JP2009294536A - Photosensitive resin composition and method for joining substrates - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of forming a pattern by a photolithography method characteristic of low moisture absorptivity and low moisture permeability, and excellent in adhesiveness with flexible substrates, and a method for joining substrates using the resin composition. <P>SOLUTION: The photosensitive resin composition includes (A) a polyamic acid that has a 5-20C alkylene chain, or an alicyclic skeleton for a main chain, (B) a photopolymerization compound, (C) a photopolymerization initiator, and (D) a silane compound containing an epoxy group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition suitably used as an adhesive for a flexible substrate. The present invention also relates to a method for bonding a substrate using the photosensitive resin composition.

  In recent years, adhesive resins have been used for bonding flexible substrates such as electronic paper and flexible printed wiring boards (for example, see Patent Document 1). As such an adhesive, for example, a non-photosensitive adhesive film patterned by die punching or a liquid UV curable photosensitive resin composition applied by screen printing is used. Further, along with the demand for miniaturization of parts, it is necessary to form further high-definition patterns for apparatus constituent members, and adhesive patterns by photolithography techniques are attracting attention.

As described above, the resin composition that can be formed by a photolithographic technique and used for laminating flexible substrates has a low water absorption in addition to the adhesive strength necessary for laminating flexible substrates. Sex is required. That is, for example, electronic paper has a problem that the conductive particles and insulating particles, which are display elements, are affected by humidity, and stable display characteristics cannot be obtained. Therefore, the adhesive may have low water absorption. It has been demanded.
JP 63-154780 A

  However, there has been no resin composition that has sufficient adhesive strength and low water absorption as a resin composition that can be formed by a photolithography technique and used for bonding flexible substrates.

  The present invention has been made in view of the above problems, a photosensitive resin composition capable of forming a pattern by a photolithography technique having low moisture absorption and moisture permeability and excellent adhesion to a flexible substrate, and It is an object of the present invention to provide a method for bonding a used substrate.

  In order to achieve the above object, the present invention provides (A) a polyamic acid having an alkylene chain or alicyclic skeleton having 5 to 20 carbon atoms in the main chain (hereinafter also simply referred to as “(A) polyamic acid”). And (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) an epoxy group-containing silane compound.

  Such a photosensitive resin composition is used as an interlayer adhesive for flexible substrates and the like. The said photosensitive resin composition can fully suppress a water absorption rate by having the said structure containing (A) polyamic acid which is a polyimide precursor. Moreover, by using the polyamic acid (A) that is a polyimide precursor, the photosensitive resin composition can obtain excellent solubility in a developer, and the cured product has excellent flexibility and bendability. Obtainable. Furthermore, the photosensitive resin composition can form a thick film with good resolution. Furthermore, this resin has adhesiveness by thermocompression bonding, and a hollow structure is formed when the substrates are bonded together. The hollow structure is moisture-proof by the surrounding resin composition, and can suppress various deteriorations in properties due to moisture absorption.

  In the photosensitive resin composition of the present invention, the (A) polyamic acid preferably has a structure represented by the following general formula (1).

［式（１）中、Ａｒ^１は４価の有機基であり、Ａｒ^２は２価の有機基であり、ｌは１以上の整数である。ただし、Ａｒ^１及びＡｒ^２のうち少なくとも一方は、Ａｒ^１が下記一般式（２）で表される４価の有機基であるという要件、又はＡｒ^２が下記一般式（３）で表わされる２価の有機基であるという要件を満たす。］

[In Formula (1), Ar ¹ is a tetravalent organic group, Ar ² is a divalent organic group, and l is an integer of 1 or more. However, at least one of Ar ¹ and Ar ² is a requirement that Ar ¹ is a tetravalent organic group represented by the following general formula (2), or Ar ² is represented by the following general formula (3). Satisfies the requirement of being a valent organic group. ]

［式（２）中、Ｘは炭素数５〜２０のアルキレン基を示し、Ｒ^１及びＲ^２は各々独立に炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｍ１及びｎ１は各々独立に０〜３の整数である。］

[In the formula (2), X represents an alkylene group having 5 to 20 carbon atoms, R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, m1 And n1 are each independently an integer of 0 to 3. ]

［式（３）中、Ｚは単結合又は２価の有機基を示し、Ｙ^１及びＹ^２はそれぞれ独立に炭素数５〜２０のアルキレン基を示す。］

[In Formula (3), Z represents a single bond or a divalent organic group, and Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms. ]

  Such a photosensitive resin composition can further reduce the water absorption after curing because the (A) polyamic acid has a structure represented by the general formula (1). Furthermore, this photosensitive resin composition is excellent in the sensitivity at the time of exposure, and obtains sufficient developability by containing the polyamic acid which has a structure represented by the said General formula (1) as (A) polyamic acid. In addition, a thick film can be formed with high resolution.

  In the photosensitive resin composition of this invention, it is preferable that said Z is group represented by either of following General formula (4), (5), (6).

［式（４）中、Ｒ^３は炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｍ２は０〜４の整数を示す。なお、ｍ２が２以上の場合、複数存在するＲ^３は同一でも異なっていてもよい。］

Wherein (4), ^{R 3} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 2 to 10 carbon atoms having 1 to 10 carbon atoms, m2 is an integer of 0-4. In addition, when m2 is 2 or more, a plurality of R ³ may be the same or different. ]

［式（５）中、Ｒ^４は炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｎ２は０〜４の整数を示す。なお、ｎ２が２以上の場合、複数存在するＲ^４は同一でも異なっていてもよい。］

Wherein (5), ^{R 4} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 2 to 10 carbon atoms having 1 to 10 carbon atoms, n2 is an integer of 0-4. In the case of n2 is 2 or more, R ⁴ existing in plural numbers may be the same or different. ]

［式（６）中、Ｒ^５は炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｐは０〜４の整数を示す。なお、ｐが２以上の場合、複数存在するＲ^５は同一でも異なっていてもよい。］

Wherein (6), ^{R 5} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 2 to 10 carbon atoms having 1 to 10 carbon atoms, p is an integer of 0-4. When p is 2 or more, a plurality of R ⁵ may be the same or different. ]

  In the photosensitive resin composition, the water absorption after curing can be further reduced when the Z is a group represented by any one of the following general formulas (4), (5), and (6). . Further, such a photosensitive resin composition has excellent sensitivity at the time of exposure because Z is a group represented by any one of the following general formulas (4), (5), and (6), and sufficient development. In addition, it is possible to form an image with a thick film with high resolution.

The present invention also includes: i) an exposure step of irradiating the above-mentioned photosensitive resin composition with an actinic ray to photocure the exposed portion; and ii) a temporary curing step of precuring the photosensitive resin composition after photocuring. And iii) an adhering step for adhering the substrates disposed via the photosensitive resin composition after temporary curing;
A method for bonding a substrate comprising:

  According to the bonding method of the present invention, since the above-described photosensitive resin composition is used, the bonding strength between the substrates to be bonded is sufficiently high, and the water absorption of the bonded portion is low.

  In the bonding method of the present invention, in the bonding step, it is preferable to bond the substrates disposed via the pre-cured photosensitive resin composition by thermocompression bonding. In the bonding method of the present invention, the substrate is preferably an organic film.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form a pattern with the photolithographic technique which is low in moisture absorption and moisture permeability, and is excellent in adhesiveness with a flexible substrate, and the adhesion method of a board | substrate using the same are obtained. . Furthermore, according to the photosensitive resin composition of this invention, an adhesive pattern can be collectively formed on a flexible substrate by photolithography, and it can adhere | attach with another flexible substrate by thermocompression bonding. Moreover, the completed hollow space is moisture-proof by the surrounding resin composition, and can suppress various characteristic deterioration by moisture absorption.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The photosensitive resin composition of the present invention contains (A) polyamic acid, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) an epoxy group-containing silane compound. Hereinafter, each component will be described in detail.

  (A) The polyamic acid has an alkylene chain or alicyclic skeleton having 5 to 20 carbon atoms in the main chain. The number of carbon atoms in the main chain of the alkylene chain is preferably 6 to 16, and more preferably 7 to 14. When the carbon number is less than 5, the water absorption rate and elastic modulus of the resin tend to increase. When the carbon number exceeds 20, the heat resistance and the like tend to decrease.

  As the (A) polyamic acid, a polyamic acid having a structure represented by the following formula (1) is particularly preferable.

［式（１）中、Ａｒ^１は４価の有機基であり、Ａｒ^２は２価の有機基であり、ｌは１以上の整数である。ただし、Ａｒ^１及びＡｒ^２のうち少なくとも一方は、Ａｒ^１が下記一般式（２）で表される４価の有機基であるという要件、又はＡｒ^２が下記一般式（３）で表わされる２価の有機基であるという要件を満たす。］

[In Formula (1), Ar ¹ is a tetravalent organic group, Ar ² is a divalent organic group, and l is an integer of 1 or more. However, at least one of Ar ¹ and Ar ² is a requirement that Ar ¹ is a tetravalent organic group represented by the following general formula (2), or Ar ² is represented by the following general formula (3). Satisfies the requirement of being a valent organic group. ]

［式（２）中、Ｘは炭素数５〜２０のアルキレン基を示し、Ｒ^１及びＲ^２は各々独立に炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｍ１及びｎ１は各々独立に０〜３の整数である。］

[In the formula (2), X represents an alkylene group having 5 to 20 carbon atoms, R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, m1 And n1 are each independently an integer of 0 to 3. ]

［式（３）中、Ｚは単結合又は２価の有機基を示し、Ｙ^１及びＹ^２はそれぞれ独立に炭素数５〜２０のアルキレン基を示す。］

[In Formula (3), Z represents a single bond or a divalent organic group, and Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms. ]

［式（４）中、Ｒ^３は炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｍ２は０〜４の整数を示す。なお、ｍ２が２以上の場合、複数存在するＲ^３は同一でも異なっていてもよい。］

［式（５）中、Ｒ^４は炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｎ２は０〜４の整数を示す。なお、ｎ２が２以上の場合、複数存在するＲ^４は同一でも異なっていてもよい。］

［式（６）中、Ｒ^５は炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｐは０〜４の整数を示す。なお、ｐが２以上の場合、複数存在するＲ^５は同一でも異なっていてもよい。］ Furthermore, in the above general formula (3), Z is a group represented by any one of the following general formulas (4), (5), and (6), and (A) polyamic acid is used, so that low temperature curing (˜ 200 ° C.), low warpage, heat resistance (5% weight loss temperature), insulation, low water absorption, and other performances can be further improved.

Wherein (4), ^{R 3} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 2 to 10 carbon atoms having 1 to 10 carbon atoms, m2 is an integer of 0-4. In addition, when m2 is 2 or more, a plurality of R ³ may be the same or different. ]

Wherein (5), ^{R 4} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 2 to 10 carbon atoms having 1 to 10 carbon atoms, n2 is an integer of 0-4. In the case of n2 is 2 or more, R ⁴ existing in plural numbers may be the same or different. ]

Wherein (6), ^{R 5} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 2 to 10 carbon atoms having 1 to 10 carbon atoms, p is an integer of 0-4. When p is 2 or more, a plurality of R ⁵ may be the same or different. ]

  In addition, it is preferable that polyamic acid does not contain ether bonds, such as a polyalkyleneoxy group. The ether bond is fragile at high temperatures, which causes a decrease in the heat resistance (5% weight loss temperature) of the resin. Furthermore, when it has an ether bond, it is easy to absorb water and becomes a factor that adversely affects insulation properties (HAST) and the like.

As (A) polyamic acid, for example, polyamic acid obtained by reacting (I) tetracarboxylic dianhydride and (II) diamine can be used.
In order to obtain (A) polyamic acid, either or both of (I) tetracarboxylic dianhydride and (II) diamine have an alkylene chain having 5 to 20 carbon atoms in the main chain. preferable. Thereby, low temperature curability, flexibility, low water absorption, low warpage, and resist wettability at the time of thermocompression bonding can be realized.
Moreover, heat resistance is improved by including an alicyclic hydrocarbon group and / or an aromatic group in one or both main chains of (I) tetracarboxylic dianhydride and (II) diamine. be able to.

  As the (I) tetracarboxylic dianhydride having an alkylene chain having 5 to 20 carbon atoms in the main chain, for example, a compound represented by the following general formula (8) can be used.

［式（８）中、Ｘは炭素数５〜２０のアルキレン基を示す。］

[In formula (8), X shows a C5-C20 alkylene group. ]

  Examples of the compound represented by the above formula (8) include pentamethylene bis trimellitate dianhydride, hexamethylene bis trimellitate dianhydride, heptamethylene bis trimellitate dianhydride, octamethylene bis trimellitate dianhydride. Nonamethylene bis trimellitate dianhydride, decamethylene bis trimellitate dianhydride, dodecamethylene bis trimellitate dianhydride and the like. These are used alone or in combination of two kinds.

  Examples of (I) tetracarboxylic dianhydride other than (I) tetracarboxylic dianhydride having an alkylene chain of 5 to 20 carbon atoms in the main chain include, for example, pyromellitic dianhydride, 1,2 , 3,4-Benzenetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,4,5-cyclopentanetetracarboxylic anhydride, 1,2,4,5 -Cyclohexanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,3 ', 4,4'-bicyclohexyltetracarboxylic anhydride, 3,3', 4,4'- Biphenyltetracarboxylic anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4 4'-Ben Zophenone tetracarboxylic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic anhydride (4,4′-oxydiphthalate) Acid dianhydride), 2,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,3,3 ′, 4'-diphenylsulfonetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 3,4,9,10 Perylenetetracarboxylic dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] nonane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) ) Phenyl] decane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] tridecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) ) Phenyl] tetradecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) ) Phenyl] -2-methyldecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-methyloctane dianhydride, , 1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-ethylpentadecane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyl) Oxy) phenyl] dodecane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] decane dianhydride, 2,2-bis [3,5- Dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] tridecane dianhydride, 2,2-bis [3,5-diethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] pentadecane dianhydride 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] cyclohexane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) Si) phenyl] propylcyclohexane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] heptylcyclohexane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) Tetrafluoropropane dianhydride, 4,4-bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride, and the like can be used. These are used alone or in combination of two or more.

  Examples of the (II) diamine having an alkylene chain of 5 to 20 carbon atoms in the main chain include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 2,11-diaminododecane, , 12-diaminooctadecane, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 3-methoxy Examples thereof include aliphatic diamines such as hexamethylene diamine, and compounds represented by the following general formulas (9), (10) and / or (11). These are used alone or in combination of two or more. The compound represented by the general formula (10) includes [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene (trade name “Versamine 551”, Cognis Japan Ltd.) is available as a commercial product.

［式（９）中、Ｙ¹及びＹ²それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ⁶は炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｑは０〜４の整数を示す。なお、ｑが２以上の場合、複数存在するＲ⁶は同一でも異なっていてもよい。］

[In Formula (9), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, and R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 1 carbon atom. -3 represents an alkoxy group, and q represents an integer of 0-4. When q is 2 or more, a plurality of R ⁶ may be the same or different. ]

［式（１０）中、Ｙ¹及びＹ²それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ⁷は炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｒは０〜４の整数を示す。なお、ｒが２以上の場合、複数存在するＲ⁷は同一でも異なっていてもよい。］

[In Formula (10), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, and R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 1 carbon atom. -3 represents an alkoxy group, and r represents an integer of 0-4. When r is 2 or more, a plurality of R ⁷ may be the same or different. ]

（式（１１）中、Ｙ¹及びＹ²それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ⁸は炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｓは０〜４の整数を示す。なお、ｓが２以上の場合、複数存在するＲ⁸は同一でも異なっていてもよい。）

(In Formula (11), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, and R ⁸ is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 1 carbon atom. -3 represents an alkoxy group, and s represents an integer of 0 to 4. When s is 2 or more, a plurality of R ⁸ may be the same or different.

  Examples of (II) diamine other than (II) diamine having an alkylene chain having 5 to 20 carbon atoms in the main chain include, for example, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-. Diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl -5,5'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-tylenebis (cyclohexylamine), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-dimethoxy- 4,4′-diaminodiphenylmethane, 3,3′diethoxy-4,4′-diaminodiphenylmethane, bis (3-aminophenyl) ether Bis (4-aminophenyl) ether, 3,4′-diaminodiphenyl ether, 3,3′-diethyl-4,4′-diaminodiphenyl ether, 3,3′-dimethoxy-4,4′-diaminodiphenyl ether, bis [4 -(4-aminophenoxy) phenyl] ether, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-diethyl-4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy- 4,4′-diaminodiphenylsulfone, 3,3′-diethoxy-4,4′-diaminodiphenylsulfone, 3,3′-dimethyl-4,4′-diaminodiphenylpropane, 3,3′-diethyl-4, 4'-diaminodiphenylpropane, 3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,3 ' -Diethoxy-4,4'-diaminodiphenylpropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenyl) propane, 2,2-bis (4 -Aminophenyl) propane, 4,4'-diaminodiphenyl sulfide, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 3,3'-diethyl-4,4'-diaminodiphenyl sulfide, 3,3 '-Dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 2,2'-diaminodiethyl sulfide, 2,4'-diaminodiphenyl sulfide, m-phenylene Diamine, p-phenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 1,2-bi (4-aminophenyl) ethane, 1,2-bis (4-aminophenyl) ethane, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, o-toluidinesulfone, bis [4- ( 4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-diaminodibenzyl sulfoxide, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) Diphenylsilane, bis (4-aminophenyl) ethylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) -N-phenylamine, bis (4-aminophenyl) -N-methylamine 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1, -Diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 1,4-diamino-2-methylnaphthalene, 1,5-diamino-2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,4 ′ -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-bis (4- Minophenoxy) biphenyl, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene, 1-methoxy-2,4-diaminobenzene, 1,3-diamino- 4,6-dimethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2-methoxy-5-methylbenzene, 1,4-diamino-2,3,5,6-tetra Methylbenzene, 1,4-bis (2-methoxy-4-aminopentyl) benzene, 1,4-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,4-bis (4-aminophenoxy) Benzene, o-xylenediamine, m-xylenediamine, p-xylenediamine, 9,10-bis (4-aminophenyl) anthracene, 3,3′-dia Nobenzophenone, 4,4′-diaminobenzophenone, 4-aminophenyl-3-aminobenzoate, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane 2- (3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane, 1,1-bis [4- (4-aminophenoxy) Phenyl] -1-phenyl-2,2,2-trifluoroethane, 1,3-bis (3-aminophenyl) hexafluoropropane, , 3-bis (3-aminophenyl) decafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoro Examples include propane, 2,2-bis (5-amino-4-methylphenyl) hexafluoropropane, 1,4-bis (3-aminophenyl) but-1-ene-3-yne, and the like. These are used alone or in combination of two or more.

  (A) The polyamic acid is, for example, an approximately equimolar amount of (I) tetracarboxylic dianhydride and (II) diamine in an organic solvent at a reaction temperature of 80 ° C. or lower, preferably 50 ° C. or lower. It can be obtained by a time addition polymerization reaction.

  Examples of the solvent for reacting (I) tetracarboxylic dianhydride with the above (II) diamine include, for example, nitrogen-containing solvents (N, N′-dimethylsulfoxide, N, N′-dimethylformamide, N, N′-diethylformamide, N, N′-dimethylacetamide, N, N′-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide N-methylpyrrolidone, etc.), lactones (γ-butyrolactone, γ-valerolactone, γ-caprolactone, ε-caprolactone, α-acetyl-γ-butyrolactone, etc.), alicyclic ketones (cyclohexanone, 4-methylcyclohexanone, etc.), ethers (3-methyl-3-methoxybutyl acetate) And diethylene glycol dimethyl ether acetate). Among these, lactones, alicyclic ketones, and ethers are preferable from the viewpoint of solubility and water absorption, and γ-butyrolactone is particularly preferable. These are used alone or in combination of two or more.

The combination of (I) tetracarboxylic dianhydride and (II) diamine is preferably selected in consideration of the heat resistance, mechanical characteristics, and electrical characteristics of the polyimide resin film after final curing.
Moreover, in order to improve the adhesiveness and developability of (A) polyamic acid, it is preferable to introduce aminobenzimidazole or a derivative thereof into (A) polyamic acid. Examples of aminobenzimidazole and derivatives thereof include 2-aminobenzimidazole, 2-amino-6-methyl-benzimidazole, 2-amino-6-ethyl-benzimidazole, 2-amino-6-butyl-benzimidazole, Examples include 2-amino-6-nitro-benzimidazole. Among these, 2-amino-benzimidazole is preferable from the viewpoint of adhesiveness.
The amount introduced when aminobenzimidazole or a derivative thereof is introduced is preferably 0.1 to 10 mol, more preferably 1 to 5 mol, based on 100 mol of (A) polyamic acid. Particularly preferred is 3 moles. If the introduction amount of aminobenzimidazole or a derivative thereof is less than 0.1 mol, the effect of improving adhesiveness tends to be insufficient, and if it exceeds 10 mol, developability and storage stability tend to be lowered.

  (A) The weight average molecular weight of the polyamic acid is preferably 10,000 to 70,000, more preferably 20,000 to 65,000, and particularly preferably 30,000 to 60,000. If the weight average molecular weight is less than 10,000, the cured film tends to be brittle, and if it exceeds 60,000, the developability tends to decrease.

  The content of (A) polyamic acid is preferably 20 to 80 parts by mass, and 30 to 60 parts by mass with respect to 100 parts by mass of the total amount of (A) polyamic acid and (B) photopolymerizable compound. More preferably. When this content is less than 20 parts by mass, the developability tends to be lower than when the content is within the above range. When the content exceeds 80 parts by mass, the content is within the above range. Compared with the case where it exists in the inside, it exists in the tendency for the resolution to fall or the imidation rate at low temperature to fall.

  (B) The photopolymerizable compound may be any polymerizable compound having at least one ethylenically unsaturated group. From the viewpoint of compatibility with polyamic acid, solubility in a developer, and heat resistance of a cured film. From, for example, the novolac type epoxy resin represented by the following general formula (21), the bisphenol A type epoxy resin or the bisphenol F type epoxy resin represented by the following general formula (22), and the following general formula (23) It preferably contains a vinyl group-containing epoxy resin obtained by reacting at least one epoxy resin (a) selected from the group consisting of salicylaldehyde type epoxy resins and a vinyl group-containing monocarboxylic acid (b). .

［式中、Ｘは水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）、Ｒは水素原子又はメチル基、ｎは１以上の整数である。］

[Wherein, X is a hydrogen atom or glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), R is a hydrogen atom or methyl group, and n is an integer of 1 or more. . ]

Further, the vinyl group-containing epoxy resin is a novolac type epoxy resin represented by the general formula (21), a bisphenol cage type epoxy resin or a bisphenol F type epoxy resin represented by the general formula (22), and the general formula (23 And a resin obtained by reacting at least one epoxy resin (a) selected from the group consisting of salicylaldehyde type epoxy resins represented by (1) with a vinyl group-containing monocarboxylic acid (b), saturated or unsaturated It is also preferable to include a resin obtained by reacting the group-containing polybasic acid anhydride (c).
Among these vinyl group-containing epoxy resins, an acid-modified phenol novolac epoxy resin containing a vinyl group represented by the following formula is preferable.

［式中、ｍとｎとの比は、１００／０〜０／１００である。］

[Wherein, the ratio of m to n is 100/0 to 0/100. ]

Examples of the vinyl group-containing monocarboxylic acid (b) include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyano. Cinnamic acid and the like can be mentioned. These are used alone or in combination of two or more.
Examples of the saturated or unsaturated group-containing polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrophthalic anhydride. Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like. These are used alone or in combination of two or more.

  The (B) photopolymerizable compound is, for example, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, a bisphenol A (meth) acrylate compound, a glycidyl group-containing compound, α, β. A compound obtained by reacting an unsaturated carboxylic acid, nonylphenoxypolyethyleneoxyacrylate, a phthalic acid compound, an alkyl (meth) acrylate, or the like may be used. These are used alone or in combination of two or more.

Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. These are used alone or in combination of two or more.
Here, “EO” represents ethylene oxide, and an EO-modified compound represents one having a block structure of an ethylene oxide group. “PO” represents propylene oxide, and a PO-modified compound has a propylene oxide group block structure.

  The content of (B) the photopolymerizable compound is preferably 20 to 80 parts by mass, and preferably 30 to 70 parts by mass with respect to 100 parts by mass of the total amount of (A) polyamic acid and (B) photopolymerizable compound. More preferably, it is 35-65 mass parts, It is still more preferable that it is 40-60 mass parts. When this content is less than 20 parts by mass, the resolution tends to decrease or the imidization rate at low temperatures tends to decrease compared to the case where the content is within the above range.

  (C) The photopolymerization initiator is not particularly limited as long as it generates a free radical by active light. For example, an aromatic ketone, a quinone, a benzoin ether compound, a benzyl derivative, an oxime ester compound, 2, 4, 5-triarylimidazole dimers, acridine derivatives, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds can be used.

  Examples of aromatic ketones include benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 -One, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, and the like.

  Examples of quinones include 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenyl. Anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone and the like can be mentioned.

  Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether.

  Examples of the benzyl derivative include benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, and benzyldimethyl ketal.

  Examples of the oxime ester compound include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (trade name: Irgacure-OXE-01, manufactured by Ciba Specialty Chemicals) ), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) (trade name: OXE-02, manufactured by Ciba Specialty Chemicals) 1-phenyl-1,2-propanedione-2- [O- (ethoxycarbonyl) oxime] (trade name: Quanture-PDO, manufactured by Nippon Kayaku Co., Ltd.), and the like.

  Examples of the 2,4,5-triarylimidazole dimer include 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2- Yl] -4,5-diphenylimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4, Examples include 5-diphenylimidazole dimer.

  Examples of the acridine derivative include 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, and the like.

  (C) A photoinitiator may be synthesize | combined by a conventional method and a commercially available thing may be obtained. Examples of the available (C) photopolymerization initiator include Irgacure-369 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgacure-907 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), and Irgacure. -651 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.).

  Among the above-mentioned (C) photopolymerization initiators, benzyldimethyl ketal (trade name: Irgacure-651, manufactured by Ciba Specialty Chemicals Co., Ltd.) is particularly preferable from the viewpoint of improving sensitivity and compatibility with a solvent. The said (C) photoinitiator can be used individually by 1 type or in combination of 2 or more types.

  (C) The content of the photopolymerization initiator is preferably 1 to 20% by mass and more preferably 1 to 10% by mass based on the total solid content of the photosensitive resin composition. (C) When the content of the photopolymerization initiator is out of the above range, the sensitivity of the photosensitive resin composition is decreased or the compatibility is decreased as compared with the case where the content is in the above range. There is a tendency.

  (D) The epoxy group-containing silane compound may be synthesized by a conventional method, or a commercially available product may be obtained. Examples of the available (D) epoxy group-containing silane compound include KBM-303 (trade name, manufactured by Shin-Etsu Silicone), SZ-6040 (trade name, manufactured by GE Toshiba Silicone), and the like.

  (D) The content of the epoxy group-containing silane compound is preferably 0.1 to 1.5 parts by mass based on 100 parts by mass of the total amount of (A) polyamic acid and (B) photopolymerizable compound. 0.3 to 1.4 parts by mass is more preferable, and 0.6 to 1.3 parts by mass is particularly preferable. (D) When the content of the epoxy group-containing silane compound is out of the above range, the adhesiveness of the photosensitive resin composition may be reduced or the developer solubility may be lower than when the content is within the above range. It tends to decrease.

  The photosensitive resin composition of the present invention may further contain (E) a crosslinking agent. (E) Although it does not restrict | limit especially as a crosslinking agent, An epoxy compound, a blocked isocyanate compound, etc. are mentioned. Specifically, YH-434L (trade name, manufactured by Toto Kasei Co., Ltd., amine type epoxy resin) is preferable as the epoxy compound. Specifically, BL-3175 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., blocked isocyanate) is preferable as the blocked isocyanate compound. When these crosslinking agents are added, the adhesiveness of the cured photosensitive resin composition to the substrate can be further improved.

  When (E) a crosslinking agent is contained in the photosensitive resin composition, the content is preferably 10 to 60 parts by mass, and 30 to 40 parts by mass with respect to 100 parts by mass of (A) polyamic acid. More preferably. When the content of (E) the cross-linking agent is out of the above range, the cured film after curing becomes fragile as compared with the case where the content is within the above range, or (A) polyamic acid and (E) cross-linking agent There is a tendency that the compatibility with is lowered.

  A sensitizer (F) can be further added to the photosensitive resin composition of the present invention. Examples of (F) sensitizers include Michler's ketone, 4,4-diethylaminobenzophenone, 3,3′-carbonylbis (diethylaminocoumarin), and the like. (F) As a sensitizer, from the viewpoints of sensitivity of the photosensitive resin composition and compatibility with a solvent, coumarins are preferable, and Coumarin 102 (trade name, manufactured by Acros Corporation) is particularly preferable. (F) A sensitizer is used individually by 1 type or in combination of 2 or more types.

  When the photosensitive resin composition contains the (F) sensitizer, the content is preferably 0.1 to 1% by mass based on the total solid content of the photosensitive resin composition. (F) When the content of the sensitizer is out of the above range, the sensitivity of the photosensitive resin composition is decreased or the compatibility with the solvent is decreased as compared with the case where the content is within the above range. Tend.

  In addition, the photosensitive resin composition of the present invention contains a silane coupling agent such as aminosilane and γ-ureidosilane in order to further improve the adhesion between the photosensitive resin composition and the substrate, if necessary. You may go out.

  The photosensitive resin composition of the present invention is used as described above (A) polyamic acid, (B) photopolymerizable compound, (C) photopolymerization initiator, (D) epoxy group-containing silane compound, and as required. The components can be obtained by mixing with a solvent.

  Although it does not restrict | limit especially as a solvent used at this time, For example, the polar solvent which has N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, propylene glycol monomethyl ether acetate etc. as a main component And a solvent such as γ-butyrolactone. These solvents are used alone or in combination of two or more.

Next, a method for forming a pattern using the photosensitive resin composition of the present invention will be described.
First, the above-mentioned photosensitive resin composition is applied on a substrate. As the substrate, silicon, alumina ceramic, glass, glass ceramic, aluminum nitride, semiconductor, organic film or the like is used. In particular, the photosensitive resin composition of the present invention exhibits a particularly excellent effect in adhesion to an organic film. Examples of the organic film include polycarbonate, polyamide, polyimide, polyethylene terephthalate, polyethylene sulfide, polyphenylene sulfide, polypropylene, polyphenylene ether, and polyester.

  Examples of the coating method include, but are not limited to, spin coating using a spinner, spray coating, dipping, roll coating, and the like.

  The coating thickness varies depending on the coating means, the solid content concentration and the viscosity of the photosensitive resin composition, etc., but is usually applied so that the thickness of the dried film (photosensitive resin composition layer) is 1 to 300 μm. Is done. In order to make the film thickness after drying become 1 to 300 μm, it is preferable to dissolve the photosensitive resin composition of the present invention with a solvent and adjust the viscosity to 1 to 50 Pa · s, preferably 20 to 20 μm. It is more preferable to adjust to 40 Pa · s. Further, the solid content concentration of the photosensitive resin composition is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass. When the film thickness of the obtained film exceeds 300 μm, the resolution tends to decrease.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition layer. Drying is preferably carried out in the range of 60 to 120 ° C. for 1 minute to 1 hour using an oven, a hot plate or the like.

  Next, a mask having a desired pattern is placed on the photosensitive resin composition layer as necessary, and exposure is performed by irradiating actinic rays through the mask. Examples of the actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. Among these, ultraviolet rays and visible rays are particularly preferable.

  A pattern can be formed by removing an unexposed part using a developing solution after exposure. Here, as the developer, an organic solvent such as N-methylpyrrolidone or ethanol, or an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide or the like is used. be able to. Among these, since there are few metallic ion compounds, it is preferable to use tetramethylammonium hydroxide for development of the photosensitive resin composition.

  Further, after the development, if necessary, rinse with water or an alcohol such as methanol, ethanol, isopropyl alcohol or the like.

In the case where pattern formation of the photosensitive resin composition layer is not performed, development can be omitted.
Next, by preheating the photosensitive resin composition layer after photocuring, the photosensitive resin composition layer is temporarily cured to form a temporarily cured film. Here, the temporary curing is performed, for example, for 1-2 hours while increasing the temperature stepwise. Preheating is preferably performed at 120 to 200 ° C. In the case of performing preliminary heating by raising the temperature stepwise, for example, a method in which heat treatment is performed at 120 ° C., 150 ° C., and 180 ° C. for 20 minutes, and then heat treatment is performed at 200 ° C. for 30 minutes or more.

  In the substrate bonding method of the present invention, by performing the above preheating, when the substrates are finally bonded (main bonding), the substrate and the adhesive (cured film of the photosensitive resin composition layer) It is possible to suppress the generation of voids between them, and when the substrates are finally bonded to each other (main bonding), the cured film is sufficiently wetted and spread on the adherend, and sufficient adhesive strength is obtained. .

  A microcomponent having a coating (preliminarily cured film) of the photosensitive adhesive composition of the present invention on a substrate is then a substrate such as an organic film, glass, silicon, ceramic, etc., which becomes an adherend, Adhere by crimping.

  The thermocompression bonding temperature is preferably 120 to 200 ° C. In addition, the pressure bonding time is preferably 1 minute to 2 hours. As a result, the temporarily cured film is fully cured and the substrates are bonded to each other.

  Organic film materials and semiconductor element materials are desirably cured at low temperatures, and the acrylic resin in the photosensitive adhesive composition may be decomposed at high temperatures, so it must be cured at low temperatures. Is desirable. Therefore, it is preferable to perform adhesion at 120 to 200 ° C., for example, preferably at 150 ° C. for about 60 minutes.

  In addition, when the press bonding time is less than 1 minute, there is a tendency that the temporarily cured film may not be sufficiently wetted and spread, and when it is 2 hours or longer, the adhesive strength is reduced due to deterioration of the photosensitive resin composition. Tend.

  The photosensitive resin composition and the substrate bonding method of the present invention described above can provide a sufficiently high adhesive strength when bonding between arbitrary substrates, and voids between the substrate and the adhesive (cured film). Generation | occurrence | production can fully be suppressed. Furthermore, the photosensitive adhesive composition of the present invention and the method for bonding a substrate can form a high-definition pattern by photolithography, and have high adhesive strength, hermetic sealability, developability, low water absorption, Satisfies characteristics such as low ion impurities and high reliability. The photosensitive adhesive composition and the substrate bonding method of the present invention are effective for adhering flexible substrates, for example, a spacer / adhesive between a PET film and a PET film in an electronic paper or a flexible printed wiring. It can be suitably used as an insulating film and adhesive for the plate. In addition, it is effective for use in producing a hollow package structure for various sensors. For example, in the field of CCD / CMOS image sensors, it can be suitably used for bonding an image sensor chip and a glass for protecting the image sensor chip.

  Moreover, the film formed with the photosensitive resin composition by this invention can also be used for a surface protective film or an interlayer insulation film.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a reference example, this invention is not limited to these.

(Synthesis Example 1)
Into a 300 mL four-necked separable flask, Versamine 551 (trade name, [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene, manufactured by Cognis Japan, Inc.) 15. 73 g (0.028 mol), 4,4′-diaminodiphenylsulfone 3.54 g (0.014 mol) and N-methylpyrrolidone 30.0 g were added and stirred at room temperature for 15 minutes. Next, a mixed solution of 22.10 g (0.043 mol) of 1,10- (decamethylene) bis (trimellitate) dianhydride and 30.00 g of N-methylpyrrolidone was added over 15 minutes. After completion of the addition, the resulting mixture was heated to 60 ° C. and stirred for 8 hours to obtain an N-methylpyrrolidone solution of polyamic acid. Solid content in the obtained solution was 40 mass%, the weight average molecular weight of polyamic acid was 35000, and dispersity (weight average molecular weight / number average molecular weight) was 1.7. “Versamine 551” is a diamine compound including a compound represented by the following formula (12) and / or a compound in which an unsaturated portion of the compound represented by the following formula (12) is hydrogenated.

(Synthesis Example 2)
Into a 300 mL four-necked separable flask, Versamine 551 (trade name, [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene, manufactured by Cognis Japan Co., Ltd.) 61 g (0.035 mol) and 30 g of N-methylpyrrolidone were added and stirred at room temperature for 15 minutes. Next, 20.39 g (0.039 mol) of 1,10- (decamethylene) bis (trimellitate) dianhydride and 30 g of NMP were added over 15 minutes. After completion of the addition, the resulting mixture was heated to 60 ° C. and stirred for 8 hours to obtain an N-methylpyrrolidone solution of polyamic acid. Solid content in the obtained solution was 40 mass%, the weight average molecular weight of polyamic acid was 40000, and dispersity (weight average molecular weight / number average molecular weight) was 3.4.

(Synthesis Example 3)
In a 300 mL four-necked separable flask, 3.50 g (0.013 mol) of 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4 1.55 g (0.006 mol) of '-diaminodiphenylsulfone and 5.0 g of N-methylpyrrolidone were added and stirred at room temperature for 15 minutes. Next, a mixed solution of 27.13 g (0.052 mol) of 1,10- (decamethylene) bis (trimellitate) dianhydride and 15.00 g of N-methylpyrrolidone was added over 15 minutes. After completion of the addition, the resulting mixture was heated to 60 ° C. and stirred for 8 hours to obtain an N-methylpyrrolidone solution of polyamic acid. Solid content in the obtained solution was 60 mass%, the weight average molecular weight of polyamic acid was 51000, and dispersity (weight average molecular weight / number average molecular weight) was 3.0.

(Synthesis Example 4)
To a 300 mL four-necked separable flask, 12.89 g (0.052 mol) of 4,4′-diaminodiphenylsulfone and 10.0 g of γ-butyrolactone were added and stirred at 40 ° C. for 15 minutes. Next, 16.44 g (0.053 mol) of 4,4′-oxydiphthalic dianhydride and 29.66 mL of γ-butyrolactone were added over 15 minutes. After completion of the addition, the temperature was raised to 60 ° C. and stirred for 5 hours to obtain a polyamic acid γ-butyrolactone solution. The solid content in the obtained solution was 40% by weight, the weight average molecular weight of the polyamic acid was 40000, and the dispersity (weight average molecular weight / number average molecular weight) was 2.0.

In addition, the weight average molecular weight and number average molecular weight of the polyamic acid prepared in Synthesis Examples 1 to 4 were measured by gel permeation chromatography (GPC) and calculated by a calibration curve using standard polystyrene. The conditions for GPC are as follows.
[GPC conditions]
Gel Permeation Chromatography (GPC)
LV4000UV Detector (manufactured by Hitachi, Ltd.)
L6000 Pump (manufactured by Hitachi, Ltd.)
C-R4A Chromatopack (manufactured by Shimadzu Corporation)
Column: Gelpack GL-S300MDT-5 × 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L)
H3PO4 (0.06 mol / L)
Flow rate: 1 mL / min

(Examples 1-5 and Comparative Examples 1-6)
The (A) polyamic acid solution, (B) photopolymerizable compound, (C) photopolymerization initiator, and (D) epoxy group-containing silane compound synthesized in each of the above synthesis examples are shown in Table 1 below. It mixed by (mass part) and the solution of the photosensitive resin composition of Examples 1-5 and Comparative Examples 1-6 was obtained. In addition, the number in Table 1 has shown the mass part of solid content. Moreover, each component in Table 1 is shown below.
Hitaroid 7660 (trade name, acid-modified phenol novolac type epoxy resin containing vinyl group, manufactured by Hitachi Chemical Co., Ltd.)
I-651 (trade name, benzyl dimethyl ketal, manufactured by Ciba Specialty Chemicals Co., Ltd.).
AY43-031 (trade name, ureidopropyltriethoxysilane, manufactured by Toray Dow Corning Silicone)
KBM-503 (trade name, γ-methacryloyltrimethoxysilane, manufactured by Shin-Etsu Silicone)
SZ-6040 (trade name, γ-glycidyl cypropyl triethoxysilane, manufactured by Toray Dow Corning Silicone)

  About the photosensitive resin composition obtained in Examples 1-5 and Comparative Examples 1-6, the wettability evaluation, the adhesive evaluation, the water absorption measurement, and the developer solubility evaluation are performed by the methods shown below. went. The results are shown in Table 1.

<Evaluation of wettability>
PET film (manufactured by Teijin DuPont)
O: When a polyethylene terephthalate film (PET film) is pressure-bonded to a photosensitive resin composition heated to 100 ° C. with a hot plate, the PET film easily sticks and is difficult to peel.
(Triangle | delta): When a PET film is crimped | bonded to the photosensitive resin composition heated at 100 degreeC with the hotplate, the sticking PET film can peel.
X: When a PET film is pressure-bonded to a photosensitive resin composition heated to 100 ° C. with a hot plate, the attached PET film does not stick.

<Evaluation of adhesiveness>
A PET film having a width of 1 cm and a length of 5 cm is pressure-bonded to the photosensitive resin composition at 100 ° C. and cured at 150 ° C. for 1 hour to prepare a test piece. After that, when measuring the peel strength using a tensile tester,
A: Peel strength is greater than 700 N / m.
○: The peel strength is in the range of 300 to 700 N / m.
X: Peel strength is less than 300 N / m.

<Measurement of water absorption rate>
The solution of the photosensitive resin composition having the above composition was uniformly applied on a glass plate having a thickness of 1 mm using an applicator, and dried on a hot plate at 110 ° C. for 5 minutes. A photosensitive resin film having a thickness of 70 μm after drying was obtained. The photosensitive resin film was exposed at an exposure amount of 500 mJ / cm ² using a proximity exposure machine (trade name: UX-1000SM) manufactured by USHIO INC. And photocured. Thereafter, it was heat-cured at 120 ° C. for 40 minutes, and heat-cured at 220 ° C. for 60 minutes. The obtained film was immersed in purified water for 24 hours together with the glass plate, and the water absorption was determined by the following formula (a) from the weight change before and after.
Water absorption (%) = (weight of cured film after immersion−weight of cured film before immersion) / (weight of cured film before immersion) × 100 (a)
○: Water absorption <1.0%
X: Water absorption> 1.0%

<Developer solubility evaluation>
The solution of the photosensitive resin composition having the above composition was uniformly applied on a silicon substrate using a spin coater and dried on a hot plate at 110 ° C. for 5 minutes. A 2.38 mass% tetramethylammonium hydroxide aqueous solution is dropped onto a 70 μm-thick photosensitive resin film after drying, the time taken for the film to completely dissolve is measured, and the dissolution rate is expressed by the following formula (b). Asked.
Dissolution rate (nm / sec) = film thickness (nm) / dissolution time (sec) (b)
A: Dissolution rate 500 nm / sec or more B: Dissolution rate 200 nm / sec or more 500 nm / sec or less X: Dissolution rate 200 nm / sec or less

Claims (6)

(A) a polyamic acid having a C5-C20 alkylene chain or alicyclic skeleton in the main chain;
(B) a photopolymerizable compound;
(C) a photopolymerization initiator;
(D) A photosensitive resin composition containing an epoxy group-containing silane compound. The photosensitive resin composition of Claim 1 in which the polyamic acid which has a C5-C20 alkylene chain or alicyclic skeleton in said (A) main chain has a structure represented by following General formula (1). object.

[In Formula (1), Ar ¹ is a tetravalent organic group, Ar ² is a divalent organic group, and l is an integer of 1 or more. However, at least one of Ar ¹ and Ar ² is a requirement that Ar ¹ is a tetravalent organic group represented by the following general formula (2), or Ar ² is represented by the following general formula (3). Satisfies the requirement of being a valent organic group. ]

[In the formula (2), X represents an alkylene group having 5 to 20 carbon atoms, R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, m1 And n1 are each independently an integer of 0 to 3. ]

[In Formula (3), Z represents a single bond or a divalent organic group, and Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms. ] The photosensitive resin composition of Claim 2 whose said Z is group represented by either of the following general formula (4), (5), (6).

Wherein (4), ^{R 3} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 2 to 10 carbon atoms having 1 to 10 carbon atoms, m2 is an integer of 0-4. In addition, when m2 is 2 or more, a plurality of R ³ may be the same or different. ]

Wherein (5), ^{R 4} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 2 to 10 carbon atoms having 1 to 10 carbon atoms, n2 is an integer of 0-4. In the case of n2 is 2 or more, R ⁴ existing in plural numbers may be the same or different. ]

Wherein (6), ^{R 5} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 2 to 10 carbon atoms having 1 to 10 carbon atoms, p is an integer of 0-4. When p is 2 or more, a plurality of R ⁵ may be the same or different. ] In the photosensitive resin composition as described in any one of Claims 1-3,
i) an exposure step of irradiating actinic rays and photocuring the exposed portion;
ii) a temporary curing step of temporarily curing the photo-cured photosensitive resin composition;
iii) an adhering step for adhering the substrates disposed via the pre-cured photosensitive resin composition;
A method for bonding a substrate comprising:   5. The method for bonding substrates according to claim 4, wherein, in the bonding step, the substrates disposed via the photosensitive resin composition after temporary curing are bonded together by thermocompression bonding.   The method for bonding substrates according to claim 4 or 5, wherein the substrate is an organic film.