JP3529237B2 - Photopolymerizable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition and a photopolymerizable resin laminate, and more specifically to an alkali developable photopolymerizable composition and a photopolymerizable resin laminate suitable for making a printed circuit board. Regarding

[0002]

2. Description of the Related Art Conventionally, a so-called dry film resist (hereinafter abbreviated as DFR) composed of a support layer and a photopolymerizable layer has been used as a resist for producing a printed circuit. DF
R is generally prepared by laminating a photopolymerizable composition on a support film, and in many cases further laminating a protective film on the composition. As a material for the photopolymerizable layer, an alkali developing type material using a weak alkaline aqueous solution as a developing solution is generally used.

In order to produce a printed circuit board using DFR, first the protective film is peeled off, and then the DFR is laminated on a permanent circuit-forming substrate such as a copper clad laminate using a laminator or the like to form a wiring pattern mask film. And the like to expose. Next, if necessary, the supporting film is peeled off, and the photopolymerizable composition in the unexposed portion is dissolved or dispersed by a developing solution to form a cured resist image on the substrate. After that, using the formed resist image as a mask, the metal surface of the substrate is etched or treated by plating,
Then, the resist image is peeled off using an alkaline aqueous solution stronger than the developing solution to form a printed wiring board or the like. Particularly in recent years, a so-called tenting method in which a through hole is covered with a cured film and then etched is often used because of the simplicity of the process. As the etching liquid used here, cupric chloride, ferric chloride, copper ammonia complex solution, or the like is used.

Recently, as finer patterns have been made with the increase in density of printed circuit boards, high resolution DFRs have been developed.
Is required. Also, if the finely formed resist image is not in close contact with the pressure of the spray or the like in the developing or etching process, the wire will be broken and lead to a defect.
Therefore, it is required that the fine line adhesion of the resist image is good. Further, in order to improve productivity, it is often required that the development time and the peeling time are fast.

[0005]

The improvement of resolution and adhesion to fine lines is achieved by suppressing the swelling property during development by using a resist component containing only a compound having a hydrophobic group such as propylene glycol chain. However, when such a resist component is used, the compatibility with the base polymer is deteriorated, scum is generated during development, and the development time is delayed. On the other hand, if only a compound having a hydrophilic group such as ethylene glycol chain is contained in the resist component in order to shorten the development time, the swelling property at the time of development is increased and the resolution is deteriorated. Therefore, there has been a demand for a photopolymerizable composition that simultaneously satisfies the characteristics of high resolution and high speed development corresponding to high density and high productivity of printed wiring boards.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, as a result of a combination of a specific linear polymer and a specific photopolymerizable unsaturated compound, high resolution and high speed development are achieved. It was found that a processable property was obtained, and the present invention was completed. That is, the first invention of the present application is (a) (i) a non-acidic vinyl compound having one polymerizable unsaturated group in the molecule and having a phenyl group, (ii) a polymerizable unsaturated group in the molecule. A carboxylic acid or acid anhydride having one
And (iii) one or more selected from the group consisting of an alkyl (meth) acrylate having 1 to 6 carbon atoms of an alkyl group, and a hydroxyl (meth) acrylate having a hydroxyl alkyl group of 2 to 6 carbon atoms. A linear polymer having a weight average molecular weight of 30,000 or more and less than 60,000, 20 to 90% by weight, and (b) a photopolymerizable compound represented by the following formula (I): Unsaturated compounds, 5-60% by weight,

[0007]

[Chemical 2]

(In the formula, R 1 and R 2 are H or CH 3, and they may be the same or different.
A and B are -CH (CH3) CH2- or -CH2CH2-
And these are different. m1 + m2 is 2-16, n1
+ N2 is a positive integer of 2-16. ), And (c) 4,4-bis (dimethylamino) benzophenone
Or 4,4-bis (diethylamino) benzophenone
And 2- (O-chlorophenyl) -4,5-diphenyl
A photopolymerization initiator comprising a combination of midazolyl dimers ,
It is a photopolymerizable composition containing 0.01 to 30% by weight.

The second invention of the present application is (iv) a carboxylic acid or an acid anhydride having one polymerizable unsaturated group in the molecule, (v) an alkyl group (meth) having 1 to 6 carbon atoms.
A weight average molecular weight obtained by copolymerizing one or more compounds selected from the group consisting of an acrylate, a hydroxyl (meth) acrylate having a hydroxylalkyl group having 2 to 6 carbon atoms, and a vinyl compound having a phenyl group, The linear polymer having a molecular weight of 10,000 or more and less than 30,000 is (a)
The photopolymerizable composition according to (1) above, which further comprises a weight ratio of 95/5 to 40/60 with respect to the linear polymer.

The third invention of the present application is a photopolymerizable resin laminate in which a layer comprising the photopolymerizable composition of the first invention or the second invention is provided on a support. In the first to third inventions, as the photopolymerization initiator (c), 4,4-bis (dimethylamino) benzophenone or 4,4-bis (diethylamino) benzophenone and 2- (O-chlorophenyl) -4,5 are used. The use of a combination of diphenyl imidazolyl dimers is a preferred embodiment.

The present invention will be described in detail below. The amount of the carboxyl group contained in the linear polymer of the component (a) of the present invention (hereinafter referred to as P) needs to be 100 to 600 in terms of acid equivalent, and preferably 300 to 400. The carboxyl group in the linear copolymer P is necessary to give the DFR developability and releasability to an aqueous alkaline solution. When the acid equivalent is less than 100, the compatibility with the coating solvent or other composition, for example, the photopolymerizable unsaturated compound (monomer) is lowered, and when it exceeds 600, the developability and the peelability are lowered.

Here, the acid equivalent means the weight of the polymer having 1 equivalent of a carboxyl group therein. The acid equivalent is measured by potentiometric titration. The molecular weight is determined as a weight average molecular weight (converted to polystyrene) by gel permeation chromatography (GPC). The weight average molecular weight of the linear polymer P used in the present invention needs to be 30,000 or more and less than 60,000. When the molecular weight of the linear polymer P is 60,000 or more, developability and resolution are deteriorated, and when it is less than 30,000, the viscosity of the photosensitive layer is decreased and edge fuses protruding from the end surface of the roll are apt to occur.

The copolymerization component (i) of the linear copolymer P used in the present invention is a non-acidic vinyl compound having one polymerizable unsaturated group in the molecule and a phenyl group as an essential component. To do. Examples of these compounds include styrene, methylstyrene, and styrene derivatives. Styrene is particularly preferable as the vinyl compound having a phenyl group.

The copolymerization component (ii) of the linear copolymer P used in the present invention is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples of these compounds include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. The copolymerization component (iii) of the linear copolymer P used in the present invention includes an alkyl group 1 to
One or more compounds selected from the group consisting of an alkyl (meth) acrylate having 6 carbon atoms and a hydroxyl (meth) acrylate having a hydroxylalkyl group of 2 to 6 carbon atoms. Examples of these compounds include methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate,
n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyl ethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like can be mentioned.

The linear copolymer P used in the present invention has good resolution and high-speed developability when used alone, but (iv)
Carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule, and (v) alkyl group (meth) acrylate having 1 to 6 carbon atoms, hydroxyl alkyl group having 2 to 6 carbon atoms One or more compounds selected from the group consisting of a hydroxyl (meth) acrylate having an atom and a vinyl compound having a phenyl group,
When used in combination with a linear polymer (hereinafter referred to as Q) having a weight average molecular weight of 10,000 to less than 30,000, which is obtained by copolymerizing the above, a more rapid development process is possible. Here, P / Q (weight ratio) when used in combination is 95/5 to 40/60. If the weight ratio of the linear polymer Q is less than 5%, the effect of more rapid development processing is not obtained, and if it exceeds 60%, edge fuses are likely to occur.

The amount of the carboxyl group contained in the linear copolymer Q used in the present invention must be 100 to 600 in terms of acid equivalent, preferably 200 to 400. The molecular weight of the linear copolymer B needs to be 10,000 or more and less than 30,000. When the molecular weight of the linear copolymer Q is 30,000 or more, the effect of more rapid development processing is reduced, and when it is less than 10,000, the edge fuse property is significantly deteriorated.

Here, the acid equivalent means the weight of the polymer having 1 equivalent of a carboxyl group therein. The acid equivalent is measured by potentiometric titration. The molecular weight is determined as a weight average molecular weight (converted to polystyrene) by gel permeation chromatography (GPC). Further, the carboxyl group in the linear copolymer used in the present invention is necessary for giving DFR developability and releasability to an alkaline aqueous solution. When the acid equivalent is less than 100, the compatibility with the coating solvent or other composition such as a monomer is lowered, and when it exceeds 600, the developability and the peelability are lowered.

The copolymerization component (iv) of the linear copolymer Q is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples of these compounds include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. The copolymerization component (v) of the linear copolymer Q is an alkyl (meth) having an alkyl group of 1 to 6 carbon atoms.
One or more compounds selected from the group consisting of acrylates, hydroxyl (meth) acrylates having a hydroxylalkyl group of 2 to 6 carbon atoms, and vinyl compounds having a phenyl group. Examples of these compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth). Acrylate, tert-butyl (meth) acrylate,
2-hydroxyl ethyl (meth) acrylate, 2-hydroxyl propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, styrene, methyl styrene, etc. are mentioned.

The amount of the binder resin (a) contained in the photopolymerizable composition of the present invention is in the range of 20 to 90% by weight, preferably 30 to 70% by weight. When the amount of the binder resin (a) is less than 20% by weight or more than 90% by weight, the cured image formed by exposure has sufficient characteristics as a resist (for example, sufficient resistance in tenting, etching, various plating steps). ) Is not included.

The photopolymerizable unsaturated compound (b) constituting the photopolymerizable composition of the present invention is preferably a photopolymerizable unsaturated compound represented by the following formula (I).

[0021]

[Chemical 3]

(In the formula, R 1 and R 2 are H or CH 3, and they may be the same or different.
A and B are -CH (CH3) CH2- or -CH2CH2-
And these are different. m1 + m2 is 2-16, n1
+ N2 is a positive positive number of 2 to 16. When A and B are only compounds having a hydrophobic group such as a propylene glycol chain, compatibility with the base polymer is deteriorated and scum is generated during development. Also,
The development time also becomes slow. On the other hand, when A and B are only compounds having a hydrophilic group such as ethylene glycol chain, the swelling property at the time of development is increased and the resolution is deteriorated. In order to achieve both developability and resolution, it is effective to have both ethylene glycol chains and propylene glycol chains in the molecule. When m1 + m2 and n1 + n2 exceed 16, the double bond concentration decreases and sufficient sensitivity cannot be obtained. m1 + m2
And n1 + n2 is more preferably 4-12.
One or more kinds of photopolymerizable unsaturated compounds other than the photopolymerizable unsaturated compound represented by the formula (I) may be used in combination.
Examples of the photopolymerizable unsaturated compound other than the formula (I) used in combination include 2-hydroxy-3-phenoxypropyl acrylate, phenoxypolyethylene glycol acrylate, 1,6-hexanediol di (meth) acrylate, 1,4- Cyclohexanediol di (meth) acrylate, polyoxyalkylene glycol di (meth) acrylate such as polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polyoxyethylene polyoxypropylene glycol di (meth) acrylate, 2 (P-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyl trimethylol Lopantri (meth) acrylate,
Polyoxyethyl trimethylolpropane triacrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, 2,2-bis (4-methacryloxy) Mention may be made of pentaethoxyphenyl) propane, polyfunctional (meth) acrylates containing a urethane group, and the like. Further, it is preferable to use a compound having a hydrophilic group such as an ethylene glycol chain for the high speed development processing.

The amount of such a photopolymerizable unsaturated compound used is selected from the range of 5 to 60% by weight. If it is less than 5% by weight, the sensitivity and the film strength are not sufficient, and the amount is 60% by weight.
If it exceeds the above range, the photopolymerizable layer may significantly protrude during storage when used for DFR, which is not preferable. Further, the compound of the formula (I) is preferably contained in an amount of 30% or more based on the total amount of the photopolymerizable unsaturated compound.

Examples of the photopolymerization initiator (c) that can be used in the present invention include known initiators that are 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, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2
-Chloroanthraquinone, 2-methylanthraquinone,
Quinones such as 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl 1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, benzophenone, Michler's ketone [4,4-bis (dimethylamino) ) Benzophenone], 4,4-bis (diethylamino) benzophenone and other aromatic ketones, benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethylbenzoin and other benzoin ethers, benzyl dimethyl ketal, benzyl diethyl ketal, 2- A biimidazole compound such as (O-chlorophenyl) -4,5-diphenylimidazolyl dimer, a combination of thioxanthones and alkylaminobenzoic acid,
For example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, 2-chlorothioxanthone and ethyl dimethylaminobenzoate, a combination of isopropylthioxanthone and ethyl dimethylaminobenzoate, and 2- (O
-Chlorophenyl) -4,5-diphenylimidazolyl dimer in combination with Michler's ketone, acridines such as 9-phenylacridine, 1-phenyl-1,2
Examples include oxime esters such as -propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime and the like. Preferred examples of these initiators include thioxanthones such as diethylthioxanthone and chlorothioxanthone, dialkylaminobenzoic acid esters such as ethyl dimethylaminobenzoate, benzophenone and 4,
4-bis (dimethylamino) benzophenone, 4,4
-Bis (diethylamino) benzophenone, 2- (O
-Chlorophenyl) -4,5-diphenylimidazolyl dimer, and combinations thereof. Particularly, for high resolution, 4,4-bis (dimethylamino) benzophenone or a combination of 4,4-bis (diethylamino) benzophenone and 2- (O-chlorophenyl) -4,5-diphenylimidazolyl dimer is effective. .

The amount of the photopolymerization initiator (c) contained in the photopolymerizable composition of the present invention is 0.01 to 30% by weight, preferably 0.05 to 10% by weight. . When the photopolymerization initiator exceeds 30% by weight, the active absorptivity of the photopolymerizable composition becomes high, and when used as a photopolymerizable resin laminate, curing by polymerization of the bottom portion of the photopolymerizable layer is insufficient. become. Further, if the photopolymerization initiator is less than 0.01% by weight, sufficient sensitivity cannot be obtained.

In order to improve the thermal stability and storage stability of the photopolymerizable composition of the present invention, it is preferable to add a radical polymerization inhibitor to the photopolymerizable composition. Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol,
2,2-methylenebis (4-ethyl-6-tert-butylphenol), 2,2-methylenebis (4-methyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like can be mentioned.

The photopolymerizable composition of the present invention may contain a coloring substance such as a dye or a pigment. Examples of such coloring substances include fuchsin, phthalocyanine green, auramine base, chalcoxide green S, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond green and the like. To be

Further, a color-forming dye that develops color upon irradiation with light may be incorporated in the photopolymerizable composition of the present invention. As a coloring dye, a leuco dye or a fluoran dye,
A combination of halogen compounds may be mentioned. Examples of leuco dyes include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet] and tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green]. On the other hand, as the halogen compound, amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon bromide, tris (2,
3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,
1-trichloro-2,2-bis (p-chlorophenyl)
Examples thereof include ethane, hexachloroethane, and triazine compounds.

Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. Further, among such color-forming dyes, a combination of tribromomethylphenyl sulfone and a leuco dye or a combination of a triazine compound and a leuco dye is useful.

Further, a small amount of a glycidyl ether compound may be added to the photopolymerizable composition of the present invention as a thermal color-developing agent. Specific examples thereof include polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and bisphenol A-PO2 mol-added diglycidyl ether.

If desired, the photopolymerizable composition of the present invention may contain additives such as a plasticizer. Examples of such additives include phthalic acid esters such as diethyl phthalate. In the case of a photopolymerizable resin laminate for DFR, a support layer supporting the photopolymerizable layer is laminated on the photopolymerizable layer containing the photopolymerizable composition. As a material for the support layer, a transparent material that transmits active light is desirable. Examples of the material for the support layer that transmits active light include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, and polymethyl methacrylate. Examples thereof include a copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film and a cellulose derivative film. Those obtained by stretching these flumes as necessary can also be used. From the viewpoint of image forming property and economy, it is advantageous that the film has a small thickness, but it is generally 10 to 30 μm in order to maintain strength.

On the surface of the photopolymerizable layer opposite to the support layer,
A protective layer is laminated as needed. It is an important characteristic of the protective layer that the protective layer has a smaller adhesion to the photopolymerizable layer than the supporting layer, and thus the protective layer can be easily peeled off. Examples of the material for such a protective layer include a polyethylene film and a polypropylene film.

The thickness of the photopolymerizable layer varies depending on the use, but it is 5 to 100 m, preferably, for making a printed circuit board.
5 to 90 μm , and the thinner the photopolymerization layer, the higher the resolution. Further, the thicker the photopolymerization layer, the higher the film strength. The process for producing a printed circuit board using this photopolymerizable resin laminate is performed by a known technique, and the process will be briefly described below.

When there is a protective layer, the protective layer is first peeled off, and then the photopolymerizable layer is laminated on the metal surface of the printed circuit board substrate by thermocompression bonding. The heating temperature at this time is generally 40 to 1
It is 60 ° C. Then, if necessary, the support layer is peeled off and imagewise exposed to actinic light through a mask film. Next, if there is a support film on the photopolymerizable layer, it is removed if necessary, and subsequently, the unexposed portion of the photopolymerizable layer is removed by development using an alkaline aqueous solution. As the alkaline aqueous solution, an aqueous solution of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or the like is used. These alkaline aqueous solutions are selected according to the characteristics of the photopolymerizable layer, but generally 0.5 to 3% sodium carbonate aqueous solution is used. Next, a metal image pattern is formed on the metal surface exposed by the development by using a known etching method or plating method. After that, the cured 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 is 1% to 5
% Aqueous solutions of sodium hydroxide and potassium hydroxide are generally used. It is also possible to add a small amount of a water-soluble organic solvent to the developing solution or the stripping solution.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION Specific embodiments of the present invention will be described below.

[0036]

Example 1 A compound having the composition shown in Table 1 (column of Example 1) was uniformly dissolved. Next, this mixed solution is made to have a thickness of 20.
A polyethylene terephthalate film having a thickness of μm was uniformly applied using a bar coater and dried in a dryer at 95 ° C. for 3 minutes. At this time, the thickness of the photopolymerizable layer was 30 μm . A 23 μm polyethylene film was laminated on the surface of the photopolymerizable layer on which no polyethylene terephthalate film was laminated to obtain a laminated film. On the other hand, 35 μm
Wet buff roll polishing the surface of a copper clad laminate laminated with rolled copper foil ( manufactured by 3M Ltd. , Scotch Bright (registered trademark )
(Standard) # 600, 2), and the photopolymerizable layer was laminated with a hot roll laminator at 105 ° C. while peeling off the polyethylene film of this laminated film.

An ultra-high pressure mercury lamp (HMW-201K, manufactured by Oak Manufacturing Co., Ltd.) is passed through this laminated body through a mask film.
B) exposed the photopolymerizable layer at 50 mJ / cm ² . Subsequently, the polyethylene terephthalate support film was peeled off, and then a 1% aqueous sodium carbonate solution at 30 ° C. was sprayed for about 25 seconds to dissolve and remove the unexposed portion, whereby a good cured image was obtained.

Further, the following evaluation was made on the laminate using the photopolymerizable composition of the present invention. (1) Measurement of minimum development time A photopolymerizable layer was laminated at 105 ° C. by a hot roll laminator while peeling off a polyethylene film of DFR from a copper clad laminate laminated with 35 μm rolled copper foil. Subsequently, after peeling off the polyethylene terephthalate support film of this laminate, spraying a 1% sodium carbonate aqueous solution at 30 ° C., measuring the minimum development time for dissolving the unexposed photopolymerizable layer, and measuring the minimum development time. As time
It was The actual development was performed for 1.5 times the minimum development time. (2) Measurement of minimum peeling time While peeling the polyethylene film of the dry film resist from the copper-clad laminate laminated with 35 μm rolled copper foil, the photopolymerizable layer was heated to 105 ° C. with a hot roll laminator.
It was laminated with. This laminate an ultra-high pressure mercury lamp (Corporation of Oak Seisakusho HMW-201KB) 50
The photopolymerizable layer was exposed at mJ / cm ² . Subsequently, the polyethylene terephthalate support film was peeled off, and then a 1% sodium carbonate aqueous solution at 30 ° C. was sprayed for about 25 seconds.
Subsequently, this laminate was immersed in a 2.5% caustic soda aqueous solution at 40 ° C., and the time for the cured film to peel from the laminate was measured, and this time was taken as the minimum peel time. The actual peeling process was performed for 1.5 times the peeling time. (3) Resolution The laminate laminated on the copper clad laminate was exposed at 50 mJ / cm ² with an ultrahigh pressure mercury lamp (HMW-201KB, manufactured by Oak Manufacturing Co., Ltd.) through a mask film having a line and space of 1: 1. Then, after peeling off the polyethylene terephthalate support film, a 1% sodium carbonate aqueous solution at 30 ° C. was sprayed for about 25 seconds. The minimum separable line width of the obtained image was defined as the resolution. (4) fine line adhesion clad in laminate laminated to the laminate through a mask film capable of single curing resist line formed ultra-high pressure mercury lamp (Corporation of Oak Seisakusho HMW-201KB)
It exposed with 50 mJ / c m ² by. Then, after peeling off the polyethylene terephthalate support film, a 1% sodium carbonate aqueous solution at 30 ° C. was sprayed for about 25 seconds.
The thin line adhesion was defined as the minimum line width at which one obtained cured resist line did not flow or chip.

[0039]

Examples 2-3, Comparative Examples 1-2 By the same method as in Example 1, photopolymerizable resin laminates having the compositions shown in Table 1 were obtained, and the minimum development time and minimum peeling time were measured, resolution, and fine line. The adhesion was evaluated. The results are shown in Table 1. <Description of Symbols> P-1: Methyl ethyl ketone solution of a terpolymer of 70% by weight of methyl methacrylate, 23% by weight of methacrylic acid and 7% by weight of butyl acrylate (solid content concentration 32%, weight average molecular weight 85,000). ) P-2: Methyl tylketone solution of terpolymer of methyl methacrylate 47% by weight, methacrylic acid 23% by weight, and styrene 30% by weight (solid content concentration 32%, weight average molecular weight 45,000) P- 3: 55% by weight of styrene, 35% by weight of acrylic acid,
Terpolymer of 10% by weight of α-methylstyrene (weight average molecular weight 15,000) M-1: trimethylolpropane triacrylate M-2: phenoxyhexaethylene glycol acrylate M-3: tetraethylene glycol diacrylate M -4: Polyethylene glycol dimethacrylate in which propylene oxide having an average of 3 moles of propylene oxide added to both ends of bisphenol A and ethylene glycol having an average of 5 moles of ethylene oxide M-5: 4 moles of ethylene in average at both ends of bisphenol A Oxidized polyethylene glycol dimethacrylate M-6: Bisphenol A: polypropylene glycol with an average of 2 moles of propylene oxide added to each end and 6 moles of ethylene oxide with an average Polymethacrylate glycol dimethacrylate A-1: benzophenone A-2: 4,4-bis (dimethylamino) benzophenone A-3: 2- (O-chlorophenyl) -4,5-diphenylimidazolyl dimer B-1: malachite Green B-2: Leuco Crystal Violet

[0040]

[Table 1]

[0041]

EFFECT OF THE INVENTION D using the photopolymerizable resin composition of the present invention
FR is capable of high-speed development processing, has good releasability, has a high resolution corresponding to fine line formation, and is useful as a DFR for producing an alkali development type circuit board.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI H05K 3/06 H05K 3/06 H J (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 2/00-2 / 60 C08F 299/00-299/08 G03F 7/004-7/033 H05K 3/06

Claims (3)

(57) [Claims] 1. (a) (i) a non-acidic vinyl compound having one polymerizable unsaturated group in the molecule and a phenyl group, (ii) one polymerizable unsaturated group in the molecule Carboxylic acid or acid anhydride, and (iii) alkyl group consisting of alkyl (meth) acrylate having 1 to 6 carbon atoms, and hydroxylalkyl group consisting of hydroxyl (meth) acrylate having 2 to 6 carbon atoms One or more compounds selected from the group, and having a weight average molecular weight of 30,000 or more 6
Less than 10,000 linear polymer, 20 to 90% by weight, (b) 5 to 60% by weight of a photopolymerizable unsaturated compound represented by the following formula (I), (In the formula, R1 and R2 are H or CH3, and these may be the same or different. A and B are -CH.
(CH3) CH2- or -CH2CH2-, which are different. m1 + m2 is 2-16, n1 + n2 is 2-16
Is a positive integer. ), And (c) 4,4-bis (dimethylamino) benzophenone
Or 4,4-bis (diethylamino) benzophenone
And 2- (O-chlorophenyl) -4,5-diphenyl
A photopolymerization initiator comprising a combination of midazolyl dimers ,
A photopolymerizable composition comprising 0.01 to 30% by weight. 2. (iv) Carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule, (v) Alkyl group Alkyl (meth) acrylate having 1 to 6 carbon atoms, Hydroxylalkyl group Having a weight average molecular weight of 10,000 or more 3 which is obtained by copolymerizing hydroxyl (meth) acrylate having 2 to 6 carbon atoms, and one or more compounds selected from the group consisting of vinyl compounds having a phenyl group. The photopolymerizable composition according to claim 1, further comprising a linear polymer of less than 10,000 in a weight ratio of 95/5 to 40/60 with respect to the linear polymer of (a). 3. A photopolymerizable resin laminate in which a layer comprising the photopolymerizable composition according to claim 1 is provided on a support.