JP3508819B2 - Photopolymerizable 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 producing 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 the photopolymerizable layer used here, at present, an alkali development type using a weak alkaline aqueous solution as a developing solution is generally used.

In order to manufacture a printed circuit board using DFR, the protective film is first peeled off, and then the DFR is laminated on a substrate for producing a permanent circuit 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.

Using the resist image thus formed as a mask, the metal surface of the substrate is etched or treated by plating, and then the resist image is peeled off using an alkaline aqueous solution stronger than the developing solution to obtain a printed wiring board. And so on. In particular, a so-called tenting method in which a through hole is covered with a cured film and then etched is frequently used due to the simplicity of the process. For etching, cupric chloride, ferric chloride, copper ammonia complex solution, etc. are used. Since the DFR is stored in a roll having a three-layer structure, the photopolymerizable layer protrudes from the end face during storage,
A phenomenon called a so-called edge fuse may occur, which is not preferable in handling.

If the unexposed photopolymerizable layer in the DFR is hard, the adhesion is poor when it is laminated on the substrate, and the photopolymerizable layer can fill the irregularities on the uneven substrate surface. A space may be created. When such a space is created, the etching liquid permeates the substrate, resulting in defects such as disconnection and chipping. Further, in the peeling process, the shape of the peeled piece is large, and if it does not break, the trouble of being entangled with the transport roll occurs.

[0006]

In order to improve the edge fuse as described above, the compounding ratio of the binder in the photopolymerizable layer may be relatively increased. Then, the substrate of the photopolymerizable layer is formed. And the flexibility of the cured film are reduced. Further, in order to improve the followability of the photopolymerizable layer to the substrate, the blending ratio of the binder in the photopolymerizable layer may be relatively reduced, but then the edge fuse is deteriorated and the peeling time is increased. The problem arises. In addition, when the molecular weight of the binder in the photopolymerizable layer is large, the shape of the peeling piece is large and there is a problem that the carrier roll is entangled. An object of the present invention is to provide a photopolymerizable composition that satisfies these characteristics at the same time.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above-mentioned problems, the following (a) a binder resin and (b) a photopolymerizable compound of the general formula (I ) When a photopolymerizable composition containing an unsaturated compound and (c) a photopolymerization initiator is used for DFR, the edge fuse property and the followability of the photopolymerizable layer to the substrate are good, and the shape of the peeling piece is small. It has been found that characteristics such as stripping can be obtained, and the present invention has been completed. That is, the present application provides the following inventions.

(1) (a) The carboxyl group content is 100 to 600 in acid equivalent and the weight average molecular weight is 2
Resin for binder 2 having 10,000 to 500,000 linear polymer A
0 to 90% by weight, (b) 3 to 60% by weight of a photopolymerizable unsaturated compound of the following formula (I ) ,

[0009]

[Chemical 2] (In the formula, R ¹ is H or CH ₃ , and X is —C ₃ H ₆
- or -C ₂ H ₄ - a and, n is a positive integer from 1 to 6. In addition, Y represents a cyclohexane ring . )

And (c) a photopolymerizable composition comprising 0.01 to 30% by weight of a photopolymerization initiator. (2) The resin (a) for a binder has a carboxyl group content of 100 to 600 in acid equivalent and a linear polymer A having a weight average molecular weight of 20,000 to 500,000, and a carboxyl group content of an acid. A linear polymer B having an equivalent weight 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 has a weight ratio A / B of 90/10. The photopolymerizable composition according to (1) above, which is a mixture of 10/90. (3) A photopolymerizable resin laminate in which a layer comprising the photopolymerizable composition according to (1) or (2) above is provided on a support.

The amount of the carboxyl group contained in the linear polymer A constituting the binder resin (a) used in the present invention is 100 to 600, preferably 300 to 400 in terms of acid equivalent. The weight average 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 it is less than 20,000, the tenting film strength and the edge fuse property deteriorate. In order to exert the effects of the present invention even better, the weight average molecular weight of the linear polymer A is preferably 150,000 to 3
It is 0,000, and more preferably 180,000 to 250,000.

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 is necessary for giving the DFR developability and releasability to an aqueous alkaline solution. When the acid equivalent is less than 100, the development resistance is lowered and the resolution and adhesion are adversely affected, and when it exceeds 600, the developability and the peelability are lowered.

The linear copolymer A can be obtained by copolymerizing one or more 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 processes, and flexibility of the cured film. Chosen to retain the properties of. For example, methyl (meth) acrylate, ethyl (meth) acrylate,
There are alkyl (meth) acrylates such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. Also, a vinyl compound having a phenyl group (for example, styrene) can be used.

The linear copolymer A, even if used alone, has a following property,
Although the adhesiveness is good, the combined use with the linear copolymer B enables a more rapid development process and makes the strip shape even smaller. When used in combination, 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 needs to be 100 to 600 in terms of acid equivalent, and preferably 300.
~ 400. The molecular weight of the linear copolymer B needs to be 30,000 to 90,000. The molecular weight of the linear copolymer B is 9
If it exceeds 10,000, the developability will decrease, and if it is less than 30,000, the tenting film strength and the edge fuse property will deteriorate.

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 is necessary for giving the DFR developability and releasability to an aqueous alkaline solution. When the acid equivalent is less than 100, the development resistance is lowered and the resolution and adhesion are adversely affected, and when it exceeds 600, the developability and the peelability are lowered.

The linear copolymer B, like A, can be obtained by copolymerizing a monomer selected from the above monomers.
A vinyl compound having a phenyl group is an essential component. Styrene is preferred as such a vinyl compound.

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 properties as a resist such as tenting, etching,
It does not have sufficient resistance in various plating processes.

[0018] photopolymerizable unsaturated compound constituting the photopolymerizable composition of the present invention (b), the compound of is used the above general formula (I), the X in the compound of general formula (I) -C ₂ H ₄ in terms of release strip shape - are preferred.
Further, if n exceeds 6, in the case of DFR, the double bond concentration becomes relatively low, so that sufficient sensitivity cannot be obtained. Further, Y is cyclo hexane ring is used.

As the photopolymerizable unsaturated compound (b), for example, as the compound of the general formula (I), a half ester compound of 2-hydroxyethyl acrylate and hexahydrophthalic acid, 2-hydroxyethyl acrylate and ethylene oxide can be used. Half-ester compound of hexahydrophthalic acid with 1 mol of compound added, half-ester compound of hexahydrophthalic acid with compound of 1-ethylene oxide added to 2-hydroxyethyl methacrylate, ethylene oxide with 2-hydroxyethyl acrylate 2-hydroxy compound, a half-ester compound of hexahydrophthalic acid
Ethyl methacrylate with 3 moles of ethylene oxide
Half-este with added compound and hexahydrophthalic acid
And the like.

[0020] The above general formula (I) except photopolymerizable unsaturated compound represented by it may also be used at the same time one or more. The general formula (I) other than the photopolymerizable unsaturated compound used simultaneously 2-hydroxy-3-phenoxypropyl acrylate, phenoxy polyethylene glycol acrylate, and monofunctional monomers such as nonylphenoxy polyethylene glycol acrylate, preferably, A photopolymerizable monomer having at least two terminal ethylene groups is used.

Examples of this are 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, poly Polyoxyalkylene glycol di (meth) acrylates such as oxyethylene polyoxypropylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate,

Trimethylolpropane tri (meth) acrylate, polyoxypropyl trimethylolpropane tri (meth) acrylate, polyoxyethyl trimethylolpropane triacrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri ( (Meth) acrylate, bisphenol A diglycidyl ether di (meth)
There are acrylates, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, and polyfunctional (meth) acrylates containing urethane groups.

Preferred examples include those represented by the following general formula ( II ) for making the shape of the peeling piece into a strip. These may be used alone, other polyfunctional,
Alternatively, it may be used in combination with a monofunctional monomer. Further, a system in which a compound having an ethylene glycol chain and a monomer of the following general formula ( II ) are used in combination is also desirable, and by using these monomers, the followability is good and the shape of the peeling piece becomes finer.

[0024]

[Chemical 3] (In the formula, n ¹ , n ² and n ³ are integers of ³ to 20, R ⁶ and R 3
⁷ represents hydrogen or a methyl group)

In the compound represented by the general formula ( II ),
When n ¹ , n ² and n ³ 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, when n ¹ , n ² and n ³ exceed 20, the concentration of photoactive sites per unit weight becomes low, and 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 these unsaturated compounds (b) used is
It is selected from the range of 3 to 60% by weight, but if this amount is less than 3% by weight, the sensitivity is low and not sufficient, and if this amount exceeds 60% by weight, the photopolymerizable layer during storage when used for DFR. This is not preferable, because the protrusion of the notch becomes remarkable.

Examples of the photopolymerization initiator (c) used in the present invention include known initiators which 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, and 2
-Phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl 1-, 4-naphthoquinone , Quinones such as 2,3-dimethylanthraquinone and 3-chloro-2-methylanthraquinone,

Benzophenone, Michler's ketone [4,
4'-bis (dimethylamino) benzophenone], 4,
Aromatic ketones such as 4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin,
Benzoin ethers such as ethylbenzoin, benzyl dimethyl ketal, benzyl diethyl ketal, 2-
A biimidazole compound such as (ο-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,
Also, a combination of 2- (ο-chlorophenyl) -4,5-diphenylimidazolyl dimer and Michler's ketone, acridines such as 9-phenylacridine, 1-phenyl-1,2-propanedione-2-ο-benzoyl Oxime, 1-phenyl-1,2-propanedione-2
There are oxime esters such as-(ο-ethoxycarbonyl) oxime.

Preferred examples of these initiators include thioxanthones such as diethylthioxanthone and chlorothioxanthone, dialkylaminobenzoic acid esters such as ethyl dimethylaminobenzoate, benzophenone,
4,4'-bis (dimethylamino) benzophenone,
4,4'-bis (diethylamino) benzophenone, 2
Mention may be made of-(ο-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 photopolymerization initiator exceeds 30% by weight, the active absorption rate of the photopolymerizable composition increases, and when used as a photopolymerizable resin laminate,
Insufficient curing due to polymerization of the bottom part of the photopolymerizable layer. Further, 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 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.

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 a color upon irradiation with light can be contained in the photopolymerizable composition of the present invention. As such a coloring dye, there is a combination of a leuco dye or a fluorane dye and a halogen compound.

Examples of leuco dyes 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, 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) ethane, hexachloroethane, triazine compounds and the like can be mentioned.

As the triazine compound, 2,4,6-
Tris (trichloromethyl) -s-triazine, 2-
(4-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine may be mentioned. 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. If necessary, the photopolymerizable composition of the present invention may contain additives such as a plasticizer. Such additives include:
Examples thereof include phthalic acid esters such as diethyl phthalate.

When the photopolymerizable resin laminate for DFR is prepared, the above photopolymerizable resin composition is coated on the support layer. As the support layer, a transparent layer that transmits active light is desirable. As the support layer that transmits active light, 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, a polymethyl methacrylate copolymer Examples thereof include films, polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films and cellulose derivative films.
These films may be stretched if necessary. The thinner the thickness, the more advantageous in terms of the image forming property and the economical efficiency, but the thickness is generally 10 to 30 μm in order to maintain the strength.

If necessary, a protective layer may be laminated on the surface opposite to the photopolymerizable layer laminated with the support layer. An important characteristic of this protective layer is that the protective layer has a sufficiently small adhesion to the photopolymerizable layer and can be easily peeled off more easily 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 use, it is 5 to 100 μm, preferably 5 to 90 μm for producing a printed circuit board, and the thinner the photopolymerizable layer, the higher the resolution. Also,
The thicker the photopolymerizable layer, the higher the film strength. A process for producing a printed circuit board using this photopolymerizable resin laminate is performed by a known technique, which 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. The support layer is then peeled off if necessary 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. An aqueous solution of sodium carbonate, potassium carbonate or the like is used as the alkaline aqueous solution. 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 by performing a known etching method or a plating method on the metal surface exposed by the development. 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. There is no particular limitation on the alkaline aqueous solution for peeling, but 1%
An aqueous solution of ˜5% sodium hydroxide or potassium hydroxide is 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.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION Specific embodiments of the present invention will be described below based on Examples. The following evaluations were performed on the laminate using the photopolymerizable composition of the present invention. (1) Edge fuse test It was stored in a roll shape at 23 ° C. and 50%, and evaluated by the following ranking depending on whether or not the photopolymerized layer exudes from the end face. ○: Can be stored for 3 months or more without bleeding from the edge. Δ: 1 month or more and less than 3 months Can be stored without exuding from the end surface. ×: Less than 1 month Can be stored without exuding from the end face.

(2) Peelability test A photopolymerizable layer was peeled off with a hot roll laminator at 105 ° C. while peeling a polyethylene film of a dry film resist from a copper clad laminate laminated with 35 μm rolled copper foil.
It was laminated with. 50 mJ / cm to this laminated body by an ultra-high pressure mercury lamp (Oak Seisakusho HMW-201KB)
^The photopolymerizable layer was exposed at 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 60 seconds. The obtained laminated plate was cut into 5 cm square pieces, dipped in a 3% caustic soda aqueous solution at 50 ° C., and the shape of the cured film peeled off from the laminated board (peeling piece shape) was ranked as follows.

LL: When the cured film is peeled from the laminate, it is peeled in a sheet form without cracks. L: When the cured film is peeled off from the laminated plate, cracks are generated and after peeling, the shape is about 10 mm to 20 mm square. M: When the cured film is peeled off from the laminated plate, cracks are generated and peeled off to form strips of about 5 mm to 10 mm square. S: When the cured film is peeled from the laminated plate, a large number of cracks are generated and after peeling, it becomes a fine piece of 5 mm square or less.

(3) Follow-up evaluation test A laminate having a line width of 100 was obtained by previously laminating, exposing, developing, etching, and removing resist on a copper-clad laminate in which 35 μm rolled copper foil was laminated using a commercially available dry film resist. , 110, 120, 130, 140, 15
A 0 μm linear groove was formed. The depth of the groove was about 10 μm. Using the grooved substrate thus produced, the above-mentioned laminate was laminated in the same manner as above. An image pattern was obtained by exposing and developing a line pattern (line width; 125 μm) that was perpendicular to the groove of the substrate through the laminate with a mask film. Further, a cupric chloride solution at 50 ° C. was sprayed for 70 seconds to etch the copper in the resist-free portion. Finally, a 3% aqueous sodium hydroxide solution at 50 ° C. was sprayed for about 80 seconds to remove the cured resist.

On the thus-prepared copper line, the number of locations where the grooved portion was not broken was counted, and the number was defined as x. On the other hand, the number of locations where etching was caused and disconnection was counted, the number was defined as y, the disconnection rate (%) was calculated by the following calculation formula, and ranked by the following method. Breakage rate (%) = 100y / (x + y) ○; Breaking rate is less than 30% △; Breaking rate is 30% or more and less than 50% ×; Breaking rate is 50% or more

[0044]

Example 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 24%, weight average molecular weight 200,000) (P -2) 210 g, trimethylolpropane triacrylate (M-1) 15 g, nonapropylene glycol diacrylate (M-2) 10 g, nonaethylene glycol diacrylate (M-3) 5 g, 2-hydroxyethyl acrylate and hexahydrophthale Half ester compound with acid (M-6) 10 g, benzophenone (A-1) 6 g, 4,4′-bis (dimethylamino)
Benzophenone (A-2) 0.2 g, malachite green (B-1) 0.04 g, leuco crystal violet (B-2) 0.4 g, tribromomethylphenyl sulfone (B-3) 0.4 g and methyl ethyl ketone (M
10 g of EK) 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 dryer 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, the surface of a copper clad laminate laminated with 35 μm rolled copper foil is wet-buffled polished (manufactured by 3M, trade name Scotchbright # 600, 2 series), and the photopolymerizable layer is hot while peeling off the polyethylene film of this laminated film It laminated at 105 degreeC with the roll laminator. An ultra-high pressure mercury lamp (Oak HMW-201K
B) exposed the photopolymerizable layer at 50 mJ / cm ² .
Subsequently, after peeling off the polyethylene terephthalate support film, a 1% aqueous sodium carbonate solution at 30 ° C. was sprayed for about 60 seconds to dissolve and remove the unexposed portion, and a good cured image was obtained. Table 1 shows the results of the edge fuse test, the peelability test, and the followability test.

Examples 2 to 10 and Comparative Examples 1 to 4 By the same method as in Example 1, photopolymerizable resin laminates having the compositions shown in Table 1 and Table 2 were obtained, and the edge fuse test, peeling test and follow-up were conducted. A sex test was conducted. The results are shown in Tables 1 and 2. The symbols used in Tables 1 and 2 are as follows.

P-1: 70% by weight of methyl methacrylate,
Methyl ethyl ketone solution of terpolymer of 23% by weight methacrylic acid and 7% by weight butyl acrylate (solid content 3
0%, weight average molecular weight 120,000) P-2: 70% by weight of methyl methacrylate, 23% by weight of methacrylic acid, 7% by weight of butyl acrylate, methyl ethyl ketone solution of terpolymer (solid concentration 24%, weight average) Molecular weight 200,000) P-3: Methyl tyl ketone solution of terpolymer of methyl methacrylate 47% by weight, methacrylic acid 23% by weight, styrene 30% by weight (solid content concentration 32%, weight average molecular weight 45,000). )

M-1: trimethylolpropane triacrylate M-2: nonapropylene glycol diacrylate M-3: nonaethylene glycol diacrylate M-4: β-hydroxypropyl-β '-(acryloyloxy) propyl phthalate M- 5: Half-ester compound of glycol dimethacrylate M-6: 2-hydroxyethyl acrylate and hexahydrophthalic acid, in which 3 mol of ethylene oxide was added to both ends of polypropylene glycol to which 8 mol of propylene oxide was added on average, and 3 mol of ethylene oxide was added to both ends on average.

M-7: a compound obtained by adding 1 mol of ethylene oxide to 2-hydroxyethyl acrylate and a half ester compound of hexahydrophthalic acid M-8: a compound obtained by adding 1 mol of ethylene oxide to 2-hydroxyethyl methacrylate. Half ester compound with hexahydrophthalic acid M-9: A compound obtained by adding 3 mol of ethylene oxide to 2-hydroxyethyl acrylate and a half ester compound with hexahydrophthalic acid M-10: Ethylene oxide with 2-hydroxyethyl methacrylate Half-ester compound of hexahydrophthalic acid with 3 mol added compound

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: Tribromomethylphenyl sulfone MEK: Methyl ethyl ketone

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

EFFECT OF THE INVENTION DFR using the photopolymerizable composition of the present invention
In particular, the edge-fusing property during storage is small, the followability when laminating on a substrate is good, and the shape of the peeling piece becomes a fine piece and has good peeling property without being entangled with the transport roll. It is useful as a DFR for plate production.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G03F 7/033 G03F 7/033 // C08L 33/00 C08L 33/00 C09D 4/02 C09D 4/02 H05K 3/06 H05K 3 / 06 H (56) Reference JP-A-1-263645 (JP, A) JP-A-3-17650 (JP, A) JP-A-5-70528 (JP, A) JP-A-9-204044 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (3)

(57) [Claims] 1. (a) The carboxyl group content is from 100 to 600 in terms of acid equivalent, and the weight average molecular weight is from 20,000 to.
Resin for binder 20 having 500,000 linear polymer A
90% by weight, (b) 3 to 60% by weight of a photopolymerizable unsaturated compound represented by the following formula (I ), (In the formula, R ¹ is H or CH ₃ , and X is —C ₃ H ₆
- or -C ₂ H ₄ - a and, n is a positive integer from 1 to 6. In addition, Y represents a cyclohexane ring . ) And (c) 0.01 to 30% by weight of a photopolymerization initiator. 2. The binder resin (a) has a carboxyl group content of 100 to 600 in terms of acid equivalent and a linear polymer A having a weight average molecular weight of 20,000 to 500,000, and a carboxyl group content. Is a linear polymer B 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 photopolymerizable composition is a mixture of A and B such that the weight ratio A / B is 90/10 to 10/90. 3. A photopolymerizable resin laminate comprising a support and a layer comprising the photopolymerizable composition according to claim 1 provided on the support.