JPWO2012086371A1 - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a photopolymerization initiator, and (C) a compound having an ethylenically unsaturated double bond, wherein (B) the photopolymerization initiator is , 2,4,5-triarylimidazole dimer or acridine compound, and (C) a compound having an ethylenically unsaturated double bond is represented by the following general formula (I): {wherein R1, R2, A, B, n1, n2, and n3 are as defined in the specification. } The photosensitive resin composition containing the compound represented by this. Such a photosensitive resin composition has excellent developer dispersion stability, suppresses the generation of aggregates, and has appropriate developability, flexibility of a cured resist, and good etching resistance.

Description

  The present invention relates to a photosensitive resin composition and the like.

  Conventionally, printed wiring boards or metal precision processing has been manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure the exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer to form a resist on the substrate. It refers to a method of forming a conductor pattern on a substrate by forming a pattern, performing etching or plating treatment to form a conductor pattern, and then removing the resist pattern from the substrate.

  In photolithography, when a photosensitive resin composition is applied onto a substrate, a photoresist solution is applied to the substrate and dried, or a support and a layer made of the photosensitive resin composition (hereinafter referred to as photosensitive resin). Any of the methods of laminating a photosensitive resin laminate on which a protective layer is sequentially laminated on a substrate is used, but the latter is often used in the production of printed wiring boards. .

A method for producing a printed wiring board using the photosensitive resin laminate will be briefly described below.
First, a protective layer such as a polyethylene film is peeled from the photosensitive resin laminate. Next, the photosensitive resin layer and the support are laminated on a substrate such as a copper-clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support are in this order. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer through a photomask having a wiring pattern. Next, the support made of polyethylene terephthalate or the like is peeled off. Next, a non-exposed portion of the photosensitive resin layer is dissolved or dispersed and removed by a developing solution such as an aqueous solution having weak alkalinity to form a resist pattern on the substrate. The step of dissolving or dispersing and removing the photosensitive resin layer in the unexposed portion with this developer is called a developing step, and the shortest time required for dissolving the photosensitive resin layer in the unexposed portion is set as the minimum developing time. The

  Not all of the photosensitive resin composition dissolves in the developer, and every time the development process is repeated, insoluble components with poor developer dispersibility increase and aggregates are generated. Aggregates adhere to the substrate and cause a short circuit failure.

Next, a known etching process or pattern plating process is performed using the formed resist pattern as a protective mask. Finally, the resist pattern is peeled from the substrate to produce a substrate having a conductor pattern, that is, a printed wiring board.
In the etching process, the etching resistance of the resist pattern is important. If the etching resistance is poor, the etching solution permeates through the gap between the resist pattern and the substrate during etching, and a part of the circuit top is etched. As for the surface appearance from the top direction, discoloration and oxidation due to soaking are observed, the reproducibility of the width of the conductor pattern is deteriorated in part, and the linearity is poor and rattling. Furthermore, when the etching resistance is poor, the conductor pattern is chipped or disconnected. These defects become more prominent as the conductor pattern becomes finer. A process of performing a known etching process using the formed resist pattern as a protective mask is called an etching process. The development process and the etching process described above are often linked, and the substrate transport speed depends on the etching process because it is necessary to completely dissolve the unnecessary conductor. At this time, the photosensitive resin layer having a short minimum development time is excessively exposed to the developer, which may impair the adhesion between the base material and the formed resist pattern. This is particularly noticeable when a thin photosensitive resin layer is used to improve image quality and etching efficiency. Also, in the development process and the etching process, when the flexibility of the cured resist is poor, a part of the resist pattern is lost due to contact with the transport roll or spraying of the developer or etchant, and the conductor pattern is missing or broken. May happen.

  Under such circumstances, means for using polybutylene glycol di (meth) acrylate or means for using a urethane compound have been reported to improve the flexibility and chemical resistance of the cured resist (see Patent Documents 1 and 2).

JP 61-228007 A Japanese Patent No. 3859934

  The chemical resistance described in Patent Documents 1 and 2 is intended for alkaline aqueous solutions or plating solutions, and does not disclose the resistance of acidic chemicals used in the etching process, and developability or cohesiveness. There is also no disclosure regarding. There is still a need to provide a photosensitive resin composition that has excellent developer dispersion stability, suppresses the generation of aggregates, and has appropriate developability, flexibility of a cured resist, and good etching resistance.

  In view of the above situation, the problems to be solved by the present invention are excellent in developer dispersion stability, suppressed generation of aggregates, and have appropriate developability, flexibility of cured resist, and good etching resistance. It is to provide a photosensitive resin composition and the like.

As a result of intensive studies and experiments to solve the above problems, the present inventor has found that such problems can be solved by the following technical means, and has completed the present invention.
That is, the present invention is as follows.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立して、水素原子又はメチル基を表し、Ａは、Ｃ_２Ｈ_４又はＣ_３Ｈ_６であり、−（Ａ−Ｏ）_ｎ１−及び−（Ａ−Ｏ）_ｎ３−において、−Ｃ_２Ｈ_４−Ｏ−及び−Ｃ_３Ｈ_６−Ｏ−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、該配列がブロックである場合には、−Ｃ_２Ｈ_４−Ｏ−及び−Ｃ_３Ｈ_６−Ｏ−のいずれが−Ｂ−Ｏ−基側であってもよく、Ｂは、炭素数４〜８の２価のアルキル鎖であり、ｎ_１は、０〜１０の整数であり、ｎ_３は、０〜１０の整数であり、ｎ_１＋ｎ_３は、０〜１０の整数であり、そしてｎ_２は１〜２０の整数である。｝
で表される化合物を含む、前記感光性樹脂組成物。[1] A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a photopolymerization initiator, and (C) a compound having an ethylenically unsaturated double bond, the (B) photopolymerization The initiator is a 2,4,5-triarylimidazole dimer or an acridine compound, and the compound (C) having the ethylenically unsaturated double bond is represented by the following general formula (I):

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ or C ₃ H ₆ , _and- (A-O) _n1 - _and- ( _{a-O) n3} - in _the sequence of -C ₂ H 4 -O- and _-C 3 _H 6 -O- repeat units may be a block be a random, sequence is a block In this case, either —C ₂ H ₄ —O— or —C ₃ H ₆ —O— may be on the —B—O— group side, and B is a divalent alkyl having 4 to 8 carbon atoms. N ₁ is an integer from 0 to 10, n ₃ is an integer from 0 to 10, n ₁ + n ₃ is an integer from 0 to 10, and n ₂ is from 1 to 20. It is an integer. }
The said photosensitive resin composition containing the compound represented by these.

｛式中、Ｒ_３及びＲ_４は、それぞれ独立して、水素原子又はメチル基であり、ｎ_４及びｎ_７は、それぞれ独立に、０〜２０の整数であり、ｎ_４＋ｎ_７は、０〜４０の整数であり、ｎ_５及びｎ_６は、それぞれ独立に、１〜２０の整数であり、ｎ_５＋ｎ_６は、２〜４０の整数であり、そして−（Ｃ_２Ｈ_４−Ｏ）−及び−（Ｃ_３Ｈ_６−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、該配列がブロックである場合には、−（Ｃ_２Ｈ_４−Ｏ）−及び−（Ｃ_３Ｈ_６−Ｏ）−のいずれがビスフェノール基側であってもよい。｝
で表される化合物をさらに含む、［１］に記載の感光性樹脂組成物。[2] As the compound (C) having an ethylenically unsaturated double bond, the following general formula (II):

{Wherein R ₃ and R ₄ are each independently a hydrogen atom or a methyl group, n ₄ and n ₇ are each independently an integer of 0 to 20, and n ₄ + n ₇ is 0 is an integer from to 40, _{n 5} and _{n 6} represents, independently, an integer from 1 to _20, n 5 + _{n 6} represents an integer of 2 to 40, and _{- (C 2} H 4 -O) The sequence of repeating units of-and-(C ₃ H ₆ -O)-may be random or block, and when the sequence is a block,-(C ₂ H ₄ -O) - and _{- (C 3 H 6 -O)} - one may be a bisphenol group side. }
The photosensitive resin composition according to [1], further comprising a compound represented by:

[3] In the general formula (II), n ₄ and n ₇ are each independently an integer of 1 to 20, and n ₄ + n ₇ is an integer of 2 to 40. Photosensitive resin composition.

  [4] Any one of [1] to [3], wherein the (A) alkali-soluble polymer is selected from alkali-soluble polymers containing styrene and / or benzyl (meth) acrylate as a copolymer component. The photosensitive resin composition as described in 2.

[5] The photosensitive resin according to any one of [1] to [4], wherein, in the general formula (I), n ₂ is an integer of 1 to 10 and n ₁ + n ₃ is 0. Composition.

  [6] The photosensitive composition according to any one of [1] to [5], further including (C) a compound having at least one urethane bond in the molecule as the compound having an ethylenically unsaturated double bond. Resin composition.

｛式中、Ｒ_５及びＲ_６は、それぞれ独立して、水素原子又はメチル基であり、ｎ_８及びｎ_９は、それぞれ独立に、３〜４０の整数であり、そして−（Ｃ_２Ｈ_４−Ｏ）−及び−（Ｃ_３Ｈ_６−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよい。｝
で表される化合物をさらに含む、［１］〜［６］のいずれか１項に記載の感光性樹脂組成物。[7] As the compound (C) having an ethylenically unsaturated double bond, the following general formula (III):

{In the formula, R ₅ and R ₆ are each independently a hydrogen atom or a methyl group, n ₈ and n ₉ are each independently an integer of 3 to 40, and — (C ₂ H ₄ The arrangement of repeating units of —O) — and — (C ₃ H ₆ —O) — may be random or block. }
The photosensitive resin composition of any one of [1]-[6] which further contains the compound represented by these.

｛式中、Ｒ_５及びＲ_６は、それぞれ独立して、水素原子又はメチル基であり、ｎ_１０〜ｎ_１２は、それぞれ独立して、１〜３０の整数である。｝

｛式中、Ｒ_５及びＲ_６は、それぞれ独立して、水素原子又はメチル基であり、ｎ_１０〜ｎ_１２は、それぞれ独立して、１〜３０の整数である。｝
で表される化合物をさらに含む、［１］〜［７］のいずれか１項に記載の感光性樹脂組成物。[8] As the compound (C) having an ethylenically unsaturated double bond, the following general formula (IV) and / or (V):

{Wherein, _{R 5} and _{R 6} are each independently a hydrogen atom or a methyl _group, n 10 _{~n 12} are each independently an integer of 1 to 30. }

{Wherein, _{R 5} and _{R 6} are each independently a hydrogen atom or a methyl _group, n 10 _{~n 12} are each independently an integer of 1 to 30. }
The photosensitive resin composition of any one of [1]-[7] which further contains the compound represented by these.

  [9] The photosensitive resin composition according to any one of [1] to [8], further including (C) a compound having an isocyanuric group in the molecule as the compound having an ethylenically unsaturated double bond. object.

  [10] The blending amount of the (A) alkali-soluble polymer is 40% by mass to 80% by mass when the total solid mass of the photosensitive resin composition is 100% by mass, and (B) photopolymerization starts. The compounding amount of the agent is 0.1% by mass to 20% by mass when the total solid content of the photosensitive resin composition is 100% by mass, and (C) the compound having an ethylenically unsaturated double bond. The photosensitive resin composition according to any one of [1] to [9], wherein the blending amount is 5% by mass to 50% by mass when the total solid content mass of the photosensitive resin composition is 100% by mass. object.

  [11] A photosensitive resin laminate in which a photosensitive resin layer made of the photosensitive resin composition according to any one of [1] to [10] is laminated on a support film.

  [12] A laminating step of laminating the photosensitive resin laminate according to [11] on a substrate, an exposure step of exposing the photosensitive resin laminate through a mask, and a developing step of removing unexposed portions. A method of manufacturing a substrate on which a resist pattern is formed.

  [13] A method of forming a circuit board by etching or plating a substrate manufactured by the method according to [12].

  According to the present invention, the developer dispersion stability is excellent, the generation of aggregates is suppressed, the film has moderate developability, the flexibility of a cured resist, and good etching resistance, and forms a good conductor pattern. Therefore, a suitable photosensitive resin composition, a photosensitive resin laminate having a photosensitive resin layer made of the composition, and the like can be provided.

Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
<Photosensitive resin composition>
In the present embodiment, the photosensitive resin composition includes (A) an alkali-soluble polymer, (B) a photopolymerization initiator, and (C) a compound having an ethylenically unsaturated double bond.

<(A) Alkali-soluble polymer>
(A) Alkali-soluble polymer is a vinyl resin containing a carboxyl group, for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide and the like. It is a polymer. (A) The alkali-soluble polymer preferably contains a carboxyl group and has an acid equivalent of 100 to 600. The acid equivalent is preferably 100 or more from the viewpoint of improving development resistance and improving resolution and adhesion, and is preferably 600 or less from the viewpoint of improving developability and peelability. The acid equivalent is more preferably 250 to 450.

  (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 or more and 500,000 or less. (A) The weight average molecular weight of the alkali-soluble polymer is 5,000 or more from the viewpoint of the properties of the developed aggregate, the properties of the unexposed film such as the edge fuse property and the cut chip property when the photosensitive resin laminate is used. In view of improving developability, 500,000 or less is preferable. Here, the edge fuse property is a phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll. The cut chip property is a phenomenon in which the chip flies when the unexposed film is cut with a cutter. If the chip adheres to the upper surface of the photosensitive resin laminate, it is transferred to the mask during the subsequent exposure process, etc. Cause. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably from 5,000 to 300,000, and even more preferably from 10,000 to 200,000.

(A) The alkali-soluble polymer can be obtained, for example, by copolymerizing one or more monomers from the following two types of monomers.
The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. In particular, (meth) acrylic acid is preferable. Here, (meth) acryl means acryl or methacryl.
The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl alcohol esters such as vinyl acetate, (meth) Examples include acrylonitrile, styrene, and styrene derivatives. In particular, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, a styrene derivative, and benzyl (meth) acrylate are preferable.

  (A) The copolymer component in the alkali-soluble polymer is preferably styrene or a styrene derivative, and the copolymerization ratio is preferably 20% by mass to 60% by mass. The copolymerization ratio is preferably 20% by mass or more from the viewpoint of having sufficient cohesiveness and etching resistance, and preferably 60% by mass or less from the viewpoint of having appropriate developability and cured film flexibility. The copolymerization ratio is more preferably 20% by mass to 50% by mass, and further preferably 20% by mass to 30% by mass. Furthermore, what copolymerized styrene or a styrene derivative, methyl (meth) acrylate, and (meth) acrylic acid as a copolymer component is preferable. In addition to the above, in order to obtain excellent resolution, the copolymerization ratio of styrene or a styrene derivative is preferably 40% by mass to 60% by mass, and further, styrene or styrene as a copolymer component. A copolymer of a derivative, methyl (meth) acrylate, and (meth) acrylic acid is preferred.

  The blending amount of the (A) alkali-soluble polymer in the photosensitive resin composition is in the range of 40% by mass to 80% by mass when the total solid content mass of the photosensitive resin composition is 100% by mass. Preferably, it is 50 mass%-70 mass%. The blending amount is preferably 40% by mass or more from the viewpoint of edge fuse properties, and is preferably 80% by mass or less from the viewpoint of development time.

<(B) Photopolymerization initiator>
The photosensitive resin composition contains a 2,4,5-triarylimidazole dimer or an acridine compound as an essential component of the (B) photopolymerization initiator. Specific examples thereof include, for example, 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) -4,5- Examples include 2,4,5-triarylimidazole dimer such as diphenylimidazole dimer, acridine derivatives such as 9-phenylacridine, 1,7-bis (9,9-acridinyl) heptane, and the like.

  Examples of the photopolymerization initiator that may be further contained in the photosensitive resin composition in addition to the 2,4,5-triarylimidazole dimer or the acridine compound include, for example, benzophenone, N, N′-tetramethyl- 4,4′-dimethylaminobenzophenone (Michler-ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1 Aromatic ketones such as-(4-monofornophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1, Quinones such as 4-naphthoquinone and 2,3-dimethylanthraquinone, benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzyl derivatives such as benzyl methyl ketal, N-phenylglycine derivatives, coumarin compounds, Examples include 4,4′-bis (diethylamino) benzophenone. These photopolymerization initiators may be used alone or in combination of two or more.

  The blending amount of the photopolymerization initiator (B) in the photosensitive resin composition is 0.1% by mass to 20% by mass when the total solid content of the photosensitive resin composition is 100% by mass. preferable. The blending amount is preferably 0.1% by mass or more from the viewpoint of obtaining sufficient sensitivity, and from the viewpoint of sufficiently transmitting light to the resist bottom surface and obtaining good high resolution, 20 It is preferable that it is below mass%. A more preferable range of the blending amount is 0.5 mass% to 10 mass%.

<(C) Compound having ethylenically unsaturated double bond>
(C) The compound having an ethylenically unsaturated double bond literally means a compound having an ethylenically unsaturated double bond. Examples of the compound (C) having an ethylenically unsaturated double bond include di (meth) acrylates. In addition, (meth) acrylate means an acrylate or a methacrylate.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立して、水素原子又はメチル基を表し、Ａは、Ｃ_２Ｈ_４又はＣ_３Ｈ_６であり、−（Ａ−Ｏ）ｎ_１−及び−（Ａ−Ｏ）ｎ_３−において、−Ｃ_２Ｈ_４−Ｏ−及び−Ｃ_３Ｈ_６−Ｏ−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、該配列がブロックである場合には、−Ｃ_２Ｈ_４−Ｏ−及び−Ｃ_３Ｈ_６−Ｏ−のいずれが−Ｂ−Ｏ−基側であってもよく、Ｂは、炭素数４〜８の２価のアルキル鎖であり、ｎ_１は、０〜１０の整数であり、ｎ_３は、０〜１０の整数であり、ｎ_１＋ｎ_３は、０〜１０の整数であり、そしてｎ_２は１〜２０の整数である。｝
で表される化合物を含む。
ここで、上記一般式（Ｉ）で表されるようなジ（メタ）アクリレートを他の発明特定事項と組み合わせて感光性樹脂組成物とする場合に、現像液分散安定性に優れ、凝集物の発生が抑制され、適度な現像性、硬化レジストの柔軟性、及び良好な耐エッチング性を有する感光性樹脂組成物が提供されるメカニズムについての詳細は不明であるが、以下のような作用が推察される。
即ち、一般式（Ｉ）で表されるジ（メタ）アクリレートは−（Ｂ−Ｏ）−で示される基を有しており、一般に使用されるエチレンオキシド基又はプロピレンオキシド基と比較して、分子鎖が長く、また側鎖を有さないために主鎖の自由度が高く、化学構造の柔軟性（テンティング性と呼ぶことがある）に優れるものと推察される。
また、エーテル結合は一般に、酸により酸素に隣接する炭素が求核置換反応を受けて開裂する傾向にあるが、一般式（Ｉ）で表されるジ（メタ）アクリレートが有する−（Ｂ−Ｏ）−で示される基は、酸による開裂反応部位の割合がエチレンオキシド基又はプロピレンオキシド基より少なく、耐酸性（耐エッチング性と呼ぶことがある）に優れるものと推察される。
更に、一般式（Ｉ）で表されるジ（メタ）アクリレートが有する−（Ｂ−Ｏ）−で示される基は高い親油性を有し、現像凝集物となり易いフェニル含有開始剤の分散安定性に優れる（凝集物の発生が抑制される）ものと推察される。
なお、適度な現像性についても、一般式（Ｉ）で表されるジ（メタ）アクリレートの有する適度な親油性に由来するものと推察される。The photosensitive resin composition has the following general formula (I) as a compound having (C) an ethylenically unsaturated double bond:

{Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ or C ₃ H ₆ , and-(A-O) n ₁ -and- In (A-O) n ₃ —, the sequence of the repeating unit of —C ₂ H ₄ —O— and —C ₃ H ₆ —O— may be random or block, and the sequence is blocked. Any one of —C ₂ H ₄ —O— and —C ₃ H ₆ —O— may be on the —B—O— group side, and B is a divalent group having 4 to 8 carbon atoms. N ₁ is an integer from 0 to 10, n ₃ is an integer from 0 to 10, n ₁ + n ₃ is an integer from 0 to 10, and n ₂ is from 1 to It is an integer of 20. }
The compound represented by these is included.
Here, when di (meth) acrylate as represented by the above general formula (I) is combined with other invention specific matters to form a photosensitive resin composition, the developer dispersion stability is excellent, Although the details of the mechanism by which the photosensitive resin composition having suppressed development, moderate developability, flexibility of the cured resist, and good etching resistance is provided are unknown, the following effects are presumed. Is done.
That is, the di (meth) acrylate represented by the general formula (I) has a group represented by-(B-O)-, and compared with a generally used ethylene oxide group or propylene oxide group, It is presumed that since the chain is long and has no side chain, the degree of freedom of the main chain is high and the chemical structure is flexible (sometimes referred to as tenting property).
In addition, ether bonds generally tend to be cleaved by the nucleophilic substitution reaction of carbon adjacent to oxygen by an acid, but the di (meth) acrylate represented by the general formula (I) has-(BO It is surmised that the group represented by (-) is superior in acid resistance (sometimes referred to as etching resistance) because the ratio of the cleavage reaction site by acid is less than that of ethylene oxide group or propylene oxide group.
Furthermore, the group represented by — (B—O) — contained in the di (meth) acrylate represented by the general formula (I) has high lipophilicity, and the dispersion stability of the phenyl-containing initiator that tends to be a development aggregate. It is presumed that the composition is excellent (the generation of aggregates is suppressed).
In addition, about moderate developability, it is guessed that it originates in moderate lipophilicity which di (meth) acrylate represented by general formula (I) has.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立して、水素原子又はメチル基を表し、そしてｎ_２は、好ましくは、１〜２０の整数であり、より好ましくは、１〜１５の整数であり、特に好ましくは１〜１０の整数である。｝で表されるポリブチレングリコールジ（メタ）アクリレートであることが、エッジフューズ性、製造容易性などの観点から好ましい。In the compound represented by the general formula (I), n ₁ and n ₃ are preferably integers of 0. That is, n ₁ + n ₃ is preferably an integer of 0. More specifically, the compound represented by the general formula (I) is, for example, the following general formula (VI):

{Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and n ₂ is preferably an integer of 1 to 20, more preferably an integer of 1 to 15. Yes, particularly preferably an integer of 1 to 10. } Is preferable from the viewpoints of edge fuse property, ease of production, and the like.

  More specifically, for example, butylene glycol di (meth) acrylate, dibutylene glycol di (meth) acrylate, tributylene glycol di (meth) acrylate, tetrabutylene glycol di (meth) acrylate, pentabylene glycol di (meth) Acrylate, hexabutylene glycol di (meth) acrylate, heptabylene glycol di (meth) acrylate, octabutylene glycol di (meth) acrylate, nonabutylene glycol di (meth) acrylate, decabutylene glycol di (meth) acrylate, undeca Butylene glycol di (meth) acrylate, dodecabutylene glycol di (meth) acrylate, tridecabutylene glycol di (meth) acrylate, tetradecabutylene glycol di Meth) acrylate, etc. pentadecanol butylene glycol di (meth) acrylate.

In the compounds represented by the general formulas (I) and (VI), n ₂ is preferably an integer of 1 to 20, more preferably an integer of 1 to 15, and an integer of 1 to 10 It is particularly preferred that n ₂ is preferably 1 or more from the viewpoint of flexibility of the cured film, and is preferably 20 or less from the viewpoint of etching resistance. More preferably, _{n 2} is an integer of 5-10.

  The compounding quantity of the compound represented by the said general formula (I) or (VI) in the photosensitive resin composition is 1 mass%-15 when the total solid content mass of the photosensitive resin composition is 100 mass%. Mass% is preferred. The blending amount is preferably 1% by mass or more from the viewpoint of obtaining a cured film flexibility, and is preferably 15% by mass or less from the viewpoint of etching resistance. A more preferable range of the blending amount is 1% by mass to 10% by mass, and a further preferable range is 3% by mass to 10% by mass.

｛式中、Ｒ_３及びＲ_４は、それぞれ独立して、水素原子又はメチル基であり、ｎ_４及びｎ_７は、それぞれ独立に、０〜２０の整数であり、ｎ_４＋ｎ_７は、０〜４０の整数であり、ｎ_５及びｎ_６は、それぞれ独立に、１〜２０の整数であり、ｎ_５＋ｎ_６は、２〜４０の整数であり、そして−（Ｃ_２Ｈ_４−Ｏ）−及び−（Ｃ_３Ｈ_６−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、該配列がブロックである場合には、−（Ｃ_２Ｈ_４−Ｏ）−及び−（Ｃ_３Ｈ_６−Ｏ）−のいずれがビスフェノール基側であってもよい。｝
で表される化合物をさらに含むことが、更に柔軟性を向上させる観点から好ましい。Moreover, the photosensitive resin composition has the following general formula (II) as a compound having (C) an ethylenically unsaturated double bond:

{Wherein R ₃ and R ₄ are each independently a hydrogen atom or a methyl group, n ₄ and n ₇ are each independently an integer of 0 to 20, and n ₄ + n ₇ is 0 is an integer from to 40, _{n 5} and _{n 6} represents, independently, an integer from 1 to _20, n 5 + _{n 6} represents an integer of 2 to 40, and _{- (C 2} H 4 -O) The sequence of repeating units of-and-(C ₃ H ₆ -O)-may be random or block, and when the sequence is a block,-(C ₂ H ₄ -O) - and _{- (C 3 H 6 -O)} - one may be a bisphenol group side. }
It is preferable from a viewpoint of further improving a softness | flexibility to further contain the compound represented by these.

Here, when the compound represented by the general formula (I) or (VI) and the compound represented by the general formula (II) are used in combination, a photosensitive resin composition having improved flexibility is obtained. The details of the mechanism to be realized are unknown, but the following actions are presumed.
That is, when the compound represented by general formula (I) or (VI) and the compound represented by the said general formula (II) are used together, it is guessed that the reactivity of photopolymerization improves. And it is guessed by this that the cured film after exposure becomes more tough and expresses good toughness.

In the general formula (II), n ₄ and n ₇ are each independently an integer of 0 to 20, n ₄ + n ₇ is an integer of 0 to 40, and n ₅ and n ₆ are each independent. And n ₅ + n ₆ is an integer of 2 to 40. The lower limit of n ₄ + n ₅ + n ₆ + n ₇ is preferably 2 or more, while the upper limit is preferably 40 or less. n ₄ + n ₅ + n ₆ + n ₇ is preferably 2 or more from the viewpoint of the flexibility of the cured film, and is preferably 40 or less from the viewpoint of resolution. From the viewpoint of etching resistance, the lower limit of the more preferable range of n ₄ + n ₅ + n ₆ + n ₇ is 4 or more and the upper limit is 20 or less, and the lower limit of the more preferable range is 6 or more and the upper limit is 12 or less. From the viewpoint of tent properties, the lower limit of the more preferable range of n ₄ + n ₅ + n ₆ + n ₇ is 16 or more and the upper limit is 40 or less, and the lower limit of the more preferable range is 30 or more and the upper limit is 40 or less. Further, each of n ₄ and n ₇ is preferably independently an integer of 1 to 10, and n ₄ + n ₇ is more preferably an integer of 1 to 20, while n ₅ + n ₆ Is more preferably an integer of 2 to 20.

  Specific examples of the compound represented by the general formula (II) include an ethylene glycol dimethacrylate obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A, or an average of 5 moles of ethylene oxide to both ends of bisphenol A, respectively. Dimethacrylate of ethylene glycol to which bisphenol A is added, average of 6 moles of ethylene oxide and average of 2 moles of propylene oxide to both ends of bisphenol A, average of 15 moles of ethylene oxide and average to both ends of bisphenol A An alkylene glycol dimethacrylate to which 2 mol of propylene oxide is added and an alkylene glycol dimethacrylate is added.

  The compounding quantity of the compound represented by the said general formula (II) in the photosensitive resin composition is 5 mass%-20 mass% when the total solid content mass of the photosensitive resin composition is 100 mass%. It is preferable. The blending amount is preferably 5% by mass or more from the viewpoint of obtaining etching resistance, and preferably 20% by mass or less from the viewpoint of flexibility of the cured film. A more preferable range of the blending amount is 5% by mass to 15% by mass, and a further preferable range is 7% by mass to 15% by mass.

｛式中、Ｒ_５及びＲ_６は、それぞれ独立して、水素原子又はメチル基であり、ｎ_８及びｎ_９は、それぞれ独立に、３〜４０の整数であり、そして−（Ｃ_２Ｈ_４−Ｏ）−及び−（Ｃ_３Ｈ_６−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよい。｝
で表される化合物をさらに含むことが、硬化膜柔軟性を向上させる観点から好ましい。The photosensitive resin composition has the following general formula (III) as a compound having (C) an ethylenically unsaturated double bond:

{In the formula, R ₅ and R ₆ are each independently a hydrogen atom or a methyl group, n ₈ and n ₉ are each independently an integer of 3 to 40, and — (C ₂ H ₄ The arrangement of repeating units of —O) — and — (C ₃ H ₆ —O) — may be random or block. }
It is preferable that the compound represented by these is further included from a viewpoint of improving a cured film softness | flexibility.

In the compound represented by the general formula (III), from the viewpoint of improving the flexibility of the cured film, n ₈ and n ₉ are each preferably preferably an integer of 3 or more and an integer of 5 or more. It is more preferable.

  Specific examples of the compound represented by the general formula (III) include, for example, polyalkylene glycol dimethacrylate in which an average of 1 mol of ethylene oxide is added to a polypropylene glycol to which an average of 9 mol of propylene oxide is added. .

  The compounding quantity of the compound represented by the said general formula (III) in the photosensitive resin composition is 1 mass%-20 mass% when the total solid content mass of the photosensitive resin composition is 100 mass%. It is preferable. The blending amount is preferably 1% by mass or more from the viewpoint of obtaining a cured film flexibility, and preferably 20% by mass or less from the viewpoint of etching resistance. A more preferable range of the blending amount is 3% by mass to 15% by mass, and a further preferable range is 5% by mass to 10% by mass.

｛式中、Ｒ_５及びＲ_６は、それぞれ独立して、水素原子又はメチル基であり、ｎ_１０〜ｎ_１２は、それぞれ独立して、１〜３０の整数である。｝

｛式中、Ｒ_５及びＲ_６は、それぞれ独立して、水素原子又はメチル基であり、ｎ_１０〜ｎ_１２は、それぞれ独立して、１〜３０の整数である。｝
で表される化合物をさらに含むことが、硬化膜柔軟性を向上させる観点から好ましい。The photosensitive resin composition has the following general formula (IV) and / or (V) as a compound having (C) an ethylenically unsaturated double bond:

{Wherein, _{R 5} and _{R 6} are each independently a hydrogen atom or a methyl _group, n 10 _{~n 12} are each independently an integer of 1 to 30. }

{Wherein, _{R 5} and _{R 6} are each independently a hydrogen atom or a methyl _group, n 10 _{~n 12} are each independently an integer of 1 to 30. }
It is preferable that the compound represented by these is further included from a viewpoint of improving a cured film softness | flexibility.

In the compound represented by the general formula (IV) or (V), from the viewpoint of improving the flexibility of the cured film, n _{10 to} n ₁₂ are preferably each independently an integer of 1 or more. More preferably, it is an integer of the above.

  Specific examples of the compound represented by the general formula (IV) or (V) include, for example, polyalkylene in which ethylene oxide is further added to both ends at an average of 7 mol each on polypropylene glycol to which an average of 18 mol of propylene oxide is added. Glycol dimethacrylate, Polyalkylene glycol dimethacrylate with an average of 3 moles added to both ends of polypropylene glycol with an average of 18 moles of propylene oxide added, and Polypropylene glycol with an average of 12 moles of propylene oxide added to ethylene. Polyalkylene glycol dimethacrylate with an average of 3 moles of oxide added to each end and polyethylene glycol with an average of 6 moles of ethylene oxide added. Etc. dimethacrylate polyalkylene glycol obtained by adding each respective average 6 moles further across the alkylene oxide.

  The compounding amount of the compound represented by the general formula (IV) or (V) in the photosensitive resin composition is 1% by mass to 30% when the total solid content mass of the photosensitive resin composition is 100% by mass. It is preferable that it is mass%. The blending amount is preferably 1% by mass or more from the viewpoint of obtaining etching resistance, and preferably 30% by mass or less from the viewpoint of flexibility of the cured film. A more preferable range of the blending amount is 5% by mass to 25% by mass, and a further preferable range is 5% by mass to 23% by mass.

  The photosensitive resin composition preferably further includes (C) a compound having at least one urethane bond in the molecule as the compound having an ethylenically unsaturated double bond. Specifically, diisocyanate compounds such as hexamethylene diisocyanate, tolylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2-hydroxypropyl (meth) acrylate, oligoethylene glycol (meta ) And urethane compounds obtained by reaction with hydroxy (meth) acrylate compounds such as oligopropylene glycol (meth) acrylate. The compound having at least one urethane bond in the molecule is, for example, a diisocyanate such as hexamethylene diisocyanate, tolylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate from the viewpoint of etching resistance. It is preferable that it is a urethane compound obtained by reaction with a compound and oligo propylene glycol (meth) acrylate.

  The compounding amount of the compound having at least one urethane bond in the molecule in the photosensitive resin composition is 5% by mass to 20% by mass when the total solid mass of the photosensitive resin composition is 100% by mass. It is preferable that The blending amount is preferably 5% by mass or more from the viewpoint of obtaining etching resistance, and preferably 20% by mass or less from the viewpoint of cohesion. A more preferable range of the blending amount is 8% by mass to 20% by mass, and a further preferable range is 8% by mass to 17% by mass.

  It is preferable that the photosensitive resin composition further includes (C) a compound having an isocyanuric group in the molecule as the compound having an ethylenically unsaturated double bond. Specifically, examples of the compound having an isocyanuric group in the molecule include ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified mono- (2-acryloxyethyl) isocyanurate, ε-caprolactone-modified bis- (2- Acryloxyethyl) isocyanurate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, isocyanuric acid ethylene oxide modified acrylate, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified triacrylate, isocyanuric acid propylene oxide Modified acrylate, isocyanuric acid propylene oxide modified diacrylate, isocyanuric acid propylene oxide modified triacrylate, and the like.

  The compounding amount of the compound having an isocyanuric group in the molecule in the photosensitive resin composition is preferably 1% by mass to 20% by mass when the total solid content mass of the photosensitive resin composition is 100% by mass. . The blending amount is preferably 1% by mass or more from the viewpoint of obtaining etching resistance, and preferably 20% by mass or less from the viewpoint of flexibility of the cured film. A more preferable range of the blending amount is 1% by mass to 15% by mass, and a further preferable range is 2% by mass to 10% by mass.

The photosensitive resin composition is (C) a compound having an ethylenically unsaturated double bond, a compound represented by the above general formulas (I) to (VI), a compound having at least one urethane bond in the molecule, In addition to the compound selected from the group consisting of compounds having an isocyanuric group in the molecule, the following photopolymerizable ethylenically unsaturated compounds can also be included:
Specifically, examples of the photopolymerizable ethylenically unsaturated compound include polypropylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, 2-di (P-hydroxyphenyl) propane (meth) acrylate, and glycerol tris. (Meth) acrylate trimethylol tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol -Rupenta (meth) acrylate, trimethylpropanetriglycidyl ether-tritri (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethyleneglycol Lumpur (meth) acrylate. These may be used alone or in combination of two or more.

  The compounding amount of the compound (C) having an ethylenically unsaturated double bond in the photosensitive resin composition is 5% by mass to 50% by mass when the total solid mass of the photosensitive resin composition is 100% by mass. It is preferable that The blending amount is preferably 5% by mass or more from the viewpoints of sensitivity, resolution, and adhesiveness, and is 50% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist. preferable. The blending amount is more preferably 25% by mass to 45% by mass.

<Leuco dyes, fluoran dyes, coloring substances>
The photosensitive resin composition may contain a leuco dye, a fluoran dye, or a coloring substance. By including these dyes, the exposed portion develops color, which is preferable in terms of visibility. Also, when an inspection machine reads an alignment marker for exposure, the contrast between the exposed portion and the unexposed portion is larger. Easy to recognize and advantageous.

  Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leucocrystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green]. In particular, from the viewpoint of good contrast, it is preferable to use leuco crystal violet as the leuco dye.

  As the fluorane dye, 2- (dibenzylamino) fluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl -6-N-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2 -Anilino-3-methyl-6-N-ethyl-N-isobutylaminofluorane, 2-anilino-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfuryl Aminofluorane, 2-anilino-3-methyl-6-piperidinoaminofluorane, 2- (o-chloroanilino) 6-diethylaminofluoran, 2- (3,4-Jikuroruanirino) -6-diethylamino fluoran and the like.

  The content of the leuco dye or fluorane dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass when the total solid content mass of the photosensitive resin composition is 100% by mass. The content is preferably 0.1% by mass or more from the viewpoint of the contrast between the exposed part and the unexposed part, and is preferably 10% by mass or less from the viewpoint of maintaining storage stability.

  Examples of the coloring substance include fuchsin, phthalocyanine green, auramin base, paramadienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue. 20, Diamond Green (Eisen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). The content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass when the total solid mass of the photosensitive resin composition is 100% by mass. The content is preferably 0.001% by mass or more from the viewpoint of improving handleability and 1% by mass or less from the viewpoint of maintaining storage stability.

<Halogen compounds>
In the embodiment of the present invention, from the viewpoint of adhesion and contrast, it is preferable to use a combination of a leuco dye and the following halogen compound in the photosensitive resin composition.
Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like. Bromomethylphenylsulfone is preferred. The content of the halogen compound in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass when the total solid mass of the photosensitive resin composition is 100% by mass. The blending amount is preferably 0.01% by mass or more from the viewpoint of obtaining adhesion and contrast, and is preferably 3% by mass or less from the viewpoint of storage stability.

<Radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles>
In addition, in order to improve the thermal stability and storage stability of the photosensitive resin composition, the photosensitive resin composition is at least one selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles. You may further contain a compound more than a seed | species.
Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2. -Ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylene Examples thereof include carboxybenzotriazole.

  The total content of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles with respect to the entire photosensitive resin composition is preferably 0.01% by mass to 3% by mass, and more preferably 0%. 0.05% by mass to 1% by mass. The content is preferably 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and is preferably 3% by mass or less from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye.

<Plasticizer>
The photosensitive resin composition may contain a plasticizer as necessary. Examples of such plasticizers include phthalates such as diethyl flate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri- Examples include n-propyl, tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.

  The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 1-30% by mass, when the total solid content mass of the photosensitive resin composition is 100% by mass. It is. The content is preferably 1% by mass or more and 50% by mass or less from the viewpoint of suppressing insufficient curing or cold flow from the viewpoint of suppressing development time delay and imparting flexibility to the cured film.

<Solvent>
Examples of the solvent that dissolves the photosensitive resin composition include ketones typified by methyl ethyl ketone (MEK), alcohols typified by methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied onto the support film is 500 mPa · s to 4000 mPa · s at 25 ° C.

<Photosensitive resin laminate>
In this Embodiment, the photosensitive resin laminated body contains the photosensitive resin layer and support film which consist of a photosensitive resin composition. Moreover, it is preferable that the photosensitive resin layer is laminated | stacked on the support film. If necessary, you may have a protective layer on the surface on the opposite side to the support film side of the photosensitive resin layer.
The support film is preferably a transparent film that transmits light emitted from the exposure light source. Examples of such support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, Examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can be stretched if necessary, and preferably have a haze of 5 or less. A thinner film is more advantageous in terms of image forming properties and economic efficiency, but a film having a thickness of 10 to 30 μm is preferably used in order to maintain the strength.

  An important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support film in terms of adhesion to the photosensitive resin layer and can be easily peeled. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Also, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm. Although the thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, it is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. . Furthermore, for etching applications that do not require high tent properties, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 10 μm to 20 μm. From the viewpoint of etching resistance, it is 10 μm or more, and from the viewpoint of resolution, it is 20 μm or less.

<Method for producing photosensitive resin laminate>
As a method for producing a photosensitive resin laminate by sequentially laminating a support film, a photosensitive resin layer, and if necessary, a protective layer, a known method can be adopted. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves them to form a uniform solution, which is first applied onto a support film using a bar coater or a roll coater, and then dried to support it. A photosensitive resin layer made of a photosensitive resin composition can be laminated on the film. Next, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Manufacturing method of substrate having resist pattern>
Hereinafter, an example of a method for producing a substrate on which a resist pattern is formed using the photosensitive resin laminate will be described. If desired, a circuit board or a printed wiring board can be produced by etching or plating the board thus produced.

A method for producing a substrate on which a resist pattern is formed and a circuit board or a printed wiring board using the substrate using the photosensitive resin laminate includes the following steps. In addition, it is possible to use either or both of the steps (4) and (4 ′).
(1) Lamination process The process of sticking the photosensitive resin laminated body on substrates, such as a copper clad laminated board and a flexible substrate, using a hot roll laminator, peeling off the protective layer of the photosensitive resin laminated body.
(2) Exposure process A mask film having a desired wiring pattern is brought into close contact with a support (for example, a support film) and exposed using an active light source, or a desired wiring pattern is exposed by direct drawing. Process.
(3) Development process The process which peels the support body on the photosensitive resin layer after exposure, and develops and removes an unexposed part using the developing solution of alkaline aqueous solution next, and forms a resist pattern on a board | substrate.
As the alkaline aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ can be used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2% by mass to 2% by mass and about 20 ° C. to 40 ° C. is generally used.
Although a resist pattern can be obtained through each of the above steps, a heating step of about 100 ° C. to 300 ° C. can be further performed in some cases. By carrying out this heating step, chemical resistance can be further improved. For heating, a hot-air, infrared, or far-infrared heating furnace can be used.
(4) Etching step A step of etching the copper surface not covered with the resist pattern by spraying an etching solution from the formed resist pattern.
An etching process is performed by the method suitable for the photosensitive resin laminated body to be used, such as acidic etching and alkali etching.
(4 ′) Plating step A step of plating a substrate on which a resist pattern is formed using copper plating, solder plating or the like.
Examples of the plating method include a method of performing electroplating using a substrate as an electrode.
(5) Stripping Thereafter, the resist pattern is stripped from the substrate with an aqueous solution having alkalinity stronger than the developer. The alkaline aqueous solution for peeling is not particularly limited, but an aqueous solution of NaOH, KOH or the like having a concentration of about 2% by mass to 5% by mass and a temperature of about 40 ° C. to 70 ° C. is generally used. A small amount of a water-soluble solvent can also be added to the stripping solution.

  As described above, the present embodiment uses a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate in which the photosensitive resin composition is laminated on a support, and the photosensitive resin laminate. The present invention relates to a method of forming a resist pattern on a substrate, the use of the resist pattern, and the like. These photosensitive resin compositions, etc. are used for the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for mounting IC chips (hereinafter referred to as lead frames), the metal foil precision processing such as the manufacture of metal masks, Representative of semiconductor package manufacturing such as BGA (ball grid array) or CSP (chip size package), TAB (Tape Automated Bonding) or COF (Chip On Film: a semiconductor IC mounted on a film-like fine wiring board) A resist pattern suitable for the manufacture of tape substrates, semiconductor bumps, ITO electrodes, address electrodes, electromagnetic wave shields and the like in the field of flat panel displays can be provided.

Hereinafter, Examples 1 to 14 and Comparative Examples 1 and 2 will be described more specifically.
First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.

(1) Preparation method of sample for evaluation The sample for evaluation in an Example and a comparative example was produced as follows.
<Preparation of photosensitive resin laminate>
A photosensitive resin composition prepared by sufficiently stirring and mixing a photosensitive resin composition and a solvent having a composition shown in Table 1 below (where each component number indicates a blending amount (part by mass) as a solid content). As a liquid, a 16 μm-thick polyethylene terephthalate film (Mitsubishi Chemical Polyester Film Co., Ltd., R130-16) as a support was evenly coated using a bar coater, and 1. The photosensitive resin composition layer was formed by drying for 5 minutes. The thickness of the photosensitive resin composition layer was 15 μm.
Next, a 19 μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) is bonded as a protective layer on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film is not laminated to form a photosensitive resin laminate. Obtained. Table 2 below shows the names of the material components in the photosensitive resin composition preparation liquid represented by abbreviations in Table 1.

<Board surface preparation>
A 1.6 mm thick copper clad laminate on which 35 μm rolled copper foil was laminated was used as an evaluation substrate for developability and etching resistance. The substrate surface was subjected to wet buffol polishing (manufactured by 3M, Scotch Bright (registered trademark) HD # 600, two passes).

<Laminate>
Laminating at a roll temperature of 105 ° C with a hot roll laminator (ALA-700, manufactured by Asahi Kasei Co., Ltd.) on a copper clad laminate surfaced and preheated to 60 ° C while peeling the polyethylene film of the photosensitive resin laminate. did. The air pressure was 0.35 MPa, and the laminating speed was 2.0 m / min.

<Exposure>
A mask film necessary for the evaluation of the photosensitive resin composition layer is placed on a polyethylene terephthalate film as a support, and Examples 1 to 6, Examples 9 to 14 and Comparative Examples 1 and 2 are ultrahigh pressure mercury lamps. (Oak Seisakusho make, HMW-801) It exposed with the exposure amount of 70 mJ / cm < ² >. For Examples 7 and 8, exposure was performed at an exposure amount of 15 mJ / cm ^{2 using} a direct drawing type exposure apparatus (manufactured by Hitachi Via Mechanics Co., Ltd., DI exposure machine DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ± 5 nm). did.

In a cured film flexibility evaluation sample, a mask film necessary for evaluation was placed on a polyethylene terephthalate film, which is a support for a photosensitive resin laminate produced as described above. Examples 1 to 6 and Example 9 -14 and Comparative Examples 1 and 2 were exposed at an exposure amount of 70 mJ / cm < ² > using an ultra-high pressure mercury lamp (OMW Seisakusho, HMW-801). For Examples 7 and 8, exposure was performed at an exposure amount of 15 mJ / cm ^{2 using} a direct drawing type exposure apparatus (manufactured by Hitachi Via Mechanics Co., Ltd., DI exposure machine DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ± 5 nm). did.

<Development>
For the evaluation substrate for developability and etching resistance, after peeling the polyethylene terephthalate film, a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. was used using an alkali developer (Fuji Kiko Co., Ltd., dry film developer). Spraying was performed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, development was performed in a time twice as long as the minimum development time to prepare a cured resist pattern. In addition, the minimum development time means the shortest time required for dissolving the photosensitive resin layer of an unexposed part as above-mentioned.
About the evaluation sample of the cured film flexibility, after peeling the polyethylene film, it was developed under the same conditions for twice the minimum development time to obtain a cured resist.

<Etching>
The evaluation substrate on which the resist pattern was formed by development was used with a copper salt etching apparatus (Tokyo Kakko Co., Ltd., salt copper etching apparatus) at a cupric chloride concentration of 250 g / L and a hydrochloric acid concentration of 3 mol / L. A certain amount of cupric chloride etching solution at 50 ° C. was sprayed for a predetermined time, and the portion of the copper foil not covered with the resist pattern on the copper-clad laminate was dissolved and removed.

<Peeling>
The evaluation substrate after etching was sprayed with a 3% by mass aqueous sodium hydroxide solution heated to 50 ° C. to peel off the cured resist.

(2) Sample Evaluation Method Next, a sample evaluation method will be described.
(I) Developability According to the method for preparing the sample for evaluation (1), a substrate was prepared, laminated, and developed to obtain a resist pattern. Based on the minimum development time, the ranking was as follows:
A: Minimum development time of 14 seconds or more B: Minimum development time of 10 seconds or more and less than 14 seconds C: Minimum development time of less than 10 seconds

(Ii) Etching resistance According to the above (1) Evaluation sample preparation method, a substrate for etching resistance evaluation that has passed 15 minutes after laminating is a line pattern mask in which the width of the exposed portion to the unexposed portion is 1: 1. Exposed through. Further, development was performed in a time twice as long as the minimum development time, and the time required for removing the copper foil by etching was defined as the minimum etching time, and etching was performed in 1.4 times the minimum etching time. The cured resist was peeled off with an aqueous sodium hydroxide solution, and the conductor pattern was observed with an optical microscope, and was ranked as follows based on the observation results:
A: The conductor pattern is formed linearly and no penetration of the etching solution is observed. B: The conductor pattern is formed linearly, but the etching solution is penetrated. C: The conductor pattern is formed linearly. Not formed, irregularities can be seen

(Iii) Flexibility of cured film According to the method for preparing a sample for evaluation (1) above, the prepared photosensitive resin laminate was exposed through a rectangular mask of 5 mm × 40 mm. Further, development was carried out in a time twice as long as the minimum development time to obtain a cured resist. The prepared cured resist of 5 mm × 40 mm was pulled at a rate of 100 mm / min with a tensile tester (Orientec Co., Ltd., RTM-500), and based on the elongation of the cured resist at that time, as follows: Ranked by:
A ^+: elongation of the cured resist is 45mm or more A: The elongation of the cured resist is more than 40mm, 45mm less B: in elongation of the cured resist is 15mm or more, 40mm less C: less than elongation of the cured resist is 15mm

(Iv) Aggregability A photosensitive layer having a thickness of 15 μm and an area of 2.0 m ^{2 in} the photosensitive resin laminate is dissolved in 200 ml of a 1% by mass Na ₂ CO ₃ aqueous solution, and spray pressure is applied using a circulating spray device. Spraying was performed at 0.1 MPa for 3 hours. Thereafter, the developer was allowed to stand for 1 day, and the generation of aggregates was observed. When a large amount of agglomerates are generated, powdery or oily substances are observed on the bottom and side surfaces of the spray device. A composition having good developer cohesiveness does not generate these aggregates at all. Aggregability was ranked as follows based on the state of occurrence of aggregates:
A: Agglomerates are not generated at all B: Agglomerates are seen at the bottom or part of the side of the spray device C: Agglomerates are seen throughout the spray device

(V) Acid equivalent of alkali-soluble polymer The acid equivalent refers to the mass of the alkali-soluble polymer having 1 equivalent of a carboxyl group therein. The acid equivalent is measured by a potentiometric titration method using Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. and 0.1 mol / L sodium hydroxide.

(Vi) Weight average molecular weight The weight average molecular weight was measured by Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) (KF) manufactured by Showa Denko KK -807, KF-806M, KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, polystyrene using polystyrene standard sample (calibration curve by Showex STANDARD SM-105 manufactured by Showa Denko KK) Calculated as a conversion.

(3) Evaluation results Table 1 shows the evaluation results of Examples and Comparative Examples.

  The photosensitive resin composition and the laminate described above are printed wiring boards, flexible printed wiring boards, metal foil precision processing such as lead frame manufacturing or metal mask manufacturing, semiconductor package manufacturing such as BGA or CSP, TAB or COF, etc. Production of tape substrates, production of semiconductor bumps, ITO electrodes or address electrodes, electromagnetic wave shields and the like can be suitably used for production.

Claims (13)

A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a photopolymerization initiator, and (C) a compound having an ethylenically unsaturated double bond, wherein (B) the photopolymerization initiator is 2,4,5-triarylimidazole dimer or acridine compound, and (C) a compound having an ethylenically unsaturated double bond is represented by the following general formula (I):

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ or C ₃ H ₆ , _and- (A-O) _n1 - _and- ( _{a-O) n3} - in _the sequence of -C ₂ H 4 -O- and _-C 3 _H 6 -O- repeat units may be a block be a random, sequence is a block In this case, either —C ₂ H ₄ —O— or —C ₃ H ₆ —O— may be on the —B—O— group side, and B is a divalent alkyl having 4 to 8 carbon atoms. N ₁ is an integer from 0 to 10, n ₃ is an integer from 0 to 10, n ₁ + n ₃ is an integer from 0 to 10, and n ₂ is from 1 to 20. It is an integer. }
The said photosensitive resin composition containing the compound represented by these. As the compound (C) having an ethylenically unsaturated double bond, the following general formula (II):

{Wherein R ₃ and R ₄ are each independently a hydrogen atom or a methyl group, n ₄ and n ₇ are each independently an integer of 0 to 20, and n ₄ + n ₇ is 0 is an integer from to 40, _{n 5} and _{n 6} represents, independently, an integer from 1 to _20, n 5 + _{n 6} represents an integer of 2 to 40, and _{- (C 2} H 4 -O) The sequence of repeating units of-and-(C ₃ H ₆ -O)-may be random or block, and when the sequence is a block,-(C ₂ H ₄ -O) - and _{- (C 3 H 6 -O)} - one may be a bisphenol group side. }
The photosensitive resin composition of Claim 1 which further contains the compound represented by these. In the general formula (II), _{n 4} and _{n 7} are each independently an integer of 1 to 20, and _n 4 + _{n 7} is an integer of 2 to 40, photosensitive claim 2 Resin composition.   The photosensitivity according to any one of claims 1 to 3, wherein the (A) alkali-soluble polymer is selected from alkali-soluble polymers containing styrene and / or benzyl (meth) acrylate as a copolymer component. Resin composition. In the general formula (I), _{n 2} is an integer of from 1 to 10, and _n 1 + _{n 3} is 0, the photosensitive resin composition according to any one of claims 1-4.   The photosensitive resin composition of any one of Claims 1-5 which further contains the compound which has at least 1 urethane bond in a molecule | numerator as said (C) compound which has an ethylenically unsaturated double bond. As the compound (C) having an ethylenically unsaturated double bond, the following general formula (III):

{In the formula, R ₅ and R ₆ are each independently a hydrogen atom or a methyl group, n ₈ and n ₉ are each independently an integer of 3 to 40, and — (C ₂ H ₄ The arrangement of repeating units of —O) — and — (C ₃ H ₆ —O) — may be random or block. }
The photosensitive resin composition of any one of Claims 1-6 which further contains the compound represented by these. As the compound (C) having an ethylenically unsaturated double bond, the following general formula (IV) and / or (V):

{Wherein, _{R 5} and _{R 6} are each independently a hydrogen atom or a methyl _group, n 10 _{~n 12} are each independently an integer of 1 to 30. }

{Wherein, _{R 5} and _{R 6} are each independently a hydrogen atom or a methyl _group, n 10 _{~n 12} are each independently an integer of 1 to 30. }
The photosensitive resin composition of any one of Claims 1-7 which further contains the compound represented by these.   The photosensitive resin composition of any one of Claims 1-8 which further contains the compound which has an isocyanuric group in a molecule | numerator as said (C) compound which has an ethylenically unsaturated double bond. The blending amount of the (A) alkali-soluble polymer is 40% by mass to 80% by mass when the total solid content of the photosensitive resin composition is 100% by mass,
The blending amount of the (B) photopolymerization initiator is 0.1% by mass to 20% by mass when the total solid content of the photosensitive resin composition is 100% by mass,
The blending amount of the compound (C) having an ethylenically unsaturated double bond is 5% by mass to 50% by mass when the total solid content mass of the photosensitive resin composition is 100% by mass. 10. The photosensitive resin composition according to any one of 9 above.   The photosensitive resin laminated body by which the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-10 is laminated | stacked on a support film.   A resist pattern comprising a laminating step of laminating the photosensitive resin laminate according to claim 11 on a substrate, an exposure step of exposing the photosensitive resin laminate through a mask, and a developing step of removing unexposed portions. A method of manufacturing a substrate on which is formed.   A method for forming a circuit board by etching or plating a board manufactured by the method according to claim 12.