TWI795530B - Silicone-modified polyimide resin composition - Google Patents

Abstract

{E為式(2)之基、F為式(3)之基、G為由二胺產生的2價之基；f+e+g=100mol%、f/(e+g)之mol比為0.9～1.1，e與g之總和為100時，e為30～90；

(R^A 為伸芳伸烷基；R¹ ，R² 為不具有脂肪族不飽合鍵結的1價烴基；R³ ，R⁴ 表示1價烴基，但R³ ，R⁴ 之任一者具有脂肪族不飽合鍵結；m為0～20，n為1～20，且滿足m+n=1～40)

(Im為端末含有環狀醯亞胺結構之基；X為選自單鍵、-O-、-S-等者)} (B)硬化劑 (C)溶劑。[Problems] The present invention provides a polyimide resin composition that can impart excellent coating properties, has good adhesion to various metal frames, has high moisture resistance, low elasticity, and can exhibit high heat resistance as a cured product. [Solution] A polyimide resin composition modified by polysiloxane, which contains: (A) polyimide resin of formula (1),

{E is the base of formula (2), F is the base of formula (3), G is the divalent base produced by diamine; f+e+g=100mol%, the mol ratio of f/(e+g) is 0.9~1.1, when the sum of e and g is 100, e is 30~90;

( ^RA is an arylene alkyl group; R ¹ and R ² are monovalent hydrocarbon groups that do not have aliphatic unsaturated bonds; R ³ and R ⁴ represent monovalent hydrocarbon groups, but any one of R ³ and R ⁴ has an aliphatic group unsaturated bond; m is 0-20, n is 1-20, and satisfies m+n=1-40)

(Im is a group containing a cyclic imide structure at the end; X is selected from a single bond, -O-, -S-, etc.)} (B) Hardener (C) Solvent.

Description

Silicone-modified polyimide resin composition

The present invention relates to polyimide resin composition modified by polysiloxane.

In recent years, epoxy resin encapsulants have been widely used to prevent semiconductor elements from being disturbed by moisture or electromagnetic waves (Patent Document 1). However, due to the low moisture resistance of epoxy resin and the high hardness of its cured product, in the packaging process of semiconductor elements, due to the difference in linear expansion coefficient, it often cannot be bonded, and also in the subsequent steps. Delamination and other conditions may occur due to poor adhesion, which will cause a problem of lower reliability in the package.

In addition, the heat resistance requirements for in-vehicle devices are increasing day by day. With this demand, even adhesives and coating materials for in-vehicle devices are required to have stable high heat resistance over a long period of time.

In this regard, because polyimide resin has high heat resistance and excellent electrical insulation, it is used as a material for printed circuit boards or heat-resistant adhesive tapes, and it can also be used in the form of resin coatings for electrical parts or semiconductor materials. Surface protection film, interlayer insulation film. However, because polyimide resin can only be dissolved in limited solvents, it is generally used to coat the substrate with polyamic acid as a polyimide precursor that is easier to dissolve in various organic solvents, and then use High-temperature treatment for dehydration and cyclization to obtain a hardened product made of polyimide resin. [Prior Art Literature] [Patent Document]

[Patent Document 1] JP-A-2009-60146

[Problem to be solved by the invention]

The present invention is proposed in view of the above-mentioned circumstances, and proposes a method that can provide excellent coating properties, but also has good adhesion to various metal frames, and has high moisture resistance, low elasticity, and high heat resistance. The purpose is the polysiloxane-modified polyimide resin composition of permanent cured product, and the adhesive agent and coating agent formed from the composition. [How to solve the problem]

The present inventors, after in-depth research to solve the above problems, found that when polysiloxane units are introduced into polyimide resins, polysiloxane-modified polyimides with low elasticity and moisture resistance can be obtained. Resins, and when aralkylene moieties are introduced into the imide skeleton, polysiloxane-modified polyimide resins with better heat resistance can be obtained, thus completing the present invention.

{式(1)中，E、F及G為以無規狀態鍵結之重複單位；E為由式(2)所示二胺基改質之聚矽氧產生的2價之基；F為由式(3)所示四羧酸二酐產生的2價之基；G為由二胺產生的2價之基；其中，f+e+g=100mol%，f/(e+g)之mol比為0.9～1.1，當前述e與g之總和為100時，前述e為30～90；

(式(2)中，R^A 表示各自獨立之碳原子數8～12的伸芳伸烷基；R¹ 及R² ，表示各自獨立之不具有脂肪族不飽合鍵結的取代或無取代的碳原子數1～10之1價烴基；R³ 及R⁴ ，表示各自獨立之取代或無取代的碳原子數1～10之1價烴基，但R³ 及R⁴ 之至少一者為具有脂肪族不飽合鍵結；m為0～20，n為1～20，且為滿足m+n=1～40之整數；又，m、n所附之括弧內之矽氧烷單位之配列，可為無規、交互或嵌段之任一者)

[式(3)中，Im表示端部含有環狀醯亞胺結構的環狀之基；X，表示由單鍵、-O-、-S-、-S(→O)-、-S(=O)₂ -、-C(=O)-、-NR^N -(R^N 表示碳原子數1～12之1價烴基)、-CR^B ₂ -(R^B 表示各自獨立之可含有氫原子或鹵素原子的碳原子數1～12之1價烴基)、-R^Ar _h -(R^Ar 表示碳原子數6～12的2價之伸芳基；h表示1～6之整數；h為2以上時，R^Ar 可互相為相同或相異皆可)、-R^Ar _h -(OR^Ar )_i -(R^Ar 及h，表示與前述內容為相同之意義；i表示1～5之整數)、碳原子數1～12之直鏈狀或分支狀伸烷基、碳原子數5～12之伸環烷基，及碳原子數7～12的伸芳伸烷基所選出的2價之基]} (B)硬化劑：0.1～10質量份，及 (C)溶劑：100～700質量份。 2.如1之聚矽氧改質之聚醯亞胺樹脂組成物，其中，前述R^A 為由下述之基所選出者；

(式中，J表示碳原子數2～6之伸烷基，附有波浪線之線表示鍵結鍵；J鍵結的鍵結鍵為鍵結於矽原子，其他的鍵結鍵為鍵結於Im)。 3.如1或2之聚矽氧改質之聚醯亞胺樹脂組成物，其中，前述Im為由下述之基所選出者；

(式中，附有波浪線之線表示鍵結鍵；氮原子所鍵結的鍵結鍵為鍵結於E或G，其他的鍵結鍵為鍵結於X)。 4.如1～3中任一項之聚矽氧改質之聚醯亞胺樹脂組成物，其中，由前述G所表示之二胺所產生的2價之基中，二胺為由：伸四甲二胺、1,4-二胺基環己烷、4,4’-二胺基二環己基甲烷、o-苯二胺、m-苯二胺、p-苯二胺、4,4’-二胺基二苯醚、2,2-雙(4-胺苯基)丙烷，及2,2-雙[4-(4-胺基苯氧基)苯基]丙所選出者。 5. 如1～4中任一項之聚矽氧改質之聚醯亞胺樹脂組成物，其中，前述(A)成份之式(1)所示之聚矽氧改質之聚醯亞胺樹脂的重量平均分子量為10,000～100,000。 6. 如1～5中任一項之聚矽氧改質之聚醯亞胺樹脂組成物，其中，前述(B)成份之硬化劑為熱分解性自由基起始劑。 7. 如1～6中任一項之聚矽氧改質之聚醯亞胺樹脂組成物，又，(D)體積密度未達1g/mL、平均一次粒徑為1～100nm，且，BET比表面積為100～300m² /g的疏水性氣相二氧化矽，相對於(A)成份100質量份時，為含有3～50質量份。 8. 如1～7中任一項之聚矽氧改質之聚醯亞胺樹脂組成物，其於25℃下之黏度為100～100,000mPa・s。 9. 一種硬化物，其為1～8中任一項之聚矽氧改質之聚醯亞胺樹脂組成物。 10.如9之硬化物，其具有： (α)25℃下之儲存彈性率為100～1,000MPa、 (β)玻璃轉移點(Tg)為100～200℃、 (γ)40℃下之水蒸氣透過率為20g/m² ・day以下，且， (δ)減少5%重量的溫度為420℃以上。 11.一種接著劑，其為由1～8中任一項之聚矽氧改質之聚醯亞胺樹脂組成物所形成者。 12.一種塗覆劑，其為由1～8中任一項之聚矽氧改質之聚醯亞胺樹脂組成物所形成者。 13.一種下述式(4)所示二胺基改質之聚矽氧的製造方法，其特徵為包含下述(i)～(iii)之步驟；

[式中，R¹ 及R² ，表示各自獨立之不具有脂肪族不飽合鍵結的取代或無取代的碳原子數1～10之1價烴基； R³ 及R⁴ ，表示各自獨立之取代或無取代的碳原子數1～10之1價烴基，但R³ 及R⁴ 之至少一者為具有脂肪族不飽合鍵結； R^C 表示由下述之基所選出的2價之基：

(式中，J表示碳原子數2～6之伸烷基，附有波浪線之線表示鍵結鍵；J鍵結的鍵結鍵為鍵結於矽原子，其他的鍵結鍵為鍵結於Im) m為0～20，n為1～20，且為滿足m+n=1～40之整數；又，m、n所附之括弧內之矽氧烷單位之配列，可為無規、交互或嵌段之任一者] (i)將(E)下述式(5)所示化合物、

(式中，R¹ 及R² ，表示與前述為相同之意義，K為末端具有不飽合基的碳原子數2～6之1價之脂肪族不飽合烴基) (F)下述式(6)或下述式(7)所示化合物：相對於前述式(5)所示化合物為2.0～2.5莫耳當量：

(式中，LG表示各自獨立之具有解離基之機能的1價之官能基)， 於 (G)過渡金屬有機錯合物觸媒：相對於前述式(5)所示化合物，依金屬之含量為0.01～5莫耳%、 (H)鹼：相對於前述式(5)所示化合物為2.0～3.0莫耳當量，及 (I)溶劑：使前述式(5)所示化合物的濃度達0.1～5.0莫耳/L之量 的存在下進行反應，而製得下述式(8)所示化合物之步驟；

(式中，R¹ 、R² 及R^C ，表示與前述具有相同之意義) (ii)將(J)前述步驟(i)所製得的前述式(8)所示化合物， 於 (K)過渡金屬觸媒：相對於前述式(8)所示化合物，依金屬之含量為0.001～1莫耳% 的存在下進行氫化反應，而製得下述式(9)所示化合物之步驟；

(式中，R¹ 、R² ，及R^C ，表示與前述具有相同之意義) (iii)將(N)前述步驟(ii)所製得的前述式(9)所示化合物、 (O)由-[R¹ R² SiO]-單位所形成的環狀矽氧烷(式中，R¹ 及R² 表示與前述為相同之意義)：相對於前述式(9)所示化合物，-[R¹ R² SiO]-單位相當於0～5莫耳當量之量、 (P)由-[R³ R⁴ SiO]-單位所形成的環狀矽氧烷(式中，R³ 及R⁴ 表示與前述為相同之意義)：相對於前述式(9)所示化合物，-[R³ R⁴ SiO]-單位相當於0.25～5莫耳當量之量，於 (Q)有機鹼觸媒：相對於前述式(9)所示化合物，0.01～5質量% 的存在下進行反應，而製得前述式(4)所示二胺基改質之聚矽氧。 14.如13之二胺基改質之聚矽氧的製造方法，其中，前述(ii)步驟為： 將(J)前述步驟(i)所製得的前述式(8)所示化合物， 於 (K)過渡金屬觸媒：相對於前述式(8)所示化合物，依金屬之含量為0.001～1莫耳%、 (L)三級烷胺化合物：相對於前述式(8)所示化合物，大於0莫耳當量、且未達2莫耳當量，及 (M)甲酸或甲酸鹽：使反應混合液達pH7以上之量 的存在下，於大氣壓下進行。 [發明之效果]That is, the present invention provides: 1. A polyimide resin composition modified by polysiloxane, characterized in that it contains: (A) a polyimide modified by polysiloxane represented by the following formula (1) Amine resin: 100 parts by mass;

{In formula (1), E, F and G are repeating units bonded in a random state; E is a divalent group produced by polysiloxane modified with diamine groups shown in formula (2); F is The divalent base produced by tetracarboxylic dianhydride shown in formula (3); G is the divalent base produced by diamine; wherein, f+e+g=100mol%, f/(e+g) The mol ratio is 0.9-1.1, when the sum of the aforementioned e and g is 100, the aforementioned e is 30-90;

(In formula (2), ^RA represents independently arylene alkylene with 8 to 12 carbon atoms; R ¹ and R ² represent independently substituted or unsubstituted carbons that do not have aliphatic unsaturated bonds A monovalent hydrocarbon group with 1 to 10 atoms; R ³ and R ⁴ represent independently substituted or unsubstituted monovalent hydrocarbon groups with 1 to 10 carbon atoms, but at least one of R ³ and R ⁴ is aliphatic Unsaturated bond; m is 0-20, n is 1-20, and is an integer satisfying m+n=1-40; and the arrangement of siloxane units in brackets attached to m and n can be any of random, interactive or block)

[In the formula (3), Im represents the cyclic base containing the cyclic imide structure at the end; X represents a single bond, -O-, -S-, -S(→O)-, -S( =O) ₂ -, -C(=O)-, -NR ^N -(R ^N represents a monovalent hydrocarbon group with 1 to 12 carbon atoms), -CR ^B ₂ -(R ^B represents each independent hydrogen atom or a monovalent hydrocarbon group with 1 to 12 carbon atoms of a halogen atom), -R ^Ar _h -(R ^Ar represents a divalent aryl group with 6 to 12 carbon atoms; h represents an integer of 1 to 6; h is 2 In the above, 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 the above; i represents an integer of 1 to 5) A divalent group selected from a linear or branched alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, and an arylene alkylene group having 7 to 12 carbon atoms] } (B) Curing agent: 0.1 to 10 parts by mass, and (C) Solvent: 100 to 700 parts by mass. 2. The polysiloxane-modified polyimide resin composition as in 1, wherein the aforementioned R ^A is selected from the following groups;

(In the formula, J represents an alkylene group with 2 to 6 carbon atoms, and the line with a wavy line represents a bonding bond; the bonding bond of J bonding is bonding to a silicon atom, and the other bonding bonding is bonding in Im). 3. The polysiloxane-modified polyimide resin composition as in 1 or 2, wherein the aforementioned Im is selected from the following groups;

(In the formula, the line with the wavy line represents the bond; the bond bonded by the nitrogen atom is bonded to E or G, and the other bonds are bonded to X). 4. The polysiloxane-modified polyimide resin composition according to any one of 1 to 3, wherein, among the divalent groups generated by the diamine represented by the aforementioned G, the diamine is composed of: Tetramethylenediamine, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4 Those selected from '-diaminodiphenyl ether, 2,2-bis(4-aminophenyl)propane, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. 5. The polysiloxane-modified polyimide resin composition according to any one of 1 to 4, wherein the polysiloxane-modified polyimide represented by the formula (1) of the aforementioned (A) component The weight average molecular weight of resin is 10,000-100,000. 6. The polysiloxane-modified polyimide resin composition according to any one of 1 to 5, wherein the curing agent of the aforementioned component (B) is a thermally decomposable radical initiator. 7. The silicone-modified polyimide resin composition of any one of 1 to 6, and (D) the bulk density is less than 1 g/mL, the average primary particle size is 1 to 100 nm, and BET The hydrophobic fumed silica having a specific surface area of 100 to 300 m ² /g is contained in an amount of 3 to 50 parts by mass relative to 100 parts by mass of the component (A). 8. The polysiloxane-modified polyimide resin composition according to any one of 1-7, which has a viscosity of 100-100,000 mPa·s at 25°C. 9. A hardened product, which is the silicone-modified polyimide resin composition according to any one of 1-8. 10. The cured product as in 9, which has: (α) storage elastic modulus at 25°C of 100-1,000 MPa, (β) glass transition point (Tg) of 100-200°C, (γ) water at 40°C The vapor transmission rate is 20g/m ² ·day or less, and the temperature at which (δ) decreases by 5% by weight is 420°C or higher. 11. An adhesive, which is formed of the silicone-modified polyimide resin composition according to any one of 1-8. 12. A coating agent, which is formed from the polysiloxane-modified polyimide resin composition according to any one of 1-8. 13. A method for producing polysiloxane modified with diamine groups represented by the following formula (4), characterized by comprising the following steps (i) to (iii);

[wherein, R ¹ and R ² represent independently substituted or unsubstituted monovalent hydrocarbon groups with 1 to 10 carbon atoms without aliphatic unsaturated bonds; R ³ and R ⁴ represent independently substituted Or an unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, but at least one of ^R3 and ^R4 has an aliphatic unsaturated bond; R ^C represents a divalent group selected from the following groups:

(In the formula, J represents an alkylene group with 2 to 6 carbon atoms, and the line with a wavy line represents a bonding bond; the bonding bond of J bonding is bonding to a silicon atom, and the other bonding bonding is bonding In Im) m is 0 to 20, n is 1 to 20, and is an integer satisfying m+n=1 to 40; and the arrangement of siloxane units in brackets attached to m and n can be random , any one of interaction or block] (i) (E) the compound represented by the following formula (5),

(wherein, R ¹ and R ² represent the same meanings as above, and K is a monovalent aliphatic unsaturated hydrocarbon group with 2 to 6 carbon atoms having an unsaturated group at the end) (F) the following formula (6) or the compound shown in the following formula (7): 2.0 to 2.5 molar equivalents relative to the compound shown in the aforementioned formula (5):

(In the formula, LG represents a monovalent functional group independently having the function of a dissociative group), in (G) transition metal organic complex catalyst: relative to the compound represented by the aforementioned formula (5), depending on the content of the metal 0.01～5 mole %, (H) base: 2.0～3.0 mole equivalents relative to the compound shown in the aforementioned formula (5), and (I) solvent: make the concentration of the compound shown in the aforementioned formula (5) reach 0.1 The reaction is carried out in the presence of ~5.0 mol/L amount, and the step of preparing the compound shown in the following formula (8);

(wherein, R ¹ , R ² and R ^C represent the same meanings as above) (ii) the compound represented by the above formula (8) prepared in (J) the above step (i), in (K) Transition metal catalyst: relative to the compound represented by the aforementioned formula (8), the hydrogenation reaction is carried out in the presence of a metal content of 0.001 to 1 mol%, and the step of preparing the compound represented by the following formula (9);

(wherein, R ¹ , R ² , and R ^C represent the same meanings as described above) (iii) (N) the compound represented by the aforementioned formula (9) prepared in the aforementioned step (ii), (O) Cyclic siloxane formed by -[R ¹ R ² SiO]-units (in the formula, R ¹ and R ² represent the same meaning as above): Relative to the compound shown in the aforementioned formula (9), -[ R ¹ R ² SiO]-unit is equivalent to 0 to 5 molar equivalents, (P) Cyclic siloxane formed by -[R ³ R ⁴ SiO]-unit (wherein, R ³ and R ⁴ Indicates the same meaning as above): With respect to the compound represented by the aforementioned formula (9), the -[R ³ R ⁴ SiO]-unit is equivalent to 0.25 to 5 molar equivalents in (Q) organic base catalyst: The reaction is carried out in the presence of 0.01-5% by mass relative to the compound represented by the aforementioned formula (9) to obtain the diamine-modified polysiloxane represented by the aforementioned formula (4). 14. The method for producing diamine-modified polysiloxane according to 13, wherein the aforementioned step (ii) is: (J) the compound represented by the aforementioned formula (8) prepared in the aforementioned step (i), in (K) Transition metal catalyst: relative to the compound represented by the aforementioned formula (8), depending on the content of the metal, it is 0.001 to 1 mol%. (L) Tertiary alkylamine compound: relative to the compound represented by the aforementioned formula (8) , greater than 0 molar equivalents and less than 2 molar equivalents, and (M) formic acid or formate salt: in the presence of an amount to make the reaction mixture reach pH 7 or more, and carry out under atmospheric pressure. [Effect of Invention]

The polysiloxane-modified polyimide resin composition of the present invention is suitable for use as a primer because of its excellent coating properties. In addition, the cured product prepared from the above composition has low elasticity, and also shows good adhesion to various metal frames or epoxy-based packaging materials, and has excellent water resistance and moisture resistance (low water resistance) vapor permeability) and heat resistance. Therefore, the polysiloxane-modified polyimide resin composition of the present invention is suitable for use as an adhesive or coating agent for electronic materials, optical materials, and vehicle-mounted equipment, and is especially suitable for use as an adhesive that must have high reliability. Adhesive or coating agent for semiconductor devices. [Mode of Implementing the Invention]

Hereinafter, the present invention will be specifically described. The polysiloxane-modified polyimide resin composition of the present invention contains: (A) polysiloxane-modified polyimide resin, (B) hardener, and (C) solvent.

(1) (A) In the silicone-modified polyimide resin of (A) component (A), the main agent (base polymer) of this composition, in the present invention, is to use the following formula (1) Expressed.

In formula (1), E, F and G, the repeating unit (but, E-E, F-F, G-G, and the combination of the adjacent units represented by E-G except that) of bond under the random state; E is represented by the following formula (2) The 2-valent group produced by the polysiloxane modified by the diamine group shown in (2); F is the 2-valent group produced by the tetracarboxylic dianhydride shown in the following formula (3); G is the 2-valent group produced by the two A divalent base produced by amine; where f+e+g=100mol%, the molar ratio of f/(e+g) is 0.9-1.1, and when the sum of e and g is 100, e is 30-90.

In formula (2), R ^A represents independently arylene alkylene with 8 to 12 carbon atoms; R ¹ and R ² represent independently substituted or unsubstituted carbon atoms that do not have aliphatic unsaturated bonds A monovalent hydrocarbon group with a number of 1 to 10; R ³ and R ⁴ represent independently substituted or unsubstituted monovalent hydrocarbon groups with a carbon number of 1 to 10, but at least one of R ³ and R ⁴ has an aliphatic Saturated bond; m is 0-20, n is 1-20, and is an integer satisfying m+n=1-40; and the arrangement of siloxane units in brackets attached to m and n can be none any of regular, interactive or block;

式(3)中，Im表示端部含有環狀醯亞胺結構的環狀之基；X，表示由單鍵、-O-、-S-、-S(→O)-、-S(=O)₂ -、-C(=O)-、 -NR^N -(R^N 表示碳原子數1～12之1價烴基)、-CR^B ₂ -(R^B 表示各自獨立之可含有氫原子或鹵素原子的碳原子數1～12之1價烴基)、-R^Ar _h -(R^Ar 表示碳原子數6～12的2價之伸芳基；h表示1～6之整數；h為2以上時，R^Ar 可互相為相同或相異皆可)、-R^Ar _h -(OR^Ar )_i -(R^Ar 及h，與上述為相同之意義，i表示1～5之整數)、碳原子數1～12之直鏈狀或分支狀伸烷基、碳原子數5～12之伸環烷基，及碳原子數7～12的伸芳伸烷基所選出的2價之基。

In the formula (3), Im represents the cyclic base containing the cyclic imide structure at the end; X represents a single bond, -O-, -S-, -S(→O)-, -S(= O) ₂ -, -C(=O)-, -NR ^N -(R ^N represents a monovalent hydrocarbon group with 1 to 12 carbon atoms), -CR ^B ₂ -(R ^B represents each independent hydrogen atom or A monovalent hydrocarbon group with 1 to 12 carbon atoms of a halogen atom), -R ^Ar _h -(R ^Ar represents a divalent aryl group with 6 to 12 carbon atoms; h represents an integer of 1 to 6; 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 have the same meaning as above, and i represents an integer of 1 to 5), carbon atom A divalent group selected from a linear or branched alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, and an arylene alkylene group having 7 to 12 carbon atoms.

In formula (2), specific examples of the divalent arylene alkylene group having 8 to 12 carbon atoms in R ^A include: 2-(1,4-phenylene)-1-ethylene, 2- (1,3-phenylene)-1-ethylene, 1-(1,4-phenylene)-1-ethylene, 1-(1,3-phenylene)-1-ethylene Base, 3-(1,4-phenylene)-1-propylene, 3-(1,3-phenylene)-1-propylidene, 2-(1,4-phenylene)- 1-Propyl, 2-(1,3-Phenyl)-1-Propyl, 2-Methyl-3-(1,4-Phenyl)-1-Propyl, 2-Methyl Base-3-(1,3-phenylene)-1-propylidene, 2-methyl-2-(1,4-phenylene)-1-propylidene, 2-methyl-2- (1,3-phenylene)-1-propylene, 4-(1,4-phenylene)-1-butylene, 4-(1,3-phenylene)-1-butylene Base, 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-pentyl, 5- (1,3-phenylene)-1-pentyl, 4-(1,4-phenylene)-1-pentyl, 4-(1,3-phenylene)-1-pentyl base, 2,2-dimethyl-4-(1,4-phenylene)-1-butylene, 2,2-dimethyl-4-(1,3-phenylene)-1- Butyl, 2,2-dimethyl-3-(1,4-phenylene)-1-butylene, 2,2-dimethyl-3-(1,3-phenylene)- 1-butylene, 6-(1,4-phenylene)-1-hexyl, 6-(1,3-phenylene)-1-hexyl, 5-(1,4-phenylene )-1-hexyl, 5-(1,3-phenylene)-1-hexyl, 2-(1,9-naphthyl)-1-ethylenyl, 2-(1,5-naphthalene )-1-ethylendyl etc. Among them, 2-(1,4-phenylene)-1-ethylene and 2-(1,3-phenylene)-1-ethylene are preferable from the viewpoint of easy acquisition.

A monovalent hydrocarbon group with 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond for R ¹ and R ² can be linear, branched, or cyclic, for example, methyl, ethyl base, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl , n-nonyl, n-decyl, decahydronaphthyl and other alkyl groups with 1 to 10 carbon atoms; ethylene, 1-propenyl, allyl (2-propenyl), hexenyl, octene Alkenyl groups with 2 to 10 carbon atoms such as phenyl, cyclopentenyl, and cyclohexenyl; aryl groups with 6 to 10 carbon atoms such as phenyl and naphthyl; tolyl, xylyl, and ethylphenyl , C7-10 alkaryl groups such as propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, etc.; C7-10 aralkyl groups such as benzyl, phenethyl, etc. Also preferably an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms, more preferably methyl, ethyl, or n-propyl, and R ¹ and R ² All of them are more preferably methyl or ethyl.

R ³ and R ⁴ monovalent hydrocarbon groups with 1 to 10 carbon atoms, in addition to the monovalent hydrocarbon groups with 1 to 10 carbon atoms that do not have aliphatic unsaturated bonds as exemplified above for R ¹ and R ² , such as , vinyl, allyl, 1-propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, octenyl and other alkenyl groups have aliphatic unsaturated bond number of carbon atoms 2 ~10 monovalent hydrocarbon groups, etc. Among them, ^R3 and ^R4 are preferably alkyl groups with 1 to 10 carbon atoms or alkenyl groups with 2 to 10 carbon atoms, and alkyl groups with 1 to 6 carbon atoms or alkenyl groups with 2 to 6 carbon atoms. A group is preferred, and a methyl group, an ethyl group, a propyl group, and a vinyl group are more preferred. In particular, one or both of R ³ and R ⁴ is an alkenyl group with 2 to 10 carbon atoms. Therefore, the combination of R ³ and R ⁴ is preferably methyl and vinyl, ethyl and vinyl Preferred are propyl, vinyl and vinyl, and vinyl and vinyl. In addition, in the above-mentioned monovalent hydrocarbon groups of R ¹ to R ⁴ , some or all of these hydrogen atoms may be substituted by halogen atoms such as fluorine, chlorine, bromine, iodine atoms.

Also, in formula (2), m is 0-20, n is 1-20, and is an integer satisfying m+n=1-40, wherein m is preferably an integer of 4-15, and n is 4-10 An integer of 5 to 40 is preferable for m+n.

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

(式中，附有波浪線之線表示鍵結鍵；鍵結鍵為鍵結於上述式(3)中之Im。m、n與上述為相同之意義)。

(In the formula, the line with the wavy line represents the bonding bond; the bonding bond is Im bonded in the above formula (3). m and n have the same meaning as above).

In formula (3), Im having a cyclic imide structure derived from tetracarboxylic dianhydride is a group having a cyclic imide structure at its end, for example, a group selected from the following formula.

(式中，附有波浪線之線表示鍵結鍵(以下相同)。又，除氮原子所連結之鍵結鍵以外，由環上碳原子所連結的鍵結鍵亦可使用作為與X之鍵結)。

(In the formula, the line with the wavy line represents the bonding bond (the same below). Also, in addition to the bonding bond connected to the nitrogen atom, the bonding bond connected to the carbon atom on the ring can also be used as the bond with X bond).

In formula (3), in -NR ^N - of X, R ^N has 1 to 12 carbon atoms, preferably a monovalent hydrocarbon group with 1 to 8 carbon atoms, such as the monovalent hydrocarbon groups exemplified by R ¹ to R ⁴ above. Hydrocarbyl, etc., especially methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc., having 1 to 8 carbon atoms A chain or cyclic alkyl group is preferred, and a methyl group is preferred. In -CR ^B ₂ - of X, R ^B is a monovalent hydrocarbon group with 1 to 12 carbon atoms that may contain a halogen atom, such as: the monovalent hydrocarbon groups exemplified above for R ¹ to R ⁴ , etc., and the halogen atom is fluorine , chlorine, bromine, iodine atoms, etc., among which methyl, ethyl, n-propyl, trifluoromethyl, 3,3,3-trifluoropropyl, cyclohexyl, etc. can be replaced by fluorine atoms An alkyl group; an aryl group such as a phenyl group are preferred. R ^B is especially preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a phenyl group.

In -R ^Ar _h - of X, specific examples of the divalent arylylene group having 6 to 12 carbon atoms in R ^Ar include phenylene, biphenylene, and naphthylene. Also, in the extended aryl group of R ^Ar , a part of its hydrogen atom can be replaced by hydroxyl group, thioether group, 2,3-side oxygen (oxo)-1-propyl group, methoxy group, ethoxy group, t -butoxy, methyl, ethyl, propyl, t-butyl, N,N-dimethylamino, cyano, methoxycarbonyl, ethoxycarbonyl, formyl, methylcarbonyl, ethyl Substituted by carbonyl group, fluorine atom, etc. Moreover, h is an integer of 1-6. Desirable R ^Ar is, for example, the groups shown below.

(式中，sub表示氫原子，或由羥基、硫醚基、2,3-側氧(oxo)-1-丙基、甲氧基、乙氧基、t-丁氧基、甲基、乙基、丙基、t-丁基、N,N-二甲胺基、氰基、甲氧基羰基、乙氧基羰基、甲醯基、甲基羰基、乙基羰基，及氟原子所選出之取代基，其取代數為1～4個之範圍內)。

(wherein, sub represents a hydrogen atom, or is composed of hydroxyl, thioether, 2,3-oxo (oxo)-1-propyl, methoxy, ethoxy, t-butoxy, methyl, ethyl group, propyl group, t-butyl group, N,N-dimethylamino group, cyano group, methoxycarbonyl group, ethoxycarbonyl group, formyl group, methylcarbonyl group, ethylcarbonyl group, and fluorine atom selected Substituents, the number of substitutions is within the range of 1 to 4).

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

Specific examples of straight-chain or branched alkylene groups having 1 to 12 carbon atoms and cycloalkylene groups having 5 to 12 carbon atoms in X include methylene, ethylene, trimethylene, 1,3-Butyl, Tetramethyl, 1,3-Pentyl, 1,4-Pentyl, Pentamethyl, Hexamethyl, Heptamethyl, Octamethyl, Nonamethyl, Decylene, 1,3-Cyclohexylene, 1,4-Cyclohexylene, 1,3-Cycloheptyl, 1,4-Cycloheptylene, etc. Specific examples of the arylene group having 7 to 12 carbon atoms include 2-(4-(2-ethen-1-yl)-1-phenylene)ethen-1-yl and the like.

In the above-mentioned formula (1), the divalent group generated by diamine represented by G is not particularly limited. In the present invention, the 2-valent group generated by diamine is used to make the heat resistance more excellent. The basis of price is good. Specific examples of diamines that can provide these divalent groups include, for example, tetramethylenediamine, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, etc. Aliphatic diamines; o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenyl)propane, 2 ,Aromatic diamines, such as 2-bis[4-(4-aminophenoxy)phenyl]propane, etc. These may be used individually or in combination of 2 or more types, respectively.

The silicone-modified polyimide resin represented by the above formula (1) is preferably end-blocked with an acid anhydride. Also, when the sum of the mols of f+e+g is 100 mol%, the mol ratio of f/(e+g) is 0.9 to 1.1, and from the viewpoint of maintaining an appropriate molecular weight, the mol ratio of f/(e+g) is 0.95-1.05 is preferable, and 0.98-1.02 is more preferable. Also, when the sum of e and g is 100, e is 30-90, and 30-70 is preferable from the viewpoint of maintaining moisture resistance.

(A) The weight average molecular weight of the polysiloxane-modified polyimide resin of the component is not specifically limited. In consideration of improving the toughness of the film obtained from the composition containing the resin, it can also improve From the standpoint of compatibility with other components such as hardeners or solubility in solvents, 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 (it is the same hereafter) using gel permeation chromatography (it abbreviates also below GPC).

(A) The polysiloxane-modified polyimide resin of component (A) can be prepared by a known method. For example, first, add tetracarboxylic dianhydride, diamine, and diamine-modified polysiloxane in which the two ends of the compound represented by the above formula (2) are respectively bonded to amine groups, into a solvent, and at low temperature, that is The reaction is carried out at about 20-50°C to produce polyamic acid which is the precursor of polyimide resin. Subsequently, the obtained polyamic acid solution is heated to a temperature of preferably 80-200°C, more preferably 140-180°C, and the acid amide of the polyamic acid is subjected to a dehydration ring-closing reaction to prepare To obtain a solution of polyimide resin modified by polysiloxane, put this solution into a solvent such as water, methanol, ethanol, acetonitrile, etc. to precipitate it, and dry the precipitate to obtain polysiloxane modified polyimide resin. Quality polyimide resin.

In addition, the above-mentioned f/(e+g) is the total number of moles of diamine and polysiloxane modified with diamine groups relative to the number of moles of tetracarboxylic dianhydride converted from the amount of material of the raw material. Ratio (mole ratio), when performing the reaction, [tetracarboxylic dianhydride (mole)/(diamine + diamine-modified polysiloxane (mole))], usually in the range of 0.9 to 1.1 , preferably in the range of 0.95 to 1.05, more preferably in the range of 0.98 to 1.02.

Examples of usable solvents for producing component (A) include N-methyl-2-pyrrolidone, cyclohexanone, γ-butyrolactone, and N,N-dimethylacetamide. Moreover, aromatic hydrocarbons, such as toluene and xylene, can also be used together, and the water produced|generated at the time of imidization can be easily removed via azeotropy. These solvents may be used alone or in combination of two or more.

In addition, from the viewpoint of adjusting the molecular weight of the silicone-modified polyimide resin, phthalic anhydride, maleic anhydride, hexahydro-1,3-isobenzofurandione, succinic anhydride, pentamethylene Anhydrides such as diacid anhydrides, anhydride-modified polysiloxanes with a silicon number of 10 to 60, or anhydrides with 3 to 6 carbon atoms such as aniline, benzylamine, propylamine, butylamine, pentylamine, hexylamine, and cyclohexylamine Monofunctional raw material for amine compounds such as linear, branched or cyclic alkylamines. Also, as the aldehyde compound, an aldehyde compound containing an alkyl group having 2 to 6 carbon atoms, such as benzaldehyde, phenylacetaldehyde, pentanonealdehyde, butyraldehyde, may be added. The amount to be added at this time is preferably in the range of 1-10 mol% in terms of the acid anhydride of the raw material, when matching the molecular weight of the target.

、喹啉、1,8-二氮雜雙環-[5,4,0]-7-十一烯(DBU)、1,4-二氮雜雙環-[2,2,2]辛烷(DABCO)等的三級胺。醯亞胺化觸媒之使用量，相對於所使用的脱水劑1莫耳，以使用0.5～10莫耳為佳。 本醯亞胺化之方法為，於步驟中該反應液無須再經過處理，故對於不易使所得之樹脂發生著色現象之觀點為有效者。In addition, in the imidization process, a method of adding a dehydrating agent and an imidization catalyst and, if necessary, heating to around 50° C. for imidization can be used. Specific examples of the above dehydrating agent include acid anhydrides such as acetic anhydride, propionic anhydride, trimethylacetic anhydride, trifluoroacetic anhydride, and benzoic anhydride. The amount of the dehydrating agent used is preferably 1 to 10 moles per 1 mole of diamine. Specific examples of imidization catalysts 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'-tetra Methylethylenediamine (TMEDA), N-methylimidazole (NMI), pyridine, 2,6-lutidine, 1,3,5-Collinine, N,N-dimethylaminopyridine, pyridine

, quinoline, 1,8-diazabicyclo-[5,4,0]-7-undecene (DBU), 1,4-diazabicyclo-[2,2,2]octane (DABCO ) and other tertiary amines. The amount of the imidization catalyst used is preferably 0.5-10 moles relative to 1 mole of the dehydrating agent used. The imidization method of this method is that the reaction solution does not need to be further processed in the step, so it is effective from the point of view that it is difficult to cause coloring of the obtained resin.

Even if at least one of diamine and tetracarboxylic dianhydride is used in plural, the reaction method is not particularly limited. For example, it is possible to use a method in which all raw materials are mixed in advance and then carry out copolymerization condensation, or A method in which two or more kinds of diamines or tetracarboxylic dianhydrides to be used are sequentially added between each reaction.

(2) (B) component The curing agent of component (B) of the present invention is preferably a thermally decomposable free radical initiator that can induce free radicals through heat to polymerize the resin to form a hardened product. As the thermally decomposable radical initiator, an azo compound or an organic peroxide can be used.

Azo compounds (organic azo compounds) include, for example, V-30, V-40, V-59, V-60, V-65, V-70, V- Azonitrile compounds such as 501, V-601; Azoamide compounds such as VA-080, VA-085, VA-086, VF-096, VAm-110, VAm-111; VA-044, VA Cyclic azoamidine compounds such as -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-di methylbutyronitrile), 1,1-azobis(cyclohexane-1-carbonitrile), 1-[(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-methylpropionamide), 2,2-azobis(N-cyclohexyl-2-methylpropionamide), 2,2-azobis[2-(2-imidazoline-2- base) propane] dihydrochloride, 2,2-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2-azobis{2-[1- (2-Hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, 2,2-azobis[2-(2-imidazolin-2-yl)propane], 2,2 -Azobis(1-imino-1-pyrrolidinyl-2-methylpropane) dihydrochloride, 2,2-azobis(2-methylpentanoneamidine) dihydrochloride, 2 ,2-Azobis[N-(2-carboxyethyl)-2-methylpentanoneamidine] tetrahydrate, dimethyl 2,2-azobis(2-methylpropionate), 4 , 4-Azobis(4-cyanovaleric acid), 2,2-Azobis(2,4,4-trimethylpentane), etc. Among them, 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, VAm-111 are better, V-30, V-40, V-59, V-60, V-65, V-70, V-501, V-601 are better .

、2,4,4-三甲基戊基過氧化新癸酸酯、α-異丙苯基過氧化新癸酸酯、t-戊基過氧2-乙基己酸酯、t-丁基過氧化異丁酸酯、二-t-丁基過氧化六氫對苯二甲酸酯、二-t-丁基過氧化三甲基己二酸酯、二‐3-甲氧基丁基過氧化二碳酸酯、二異丙基過氧化二碳酸酯、t-丁基過氧化異丙基碳酸酯、1,6-雙(t-丁基過氧羰基氧)己烷、二乙二醇雙(t-丁基過氧化碳酸酯)、t-己基過氧化新癸酸酯，或化藥AKZO(股)製之Trigonox 36-C75、Laurox 、Perkadox L-W75、Perkadox CH-50L、Trigonox TMBH、Kayacumene H、Kayabutyl H-70、Perkadox BC-FF、Kayahexa AD、Perkadox 14、Kayabutyl C、Kayabutyl D、Perkadox 12-XL25、Trigonox 22-N70(22-70E)、Trigonox D-T50、Trigonox 423-C70、Kayaester CND-C70、Trigonox 23-C70、Trigonox 257-C70、Kayaester P-70、Kayaester TMPO-70、Trigonox 121、Kayaester O、Kayaester HTP-65W、Kayaester AN、rTrigonox 42、Trigonox F-C50、Kayabutyl B、Kayacarbon EH、Kayacarbon I-20、Kayacarbon BIC-75、Trigonox 117、Kayalene 6-70等。 又，上述硬化劑，可單獨使用亦可、將2種以上組合使用亦可。Examples of organic peroxides include ketone peroxides such as Perhexa H manufactured by NOF Co., Ltd.; peroxyketals such as Perhexa TMH; hydroperoxides such as Perbutyl H-69; Percumyl D , Perbutyl C, Perbutyl D, Perbutyl O and other dialkyl peroxides; Nyper BW and other diacyl peroxides; Perbutyl Z, Perbutyl L and other peroxyesters; Peroyl TCP and other dialkyl peroxides Carbonates; diisobutyryl peroxide, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl Peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, bis(2-ethylhexyl) ) peroxydicarbonate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-butyl peroxy neoheptanoate, t-hexyl peroxy pivalate, t -Butyl peroxy pivalate, bis(3,5,5-trimethylhexyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl Peroxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di(2-ethylhexylperoxy)hexane, t-hexyl Peroxy-2-ethylhexanoate, bis(4-methylbenzoyl)peroxide, t-butylperoxy-2-ethylhexanoate, bis(3-methylbenzoyl)peroxide Formyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, 1,1-di(t-butylperoxy)- 2-Methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane alkane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis[4,4-bis-(t-butylperoxy)cyclohexyl]propane, t-hexylperoxy Oxidized isopropyl monocarbonate, t-butylperoxymaleate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2, 5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylbenzoylperoxide Ester, n-butyl-4,4-di-t-butylperoxyvalerate, bis(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, dicumyl peroxide, -t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl base peroxide, p-methane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexan-3-yl, diisopropylbenzene hydroperoxide 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl hydroperoxide , o-chlorobenzoyl peroxide, p-chlorobenzoyl peroxide, three (t-butyl peroxy) three

, 2,4,4-trimethylpentylperoxyneodecanoate, α-cumylperoxyneodecanoate, t-pentylperoxy2-ethylhexanoate, t-butyl Isobutyrate peroxide, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxytrimethyladipate, di‐3-methoxybutylperoxide Oxydicarbonate, diisopropylperoxydicarbonate, t-butylperoxyisopropylcarbonate, 1,6-bis(t-butylperoxycarbonyloxy)hexane, diethylene glycol bis (t-butyl peroxycarbonate), t-hexyl peroxyneodecanoate, or Trigonox 36-C75, Laurox, Perkadox L-W75, Perkadox CH-50L, Trigonox TMBH, Kayacumene H, Kayabutyl H-70, Perkadox BC-FF, Kayahexa AD, Perkadox 14, Kayabutyl C, Kayabutyl D, Perkadox 12-XL25, Trigonox 22-N70(22-70E), Trigonox D-T50, Trigonox 423-C70, Kayaester CND-C70, Trigonox 23-C70, Trigonox 257-C70, Kayaester P-70, Kayaester TMPO-70, Trigonox 121, Kayaester O, Kayaester HTP-65W, Kayaester AN, rTrigonox 42, Trigonox F-C50, Kayabutyl B, Kayacarbon EH, Kayacarbon I-20, Kayacarbon BIC-75, Trigonox 117, Kayalene 6-70, etc. Moreover, the said hardening|curing agent may be used individually or in combination of 2 or more types.

The addition amount of (B) component is 0.1-10 mass parts with respect to 100 mass parts of (A) components, More preferably, it is 1-5 mass parts. If the amount added is less than 0.1 parts by mass, the curability will be insufficient, and if it exceeds 10 parts by mass, a large amount of outgassing will occur from the curing agent, causing curing shrinkage, and presumably causing resin hardening.

(3) (C) component The solvent of the component (C) of the present invention is used for the purpose of lowering the viscosity of the composition, improving the applicability to substrates, etc., or workability. Specific examples of solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; dioxane, dioxolane, tetrahydrofuran, 1,2-dimethoxy Ethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis-2-(2-methoxyethoxy)ethyl ether, methyl Ether-based solvents such as 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 (EDGAC), diethylene glycol monobutyl ether acetate (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 diol acetate (1,3-BGDA), 1,6-hexanediol diacetate ( 1,6-HDDA) and other ester solvents; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, 1,3-dimethyl -Organic solvents such as amide-based solvents such as 2-imidazolinone, etc., may be used alone or in combination of two or more. (C) The solvent can be used as long as it does not impair the solubility of the silicone-modified polyimide resin of the component (A), and usually 100 to 700 parts by mass relative to the component (A).

(4) (D) Component (D) The hydrophobic fumed silica of component (D) is used to prevent liquid drooping, prevent air bubble penetration and nonuniformity during coating, maintain formability, and impart thixotropy ( thixotropy), and any components added for the purpose of reducing the elastic modulus of the cured product. In particular, the bulk density is preferably less than 1 g/mL from the standpoint of preventing the sedimentation of silica during production and effectively exerting the various effects described above. Also, the average primary particle diameter of fumed silica is preferably 1 to 100 nm. When the average primary particle size is within this range, the light scattering caused by fumed silica based on the cured product containing polysiloxane-modified polyimide composition can be suppressed, so the transparency of the cured product will not be damaged. sex. In addition, the average particle diameter is the median value (d50) of the diameter in the volume-based particle size distribution using a particle size distribution meter using an analysis method such as a laser light diffraction method. Also, the BET specific surface area of fumed silica is preferably 100 to 300 m ² /g.

The hydrophobic fumed silica of the component (D) is preferably dry silica obtained by hydrolyzing silicon halides in an oxygen-hydrogen flame. As the hydrophobic fumed silica, a commercially available product can also be used. Specific examples of commercially available products include: hydrophobic dry silica (specific surface area 160m ² /g, carbon adsorption capacity 3.0% by mass, bulk density 0.14mg/L) after surface treatment with hexamethyldisilazane , Japan Aerosil Co., Ltd., trade name: AEROSIL R8200), hydrophobic dry silica after surface treatment with hexamethyldisilazane (specific surface area 140m ² /g, carbon adsorption capacity 2.3% by mass, bulk density 0.05g/mL, manufactured by Nippon Aerosil Co., Ltd., trade name: RX200), surface-treated hydrophobic dry-type fumed silica (specific surface area 190m ² /g, bulk density 0.05g/mL, average primary particle size 15nm, manufactured by Tokuyama Co., Ltd., trade name: Reolosil DM-10), surface-treated hydrophobic dry-type fumed silica (specific surface area 230m ² /g, bulk density 0.05g/mL, average primary particle size 7nm, manufactured by Tokuyama Co., Ltd., trade name: Reolosil DM-30), surface-treated hydrophobic dry-type fumed silica (specific surface area 230m ² /g, bulk density 0.05g/mL, average primary particle size 7nm, manufactured by Tokuyama Co., Ltd., trade name: Reolosil DM-30S), surface-treated hydrophobic dry-type fumed silica (specific surface area 230m ² /g, bulk density 0.05g/mL, average primary particle size 7nm, manufactured by Tokuyama Co., Ltd., product name: Reolosil DM-30S), product name "Reolosil HM20S" (manufactured by Tokuyama Co., Ltd., average primary particle size 12nm), product name "Reolosil HM30S" (Tokuyama Co., Ltd. ), with an average primary particle size of 7 nm), product name "Reolosil HM40S" (Tokuyama Co., Ltd., average primary particle size 7 nm), product name "Reolosil ZD30S" (Tokuyama Co., Ltd., average primary particle size 7 nm) )wait.

The addition amount when adding (D) component is preferably 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 mass parts. Within this range, a composition with excellent operability such as viscosity increasing, thixotropy, and fluidity can be formed.

The silicone-modified polyimide resin composition of the present invention can be adjusted to a more suitable viscosity by adjusting the amount of hydrophobic fumed silica and the coating method. For example, in the case of using a dispenser or dipping method, the viscosity is preferably around 500-10,000mPa·s (25°C), and it is difficult to use when using screen printing and other methods. A viscosity of 10,000 to 100,000mPa·s (25°C) that causes liquid vertical flow is preferable. However, depending on the difference in coating equipment, the usable viscosity is also different, so it is not limited to the above viscosity.

The polysiloxane-modified polyimide resin composition of the present invention, for example, dissolves (A) polysiloxane-modified polyimide resin in (C) solvent to obtain polysiloxane-modified After the polyimide resin solution, add (B) curing agent, and if necessary, additional (C) solvent and (D) hydrophobic fumed silica, and then stir it.

The polysiloxane-modified polyimide composition prepared in this way can be formed into a thin film by casting method or the like. The curing conditions of the polysiloxane-modified polyimide resin composition of the present invention are not particularly limited. The curing temperature is preferably 40-200°C, more preferably 50-150°C, and the curing time is preferably 1 to 300 minutes, more preferably 10 to 240 minutes.

The polysiloxane-modified polyimide resin composition of the present invention, as mentioned above, is a type that can provide good adhesion to various metal frames, and has high moisture resistance, low elasticity, and high heat resistance. Specifically, it is also a composition that can produce (α) storage elastic modulus at 25°C of 100-1,000 MPa, (β) glass transition point (Tg) of 100-200°C, ( γ) A cured product with excellent properties such as a water vapor transmission rate at 40°C of 20 g/m ² ·day or less, and (δ) a 5% weight loss temperature of 420°C or higher. The polysiloxane-modified polyimide resin composition of the present invention used in the hardened product is suitable for use as an adhesive or a coating agent. This adhesive or coating agent can be used in electronic materials, optical materials, and vehicle-mounted equipment, and is particularly suitable for use in areas requiring high reliability of semiconductor devices.

(5) Manufacturing method of diamine-modified polysiloxane In the composition of the present invention, the above-mentioned diamine-modified polysiloxane that can be used as the raw material of the polyimide resin modified by the formula (1) can be exemplified: the polysiloxane of the above-mentioned formula (2) Diamine-modified polysiloxane represented by the following formula (4) with amine groups bonded to both ends, etc.

(式中，R¹ ～R⁴ 、m及n與上述為相同之意義，R^C 表示由下述之基所選出的2價之基；又，m、n所附之括弧內之矽氧烷單位之配列，可為無規、交互或嵌段之任一者)

(In the formula, R ¹ to R ⁴ , m and n have the same meanings as above, R ^C represents a divalent group selected from the following groups; and the siloxane in brackets attached to m and n The arrangement of units can be any of random, alternating or block)

(式中，J表示碳原子數2～6之伸烷基，附有波浪線之線表示鍵結鍵；J鍵結的鍵結鍵為鍵結於矽原子，其他的鍵結鍵為鍵結於Im)。

(In the formula, J represents an alkylene group with 2 to 6 carbon atoms, and the line with a wavy line represents a bonding bond; the bonding bond of J bonding is bonding to a silicon atom, and the other bonding bonding is bonding in Im).

The above-mentioned alkylene groups with 2 to 6 carbon atoms include, for example, ethylene, trimethyl, propyl, tetramethyl, pentamethyl, hexylene, etc. good.

The polysiloxane modified by the diamine group represented by the above formula (4) can be obtained through the step (i) Groove Heck reaction, step (ii) hydrogenation reaction, and step (iii) accompanied by siloxane cracking and rebonding. Polymerization can be obtained.

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

(式中，R¹ 及R² 與上述為相同之意義，K表示末端具有不飽合基的碳原子數2～6之1價之脂肪族不飽合烴基)。

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

(式中，LG表示具有解離基之機能的1價之官能基)。

(In the formula, LG represents a monovalent functional group having the function of a dissociated group).

(式中，R¹ 、R² 及R^C 與上述為相同之意義)。

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

In formula (5), specific examples of a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms containing an unsaturated group at the end of K include ethylene, prop-2-en-1-yl (prop -2-en-1-yl), but-3-en-1-yl (but-3-en-1-yl), pent-4-en-1-yl (pent-4-en-1-yl ), hex-5-en-1-yl (hex-5-en-1-yl), etc., vinyl is preferred. The dissociation group LG in the formula (7) can be any substituent having the function of a known dissociation group, for example, chlorine, bromine, iodine, methanesulfonyl, toluenesulfonyl, trifluoromethanesulfonyl, Aminobenzenesulfonyl, etc.

(G) Transition metals in transition metal organic complex catalysts include, for example, iron, nickel, copper, rhodium, ruthenium, palladium, tungsten, iridium, platinum, etc., and nickel or palladium is preferred. The ligand of the transition metal complex catalyst can be enumerated as: a neutral phosphine ligand of two seats, a neutral phosphine ligand of a single seat, a neutral π ligand, a Valence anionic ligands, divalent anionic ligands, single-seat neutral amine ligands, two-seat neutral amine ligands, neutral nitrile ligands, neutral sulfinyl ligands At least one kind selected from a group consisting of a base, a ligand composed of two neutral carbonyl-alkenes, etc., can also undergo ligand exchange in the reaction system depending on the reaction conditions. In particular, it is preferable to form a nickel or palladium complex in a coordination system in which the valence of nickel or palladium is 0 or 2.

Preferable ligands include those shown below, but are not limited thereto. Two neutral phosphine ligands: 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphine) base) butane, 1,1'-bis(diphenylphosphino)ferrocene, etc. Single-seat neutral phosphine ligand: 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 ligands: methyl, phenyl, hexamethylcyclopentadienyl, pentamethylcyclopentadienyl, allyl, cyclopentadienyl, alkoxy, fluorine atom, Chlorine atom, bromine atom, iodine atom, carboxylate, acetylacetone (salt), trifluoromethanesulfonate, 1,3-bis(2,6-di-isopropylphenyl)-4,5- Dihydroimidazole-2-line (lidene), 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-line, 1,3-bis(2,4,6-trimethylphenyl) imidazole-2-line, etc. Divalent anionic ligands: phthalocyanine, naphthalocyanine, porphyrin, etc. Single-seat neutral amine ligands: ammonia, pyridine, 3-chloropyridine, etc. Two neutral amine ligands: N,N,N',N'-tetramethylethylenediamine, 1,10-phenanthroline, 2,2'-bispyridyl, etc. Neutral nitrile ligands: acetonitrile, benzonitrile, etc. Neutral sulfinyl ligand: 1,2-bis(phenylsulfinyl)ethane, etc. A ligand composed of two neutral carbonyl-alkenes: dibenzylidene acetone, etc.

(G) The amount of transition metal organic complex catalyst used is 0.01 to 5 mol% relative to (E) compound (5). When (F) compound (6) or (7), due to relative (E) Compound (5) is theoretically a reaction of 2 molar equivalents, so (F) compound (6) or (7) is used in an amount of 2 to 2.5 molar equivalents, but in 2.05 to 2.2 It is preferably below the molar equivalent.

、喹啉等。 無機鹼之具體例，可列舉如：碳酸鋰、碳酸鈉、碳酸鉀等的鹼金屬碳酸鹽；碳酸氫鋰、碳酸氫鈉、碳酸氫鉀等的鹼金屬碳酸氫鹽；碳酸鎂、碳酸鈣等的第2族金屬碳酸鹽；氫氧化鋰、氫氧化鈉、氫氧化鉀等的鹼金屬氫氧化物鹽；氫氧化鎂、氫氧化鈣等的第2族金屬氫氧化物鹽等。 該些之中，(H)鹼，又以三乙胺、二異丙基乙胺、1,8-二氮雜雙環-[5,4,0]-7-十一烯(DBU)、碳酸鈉、碳酸鉀為佳。 (H)成份之使用量，相對於(E)化合物(5)，為2.0～3.0莫耳當量，較佳為2.1～2.6莫耳當量。(H) The base may be an organic base or an inorganic base. Specific examples of organic bases include: triethylamine ( _Et3N ), 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'-tetramethylethylenedi Amine (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-colin base, N,N-dimethylaminopyridine (DMAP), pyridine

, quinoline, etc. Specific examples of inorganic bases include: alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate; magnesium carbonate, calcium carbonate, etc. Group 2 metal carbonates; alkali metal hydroxide salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.; Group 2 metal hydroxide salts such as magnesium hydroxide, calcium hydroxide, etc. Among them, (H) base, triethylamine, diisopropylethylamine, 1,8-diazabicyclo-[5,4,0]-7-undecene (DBU), carbonic acid Sodium and potassium carbonate are preferred. The usage-amount of (H) component is 2.0-3.0 molar equivalents with respect to (E) compound (5), Preferably it is 2.1-2.6 molar equivalents.

(I) The solvent is preferably an aprotic polar solvent from the viewpoint of suppressing side reactions. Specific examples of polar solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; dioxane, dioxolane, tetrahydrofuran, 1,2-dimethoxy ethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis-2-(2-methoxyethoxy)ethyl ether, Ether solvents such as 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 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-extended Ester solvents such as butyl glycol acetate (1,3-BGDA) and 1,6-hexanediol diacetate (1,6-HDDA); dimethylformamide, dimethyl Amide-based solvents such as acetamide, N-methylpyrrolidone, N-methylcaprolactam, and 1,3-dimethyl-2-imidazolinone, etc. may be used alone, You may use it in combination of 2 or more types. Among these, tetrahydrofuran and dimethylformamide are preferable. (I) The solvent is used in such an amount that the concentration of (E) compound (5) reaches 0.1-5.0 mol/L.

Step (ii) is, (J) compound (8) obtained in step (i), in (K) Transition metal catalyst: 0.001 to 1 mol% in terms of metal content relative to compound (8) The step of performing a hydrogenation reaction in the presence of the following formula (9) to obtain a compound represented by the following formula (9) (hereinafter also referred to as compound (9)).

(式中，R¹ 、R² ，及R^C 與上述為相同之意義)。

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

(K) Transition metal catalysts are preferably immobilized by a carrier in view of being easy to remove and remove by means of filtration or the like after the reaction, and in view of recyclability and reuse. Examples of the carrier for immobilization include water-containing or dry activated carbon (C), alumina (Al ₂ O ₃ ), silicon dioxide (SiO ₂ ), and the like. These carriers also have the effect of adsorbing and removing impurities or coloring in the reaction system.

Specific examples of transition metal catalysts supported by 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, etc. Specific examples of transition metal catalysts supported by 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 , etc. Specific examples of transition metal catalysts supported by silicon dioxide (SiO ₂ ) include: Ni/SiO ₂ , Pd/SiO ₂ , Pt/SiO ₂ , Co/SiO ₂ , Rh/SiO 2 , Ir/SiO ₂ , SiO ₂ , Ru/SiO ₂ , Cu/SiO ₂ , Ag/SiO ₂ , Au/SiO ₂ , etc.

Among them, 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 , and Pt/SiO ₂ are preferred. From the viewpoint of easy acquisition, Pd/C, Pt/C, Rh/C, Pt-Pd/C, Pd/Al ₂ O ₃ , and Pt /Al ₂ O ₃ is preferred, and Pd/C and Pt/Al ₂ O ₃ are more preferred from the viewpoint of reactivity.

Also, these fixed transition metal catalysts can be produced by Ne-Chemcat (stock), Chuanyan Fine Chemical (stock), Sigma-Aldrich Japan Co., Ltd., Wako Pure Chemical Industry (stock), Tokyo Chemical Industry (stock), Evonik Japan Co., Ltd., etc. are commercially available, and these can be used alone, in admixture, or in the form of a composite catalyst.

(K) The amount of transition metal catalyst used is 0.001-1 mole % relative to (J) compound (8), based on metal content, and 0.001-0.1 mole when considering filterability or catalyst cost % is better.

In addition, step (ii) can also be hydrogenated under atmospheric pressure in the presence of the following (J) to (M). (J) compound (8) obtained in step (i), (K) Transition metal catalyst: based on metal content, 0.001-1 mol% (L) tertiary alkylamine compounds: less than 2 molar equivalents, and (M) Formic acid or formate: make the reaction mixture reach pH 7 or more In addition, the usage-amount of (K) and (L) is a ratio with respect to compound (8).

(L) Specific examples of tertiary alkylamine compounds include: trimethylamine, triethylamine (Et ₃ N), diisopropylethylamine (DIPEA), tri-n-butylamine, tri-n-pentylamine Amine, 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), etc., among them, triethylamine, diisopropylethylamine, 1,8-diazabicyclo-[5,4 ,0]-7-undecene (DBU) is preferred, and triethylamine is preferred.

(L) The amount of tertiary alkylamine compound added is more than 0 molar equivalent and less than 2 molar equivalent relative to compound (8), preferably 0.5-1.5 molar equivalent, and 1 molar equivalent is better. When it is 0 molar equivalent, the reaction cannot be carried out, when it is less than 0.5 molar equivalent, the reaction may be delayed, and when it is greater 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 salts 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, etc. Among these, formic acid, ammonium formate and sodium formate are preferable, and formic acid is more preferable. These formic acids and formate salts are readily available as commercially available products from Wako Pure Chemical Industries, Ltd. and the like.

(M) The amount of formic acid or formate used is such that the pH of the reaction mixture will not be shifted to the acidic side. That is, the amount of (M) formic acid or formate salt used is such that the reaction liquid mixture becomes pH 7 or higher, preferably pH 7-pH10, more preferably pH 7-pH9. Excessive addition will cause the reaction system to become acidic, and the unsubstituted or substituted alkenyl ether will be decomposed by acid to generate aldehydes. It is preferable to add the amount to be less than equimolar equivalent to (L) tertiary alkylamine compound, because formic acid or formate will be decomposed and evaporated during the hydrogenation reaction, so it is also During the reaction, (M) formic acid or a formate salt can be added in an amount that does not cause the reaction solution to shift from pH 7 to the acidic side.

In step (ii), when using a solvent, it is better to use a polar organic solvent. Polar organic solvents include, for example, amide compounds, nitrile compounds, ketone compounds, alcohol compounds, straight chain, branched or cyclic saturated or unsaturated solvents with 1 to 8 carbon atoms, Among the hydrocarbon compounds, ether compounds in which 1 to 3 carbon atoms are substituted by oxygen atoms, etc., among them, straight chain, branched or cyclic nitrile compounds and alcohol compounds having 1 to 6 carbon atoms are preferable.

Specific examples of these polar organic solvents include: N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc), 1,3-dimethyl -2-imidazolinone (DMI), 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-imidazolinone (DMPU), acetone, methyl ethyl ketone (MEK) , methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cyclopentanone, cyclooctanone, methyl cyclopentanone, 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-butanol, i-butanol , sec-butanol, t-butanol, ethylene glycol, propylene glycol, 1,2-dihydroxypropane, 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, etc. Among these, DMF, acetone, THF, and IPA are preferred.

Also, when the reaction is carried out from the step (i) to in situ, the solvent used in the step (i) can be used. In addition, in the hydrogenation reaction, when it is desired to accelerate the reaction in a polar solvent, the above-mentioned polar solvent may be further added.

As the hydrogen source for the above hydrogenation reaction, hydrogen gas can be used. The hydrogenation reaction is preferably carried out at 1 atmosphere. From the point of view of using hydrogen in a safe storage state, use the Q-Tube(TM) glass pressure pump manufactured by Sigma-Aldrich Japan Co., Ltd., or the air pressure adjustment diffuser manufactured by Sugiyama-Gen Co., Ltd. good. The reaction temperature is preferably 20-60°C, more preferably 30-50°C.

^{Step (iii) is, (N) compound (9) obtained in step (ii), (O) a cyclic siloxane (R 1 and R 2} and The above is the same content): -[R ¹ R ² SiO]-unit is equivalent to 0-5 molar equivalents, (P) Cyclic siloxane formed by -[R ³ R ⁴ SiO]-unit (R ³ and R ⁴ are the same as above): -[R ³ R ⁴ SiO]- unit is equivalent to 0.25 to 5 molar equivalents, in the presence of (Q) organic base catalyst: 0.01 to 5% by mass Carrying out the reaction to prepare the polysiloxane modified by the diamine group represented by the formula (4). In addition, the usage-amount of (O), (P) and (Q) is a ratio with respect to compound (9).

(O) Specific examples of cyclic siloxanes formed by -[R ¹ R ² SiO]- units include: hexamethyltrisiloxane, nonamethylcyclotetrasiloxane, decamethyl Pentasiloxane, etc. (P) Specific examples of cyclic siloxanes formed from -[R ³ R ⁴ SiO]- units include: 1,3,5,7-tetramethyl-1,3,5,7- Tetraethylenecyclotetrasiloxane, 1,3,5-trimethyl-1,3,5-triethylenecyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3, 5,7,9-pentaethylenecyclotetrasiloxane, etc.

(Q) Organic base catalysts, such as: quaternary alkyl ammonium salts and the like. Specific examples of quaternary alkylammonium salts include tetrabutylammonium hydride, tetramethylammonium hydride, and the like. The amount of organic base catalyst used is 0.01 to 5% by mass relative to compound (9), and additional amount can be used as long as it does not exceed 5% by mass of the total amount added during the reaction.

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

(式中，m及n與上述為相同之意義)。

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

[Example]

Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples, but the present invention is not limited by these examples. In addition, in this example, the molecular weight was measured using the GPC apparatus HLC-8320GPC manufactured by Tosoh Co., Ltd., and the mobile phase used tetrahydrofuran (THF) and performed polystyrene conversion. The infrared absorption spectrum (IR) was measured using NICOLET6700 (manufactured by Thermo Fisher Scientific Co., Ltd.). For ¹ H NMR measurement, AVANCE III manufactured by Bruker Biospin was used. The glass transition point was measured using DMS7100 manufactured by Hitachi High-Tech Co., Ltd., and the temperature at which tan δ reached the maximum was used as the glass transition point. The temperature at which the weight decreased by 5% was measured using TGA Q-500 manufactured by TA Instruments. The viscosity at 25° C. was measured using a rotary viscometer. In addition, in the following examples, "part" means a part by mass.

[1] Synthesis of raw material compounds [Synthesis Example 1] 212 g of 1-bromo-4-nitrobenzene (1.05 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) , 1,3-diethylene-1,1,3,3-tetramethyldisiloxane 93g (0.5mol, manufactured by Tokyo Chemical Industry Co., Ltd.), potassium carbonate 165g (1.2mol, manufactured by Wako Pure Chemical Industry Co., Ltd. )), and N,N-dimethylformamide 1,000mL (0.5M, Wako Pure Chemical Industries Co., Ltd.), after argon substitution, add tris(benzylideneacetone)dipalladium(0) 45 mg (0.01 mol%, Sigma Aldrich Japan Co., Ltd.). The temperature of the reaction mixture was raised to 100°C, and the reaction was carried out at this temperature for 6 hours. After confirming that the peak due to vinyl groups at 5.2 ppm disappeared using ¹ H NMR, the temperature was returned to 25° C., filtered using No. 2 filter paper, and then neutralized by adding 1 M potassium hydrogensulfate aqueous solution and butyl acetate. Thereafter, the butyl acetate layer was separated, and the aqueous layer was extracted twice with butyl acetate. After the obtained butyl acetate layer was concentrated, it was washed continuously with 1M aqueous sodium thiosulfate solution and saturated saline, then anhydrous sodium sulfate, silica gel and a stirrer were added, and stirred at 25°C for 12 hours. Thereafter, filter with No. 2 filter paper, distill off the solvent, remove the precipitated solid (1-bromo-4-nitrobenzene), recrystallize in a hexane-butyl acetate mixed solution, and 1-Bromo-4-nitrobenzene was taken out and removed. The solvent was distilled off and dried under reduced pressure to obtain 193 g of dinitro-modified disiloxane represented by the following formula as a brown solid (90% yield). 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 gas introduction tube, and a stirrer, and dissolved with argon gas. After 181 mg (0.01 mol %) of 5% Pd/C (50% wet product, Wako Pure Chemical Industries, Ltd.) was added thereto, hydrogen substitution was performed. The hydrogenation reaction was carried out at 25° C. for 12 hours, and the reaction was terminated after confirming the disappearance of the olefin signal and the displacement of the proton on the aromatic ring by ¹ H NMR. The catalyst was filtered out from the reaction mixture, and the solvent was distilled off to obtain 159 g of a yellow oily diamine-modified disiloxane represented by the following formula (95% yield). 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，括弧內之矽氧烷單位的配列順序並無特定)。[Synthesis Example 3] Add 37 g (0.1 mol) of the diamino-modified disiloxane obtained in Synthesis Example 2 and 30 g of nonamethylcyclotetrasiloxane into a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube and a stirrer (0.1mol, produced by Tokyo Chemical Industry Co., Ltd.), 1,3,5,7-tetramethyl-1,3,5,7-tetraethylenecyclotetrasiloxane 34g (0.1mol, produced by Tokyo Chemical Industry Co., Ltd. )), 3.7 g of tetrabutylammonium hydride (0.10 parts, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100° C. for 12 hours. After cooling to 25° C., the volatile components were distilled off under reduced pressure to obtain 79 g (yield: 78%) of light yellow polysiloxane modified with diamine groups represented by the following formula (i). The obtained diamine-modified polysiloxane had an amine equivalent weight of 998 mol/g.

(In the formula, the arrangement order of the siloxane units in brackets is not specified).

[Synthesis Example 4] 44.4 g (0.1 mol, Tokyo Chemical Industry Co., Ltd.), 4,4'-(4,4'-isopropadienediphenyl-1,1'-diyldioxy)diphenylamine (2,2-bis[4-( 4-aminophenoxy)phenyl]propane) 12.3g (0.03mol, manufactured by Tokyo Chemical Industry Co., Ltd.), phthalic anhydride 1.48g (0.01mol, manufactured by Wako Pure Chemical Industries, Ltd.), and cyclo 396g of hexanone, after stirring at 25°C for 2 hours, then at 25°C, drop 139.7g (0.07mol) of the polysiloxane modified with the diamine group shown in the above formula (i) obtained in Synthesis Example 3 After the dropwise addition, stir at 25°C for 12 hours. After completion of the stirring, 40 g of toluene was added to the reaction container, and azeotropic dehydration was performed at 145°C. Toluene was dropped into the obtained reaction solution, and polysiloxane-modified polyimide resin was obtained through reprecipitation. In the infrared absorption spectrum of this resin, no absorption peaks due to unreacted polyamic acid were observed, and it was confirmed that there were imide group absorption peaks at 1,780 cm- ¹ and 1,720 cm- ¹ . Moreover, the weight average molecular weight of this resin measured using GPC was 26,500.

[Synthesis Example 5] Add 44.4 g (0.1 mol) of hexafluorodianhydride (6FDA), 4,4'-(4,4'-isopropanedi Diphenyl-1,1'-diyldioxy)diphenylamine 14.4g (0.035mol), phthalic anhydride 1.48g (0.01mol), and cyclohexanone 380g, stirred at 25°C for 2 hours, At 25°C, add 129.7 g (0.065 mol) of polysiloxane modified with diamine groups represented by the above formula (i) obtained in Synthesis Example 3 dropwise, and stir at 25°C for 12 hours after the dropping is completed . After completion of stirring, 38 g of toluene was added to the reaction container, and azeotropic dehydration was performed at 145°C. The resulting reaction solution was dropped into methanol for reprecipitation to obtain a polysiloxane-modified polyimide resin with a siloxane content of 55% by mass. In the infrared absorption spectrum of this resin, no absorption peaks due to unreacted polyamic acid were observed, and it was confirmed that there were imide group absorption peaks at 1,780 cm- ¹ and 1,720 cm- ¹ . Moreover, the weight average molecular weight of this resin measured using GPC was 24,500.

[Synthesis Example 6] Add 44.4 g (0.1 mol) of hexafluorodianhydride (6FDA), 4,4'-(4,4'-isopropanedi Diphenyl-1,1'-diyldioxy)diphenylamine (2,2-bis[4-(4-aminophenoxy)phenyl]propane) 12.3g (0.03mol), xylylene 1.48g (0.01mol) of acid anhydride and 336g of cyclohexanone were stirred at 25°C for 2 hours, then 112.0g (0.07 mol), after the dropwise addition, stirred at 25°C for 12 hours. After completion of stirring, 56 g of toluene was added to the reaction container, and azeotropic dehydration was performed at 145°C. The resulting reaction solution was dropped into methanol for reprecipitation to obtain a polysiloxane-modified polyimide resin with a siloxane content of 79% by mass. In the infrared absorption spectrum of this resin, no absorption peaks due to unreacted polyamic acid were observed, and it was confirmed that there were imide group absorption peaks at 1,780 cm- ¹ and 1,720 cm- ¹ . Moreover, the weight average molecular weight of this resin measured using GPC was 36,000.

(式中，括弧內之矽氧烷單位的配列順序並無特定)。

(In the formula, the arrangement order of the siloxane units in brackets is not specified).

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

[Examples 2 to 7 and Comparative Examples 1 to 4] Except for changing the composition shown in Table 1, the others were all according to the same method as in Example 1, to obtain a polysiloxane-modified polyimide resin.

Table 1 shows the composition content and the viscosity system of the composition at 25° C. of the above-mentioned examples and comparative examples. In addition, the abbreviations etc. of each component in a table|surface are as follows. ・Perbutyl O: t-Butylperoxy-2-ethylhexanoate manufactured by NOF Co., Ltd. ・V-601: Dimethyl 2,2'-azobis(2-methylpropionate) manufactured by Wako Pure Chemical Industries, Ltd. ・Kayalene 6-70: 1,6-bis(t-butyl-peroxycarbonyloxy)hexane manufactured by Kayaku AKZO Co., Ltd. ・Reolosil DM-30S: Hydrophobic dry-type fumed silica manufactured by Tokuyama Co., Ltd. ・Propylene glycol monomethyl ether acetate (PGMEA)

Adhesion and storage elastic modulus were measured and evaluated for the cured products of the compositions prepared in the above-mentioned examples and comparative examples according to the following methods. These results are described in Table 2 together with the glass transition point, the temperature at which the weight decreased by 5%, and the like. (1) Adhesion Coat the silicone-modified polyimide resin composition on various substrates with a thickness of 80 μm, and then proceed in the order of 50°C/30 minutes, 100°C/60 minutes, 150°C/120 minutes heat hardening to obtain a hardened film. The adhesiveness of the film was evaluated by the checkerboard hole peeling test (JIS K5400), and the number X of holes remaining in 100 meshes was expressed as (X/100). Glass plate: Manufactured by Matsunami Glass Industry Co., Ltd. Oxygen-free copper plate: manufactured by Standard Test Sample Co., Ltd. (2) Storage elasticity rate Coat the silicone-modified polyimide resin composition on a fluorine-coated iron plate, and heat-cure in the order of 50°C/30 minutes, 100°C/60 minutes, and 150°C/120 minutes. Thus, a sheet having a thickness of 0.3 mm was obtained. The storage modulus of the sheet was measured using DMS7100 manufactured by Hitachi High-Tech Co., Ltd.

Also, the water vapor transmission rate of the cured products of the compositions obtained in the above-mentioned Examples 1, 4, 5 and 7 was measured according to the following method. The results are shown in Table 3. (3) Water vapor permeability The polysiloxane-modified polyimide resin composition prepared in accordance with Examples 1, 4, 5 and 7 was coated on a fluorine-coated iron plate, followed by 50°C/30 minutes, 100 ℃/60 minutes, 150 ℃/120 minutes for thermal curing in order to obtain a 1mm thick sheet. The water vapor transmission rate of the sheet was measured at 40° C. (JIS K7129A) using an L80-5000 water vapor transmission rate meter (manufactured by Systech Instruments). The results are shown in Table 3.

As shown in Table 2, the cured products obtained from the compositions obtained in Examples were found to have excellent adhesion to glass plates and copper plates, and were comparable to those obtained from the compositions of Comparative Examples. Compared with hardened products, it also has high elastic modulus and excellent heat resistance. Also, as shown in Table 3, it is known that the cured products obtained from the compositions of Examples 1, 4, 5, and 7 have low water vapor transmission rates.

Claims (14)

A polysiloxane-modified polyimide resin composition, characterized in that it contains: (A) a polysiloxane-modified polyimide resin represented by the following formula (1): 100 parts by mass, Ee- Ff-Gg (1) {In the formula (1), E, F and G are repeating units bonded in a random state; E is produced by the polysiloxane modified by the diamine group shown in the formula (2) The base of valence; F is the base of 2 valences produced by tetracarboxylic dianhydride shown in formula (3); G is the base of 2 valences produced by diamine; Wherein, f+e+g=100mol%, f/ The mol ratio of (e+g) is 0.9~1.1, when the sum of aforementioned e and g is 100, aforementioned e is 30~90;

(In formula (2), R ^A represents independently arylene alkylene with 8 to 12 carbon atoms; R ¹ and R ² represent independently substituted or unsubstituted carbons that do not have aliphatic unsaturated bonds A monovalent hydrocarbon group with 1 to 10 atoms; R ³ and R ⁴ represent independently substituted or unsubstituted monovalent hydrocarbon groups with 1 to 10 carbon atoms, but at least one of R ³ and R ⁴ is aliphatic Unsaturated bond; m is 0~20, n is 1~20, and is an integer satisfying m+n=1~40; and the arrangement of siloxane units in brackets attached to m and n can be Any one of random, alternating or block)-Im-X-Im- (3) [In the formula (3), Im represents a cyclic base containing a cyclic imide structure at the end; Single bond, -O-, -S-, -S(→O)-, -S(=O) ₂ -, -C(=O)-, -NR ^N -(R ^N represents carbon number 1~12 monovalent hydrocarbon group), -CR ^B ₂ -(R ^B represents independent monovalent hydrocarbon groups with 1 to 12 carbon atoms that may contain hydrogen atoms or halogen atoms), -R ^Ar _h -(R ^Ar represents the number of carbon atoms 6~12 divalent aryl extension; h represents an integer of 1~6; when h is 2 or more, R ^Ar can be the same or different from each other), -R ^Ar _h -(OR ^Ar ) _i -( R ^Ar and h represent the same meaning as the above; i represents an integer from 1 to 5), linear or branched alkylene with 1 to 12 carbon atoms, and cycloalkylene with 5 to 12 carbon atoms group, and a divalent group selected from an arylene group with 7 to 12 carbon atoms]} (B) curing agent: 0.1 to 10 parts by mass, and (C) solvent: 100 to 700 parts by mass. The polysiloxane-modified polyimide resin composition as claimed in claim 1, wherein the aforementioned R ^A is a group selected from the following groups;

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

(In the formula, the line with the wavy line represents the bond; the bond bonded by the nitrogen atom is bonded to E or G, and the other bonds are bonded to X). Such as the polyimide resin composition modified by polysiloxane according to claim 1 or 2, in the divalent group generated by the diamine represented by the aforementioned G, the diamine is selected from the group consisting of tetramethylenediamine, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diamino Diphenyl ether, 2,2-bis(4-aminophenyl)propane, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. Such as the polysiloxane-modified polyimide resin composition of claim 1 or 2, wherein, the weight average of the polysiloxane-modified polyimide resin shown in the formula (1) of the aforementioned (A) component The molecular weight is 10,000~100,000. The silicone-modified polyimide resin composition according to Claim 1 or 2, wherein the curing agent of the aforementioned component (B) is a thermally decomposable free radical initiator. The silicone-modified polyimide resin composition as claimed in claim 1 or 2, wherein (D) the bulk density is less than 1 g/mL, the average primary particle size is 1-100 nm, and the BET specific surface area is 100 The hydrophobic fumed silica of ~300 m ² /g is contained in 3 to 50 parts by mass relative to 100 parts by mass of the component (A). For example, the silicone-modified polyimide resin composition of claim 1 or 2 has a viscosity of 100-100,000 mPa‧s at 25°C. A hardened product, which is the polysiloxane-modified polyimide resin composition according to any one of claims 1-8. The hardened product of Claim 9, which is: (α) storage elastic modulus at 25°C of 100-1,000 MPa, (β) glass transition point (Tg) of 100-200°C, (γ) water at 40°C The vapor transmission rate is 20g/m ² ‧day or less, and the temperature at which (δ) decreases by 5% by weight is 420°C or higher. An adhesive, characterized in that it is formed of the polysiloxane-modified polyimide resin composition according to any one of claims 1-8. A coating agent, characterized in that it is formed of the polysiloxane-modified polyimide resin composition according to any one of claims 1-8. A method for producing polysiloxane modified with diamine groups represented by the following formula (4), characterized by comprising the following steps (i) to (iii):

[In the formula, R ¹ and R ² represent independently substituted or unsubstituted monovalent hydrocarbon groups with 1 to 10 carbon atoms without aliphatic unsaturated bonds; R ³ and R ⁴ represent independently substituted Or an unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, but at least one of ^R3 and ^R4 has an aliphatic unsaturated bond; R ^C represents a divalent group selected from the following groups:

(In the formula, J represents an alkylene group with 2 to 6 carbon atoms, and the line with a wavy line represents a bond; the bond of J bond is bonded to a silicon atom, and the other bonds are bonds In Im) m is 0~20, n is 1~20, and is an integer satisfying m+n=1~40; and the arrangement of siloxane units in brackets attached to m and n can be random , any one of interaction or block]; (i) (E) the compound shown in the following formula (5):

(wherein, R ¹ and R ² represent the same meaning as above, and K is a monovalent aliphatic unsaturated hydrocarbon group with 2 to 6 carbon atoms having an unsaturated group at the end), (F) the following Formula (6) or the compound shown in the following formula (7): relative to the compound shown in the aforementioned formula (5), it is 2.0 ~ 2.5 molar equivalents,

(In the formula, LG represents a monovalent functional group independently having the function of a dissociative group), in (G) transition metal organic complex catalyst: relative to the compound shown in the aforementioned formula (5), depending on the content of the metal 0.01 ~ 5 mole %, (H) base: 2.0 ~ 3.0 mole equivalents relative to the compound shown in the aforementioned formula (5), and (I) solvent: make the concentration of the compound shown in the aforementioned formula (5) reach 0.1 React under the presence of the amount of ~5.0 mol/L, and make the step of the compound shown in following formula (8);

(wherein, R ¹ , R ² and R ^C represent the same meanings as above) (ii) (J) the compound represented by the aforementioned formula (8) prepared in the aforementioned step (i), in (K) Transition metal catalyst: relative to the compound represented by the aforementioned formula (8), the hydrogenation reaction is carried out in the presence of a metal content of 0.001-1 mol%, and the step of preparing the compound represented by the following formula (9);

(wherein, R ¹ , R ² , and R ^C represent the same meanings as above) (iii) (N) the compound represented by the aforementioned formula (9) prepared in the aforementioned step (ii), (O) Cyclic siloxane formed by -[R ¹ R ² SiO]-units (in the formula, R ¹ and R ² represent the same meaning as above): Relative to the compound shown in the aforementioned formula (9), -[ R ¹ R ² SiO]-unit is equivalent to 0~5 molar equivalents, (P) Cyclic siloxane formed by -[R ³ R ⁴ SiO]-unit (wherein, R ³ and R ⁴ Representing the same meaning as above): relative to the compound shown in the aforementioned formula (9), -[R ³ R ⁴ SiO]-units are in the amount of 0.25~5 molar equivalents, in (Q) organic base catalyst: relative The compound represented by the aforementioned formula (9) is reacted in the presence of 0.01-5% by mass to obtain the diamine-modified polysiloxane represented by the aforementioned formula (4). The method for producing diamine-modified polysiloxane as claimed in item 13, wherein the aforementioned step (ii) is: (J) the compound represented by the aforementioned formula (8) prepared in the aforementioned step (i), in (K) Transition metal catalyst: relative to the compound represented by the aforementioned formula (8), the content of the metal is 0.001~1 mol% (L) tertiary alkylamine compound: relative to the compound shown in the aforementioned formula (8), it is greater than 0 molar equivalent and less than 2 molar equivalent, and (M) formic acid or formate: make the reaction mixture reach In the presence of an amount of pH 7 or higher, it is carried out under atmospheric pressure.