above, i represents an integer of 1 to 5), a linear or branched alkylene group having 1 to 12 carbon atoms, and a cycloalkyl having 5 to 12 carbon atoms. Represents a divalent group selected from a ren group and an arylene alkylene group having 7 to 12 carbon atoms. ]}
(B) a curing agent: 0.1 to 10 parts by mass, and (C) a solvent: 100 to 700 parts by mass of a silicone-modified polyimide resin composition,
2. The silicone-modified polyimide resin composition, wherein R ^A is selected from the following groups:

(In the formula, J represents an alkylene group having 2 to 6 carbon atoms, and a wavy line represents a bond. A bond bonded to J is bonded to a silicon atom, and other bonds are Bind to Im.)
3. 1 or 2 silicone-modified polyimide resin composition, wherein the Im is selected from the following groups:

(In the formula, a wavy line indicates a bond. A bond bonded to a nitrogen atom is bonded to E or G, and another bond is bonded to X.)
4). In the divalent group derived from the diamine represented by G, the diamine is tetramethylenediamine, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, o-phenylenediamine, m-phenylenediamine, p- Any of 1 to 3 selected from phenylenediamine, 4,4′-diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane A silicone-modified polyimide resin composition,
5. The silicone-modified polyimide resin composition of any one of 1 to 4, wherein the weight-average molecular weight of the silicone-modified polyimide resin represented by the formula (1) of the component (A) is 10,000 to 100,000,
6). The silicone-modified polyimide resin composition according to any one of 1 to 5, wherein the curing agent of the component (B) is a thermally decomposable radical initiator,
7. Furthermore, (D) hydrophobic fumed silica having a bulk density of less than 1 g / mL, an average primary particle size of 1 to 100 nm, and a BET specific surface area of 100 to 300 m ² / g is added to 100 parts by mass of component (A). 1 to 6 silicone-modified polyimide resin composition containing 3 to 50 parts by weight,
8). The silicone-modified polyimide resin composition according to any one of 1 to 7 having a viscosity at 25 ° C of 100 to 100,000 mPa · s,
9. Cured product of any one of the silicone-modified polyimide resin compositions 1 to 8,
10. (Α) Storage elastic modulus at 25 ° C. of 100 to 1,000 MPa, (β) Glass transition point (Tg) of 100 to 200 ° C., (γ) Water vapor permeability at 40 ° C. of 20 g / m ² · day or less, And (δ) a cured product of 9 having a 5% weight loss temperature of 420 ° C. or higher,
11. An adhesive comprising the silicone-modified polyimide resin composition of any one of 1 to 8,
12 A coating agent comprising the silicone-modified polyimide resin composition of any one of 1 to 8,
13. The following formula (4) including the following steps (i) to (iii)

[Wherein, R ¹ and R ² independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which does not have an aliphatic unsaturated bond;
R ³ and R ⁴ each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least one of R ³ and R ⁴ has an aliphatic unsaturated bond. And
R ^C represents a divalent group selected from the following groups:

(In the formula, J represents an alkylene group having 2 to 6 carbon atoms, and a wavy line represents a bond. A bond bonded to J is bonded to a silicon atom, and other bonds are Bind to Im.)
m represents an integer satisfying 0 to 20, n is 1 to 20, and m + n = 1 to 40. The arrangement of siloxane units in parentheses with m and n may be random, alternating or block. ]
A process for producing a diamino-modified silicone represented by
(I) (E) a compound represented by the following formula (5),

(In the formula, R ¹ and R ² represent the same meaning as described above, and K is a monovalent aliphatic unsaturated hydrocarbon group having 2 to 6 carbon atoms having an unsaturated group at the terminal.)
(F) A compound represented by the following formula (6) or the following formula (7): 2.0 to 2.5 molar equivalents relative to the compound represented by the formula (5),

(In the formula, LG represents a monovalent functional group that functions as a leaving group independently of each other.)
(G) transition metal organic complex catalyst: 0.01-5 mol% as a metal content with respect to the compound represented by the formula (5),
(H) Base: 2.0 to 3.0 molar equivalents relative to the compound represented by Formula (5), and (I) Solvent: The concentration of the compound represented by Formula (5) is 0.1 to 5 The reaction is carried out in the presence of an amount of 0.0 mol / L, and the following formula (8)

(In the formula, R ¹ , R ² and R ^C have the same meaning as described above.)
Obtaining a compound represented by:
(Ii) (J) the compound represented by the formula (8) obtained in the step (i), and (K) a transition metal catalyst: as a metal content with respect to the compound represented by the formula (8) 0.001 to 1 mol%
The hydrogenation reaction is carried out in the presence of

(In the formula, R ¹ , R ² , and R ^C represent the same meaning as described above.)
Obtaining a compound represented by:
(Iii) (N) the compound represented by the formula (9) obtained in the step (ii),
Cyclic siloxane composed of (O)-[R ¹ R ² SiO] -unit (wherein R ¹ and R ² have the same meanings as described above): with respect to the compound represented by the formula (9) R ¹ R ² SiO] —the amount by which the units are 0 to 5 molar equivalents,
Cyclic siloxane composed of (P)-[R ³ R ⁴ SiO] -unit (wherein R ³ and R ⁴ have the same meanings as described above): for the compound represented by the formula (9)-[ R ³ R ⁴ SiO] —the amount of units to be 0.25 to 5 molar equivalents, and (Q) organic base catalyst: 0.01 to 5% by mass relative to the compound represented by the formula (9)
13. A step of obtaining a diamino-modified silicone represented by the formula (4) by reacting in the presence of The step (ii)
(J) the compound represented by the formula (8) obtained in the step (i),
(K) Transition metal catalyst: 0.001 to 1 mol% as a metal content with respect to the compound represented by the formula (8)
(L) Tertiary alkylamine compound: more than 0 mole equivalent and less than 2 mole equivalent with respect to the compound represented by the formula (8), and (M) formic acid or formate salt: an amount such that the reaction mixture becomes pH 7 or more. A method for producing 13 diamino-modified silicones carried out at atmospheric pressure in the presence of

The silicone-modified polyimide resin composition of the present invention is suitable as a primer because of its excellent coatability.
Further, the cured product obtained from the above composition has low elasticity and exhibits good adhesion to various metal frames and epoxy-based encapsulants, and has water resistance, moisture resistance (low water vapor permeability) and Excellent heat resistance.
Therefore, the silicone-modified polyimide resin composition of the present invention can be suitably used as an adhesive or coating agent for electronic materials, optical materials, and in-vehicle devices, and particularly for bonding a semiconductor device that requires high reliability. It can be suitably used as an agent or a coating agent.

Hereinafter, the present invention will be specifically described.
The silicone-modified polyimide resin composition according to the present invention includes (A) a silicone-modified polyimide resin, (B) a curing agent, and (C) a solvent.

(1) Component (A) The silicone-modified polyimide resin of component (A) is the main agent (base polymer) of the present composition, and in the present invention, the one represented by the following formula (1) is used.
Ee-Ff-Gg (1)

  In formula (1), E, F, and G are repeating units that are randomly bonded (except for combinations of adjacent units represented by EE, FF, GG, and EG). Yes, E is a divalent group derived from a diamino-modified silicone represented by the following formula (2), and F is a divalent group derived from a tetracarboxylic dianhydride represented by the following formula (3). , G is a diamine-derived divalent group. However, f + e + g = 100 mol%, the molar ratio of f / (e + g) is 0.9 to 1.1, and when the sum of e and g is 100, e is 30 to 90.

In Formula (2), R ^A independently represents an arylene alkylene group having 8 to 12 carbon atoms, and R ¹ and R ² independently represent a substituted or unsubstituted group having no aliphatic unsaturated bond And R ³ and R ⁴ each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ^At least one of ³ and R ⁴ has an aliphatic unsaturated bond, m represents an integer satisfying 0 to 20, n represents 1 to 20, and m + n = 1 to 40. The arrangement of siloxane units in parentheses with m and n may be random, alternating or block.

-Im-X-Im- (3)
In formula (3), Im represents a cyclic group including a cyclic imide structure at the end, and X represents a single bond, —O—, —S—, —S (→ O) —, —S (═O). _{2 -, - C (= O} ) -, - NR N -, (R N represents a monovalent hydrocarbon group having 1 to 12 carbon _{^{atoms.) - CR B 2 - (}} R B is, independently of one another And represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may contain a hydrogen atom or a halogen atom.), -R ^Ar _h- (R ^Ar is a divalent hydrocarbon having 6 to 12 carbon atoms). Represents an arylene group, and h represents an integer of 1 to 6. When h is 2 or more, R ^Ar may be the same or different from each other), —R ^Ar _h — (OR ^Ar ) _i — (R ^Ar and h represent the same meaning as described above, and i represents an integer of 1 to 5.), a linear or branched alkylene group having 1 to 12 carbon atoms, and a cycloalkylene having 5 to 12 carbon atoms. And a divalent group selected from an arylene alkylene group having 7 to 12 carbon atoms.

In the formula (2), specific examples of the divalent arylene alkylene group having 8 to 12 carbon atoms of R ^A include 2- (1,4-phenylene) -1-ethylene and 2- (1,3-phenylene). -1-ethylene, 1- (1,4-phenylene) -1-ethylene, 1- (1,3-phenylene) -1-ethylene, 3- (1,4-phenylene) -1-propylene, 3- ( 1,3-phenylene) -1-propylene, 2- (1,4-phenylene) -1-propylene, 2- (1,3-phenylene) -1-propylene, 2-methyl-3- (1,4- Phenylene) -1-propylene, 2-methyl-3- (1,3-phenylene) -1-propylene, 2-methyl-2- (1,4-phenylene) -1-propylene, 2-methyl-2- ( 1,3-phenylene) -1-propylene, 4- (1, -Phenylene) -1-butylene, 4- (1,3-phenylene) -1-butylene, 3- (1,4-phenylene) -1-butylene, 3- (1,3-phenylene) -1-butylene, 3-methyl-4- (1,4-phenylene) -1-butylene, 3-methyl-4- (1,3-phenylene) -1-butylene, 3-methyl-3- (1,4-phenylene)- 1-butylene, 3-methyl-3- (1,3-phenylene) -1-butylene, 5- (1,4-phenylene) -1-pentylene, 5- (1,3-phenylene) -1-pentylene, 4- (1,4-phenylene) -1-pentylene, 4- (1,3-phenylene) -1-pentylene, 2,2-dimethyl-4- (1,4-phenylene) -1-butylene, 2, 2-Dimethyl-4- (1,3-phenylene) -1-butylene Groups 2,2-dimethyl-3- (1,4-phenylene) -1-butylene, 2,2-dimethyl-3- (1,3-phenylene) -1-butylene, 6- (1,4-phenylene) ) -1-hexylene, 6- (1,3-phenylene) -1-hexylene, 5- (1,4-phenylene) -1-hexylene, 5- (1,3-phenylene) -1-hexylene, 2- (1,9-naphthylene) -1-ethylene, 2- (1,5-naphthylene) -1-ethylene group and the like.
Among these, 2- (1,4-phenylene) -1-ethylene group and 2- (1,3-phenylene) -1-ethylene group are preferable because of availability.

The monovalent hydrocarbon group having 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond of R ¹ and R ² may be linear, branched, or cyclic. For example, methyl, ethyl, n- 1 carbon atom such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, decalyl group -10 alkyl groups; alkenyl groups having 2 to 10 carbon atoms such as vinyl, 1-propenyl, allyl (2-propenyl), hexenyl, octenyl, cyclopentenyl, and cyclohexenyl groups; carbon atoms such as phenyl and naphthyl groups 6-10 aryl groups; tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexyl Examples thereof include alkylaryl groups having 7 to 10 carbon atoms such as silphenyl groups; aralkyl groups having 7 to 10 carbon atoms such as benzyl and phenethyl groups, etc., but alkyl groups having 1 to 10 carbon atoms are preferable, and carbon atoms An alkyl group having 1 to 4 is more preferable, a methyl group, an ethyl group, and an n-propyl group are more preferable, and R ¹ and R ² are more preferably a methyl group or an ethyl group.

The monovalent hydrocarbon group having 1 to 10 carbon atoms of R ³ and R ^{4 is} a monovalent hydrocarbon group having 1 to 10 carbon atoms which does not have an aliphatic unsaturated bond exemplified as R ¹ and R ² above. And monovalent hydrocarbon groups having 2 to 10 carbon atoms having an aliphatic unsaturated bond such as alkenyl groups such as vinyl, allyl, 1-propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, octenyl and the like. It is done.
Among them, as R ³ and R ⁴ , an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms or an alkenyl having 2 to 6 carbon atoms is preferable. A group is more preferable, and a methyl group, an ethyl group, a propyl group, and a vinyl group are even more preferable.
In particular, it is preferable that one or both of R ³ and R ⁴ is an alkenyl group having 2 to 10 carbon atoms. Therefore, the combination of R ³ and R ⁴ includes a methyl group, a vinyl group, and an ethyl group. A vinyl group, a propyl group and a vinyl group, and a vinyl group and a vinyl group are preferred.
In the monovalent hydrocarbon group of R ^{1 to} R ⁴ , part or all of the hydrogen atoms may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine atom.

  In the formula (2), m represents an integer satisfying 0 to 20, n is 1 to 20, and m + n = 1 to 40, m is preferably an integer of 4 to 15, and n is An integer of 4 to 10 is preferable, and m + n is preferably an integer of 5 to 40.

  Specific examples of the group represented by the formula (2) include, but are not limited to, the following.

（式中、波線を付した線は結合手を示す。結合手は上記式（３）中のＩｍに結合する。ｍ、ｎは上記と同じ意味を表す。）

(In the formula, a wavy line indicates a bond. The bond is bonded to Im in the above formula (3). M and n have the same meaning as described above.)

  In formula (3), Im having a cyclic imide structure derived from tetracarboxylic dianhydride is a group containing a cyclic imide structure at the end, and examples thereof include groups selected from the following formulas.

（式中、波線が付された手は結合手を示す（以下、同じ）。なお、窒素原子から出ている結合手以外の環上炭素原子から出ている結合手はＸとの結合に使用される。）

(In the formula, a hand with a wavy line indicates a bond (hereinafter the same). Note that a bond from an on-ring carbon atom other than a bond from a nitrogen atom is used for bonding to X. )

In formula (3), in —NR ^N — of X, examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms of R ^N , are exemplified by the above R ^{1 to} R ⁴ . Monovalent hydrocarbon groups and the like, and particularly those having 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl group and the like. A linear or cyclic alkyl group is preferred, and a methyl group is most preferred.
In -CR ^B _2-of X, the monovalent hydrocarbon group having 1 to 12 carbon atoms which may contain the halogen atom of R ^B includes monovalent hydrocarbon groups exemplified for the above R ^{1 to} R ⁴ Examples of the halogen atom include fluorine, chlorine, bromine, iodine atom, etc. Among them, methyl, ethyl, n-propyl, trifluoromethyl, 3,3,3-trifluoropropyl, cyclohexyl group, etc. An alkyl group which may be substituted with a fluorine atom; an aryl group such as a phenyl group is preferred.
Particularly, as the R ^B, a hydrogen atom, a methyl group, a trifluoromethyl group, a phenyl group is preferred.

Specific examples of the divalent arylene group having 6 to 12 carbon atoms in R ^Ar in —R ^Ar _h — of X include phenylene, biphenylene, naphthylene group and the like. In addition, the arylene group of R ^Ar has a part of its hydrogen atom as a hydroxyl group, sulfide group, 2,3-oxo-1-propyl group, methoxy group, ethoxy group, t-butoxy group, methyl group, ethyl group, It may be substituted with a propyl group, t-butyl group, N, N-dimethylamino group, cyano group, methoxycarbonyl group, ethoxycarbonyl group, formyl group, methylcarbonyl group, ethylcarbonyl group, fluorine atom or the like.
H is an integer of 1-6.
Suitable R ^Ar includes the groups shown below.

（式中、ｓｕｂは水素原子、または水酸基、スルフィド基、２，３−オキソ−１−プロピル基、メトキシ基、エトキシ基、ｔ−ブトキシ基、メチル基、エチル基、プロピル基、ｔ−ブチル基、Ｎ，Ｎ−ジメチルアミノ基、シアノ基、メトキシカルボニル基、エトキシカルボニル基、ホルミル基、メチルカルボニル基、エチルカルボニル基、およびフッ素原子から選択される置換基を表し、置換数は１〜４個の範囲内である。）

(In the formula, sub is a hydrogen atom or a hydroxyl group, sulfide group, 2,3-oxo-1-propyl group, methoxy group, ethoxy group, t-butoxy group, methyl group, ethyl group, propyl group, t-butyl group. Represents a substituent selected from N, N-dimethylamino group, cyano group, methoxycarbonyl group, ethoxycarbonyl group, formyl group, methylcarbonyl group, ethylcarbonyl group, and fluorine atom, and the number of substitutions is 1 to 4 Is within the range.)

In —R ^Ar _h (OR ^Ar ) _i — of X, R ^Ar and h have the same meaning as described above, and i represents an integer of 1 to 5.
Specific examples of —R ^Ar _h (OR ^Ar ) _i include the following groups. In the following formula, —O— may be bonded to any position, and the number of bonds is in the range of 1 to 4.

Specific examples of the linear or branched alkylene group having 1 to 12 carbon atoms and the cycloalkylene group having 5 to 12 carbon atoms of X include methylene, ethylene, trimethylene, 1,3-butylene, tetramethylene, 1 , 3-pentylene, 1,4-pentylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,3-cycloheptylene, 1,4 -A cycloheptylene group etc. are mentioned.
Specific examples of the arylene alkylene group having 7 to 12 carbon atoms include a 2- (4- (2-eth-1-ylene) -1-phenylene) eth-1-ylene group.

The divalent group derived from diamine represented by G in the above formula (1) is not particularly limited, but in the present invention, a divalent group derived from diamine which is superior in heat resistance is preferable.
Specific examples of diamines that give such divalent groups include aliphatic diamines such as tetramethylene diamine, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexyl methane; o-phenylene diamine, m-phenylene diamine. , Aromatic diamines such as p-phenylenediamine, 4,4′-diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, etc. These may be used alone or in combination of two or more.

The terminal of the silicone-modified polyimide resin represented by the above formula (1) is preferably blocked with an acid anhydride.
Further, the sum of the moles of f + e + g is 100 mol% and the mole ratio of f / (e + g) is 0.9 to 1.1. In order to maintain an appropriate molecular weight, the mole ratio of f / (e + g) is 0.95 to 1.05 is preferable, and 0.98 to 1.02 is more preferable.
Further, when the sum of e and g is 100, e is 30 to 90, but 30 to 70 is preferable in consideration of moisture resistance.

(A) Although the weight average molecular weight of the silicone modified polyimide resin of a component is not specifically limited, While improving the toughness of the film | membrane obtained from the composition containing the said resin, it is compatible with other components, such as a hardening | curing agent. In consideration of enhancing solubility in water and solvent, 10,000 to 100,000 is preferable, and 15,000 to 70,000 is more preferable.
In addition, the weight average molecular weight in this invention is a polystyrene conversion value by gel permeation chromatography (hereinafter abbreviated as GPC) (hereinafter the same).

The component (A) silicone-modified polyimide resin can be produced by a known method.
For example, tetracarboxylic dianhydride, diamine, and diamino-modified silicone having amino groups bonded to both ends of the compound represented by the above formula (2) are charged in a solvent at low temperature, that is, about 20 to 50 ° C. To produce polyamic acid which is a precursor of polyimide resin. Next, the solution of the obtained polyamic acid is preferably heated to a temperature of 80 to 200 ° C., more preferably 140 to 180 ° C., and the acid amide of the polyamic acid is subjected to a dehydration ring-closing reaction, whereby a silicone-modified polyimide resin is obtained. A silicone-modified polyimide resin can be obtained by putting the solution into a solvent such as water, methanol, ethanol, acetonitrile, etc., and precipitating the solution, and drying the precipitate.

  The above f / (e + g) is a ratio (molar ratio) of the total number of moles of diamine and diamino-modified silicone with respect to the number of moles of tetracarboxylic dianhydride, calculated from the amount of the raw material. [Tetracarboxylic dianhydride (mol) / (diamine + diamino modified silicone (mol))] is usually 0.9 to 1.1, preferably 0.95 to 1.05, more preferably 0.98 to Adjust to a range of 1.02.

  Examples of the solvent that can be used for the production of the component (A) include N-methyl-2-pyrrolidone, cyclohexanone, γ-butyrolactone, N, N-dimethylacetamide and the like. It is also possible to use aromatic hydrocarbons such as toluene and xylene together to facilitate removal of water produced during imidization by azeotropic distillation. These solvents may be used alone or in combination of two or more.

In order to adjust the molecular weight of the silicone-modified polyimide resin, phthalic anhydride, maleic anhydride, hexahydro-1,3-isobenzofurandone, succinic anhydride, glutaric anhydride, acid anhydride having 10 to 60 silicon atoms Acid anhydrides such as product-modified silicones, and amines such as linear, branched or cyclic alkylamines having 3 to 6 carbon atoms such as aniline, benzylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, etc. It is also possible to add monofunctional raw materials of the compound.
As the aldehyde compound, an aldehyde compound containing an alkyl having 2 to 6 carbon atoms such as benzaldehyde, phenylacetaldehyde, propionaldehyde, or butyraldehyde can be added.
In this case, the addition amount is preferably in the range of 1 to 10 mol% in accordance with the target molecular weight with respect to the raw acid anhydride.

In the imidization process, a method of adding a dehydrating agent and an imidization catalyst and heating to around 50 ° C. to imidize as necessary may be used.
Specific examples of the dehydrating agent include acid anhydrides such as acetic anhydride, propionic anhydride, pivalic anhydride, trifluoroacetic anhydride, and benzoic anhydride. The amount of the dehydrating agent used is preferably 1 to 10 mol per 1 mol of diamine.
Specific examples of the imidization catalyst include triethylamine (Et ₃ N), diisopropylethylamine (DIPEA), tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri- -N-octylamine, N-methylpyrrolidine, N-methylpiperazine, N-methylmorpholine, N, N, N ', N'-tetramethylethylenediamine (TMEDA), N-methylimidazole (NMI), pyridine, 2, 6-lutidine, 1,3,5-collidine, N, N-dimethylaminopyridine, pyrazine, quinoline, 1,8-diazabicyclo- [5,4,0] -7-undecene (DBU), 1,4-diazabicyclo -Tertiary amines such as [2,2,2] octane (DABCO). The amount of the imidization catalyst used is preferably 0.5 to 10 mol with respect to 1 mol of the dehydrating agent used.
This imidization method is effective in that the reaction solution is not exposed to high temperatures during the process and the resulting resin is difficult to be colored.

  When using at least one of diamine and tetracarboxylic dianhydride, the reaction method is not particularly limited. For example, a method in which all raw materials are mixed in advance and then copolycondensed, or two or more types to be used are used. A method of sequentially adding diamines or tetracarboxylic dianhydrides while reacting individually can be employed.

(2) Component (B) As the curing agent which is the component (B) of the present invention, a thermally decomposable radical initiator capable of generating a radical by heat and polymerizing a resin to form a cured product is preferable.
As the thermally decomposable radical initiator, an azo compound or an organic peroxide can be used.

  Examples of the azo compound (organic azo compound) include V-30, V-40, V-59, V-60, V-65, V-70, V-501, and V- manufactured by Wako Pure Chemical Industries, Ltd. Azonitrile compounds such as 601; azoamide compounds such as VA-080, VA-085, VA-086, VF-096, VAm-110 and VAm-111; cyclic azoamidine compounds such as VA-044 and VA-061; Azoamidine compounds such as V-50 and VA-057; 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2 -Azobis (2-methylpropionitrile), 2,2-azobis (2,4-dimethylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), 1-[( -Cyano-1-methylethyl) azo] formamide, 2,2-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2-azobis [ 2-methyl-N- (2-hydroxybutyl) propionamide], 2,2-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2-azobis (N-butyl-2-methyl) Propionamide), 2,2-azobis (N-cyclohexyl-2-methylpropioamide), 2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2-azobis [ 2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2-azobis {2- [1- (2-hydroxyethyl) -2- Midazolin-2-yl] propane} dihydrochloride, 2,2-azobis [2- (2-imidazolin-2-yl) propane], 2,2-azobis (1-imino-1-pyrrolidino-2-methylpropane) Dihydrochloride, 2,2-azobis (2-methylpropionamidine) dihydrochloride, 2,2-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, dimethyl 2,2-azobis ( 2-methylpropionate), 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2,4,4-trimethylpentane), etc. Among these, V-30, V -40, V-59, V-60, V-65, V-70, V-501, V-601, VA-080, VA-085, VA-086 , VF-096, VAm-110, and VAm-111 are preferable, and V-30, V-40, V-59, V-60, V-65, V-70, V-501, and V-601 are more preferable.

Examples of organic peroxides include ketone peroxides such as Perhexa H manufactured by Nippon Oil &Fats; Peroxyketals such as Perhexa TMH; hydroperoxides such as Perbutyl H-69; Parkmill D, Perbutyl C, Perbutyl Dialkyl peroxides such as D and perbutyl O; Diacyl peroxides such as Nyper BW; Peroxyesters such as perbutyl Z and perbutyl L; Peroxydicarbonates such as peroyl TCP; Diisobutyryl peroxide and cumyl peroxide Neodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-Buchi Chlohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t- Hexyl peroxypivalate, t-butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2- Ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methyl Benzoyl) peroxide, t-butylperoxy-2-ethylhexanoe Di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, dibenzoyl peroxide, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di [4,4-di- (t-butylperoxy) cyclohexyl] propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5 5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyiso Propyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2, 2-di (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-di-t-butylperoxyvalerate, di (2-t-butylperoxyisopropyl) benzene, di- Milperoxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumylperoxide, di-t-butylperoxide, p- Methane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hex N-yne, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, o- Chlorobenzoyl peroxide, p-chlorobenzoyl peroxide, tris (t-butylperoxy) triazine, 2,4,4-trimethylpentylperoxyneodecanoate, α-cumylperoxyneodecanoate, t-amyl Peroxy 2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxytrimethyladipate, di-3-methoxybutylperoxydicarbonate, Diisopropyl Ruperoxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis (t-butylperoxycarbonyloxy) hexane, diethylene glycol bis (t-butylperoxycarbonate), t-hexylperoxyneodecanoate, Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd., Laurox, Parkardox L-W75, Parkardox CH-50L, Trigonox TMBH, Kayacumene H, Kayabutyl H-70, Parkadox BC-FF, Kayahexa AD, Parkardox 14, Kayabutyl C, Kayabutyl D, Parkadox 12-XL25, Trigonox 22-N70 (22-70E), Trigonox D-T50, Trigonox 423-C70, Kaya Esters CND-C70, Tri Knox 23-C70, Trigonox 257-C70, Kaya ester P-70, Kaya ester TMPO-70, Trigonox 121, Kaya ester O, Kaya ester HTP-65W, Kaya ester AN, Trigonox 42, Trigonox F-C50, Kayabutyl B, Examples thereof include Kaya-Carbon EH, Kaya-Carbon I-20, Kaya-Carbon BIC-75, Trigonox 117, and Kayalen 6-70.
In addition, the hardening | curing agent mentioned above may be used independently, or may be used in combination of 2 or more type.

  (B) Although the compounding quantity of a component is 0.1-10 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-5 mass parts. If the blending amount is less than 0.1 parts by mass, the curability is insufficient, and if it exceeds 10 parts by mass, a large amount of outgas derived from the curing agent is generated, curing shrinkage occurs, or the resin becomes harder than expected. .

(3) (C) component The solvent which is (C) component of this invention is used in order to reduce the viscosity of a composition and to improve the applicability | paintability to a board | substrate etc. and workability | operativity.
Specific examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; dioxane, dioxolane, tetrahydrofuran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis ( Ether solvents such as 2-methoxyethoxy) ethane, bis-2- (2-methoxyethoxy) ethyl ether, methyl tert-butyl ether; butyl acetate, isobutyl acetate, amyl acetate, γ-valerolactone, manufactured by Daicel Corporation Sertol series 3-methoxybutyl acetate (MBA), ethylene glycol monobutyl ether acetate (BMGAC), diethylene glycol monoethyl ether acetate (EDGAC), diethylene glycol monobutyl ether acetate Tate (BDGAC), cyclohexanol acetate (CHXA), dipropylene glycol dimethyl ether (DMM), dipropylene glycol methyl-n-propyl ether (DPMNP), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol methyl ether acetate (DPMA) ), 1,4-butanediol diacetate (1,4-BDDA), 1,3-butylene glycol acetate (1,3-BGDA), 1,6-hexanediol diacetate (1,6-HDDA), etc. Ester solvents; organic solvents such as amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, and 1,3-dimethyl-2-imidazolidinone; These may be used alone or in combination of two or more.
(C) A solvent can be used in the range which does not impair the solubility of the silicone modified polyimide resin of (A) component, and can normally be used at 100-700 mass parts with respect to (A) component.

(4) Component (D) Hydrophobic fumed silica of component (D) prevents liquid sag, prevents air bubbles and unevenness during coating, maintains moldability, imparts thixotropy, and reduces cured products. It is an optional component added for the purpose of increasing the elastic modulus.
In particular, it is preferable that the bulk density is less than 1 g / mL in order to prevent sedimentation of silica at the time of preparation and to efficiently exhibit the above effects.
The average primary particle size of fumed silica is preferably 1 to 100 nm. When the average primary particle size is within this range, light scattering by the fumed silica of the cured product of the silicone-modified polyimide-containing composition is suppressed, and thus the transparency of the cured product is not impaired. The average particle diameter can be obtained as a median diameter (d50) in a volume-based particle size distribution by a particle size distribution meter using an analysis means such as a laser beam diffraction method.
Furthermore, the BET specific surface area of fumed silica is preferably 100 to 300 m ² / g.

The hydrophobic fumed silica as component (D) is preferably dry silica produced by hydrolyzing silicon halide in an oxygen-hydrogen flame.
A commercially available product may be used as the hydrophobic fumed silica. Specific examples of commercially available products include hydrophobic dry silica surface-treated with hexamethyldisilazane (specific surface area 160 m ² / g, adsorbed carbon amount 3.0 mass%, bulk density 0.14 mg / L, Nippon Aerosil Co., Ltd. ), Product name: AEROSIL R8200), hydrophobic dry silica surface-treated with hexamethyldisilazane (specific surface area 140 m ² / g, adsorbed carbon amount 2.3 mass%, bulk density 0.05 g / mL, Nippon Aerosil) Product name: RX200), surface-treated hydrophobic dry fumed silica (specific surface area 190 m ² / g, bulk density 0.05 g / mL, average primary particle size 15 nm, manufactured by Tokuyama Corp., product Name: Leolosil DM-10), surface-treated hydrophobic dry fumed silica (specific surface area 230 m ² / g, bulk density 0.05 g / mL, average primary particle size 7 nm, ( Manufactured by Tokuyama Co., Ltd., trade name: Leolosil DM-30), surface-treated hydrophobic dry fumed silica (specific surface area 230 m ² / g, bulk density 0.05 g / mL, average primary particle size 7 nm, Tokuyama Corporation) Manufactured, trade name: Leolosil DM-30S), surface-treated hydrophobic dry fumed silica (specific surface area 230 m ² / g, bulk density 0.05 g / mL, average primary particle size 7 nm, manufactured by Tokuyama Corporation, product Name: Leolosil DM-30S), trade name “Leolosil HM20S” (manufactured by Tokuyama Corporation, average primary particle diameter 12 nm), trade name “Leolosil HM30S” (manufactured by Tokuyama Corporation, average primary particle diameter 7 nm), trade name “Reoroseal HM40S” (manufactured by Tokuyama Co., Ltd., average primary particle size 7 nm), trade name “Leolosil ZD30S” (manufactured by Tokuyama Co., Ltd. It includes primary particle size 7 nm) and the like.

  (D) When adding a component, Preferably the addition amount is 3-50 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 3-30 mass parts, More preferably, it is 3- 20 parts by mass. If it is such a range, it can be set as the composition which has thickening property, thixotropy, and fluidity | liquidity and was excellent in workability | operativity.

The silicone-modified polyimide resin composition of the present invention can be adjusted to a suitable viscosity according to the coating method by adjusting the amount of hydrophobic fumed silica added.
For example, when applying with a dispenser or using dipping, a viscosity of about 500 to 10,000 mPa · s (25 ° C.) is preferable, and a viscosity of 10,000 to 100,000 mPa · s (25 ° C.) is preferred.
However, since the usable viscosity differs depending on the coating device or the like, the viscosity is not limited to the above.

  In the silicone-modified polyimide resin composition of the present invention, for example, (A) a silicone-modified polyimide resin is dissolved in a (C) solvent to prepare a silicone-modified polyimide resin solution, and then (B) a curing agent is added thereto as necessary. Additional (C) solvent and (D) hydrophobic fumed silica can be added and stirred.

The silicone-modified polyimide composition thus obtained can be formed into a film by a casting method or the like.
The curing conditions for the silicone-modified polyimide resin composition of the present invention are not particularly limited, but the curing temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C, and the curing time is preferably 1 to 300. Minutes, more preferably 10 to 240 minutes.

As described above, the silicone-modified polyimide resin composition of the present invention provides a cured product that has good adhesion to various metal frames, high moisture resistance, low elasticity, and high heat resistance. (Α) Storage elastic modulus at 25 ° C. of 100 to 1,000 MPa, (β) Glass transition point (Tg) of 100 to 200 ° C., (γ) Water vapor permeability at 40 ° C. of 20 g / m ² · In some cases, a cured product having excellent characteristics of not more than day and (δ) 5% weight loss temperature of 420 ° C. or more may be obtained.
The silicone-modified polyimide resin composition of the present invention that provides such a cured product can be suitably used as an adhesive or a coating agent.
This adhesive and coating agent can be used for electronic materials, optical materials, in-vehicle devices, and the like, and can be suitably used particularly in the field of using semiconductor devices that require high reliability.

(5) Manufacturing method of diamino modified silicone As said diamino modified silicone used as the raw material of the silicone modified polyimide resin shown by Formula (1) to the composition of this invention, an amino group is each in the both terminal of said Formula (2). Examples thereof include diamino-modified silicones represented by the following formula (4).

（式中、Ｒ¹〜Ｒ⁴、ｍおよびｎは上記と同じ意味を表し、Ｒ^Cは、下記の基から選ばれる２価の基を表す。なお、ｍ、ｎが付された括弧内のシロキサン単位の配列は、ランダム、交互またはブロックのいずれであってもよい。）

(In the formula, R ^{1 to} R ⁴ , m and n represent the same meaning as described above, and R ^C represents a divalent group selected from the following groups. (The arrangement of the siloxane units may be random, alternating, or block.)

（式中、Ｊは、炭素原子数２〜６のアルキレン基を表し、波線を付した線は結合手を表す。Ｊに結合している結合手はケイ素原子に結合し、他の結合手はＩｍに結合する。）

(In the formula, J represents an alkylene group having 2 to 6 carbon atoms, and a wavy line represents a bond. A bond bonded to J is bonded to a silicon atom, and other bonds are Bind to Im.)

  Examples of the alkylene group having 2 to 6 carbon atoms include ethylene, trimethylene, propylene, tetramethylene, pentamethylene, and hexamethylene groups, and an ethylene group is preferable.

  The diamino-modified silicone represented by the above formula (4) can be produced through step (i) Mizorogi-Heck reaction, step (ii) hydrogenation reaction, step (iii) polymerization reaction involving siloxane cleavage and recombination.

In step (i), (E) a compound represented by the following formula (5) (hereinafter referred to as compound (5)),
(F) Compound represented by the following formula (6) or the following formula (7) (hereinafter referred to as compound (6) or (7)): 2.0 to 2.5 molar equivalent (G) transition metal organic complex catalyst: 0.01-5 mol%,
(H) The reaction is carried out in the presence of 2.0 to 3.0 molar equivalents, and (I) the solvent: the concentration of compound (5) is 0.1 to 5.0 mol / L. In this step, a compound represented by formula (8) (hereinafter referred to as compound (8)) is obtained.
In addition, the usage-amount of (F) and (G) is a ratio with respect to a compound (5).

（式中、Ｒ¹およびＲ²は上記と同じ意味を表し、Ｋは、末端に不飽和基を有する炭素原子数２〜６の１価の脂肪族不飽和炭化水素基を表す。）

(In the formula, R ¹ and R ² represent the same meaning as described above, and K represents a monovalent aliphatic unsaturated hydrocarbon group having 2 to 6 carbon atoms having an unsaturated group at the terminal.)

（式中、ＬＧは脱離基として機能する１価の官能基）

(In the formula, LG is a monovalent functional group that functions as a leaving group)

（式中、Ｒ¹、Ｒ²およびＲ^Cは上記と同じ意味を表す。）

(Wherein R ¹ , R ² and R ^C represent the same meaning as described above.)

In the formula (5), specific examples of the monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms containing an unsaturated group at the terminal of K include vinyl, prop-2-en-1-yl group (prop -2-en-1-yl), but-3-en-1-yl group (but-3-en-1-yl), penta-4-en-1-yl group (pent-4-en-1) -Yl), a hexa-5-en-1-yl group (hex-5-en-1-yl) and the like, and a vinyl group is more preferable.
The leaving group LG in the formula (7) may be any substituent that functions as a known leaving group, and examples thereof include chloro, bromo, iodine, mesyl, tosyl, trifluoromethanesulfonyl, and nosyl groups.

(G) Examples of the transition metal in the transition metal organic complex catalyst include iron, nickel, copper, rhodium, ruthenium, palladium, tungsten, iridium, platinum and the like, and nickel or palladium is preferable.
As ligands for transition metal complex catalysts, bidentate neutral phosphine ligands, monodentate neutral phosphine ligands, neutral π ligands, monovalent anionic ligands, divalent anions Neutral ligand, monodentate neutral amine ligand, bidentate neutral amine ligand, neutral nitrile ligand, neutral sulfinyl ligand, bidentate neutral carbonyl-olefin And at least one selected from the group consisting of a ligand and the like. In some cases, ligand exchange may be performed in the system.
In particular, a nickel or palladium complex that is coordinated so that the valence of nickel or palladium is zero or divalent is preferable.

Suitable ligands include, for example, the following, but are not limited thereto.
Bidentate neutral phosphine ligands: 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1 ′ -Bis (diphenylphosphino) ferrocene, etc. Monodentate neutral phosphine ligands: tri (n-butyl) phosphine, tri (t-butyl) phosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, Tri (p-tolyl) phosphine, tri (2-furfuryl) phosphine, triphenylphosphine, etc. Neutral π ligand: benzene, cyclobutadiene, cyclooctadiene, etc. Monovalent anionic ligand: methyl, phenyl, hexa Methylcyclopentadienyl, pentamethylcyclopentadienyl, allyl, cyclopentadienyl, alkoxy, fluorine Atom, chlorine atom, bromine atom, iodine atom, carboxylate, acetylacetonate, trifluoromethanesulfonate, 1,3-bis (2,6-di-isopropylphenyl) -4,5-dihydroimidazole-2 -Ridene, 1,3-bis (2,6-di-isopropylphenyl) imidazol-2-lidene, 1,3-bis (2,4,6-trimethylphenyl) imidazole-2-lidene, etc. Anionic ligand: phthalocyanine, naphthalocyanine, porphyrin, etc. Monodentate neutral amine ligand: ammonia, pyridine, 3-chloropyridine, etc. Bidentate neutral amine ligand: N, N, N ′, N ′ -Tetramethylethylenediamine, 1,10-phenanthoroline, 2,2'-bipyridyl, etc. Neutral nitrile ligand: acetonitrile, benzonitrile, etc. Sulfinyl ligand: 1,2-bis (phenylsulfinyl) ethane, etc. Ligand composed of bidentate neutral carbonyl-olefin: dibenzylideneacetone, etc.

  (G) The usage-amount of a transition metal organic complex catalyst is 0.01-5 mol% with respect to (E) compound (5), and (F) compound (6) or (7) is (E) compound. Since the reaction is theoretically 2 molar equivalents relative to (5), the amount of (F) compound (6) or (7) used is 2 to 2.5 molar equivalents, but 2.05 to 2.2. A molar equivalent or less is preferred.

(H) The base may be an organic base or an inorganic base.
Specific examples of the organic base include triethylamine (Et ₃ N), diisopropylethylamine (DIPEA), tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri- n-octylamine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine (TMEDA), N-methylimidazole (NMI), 1,8-diazabicyclo -[5,4,0] -7-undecene (DBU), 1,4-diazabicyclo- [2,2,2] octane (DABCO), pyridine, 2,6-lutidine, 1,3,5-collidine, N, N-dimethylaminopyridine (DMAP), pyrazine, quinoline and the like can be mentioned.
Specific examples of the inorganic base include alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; magnesium carbonate, calcium carbonate, etc. Group 2 metal carbonates; alkali metal hydroxide salts such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Group 2 metal hydroxide salts such as magnesium hydroxide and calcium hydroxide Can be mentioned.
Among these, as the (H) base, triethylamine, diisopropylethylamine, 1,8-diazabicyclo- [5,4,0] -7-undecene (DBU), sodium carbonate, and potassium carbonate are preferable.
(H) The usage-amount of a component is 2.0-3.0 molar equivalent with respect to (E) compound (5), Preferably it is 2.1-2.6 molar equivalent.

As the solvent (I), an aprotic polar solvent is preferable in order to suppress side reactions.
Specific examples of the polar solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; dioxane, dioxolane, tetrahydrofuran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis Ether solvents such as (2-methoxyethoxy) ethane and bis-2- (2-methoxyethoxy) ethyl ether methyl tert-butyl ether; butyl acetate, isobutyl acetate, amyl acetate, γ-valerolactone, 3-methoxybutyl acetate ( MBA), ethylene glycol monobutyl ether acetate (BMGAC), diethylene glycol monoethyl ether acetate (EDGACC), cyclohexanol acetate (CHXA), dipropylene glycol dimethyl ester Ter (DMM), dipropylene glycol methyl-n-propyl ether (DPMNP), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol methyl ether acetate (DPMA), 1,4-butanediol diacetate (1,4- BDDA), 1,3-butylene glycol acetate (1,3-BGDA), ester solvents such as 1,6-hexanediol diacetate (1,6-HDDA); dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Examples include amide solvents such as N-methylcaprolactam and 1,3-dimethyl-2-imidazolidinone, and these may be used alone or in combination of two or more.
Among these, tetrahydrofuran and dimethylformamide are preferable.
(I) The solvent is used in such an amount that the concentration of (E) compound (5) is 0.1 to 5.0 mol / L.

Step (ii)
(J) Compound (8) obtained in step (i), and (K) transition metal catalyst: 0.001 to 1 mol% as a metal content with respect to compound (8)
Is a step of obtaining a compound represented by the following formula (9) (hereinafter referred to as compound (9)) by performing a hydrogenation reaction in the presence of

（式中、Ｒ¹、Ｒ²、及びＲ^Cは、上記と同じ意味を表す。）

(In the formula, R ¹ , R ² , and R ^C represent the same meaning as described above.)

(K) The transition metal catalyst is preferably fixed to a carrier from the viewpoint of being easily removed by an operation such as filtration after completion of the reaction, and from the viewpoint of recovery and reuse.
Examples of the carrier for immobilization include water-containing or dried activated carbon (C), alumina (Al ₂ O ₃ ), silica (SiO ₂ ) and the like. These carriers also have the effect of adsorbing and removing impurities and coloring in the reaction system.

Specific examples of the transition metal catalyst supported on the activated carbon (C) include Ni / C, Pd / C, Pd (OH) ₂ / C, Pt / C, Co / C, Rh / C, Ir / C, Ru / C, Cu / C, Ag / C, Au / C, Pt—Co / C, Pt—Pd / C, and the like.
Specific examples of the transition metal catalyst supported on alumina (Al ₂ O ₃ ) include Ni / Al ₂ O ₃ , Pd / Al ₂ O ₃ , Pt / Al ₂ O ₃ , Co / Al ₂ O ₃ , Rh / _{Al 2 O 3, Ir / Al} 2 O 3, Ru / Al 2 O 3, Cu / Al 2 O 3, Ag / Al 2 O 3, Au / Al 2 O 3 and the like.
Specific examples of the transition metal catalyst supported on silica (SiO ₂ ) include Ni / SiO ₂ , Pd / SiO ₂ , Pt / SiO ₂ , Co / SiO ₂ , Rh / SiO ₂ , Ir / SiO ₂ , Ru / Examples thereof include SiO ₂ , Cu / SiO ₂ , Ag / SiO ₂ , Au / SiO _{2 and the} like.

Among these, Pd / C, Pd (OH) ₂ / C, Pt / C, Rh / C, Ir / C, Ru / C, Pt—Pd / C, Pd / Al ₂ O ₃ , Pt / Al ₂ O ₃ , Pd / SiO ₂ , Pt / SiO ₂ are preferable, and Pd / C, Pt / C, Rh / C, Pt—Pd / C, Pd / Al ₂ O ₃ , Pt / Al ₂ O ₃ are preferable because of their availability. From the viewpoint of reactivity, Pd / C and Pt / Al ₂ O ₃ are even more preferable.

  These immobilized transition metal catalysts include N.E. Chemcat Co., Ltd., Kawaken Fine Chemical Co., Ltd., Sigma-Aldrich Japan G.K., Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., They are available as commercial products from Evonik Japan Co., Ltd., and these can be used alone or in the form of a mixed or composite catalyst.

  (K) The amount of the transition metal catalyst used is 0.001 to 1 mol% as the metal content with respect to (J) compound (8), and 0.001 to 0.005 in terms of filterability and catalyst cost. 1 mol% is preferred.

In step (ii), a hydrogenation reaction can also be performed under atmospheric pressure in the presence of the following (J) to (M).
(J) Compound (8) obtained in step (i),
(K) Transition metal catalyst: 0.001 to 1 mol% as metal content
(L) Tertiary alkylamine compound: less than 2 molar equivalents, and (M) formic acid or formate: an amount such that the reaction mixture has a pH of 7 or more. The amount of (K) and (L) used is the compound (8 ).

(L) Specific examples of the tertiary alkylamine compound include trimethylamine, triethylamine (Et ₃ N), diisopropylethylamine (DIPEA), tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, Tri-n-heptylamine, tri-n-octylamine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine (TMEDA), N-methylimidazole (NMI), 1,8-diazabicyclo- [5,4,0] -7-undecene (DBU), 1,4-diazabicyclo- [2,2,2] octane (DABCO) and the like, among which triethylamine , Diisopropylethylamine, 1,8-diazabicyclo- [5,4,0]- - undecene (DBU) is preferred, triethylamine is more preferable.

  (L) The amount of tertiary alkylamine compound added is more than 0 molar equivalents and less than 2 molar equivalents relative to compound (8), preferably 0.5 to 1.5 molar equivalents, and 1 molar equivalent. Is more preferable. If the amount is less than 0.5 molar equivalent, the reaction may be slow. If the amount is more than 2 molar equivalent, the catalyst may be poisoned and the reaction may be difficult to proceed.

  (M) Specific examples of formic acid or formate include formic acid, ammonium formate, pyridinium formate, lithium formate, sodium formate, potassium formate, cesium formate, magnesium formate, calcium formate, thallium formate, copper formate, cadmium formate, lead formate Zinc formate, nickel formate, manganese formate, and the like. Among these, formic acid, ammonium formate, and sodium formate are preferable, and formic acid is more preferable. These formic acid and formate are commercially available from Wako Pure Chemical Industries, Ltd.

(M) Formic acid or formate is used in such an amount that the pH of the reaction mixture does not become acidic. That is, (M) formic acid or formate is used in such an amount that the reaction mixture becomes pH 7 or more, preferably pH 7 to pH 10, more preferably pH 7 to pH 9. If it is added excessively, the reaction system becomes acidic, and an aldehyde may be generated by the decomposition of the unsubstituted or substituted alkenyl ether with an acid.
In particular, (L) it is preferable to add at an equimolar equivalent or less with respect to the tertiary alkylamine compound, but during the hydrogenation reaction, formic acid or formate is consumed by decomposition, volatilization, etc. An amount of (M) formic acid or formate that does not make the solution more acidic than pH 7 may be added.

In the step (ii), when a solvent is used, it is preferable to use a polar organic solvent.
Examples of the polar organic solvent include an amide compound having 1 to 8 carbon atoms, a nitrile compound, a ketone compound, an alcohol compound, and a carbon atom of a linear, branched or cyclic saturated or unsaturated hydrocarbon compound having 1 to 8 carbon atoms. Examples include ether compounds in which 1 to 3 of them are substituted with oxygen atoms, and among these, linear, branched or cyclic nitrile compounds and alcohol compounds having 1 to 6 carbon atoms are more preferable.

  Specific examples of such polar organic solvents include N, N′-dimethylformamide (DMF), N, N′-dimethylformacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (DMPU), acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cyclopentanone, Cyclooctanone, methylcyclopentyl ketone, diethyl ether, t-butyl methyl ether (TBME), dibutyl ether, cyclopentyl methyl ether (CPME), diphenyl ether, dimethoxymethane (DMM), 1,2-dimethoxyethane, diethylene glycol dimethyl ether , Tetrahydrofuran (THF), tetrahydropyran (THP), dioxane, 2-methyltetrahydrofuran, 2-ethyltetrahydrofuran, acetonitrile, propionitrile, butyronitrile, methanol, ethanol, 1-propanol, 2-propanol (IPA), n- Butyl alcohol, i-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, 1,2-dihydroxypropane, 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol, etc. Among these, DMF, acetone, THF, and IPA are preferable.

  However, when the reaction is performed in situ from step (i), the solvent of step (i) can be used as it is. In addition, since the hydrogenation reaction is accelerated in a polar solvent, the above polar solvent may be further added.

Hydrogen gas can be used as a hydrogen source for the hydrogenation reaction.
The hydrogenation reaction is preferably performed at 1 atm.
When using hydrogen gas while storing it safely, you can use a pressure tube made of Q-Tube (TM) glass made by Sigma-Aldrich Japan GK or a gas pressure adjustment bubbler made by Sgiamagen. Is preferred.
The reaction temperature is preferably 20 to 60 ° C, more preferably 30 to 50 ° C.

Step (iii)
(N) Compound (9) obtained in step (ii),
A cyclic siloxane composed of (O)-[R ¹ R ² SiO] -units (R ¹ and R ² are the same as described above):-[R ¹ R ² SiO] -unit in an amount of 0 to 5 molar equivalents;
A cyclic siloxane composed of (P)-[R ³ R ⁴ SiO]-units (R ³ and R ⁴ are the same as described above):-[R ³ R ⁴ SiO] -unit is 0.25 to 5 molar equivalents, and (Q) Organic base catalyst: 0.01 to 5% by mass
Is a step of obtaining a diamino-modified silicone represented by the formula (4) by reacting in the presence of
In addition, the usage-amount of (O), (P) and (Q) is a ratio with respect to a compound (9).

Specific examples of the cyclic siloxane composed of (O)-[R ¹ R ² SiO] -unit include hexamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylpentasiloxane, and the like.
Specific examples of the cyclic siloxane composed of (P)-[R ³ R ⁴ SiO] -unit include 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1, Examples include 3,5-trimethyl-1,3,5-trivinylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinylcyclotetrasiloxane.

(Q) Examples of the organic base catalyst include quaternary alkyl ammonium salts.
Specific examples of the quaternary alkylammonium salt include tetrabutylammonium hydroxide, tetramethylammonium hydroxide and the like.
The usage-amount of an organic base catalyst is 0.01-5 mass% with respect to a compound (9), and you may add in the quantity which does not exceed 5 mass% of total addition in the middle of reaction.

  Specific examples of the diamino-modified silicone represented by the above formula (4) obtained by the above production method are shown below, but are not limited thereto.

（式中、ｍおよびｎは、上記と同じ意味を表す。）

(In the formula, m and n represent the same meaning as described above.)

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to these Examples.
Moreover, in the present Example, the molecular weight measurement was performed in terms of polystyrene using a GPC apparatus HLC-8320GPC manufactured by Tosoh Corporation and using tetrahydrofuran (THF) as a mobile phase. For the infrared absorption spectrum (IR) measurement, NICOLET 6700 (manufactured by Thermo Fisher Scientific Co., Ltd.) was used. AVANCE III manufactured by Bruker BioSpin Corporation was used for ¹ H NMR measurement. For the glass transition point measurement, DMS7100 manufactured by Hitachi High-Tech Science Co., Ltd. was used, and the temperature when tan δ was maximized was defined as the glass transition point. For measuring the 5% weight loss temperature, TGA Q-500 manufactured by TA Instruments was used. The viscosity at 25 ° C. was measured with a rotational viscometer.
In the following examples, “part” means part by mass.

[1] Synthesis of raw material compound [Synthesis Example 1]
In a reaction vessel equipped with a thermometer, a nitrogen introduction tube and a stirring bar, 212 g of 1-bromo-4-nitrobenzene (1.05 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1,3-divinyl-1,1,3, 93 g of 3-tetramethyldisiloxane (0.5 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 165 g of potassium carbonate (1.2 mol, manufactured by Wako Pure Chemical Industries, Ltd.), and 1,000 mL of N, N-dimethylformamide ( 0.5M, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and after substitution with argon, 45 mg (0.01 mol%, Sigma-Aldrich Japan LLC) of tris (benzylideneacetone) dipalladium (0) was added. The reaction mixture was heated to 100 ° C. and reacted at the same temperature for 6 hours.
After confirming the disappearance of the 5.2 ppm vinyl group-derived peak from ¹ H NMR, the temperature was returned to 25 ° C. It filtered using 2 filter paper, and neutralized by adding 1M potassium hydrogen sulfate aqueous solution and butyl acetate. Thereafter, the butyl acetate layer was separated, and the aqueous layer was further extracted twice with butyl acetate. After the obtained butyl acetate layers were combined, washing was continued with 1M aqueous sodium thiosulfate solution and saturated saline, anhydrous sodium sulfate, silica gel and a stirrer were added, and the mixture was stirred at 25 ° C. for 12 hours. . Then, no. Filter using 2 filter paper, and after removing the solvent, remove the precipitated solid (1-bromo-4-nitrobenzene) and recrystallize with hexane-butyl acetate mixed solution to remove 1-bromo-4-nitrobenzene. Removed. The solvent was distilled off, and after drying under reduced pressure, 193 g (yield 90%) of dinitro-modified disiloxane represented by the following formula in the form of a brown solid was obtained.
¹ H NMR (δ: ppm), 0.1 (s, 12H), 5.9 (d, 2H), 7.1 (d, 2H), 8.0 (d, 4H), 8.4 (d , 4H).

[Synthesis Example 2]
193 g of the dinitro-modified disiloxane obtained in Synthesis Example 1 and 300 mL of THF were added to a reaction vessel equipped with a thermometer, a nitrogen introduction tube, and a stirrer, and after the dissolution, argon substitution was performed. 5% Pd / C (50% wet product, Wako Pure Chemical Industries, Ltd.) 181 mg (0.01 mol%) was added thereto, and hydrogen gas replacement was performed. A hydrogenation reaction was carried out at 25 ° C. for 12 hours, and the reaction was stopped after confirming disappearance of the olefin signal and shift of protons on the aromatic ring from ¹ H NMR.
The catalyst was filtered off from the reaction mixture, and the solvent was distilled off to obtain 159 g (yield 95%) of diamino-modified disiloxane represented by the following formula in the form of a yellow oil.
¹ H NMR (δ: ppm), 0.2 (s, 12H), 0.9 (t, 4H), 2.4 (t, 4H), 6.5 (d, 2H), 6.9 (d , 4H).

（式中、括弧内のシロキサン単位の配列順は不定である。） [Synthesis Example 3]
In a reaction vessel equipped with a thermometer, a nitrogen introduction tube and a stirrer, 37 g (0.1 mol) of the diamino-modified disiloxane obtained in Synthesis Example 2 and 30 g of octamethylcyclotetrasiloxane (0.1 mol, Tokyo Chemical Industry Co., Ltd.) )), 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane 34 g (0.1 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and tetrabutylammonium hydro 3.7 g of xoxide (0.10 parts, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 100 ° C. for 12 hours. After cooling to 25 ° C., the volatile component was distilled off under reduced pressure to obtain 79 g (yield 78%) of diamino-modified silicone represented by the following formula (i) of pale yellow. The amine equivalent of the obtained diamino-modified silicone was 998 mol / g.

(In the formula, the arrangement order of the siloxane units in parentheses is indefinite.)

[Synthesis Example 4]
In a reaction vessel equipped with a thermometer, a nitrogen introduction tube and a stirrer, 44.4 g (0.1 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane ), 4,4 ′-(4,4′-isopropyldienediphenyl-1,1′-diyldioxy) dianiline (2,2-bis [4- (4-aminophenoxy) phenyl] propane) 12.3 g (0. 03 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1.48 g of phthalic anhydride (0.01 mol, manufactured by Wako Pure Chemical Industries, Ltd.), and 396 g of cyclohexanone were added and stirred at 25 ° C. for 2 hours, then Synthesis Example 3 139.7 g (0.07 mol) of the diamino-modified silicone represented by the above formula (i) obtained in 1 above was added dropwise at 25 ° C., and the mixture was stirred at 25 ° C. for 12 hours after completion of the addition. After completion of the stirring, 40 g of toluene was added to the reaction vessel, and azeotropic dehydration was performed at 145 ° C.
The obtained reaction solution was dropped into methanol, and a silicone-modified polyimide resin was obtained by reprecipitation. Absorption based on unreacted polyamic acid was not observed in the infrared absorption spectrum of this resin, and absorption of imide groups was confirmed at 1,780 cm ⁻¹ and 1,720 cm ⁻¹ . Moreover, the weight average molecular weight of this resin by GPC was 26,500.

[Synthesis Example 5]
In a reaction vessel equipped with a stirring blade, a thermometer and a nitrogen introduction tube, 44.4 g (0.1 mol) of 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane, 4,4 ′-( 4,4′-Isopropyldienediphenyl-1,1′-diyldioxy) dianiline (14.4 g, 0.035 mol), 1.48 g (0.01 mol) of phthalic anhydride, and 380 g of cyclohexanone were charged and stirred at 25 ° C. for 2 hours. Thereafter, 129.7 g (0.065 mol) of the diamino-modified silicone represented by the above formula (i) obtained in Synthesis Example 3 was dropped at 25 ° C., and the mixture was stirred at 25 ° C. for 12 hours. After the completion of stirring, 38 g of toluene was added to the reaction vessel, and azeotropic dehydration was performed at 145 ° C.
The obtained reaction solution was dropped into methanol for reprecipitation to obtain a silicone-modified polyimide resin having a siloxane amount of 55% by mass. Absorption based on unreacted polyamic acid was not observed in the infrared absorption spectrum of this resin, and absorption was confirmed in imide groups at 1,780 cm ⁻¹ and 1,720 cm ⁻¹ . Moreover, the weight average molecular weight of this resin by GPC was 24,500.

[Synthesis Example 6]
In a reaction vessel equipped with a stirring blade, a thermometer and a nitrogen introduction tube, 44.4 g (0.1 mol) of 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane, 4,4 ′-( 12.4 g (0.03 mol) of 4,4′-isopropyldienediphenyl-1,1′-diyldioxy) dianiline (2,2-bis [4- (4-aminophenoxy) phenyl] propane), phthalic anhydride 48 g (0.01 mol) and 336 g of cyclohexanone were charged and stirred at 25 ° C. for 2 hours, and then 112.0 g (0.07 mol) of diamino-modified silicone represented by the following formula (ii) was added dropwise at 25 ° C. Then, it stirred at 25 degreeC for 12 hours. After completion of the stirring, 56 g of toluene was added to the reaction vessel, and azeotropic dehydration was performed at 145 ° C. The obtained reaction solution was dropped into methanol to perform reprecipitation to obtain a silicone-modified polyimide resin having a siloxane amount of 79% by mass. Absorption based on unreacted polyamic acid was not observed in the infrared absorption spectrum of this resin, and absorption of imide groups was confirmed at 1,780 cm ⁻¹ and 1,720 cm ⁻¹ . Moreover, the weight average molecular weight of this resin by GPC was 36,000.

（式中、括弧内のシロキサン単位の配列順は不定である。）

(In the formula, the arrangement order of the siloxane units in parentheses is indefinite.)

[2] Production of silicone-modified polyimide resin composition [Example 1]
To 100 parts of the silicone-modified polyimide resin obtained in Synthesis Example 4, 236 parts of propylene glycol monomethyl ether acetate (PGMEA) was added and dissolved and stirred to obtain a dissolved product. To this solution, 1 part of Kayalen 6-70 (manufactured by Kayaku Akzo Co., Ltd.) was added and mixed and stirred to obtain a silicone-modified polyimide resin composition.

[Examples 2 to 7 and Comparative Examples 1 to 4]
A silicone-modified polyimide resin was produced in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1.

Table 1 shows the compositions of the above Examples and Comparative Examples and the viscosity at 25 ° C. of the compositions.
The abbreviations and the like of each component in the table are as follows.
Perbutyl O: t-butyl peroxy-2-ethylhexanoate manufactured by NOF Corporation V-601: dimethyl 2,2′-azobis (2-methylpropionate) manufactured by Wako Pure Chemical Industries, Ltd.
Kayalen 6-70: 1,6-bis (t-butyl-peroxycarbonyloxy) hexane manufactured by Kayaku Akzo Co., Ltd. Leolosil DM-30S: Hydrophobic dry fumed silica manufactured by Tokuyama Co., Ltd. Propylene glycol monomethyl Ether acetate (PGMEA)

About the hardened | cured material of the composition prepared by said each Example and comparative example, adhesiveness and storage elastic modulus were measured and evaluated by the following method. These results are shown in Table 2 together with the glass transition point and the 5% weight loss temperature.
(1) Adhesion A silicone-modified polyimide resin composition is applied on various substrates so as to have a thickness of 80 μm, and is thermally cured in order of 30 minutes at 50 ° C., 60 minutes at 100 ° C., and 120 minutes at 150 ° C. A cured film was obtained.
The adhesion of this film was evaluated by the method of cross-cut peel test (JIS K5400), and the number X of squares remaining in 100 squares was indicated by (X / 100).
Glass plate: Oxygen-free copper plate manufactured by Matsunami Glass Industry Co., Ltd .: Stand test piece (2) Storage elastic modulus A silicone-modified polyimide resin composition was applied on an iron plate coated with fluorine-based coating, and 30 minutes at 50 ° C. The sheet was thermally cured in order of 60 minutes at 100 ° C. and 120 minutes at 150 ° C. to prepare a sheet having a thickness of 0.3 mm. About this sheet | seat, the storage elastic modulus was measured using Hitachi High-Tech Science Co., Ltd. DMS7100.

Further, the water vapor permeability of the cured products of the compositions prepared in Examples 1, 4, 5 and 7 was measured by the following method. The results are shown in Table 3.
(3) Water Vapor Permeability The silicone-modified polyimide resin composition prepared in Examples 1, 4, 5, and 7 was applied on an iron plate on which a fluorine-based coating was applied, and was performed at 50 ° C. for 30 minutes and at 100 ° C. for 60 minutes. For 1 minute at 150 ° C. for 120 minutes. About this sheet | seat, the water vapor transmission rate was measured on condition of 40 degreeC (JISK7129A) using the L80-5000 type | mold water vapor transmission meter (made by System Instruments). The results are shown in Table 3.

As shown in Table 2, the cured product prepared from the composition obtained in each example is excellent in adhesion to the glass plate and the copper plate, and has an elastic modulus as compared with the cured product prepared from the composition of the comparative example. It can be seen that the heat resistance is high.
Moreover, as Table 3 shows, the hardened | cured material produced from the composition of Example 1, 4, 5, 7 shows that water vapor permeability is low.

Claims (14)

(A) Silicone-modified polyimide resin represented by the following formula (1): 100 parts by mass,
Ee-Ff-Gg (1)
{In Formula (1), E, F, and G are repeating units that are randomly bonded, E is a divalent group derived from diamino-modified silicone represented by Formula (2), and F is a formula ( 3) is a divalent group derived from a tetracarboxylic dianhydride, and G is a divalent group derived from a diamine. However, f + e + g = 100 mol%, the molar ratio of f / (e + g) is 0.9 to 1.1, and when the sum of e and g is 100, the e is 30 to 90.

(In the formula (2), R ^A independently represents an arylene alkylene group having 8 to 12 carbon atoms, and R ¹ and R ² independently represent a substituted or non-substituted group having no aliphatic unsaturated bond. A substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ and R ⁴ each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, At least one of R ³ and R ⁴ has an aliphatic unsaturated bond, m represents 0 to 20, n represents an integer satisfying 1 to 20, and m + n = 1 to 40. (The arrangement of siloxane units in parentheses to which n is attached may be random, alternating, or block.)
-Im-X-Im- (3)
[In the formula (3), Im represents a cyclic group including a cyclic imide structure at the end, and X represents a single bond, —O—, —S—, —S (→ O) —, —S (═O _{) 2 -, - C (=} O) -, - NR N - (R N represents a monovalent hydrocarbon group having 1 to 12 carbon _{^{atoms), -. CR B 2 -}} (R B are each independently And a monovalent hydrocarbon group having 1 to 12 carbon atoms which may contain a hydrogen atom or a halogen atom.), -R ^Ar _h- (R ^Ar is a divalent group having 6 to 12 carbon atoms). And h represents an integer of 1 to 6. When h is 2 or more, R ^Ar may be the same or different from each other.), —R ^Ar _h — (OR ^Ar ) _i — ( R ^Ar and h represent the same meaning as described above, i represents an integer of 1 to 5), a linear or branched alkylene group having 1 to 12 carbon atoms, and a cycloalkyl having 5 to 12 carbon atoms. Represents a divalent group selected from a ren group and an arylene alkylene group having 7 to 12 carbon atoms. ]}
A silicone-modified polyimide resin composition comprising (B) a curing agent: 0.1 to 10 parts by mass and (C) a solvent: 100 to 700 parts by mass. The silicone-modified polyimide resin composition according to claim 1, wherein R ^A is selected from the following groups.

(In the formula, J represents an alkylene group having 2 to 6 carbon atoms, and a wavy line represents a bond. A bond bonded to J is bonded to a silicon atom, and other bonds are Bind to Im.) The silicone-modified polyimide resin composition according to claim 1 or 2, wherein the Im is selected from the following groups.

(In the formula, a wavy line indicates a bond. A bond bonded to a nitrogen atom is bonded to E or G, and another bond is bonded to X.)   In the divalent group derived from the diamine represented by G, the diamine is tetramethylenediamine, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, o-phenylenediamine, m-phenylenediamine, p- 4. 1-3 selected from phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane. The silicone-modified polyimide resin composition according to any one of the above.   The silicone-modified polyimide resin composition according to any one of claims 1 to 4, wherein the weight average molecular weight of the silicone-modified polyimide resin represented by the formula (1) of the component (A) is 10,000 to 100,000. .   The silicone-modified polyimide resin composition according to any one of claims 1 to 5, wherein the curing agent of the component (B) is a thermally decomposable radical initiator. Furthermore, (D) hydrophobic fumed silica having a bulk density of less than 1 g / mL, an average primary particle size of 1 to 100 nm, and a BET specific surface area of 100 to 300 m ² / g is added to 100 parts by mass of component (A). The silicone-modified polyimide resin composition according to any one of claims 1 to 6, comprising 3 to 50 parts by mass relative to the mass.   The silicone-modified polyimide resin composition according to any one of claims 1 to 7, wherein the viscosity at 25 ° C is 100 to 100,000 mPa · s.   Hardened | cured material of the silicone modified polyimide resin composition of any one of Claims 1-8. (Α) Storage elastic modulus at 25 ° C. of 100 to 1,000 MPa,
(Β) Glass transition point (Tg) of 100 to 200 ° C.,
(Γ) Water vapor permeability at 40 ° C. is 20 g / m ² · day or less, and
(Δ) The cured product according to claim 9, wherein a 5% weight loss temperature is 420 ° C. or higher.   An adhesive comprising the silicone-modified polyimide resin composition according to any one of claims 1 to 8.   A coating agent comprising the silicone-modified polyimide resin composition according to claim 1. The following formula (4) including the following steps (i) to (iii)

[Wherein, R ¹ and R ² independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which does not have an aliphatic unsaturated bond;
R ³ and R ⁴ each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least one of R ³ and R ⁴ has an aliphatic unsaturated bond. And
R ^C represents a divalent group selected from the following groups:

(In the formula, J represents an alkylene group having 2 to 6 carbon atoms, and a wavy line represents a bond. A bond bonded to J is bonded to a silicon atom, and other bonds are Bind to Im.)
m represents an integer satisfying 0 to 20, n is 1 to 20, and m + n = 1 to 40. The arrangement of siloxane units in parentheses with m and n may be random, alternating or block. ]
The manufacturing method of diamino modified silicone shown by these.
(I) (E) a compound represented by the following formula (5),

(In the formula, R ¹ and R ² represent the same meaning as described above, and K is a monovalent aliphatic unsaturated hydrocarbon group having 2 to 6 carbon atoms having an unsaturated group at the terminal.)
(F) A compound represented by the following formula (6) or the following formula (7): 2.0 to 2.5 molar equivalents relative to the compound represented by the formula (5),

(In the formula, LG represents a monovalent functional group that functions as a leaving group independently of each other.)
(G) transition metal organic complex catalyst: 0.01-5 mol% as a metal content with respect to the compound represented by the formula (5),
(H) Base: 2.0 to 3.0 molar equivalents relative to the compound represented by Formula (5), and (I) Solvent: The concentration of the compound represented by Formula (5) is 0.1 to 5 The reaction is carried out in the presence of an amount of 0.0 mol / L, and the following formula (8)

(In the formula, R ¹ , R ² and R ^C have the same meaning as described above.)
Obtaining a compound represented by:
(Ii) (J) the compound represented by the formula (8) obtained in the step (i), and (K) a transition metal catalyst: as a metal content with respect to the compound represented by the formula (8) 0.001 to 1 mol%
The hydrogenation reaction is carried out in the presence of

(In the formula, R ¹ , R ² , and R ^C represent the same meaning as described above.)
Obtaining a compound represented by:
(Iii) (N) the compound represented by the formula (9) obtained in the step (ii),
Cyclic siloxane composed of (O)-[R ¹ R ² SiO] -unit (wherein R ¹ and R ² have the same meanings as described above): with respect to the compound represented by the formula (9) R ¹ R ² SiO] —the amount by which the units are 0 to 5 molar equivalents,
Cyclic siloxane composed of (P)-[R ³ R ⁴ SiO] -unit (wherein R ³ and R ⁴ have the same meanings as described above): for the compound represented by the formula (9)-[ R ³ R ⁴ SiO] —the amount of units to be 0.25 to 5 molar equivalents, and (Q) organic base catalyst: 0.01 to 5% by mass relative to the compound represented by the formula (9)
A step of obtaining a diamino-modified silicone represented by the formula (4) by reacting in the presence of The step (ii)
(J) the compound represented by the formula (8) obtained in the step (i),
(K) Transition metal catalyst: 0.001 to 1 mol% as a metal content with respect to the compound represented by the formula (8)
(L) Tertiary alkylamine compound: more than 0 mole equivalent and less than 2 mole equivalent with respect to the compound represented by the formula (8), and (M) formic acid or formate salt: an amount such that the reaction mixture becomes pH 7 or more. The method for producing a diamino-modified silicone according to claim 13, which is carried out at atmospheric pressure in the presence of.