JP2003186183A - Photosensitive resin composition and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition free of generation of agglomerate in development, exposable by irradiation with UV, developable with an alkaline aqueous solution and excellent in image forming properties such as sensitivity and resolution. <P>SOLUTION: The photosensitive resin composition is characterized in containing (a) 20 to 90 mass% thermoplastic polymer containing unsaturated carboxyl groups, (b) 5 to 75 mass% addition-polymerizable monomer, (c) 0.01 to 30 mass% photopolymerization initiator and (d) 0.01 to 30 mass% compound of formula (I) (where R<SB>1</SB>to R<SB>4</SB>are each H or a 1 to 30C fatty acid acyl group; k, l, m and n are each an integer of ≥0, k+l+m+n=0 to 40; and A is C<SB>2</SB>H<SB>4</SB>and/or C<SB>3</SB>H<SB>6</SB>). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides an alkaline aqueous solution which is suitable for manufacturing printed wiring boards, IC chip mounting lead frames (hereinafter referred to as lead frames), and metal foil precision processing such as metal mask manufacturing. The present invention relates to a developable photosensitive resin composition and a photosensitive resin laminate using the same.

[0002]

2. Description of the Related Art Conventionally, a printed wiring board is manufactured by a photoresist method. The photoresist method is a method of applying a photosensitive resin composition onto a substrate such as a copper-clad laminate and subjecting it to pattern exposure for polymerization and curing, then removing the unexposed portion with a developer, and performing etching or plating treatment. This is a method in which a cured portion is peeled and removed from a substrate such as a copper-clad laminate after being applied to form a pattern. In the photoresist method, in many cases, a photosensitive resin laminate (referred to as a dry film resist) is prepared by laminating a photosensitive resin composition on a support layer and optionally a protective layer on the photosensitive resin layer. used.

A method for producing a printed wiring board using a dry film resist will be briefly described below.
If the dry film resist has a protective layer, peel it off, then stack the photosensitive resin layer using a laminator, etc. on a permanent circuit forming substrate such as a copper clad laminate, and expose it with ultraviolet light through a mask film, etc. The wiring pattern is printed by. Then, if necessary, the support layer is peeled off, and the unexposed portion is dissolved or dispersed and removed by a developing solution such as a weak alkaline aqueous solution to develop the resist image on the substrate. Using the formed resist image as a protective mask, publicly known etching treatment or pattern plating treatment is performed, and the resist is peeled off to manufacture a printed wiring board.

On the other hand, as a method for precision processing of a metal foil such as a lead frame and a metal mask, a stamping method in which a die is used for punching and an etching process in which a photosensitive resin is used to form an image by a photographic method and then etching is performed. There are two types of law. In recent years, with the trend toward lighter, thinner, shorter and smaller semiconductor devices, and a large number of products in small quantities, the stamping method cannot handle the rise in die costs due to the large number of products in small quantities, the high density of wiring, and the narrowness associated with miniaturization. Since there are problems such as the inability to manufacture products, the etching method is more advantageous for making light, thin, short, compact, and small-lot, high-mix production.

As a photosensitive resin used in the etching method, a liquid resist prepared by adding dichromate as a photosensitive group to a water-soluble polymer (PVA, casein, etc.) such as a synthetic colloid or a natural colloid has been conventionally used. It was This liquid resist has problems such as large investment in equipment for coating, difficulty in uniform coating, low sensitivity, and treatment of chromium waste liquid generated during the process. In order to solve these problems, it has recently been proposed to use a dry film resist as a photoresist for precision processing of a metal foil substrate.

However, when an alkali developing type photosensitive resin composition for developing the unexposed area with a weak alkaline aqueous solution is used, the unpolymerized composition is dispersed in the developing solution and the dispersion is collected. The developer becomes agglomerates and re-attaches to the substrate, causing a short circuit defect. Also, when the developer is circulated through the filter to prevent the generation of aggregates, if the amount of aggregates is large, the frequency of filter replacement may increase and the cleaning interval of the developing machine may become shorter. Then, a management problem occurs. Therefore, an attempt to improve hydrophilicity of the aggregate by adding a hydrophilic group such as an ethylene oxide chain to a monomer or a polymer, or an attempt to reduce the aggregate by using a nonylphenol type monomer (JP-A-7-92763). Gazette) has been made, but these cannot completely solve the problem. For this reason,
There is a demand for a novel photosensitive resin composition that eliminates the generation of aggregates of a developer. Further, with the recent miniaturization of printed wiring boards, resolution of photosensitive resin is required, and from the viewpoint of productivity, improvement of sensitivity of photosensitive resin is required to shorten exposure time.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to overcome the above-mentioned problems, to eliminate aggregates generated during development, to be exposed by ultraviolet irradiation, to be developed by an alkaline aqueous solution, sensitivity, resolution, etc. Another object of the present invention is to provide a photosensitive resin composition excellent in image forming property and a photosensitive resin laminate using the same.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors achieved the above problems by using a photosensitive resin composition containing a specific compound as an essential component. They found that they could obtain the present invention and completed the present invention. That is, the present invention comprises the following aspects. (1) (a) 20 to 90% by mass of a thermoplastic polymer having an α, β-unsaturated carboxyl group-containing monomer as a copolymerization component and having an acid equivalent of 100 to 600 and a weight average molecular weight of 20,000 to 500,000. , (B) Addition polymerizable monomer having at least one polymerizable ethylenic unsaturated bond in the molecule 5 to 75
% To (c) a photopolymerization initiator of 0.01 to 30% by mass as an essential component, further comprising (d) a compound of the following general formula (I) in an amount of 0.01 to 3
A photosensitive resin composition comprising 0% by mass.

[0009]

[Chemical 2]

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen or a fatty acid acyl group having 1 to 30 carbon atoms. K, l,
m and n are integers of 0 or more, and k + l + m + n is 0 to 40. Also, A is -CH (CH ₃₎ CH ₂ - and / or -
CH ₂ CH (CH ₃₎ - and / or -CH ₂ CH ₂ - and is, - (A-O) - repeating structure of may be a random, may be a block. )

(2) The photosensitive resin composition according to (1), wherein the photopolymerization initiator (c) is a triarylimidazolyl dimer or a derivative thereof. (3) A photosensitive resin laminate comprising a support layer and a layer comprising the photosensitive resin composition according to (1) or (2) provided on the support layer.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component constituting the present invention will be described in detail. The present invention is characterized in that (d) the compound represented by the following general formula (I) is used in the photosensitive resin composition.

[0013]

[Chemical 3]

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen or a fatty acid acyl group having 1 to 30 carbon atoms. K, l,
m and n are integers of 0 or more, and k + l + m + n is 0 to 40. Also, A is -CH (CH ₃₎ CH ₂ - and / or -
CH ₂ CH (CH ₃₎ - and / or -CH ₂ CH ₂ - and is, - (A-O) - repeating structure of may be a random, may be a block. )

(D) By using the compound represented by the general formula (I) in the photosensitive resin composition in an amount of 0.01 to 30% by mass, a photosensitive resin composition having excellent image forming properties such as sensitivity and resolution can be obtained. Therefore, it has an effect that there is no aggregate generated during development. The fatty acid acyl group having 1 to 30 carbon atoms includes a saturated fatty acid acyl group having 1 to 30 carbon atoms and an unsaturated fatty acid acyl group having 1 to 30 carbon atoms. Carbon number 1
Examples of the saturated fatty acid acyl group of 30 include formyl group, acetyl group, propionyl group, butyryl group, lauryl group, myristyl group, palmityl group, stearyl group and the like. Examples of the unsaturated fatty acid acyl group having 1 to 30 carbon atoms include an acryl group, a propinoyl group, a methacryl group, and an oleyl group.

(D) Examples of the compound represented by the general formula (I) include, but are not limited to, the following compounds. Examples of the ester type include sorbitan laurate [R ₁ : lauryl group, R ₂ = R ₃ = R ₄ : hydrogen, k + l + m + n = 0 (Example: Newcol (trademark) 20 manufactured by Nippon Emulsifier Co., Ltd.]], Sorbitan stearate
[R ₁ : stearyl group, R ₂ = R ₃ = R ₄ : hydrogen, k + 1 +
m + n = 0 (eg, Sanyo Kasei Kogyo KK, Ionet (trademark) S-60C)], sorbitan oleate [R ₁ :
Oleyl group, R ₂ = R ₃ = R ₄ : hydrogen, k + l + m + n =
0 (Example: Sanyo Chemical Industry Co., Ltd., Ionette (trademark) S
-80C)], sorbitan palmitate [R _1: palmityl _{group, R 2 = R 3 = R} 4: hydrogen, k + l + m + n = 0
(Example: Toho Chemical Industry Co., Ltd., Sorbon (trademark) S-4
0)], sorbitan coconut oil fatty acid ester [R ₁ : acyl group of coconut oil fatty acid (where coconut oil is a fat obtained from the core meat of the palm family, which fatty acid is saturated with lauric acid, myristic acid, etc. A mixture of a fatty acid and an unsaturated fatty acid such as oleic acid and linoleic acid), R ₂ = R ₃ = R ₄ : hydrogen, k + l + m + n = 0 (eg Sanyo Chemical Industries, Ltd.,
Ionet (TM) S-20), sorbitan trioleate _{[R 1 = R 2 = R} 4: oleyl, R3: hydrogen, k + l
+ M + n = 0 (Example: Sanyo Chemical Industry Co., Ltd. product, Ionet (trademark) S-85) etc. and those mixtures etc. are mentioned.

With a complex type of sorbitan and oxyethylene chain
Then polyoxyethylene sorbitan laurate
[R₁: Lauryl group, R₂= R₃= R_Four: Hydrogen, k + 1 + m
+ N = 20, A: -CH₂CH₂-(Example: Nippon Emulsifier
Manufactured by New Coal (trademark) 25)], polyoxy
Ethylene sorbitan stearate [R₁: Stearyl group,
R₂= R ₃= R_Four: Hydrogen, k + 1 + m + n = 20, A:-
CH₂CH₂-(Example: Ionet manufactured by Sanyo Chemical Industry Co., Ltd.)
(Trademark) T-60C)], polyoxyethylene sorbita
Monooleate [R₁: Oleyl group, R₂= R₃= R_Four:water
Elementary, k + l + m + n = 8 or 20, A: -CH₂CH₂−
(Example: New Emulsifier Co., Ltd., Newcol ™ 82)
Or 85)], polyoxyethylene sorbitan palmite
Red [R₁: Palmityl group, R₂= R₃= R_Four: Hydrogen, k +
1 + m + n = 20, A: -CH₂CH₂-(Example: Toho Chemical
Sorbon (trademark) T-40 manufactured by Kogyo Co., Ltd.], Polio
Xyethylene sorbitan trioleate [R₁= R₂=
R_Four: Oleyl group, R3: hydrogen, k + l + m + n = 2
0, A: -CH₂CH₂-(Example: Nihon Emulsifier Co., Ltd., Ni
Eucor (trademark) 3-85)], polyoxyethylene
Sorbitan coconut oil fatty acid ester [R₁: Of coconut oil fatty acid
Acyl group, R₂= R₃= R_Four: Hydrogen, k + 1 + m + n = 2
0, A: -CH₂CH₂-(Example: Sanyo Chemical Industry Co., Ltd.,
Ionette (trademark) T-20C)], polyalkyleneso
Rubitan fatty acid ester [R₁: Acyl group of mixed fatty acids
(Oleic acid: 66%, stearic acid: 2%, carbon number 2
0 saturated and unsaturated fatty acids: 18%, saturated with 16 carbons
And unsaturated fatty acids: 7%, saturated with more than 20 carbon atoms
And unsaturated fatty acids: 7%), R₂= R₃= R_Four: Hydrogen, k +
l + m + n = 30, A: -CH₂CH₂-/-CH (CH
₃) CH₂-Or CH₂CH (CH₃)-= 2/1 (example: day
New Emulsifier Co., Ltd., Newcor (trademark) 95-F
J)] and the like and mixtures thereof.

These compounds represented by the general formula (I) may be used alone or in combination of two or more kinds.
The compound represented by the general formula (I) is contained in the photosensitive resin composition in an amount of 0.01 to 30% by mass, and a more preferable range is 0.1 to 15% by mass. The above general formula (I)
When the amount of the compound represented by 1 is less than 0.01% by mass, a sufficient effect of reducing aggregates at the time of development cannot be obtained, and when it exceeds 30% by mass, photopolymerization does not proceed efficiently and sensitivity due to development is increased. , The image forming properties such as resolution are inferior.

As the thermoplastic polymer (a), α, β-
An unsaturated carboxyl group-containing monomer is used as a copolymer component having an acid equivalent of 100 to 600 and a weight average molecular weight of 20,000 to 500,000. Here, the acid equivalent means the mass of the polymer having 1 equivalent of a carboxyl group therein. The carboxyl group in the thermoplastic polymer is necessary because the photosensitive resin composition has developability and releasability with respect to an aqueous alkaline solution. If the acid equivalent is less than 100, the compatibility with the coating solvent or other composition, for example, the monomer is reduced,
When it exceeds 600, the developability and the peeling property are deteriorated. Further, when the molecular weight exceeds 500,000, the developability decreases, and when it is less than 20,000, it becomes difficult to maintain a uniform thickness when used in a dry film resist, and the resistance to a developing solution deteriorates. .

The acid equivalent was measured with a Hiranuma reporting titrator (COM-555) at 0.1 m.
It is carried out by potentiometric titration with an ol / L NaOH aqueous solution. The molecular weight is determined by gel permeation chromatography (differential refractometer: RI-1530, manufactured by JASCO Corporation,
Pump: PU-1580, Degasser: DG-980-
50, column oven: CO-1560, column: KF-8025, KF-806Mx2, KF-807, in that order.
Eluent: THF, using a calibration curve based on a polystyrene standard sample) to obtain the weight average molecular weight.

In the alkali-developable photosensitive resin composition, the above-mentioned thermoplastic polymer is generally used in the following 2
It can be obtained by copolymerizing one or more kinds of monomers from each kind. The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. For example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester and the like. Among them, (meth) acrylic acid is particularly preferable.

The second monomer is non-acidic, has one polymerizable unsaturated group in the molecule, has resistance to developing, etching and plating steps of the photosensitive resin layer, and has flexibility of the cured film. Etc. are selected to maintain various properties such as. Examples of such a monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-
Butyl (meth) acrylate, iso-butyl (meth)
Acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
In addition to hydroxypropyl (meth) acrylates, vinyl alcohol esters such as vinyl acetate, (meth) acrylonitrile, styrene or a polymerizable styrene derivative may be mentioned. It can also be obtained by polymerizing only the above-mentioned carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule.

The amount of the thermoplastic polymer contained in the photosensitive resin composition should be in the range of 20 to 90% by mass, preferably 25 to 70% by mass. If the amount of the thermoplastic polymer is more than 90% by mass or less than 20% by mass, the cured image formed by exposure cannot sufficiently exhibit the performance as a resist.

(B) The addition-polymerizable monomer having at least one terminal ethylenically unsaturated group accounts for 5 to 75% by mass of the photosensitive resin composition. (B) Examples of addition-polymerizable monomers having at least one terminal ethylenically unsaturated group include 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 (OE-A200 manufactured by Nippon Shokubai Kagaku), 4-normal octylphenoxypentapropylene glycol acrylate,
2,2-bis [{4- (meth) acryloxypolyethoxy} phenyl] propane, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, and polypropylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, polyoxyethylene polyoxypropylene glycol di (meth) acrylate and other polyoxyalkylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, Glycerol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) ac Rate, 2,2-bis (4
-Methacryloxypentaethoxyphenyl) propane,
Examples thereof include urethane group-containing polyfunctional (meth) acrylates such as urethane compounds of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate, and isocyanuric acid ester compounds. These may be used alone or in combination of two or more.

(B) The addition-polymerizable monomer having at least one terminal ethylenically unsaturated group is contained in the photosensitive resin composition in an amount of 5 to 75% by mass, more preferably 15 to 70% by mass. is there. 5% by mass of addition-polymerizable monomer having at least one terminal ethylenically unsaturated group
If it is less than 75, curing failure and delay of development time are caused,
When the content exceeds the mass%, cold flow and delay of peeling of the cured resist are caused.

Examples of the photopolymerization initiator (c) include known initiators that can be activated by various actinic rays such as ultraviolet rays to initiate polymerization. Examples of such a photopolymerization initiator include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, and 2
-Phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-
Quinones such as 1,4-naphthoquinone, 2,3-dimethylanthraquinone and 3-chloro-2-methylanthraquinone, benzophenone, Michler's ketone [4,4′-
Bis (dimethylamino) benzophenone], 4,4'-
Aromatic ketones such as bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, benzoin ethers such as methyl benzoin and ethyl benzoin, and benzyl dimethyl ketal, benzyl diethyl ketal, triaryl imidazolyl dimer, and other vinyl ketones. Imidazole compounds and their derivatives, N-phenylglycines such as N-phenylglycine, N-methyl-N-phenylglycine and N-ethyl-N-phenylglycine, combinations of thioxanthones and alkylaminobenzoic acid, such as ethylthioxanthone A combination of ethyl dimethylaminobenzoate, 2-chlorothioxanthone and ethyl dimethylaminobenzoate, isopropylthioxanthone and ethyl dimethylaminobenzoate, or , The combination of the biimidazole compounds and derivatives thereof and Michler's ketone, such as triarylimidazolyl dimers, acridines, such as 9-phenyl acridine, 1-phenyl-1,2-propane dione -
2-o-benzoin oxime, 1-phenyl-1,2-
There are oxime esters such as propanedione-2- (o-ethoxycarbonyl) oxime. Preferred examples of these initiators include thioxanthones such as diethylthioxanthone and chlorothioxanthone, dialkylaminobenzoic acid esters such as ethyl dimethylaminobenzoate, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4, Examples thereof include 4′-bis (diethylamino) benzophenone, biimidazole compounds such as triarylimidazolyl dimers and derivatives thereof, 9-phenylacridine, N-phenylglycines, and combinations thereof. Examples of the biimidazole compound such as triarylimidazolyl dimer and derivatives thereof include 2- (o-chlorophenyl) -4,
5-diphenylimidazolyl dimer, 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) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- ( 3,4-dimethoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2
-Fluorophenyl) -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- (2,2
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, 2,2'-bis- (2,3,4,5,6-pentafluoro Phenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer and the like.

These may be used alone or in combination of two or more. In particular, 2- (o-chlorophenyl) -4,
The 5-diphenylimidazolyl dimer is a photoinitiator which is very effective for the resolution and the strength of the cured film, and is preferably used. The amount of the photopolymerization initiator contained in the photosensitive resin composition of the present invention is 0.01 to 30% by mass, preferably 0.05 to 10% by mass. 3 photopolymerization initiators
When it exceeds 0% by mass, the active absorption rate of the photosensitive resin composition increases, and when used as a dry film resist,
Curing by photopolymerization at the bottom of the photosensitive resin layer becomes insufficient. Further, if the amount of the photopolymerization initiator is less than 0.01% by mass, sufficient sensitivity cannot be obtained.

In the present invention, coloring substances such as dyes and pigments can be used in the photosensitive resin composition. For example, Phthalocyanine Green, Crystal Violet, Methyl Orange, Nile Blue 2B, Victoria Blue,
Examples include malachite green, basic blue 20, diamond green and the like. The color changing agent may be added to the photosensitive resin composition so that a visible image can be provided by exposure. As such a color-forming dye, there is a leuco dye or a combination of a fluoran dye and a halogen compound. Examples of the dye used here include, in addition to the above dyes, halogen compounds such as amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide and tribromomethylphenyl. Sulfone, carbon tetrabromide, tris (2,3-dilvomopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide,
1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, triazine compounds and the like can be mentioned.

Further, in order to improve the thermal stability of the present invention and the storage stability of the photosensitive resin composition, it is preferable that the photosensitive resin composition contains a radical polymerization inhibitor or benzotriazoles. . Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, and 2,2′-methylenebis. (4-
Methyl-6-tert-butylphenol), 2,2 '
-Methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.
The addition amount of the radical polymerization inhibitor is preferably 0.000.
1 to 3% by mass, more preferably 0.0005 to 1
It is% by mass. If it is less than 0.0001% by mass, the photosensitive resin composition does not show sufficient storage stability, and if it exceeds 3% by mass, the photosensitivity is lowered.

Examples of the benzotriazoles include:
Carboxybenzotriazole or the following general formula (II)
There is a compound shown in.

[0031]

[Chemical 4]

(In the formula, R ₅ and R ₆ are hydrogen or have a carbon number of 1 to
6 is an alkyl group, and x is an integer of 1 to 3. )

Examples of the compound represented by the above formula (II) include N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole and N- (N, N-).
Examples include di-2-hydroxyethyl) aminomethylenebenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. The addition amount of carboxybenzotriazole or the compound represented by the formula (II) is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass. If it is less than 0.01% by mass, the photosensitive resin composition does not show sufficient storage stability, and if it exceeds 3% by mass, the photosensitivity is lowered. These radical polymerization inhibitors and benzotriazole compounds may be used alone or in combination of two or more kinds.

The photosensitive resin composition of the present invention may contain additives such as a plasticizer, if necessary. Examples of such additives include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether,
Polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether and other glycol esters, phthalic acid esters such as diethyl phthalate, o- Toluene sulfonic acid amide, p-toluene sulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate and the like can be mentioned.

The dry film resist of the present invention comprises a layer of a photosensitive resin composition and a support layer for supporting the photosensitive resin layer. If necessary, a protective layer may be provided on the surface opposite to the support layer. As the support layer, a transparent layer that transmits active light is desirable. As the support layer that transmits active light,
Polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethylmethacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer Examples include a united film, a polyamide film, a cellulose derivative film, and the like. These films may be stretched if necessary. The thinner the thickness, the more advantageous in terms of image forming property and economical efficiency, but it is necessary to maintain the strength.
Those having a thickness of up to 30 μm are common.

An important characteristic of the protective layer is that the protective layer is sufficiently smaller than the supporting layer in terms of adhesion to the photosensitive resin layer and can be easily peeled off. For example, there are polyethylene film, polypropylene film and the like. Further, the film having excellent releasability disclosed in JP-A-59-202457 can be used. Although the thickness of the photosensitive resin layer varies depending on the use, it is preferably 5 to 100 μm, more preferably 10 to 80 μm for producing a printed wiring board and a metalworking substrate, and the thinner the resolution, the better. Further, the thicker the film, the higher the film strength.

Next, a process for producing a printed wiring board using the photosensitive resin laminate of the present invention as a dry film resist will be described. First, if a protective layer is present, the protective layer is peeled off using a laminator, and then the photosensitive resin layer is laminated by thermocompression bonding to the metal surface. In this case, the photosensitive resin layer may be laminated on only one side of the metal surface, or may be laminated on both sides.
The heating temperature at this time is generally 40 to 160 ° C. In addition, adhesion and chemical resistance are improved by performing the pressure bonding twice or more. At this time, for the crimping, a two-stage laminator equipped with two rolls may be used, or it may be crimped by repeatedly passing through the rolls (for the two-stage laminator, see Japanese Patent Laid-Open No. 63- 7477 gazette). Then, if necessary, the support layer is peeled off and imagewise exposed to actinic light through a mask film.

Next, if there is a supporting layer on the photosensitive resin layer after exposure, if necessary, this is removed, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to form a resist image. obtain. As the alkaline aqueous solution, Na ₂ CO ₃ , K
An aqueous solution such as ₂ CO ₃ is used. These are selected according to the characteristics of the photosensitive resin layer, but a concentration of 0.2 to 2% by mass,
An aqueous Na ₂ CO ₃ solution at 20 to 40 ° C is generally used. A surface active agent, a defoaming agent, and a small amount of an organic solvent for accelerating the development may be mixed in the alkaline aqueous solution.

The resist image thus obtained is
In some cases, a heating step at 100 to 300 ° C can be used. By carrying out this heating step, chemical resistance can be further improved. Next, a metal image pattern is formed on the copper surface exposed by development using a known method such as an etching method or a plating method. After that, the resist image is peeled off with an alkaline aqueous solution which is generally stronger than the alkaline aqueous solution used in the development. The alkaline aqueous solution for peeling is also not particularly limited, but it is 2 to 5% by mass.
An aqueous solution of NaOH and KOH having a concentration of 40 to 70 ° C. is generally used. It is possible to add a small amount of water-soluble solvent to the stripping solution.

The method for preparing an evaluation sample, the evaluation method and the like in the present invention will be specifically described below. (Preparation of Photosensitive Resin Laminate) The photosensitive resin compositions having the compositions shown in the following examples and comparative examples were well stirred and mixed, and were uniformly applied to the surface of a polyethylene terephthalate film having a thickness of 20 μm as a supporting layer using a bar coater. Apply, 95 ℃
To dry for 4 minutes to form a photosensitive resin layer.
The thickness of the photosensitive resin layer was 40 μm. Then, 30 μm as a protective layer on the photosensitive resin layer side of the laminate composed of the photosensitive resin layer and the polyethylene terephthalate film
A thick polyethylene film was adhered to obtain a photosensitive resin laminate.

(Lamination) The surface of a 1.6 mm-thick copper clad laminate laminated with 35 μm rolled copper foil was wet-buffled polished (ScotchBright (registered trademark) HD # 600, manufactured by 3M Co., Ltd., two passes). While peeling off the polyethylene film of the photosensitive resin laminate prepared by the above method, the photosensitive resin layer was laminated at 105 ° C. by a hot roll laminator (AL-70 manufactured by Asahi Kasei Co., Ltd.). The air pressure was 0.34 MPa and the laminating speed was 1.5 m / min.

(Exposure) The photosensitive resin layer was exposed with no mask film or through a mask film required for evaluation at 60 mJ / cm ² with an ultra-high pressure mercury lamp (HMW-801 manufactured by Oak Manufacturing Co., Ltd.). (Development) After the polyethylene film was peeled off, a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required for the photosensitive resin layer in the unexposed portion to completely dissolve was defined as the minimum development time.

(Evaluation of cohesiveness) The photosensitive resin layer in the photosensitive resin laminate having a thickness of 40 μm and an area of 0.15 m ² prepared by the above method was used as 200 ml of 1 mass% Na ₂ CO ₃
The solution was dissolved in an aqueous solution and sprayed with a circulating spray device at a spray pressure of 0.1 MPa for 3 hours to observe the generation of aggregates. When a large amount of aggregates are generated, powdery or oily substances are observed on the bottom and side faces of the spray device. If no agglomerates are generated, these are not seen at all.

(Evaluation of Sensitivity) 27-step step tablet (manufactured by Asahi Kasei Co., Ltd., optical density D = 0.50 to 1.80, ΔD =) in which the brightness changes from transparent to black in 27 steps
0.05) was used for development with a development time twice as long as the minimum development time, and the number of steps corresponding to when the metal foil substrate was exposed after development was taken as the sensitivity value. Here, it is practically preferable that the value of sensitivity is 12 to 14, and when it is 11 or less, curing of the exposed portion may be insufficient and sufficient solvent resistance may not be obtained.

(Evaluation of Resolution) The substrate 15 minutes after laminating was exposed through a line pattern in which the width of the exposed portion and the unexposed portion was 1: 1. The development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which the cured resist line was normally formed was taken as the value of resolution. Where 40
A value of less than μm is effective for fine pattern formation.
If the value exceeds 0 μm, it becomes difficult to form a fine pattern. Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples. The present invention is not limited to the following examples. Table 1 shows the evaluation results.

[0046]

Example 1 (Component) Methyl methacrylate / methacrylic
Acid / n-butyl acrylate (mass ratio 65/25/1
0), the acid equivalent is 344, and the weight average
30% methyl ethyl keto copolymer having a molecular weight of 200,000
25 parts by mass of non-volatile components of the solution Methyl methacrylate / methacrylic acid / styrene (weight ratio
Has a composition of 50/25/25) and an acid equivalent of 344
Of the copolymer with a weight average molecular weight of 50,000
Non-volatile component of chill ethyl ketone solution 24 parts by mass 4-nonylphenylheptaethylene glycol dipropy
Lenglycol acrylate (NOF CORPORATION, LS)
-100A) 10 parts by mass Tetraethylene glycol dimethacrylate 3 parts by mass Triethylene glycol dodecapropylene glycol
Polyethylene glycol α, ω-dimethacrylate 1
6 parts by mass Hexamethylene diisocyanate and pentapropylene
Urethane compound with recall monomethacrylate 16 quality
Quantity part 4,4'-bis (diethylamino) benzophenone
0.2 parts by mass 2- (o-chlorophenyl) -4,5-diphenylimi
Dazolyl dimer 4 parts by mass Sorbitan coconut oil fatty acid ester [R₁: Of coconut oil fatty acid
Acyl group, R₂= R₃= R _Four: Hydrogen, k + 1 + m + n = 0
(Sanyo Kasei Kogyo Co., Ltd., Ionette (trademark) S-2
0)] 4 parts by mass (content in photosensitive resin composition: 3.
9 mass%) Malachite green 0.04 parts by mass Leuco Crystal Violet 0.5 parts by mass Based on the above sample preparation method
An evaluation sample was prepared and evaluated.

[0047]

Example 2 4 parts by mass of sorbitan coconut oil fatty acid ester (component) in Example 1 was added to polyoxyethylene sorbitan laurate [R ₁ : lauryl group, R ₂ = R ₃ =
R _4: hydrogen, k + l + m + n = 20, A: -CH 2 CH 2
-(Nippon Emulsifier Co., Ltd., Newcol ™ 2)
5)] 4 parts by mass (content in photosensitive resin composition: 3.9
The same procedure as in Example 1 was performed except that the content was changed to (mass%).

[0048]

Example 3 (Component) Methyl methacrylate / methacrylic
Has acid / styrene (weight ratio 50/25/25) composition
The acid equivalent is 344 and the weight average molecular weight is 50,000.
Nonvolatile Composition of 43% Methyl Ethyl Ketone Solution of Copolymer
48 parts by mass 2,2-bis (4-methacryloxypentaethoxyphen)
Nil) propane (Shin-Nakamura Chemical Co., Ltd., BPE-50
0) 30 parts by mass Triethoxymethylolpropane triacrylate (new
Nakamura Chemical Co., Ltd., A-TMPT-3EO 8 parts by mass 4,4'-bis (diethylamino) benzophenone
0.2 parts by mass 2- (o-chlorophenyl) -4,5-diphenylimi
Dazolyl dimer 4 parts by mass Sorbitan coconut oil fatty acid ester [R₁: Of coconut oil fatty acid
Acyl group, R₂= R₃= R _Four: Hydrogen, k + 1 + m + n =
0, A: -CH₂CH₂-(Sanyo Kasei Co., Ltd., Io
Net (trademark) S-20)] 2 parts by weight (photosensitive resin assembly
Content in product: 2.2% by mass) Malachite green 0.04 parts by mass Leuco Crystal Violet 0.5 parts by mass A photosensitive resin laminate was prepared in the same manner as in Example 1 and evaluated.
Valuable.

[0049]

[Comparative Example 1] Example 1 except that 4 parts by weight of the sorbitan coconut oil fatty acid ester (component) in Example 1 was changed to 60 parts by weight (content in the photosensitive resin composition: 37.8% by weight). I went the same way.

[0050]

[Comparative Example 2] Example 2 except that 4 parts by mass of the (component) sorbitan coconut oil fatty acid ester in Example 1 was changed to 0.001 parts by mass (content in the photosensitive resin composition: 0.001% by mass) The same procedure as 1 was performed. The results of Examples and Comparative Examples are summarized in Table 1.

[0051]

[Table 1]

[0052]

INDUSTRIAL APPLICABILITY The present invention has the effect of completely eliminating aggregates generated at the time of development, can be exposed by ultraviolet irradiation, can be developed by an alkaline aqueous solution, and has excellent image forming properties such as sensitivity and resolution. A resin composition and a photosensitive resin laminate using the same can be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 2/46 C08F 2/46 4/00 4/00 291/06 291/06 H05K 3/00 H05K 3 / 00 F F-term (reference) 2H025 AA01 AA02 AA04 AB11 AB15 AB17 AC01 AD01 BC13 BC42 CA28 CB43 CB51 CB55 CC01 CC04 CC06 CC20 FA17 4J011 PA35 PA69 PA70 PA90 PB40 PC02 PC08 QA03 QA12 QA22 QA33 QA34 QA37 QA39 QA46 QB16 SA78 TA08 TA09 UA06 VA01 WA01 4J015 EA04 4J026 AA17 AA43 AA45 AA48 AA49 AA53 AA54 AA55 AC23 AC33 AC36 BA28 BA30 BA50 BB01 BB02 DB06 DB11 DB29 DB36 GA06

Claims (3)

[Claims] 1. An (a) α, β-unsaturated carboxyl group-containing monomer as a copolymerization component, which has an acid equivalent of 100 to 600,
20-500,000 weight average molecular weight of the thermoplastic polymer
90% by mass, (b) addition polymerizable monomer 5 having at least one polymerizable ethylenically unsaturated bond in the molecule
To 75% by mass and (c) 0.01 to 30% by mass of a photopolymerization initiator as essential components, further comprising (d) 0.01 of a compound represented by the following general formula (I).
-30 mass% is contained, The photosensitive resin composition characterized by the above-mentioned. [Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen or a fatty acid acyl group having 1 to 30 carbon atoms. K, 1, m and n are 0.
In the above integers, k + 1 + m + n is 0-40. Also, A is -CH (CH ₃₎ CH ₂ - and / or -CH ₂ C
H (CH ₃₎ - and / or -CH ₂ CH ₂ -, -
The repeating structure of (AO)-is random,
It may be a block. ) 2. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (c) is a triarylimidazolyl dimer or a derivative thereof. 3. A photosensitive resin laminate comprising a support layer and a layer comprising the photosensitive resin composition according to claim 1 or 2 provided on the support layer.