JPH1172910A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photopolymerizable resin composition small in edge fuse tendency during storage and good in strippability and useful as a resist for forming a circuit board by incorporating a specified binder resin and a specified compound in each specified amount. SOLUTION: This photopolymerizable composition contains the binder resin in an amount of 20-90 wt.% and a 5-60 wt.% photopolymerizable unsaturated compound and a 0.01-30 wt.% photopolymerization initiator and a 1-20 wt.% compound represented by the formula: R1 -O-(CH2 CH2 O)n1 -R2 in which each of R1 and R2 is H or CH3 ; and n1 is an integer of 3-25. The binder resin is a linear polymer containing carboxylic groups having an acid equivalent of 100-600 and a weight average molecular weight of 20,000-500,000, and linear polymer is obtained by copolymerizing a monomer having one polymerizable unsaturated group in the molecule with a monomer having one carboxylic acid or acid anhydride group and one nonacidic and polymerizable unsaturated group in the molecule.

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 circuit 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 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. The photopolymerizable 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 circuit board using a DFR, a protective film is first peeled off, and then a DFR is laminated using a laminator or the like on a permanent circuit forming substrate such as a copper-clad laminate, 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 the etching, cupric chloride, ferric chloride, a copper-ammonia complex solution or the like is used. Since the DFR is stored in a roll state having a three-layer structure, a phenomenon called a so-called edge fuse in which the photopolymerizable layer protrudes from an end face during storage may occur, which is not preferable in handling. In addition, if the unexposed photopolymerizable layer in the DFR is hard, the adhesiveness is poor when the photopolymerizable layer is laminated on the substrate, and the photopolymerizable layer cannot fill the unevenness on the surface of the uneven substrate. May occur. When such a space is formed, the etchant penetrates the substrate, thereby causing defects such as disconnection and chipping. Further, in the peeling step, the shape of the peeled piece is large, and if it is not crushed, a trouble such as entanglement with the transport roll occurs.

[0005]

In order to improve the edge fuse as described above, the proportion of the binder in the photopolymerizable layer may be relatively increased. And the flexibility of the cured film is reduced. In addition, in order to improve the followability of the photopolymerizable layer to the substrate, the proportion of the binder in the photopolymerizable layer may be relatively reduced, but then the edge fuse becomes worse and the peeling time increases. The problem arises. In addition, when the molecular weight of the binder in the photopolymerizable layer is large, the shape of the peeled piece is large, which causes a problem that the binder is entangled with the transport roll. Therefore, a photopolymerizable composition satisfying these characteristics at the same time has been desired.

[0006]

As a result of intensive studies to solve the above-mentioned problems, a photopolymerizable composition containing a linear polymer and a polyethylene glycol or polyoxyethylene methyl ether compound as claimed in the claims. When the material is used for the DFR, it has been found that the edge fuse property and the followability of the photopolymerizable layer to the substrate are improved, and characteristics such as a stripped strip shape are obtained. Reached.

That is, the present application provides the following inventions. (1) (a) Carboxyl group content is 100 to 100 in acid equivalent.
A binder resin comprising the linear polymer A having a weight average molecular weight of 20,000 to 500,000 and a weight average molecular weight of 20,000 to 200,000, 20 to 90% by weight, (b) a photopolymerizable unsaturated compound, 5 to 60% by weight, A photopolymerizable composition comprising (c) a photopolymerization initiator, 0.01 to 30% by weight, and (d) 1 to 20% by weight of a compound represented by the following general formula (I). .

R 1 —O— (CH 2 CH 2 O) n 1 —R 2 (I) (R 1 and R 2 are H or CH 3, and n 1 represents an integer of 3 to 25) The weight of the linear polymer A used here The average molecular weight is preferably 150,000 to 300,000, and more preferably 180,000 to 250,000. (2) The binder resin (a) has a linear polymer A having a carboxyl group content of 100 to 600 in acid equivalent and a weight average molecular weight of 20,000 to 500,000, and a carboxyl group content of acid. A linear polymer B having a phenyl group-containing vinyl compound having an equivalent weight of 100 to 600 and a weight average molecular weight of 30,000 to 90,000 as one of the copolymerization components is a weight ratio, and A / B is 90/10. The photopolymerizable composition according to the above (1), which is mixed so as to be と 10 to 90/90.

[0009] The weight average molecular weight of the linear polymer A used here is preferably 150,000 to 300,000, more preferably 180,000 to 250,000. (3) A photopolymerizable resin laminate in which a layer comprising the photopolymerizable composition according to (1) or (2) is provided on a support. In the compound of the general formula (I) used in the present invention, n
If 1 is less than 3, DFR will have poor edge fusing properties, and if n1 exceeds 25, the solubility will be poor when dissolving and blending with a solvent such as methyl ethyl ketone to obtain a photopolymerizable composition. It is not preferable. Linear Polymer A Constituting Resin (a) for Binder Used in the Present Invention
The amount of carboxyl groups contained in the acid is equivalent to 100 to 60
It must be 0, preferably 300 to 400. Further, the molecular weight of the linear polymer A needs to be 20,000 to 500,000. When the molecular weight of the linear polymer A exceeds 500,000, the developability decreases, and when the molecular weight is less than 20,000, the tenting film strength and the edge fuse property deteriorate. In order to further exert the effects of the present invention, the molecular weight of the linear polymer A is preferably 150,000 to 300,000, and more preferably 180,000 to 20,000.
50,000.

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). Further, the carboxyl group in the linear copolymer is necessary for giving the DFR developability and releasability to an aqueous alkali solution. If the acid equivalent is less than 100, the development resistance is reduced and the resolution and adhesion are adversely affected, and if it is more than 600, the developability and peelability are reduced.

The linear copolymer A can be obtained by copolymerizing one or more of each of the following two types of monomers. 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. The second monomer is non-acidic, has one polymerizable unsaturated group in the molecule, and has various properties such as developability of the photopolymerizable layer, resistance in etching and plating steps, and flexibility of the cured film. Selected to retain properties. For example, methyl (meth) acrylate, ethyl (meth) acrylate,
There are alkyl (meth) acrylates such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. Further, a vinyl compound having a phenyl group (eg, styrene) can also be used.

The linear copolymer A is capable of following even when used alone.
Although the adhesiveness is good, when used in combination with the linear copolymer B, more rapid development processing is possible, and the shape of the peeled piece is further reduced. When used together, the A / B (weight ratio) is 90/10 to 10/90. The amount of the carboxyl group contained in the linear copolymer B used in the present invention must be 100 to 600 in terms of acid equivalent, and is preferably 300 to 300.
~ 400. Further, the molecular weight of the linear copolymer B needs to be 30,000 to 90,000. When the molecular weight of the linear copolymer B is 9
If it exceeds 10,000, the developability decreases, and if it is less than 30,000, the tenting film strength and the edge fusing property deteriorate.

Here, the acid equivalent means 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). Further, the carboxyl group in the linear copolymer is necessary for giving the DFR developability and releasability to an aqueous alkali solution. If the acid equivalent is less than 100, the development resistance is reduced and the resolution and adhesion are adversely affected, and if it is more than 600, the developability and peelability are reduced.

The linear copolymer B can be obtained by copolymerizing a monomer selected from the above-mentioned monomers, similarly to A.
A vinyl compound having a phenyl group is an essential component. Styrene is preferred as the vinyl compound. The amount of the resin for binder (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.
% 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 the exposure has sufficient properties as a resist, such as tenting, etching, and various plating processes. Does not have sufficient resistance.

As the photopolymerizable unsaturated compound (b) constituting the photopolymerizable composition of the present invention, 2-hydroxy-
Monofunctional monomers such as 3-phenoxypropyl acrylate, phenoxy polyethylene glycol acrylate, and nonylphenoxy polyethylene glycol acrylate, and preferably, photopolymerizable monomers having at least two terminal ethylene groups are used. For this example,
1,6-hexanediol di (meth) acrylate,
Polyoxyalkylene glycol di (meth) acrylates such as 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polyoxyethylene polyoxypropylene glycol di (meth) acrylate A) acrylate, 2 di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyl tri Methylolpropane triacrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate Bisphenol A diglycidyl ether di (meth) acrylate, 2,2-bis (4
-Methacryloxypentaethoxyphenyl) propane,
And polyfunctional (meth) acrylates containing urethane groups.

Preferred examples include a compound having an ethylene glycol chain which is a hydrophilic group or a compound represented by the following general formula (II) in order to make the shape of the strip into strips. These may be used alone or in combination with other polyfunctional or monofunctional monomers. Also,
A compound having an ethylene glycol chain and a compound represented by the following general formula (I)
It is also desirable to use a system in which the monomer (I) is used in combination. By using these monomers, the followability is good and the shape of the peeled piece becomes finer.

[0017]

Embedded image

(Where n2, n3 and n4 are integers of 3 to 20, and R3 and R4 are hydrogen or a methyl group) In the compound represented by the general formula (II), n2, n3,
When n4 is smaller than 3, the boiling point of the compound decreases,
The odor of the resist becomes strong, making it extremely difficult to use.
On the other hand, if n2, n3, and n4 exceed 20, the concentration of photoactive sites per unit weight decreases, so that practical sensitivity cannot be obtained. The compound represented by the general formula (II) can be synthesized by a method in which a product obtained by reacting propylene oxide and ethylene oxide is esterified with acrylic acid or methacrylic acid in the presence of a suitable acid catalyst.

The amount of the unsaturated compound (b) used is
The amount is selected from the range of 5 to 60% by weight, but if this amount is less than 5% by weight, the sensitivity is not sufficient. It is not preferable because the protrusion of the layer becomes remarkable. Examples of the photopolymerization initiator (c) used in the present invention include known initiators that are activated by various actinic rays, for example, ultraviolet rays and start polymerization.

As such a photopolymerization initiator, for example,
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 (dimethyl Amino) benzophenone], aromatic ketones such as 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethylben Benzoin ethers such as in, benzyl dimethyl ketal, benzyl diethyl ketal, 2-(o over-chlorophenyl) over 4,5 over diphenyl imidazolylmethyl dimers such biimidazole compounds of the combination of thioxanthones and alkylamino benzoic acid,
For example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, a combination of isopropylthioxanthone and ethyl dimethylaminobenzoate, or 2- (ο
-Chlorophenyl) -4,5 diphenylimidazolyl dimer and Michler's ketone, acridines such as 9-phenylacridine, 1-phenyl-1,2
Oxime esters such as -propanedione-2-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, dialkylaminobenzoic esters such as ethyl dimethylaminobenzoate, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 2- (o-chlorophenyl) -4,5 diphenylimidazolyl dimer, and combinations thereof.

The amount of the photopolymerization initiator 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 amount of the photopolymerization initiator exceeds 30% by weight, the active absorption of the photopolymerizable composition increases, and when used as a photopolymerization laminate, curing at the bottom portion of the photopolymerization layer by polymerization becomes insufficient. Also,
If the amount of the photopolymerization initiator is less than 0.01% by weight, sufficient sensitivity cannot be obtained.

Further, in order to improve the thermal stability and 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, 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 capable of forming a color upon irradiation with light can be contained in the photopolymerizable composition of the present invention. As a color-forming dye, a leuco dye or a fluoran dye,
There are combinations of halogen compounds. 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 (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.

Examples of the triazine compound include 2,4,6 tris (trichloromethyl) -s-triazine and 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. Such additives include:
For example, phthalic esters such as diethyl phthalate can be mentioned. When a photopolymerizable resin laminate for DFR is used, the 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, preferably 5 to 90 μm for producing a printed circuit board. The thinner the photopolymerizable layer, the higher the resolution. Also,
The thicker the photopolymerizable layer, the higher the film strength. The process of producing a printed circuit 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 removed, and then the photopolymerizable layer is laminated on the metal surface of the substrate for a printed circuit board by heating and pressing. The heating temperature at this time is generally 40 to 1
60 ° 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 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, 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. The alkaline aqueous solution for peeling is not particularly limited, but an aqueous solution of 1% to 5% 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.

[0028]

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

[0029]

Example 1 A compound having the composition shown in Table 1 (column of Example 1) was uniformly dissolved. Next, this mixed solution is applied to a thickness of 20 μ
m of polyethylene terephthalate film using a bar coater, and dried in a drier at 95 ° C. for 4 minutes. At this time, the thickness of the photopolymerizable layer was 40 μm. A 25 μm polyethylene film was laminated on the surface of the photopolymerizable layer on which the polyethylene terephthalate film was not laminated to obtain a laminated film. On the other hand, 35 μm
The surface of the copper-clad laminate obtained by laminating the rolled copper foil is polished by wet baffle (trade name: Scotch Bright # 60, manufactured by 3M)
0 or 2), and the photopolymerizable layer was laminated at 105 ° C. using a hot roll laminator while peeling off the polyethylene film of the laminated film. An ultra-high pressure mercury lamp (Oak Works H
(MW-201 KB) to expose the photopolymerizable layer at 50 mJ / 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 to dissolve and remove the 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) Edge fuse test It was stored in a roll at 23 ° C. and 50%, and evaluated according to the following ranking depending on whether or not the photopolymerizable layer had exuded from the end face. ；: Can be stored for 6 months or more without exuding from the end face.

Δ: One month or more and less than six months can be stored without exuding from the end face. ×: can be stored for less than one month without exuding from the end face. (2) Peelability test While peeling off the polyethylene film of the dry film resist on a copper-clad laminate on which 35 μm rolled copper foil was laminated, the photopolymerizable layer was heated at 105 ° C. using a hot roll laminator.
Was laminated. An ultra-high pressure mercury lamp (HMW-201KB, manufactured by Oak Manufacturing Co., Ltd.) was used to apply 50 mJ / cm 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 obtained laminate was cut into 5 cm squares, immersed in a 3% aqueous solution of caustic soda at 50 ° C., and the shape of the cured film peeled from the laminate (peeled piece shape) was ranked as follows.

LL: When the cured film is peeled off from the laminate, it is peeled off in the form of a sheet without cracks. L: When the cured film is peeled off from the laminate, it is cracked and peeled off, and has a shape of about 10 mm to 20 mm square. M: When the cured film is peeled off from the laminated board, cracks are formed and peeled off, and then a small piece of about 5 mm to 10 mm square is formed.

S: When the cured film is peeled off from the laminate, a large number of cracks are formed and the film is peeled off to form fine pieces of 5 mm square or less. (3) Followability evaluation test Lamination-exposure-development-etching-resist peeling was performed on a copper-clad laminate obtained by laminating a rolled copper foil of 35 μm using a commercially available dry film resist, and the line width was 100, 110, 120. , 130, 140, 15
A linear groove of 0 μm was formed. The depth of the groove was about 10 μm.

Using the grooved substrate thus produced, the above laminate was laminated in the same manner as above. An image pattern was obtained by exposure and development using a line pattern (line width: 125 μm) perpendicular to the groove of the substrate through a mask film through the laminate. In addition, 5
A cupric chloride solution at 0 ° C. was sprayed for 70 seconds to etch the copper in portions where there was no resist. Finally 3% of 50 ℃
The cured resist was removed by spraying an aqueous solution of sodium hydroxide for about 80 seconds. On the copper line made in this way,
The number of places where the grooves were previously not broken was counted, and the number was x. On the other hand, the number of portions that were disconnected due to etching was counted, the number was set as y, and the disconnection rate (%) was calculated by the following formula, and ranked according to the following method.

Disconnection rate (%) = 100y / (x + y) ；: Disconnection rate is less than 30% Δ: Disconnection rate is 30% or more and less than 50% ×: Disconnection rate is 50% or more

[0036]

Examples 2 to 6 and Comparative Examples 1 to 3 Photopolymerizable resin laminates having the compositions shown in Table 1 were obtained in the same manner as in Example 1, and were subjected to an edge fuse test, a peeling test and a follow-up test. Was.
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: 30%, weight average molecular weight: 120,000) P -2: Methyl methacrylate 70% by weight, methacrylic acid 23% by weight, butyl acrylate 7% by weight terpolymer copolymer in methyl ethyl ketone (solid content 24%, weight average molecular weight 200,000) P-3: methacrylic acid Methyl tyl ketone solution of a terpolymer of 47% by weight of methyl, 23% by weight of methacrylic acid and 30% by weight of styrene (solid content: 32%, weight average molecular weight: 45,000) M-1: trimethylolpropane triacrylate M-2: Ethylene oxide is further added to both ends of polypropylene glycol having an average of 8 mol of propylene oxide added. Dimethacrylate of glycol with an average of 3 mol added M-3: nano propylene glycol diacrylate M-4: nano ethylene glycol diacrylate M-5: phenoxy hexaethylene glycol acrylate 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 B-3: tribromomethylphenylsulfone C -1: polyethylene glycol (average molecular weight 400) C-2: polyoxyethylene monomethyl ether (average molecular weight 550) C-3: polypropylene glycol (average molecular weight 200)
0)

[0037]

[Table 1]

[0038]

EFFECT OF THE INVENTION D using the photopolymerizable resin composition of the present invention
FR has a small edge-fusing property especially during storage, has good follow-up properties when laminating to a substrate, and has a good peeling property without a stripped strip shape and entangled with a transport roll. It is useful as a DFR for manufacturing circuit boards.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/033 G03F 7/033 H05K 3/06 H05K 3/06 J

Claims (3)

[Claims] (1) A carboxyl group content is 1 in acid equivalent.
And a weight average molecular weight of 20,000-5.
Binder resin composed of 100,000 linear polymers A, 20 to 20
90% by weight, (b) a photopolymerizable unsaturated compound, 5 to 6
0% by weight, (c) a photopolymerization initiator, 0.01 to 30% by weight, and (d) a compound 1 represented by the following general formula (I)
A photopolymerizable composition comprising 20% by weight. R1-O- (CH2CH2O) n1-R2 (I) (R1, R2 are H or CH3, and n1 represents an integer of 3 to 25) 2. The resin (a) for a binder is a linear polymer A having a carboxyl group content of 100 to 600 as an acid equivalent and a weight average molecular weight of 20,000 to 500,000, and a carboxyl group content. Is a copolymer having an acid equivalent of 100 to 600, and a vinyl compound having a phenyl group having a weight average molecular weight of 30,000 to 90,000 as one of the copolymerization components. The photopolymerizable composition according to claim 1, wherein the composition is mixed so as to be / 10 to 10/90. 3. A photopolymerizable resin laminate comprising a support and a layer comprising the photopolymerizable composition according to claim 1 provided on a support.