JP2000231190A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain characteristics of high resolution and good plating resistance by using a specified linear polymer and a specified photopolymerizable unsatd. compd. SOLUTION: The compsn. contains 20 to 90 wt.% of a nonlinear polymer having the weight average mol.wt. between 3×104 and 6×104, 3 to 30 wt.% of a photopolymerizable unsatd. compd. expressed by the formula, 5 to 40 wt.% of a photopolymerizable compd. having at least two end ethylene groups, and 0.01 to 30 wt.% of a photopolymn. initiator. The nonlinear polymer is prepared by copolymn. of a nonacidic compd. having polymerizable unsatd. groups and phenyl groups in the molecule, a carboxylic acid or acid anhydride, and one or more compds. selected from alkyl(meth)acrylates having 1-6C alkyl groups and hydroxyl (meth)acrylates having 2-6C hydroxyalkyl groups. The proportion of the total amt. of the photopolymerizable unsatd. compds. to the whole weight of the compsn. is 7 to 60 wt.%. In the formula, R1 is H or CH3 and n1 is an integer 3 to 16.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable composition and a photopolymerizable resin laminate, and more particularly to an alkali-developable photopolymerizable composition and a photopolymerizable resin laminate suitable for making a printed wiring board. About.

[0002]

2. Description of the Related Art Conventionally, a so-called dry film resist (hereinafter abbreviated as DFR) comprising a support layer and a photopolymerizable layer has been used as a resist for producing printed wiring.
DFR is generally prepared by laminating a photopolymerizable composition on a support film, and often further laminating a protective film on the composition. The photopolymer layer used here is generally of an alkali developing type using a weak alkaline aqueous solution as a developing solution.

In order to form a printed wiring board using a DFR, a protective film is first peeled off, and then a DFR is laminated on a substrate for forming a permanent circuit such as a copper-clad laminate using a laminator or the like, and a wiring pattern mask film is formed. And the like. Next, if necessary, the support film is peeled off, and the unpolymerized portion of the photopolymerizable composition is dissolved or dispersed and removed with a developer to form a cured resist image on the substrate.

Using the resist image thus formed as a mask, the metal surface of the substrate is etched or plated, and then the resist image is peeled off using an alkaline aqueous solution stronger than a developing solution. Etc. are formed. In particular, recently, a so-called tenting method of covering a through hole (through hole) with a cured film and thereafter etching the same has been frequently used because of simplicity of the process. For etching, cupric chloride, ferric chloride, a copper-ammonia complex solution or the like is used.

[0005] Recently, as the fine patterning of printed wiring boards has progressed to fine patterns, high resolution and high adhesion DFRs have been required, and particularly high resolution has been required for DFRs for packages such as BGA. . Also, B
For fine patterns such as GA, the formation of conductors by plating is the mainstream, and DFR requires plating resistance.

[0006]

Heretofore, it has been very difficult to maintain plating resistance in fine pattern applications, even if high resolution is imparted to the DFR. In particular,
In the fine pattern, the finer the resist line, the more often the resist line is pushed as the plating grows in the plating step, and the plating is often clogged.

[0007]

As a result of intensive studies to solve the above-mentioned problems, the use of a specific linear polymer and a specific photopolymerizable unsaturated compound has resulted in high resolution and high resistance. It has been found that good characteristics of plating property can be obtained, and the present invention has been completed. That is, the first invention of the present application is:
(A) (i) a compound which is non-acidic and has a polymerizable unsaturated group and a phenyl group in the molecule, (ii) a carboxylic acid or acid anhydride having a polymerizable unsaturated group in the molecule, and (iii) A) an alkyl (meth) acrylate having an alkyl group having 1 to 6 carbon atoms and one or more compounds selected from the group consisting of a hydroxyl (meth) acrylate having a hydroxyalkyl group having 2 to 6 carbon atoms; And a linear polymer having a weight average molecular weight of 30,000 to 60,000, 20 to 90% by weight, (b) a photopolymerizable unsaturated compound represented by the following formula (I), 3 to 30% by weight ,

[0008]

Embedded image

(Wherein R1 is H or CH3, n1
Is an integer of 3 to 16. (C) a photopolymerizable unsaturated compound having at least two terminal ethylene groups, 5 to 40% by weight, (d) a photopolymerization initiator,
0.01 to 30% by weight, and based on the total weight of the composition, the photopolymerizable unsaturated compound of (b) and (c)
Wherein the ratio of the total amount to the photopolymerizable unsaturated compound is 7 to 60% by weight.

The second invention of the present application is the first invention, wherein the photopolymerizable unsaturated compound (c) is represented by the following formula (I)
A photopolymerizable composition comprising one or both of the compounds represented by I) and (III).

[0011]

Embedded image

(Wherein R ₂ and R ₃ are H or CH ₃ , which may be the same or different; n 2, n 3,
n4 is an integer of 3 to 20. )

[0013]

Embedded image

(Wherein, R ₄ and R ₅ are H or CH ₃ , which may be the same or different.
A, B is -CH (CH ₃₎ CH ₂ - or -CH ₂ CH
_2- , which are different. n5 + n6 is 2 to 16,
n7 + n8 is an integer of 2 to 16, and n5, n6, n7 and n8 are positive integers. The third invention of the present application is a photopolymer 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, the photopolymerization initiator (d) may be 4,4'-bis (dimethylamino) benzophenone or 4,4'-bis (diethylamino) benzophenone and 2- (o -Chlorophenyl)-
It is a preferred embodiment to use a combination of 4,5-diphenylimidazolyl dimers. Hereinafter, the present invention will be described in detail.

It is essential that the photopolymerizable composition of the present invention contains the photopolymerizable unsaturated compound represented by the general formula (I) as the component (b). The compound of the general formula (I) can be obtained by an esterification reaction between polypropylene glycol and acrylic acid or methacrylic acid. When n is less than 3 in the compound of the general formula (I), the effect on plating resistance is not sufficient, and when n exceeds 16, sufficient sensitivity is not obtained.

The compound of the formula (I) must be contained in the photopolymerizable composition of the present invention in an amount of 3 to 30% by weight.
More preferably, the content is 15% by weight. If this amount is less than 3% by weight, the effect on plating resistance is not sufficient, and if this amount exceeds 30% by weight, sufficient sensitivity is lost. It is essential that the photopolymerizable composition of the present invention contains a photopolymerizable compound having at least two terminal ethylene groups as the component (c). Among such photopolymerizable compounds having at least two terminal ethylene groups, particularly preferred compounds are those represented by the aforementioned general formulas (II) and (II).
And the compounds of I).

In the compound represented by the general formula (II), when n2, n3 and n4 are smaller than 3, the boiling point of the compound is lowered, the odor of the resist becomes strong, and the use becomes extremely difficult. On the other hand, if n2, n3 and n4 exceed 20, practical sensitivity cannot be obtained. Further, in the compound represented by the general formula (III), when A and B are only compounds having a hydrophobic group such as a propylene glycol chain, the compatibility with the base polymer is deteriorated, and scum is generated during development. Cause. In addition, the development time becomes longer. When A and B are only compounds having a hydrophilic group such as an ethylene glycol chain, the swelling property during development increases and the resolution deteriorates.
In order to achieve both developability and resolution, it is effective to have both ethylene glycol chains and propylene glycol chains in the molecule. On the other hand, if n5 + n6 and n7 + n8 exceed 16, the double bond concentration will decrease and sufficient sensitivity will not be obtained. n
5 + n6 and n7 + n8 are preferably from 4 to 12. The general formula (I
Examples of the photopolymerizable compound of the component (c) other than I) and (III) include 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, and polypropylene glycol di ( Meta)
Polyoxyalkylene glycol di (meth) acrylate such as acrylate, polyethylene glycol di (meth) acrylate, polyoxyethylene polyoxypropylene glycol di (meth) acrylate, and 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol Tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane triacrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl Ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, 2,2-bis (4-methacryloyl (Xypentaethoxyphenyl) propane, and a polyfunctional (meth) acrylate containing a urethane group. These photopolymerizable compounds can be used alone or in combination of two or more.
It can also be used in combination with the compounds of I) and (III).

The amount of these compounds used is preferably 5 to 40% by weight, and the total amount of the compound and the compound of the formula (I) must be 7 to 60% by weight. If it is less than 7% by weight, the sensitivity is not sufficient, and if it exceeds 60% by weight, the photopolymerizable layer protrudes significantly during storage, which is not preferable. The amount of the carboxyl group contained in the linear polymer of the component (a) used in the photopolymerizable composition of the present invention needs to be 100 to 600 in terms of acid equivalent, and is preferably 300 to 400. The carboxyl group in the linear polymer is necessary to give the DFR developability and releasability to an aqueous alkali solution. If the acid equivalent is less than 100, the compatibility with a coating solvent or another composition, for example, a photopolymerizable unsaturated compound (monomer) decreases, and if it exceeds 600, the developability and the releasability decrease.
Further, the molecular weight of the linear polymer of the present invention needs to be 30,000 to 60,000. If the molecular weight of the linear polymer exceeds 60,000, the resolution is reduced, and if it is less than 30,000, the photopolymerizable layer protrudes significantly during storage, which is not preferable.

Here, the acid equivalent refers to the weight of a polymer having one equivalent of a carboxyl group therein. The measurement of the acid equivalent is performed by a potentiometric titration method. The molecular weight is determined as a weight average molecular weight (in terms of polystyrene) by gel permeation chromatography (GPC). The copolymer component (i) of the linear polymer used as the component (a) is non-acidic and has a polymerizable unsaturated group in the molecule,
A compound having a phenyl group is an essential component. Such compounds include, for example, styrene, methylstyrene, and styrene derivatives, and in the present invention, styrene is particularly preferred.

The copolymer component (ii) of the linear polymer used as the component (a) is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Such compounds include, for example, (meth) acrylic acid, fumaric acid,
Cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester and the like. The copolymer component (iii) of the linear polymer used as the component (a) is an alkyl (meth) having 1 to 6 carbon atoms of an alkyl group.
An acrylate and one or more compounds selected from the group consisting of hydroxyl (meth) acrylates in which the hydroxylalkyl group has 2 to 6 carbon atoms. Such compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-
Examples thereof include butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

As the photopolymerization initiator of the component (d) used in the photopolymerizable composition of the present invention, various actinic rays,
For example, known initiators that can be activated by ultraviolet rays or the like to initiate polymerization can be used. Examples of such a photopolymerization initiator include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone and 1-chloro. Anthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4
-Naphthoquinone, 2,3-dimethylanthraquinone, 3
Quinones such as -chloro-2-methylanthraquinone;
Benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], aromatic ketones such as 4,4'-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, etc. Benzoin ethers, benzyldimethyl ketal, benzyl diethyl ketal, biimidazole compounds such as 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, a combination of thioxanthones and alkylaminobenzoic acid, for example, ethylthioxanthone Ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, a combination of isopropylthioxanthone and ethyl dimethylaminobenzoate, -(Ο-chlorophenyl)-
Combination of 4,5-diphenylimidazolyl dimer with Michler's ketone, acridines such as 9-phenylacridine, 1-phenyl-1,2-propanedione-2
Oxime esters such as -o-benzoyl oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime and the like. Preferred examples of these initiators include thioxanthones such as diethylthioxanthone and chlorothioxanthone, dialkylaminobenzoates such as ethyl dimethylaminobenzoate, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4'-bis (diethylamino) benzophenone, 2- (o-chlorophenyl)-
Mention may be made of 4,5-diphenylimidazolyl dimers and combinations thereof.

In order to impart a particularly high resolution, 4,4'-bis (dimethylamino) benzophenone or 4,4'-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5 -Combinations of diphenylimidazolyl dimers are effective. The amount of the photopolymerization initiator contained in the photopolymerizable composition of the present invention,
0.01 to 30% by weight, preferably 0.0 to 30% by weight.
5 to 10% by weight. 30% by weight of photopolymerization initiator
When the ratio exceeds the above, the active absorptivity of the photopolymerizable composition becomes high, and when used as a photopolymerized laminate, the curing at the bottom portion of the photopolymerized layer by polymerization becomes insufficient. If the amount of the photopolymerization initiator is less than 0.01% by weight, sufficient sensitivity cannot be obtained.

In order to improve the thermal stability and the storage stability of the photopolymerizable composition of the present invention, it is preferable that the photopolymerizable composition contains a radical polymerization inhibitor. Examples of such a radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, and 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.

The photopolymerizable composition of the present invention may contain coloring substances such as dyes and pigments. 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. Can be

Further, a coloring dye which develops color upon irradiation with light may be contained in the photopolymerizable composition of the present invention. Examples of the coloring dye include a combination of a leuco dye or a fluoran dye and a halogen compound. Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and the like.

On the other hand, examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, and tris bromide. (2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p
-Chlorophenyl) ethane, hexachloroethane, triazine compounds, and the like.

As the triazine compound, 2,4,6-
Tris (trichloromethyl) -s-triazine, 2-
(4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. Among such color-forming dyes, a combination of tribromomethylphenylsulfone and a leuco dye or a combination of a triazine compound and a leuco dye is useful. Further, the photopolymerizable composition of the present invention may contain additives such as a plasticizer, if necessary.

When a photopolymerizable resin laminate for DFR is used, the above photopolymerizable resin composition is coated on a support layer.
The support layer is desirably a transparent layer that transmits active light. Examples of 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 a polymethyl methacrylate copolymer film. , A polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, and the like. These films may be stretched if necessary. A thinner thickness is advantageous in terms of image forming properties and economy, but is generally 10 to 30 μm from the viewpoint of maintaining strength.

A protective layer is laminated on the surface opposite to the photopolymerizable layer laminated with the support layer, if necessary. It is an important characteristic of the protective layer that the protective layer has a sufficiently small adhesive force with the photopolymerizable layer and can be easily peeled off than the support layer. Examples of such a protective layer include a polyethylene film and a polypropylene film. Although the thickness of the photopolymerizable layer varies depending on the application, it is 5 to 100 μm for production of a printed wiring board, preferably 5 to 90 μm.
m, and the resolving power improves as the photopolymerization layer becomes thinner. Further, as the photopolymerized layer is thicker, the film strength is improved. The process of producing a printed wiring board using the photopolymerizable resin laminate is performed by a known technique, but will be briefly described below.

If 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 substrate for a printed wiring board by heating and pressing. The heating temperature at this time is generally 40
１６０160 ° C. Next, if necessary, the support layer is peeled off, and image exposure is performed with actinic light through a mask film. Next, if there is a support film on the photopolymerizable layer, the support film is removed if necessary, and then the unexposed portion of the photopolymerizable layer is developed and removed using an alkaline aqueous solution. As the aqueous alkaline solution, an aqueous solution of sodium carbonate, potassium carbonate, or the like is used. These alkaline aqueous solutions are selected according to the characteristics of the photopolymerizable layer, and generally, a 0.5 to 3% aqueous sodium carbonate solution is used.

Next, a metal image pattern is formed on the metal surface exposed by the development by performing either a known etching method or a plating method. Thereafter, the cured resist image is peeled off with an aqueous alkaline solution which is generally stronger than the aqueous alkaline solution used for development. There is no particular limitation on the alkaline aqueous solution for stripping.
% To 5% aqueous solution of sodium hydroxide or potassium hydroxide is generally used. It is also possible to add a small amount of a water-soluble organic solvent to a developer or a stripper.

[0033]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described with reference to examples.

[0034]

Example 1 A photopolymerizable composition having the composition shown in Table 1 (column of Example 1) was uniformly dissolved. Next, this mixed solution was uniformly applied to a polyethylene terephthalate film having a thickness of 20 μm using a bar coater, and dried in a drier at 95 ° C. for 3 minutes. At this time, the thickness of the photopolymerizable layer was 25 μm. Next, a laminated film was obtained by laminating a 25 μm polyethylene film on the surface of the photopolymerizable layer on which the polyethylene terephthalate film was not laminated. On the other hand, the surface of the copper-clad laminate on which 35 μm rolled copper foil was laminated was wet-buffered with a buffing roll (trade name: Scotch Bright # 600, manufactured by 3M), and the photopolymerizable layer was heated while peeling off the polyethylene film of the laminated film. Lamination was performed at 105 ° C. with a roll laminator. The laminate was passed through a mask film and passed through an ultra-high pressure mercury lamp (Oak Seisakusho HMW-801) at 70 mJ.
The photopolymerizable layer was exposed at / cm ² . Subsequently, the polyethylene terephthalate support film was peeled off, and then 30% of 1%.
An aqueous solution of sodium carbonate was sprayed for about 60 seconds to dissolve and remove unexposed portions, whereby a good cured image was obtained.

The following evaluation was performed on the laminate using the photopolymerizable composition of the present invention. (1) Measurement of minimum development time While peeling off the polyethylene film of the dry film resist on a copper-clad laminate laminated with 35 μm rolled copper foil, the photopolymerizable layer was heated at 105 ° C. by a hot roll laminator.
Was laminated. Subsequently, after the polyethylene terephthalate support film of the laminate was peeled off, it was heated at 30 ° C.
% Sodium carbonate aqueous solution was sprayed, and the minimum development time for dissolving the unexposed photopolymerizable layer was measured, and this time was defined as the minimum development time. Actual development is the minimum development time of 3
Performed twice as long. (2) Resolution 70 mJ / by an ultra-high pressure mercury lamp (Oak Seisakusho HMW-801) through a mask film having a line and space of 1: 1 on the laminate laminated on the copper-clad laminate.
Exposure was in cm ² . Subsequently, after peeling off the polyethylene terephthalate support film, a 1% aqueous solution of sodium carbonate at 30 ° C. was sprayed for about 60 seconds. The minimum line width of the obtained image that can be separated was defined as the resolution.

(3) Plating resistance The photopolymerizable layer was removed from a copper-clad laminate obtained by laminating 35 μm rolled copper foil by a hot roll laminator while peeling off the polyethylene film as a dry film resist.
Was laminated. 70 mJ / cm was passed through a mask film having a line and space of 1: 1 with an ultra-high pressure mercury lamp (Oak Seisakusho HMW-801).
2 exposed the photopolymerizable layer. Subsequently, after peeling off the polyethylene terephthalate support film, a 1% aqueous solution of sodium carbonate at 30 ° C. was sprayed for about 60 seconds. The thus obtained laminated plate having a cured image was subjected to copper sulfate plating under the following conditions, and the cured resist was removed by spraying a 3% aqueous solution of caustic soda at 50 ° C. The copper sulfate plating line of L / S = 30/30 μm after the removal of the cured resist was observed with an optical microscope, and ranked as follows.

(Plating conditions) Pretreatment: acid degreasing agent FRX
(10% aqueous solution, manufactured by Atotech Japan) Immerse in a bath at 40 ° C for 4 minutes. Thereafter, it is washed with water, immersed in an APS aqueous solution (ammonium persulfate aqueous solution, concentration: 200 g / L) at room temperature for 1 minute, and immersed in a 10% sulfuric acid aqueous solution for 2 minutes after washing with water. Copper sulfate plating: 2.0 A / dm2 with the following plating bath composition
The plating was performed at a current density of 45 minutes. <Copper sulfate plating bath composition> Pure water: 58.9% Copper sulfate conc (Meltex): 30% Concentrated sulfuric acid: 10% Concentrated hydrochloric acid: 0.1% Copper cream 125 (Meltex): 1% (Plating resistance rank) ：: A good plating line is formed without secondary copper plating burrs. △: The undercut width of the secondary copper plating is 10 μm on one side of the line
There is a degree. ×: The undercut of the secondary copper plating is 10 μm on one side of the line
That's it.

[0038]

Examples 2 to 6 and Comparative Examples 1 to 5 Photopolymerizable resin laminates having the compositions shown in Table 1 were obtained in the same manner as in Example 1, and the minimum development time was measured, and the resolution and plating resistance were evaluated. Was done. Table 1 shows the results. <Symbol explanation> 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: 32%, weight average molecular weight: 85,000) P-2) Methyl tyl ketone solution of a terpolymer of 47% by weight of methyl methacrylate, 23% by weight of methacrylic acid, and 30% by weight of styrene (solid content: 32%, weight average molecular weight: 45,000) 1: Trimethylolpropane triacrylate M-2: Nano propylene glycol diacrylate M-3: Nano ethylene glycol diacrylate M-4: β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate M-5: Average 6 mol Is a half ester of glycol and methacrylic acid to which propylene oxide has been added.

M-6: Half ester of glycol and methacrylic acid with an average of 9 moles of propylene oxide added. M-7: Half ester of methacrylic acid with glycol having an average of 14 moles of propylene oxide added. M-8: Dimethacrylate of glycol in which ethylene oxide is further added to both ends of polypropylene glycol having an average of 8 moles added to an average of 8 moles of propylene oxide M-9: 3 moles of propylene oxide is added to both ends of bisphenol A on average M-10: Reacted product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Blenmer PP1000 manufactured by NOF CORPORATION) A-1: Benzophenone A-2: 4,4'-bis (dimethylamino) benzophenone A-3: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer B-1: Malachite green -2: leuco crystal violet

[0040]

[Table 1]

[0041]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 2/48 C08F 2/48 4J038 212/00 212/00 4J100 220/00 220/00 290/06 290 / 06 C08K 5/00 C08K 5/00 C08L 25/00 C08L 25/00 33/00 33/00 55/00 55/00 C09D 125/00 C09D 125/00 133/00 133/00 135/00 135/00 G03F 7/004 512 G03F 7/004 512 7/028 7/028 F term (reference) 2H025 AA00 AA02 AA14 AB15 AC01 AD01 BC13 BC34 BC43 BC65 BC83 BC86 CA00 CB14 CB41 CB43 CB45 CB55 FA17 FA43 4F100 AB17 AB33 AH02AK02AHA BA02 BA03 CA30A GB43 JA07A JL00 YY00A 4J002 BC04W BC09W BG01W BG04W BG05W BG06W CH05X CH05Y EE036 EE056 EN116 EU116 EV316 FD090 FD200 FD206 GF00 GP03 4J011 CA05 CA08 CC04 CC10 PA24 PC43 PA65 PA69 PC40 3 QA13 QA22 QA23 QA24 QB16 RA03 RA04 RA17 SA21 SA22 SA25 SA32. PA17 PB09 PC02 PC08 4J100 AB02P AB03P AJ01Q AJ02Q AJ08Q AJ09Q AK32Q AL03R AL04R AL08P AL09R AL36Q AL66P BA03P BA08P DA01 FA03 JA37 JA38

Claims (3)

[Claims] (1) (a) (i) a compound which is non-acidic and has a polymerizable unsaturated group and a phenyl group in a molecule;
(Ii) a carboxylic acid or acid anhydride having a polymerizable unsaturated group in the molecule, and (iii) an alkyl (meth) acrylate having an alkyl group having 1 to 6 carbon atoms, and 2 to 2 carbon atoms.
A linear polymer having a weight average molecular weight of 30,000 or more and 60,000 or less, obtained by copolymerizing at least one compound selected from the group consisting of hydroxyl (meth) acrylates having 6 hydroxyalkyl groups; 90% by weight, (b)
Photopolymerizable unsaturated compound represented by the following formula (I), 3 to 3
0% by weight (In the formula, R1 is H or CH3, and n1 is an integer of 3 to 16.) (c) 5 to 40% by weight of a photopolymerizable unsaturated compound having at least two terminal ethylene groups, (d) Photopolymerization initiator,
0.01 to 30% by weight, and based on the total weight of the composition, the photopolymerizable unsaturated compound of (b) and (c)
Wherein the ratio of the total amount to the photopolymerizable unsaturated compound is 7 to 60% by weight. 2. As the photopolymerizable unsaturated compound (c),
The photopolymerizable composition according to claim 1, wherein the composition contains one or both of the compounds represented by the following formulas (II) and (III). Embedded image (Wherein R ₂ and R ₃ are H or CH ₃ , which may be the same or different. N 2, n 3 and n 4 are 3 to 2
It is an integer of 0. ) (Wherein, R ₄ and R ₅ are H or CH ₃ , which may be the same or different. A and B are each —CH
(CH ₃ ) CH ₂ — or —CH ₂ CH ₂ —, which are different. n5 + n6 is 2 to 16, n7 + n8 is 2 to
It is an integer of 16 and n5, n6, n7 and n8 are positive integers. ) 3. A photopolymerizable resin laminate comprising a support and a layer comprising the photopolymerizable composition according to claim 1 provided thereon.