JP2015152854A - Photosensitive resin composition, photosensitive resin laminate, and resist pattern forming method - Google Patents

Abstract

Provided is a photosensitive resin composition capable of suppressing etching residue or plating failure. A photosensitive resin composition comprising (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; and (C) a photopolymerization initiator, the photosensitive resin composition on a copper substrate. When the photosensitive resin composition is laminated, heated at 60 ° C., and then developed at 1.2 times the minimum development time, the photosensitive resin has a heating time of 7 hours or more required for producing a development residue. A composition is provided. [Selection] Figure 1

Description

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

  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 a protective layer, if necessary, 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, a photosensitive resin layer and a support are laminated on a substrate, for example, 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 are increasing for dry film resists. In addition, high sensitivity of dry film resist 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 nm 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, since the storage stability of the hue and the stability over time after lamination are low, there is a problem that the hue stability such as decolorization and color development is lowered, and the sensitivity is changed due to high temperature and long-term storage.

  Regarding the above problem, 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

  The photosensitive resin composition is required to have higher production efficiency, while having less etching residue or plating failure and higher quality. However, the photosensitive resin compositions described in Patent Documents 1, 3 and 4 and the photopolymerizable mixture described in Patent Document 2 still have room for improvement in terms of etching residues and plating.

  Therefore, this invention makes it a subject to provide the photosensitive resin composition which can suppress an etching residue or plating mounting defect.

In order to solve the above problems, the present invention adopts the following means:
[1]
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond; and (C) a photopolymerization initiator;
A photosensitive resin composition comprising:
When the photosensitive resin composition is laminated on a copper substrate, heated at 60 ° C., and then developed at 1.2 times the minimum development time, the heating time required for developing residue to be produced is 7 hours or more. ,
The photosensitive resin composition.
[2]
Said (A) alkali-soluble polymer: 10 mass%-90 mass%;
(B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass;
The photosensitive resin composition according to [1], comprising:
[3]
Exposure required to cure the photosensitive resin composition when the photosensitive resin composition exposed through a mask having an optical density (OD) of 0.70 is developed in a time twice as long as the minimum development time. the amount (mJ / cm ²⁾ is, at 16 mJ / cm ² or less, [1] or photosensitive resin composition according to [2].
[4]
(D) Benzotriazole derivative: 0.1% by mass to 10% by mass;
The photosensitive resin composition according to any one of [1] to [3], further comprising:
[5]
As the (D) benzotriazole derivative, the following general formula (I):
{Wherein R _{1 to} R ₄ are each independently hydrogen or an alkyl group, or at least one of R _{1 to} R ₄ is a carboxyl group, and the rest of R _{1 to} R ₄ are each Independently, hydrogen or an alkyl group, and R ₅ is hydrogen, an alkyl group, or the following general formula (II):
(Wherein R ₆ and R ₇ are each independently hydrogen, an alkyl group or a hydroxylalkyl group, and n is an integer of 1 to 4). }
The photosensitive resin composition of any one of [1]-[4] containing the compound represented by these.
[6]
The photosensitive resin composition of any one of [1]-[5] containing 0.01 mass%-0.2 mass% N-arylamino acid as said (C) photoinitiator.
[7]
The photosensitive resin composition of any one of [1]-[6] containing 0.1 mass%-20 mass% acridine derivative as said (C) photoinitiator.
[8]
(E) Epoxy compound: 0.20 mass% to 10 mass%;
The photosensitive resin composition according to any one of [1] to [7], further comprising:
[9]
As the (E) epoxy compound, the following general formula (III):
{In the formula, X is an oxygen atom, or -O-X ₁ -O- (wherein X ₁ is a linear or branched alkylene group having 1 to 100 carbon atoms, or an alicyclic group having 3 to 10 carbon atoms. And a divalent group containing at least one hydrocarbon group selected from the group consisting of an alkylene group and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group includes a halogen atom, an oxygen atom, and a nitrogen atom R ₈ and R ₉ are each independently a linear or branched alkylene group having 1 to 100 carbon atoms, which may be substituted with at least one atom selected from the group consisting of A divalent group containing at least one hydrocarbon group selected from the group consisting of an alicyclic alkylene group having 3 to 10 carbon atoms and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is Halogen atom, oxygen atom And it may be substituted with at least one atom selected from the group consisting of nitrogen atom, and when R ₈ and R ₉ are present together, R ₈ and R _9, which may be the same or different, When R ₈ and R ₉ are different, the sequence of repeating units of — (R ₈ —O) — and — (R ₉ —O) — may be block or random; and m and n are each independently , An integer from 0 to 50, and m + n is an integer from 1 to 50. }
The photosensitive resin composition of any one of [1]-[8] containing the compound represented by these.
[10]
A photosensitive resin laminate in which a photosensitive resin layer made of the photosensitive resin composition according to any one of [1] to [8] is laminated on a support.
[11]
[10] A lamination step of laminating the photosensitive resin laminate on the substrate, an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and developing and removing an unexposed portion of the photosensitive resin layer A method for forming a resist pattern, comprising a development step.
[12]
The resist pattern forming method according to [11], wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern or an exposure method of projecting a photomask image through a lens.
[13]
The resist pattern forming method according to [12], wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can suppress an etching residue or plating mounting defect can be provided.

FIG. 1 is a photograph of a developed surface of the evaluation substrate taken after the laminated evaluation substrate was heated and developed for 3 hours in the heat storage evaluation of Comparative Example 2.

  Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be specifically described.

<Photosensitive resin composition>
In this embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator. When this photosensitive resin composition is laminated on a copper substrate, heated at 60 ° C., and then developed at 1.2 times the minimum development time, the heating time required for developing residue to be produced is 7 hours or more, 8 More than 9 hours or more or more than 9 hours.

  Conventionally, when manufacturing a printed wiring board, for example, a photosensitive resin composition is laminated on a copper-clad laminate, and processes such as exposure, development, and etching are employed in subsequent steps. Here, laminating is usually performed while heating, and then cooled and supplied to the next step. In recent years, it has been demanded that the cooling step is simple from the viewpoint of improving the production rate. As a result, the laminate substrate is maintained at a high temperature for a long time, the thermal load on the photosensitive resin composition tends to increase, an unexpected curing reaction proceeds, and etching residues or plating defects are poor. It can be a cause. That is, due to an unexpected curing reaction, a cured portion is generated even in an unexposed portion, and a portion that should be removed during development remains without being removed. For portions where the resist is not sufficiently removed, the etching solution or the plating solution cannot reach the substrate, resulting in an etching residue or plating failure.

  According to the photosensitive resin composition according to the present embodiment, even when stored for a certain period of time under high temperature conditions, the progress of curing is moderately suppressed, so that etching residues or plating defects are suppressed.

In the present embodiment, when the photosensitive resin composition is exposed through a mask having an optical density (OD) of 0.70 and developed in a time twice as long as the minimum development time, this photosensitive resin composition is used. exposure required to cure the object (mJ / cm ²⁾ is, 16 mJ / cm ² or less, or is preferably 14 mJ / cm ² or less. A photosensitive resin composition having an exposure amount of 16 mJ / cm ² or less necessary for curing under these conditions is preferable from the viewpoint of the adhesiveness of the cured resist when the exposure time is shortened in order to obtain high productivity.

  In this embodiment, it is preferable that the photosensitive resin composition further includes (D) a benzotriazole derivative and / or (E) an epoxy compound in addition to the components (A) to (C). The above components (A) to (E) and other components will be described below.

(A) Alkali-soluble polymer Generally, (A) 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 because the photosensitive resin composition has 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. From the viewpoint of ensuring compatibility with other components in the solvent or the photosensitive resin composition, in particular, (B) a compound having an ethylenically unsaturated double bond described later, the acid equivalent is preferably 100 or more, From the viewpoint of maintaining developability and peelability, the acid equivalent is preferably 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. From the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, the weight average molecular weight is preferably 5,000 or more, and from the viewpoint of maintaining developability, the weight average molecular weight is 500, 000 or less is preferable. More preferably, the weight average molecular weight is 20,000 to 100,000.

  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. Of these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are particularly preferable.

  Content of the (A) alkali-soluble polymer in the photosensitive resin composition of the present invention (however, based on the total amount of solid content of the photosensitive resin composition. The same applies to the components.) Is 10% by mass to 90% by mass, preferably 20% by mass to 80% by mass, and more preferably 25% by mass to 70% by mass. This content is 10% by mass or more from the viewpoint of maintaining alkali developability, and is 90% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.

(B) Compound having an ethylenically unsaturated double bond (B) The compound having an ethylenically unsaturated double bond is a monomer having an addition polymerization property by having an ethylenically unsaturated group. From the viewpoint of high resolution and edge fuse resistance, the compound (B) having an ethylenically unsaturated double bond is represented by the following general formula (IV):
{In the formula:
R ₁₀ and R ₁₁ 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-(AO)-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 (IV), r and s are each preferably 1 or more from the viewpoints of 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 (IV), 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 general formula (IV) include polyethylene glycol dimethacrylate (for example, Shin-Nakamura Chemical Co., Ltd.) in which 2 mol 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 6 moles of ethylene oxide and 2 moles of propylene oxide added to each end, and 15 moles of ethylene oxide and 2 moles of propylene oxide on both ends of bisphenol A, respectively. Dimethacrylate of the added polyalkylene glycol.

  (B) Examples other than the compound represented by the general formula (IV) that can be used as a compound having an ethylenically unsaturated double bond include known compounds having at least one terminal ethylenically unsaturated group. It is done.

  (B) More specific examples of the compound having an ethylenically unsaturated double bond include, for example, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, A reaction product of a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate and propylene oxide (for example, product name OE-A 200 manufactured by Nippon Shokubai Chemical Co., Ltd.), 4-normal octylphenoxypentapropylene glycol acrylate, 1,6- Polyoxins such as hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polyethylene glycol diacrylate Sialkylene glycol diacrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2, Multifunctional group (meth) acrylate containing urethane group such as 2-bis (4-methacryloxypentaethoxyphenyl) propane, urethanized product of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate, and polyfunctionality of isocyanuric acid ester compound (Meth) acrylate is mentioned. These may be used alone or in combination of two or more.

  Content of the compound which has (B) ethylenically unsaturated double bond in the photosensitive resin composition of this invention is 5 mass%-70 mass%, Preferably, it is 5 mass%-60 mass%. More preferably, it is 15 mass%-60 mass%. This content is 5% by mass or more from the viewpoint of suppressing poor curing and delay in development time, and is 70% 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 mass%-20 mass%. This content is 0.1% by mass or more from the viewpoint of sensitivity, and 20% by mass or less from the viewpoint of resolution. Preferable content is 0.1 mass%-15 mass%, and 0.1 mass%-10 mass% are still more preferable. (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.

  Content of the N-aryl amino acid in the photosensitive resin composition is 0.01 mass%-0.2 mass%. This content is 0.01% by mass or more from the viewpoint of sensitivity, and is 0.2% by mass or less from the viewpoint of resolution.

  (C) As a photopolymerization initiator, 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) are used in combination. You can also. 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.

  Content of the acridine derivative in the photosensitive resin composition is 0.1 mass%-20 mass%. This content is 0.1% by mass or more from the viewpoint of sensitivity, and 20% by mass or less from the viewpoint of resolution.

  In addition to the above, (C) as a compound that can be used as a photopolymerization initiator, 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) Benzotriazole derivative (D) As the benzotriazole derivative, for example, the following general formula (I):
{Wherein R _{1 to} R ₄ are each independently hydrogen or an alkyl group, or at least one of R _{1 to} R ₄ is a carboxyl group, and the rest of R _{1 to} R ₄ are each Independently, hydrogen or an alkyl group, and R ₅ is hydrogen, an alkyl group, or the following general formula (II):
(Wherein R ₆ and R ₇ are each independently hydrogen, an alkyl group or a hydroxylalkyl group, and n is an integer of 1 to 4). }
The compound represented by these is mentioned.
Among these, it is preferable that R ₅ contains a 1-N-dibutylaminomethyl group from the viewpoint of extending the time to reach the development residue.

  Examples of the compound represented by the general formula (I) include benzotriazole, carboxybenzotriazole, N (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, and N (N, N-di-2). -Hydroxyethyl) aminomethylenebenzotriazole, N (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole, 1-N-diethylaminomethylcarboxybenzotriazole, 1-N-dipropylaminomethylcarboxybenzotriazole, Examples thereof include 1-N-dibutylaminomethylcarboxybenzotriazole.

  From the viewpoint of lamination and hold time stability after exposure (storage stability), it is preferable to use 1-N-dibutylaminomethylcarboxybenzotriazole.

  The amount of the (D) benzotriazole derivative contained in the photosensitive resin composition of the present invention is in the range of 0.1% by mass to 10% by mass and in the range of 0.2% by mass to 5% by mass. It is preferable that the range is 0.3% by mass to 3% by mass. This amount is 0.1% by mass or more from the viewpoint of lamination and hold time stability after exposure, and is 10% by mass or less from the viewpoint of resolution.

(E) Epoxy compound (E) An epoxy compound is a compound which has an epoxy group. In the present embodiment, (E) the acid scavenging action of the epoxy compound effectively prevents coloring during storage of the dry film resist and provides good storage stability of the hue, and also has good resolution. can get.

  (E) As an epoxy compound, an alkylene oxide compound etc. are mentioned, for example. The alkylene oxide compound preferably contains at least two glycidyl groups in the molecule.

Examples of the alkylene oxide compound include the following general formula (III):
{In the formula, X is an oxygen atom, or -O-X ₁ -O- (wherein X ₁ is a linear or branched alkylene group having 1 to 100 carbon atoms, or an alicyclic group having 3 to 10 carbon atoms. And a divalent group containing at least one hydrocarbon group selected from the group consisting of an alkylene group and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group includes a halogen atom, an oxygen atom, and a nitrogen atom R ₈ and R ₉ are each independently a linear or branched alkylene group having 1 to 100 carbon atoms, which may be substituted with at least one atom selected from the group consisting of A divalent group containing at least one hydrocarbon group selected from the group consisting of an alicyclic alkylene group having 3 to 10 carbon atoms and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is , Halogen atom, oxygen source , And may be substituted with at least one atom selected from the group consisting of nitrogen atom, and when R ₈ and R ₉ are present together, R ₈ and R _9, which may be the same or different , R ₈ and R ₉ are different, the sequence of repeating units of — (R ₈ —O) — and — (R ₉ —O) — may be block or random; and m and n are each independently And m + n is an integer of 1-50. }
The compound represented by these is mentioned.

  X in the general formula (III) 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 the hydroxyl group of hydrogenated bisphenol A from the viewpoint of resolution. A divalent group obtained by removing hydrogen from hydrogen (hereinafter also referred to as hydrogenated bisphenol A type group) is preferable, and a bisphenol A type group is more preferable.

  As preferable examples of the alkylene oxide compound, when X in the general formula (III) is an oxygen atom, ethylene glycol diglycidyl ether (for example, Epolite 40E manufactured by Kyoeisha Chemical Co., Ltd.), diethylene glycol diglycidyl ether (for example, Kyoeisha Chemical ( Epolite 100E), 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 di Glycidyl ether, octaethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether (for example, Epolite 400 manufactured by Kyoeisha Chemical Co., Ltd.) ), Decaethylene glycol 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 Cole diglycidyl ether, ditetramethylene glycol diglycidyl ether, tritetramethylene glycol diglycidyl ether, tetratetramethylene glycol diglycidyl ether, pentatetramethylene glycol diglycidyl ether, hexatetramethylene glycol diglycidyl ether, heptatetramethylene glycol di Glycidyl 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 mol of ethylene glycol and propylene glycol, respectively Diglycidyl ether, ethylene glycol and propylene containing 3 moles each Diglycidyl ether containing 1 mol and 4 mol of lenglycol, diglycidyl ether containing 1 mol and 5 mol of ethylene glycol and propylene glycol, respectively, 1 mol and 9 mol of ethylene glycol and propylene glycol, respectively Diglycidyl ether containing 2 mol and 1 mol each of ethylene glycol and propylene glycol, diglycidyl ether containing 2 mol and 2 mol of ethylene glycol and propylene glycol respectively, and ethylene glycol Diglycidyl ether containing 2 mol and 3 mol of propylene glycol, and 2 mol and 4 mol of ethylene glycol and propylene glycol, respectively. Glycidyl ether, diglycidyl ether containing 2 mol and 5 mol of ethylene glycol and propylene glycol, diglycidyl ether containing 2 mol and 8 mol of ethylene glycol and propylene glycol, respectively, ethylene glycol and propylene glycol Diglycidyl ether containing 3 mol and 1 mol respectively, Diglycidyl ether containing 3 mol and 2 mol of ethylene glycol and propylene glycol, respectively, Diglycidyl ether containing 3 mol and 3 mol of ethylene glycol and propylene glycol respectively. Diglycidyl ether, ethylene glycol and propylene glycol each containing 3 mol and 4 mol of glycidyl ether, ethylene glycol and propylene glycol, respectively Diglycidyl ether containing 3 moles and 5 moles, respectively, Diglycidyl ether containing 3 moles and 7 moles each of ethylene glycol and propylene glycol, 5 moles and 1 mole respectively of ethylene glycol and propylene glycol Diglycidyl ether containing, diglycidyl ether containing 5 mol and 2 mol of ethylene glycol and propylene glycol, respectively, diglycidyl ether containing 5 mol and 3 mol of ethylene glycol and propylene glycol, respectively, ethylene glycol and propylene Diglycidyl ether containing 5 mol and 4 mol of glycol, respectively, Diglycidyl 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, ethylene glycol and propylene glycol Diglycidyl ether containing 6 mol and 3 mol respectively, Diglycidyl ether containing 6 mol and 4 mol of ethylene glycol and propylene glycol respectively, Diglycidyl ether containing 7 mol and 1 mol of ethylene glycol and propylene glycol respectively. Diglycidyl ether, ethylene glycol and propylene glycol containing 7 mol and 2 mol of glycidyl ether, ethylene glycol and propylene glycol, respectively Diglycidyl ether containing 7 mol and 3 mol of each, diglycidyl ether containing 8 mol and 1 mol of ethylene glycol and propylene glycol, respectively, and 8 mol and 2 mol of ethylene glycol and propylene glycol, respectively. Diglycidyl ether, diglycidyl ether containing 9 mol and 1 mol of ethylene glycol and propylene glycol, neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl Ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

  When X in the general formula (III) is a bisphenol A type group, preferred examples of the alkylene oxide compound include diglycidyl ether of bisphenol A-propylene oxide 2 mol adduct (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 Examples include tylene oxide 6 mol adduct diglycidyl ether, bisphenol A-ethylene oxide 8 mol adduct diglycidyl ether, and bisphenol A-ethylene oxide 10 mol adduct diglycidyl ether.

  When X in the general formula (III) is a hydrogenated bisphenol A type group, preferred examples of the alkylene oxide compound 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 diglycidyl ether, hydrogenated bisphenol A-propylene oxide 8 mol adduct diglycidyl ether, hydrogenated bisphenol A-propylene oxide 10 mol adduct diglycidyl ether and the like.

  Content of the (E) epoxy compound in the photosensitive resin composition is 0.20 mass%-10 mass%. This content is 0.20% by mass or more from the viewpoint of securing the storage stability of the hue of the dry film resist and obtaining good resolution, and 10% by mass from the viewpoint of obtaining sufficient sensitivity. It is as follows. From the same viewpoint, the content is more preferably 0.35% by mass to 10% by mass.

Other components In addition to the above components (A) to (E), the photosensitive resin composition may contain additives, such as discoloring agents, dyes, plasticizers, antioxidants, organic halogen compounds, and radicals, as necessary. 1 or more compounds selected from the group consisting of polymerization inhibitors).

  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) , Made by Hodogaya Chemical Industry , 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 0.001% by mass to 0.3% by mass, and more preferably 0.01% by mass 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 mass%-50 mass%, More preferably, it is 1 mass%-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).

  The content of the antioxidant in the photosensitive resin composition is preferably 0.01% by mass to 0.8% by mass, and more preferably 0.01% by mass to 0.3% by 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% by mass to 3% by mass.

  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.

  Content of the radical polymerization inhibitor in the photosensitive resin composition is 0.01 mass%-3 mass%, Preferably it is 0.05 mass%-1 mass%. This 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>
You may use the photosensitive resin composition as a photosensitive resin composition formulation liquid formed by adding a solvent to this. 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 mPa · sec 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 laminated on the support. In addition to the photosensitive resin layer and the support that supports the layer, the photosensitive resin laminate may include a protective layer on the surface opposite to the support forming side of the photosensitive resin layer, if necessary. good.

  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. A film having a haze of 5 or less is preferred. The thinner the film, the more advantageous in terms of image formation and economy, but it is preferably 10 μm to 30 μm 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 and can be easily peeled with respect to the adhesive force 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 μm to 100 μm, more preferably 10 μm to 50 μm.

  The thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, more preferably 7 μm 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.

  A conventionally known method can be employed as a method for producing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and if necessary, a protective layer.

  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 is a lamination step of laminating the above-described photosensitive resin laminate of the present invention on a substrate, an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and a photosensitive resin after exposure. Provided is a resist pattern forming method including a developing step of sequentially forming a resist pattern by removing an unexposed portion in a 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 below.

  In the lamination step, a photosensitive resin layer is formed on the 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 the time of lamination is generally 40 ° C 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 repeatedly passed through the roll and pressure bonded.

  In the exposure step, the photosensitive resin composition is exposed to active light using an exposure machine. The exposure can be performed after peeling the support if necessary. 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.

  Maskless exposure may be used in the exposure process. Maskless exposure can be performed by an exposure method by directly drawing a drawing pattern without using a photomask, or by an exposure method in which an image of a photomask is projected through a lens. Among these, the exposure method by direct drawing of a drawing pattern is preferable.

  An exposure method by direct drawing of a drawing pattern can be performed by a direct drawing apparatus. As the light source, a semiconductor laser having a wavelength of 350 μm 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.

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 of 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% by mass to 2% by mass is common. A surface active agent, an antifoaming agent, a small amount of an organic solvent for accelerating development may be added to the alkaline aqueous solution. In addition, it is preferable to keep constant the temperature of this developing solution in a development process in the range of 20 to 40 degreeC.

  Although a resist pattern is obtained by the above-mentioned process, depending on the case, the heating process of 100 to 300 degreeC can also be performed further. 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.

  In addition, the photosensitive resin composition of the present embodiment is used for the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for mounting IC chips, 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) Can be used for the manufacture of semiconductor bumps, and the manufacture of members such as ITO electrodes, address electrodes, and electromagnetic wave shields in the field of flat panel displays.

  Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless departing from the gist thereof. The physical properties in the examples were measured by the following methods.

<Measurement of weight average molecular weight>
The weight average molecular weight of the polymer was determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve with Shodex STANDARD SM-105 manufactured by Showa Denko KK) as polystyrene conversion It is done.

(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>
The components shown in Table 1 below (however, the numbers of each component indicate the blending amount (parts by mass) as a solid content) and the solvent were sufficiently stirred and mixed to prepare a photosensitive resin composition preparation solution.

  Using a bar coater, uniformly apply this prepared solution to the surface of a 19 μm-thick polyethylene terephthalate film (G2-19, manufactured by Teijin DuPont Films, Ltd.) prepared as a support, and in a dryer at 95 ° C. And dried for 5 minutes to form a photosensitive resin composition layer. The thickness of the photosensitive resin composition layer was 30 μm.

  Next, a 19 μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-18) is laminated as a protective layer on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film is not laminated. Got the body. In the following Table 2, the names of the material components in the photosensitive resin composition preparation liquid represented by abbreviations in Table 1 are shown.

<Board surface preparation>
As an evaluation substrate for developability and etching resistance, a copper clad laminate having a thickness of 0.4 mm on which 35 μm rolled copper foil was laminated was used. The substrate surface was subjected to jet scrub polishing at a spray pressure of 0.2 MPa using an abrasive (Nihon Carlit Co., Ltd., Sac Random R (registered trademark # 220)).

<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 1.5 m / min.

<Exposure>
Asahi Kasei 27-step tablet (O.D. = 0.50-1.80,) by direct drawing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ± 5 nm) (ΔOD = 0.05) or using a predetermined DI exposure mask pattern, exposure was performed at an exposure amount of 16 mJ / cm ² under the condition of an illuminance of 90 mW / cm ² .

<Development>
For the evaluation substrate for developability and etching resistance, the polyethylene terephthalate film was peeled off, and then 1 mass% Na ₂ CO _{3 at} 30 ° C. using an alkali developer (produced by Fuji Kiko Co., Ltd., dry film developer). The aqueous solution was sprayed 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. Here, the minimum development time is the minimum time required for the photosensitive resin layer of the unexposed portion of the unheated resist to completely dissolve.

(2) Sample Evaluation Method Next, a sample evaluation method will be described.
(I) Sensitivity evaluation The substrate for sensitivity and resolution evaluation after 15 minutes from the lamination was exposed through a mask of Asahi Kasei 27-step tablet. Development was carried out in a time twice as long as the minimum development time, and the sensitivity of the photosensitive resin composition was evaluated by measuring the number of remaining film limit steps in the mask portion. The sensitivity is the exposure amount (mJ / cm ² ) required to leave the four corners of the cured resist pattern in 5 stages (OD = 0.70) of Asahi Kasei 27-step tablet.

(Ii) Resolution Evaluation A substrate for sensitivity and resolution evaluation that has passed 15 minutes after lamination is exposed to 16 mJ / cm ² under a condition of an illuminance of 90 mW / cm ² through a line pattern mask having a ratio of the exposed part to the unexposed part of 1: 1. The exposure amount was as follows. Development was performed with a development time twice as long as the minimum development time, and the minimum mask line width in which a cured resist line was normally formed was measured as a resolution value.

(Iii) Evaluation of Adhesiveness The substrate for sensitivity and resolution evaluation 15 minutes after lamination was exposed through a line pattern mask having a ratio of the exposed area to the unexposed area of 1: 100. Development was performed with a development time twice as long as the minimum development time, and the minimum mask line width in which a cured resist line was normally formed was measured as an adhesion value.

(Iv) Thermal storage evaluation In accordance with the method for preparing the sample for evaluation (1) above, the laminated evaluation substrate was heated at 60 ° C. using an oven (FC-610, manufactured by Advantech Toyo Co., Ltd.). Development was performed at a development time 1.2 times the minimum development time on the unheated evaluation substrate, and the heating time at which development residues began to appear was measured. Here, “development residue starts to come out” means that a development residue (organic component) of 1% or more of the substrate area laminated on the evaluation substrate after development remains. For example, as shown in FIG. 1, after the laminated evaluation substrate is heated and developed for a predetermined time, the presence or absence of a development residue is confirmed by observing a photograph of the developed surface of the substrate. Can do.

(3) Evaluation result The evaluation result of an Example and a comparative example is shown in following Table 1.

  As shown in Table 1, the photosensitive resin composition of this example was prepared by preparing the sample for evaluation under specific conditions, heating it at 60 ° C., and then developing it at 1.2 times the minimum development time. The photosensitive resin composition has a heating time of 7 hours or more required for developing residue. By selecting and using such a photosensitive resin composition, even when the photosensitive resin composition of the present example is stored for a certain period of time under high temperature conditions, etching residue or plating failure can be suppressed. . On the other hand, in Comparative Example 2, it can be seen from the photographs of the developed surface of the evaluation sample shown in Table 1 and FIG. 1 that a development residue starts to appear when the evaluation sample is heated for at least 2 hours. Further, in Comparative Example 2, when the evaluation sample is heated for 3 hours and the area ratio of the development residue to the development surface of the substrate is calculated from the photograph shown in FIG. 1, a development residue of 37% of the substrate area is generated. I understand that.

  The above-mentioned photosensitive resin composition, 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, the metal foil precision processing such as the manufacture of metal masks, BGA (ball grid array) and Manufacture of semiconductor packages such as CSP (chip size package), manufacture of tape substrates represented by TAB (Tape Automated Bonding) and COF (Chip On Film: a semiconductor IC mounted on a film-like fine wiring board), semiconductor It can be used for the production of bumps and for the production of members such as ITO electrodes, address electrodes, and electromagnetic wave shields in the field of flat panel displays.

Claims (13)

(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond; and (C) a photopolymerization initiator;
A photosensitive resin composition comprising:
When the photosensitive resin composition is laminated on a copper substrate, heated at 60 ° C., and then developed at 1.2 times the minimum development time, the heating time required for developing residue to be produced is 7 hours or more. ,
The photosensitive resin composition. Said (A) alkali-soluble polymer: 10 mass%-90 mass%;
(B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass;
The photosensitive resin composition of Claim 1 containing this. Exposure required to cure the photosensitive resin composition when the photosensitive resin composition exposed through a mask having an optical density (OD) of 0.70 is developed in a time twice as long as the minimum development time. the amount (mJ / cm ²⁾ is, at 16 mJ / cm ² or less, the photosensitive resin composition according to claim 1 or 2. (D) Benzotriazole derivative: 0.1% by mass to 10% by mass;
The photosensitive resin composition according to any one of claims 1 to 3, further comprising: As the (D) benzotriazole derivative, the following general formula (I):
{Wherein R _{1 to} R ₄ are each independently hydrogen or an alkyl group, or at least one of R _{1 to} R ₄ is a carboxyl group, and the rest of R _{1 to} R ₄ are each Independently, hydrogen or an alkyl group, and R ₅ is hydrogen, an alkyl group, or the following general formula (II):
(Wherein R ₆ and R ₇ are each independently hydrogen, an alkyl group or a hydroxylalkyl group, and n is an integer of 1 to 4). }
The photosensitive resin composition of any one of Claims 1-4 containing the compound represented by these.   The photosensitive resin composition of any one of Claims 1-5 containing 0.01 mass%-0.2 mass% N-arylamino acid as said (C) photoinitiator.   The photosensitive resin composition of any one of Claims 1-6 containing 0.1 mass%-20 mass% acridine derivative as said (C) photoinitiator. (E) Epoxy compound: 0.20 mass% to 10 mass%;
The photosensitive resin composition according to any one of claims 1 to 7, further comprising: As the (E) epoxy compound, the following general formula (III):
{In the formula, X is an oxygen atom, or -O-X ₁ -O- (wherein X ₁ is a linear or branched alkylene group having 1 to 100 carbon atoms, or an alicyclic group having 3 to 10 carbon atoms. And a divalent group containing at least one hydrocarbon group selected from the group consisting of an alkylene group and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group includes a halogen atom, an oxygen atom, and a nitrogen atom R ₈ and R ₉ are each independently a linear or branched alkylene group having 1 to 100 carbon atoms, which may be substituted with at least one atom selected from the group consisting of A divalent group containing at least one hydrocarbon group selected from the group consisting of an alicyclic alkylene group having 3 to 10 carbon atoms and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is Halogen atom, oxygen atom And it may be substituted with at least one atom selected from the group consisting of nitrogen atom, and when R ₈ and R ₉ are present together, R ₈ and R _9, which may be the same or different, When R ₈ and R ₉ are different, the sequence of repeating units of — (R ₈ —O) — and — (R ₉ —O) — may be block or random; and m and n are each independently , An integer from 0 to 50, and m + n is an integer from 1 to 50. }
The photosensitive resin composition of any one of Claims 1-8 containing the compound represented by these.   The photosensitive resin laminated body by which the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-8 is laminated | stacked on the support body.   A laminating step of laminating the photosensitive resin laminate according to claim 10 on a substrate, an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and developing and removing an unexposed portion of the photosensitive resin layer. A method for forming a resist pattern, comprising a development step.   The resist pattern forming method according to claim 11, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern or an exposure method of projecting a photomask image through a lens.   The resist pattern forming method according to claim 12, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern.