JP5763944B2 - Photosensitive resin composition, photosensitive resin laminate, resist pattern forming method and conductor pattern manufacturing method - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate obtained by laminating the photosensitive resin composition on a support, and a substrate using the photosensitive resin laminate. The present invention relates to a method of forming a resist pattern on the surface and uses of the resist pattern. More specifically, the present invention relates to the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for IC chips (hereinafter referred to as lead frames), the precision processing of metal foils such as the manufacture of metal masks, BGA (ball Tape substrate represented by semiconductor package manufacturing such as grid array (CSP) and chip size package (TAB), TAB (Tape Automated Bonding) and COF (Chip On Film: a semiconductor IC mounted on a film-like fine wiring board) The present invention relates to a photosensitive resin composition that provides a resist pattern suitable for the manufacture of semiconductor bumps, semiconductor bumps, and members such as ITO electrodes, address electrodes, and electromagnetic wave shields in the field of flat panel displays.

  Conventionally, a printed wiring board is generally 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, and an exposed portion of the photosensitive resin composition is polymerized and cured (in the case of a negative type) or solubilized in a developer (positive). Mold) and unexposed areas (in the case of negative molds) or exposed areas (in the case of positive molds) are removed with a developer to form a resist pattern on the substrate, and etching or plating is performed to form a conductor pattern. After forming, the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate.

  In the above-described photolithography method, usually, when the photosensitive resin composition is applied onto the substrate, a solution of the photosensitive resin composition is applied to the substrate and dried, or from the support or the photosensitive resin composition. Of a photosensitive resin laminate (hereinafter also referred to as “dry film resist”) in which a layer (hereinafter also referred to as “photosensitive resin layer”) and, if necessary, a protective layer are sequentially laminated, are laminated on a substrate. Either is used. In the production of printed wiring boards, the latter dry film resist is often used.

  A method for producing a printed wiring board using a negative dry film resist will be briefly described below.

  First, when the dry film resist has a protective layer, for example, a polyethylene film, it is peeled off from the photosensitive resin layer. 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 with ultraviolet rays such as i rays (365 nm) emitted from an ultrahigh pressure mercury lamp 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. 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.

  With the recent miniaturization of wiring intervals in printed wiring boards, demands for high resolution and high adhesion have been increasing for dry film resists. High sensitivity is also required from the viewpoint of productivity improvement. On the other hand, the exposure methods are also diversified according to applications, and maskless exposure, which eliminates the need for a photomask by direct drawing with a laser, has been rapidly expanding in recent years. As a light source for maskless exposure, light having a wavelength of 350 to 410 nm, particularly i-line or h-line is often used. Therefore, it is important to be able to form a highly sensitive resist pattern for light sources in these wavelength ranges.

  Such a photosensitive resin composition for maskless exposure is difficult to simultaneously improve sensitivity, resolution, and adhesion as compared with conventional ones. Furthermore, there is a problem that hue storage stability and stability over time after laminating are low, hue stability such as decolorization and color development is lowered, and sensitivity changes due to high temperature and long-time storage.

  Patent Document 1 describes a photosensitive resin composition to which an oxetane compound is added in order to achieve both high sensitivity and high resolution.

  Patent Document 2 describes a photopolymerizable mixture containing a compound having at least one epoxy group in order to improve storage stability of hue.

  Patent Documents 3 and 4 each include a photosensitive resin composition containing a compound having one epoxy group, at least one unsaturated bond, and at least one alicyclic epoxy group, It describes that it is excellent in etching resistance.

Japanese Patent No. 3765272 JP-A-1-161001 JP-A-10-161308 JP-A-10-198027

  However, since the photosensitive resin composition described in Patent Document 1 contains a photoacid generator, the storage stability of the hue is poor, and satisfactory sensitivity cannot be expressed in the maskless exposure method. The mixture described in Patent Document 2 also cannot exhibit satisfactory sensitivity in the maskless exposure method, and also has poor resolution. In the photosensitive resin compositions described in Patent Documents 3 and 4, since the addition amount of the epoxy compound is large, the maskless exposure method cannot exhibit satisfactory sensitivity.

  For the above reasons, as a photosensitive resin composition for a dry film resist, it has high sensitivity and high resolution, excellent adhesion, and excellent hue stability during storage of a dry film solution and a dry film, and a laminate. There is a demand for a photosensitive resin composition that gives later stability over time.

  The present invention is a negative photosensitive resin composition that is excellent in sensitivity, resolution, and adhesion, does not cause decolorization during storage of a dry film, and can be developed with an alkaline aqueous solution, and a photosensitive resin composition using the photosensitive resin composition It aims at providing the method of forming a resist pattern on a board | substrate using a photosensitive resin laminated body, this photosensitive resin laminated body, and the use of this resist pattern.

  The above object can be achieved by the following configuration of the present invention.

［式中：
Ｘは、酸素原子、又は式−Ｏ−Ｘ¹−Ｏ−で表される基であり、式中Ｘ¹は炭素数１〜１００の直鎖もしくは分岐のアルキレン基、炭素数３〜１０の脂環式アルキレン基、及び炭素数５〜２０のアリーレン基からなる群から選ばれる少なくとも１つの炭化水素基を含有する２価基であり、該炭化水素基はハロゲン原子、酸素原子、及び窒素原子からなる群から選ばれる少なくとも１つの原子で置換されていてもよく；
Ｒ¹及びＲ²は、各々独立に炭素数２〜１０の直鎖又は分岐のアルキレン基であり、かつ複数存在する場合のＲ¹及びＲ²はそれぞれ同一でも異なっていてもよく、異なる場合、−（Ｒ¹−Ｏ）−及び−（Ｒ²−Ｏ）−の繰り返し単位の配列はブロックでもランダムでもよく；そして
ｍ及びｎは、各々独立に０〜５０の整数であり、かつｍ＋ｎは１〜５０の整数である。］
で表されるアルキレンオキシド化合物：０．１０〜１．０質量％を含有する、感光性樹脂組成物。
［２］ 上記一般式（Ｉ）で表されるアルキレンオキシド化合物が、下記一般式（ＩＩ）：

［式中：
Ｒ¹及びＲ²は、各々独立に炭素数２〜１０の直鎖又は分岐のアルキレン基であり、かつ複数存在する場合のＲ¹及びＲ²はそれぞれ同一でも異なっていてもよく、異なる場合、−（Ｒ¹−Ｏ）−及び−（Ｒ²−Ｏ）−の繰り返し単位の配列はブロックでもランダムでもよく；そして
ｍ及びｎは、各々独立に０〜５０の整数であり、かつｍ＋ｎは１〜５０の整数である。］
で表される化合物である、上記［１］に記載の感光性樹脂組成物。
［３］ 該（ｂ）エチレン性不飽和付加重合性モノマーが、下記一般式（ＩＩＩ）：

［式中：
Ｒ³及びＲ⁴は、各々独立にＨ又はＣＨ₃であり；
Ａは、Ｃ₂Ｈ₄であり、Ｂは、Ｃ₃Ｈ₆であり、−（Ａ−Ｏ）−及び−（Ｂ−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、ブロックの場合−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−のいずれがビスフェノールＡ基側でもよく；
ｒ及びｓは、各々独立に１〜２９の整数であり、かつｒ＋ｓは２〜３０の整数であり；そして
ｘ及びｙは、各々独立に０〜２９の整数であり、かつｘ＋ｙは０〜３０の整数である。］
で表される光重合可能な不飽和化合物からなる群から選ばれる少なくとも１種の化合物を含有する、上記［１］又は［２］に記載の感光性樹脂組成物。
［４］ 支持体と、該支持体上に積層された、上記［１］〜［３］のいずれかに記載の感光性樹脂組成物からなる感光性樹脂層とを有する、感光性樹脂積層体。
［５］ 上記［４］に記載の感光性樹脂積層体を用いて基板の上に感光性樹脂層を形成するラミネート工程、
該感光性樹脂層を露光する露光工程、及び
該露光後の感光性樹脂層における未露光部を現像液で除去することによってレジストパターンを形成する現像工程
を順に含む、レジストパターン形成方法。
［６］ 上記［４］に記載の感光性樹脂積層体を用いて、金属板又は金属皮膜絶縁板である基板の上に感光性樹脂層を形成するラミネート工程、
該感光性樹脂層を露光する露光工程、
該露光後の感光性樹脂層における未露光部を現像液で除去することによってレジストパターンを形成する現像工程、及び
該レジストパターンが形成された基板をエッチング又はめっきする導体パターン形成工程
を順に含む、導体パターンの製造方法。 [1] (a) Alkali-soluble polymer containing carboxyl group: 20 to 80% by mass, (b) Ethylenically unsaturated addition polymerizable monomer: 5 to 60% by mass, (c) Photopolymerization initiator: 0. 1 to 20% by mass, and (d) the following general formula (I):

[Where:
X is an oxygen atom or a group represented by the formula —O—X ¹ —O—, wherein X ¹ is a linear or branched alkylene group having 1 to 100 carbon atoms, or a fat having 3 to 10 carbon atoms. A divalent group containing at least one hydrocarbon group selected from the group consisting of a cyclic alkylene group and an arylene group having 5 to 20 carbon atoms, the hydrocarbon group comprising a halogen atom, an oxygen atom and a nitrogen atom; Optionally substituted with at least one atom selected from the group consisting of:
R ¹ and R ² are each independently a linear or branched alkylene group having 2 to 10 carbon atoms, and when there are a plurality of R ¹ and R ² may be the same or different, The arrangement of repeating units of-(R ¹ -O)-and-(R ² -O)-may be block or random; and m and n are each independently an integer of 0 to 50, and m + n is 1 It is an integer of ~ 50. ]
The photosensitive resin composition containing the 0.10-1.0 mass% alkylene oxide compound represented by these.
[2] The alkylene oxide compound represented by the general formula (I) is represented by the following general formula (II):

[Where:
R ¹ and R ² are each independently a linear or branched alkylene group having 2 to 10 carbon atoms, and when there are a plurality of R ¹ and R ² may be the same or different, The arrangement of repeating units of-(R ¹ -O)-and-(R ² -O)-may be block or random; and m and n are each independently an integer of 0 to 50, and m + n is 1 It is an integer of ~ 50. ]
The photosensitive resin composition according to the above [1], which is a compound represented by the formula:
[3] The (b) ethylenically unsaturated addition polymerizable monomer is represented by the following general formula (III):

[Where:
R ³ and R ⁴ are each independently H or CH ₃ ;
A is C ₂ H ₄ , B is C ₃ H ₆ , and the sequence of repeating units of — (A—O) — and — (B—O) — is a block even if it is random. In the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenol A group side;
r and s are each independently an integer from 1 to 29, and r + s is an integer from 2 to 30; and x and y are each independently an integer from 0 to 29, and x + y is from 0 to 30. Is an integer. ]
The photosensitive resin composition as described in [1] or [2] above, which contains at least one compound selected from the group consisting of photopolymerizable unsaturated compounds represented by:
[4] A photosensitive resin laminate comprising a support and a photosensitive resin layer made of the photosensitive resin composition according to any one of [1] to [3], which is laminated on the support. .
[5] A laminating step of forming a photosensitive resin layer on a substrate using the photosensitive resin laminate according to [4],
A resist pattern forming method comprising: an exposure step of exposing the photosensitive resin layer; and a development step of forming a resist pattern by removing an unexposed portion in the photosensitive resin layer after the exposure with a developer.
[6] A laminating step of forming a photosensitive resin layer on a substrate that is a metal plate or a metal film insulating plate using the photosensitive resin laminate according to [4],
An exposure step of exposing the photosensitive resin layer;
A development step of forming a resist pattern by removing a non-exposed portion in the photosensitive resin layer after the exposure with a developer, and a conductor pattern formation step of etching or plating the substrate on which the resist pattern is formed, A method for producing a conductor pattern.

  The present invention is a negative photosensitive resin composition that is excellent in sensitivity, resolution, and adhesion, has good hue storage stability, and can be developed with an alkaline aqueous solution, and a photosensitive resin using the photosensitive resin composition Provided are a laminate, a method for forming a resist pattern on a substrate using the photosensitive resin laminate, and a use of the resist pattern. The present invention can be suitably used for manufacturing printed wiring boards, lead frames, semiconductor packages, and flat displays, for example.

  Hereinafter, the present invention will be specifically described.

<Photosensitive resin composition>
In one embodiment of the present invention, (a) an alkali-soluble polymer containing a carboxyl group (hereinafter also referred to as “(a) alkali-soluble polymer”): 20 to 80% by mass, (b) ethylenically unsaturated addition polymerization Monomer (hereinafter also referred to as “(b) addition polymerizable monomer”): 5 to 60% by mass, (c) photopolymerization initiator: 0.1 to 20% by mass, and (d) the following general formula (I) :

[Where:
X is an oxygen atom or a group represented by the formula —O—X ¹ —O—, wherein X ¹ is a linear or branched alkylene group having 1 to 100 carbon atoms, or a fat having 3 to 10 carbon atoms. A divalent group containing at least one hydrocarbon group selected from the group consisting of a cyclic alkylene group and an arylene group having 5 to 20 carbon atoms, the hydrocarbon group comprising a halogen atom, an oxygen atom and a nitrogen atom; Optionally substituted with at least one atom selected from the group consisting of:
R ¹ and R ² are each independently a linear or branched alkylene group having 2 to 10 carbon atoms, and when there are a plurality of R ¹ and R ² may be the same or different, The arrangement of repeating units of-(R ¹ -O)-and-(R ² -O)-may be block or random; and m and n are each independently an integer of 0 to 50, and m + n is 1 It is an integer of ~ 50. ]
(Hereinafter also referred to as “(d) alkylene oxide compound”): a photosensitive resin composition containing 0.10 to 1.0% by mass.

(A) Alkali-soluble polymer (a) The alkali-soluble polymer contains a carboxyl group. (A) The alkali-soluble polymer typically contains a carboxyl group-containing monomer as a copolymerization component, the carboxyl group content is 100 to 600 in terms of acid equivalent, and the weight average molecular weight is 5,000 to 500, 000 thermoplastic copolymer.

  (A) The carboxyl group in the alkali-soluble polymer is necessary for the photosensitive resin composition to have developability and releasability with respect to a developer and a stripper composed of an aqueous alkali solution. The acid equivalent is preferably 100 to 600, more preferably 250 to 450. 100 or more are preferable from the viewpoint of ensuring compatibility with other components in the solvent or the photosensitive resin composition, particularly (b) addition polymerizable monomer described later, and the viewpoint of maintaining developability and peelability. To 600 or less. Here, an acid equivalent means the mass (gram) of the thermoplastic copolymer which has a 1 equivalent carboxyl group in it. The acid equivalent is measured by potentiometric titration with a 0.1 mol / L NaOH aqueous solution using a titrator (for example, Hiranuma Reporting Titrator (COM-555)).

The weight average molecular weight of the thermoplastic copolymer is preferably 5,000 to 500,000. 5,000 or more are preferable from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, and 500,000 or less is preferable from the viewpoint of maintaining developability. More preferably, the weight average molecular weight is 20,000 to 100,000. In this specification, the weight average molecular weight means a weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko KK). The weight average molecular weight can be measured under the following conditions using, for example, gel permeation chromatography manufactured by JASCO Corporation.
Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-980-50
Column oven: CO-1560
Column: KF-8025, KF-806M × 2, KF-807 in order
Eluent: THF

  The thermoplastic copolymer is preferably obtained by copolymerizing a copolymer component composed of one or more first monomers described later and one or more second monomers described later.

  The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. Here, (meth) acryl indicates acryl or methacryl. The same applies hereinafter.

  The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl. (Meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate And esters of vinyl alcohol such as vinyl acetate, (meth) acrylonitrile, styrene, and polymerizable styrene derivatives. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are particularly preferable.

  The amount of the (a) alkali-soluble polymer contained in the photosensitive resin composition of the present invention (however, based on the total amount of solid content of the photosensitive resin composition. Unless otherwise specified, The same for each component contained.) Is in the range of 20 to 80% by mass, preferably in the range of 25 to 70% by mass. This amount is 20% by mass or more from the viewpoint of maintaining alkali developability, and is 80% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.

(B) Addition-polymerizable monomer (b) An addition-polymerizable monomer is a monomer which has addition-polymerization property by having an ethylenically unsaturated group. From the viewpoint of high resolution and edge fuse resistance, the (b) addition polymerizable monomer is represented by the following general formula (III):

[Where:
R ³ and R ⁴ are each independently H or CH ₃ ;
A is C ₂ H ₄ , B is C ₃ H ₆ , and the sequence of repeating units of — (A—O) — and — (B—O) — is a block even if it is random. In the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenol A group side;
r and s are each independently an integer from 1 to 29, and r + s is an integer from 2 to 30; and x and y are each independently an integer from 0 to 29, and x + y is from 0 to 30. Is an integer. ]
It is preferable to contain at least one compound selected from the group consisting of photopolymerizable unsaturated compounds represented by:

  In the general formula (III), r and s are each preferably 1 or more from the viewpoint of the flexibility and tenting properties of the cured film, and preferably 29 or less from the viewpoint of resolution. Further, r + s is preferably 2 or more from the viewpoint of flexibility and tenting properties of the cured film, and preferably 30 or less from the viewpoint of resolution. On the other hand, x and y are each preferably 29 or less from the viewpoint of resolution, and x + y is preferably 30 or less from the viewpoint of resolution. More preferable ranges of r, s, x and y are such that r and s are each 2 or more and 18 or less, and x and y are each 18 or less.

  In the compound represented by the general formula (III), r + s + x + y is preferably 2 or more from the viewpoint of flexibility and tenting properties of the cured film, and preferably 40 or less from the viewpoint of resolution.

  Specific examples of the photopolymerizable unsaturated compound represented by the above general formula (III) include polyethylene glycol dimethacrylate (for example, Shin-Nakamura Chemical Co., Ltd.) in which an average of 2 moles of ethylene oxide is added to both ends of bisphenol A. NK ester BPE-200), polyethylene glycol dimethacrylate (for example, NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) and bisphenol A Polyalkylene glycol dimethacrylate with an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide at each end, and an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide at both ends of bisphenol A Dimethacrylate polyalkylene glycol obtained by adding the like.

  The content of the photopolymerizable unsaturated compound represented by the general formula (III) in the photosensitive resin composition is preferably 3% by mass or more from the viewpoint of sensitivity, and 70% by mass from the viewpoint of edge fuse resistance. % Or less is preferable. The content is more preferably 10 to 65% by mass, still more preferably 15 to 55% by mass.

  (B) Examples other than the compound represented by the general formula (III) that can be used as the addition polymerizable monomer include known compounds having at least one terminal ethylenically unsaturated group.

  (B) As more specific examples of addition polymerizable monomers, for example, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, phthalic anhydride and 2- Reaction product of half-ester compound with hydroxypropyl acrylate and propylene oxide (for example, Nippon Shokubai Chemical Co., Ltd., trade name OE-A 200), 4-normal octylphenoxypentapropylene glycol acrylate, 1,6-hexanediol (meth) acrylate Polyoxyalkylene glyco such as 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol diacrylate Rudiacrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, polyfunctional group (meth) acrylate containing urethane group such as urethanized product of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate, and polyfunctional (meth) of isocyanuric acid ester compound An acrylate is mentioned. These may be used alone or in combination of two or more.

  The amount of the (b) addition polymerizable monomer contained in the photosensitive resin composition of the present invention is in the range of 5 to 60% by mass, more preferably 15 to 60% by mass. This amount is 5% by mass or more from the viewpoint of suppressing poor curing and a delay in development time, and is 60% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist.

(C) Photopolymerization initiator (c) As the photopolymerization initiator, a photopolymerization initiator generally used in the field of photosensitive resins can be used. Content of the (c) photoinitiator in the photosensitive resin composition is 0.1-20 mass%. The content is 0.1% by mass or more from the viewpoint of sensitivity, and 20% by mass or less from the viewpoint of resolution. A preferable content is 0.1 to 15% by mass, and more preferably 0.1 to 10% by mass. (C) A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more types.

  (C) Preferable examples of the photopolymerization initiator include N-aryl amino acids. Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among these, N-phenylglycine is particularly preferable. In addition, as the photopolymerization initiator (c) in the present invention, the above N-aryl amino acid and a hexaarylbisimidazole derivative (hereinafter also referred to as a diaryl of a triarylimidazolyl derivative or a triarylimidazolyl dimer). It can also be used together. Examples of the triarylimidazolyl dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter referred to as 2,2′-bis (2-chlorophenyl) -4,4 ′, 5, 5'-tetraphenyl-1,1'-bisimidazole), 2,2 ', 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4', 5'- Diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer, 2,4,5-tris- (o-chlorophenyl) -diphenyl Imidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2-fluoropheny ) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3-difluoromethylphenyl) -4,4 ′, 5 5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) ) -Imidazolyl dimer, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2 '-Bis- (2,6-difluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4) -Trifluorophenyl) -4,4 ', 5,5' Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) ) -Imidazolyl dimer, 2,2′-bis- (2,3,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5,5'- Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3- Methoxyphenyl) -imidazolyl dimer and 2,2′-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) ) -Imidazolyl dimer. In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on the resolution and the strength of the cured film, and is preferably used.

  Also, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9 -Acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, acridine derivatives such as 1,12-bis (9-acridinyl) dodecane are also represented by (c ) It is preferably used as an example of a photopolymerization initiator.

  In addition to the above, compounds that can be used as the photopolymerization initiator (c) include, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methyl Quinones such as anthraquinone, benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], and aromatic ketones such as 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether , Benzoin ethers such as tilbenzoin and ethylbenzoin, benzyl dimethyl ketal, benzyl diethyl ketal, combinations of thioxanthones and alkylaminobenzoic acid, and 1-phenyl-1,2-propanedione-2-O-benzoin oxime, And oxime esters such as 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime.

  Examples of the combination of the above thioxanthones and alkylaminobenzoic acid include, for example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and dimethylaminobenzoic acid, and isopropylthioxanthone and dimethylamino. A combination with ethyl benzoate is mentioned.

  A combination of a hexaarylbisimidazole derivative and an aromatic ketone is preferable.

  It is also a preferred embodiment of the present invention to contain a pyrazoline compound. Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -Pyrazolin and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferred.

(D) Alkylene oxide compound (d) The alkylene oxide compound contains two glycidyl groups in the molecule and has the following general formula (I):

[Where:
X is an oxygen atom or a group represented by the formula —O—X ¹ —O—, wherein X ¹ is a linear or branched alkylene group having 1 to 100 carbon atoms, or a fat having 3 to 10 carbon atoms. A divalent group containing at least one hydrocarbon group selected from the group consisting of a cyclic alkylene group and an arylene group having 5 to 20 carbon atoms, the hydrocarbon group comprising a halogen atom, an oxygen atom and a nitrogen atom; Optionally substituted with at least one atom selected from the group consisting of:
R ¹ and R ² are each independently a linear or branched alkylene group having 2 to 10 carbon atoms, and when there are a plurality of R ¹ and R ² may be the same or different, The arrangement of repeating units of-(R ¹ -O)-and-(R ² -O)-may be block or random; and m and n are each independently an integer of 0 to 50, and m + n is 1 It is an integer of ~ 50. ]
It is represented by In the present invention, the acid scavenging action of the above (d) alkylene oxide compound effectively prevents the dry film resist from being colored during storage, thereby providing good storage stability of the hue, and good solution. Imageability is obtained.

X in the general formula (I) is an oxygen atom or a hydrocarbon chain having both ends substituted with an oxygen atom, as represented by the above formula —O—X ¹ —O—. X ¹ − in the above formula —O—X ¹ —O— is a linear or branched alkylene group having 1 to 100 carbon atoms, an alicyclic alkylene group having 3 to 10 carbon atoms, and carbon from the viewpoint of solubility. It is a divalent group containing at least one hydrocarbon group selected from the group consisting of several 5 to 20 arylene groups. X is an oxygen atom, a divalent group obtained by removing hydrogen from the hydroxyl group of bisphenol A (hereinafter, also referred to as bisphenol A type group), and a divalent group obtained by removing hydrogen from the hydroxyl group of hydrogenated bisphenol A from the viewpoint of resolution. A group (hereinafter also referred to as hydrogenated bisphenol A type group) is particularly preferred, and a bisphenol A type group is most preferred.

  The alkyleneoxy compound in which X in the general formula (I) is a bisphenol A type group is specifically represented by the following general formula (II):

[Where:
R ¹ and R ² are each independently a linear or branched alkylene group having 2 to 10 carbon atoms, and when there are a plurality of R ¹ and R ² may be the same or different, The arrangement of repeating units of-(R ¹ -O)-and-(R ² -O)-may be block or random; and m and n are each independently an integer of 0 to 50, and m + n is 1 It is an integer of ~ 50. ]
It is represented by

R ¹ and R ² in the general formula (I) are each independently a linear or branched alkylene group having 2 to 10 carbon atoms, and when there are a plurality of R ¹ and R ² , they are the same or different. If different, the arrangement of the repeating units of — (R ¹ —O) — and — (R ² —O) — may be block or random.

R ¹ and R ² are particularly preferably an ethylene group, a propylene group, a tetramethylene group, a neopentyl group, and a hexamethylene group from the viewpoint of resolution.

  From the viewpoint of resolution, m and n are each independently an integer of 0 to 50, and m + n is an integer of 1 to 50. From the viewpoint of viscosity suitable for the production of the photosensitive resin composition, m + n is preferably an integer of 1 to 20, and more preferably an integer of 1 to 10 from the viewpoint of resolution.

  (D) As a preferable example of the alkylene oxide compound, when X is an oxygen atom, ethylene glycol diglycidyl ether (for example, Epolite 40E manufactured by Kyoeisha Chemical Co., Ltd.), diethylene glycol diglycidyl ether (for example, Epolite 100E manufactured by Kyoeisha Chemical Co., Ltd.) ), Triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether (for example, Epolite 200E manufactured by Kyoeisha Chemical Co., Ltd.), pentaethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, heptaethylene glycol diglycidyl ether, octaethylene Glycol diglycidyl ether, nonaethylene glycol diglycidyl ether (for example, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), decaethylene Recall diglycidyl ether, propylene glycol diglycidyl ether (for example, Epolite 70P manufactured by Kyoeisha Chemical Co., Ltd.), dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether (for example, Epolite 200P manufactured by Kyoeisha Chemical Co., Ltd.), tetrapropylene glycol Diglycidyl ether, pentapropylene glycol diglycidyl ether, hexapropylene glycol diglycidyl ether, heptapropylene glycol diglycidyl ether (for example, Epolite 400P manufactured by Kyoeisha Chemical Co., Ltd.), octapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether Decapropylene glycol diglycidyl ether,

  Tetramethylene glycol diglycidyl ether, ditetramethylene glycol diglycidyl ether, tritetramethylene glycol diglycidyl ether, tetratetramethylene glycol diglycidyl ether, pentatetramethylene glycol diglycidyl ether, hexatetramethylene glycol diglycidyl ether, heptatetramethylene Glycol diglycidyl ether, octatetramethylene glycol diglycidyl ether, nonatetramethylene glycol diglycidyl ether, diglycidyl ether containing 1 mol and 2 mol of ethylene glycol and propylene glycol, respectively, 1 each of ethylene glycol and propylene glycol Diglycidyl ether, ethylene containing 3 moles and 3 moles each Diglycidyl ether containing 1 mol and 4 mol of recall and propylene glycol, respectively, Diglycidyl ether containing 1 mol and 5 mol of ethylene glycol and propylene glycol, respectively, 1 mol of ethylene glycol and propylene glycol, respectively Diglycidyl ether containing 9 mol each, diglycidyl ether containing 2 mol and 1 mol of ethylene glycol and propylene glycol, diglycidyl ether containing 2 mol and 2 mol of ethylene glycol and propylene glycol, respectively, ethylene Diglycidyl ether containing 2 mol and 3 mol of glycol and propylene glycol, respectively, 2 mol of ethylene glycol and propylene glycol, respectively Diglycidyl ether containing by mole of ethylene glycol and propylene glycol and the diglycidyl ethers containing each 2 moles and 5 moles, respectively, diglycidyl ethers containing ethylene glycol and propylene glycol by 2 moles and 8 moles, respectively,

  Diglycidyl ether containing 3 mol and 1 mol of ethylene glycol and propylene glycol, respectively, Diglycidyl ether containing 3 mol and 2 mol of ethylene glycol and propylene glycol, respectively, 3 mol of ethylene glycol and propylene glycol, respectively And diglycidyl ether containing 3 mol each, diglycidyl ether containing 3 mol and 4 mol ethylene glycol and propylene glycol, diglycidyl ether containing 3 mol and 5 mol ethylene glycol and propylene glycol, respectively. Diglycidyl ether containing 3 mol and 7 mol of ethylene glycol and propylene glycol, respectively, and 5 each of ethylene glycol and propylene glycol Diglycidyl ether containing 5 moles and 2 moles of ethylene glycol and propylene glycol, respectively, and diglycidyl ether containing 5 moles and 3 moles of ethylene glycol and propylene glycol, respectively. Diglycidyl ether containing 5 mol and 4 mol of ethylene glycol and propylene glycol, respectively, diglycidyl ether containing 5 mol and 5 mol of ethylene glycol and propylene glycol, respectively.

  Diglycidyl ether containing 6 mol and 1 mol of ethylene glycol and propylene glycol, respectively, Diglycidyl ether containing 6 mol and 2 mol of ethylene glycol and propylene glycol, respectively, 6 mol of ethylene glycol and propylene glycol, respectively And diglycidyl ether containing 3 mol each, diglycidyl ether containing 6 mol and 4 mol ethylene glycol and propylene glycol, diglycidyl ether containing 7 mol and 1 mol ethylene glycol and propylene glycol respectively, Diglycidyl ether containing 7 mol and 2 mol of ethylene glycol and propylene glycol, respectively, and 7 each of ethylene glycol and propylene glycol And diglycidyl ether containing 3 moles of ethylene, diglycidyl ether containing 8 moles and 1 mole of ethylene glycol and propylene glycol, respectively, and diglycidyl ether containing 8 moles and 2 moles of ethylene glycol and propylene glycol, respectively. Diglycidyl ether, neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, 9 mol and 1 mol of ethylene glycol and propylene glycol, respectively) Kyoeisha Chemical Co., Ltd. Epolite 1600) and the like.

  Preferred examples of the (d) alkylene oxide compound when X is a bisphenol A type group include bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A- Propylene oxide 4 mol adduct diglycidyl ether, bisphenol A-propylene oxide 6 mol adduct diglycidyl ether, bisphenol A-propylene oxide 8 mol adduct diglycidyl ether, bisphenol A-propylene oxide 10 mol adduct diglycidyl ether, bisphenol A-ethylene oxide 2 mol adduct diglycidyl ether, bisphenol A-ethylene oxide 4 mol adduct diglycidyl ether, bisphenol A-ethyleneoxy 6 mol adduct diglycidyl ether, bisphenol A- ethylene oxide 8 mol adduct diglycidyl ether, bisphenol A- ethylene 10 mol adduct diglycidyl ether, and the like.

  Preferred examples of (d) alkylene oxide compounds when X is a hydrogenated bisphenol A type group include hydrogenated bisphenol A-ethylene oxide 2 mol adduct diglycidyl ether, hydrogenated bisphenol A-ethylene oxide 4 mol adduct diglycidyl ether. Hydrogenated bisphenol A-ethylene oxide 6 mol adduct diglycidyl ether, hydrogenated bisphenol A-ethylene oxide 8 mol adduct diglycidyl ether, hydrogenated bisphenol A-ethylene oxide 10 mol adduct diglycidyl ether, hydrogenated bisphenol A-propylene oxide 2 mol adduct diglycidyl ether, hydrogenated bisphenol A-propylene oxide 4 mol adduct diglycidyl ether, hydrogenated bisphenol A-propylene oxide 6 mol adduct digli Examples thereof include sidyl ether, hydrogenated bisphenol A-propylene oxide 8 mol adduct diglycidyl ether, and hydrogenated bisphenol A-propylene oxide 10 mol adduct diglycidyl ether.

  Content of the said (d) alkylene oxide compound in the photosensitive resin composition in this invention is the range of 0.10-1.0 mass%, and a more preferable range is 0.20-0.50 mass%. is there. The content is 0.10% by mass or more, preferably 0.20% by mass or more from the viewpoint of ensuring the storage stability of the hue of the dry film resist and obtaining good resolution. Moreover, it is 1.0 mass% or less from a viewpoint of obtaining sufficient sensitivity, Preferably it is 0.50 mass% or less.

(Other ingredients)
The photosensitive resin composition of the present invention comprises (a) an alkali-soluble polymer, (b) an addition polymerizable monomer, (c) a photopolymerization initiator, and (d) an alkylene oxide compound as essential components. In addition to the above, additives such as the following discoloring agents, dyes, plasticizers, antioxidants, organic halogen compounds, and stabilizers (radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles) One or more compounds selected from the group consisting of:

  Examples of the color changing agent include leuco dyes and fluoran dyes. Examples of leuco dyes include leuco crystal violet and leucomalachite green.

  The content of the color changing agent in the photosensitive resin composition is preferably 0.01% by mass or more from the viewpoint of recognizing good colorability (that is, color developability), and from the viewpoint of hue stability and a good image. From the viewpoint of obtaining characteristics, 5% by mass or less is preferable.

  Examples of the dye include basic green 1 [633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), malachite green oxalate [2437-29-8] (for example, Aizen Malachite). Green, trade name, manufactured by Hodogaya Chemical Co., Ltd.), brilliant green [633-03-4] fuchsin [632-99-5] methyl violet [603-47-4], methyl violet 2B [8004-87-3] crystal Violet [548-62-9] Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (for example, Aizen Victoria Pure Blue BOH, trade name) , Hodogaya Chemical ), Rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2], etc., among which basic green 1, malachite green oxalate, And Basic Blue 7 is preferred.

  The content of the dye in the photosensitive resin composition is preferably in the range of 0.001 to 0.3% by mass, and more preferably in the range of 0.01 to 0.12% by mass. The content is preferably 0.001% by mass or more from the viewpoint of recognizing good colorability, and preferably 0.3% by mass or less from the viewpoint of maintaining sensitivity.

  Examples of the plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monomethyl ether, Glycol esters such as oxypropylene monoethyl ether and polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, citric acid Triethyl acid, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate And the like.

  Content of the plasticizer in the photosensitive resin composition becomes like this. Preferably it is 0.1-50 mass%, More preferably, it is 1-20 mass%. The content is preferably 0.1% by mass or more from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, and 50% by mass from the viewpoint of suppressing insufficient curing and cold flow. The following is preferable.

  Examples of the antioxidant include triphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris (2,4-di-t-butylphenyl) phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., product) No. 2112), tris (monononylphenyl) phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 1178), and bis (monononylphenyl) -dinonylphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 329K).

  Content of antioxidant in the photosensitive resin composition becomes like this. Preferably it is the range of 0.01-0.8 mass%, More preferably, it is the range of 0.01-0.3 mass%. When the said content is 0.01 mass% or more, the effect which is excellent in the hue stability of the photosensitive resin composition expresses favorably, and the sensitivity at the time of exposure of the photosensitive resin composition is favorable. Moreover, when the said content is 0.8 mass% or less, since color developability is suppressed, hue stability is favorable and adhesiveness is also favorable.

  Examples of the organic 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, and chlorinated triazine compounds, among others In particular, tribromomethylphenylsulfone is preferably used. The content of the organic halogen compound in the photosensitive resin composition is preferably 0.01 to 3% by mass.

  As the stabilizer, one or more selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles for improving the thermal stability and / or storage stability of the photosensitive resin composition The compound of this is mentioned.

  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, and diphenylnitrosamine.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzo. Examples include triazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.

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

  The total content of the radical polymerization inhibitor, benzotriazoles and carboxybenzotriazoles in the photosensitive resin composition is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. It is. The total content is preferably 0.01% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% by mass or less from the viewpoint of maintaining good sensitivity.

<Photosensitive resin composition preparation solution>
The photosensitive resin composition of the present invention may be used as a photosensitive resin composition preparation liquid formed by adding a solvent thereto. Suitable solvents include ketones represented by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
Another aspect of the present invention provides a photosensitive resin laminate having a support and a photosensitive resin layer made of the above-described photosensitive resin composition according to the present invention, which is laminated on the support. The photosensitive resin laminate of the present invention has a protective layer on the surface of the photosensitive resin layer opposite to the support-forming side, if necessary, in addition to the photosensitive resin layer and the support that supports the layer. May be.

  The support is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support 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, polystyrene film. , A polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used. The haze is preferably 5 or less. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 μm is preferably used because the strength needs to be maintained.

  Further, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and can be easily peeled with respect to the adhesion with the photosensitive resin layer. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Further, for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

  The thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention is preferably 5 to 100 μm, more preferably 7 to 60 μm. As the thickness is thinner, the resolution is improved, and as the thickness is increased, the film strength is improved. Therefore, the thickness can be appropriately selected according to the application.

  As a method for preparing the photosensitive resin laminate of the present invention by sequentially laminating the support, the photosensitive resin layer, and if necessary, the protective layer, a conventionally known method can be employed.

  For example, the photosensitive resin composition used for forming the photosensitive resin layer is made into the above-mentioned photosensitive resin composition preparation solution, and is first coated on a support using a bar coater or a roll coater and dried. Then, a photosensitive resin layer made of the photosensitive resin composition is laminated on the support. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
Another aspect of the present invention includes a laminating step of forming a photosensitive resin layer on a substrate using the above-described photosensitive resin laminate of the present invention, an exposure step of exposing the photosensitive resin layer, and after the exposure A resist pattern forming method including a developing step of sequentially forming a resist pattern by removing an unexposed portion of the photosensitive resin layer with a developer. An example of a specific method for forming a resist pattern using the photosensitive resin laminate of the present invention will be described.

  First, in a laminating process, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. Examples of the material of the substrate include copper, SUS, glass, ITO, and the like. In this case, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature at this time is generally 40 to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the resist pattern obtained by performing this thermocompression bonding twice or more improves. At this time, a two-stage laminator provided with two rolls may be used for pressure bonding, or a laminate of the substrate and the photosensitive resin layer may be repeated several times and pressure bonded.

  Next, in the exposure step, the photosensitive resin composition is exposed to active light using an exposure machine. If necessary, the exposure can be performed after peeling the support. In the case of exposure through a photomask, the exposure amount is determined from the light source illuminance and the exposure time, and may be measured using a light meter.

  In the exposure step, a maskless exposure method may be used. In maskless exposure, exposure is performed directly on the substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the development step, unexposed portions in the exposed photosensitive resin layer are removed with a developer using a developing device. After exposure, if a support is present on the photosensitive resin layer, this is excluded. Subsequently, the unexposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution such as Na ₂ CO ₃ or K ₂ CO ₃ is preferable. These are selected in accordance with the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution having a concentration of 0.2 to 2% by mass is generally used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed. In addition, it is preferable to maintain the temperature of this developing solution in a development process at the constant temperature in the range of 20-40 degreeC.

  Although a resist pattern is obtained by the above-mentioned process, a heating process at 100 to 300 ° C. can be further performed depending on the case. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace such as hot air, infrared rays, or far infrared rays can be used.

<Conductor pattern manufacturing method>
Another aspect of the present invention is a lamination process in which a photosensitive resin layer is formed on a substrate that is a metal plate or a metal film insulating plate using the above-described photosensitive resin laminate of the present invention, and the photosensitive resin layer An exposure step of exposing the substrate, a developing step of forming a resist pattern by removing a non-exposed portion of the exposed photosensitive resin layer with a developer, and a conductor pattern for etching or plating the substrate on which the resist pattern is formed Provided is a method for producing a conductor pattern, which includes a forming step in order. That is, the method for producing a conductor pattern of the present invention is carried out by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-described resist pattern forming method, and then performing the following conductor pattern forming step. The In the conductor pattern forming step, a conductor pattern is formed on a substrate surface (for example, a copper surface) exposed by development using a known etching method or plating method on a substrate on which a resist pattern is formed by the method described above.

  Furthermore, the present invention is suitably applied in the following uses, for example.

<Manufacture of printed wiring boards>
In addition, after manufacturing a conductor pattern by the above methods according to this invention, it has a desired wiring pattern by further performing the peeling process which peels a resist pattern from a board | substrate with the aqueous solution which has alkalinity stronger than a developing solution. A printed wiring board can be obtained. In the production of a printed board, a copper-clad laminate or a flexible board is preferably used as the board. Although there is no restriction | limiting in particular about the aqueous alkali solution for peeling (henceforth "peeling liquid"), The aqueous solution of NaOH or KOH with the density | concentration of 2-5 mass% is generally used. A small amount of a water-soluble solvent can be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably in the range of 40 to 70 ° C.

<Manufacture of lead frames>
A lead frame can be manufactured by using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate, forming a resist pattern by the above-described resist pattern forming method, and then performing the following steps. First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Then, the peeling process which peels a resist pattern with the method similar to the manufacturing method of the above-mentioned printed wiring board is performed, and a desired lead frame is obtained.

<Manufacture of a substrate having an uneven pattern>
The resist pattern formed by the resist pattern forming method of the present invention can be used as a protective mask member when processing a substrate by a sandblasting method. Examples of the substrate at this time include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal material. A resist pattern is formed on these substrates by the same method as the above-described resist pattern forming method. After that, a blasting material is sprayed on the formed resist pattern to be cut to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkali stripping solution or the like, and then on the substrate. A substrate having a fine uneven pattern can be produced. A known material can be used as the blasting material used in the above-mentioned sandblasting process. For example, fine particles having a particle diameter of about 2 to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel, etc. are used. .

<Manufacture of semiconductor packages>
A semiconductor package can be manufactured by using a wafer on which circuit formation as an LSI has been completed as a substrate and forming a resist pattern on the wafer by the above-described resist pattern forming method, followed by the following steps. First, a step of forming a conductor pattern by performing columnar plating such as copper or solder on the opening exposed by development is performed. Thereafter, a peeling process for peeling the resist pattern by the same method as the above-described method for manufacturing a printed wiring board is performed, and further, a thin metal layer other than the columnar plating is removed by etching. A semiconductor package is obtained.

  Below, it shows about the preparation method of the sample for evaluation of Examples 1-8 and Comparative Examples 1-5, the evaluation method about the obtained sample, and an evaluation result.

1. Production of Evaluation Samples The photosensitive resin laminates in Examples 1 to 8 and Comparative Examples 1 to 5 were produced as follows.

<Preparation of photosensitive resin laminate>
The surface of a 16 μm thick polyethylene terephthalate film as a support is prepared by mixing the compound shown in Table 2 in the composition ratio (unit: parts by mass) shown in Table 1, stirring and mixing well. The mixture was uniformly coated using a bar coater and dried in a dryer at 95 ° C. for 3 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 30 μm.

  In the compositions shown in Tables 1 and 2, MEK represents methyl ethyl ketone, and the mass parts of P-1 to P-3 in Table 1 are solid amounts.

  Next, a 22 μm thick polyethylene film was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.

<Preparation of photosensitive resin laminate sample for hue stability evaluation>
The photosensitive resin composition solution prepared by blending the compounds shown in Table 2 at the composition ratio shown in Table 1 (unit: parts by mass), stirring and mixing well, was stored at a temperature of 40 ° C. for 3 days, and then the support. A 16 μm thick polyethylene terephthalate film was uniformly coated using a bar coater. This was dried in a dryer at 95 ° C. for 3 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 30 μm.

  Next, a 22 μm thick polyethylene film was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate sample for hue stability evaluation.

<Board surface preparation>
As a substrate for evaluating sensitivity, resolution, adhesion, and hue stability, a 1.2 mm thick copper clad laminate on which 35 μm rolled copper foil is laminated, and the surface is subjected to wet buffol polishing (manufactured by 3M Co., Ltd.). Scotch Bright (registered trademark) HD # 600, 2 times).

<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, it was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-70) on a copper clad laminate that had been leveled and preheated to 60 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
(Direct drawing type exposure method) It exposed with the direct drawing type exposure apparatus (Nippon Orbotech Co., Ltd., Paragon 9000, main wavelength 355nm).

<Development>
After the polyethylene terephthalate film is peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using an alkali developing machine (produced by Fuji Kiko Co., Ltd., a dry film developing machine), and an unexposed portion of the photosensitive resin layer Was removed by dissolution in a time twice as long as the minimum development time. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the minimum development time.

2. Evaluation Method 2.1 Sensitivity Evaluation Using a substrate that had passed 15 minutes after the above <laminate>, the substrate was exposed at an exposure amount of 25 mJ / cm ² using the above-described exposure machine with a stove 21-step tablet as a mask. Thereafter, development was carried out by the method described in <Development>, and the remaining film limit step number at that time was evaluated according to the following criteria as an index of sensitivity.
○: The maximum number of remaining film stages is 7 or more.
Δ: The maximum number of remaining film stages is 6 or more and less than 7 stages.
X: The maximum number of remaining film stages is less than 6.

2.2 Resolution Evaluation The substrate for resolution evaluation that had passed 15 minutes after the <laminate> was exposed through a line pattern mask in which the width of the exposed area to the unexposed area was 1: 1. Development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which a cured resist line was normally formed was defined as a resolution value, and the resolution was ranked as follows.
○: The resolution value is 20 μm or less.
(Triangle | delta): The value of resolution exceeds 20 micrometers and is 24 micrometers or less.
X: The resolution value exceeds 24 μm.

2.3 Evaluation of hue stability (difference in transmittance at 600 nm)
The polyethylene film was peeled off from the photosensitive resin laminate, and the transmittance of light having a wavelength of 600 nm was measured using a UV-vis spectrometer (manufactured by Shimadzu Corporation, UV-240). At this time, the same polyethylene terephthalate film as that used for the photosensitive resin laminate was put on the reference side of the spectrometer to cancel the transmittance derived from the polyethylene terephthalate film.

Sample for evaluating hue stability of a photosensitive resin laminate prepared using a photosensitive resin composition solution after storage at a temperature of 40 ° C. for 3 days and a photosensitive resin prepared using a photosensitive resin composition solution before storage The transmittance of the conductive resin laminate was compared, and the rank was classified as follows according to the difference.
○: The difference in transmittance at 600 nm is less than ± 5%.
Δ: The difference in transmittance at 600 nm is ± 5% or more and less than ± 10%.
X: The difference in transmittance at 600 nm is ± 10% or more.

2.4 Evaluation Results Table 1 shows the evaluation results of Examples 1 to 8 and Comparative Examples 1 to 5.

  As is clear from the evaluation results in Table 1, it was revealed that Examples 1 to 8 were superior in sensitivity, resolution, and adhesion compared to Comparative Examples 1 to 5.

  The present invention includes the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the manufacture of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA or CSP, the manufacture of tape substrates such as COF and TAB, the production of semiconductor bumps It can be used in a method of manufacturing a partition of a flat panel display such as manufacturing, ITO electrode, address electrode, electromagnetic wave shield and the like.

Claims (6)

(A) Alkali-soluble polymer containing carboxyl group: 20 to 80% by mass, (b) Ethylenically unsaturated addition polymerizable monomer: 5 to 60% by mass, (c) Photopolymerization initiator: 0.1 to 20 % By mass, and (d) the following general formula (I):

[Where:
X is an oxygen atom or a group represented by the formula —O—X ¹ —O—, wherein X ¹ is a linear or branched alkylene group having 1 to 100 carbon atoms, or a fat having 3 to 10 carbon atoms. A divalent group containing at least one hydrocarbon group selected from the group consisting of a cyclic alkylene group and an arylene group having 5 to 20 carbon atoms, the hydrocarbon group comprising a halogen atom, an oxygen atom and a nitrogen atom; Optionally substituted with at least one atom selected from the group consisting of:
R ¹ and R ² are each independently a linear or branched alkylene group having 2 to 10 carbon atoms, and when there are a plurality of R ¹ and R ² may be the same or different, The arrangement of repeating units of-(R ¹ -O)-and-(R ² -O)-may be block or random; and m and n are each independently an integer of 0 to 50, and m + n is 1 It is an integer of ~ 50. ]
The photosensitive resin composition which contains 0.10-1.0 mass% represented by these as a ratio with respect to the photosensitive resin composition solid content total amount . The alkylene oxide compound represented by the general formula (I) is represented by the following general formula (II):

[Where:
R ¹ and R ² are each independently a linear or branched alkylene group having 2 to 10 carbon atoms, and when there are a plurality of R ¹ and R ² may be the same or different, The arrangement of repeating units of-(R ¹ -O)-and-(R ² -O)-may be block or random; and m and n are each independently an integer of 0 to 50, and m + n is 1 It is an integer of ~ 50. ]
The photosensitive resin composition of Claim 1 which is a compound represented by these. The (b) ethylenically unsaturated addition polymerizable monomer is represented by the following general formula (III):

[Where:
R ³ and R ⁴ are each independently H or CH ₃ ;
A is C ₂ H ₄ , B is C ₃ H ₆ , and the sequence of repeating units of — (A—O) — and — (B—O) — is a block even if it is random. In the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenol A group side;
r and s are each independently an integer from 1 to 29, and r + s is an integer from 2 to 30; and x and y are each independently an integer from 0 to 29, and x + y is from 0 to 30. Is an integer. ]
The photosensitive resin composition of Claim 1 or 2 containing the at least 1 sort (s) of compound chosen from the group which consists of a photopolymerizable unsaturated compound represented by these.   The photosensitive resin laminated body which has a support body and the photosensitive resin layer which consists of a photosensitive resin composition of any one of Claims 1-3 laminated | stacked on this support body. A laminating step of forming a photosensitive resin layer on a substrate using the photosensitive resin laminate according to claim 4,
A resist pattern forming method comprising: an exposure step of exposing the photosensitive resin layer; and a development step of forming a resist pattern by removing an unexposed portion in the photosensitive resin layer after the exposure with a developer. A laminate step of forming a photosensitive resin layer on a substrate that is a metal plate or a metal film insulating plate using the photosensitive resin laminate according to claim 4,
An exposure step of exposing the photosensitive resin layer;
A development step of forming a resist pattern by removing a non-exposed portion in the photosensitive resin layer after the exposure with a developer, and a conductor pattern formation step of etching or plating the substrate on which the resist pattern is formed,
A method for producing a conductor pattern.