JP2880775B2 - Photopolymerizable composition and photopolymerizable laminate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photopolymerizable composition and a photopolymerizable laminate, and more particularly to an alkali-developable photopolymerizable composition suitable for making a printed circuit board. And a photopolymerizable laminate using the composition.

[Conventional technology]

Conventionally, a so-called dry film resist (hereinafter abbreviated as DFR) comprising a support layer and a photopolymerization layer has been used as a resist for producing a printed circuit board. DFR is generally prepared by laminating a photopolymerizable layer from a photopolymerizable composition on a support layer, and often further laminating a protective film on the composition.

To produce a printed circuit board using DFR, first, the protective film is peeled off, and then DFR is laminated on a permanent circuit producing substrate such as a copper-clad laminate. Next, if necessary, the support layer is peeled off, and exposure is performed through a wiring pattern mask film or the like. If there is a support layer after exposure, peel the support layer if necessary, dissolve the unexposed portion of the photopolymer layer with a developer,
Alternatively, they are dispersed and removed to form a cured resist image on the substrate. As the photopolymerization layer, an alkali developing type using an alkali aqueous solution as a developing solution and a solvent developing type using an organic solvent are known, but in recent years, demand for the alkali developing type DFR is increasing in terms of environmental problems or costs. .

The process for forming a circuit is the same for both types after development, and is roughly divided into two methods. The first method is to further remove the resist after etching and removing the copper surface that is not covered with the cured resist, and the second method is to perform a plating treatment of copper and solder on the copper surface. After that, the resist is removed, and the exposed copper surface is etched.

Also, in a printed circuit board manufactured using DFR, a conductive circuit forming material layer attached to the inner peripheral surface of the through hole,
For example, in most cases, one side of the permanent image forming substrate is electrically connected to the other side by a copper thin film layer. As a method of manufacturing this type of printed circuit board,
The copper through-hole method and the solder through-hole method are common, and the tenting method is widely used among the copper through-hole methods.

In the solder through-hole method, an inner peripheral surface of the through-hole is coated with a conductive circuit constituent material, for example, an etching-resistant metal for protecting a copper thin film layer, for example, solder plating, and then unnecessary portions on the substrate surface are etched. In various plating processes such as the above-described copper plating and solder plating, a plating solution permeates between the resist and the base material, and if the plating gets loose, it causes a short circuit. Therefore, DFR with excellent plating resistance is required.

Further, the cured resist formed by the exposure and the development is stripped by a stripping solution of an aqueous alkali solution such as sodium hydroxide after etching or plating. The peeling speed is preferably high from the viewpoint of productivity. In addition, when the solubility of the resist cured film in the stripping solution is high, the viscosity of the stripping solution increases, and foaming becomes remarkable. Therefore, the processing ability of the stripping solution is reduced. Furthermore, since the BOD (biochemical oxygen demand) and COD (chemical oxygen demand) of the stripper increase,
The cost required for waste liquid treatment becomes high. From the above points, it is desirable that the resist cured film is hardly soluble in the stripping solution.

DFR photopolymerization layers widely used at present include (1) unsaturated compounds having at least one ethylenic group and capable of forming a polymer with a photopolymerization initiator, (2) thermoplastic organic polymer bonding (3) photopolymerization initiator and (4) other additives (Japanese Patent Publication No. 50-9177,
Japanese Patent Publication No. 57-21697).

The most common unsaturated compounds are acrylic acid and methacrylic acid esters of aliphatic polyhydric alcohols,
Trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate and the like are known. In addition, there is known an example in which polyethylene glycol or polypropylene glycol is added to bisphenol A as an aromatic dihydric alcohol to use as acrylic acid or methacrylic acid ester.

[Problems to be solved by the invention]

However, in the former aliphatic ester, sufficient plating resistance cannot be obtained. When the latter bisphenol-based monomer is used, the plating resistance is good, but if the side chain is long, the plating resistance is reduced or the compatibility with the binder is impaired. In addition, DFRs that can be alkali-developed have sufficient resistance especially in the plating process as fine patterning progresses in recent years, and they are quickly peeled off in the peeling process, and are hardly soluble in the peeling solution. There has been a demand for a performance that simultaneously satisfies the characteristic of.

[Means for solving the problem]

As a result of intensive studies to solve the above problems, it has been found that a compound containing both ethylene glycol and propylene glycol chains in the molecule of a bisphenol A-based acrylate monomer or methacrylate monomer cannot be photopolymerized. When the compound is used as a saturated compound, it has been found that the above-mentioned resist properties are satisfied at the same time, and that the cured film has a good peeling property.

That is, the present invention is as described below in the first item (referred to as the first invention) to the fourth item (referred to as the fourth invention).

1. (a) The carboxyl group content is 100 to 600 in acid equivalent,
5 to 93% by weight of a linear polymer having a weight average molecular weight of 20,000 to 500,000. (B) Both ethylene glycol and propylene glycol chains are contained in the molecule of the bisphenol A-based acrylate or methacrylate monomer. A photopolymerizable composition comprising: 5 to 93% by weight of a photopolymerizable unsaturated compound, and (c) 0.01 to 30% by weight of a photopolymerization initiator.

2. (a) The carboxyl group content is 100 to 600 in acid equivalent,
5 to 93% by weight of a linear polymer having a weight average molecular weight of 20,000 to 500,000; (b) 5 to 93% by weight of a photopolymerizable unsaturated compound represented by the following formula (I); (Wherein, R ₁ and R ₂ are H or CH ₃ , which may be the same or different. A and B are each represented by —CH (C
H ₃ ) CH ₂ — or —CH ₂ CH ₂ —, which are different. m ₁ + m ₂ is 6 to 12, n ₁ + n ₂ is 6 to 12, and m ₁ , m ₂ ,
n ₁ and n ₂ are positive integers. ) And (c) a photopolymerizable composition comprising 0.01 to 30% by weight of a photopolymerization initiator.

3. In a photopolymerizable laminate comprising a photopolymerizable layer and a support layer, the photopolymerizable layer is composed of: (a) a line having a carboxyl group content of 100 to 600 in acid equivalent and a weight average molecular weight of 20,000 to 500,000. (B) a photopolymerizable unsaturated compound containing both an ethylene glycol chain and a propylene glycol chain in the molecule of the bisphenol A-based acrylate monomer or methacrylate monomer A photopolymerizable laminate comprising a composition containing 93% by weight and (c) 0.01 to 30% by weight of a photopolymerization initiator.

4. In a photopolymerizable laminate comprising a photopolymerization layer and a support layer, the photopolymerization layer is composed of: (a) a line having a carboxyl group content of 100 to 600 in acid equivalent and a weight average molecular weight of 20,000 to 500,000. (B) 5 to 93% by weight of a photopolymerizable unsaturated compound represented by the following formula (I): (Wherein, R ₁ and R ₂ are H or CH ₃ , which may be the same or different. A and B are each represented by —CH (C
H ₃ ) CH ₂ — or —CH ₂ CH ₂ —, which are different. m ₁ + m ₂ is 6 to 12, n ₁ + n ₂ is 6 to 12, and m ₁ , m ₂ ,
n ₁ and n ₂ are positive integers. And (c) a photopolymerizable laminate comprising a composition containing 0.01 to 30% by weight of a photopolymerization initiator.

In particular, when the compound represented by the general formula (I) is used as a photopolymerizable unsaturated compound, the cured resist shows sufficient resistance especially in the plating step and has good peelability in the peeling step. And the characteristic that the cured film is rich in flexibility.

In the photopolymerizable unsaturated compound represented by the formula (I) used in the present invention, when only an ethylene glycol chain is used, if the side chain is lengthened to improve releasability, hydrophilicity increases, swelling is likely to occur, and plating resistance is increased. Sex is impaired. When only a propylene glycol chain is used, similarly, if the side chain is lengthened in order to improve the releasability, the compatibility with the binder is deteriorated, so that a uniform composition is not obtained and phase separation occurs.

The photopolymerizable composition of the present invention includes (b) the first invention.
It is necessary that the content of the photopolymerizable unsaturated compound is 5 to 93% by weight, more preferably 20 to 60% by weight.

When the amount of the photopolymerizable unsaturated compound is 93% by weight or more, the film imparting property and tackiness are deteriorated, and when the amount is less than 5% by weight, a sufficiently cured image is not formed by exposure, and properties as a resist, such as tenting, It cannot have resistance to etching and various plating steps.

In the present invention, one or more photopolymerizable unsaturated compounds other than the aforementioned photopolymerizable unsaturated compounds may be used simultaneously. Examples of the photopolymerizable unsaturated compound other than the formula (I) used simultaneously include 2-hydroxy-3
-Phenoxypropyl acrylate, phenoxytetraethylene glycol acrylate, β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, 1,4-tetramethylene glycol di (meth) acrylate (this represents methacrylate and acrylate; the same applies hereinafter). , 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol (meth) acrylate, octapropylene glycol di (meth) acrylate, glycerol (meth) acrylate, 2-di (P-hydroxyphenyl) propanedi (meth) ) Acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyl Trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, And diallyl phthalate.

The amount of the carboxyl group contained in the linear polymer used in the present invention must be 100 to 600 in acid equivalent, 300 to 400
Is preferred. The molecular weight must be 20,000 to 500,000,
Preferably it is 50,000 to 200,000. Here, the acid equivalent refers to the weight of a polymer having one equivalent of a carboxyl group therein. The carboxyl group in the polymer is necessary for having developability and releasability in an aqueous alkali solution. Acid equivalent
If it is less than 100, the compatibility with the coating solvent or another composition such as a monomer will be reduced, and if it is more than 600, the developability and the releasability will be reduced. On the other hand, if the molecular weight is 500,000 or more, the developability is reduced. In addition, the measurement of the acid equivalent was performed using Hiranuma Reporting Titrator CONTITE
Performed by potentiometric titration with 0.1N sodium hydroxide using -7. The molecular weight is determined by gel permeation chromatography (Pump; TRIROTAR-V, column;
Shodex A-80M x 2 in series, mobile phase solvent; using a calibration curve with THF and polystyrene standard sample).

The linear polymer is 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 selected so as to maintain various properties such as developability of the photopolymerized layer, resistance in etching and plating steps, and flexibility of the cured film. For example, methyl (meth) acrylate, butyl (meth) acrylate, 2-
There are alkyl (meth) acrylates such as ethylhexyl (meth) acrylate. Further, there are esters of vinyl alcohol such as vinyl acetate, and styrene or a polymerizable styrene derivative. It can also be obtained by polymerization of only a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule.

The amount of the linear polymer contained in the photopolymerizable composition is 5 to 5.
It must be in the range of 93% by weight, preferably 30-70% by weight. When the amount of the linear polymer is 93% by weight or more or less than 5% by weight, the cured image formed by exposure has sufficient resist properties, for example, sufficient resistance in tenting, etching, and various plating steps. I can't.

The photopolymerizable composition of the present invention contains a photopolymerization initiator as an essential component. The photopolymerization initiator used in the present invention is any known compound that is activated by various kinds of actinic rays, for example, ultraviolet rays, and starts polymerization. For example, 2-ethylanthraquinone, octamethylanthraquinone, 1,
2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-fe Nantraquinone, 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, such as a combination of dimethylthioxanthone and dimethylaminobenzoic acid, and a combination of a thioxanthone compound and a tertiary amine compound.

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 is 30% by weight or more, the active ray absorption of the photopolymerizable composition becomes high, and when the photopolymerizable composition is used as a photopolymerization laminate, curing at the bottom portion of the photopolymerization layer becomes insufficient. If the content is less than 0.01% by weight, sufficient sensitivity cannot be obtained.

In order to improve the thermal stability and storage stability of the photopolymerizable composition of the present invention, it is preferable that the photopolymerizable composition contains a radical polymerization inhibitor. For example, 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) and the like.

The photopolymerizable composition of the present invention may contain coloring substances such as dyes and pigments. For example, 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.

Further, a coloring dye which develops color by light irradiation may be contained. As a color-forming dye, a combination of a leuco dye and a halogen compound is well known. 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, tris (2 , 3−
Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (P-chlorophenyl) ethane, hexachloroethane and the like.

Further, the photopolymerizable composition may contain an additive such as a plasticizer, if necessary. For example, phthalic esters such as diethyl phthalate can be exemplified.

A second invention of the present invention comprises a photopolymerizable layer containing the above photopolymerizable composition, and a support layer supporting the photopolymerizable layer.

The support layer of the photopolymerization layer is desirably a transparent layer that transmits active light.

As a support layer that transmits active light, polyethylene terephthalate film, polyvinyl alcohol film,
Polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose Derivative films and the like. These films may be stretched if necessary.

In addition to the photopolymerized layer laminated on the support layer, a protective layer is laminated on the photopolymerized layer surface as needed. An important property of this protective layer is that the protective layer is sufficiently small and easily peelable as compared with the support layer in terms of adhesion to the photopolymerizable layer. For example, there are a polyethylene film and a polypropylene film. Further, a film having excellent releasability as disclosed in JP-A-59-202457 can be used.

Although the thickness of the photopolymerized layer varies depending on the application, it is 5 to 100 μm, preferably 5 to 70 μm for producing a printed circuit board, and the thinner the film, the higher the resolution. Further, the film strength increases as the thickness increases.

Next, the process of producing a printed circuit board using the photopolymerizable laminate of the present invention is based on the prior art, but will be briefly described. First, if there is a protective layer, after peeling off the protective layer,
The photopolymerized layer is laminated on the metal surface of the printed circuit board substrate by heating and pressing. The heating temperature at this time is generally 40 to 160 ° C. Next, if necessary, the support layer is peeled off, and image exposure is performed with actinic light through a mask film. Next, if a support layer is present on the photopolymerized layer after exposure, the support layer is removed if necessary, and then the unexposed portion is developed and removed using an aqueous alkali solution.
As the alkaline aqueous solution, an aqueous solution of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or the like is used. These are selected according to the characteristics of the photopolymerization layer, and a 0.5% to 3% aqueous solution of sodium carbonate is generally used. Next, by development, the exposed metal surface is etched,
Alternatively, an image pattern of a metal is formed by using any known method such as a plating method. Thereafter, the cured resist image is generally stripped off with an aqueous alkaline solution that is 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. Further, it is possible to add a small amount of a water-soluble organic solvent to a developer or a stripper.

〔Example〕

Hereinafter, specific embodiments will be described with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1 A 5-volume separable flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 2000 g of ion-exchanged water, and methylcellulose [Shin-Etsu Chemical Co., Ltd., trade name: Metroose
SH-100] Dissolve 10 g and sodium chloride 5 g, and stir at 75 ° C while mixing methyl methacrylate as a polymerizable monomer.
365 g, n-butyl acrylate 25 g, methacrylic acid 110
g, azobisisobutyronitrile 2.5 as other ingredient
g and dodecyl mercaptan (1 g).
After about one hour, the internal temperature began to rise and reached 90 ° C. When the internal temperature was lowered to 80 ° C., the water bath was raised to 80 ° C., and the mixture was stirred for 2 hours and further at 90 ° C. for 1 hour. As a result, 10
A beaded polymer with a particle size of 0-400 microns was obtained and dried. This polymer was analyzed by gel permeation chromatography to find that the weight average molecular weight was 120,000. The acid equivalent determined by potentiometric titration was 390.

Synthesis Example 2 A copolymer was synthesized in the same manner as in Synthesis Example 1 except that only the polymerizable monomer was changed to the following raw materials.

200 g of methyl methacrylate, 150 g of styrene, 25 g of n-butyl acrylate, 125 g of methacrylic acid. The weight average molecular weight of this copolymer measured by gel permeation chromatography was 60,000. Further, the acid equivalent was 346.

Example 1 In a 500 ml separable flask equipped with a stirrer and a reflux condenser, 150 g of methyl ethyl ketone and 50 g of the copolymer prepared in Synthesis Example 1 were charged, and stirred at 50 ° C. for 3 hours.
The mixture was heated and dissolved for hours. After the solution was cooled to room temperature, the monomers and other components shown in Table 1 were added, and the solution was cooled to room temperature.
Stir for hours.

Next, this mixed solution was uniformly applied to a 25 μm-thick polyethylene terephthalate film using a bar coater, and dried in a drier at 90 ° C. for 5 minutes to obtain a photopolymer layer having a thickness of 50 μm.
m of the photopolymerizable laminate was produced. Thereafter, a 35 μm polyethylene film was laminated on the surface of the photopolymerization layer on which the polyethylene terephthalate film was not laminated to obtain a laminated film. On the other hand, a copper-clad laminate obtained by laminating rolled copper foil of 35 μm was wet-type baffle [trade name, manufactured by 3M, Inc.
The photopolymerized layer was laminated at 105 ° C. with a hot roll laminator while peeling off the polyethylene film of the laminated film on the polished surface of Scotch Bright HD # 600 (twice passed) to obtain a laminate. An ultra-high pressure mercury lamp (Oak Works HMW-201) is passed through a mask film through this laminate.
The photopolymer layer was exposed to light at 80 mJ / cm ^{2 according} to KB). Subsequently, after peeling off the polyethylene terephthalate film, a 1% aqueous solution of sodium carbonate at 30 ° C. was sprayed for about 70 seconds, and the unexposed portions were dissolved and removed to obtain a good cured image.

Next, after laminating the photopolymerization layer on the copper-clad laminated substrate by the above method, it is passed through a step tablet (manufactured by KODAK, 21-step step tablet), and the above-mentioned ultrahigh-pressure mercury lamp is used for 80 μm.
mJ / cm ^{2 was} exposed. Next, after peeling off the polyethylene terephthalate film, a 1% aqueous solution of sodium carbonate at 30 ° C. was sprayed for about 70 seconds to dissolve and remove unexposed portions, washed with water and dried. At this time, the maximum number of steps on the step tablet where the film was completely left was 6 steps. (Hereinafter, this test is referred to as a sensitivity test. The greater the number of steps in a step tablet, the lower the light transmittance. Therefore, the higher the sensitivity of the resist, the higher the number of determination steps.) The laminated body was exposed at 60 mJ / cm ² using an ultra-high pressure mercury lamp. Next, after the polyethylene terephthalate film was peeled off, it was developed by spraying a 1% aqueous solution of sodium carbonate for about 70 seconds. The following two tests were performed using the developed substrate.

The first test: The cured film on this substrate was cut in length and width at intervals of 1 mm, and 10 cuts were made, and 100 base lines were made.
One out of 100 completely peeled off (hereinafter, this test is referred to as a cross cut test). The evaluation criteria are
It is as follows.

：: No peeling was observed at all measurement points.

C: Peeling was observed at 1 to 20 points out of 100 measurement points.

X: Peeling was observed at 21 or more points out of 100 measurement points.

Second test: 3% of the above-mentioned developed substrate heated to 50 ° C.
The resist was immersed in an aqueous solution of sodium hydroxide, and the time required for the cured resist to peel off from the copper surface was measured.
This test is called a peeling test).

On the other hand, the substrate after performing the cross-cut test was immersed in a 3% aqueous solution of sodium hydroxide heated to 50 ° C., and the time required for the cured resist to peel off from the copper surface was measured to be 50 seconds. This is referred to as a peelability test).

Further, the laminated body laminated on the copper-clad laminated substrate by the above-mentioned method was irradiated with ultraviolet rays of 80 mJ / cm ² by a super high pressure mercury lamp through a positive pattern mask film. Next, after peeling off the polyethylene terephthalate film, development was carried out with a 1% aqueous solution of sodium carbonate, and pretreatment, copper sulfate plating and solder plating were performed under the following conditions. A cellophane tape was applied to the fine line portion of the obtained image, and the tape was peeled off after sufficient pressure bonding. However, there was no peeling of the resist (hereinafter, this test is referred to as a plating resistance test).

<Pretreatment conditions> 50 ° C PC-455 (Meltec) 25% 3 minutes immersion → water washing → 20% ammonium persulfate aqueous solution 1 minute immersion → 10%
Aqueous solution of sulfuric acid → water washing <copper sulfate plating conditions> Meltex Co., Ltd., trade name "Copper sulfate Conc" 19% at room temperature for 30 minutes plating at a current density of 2.5A / dm ² in a plating solution diluted to 3.6 times with sulfuric acid I do.

<Solder plating conditions> Solder plating solution manufactured by McDermid (Tin / Lead = 6/4)
And plating at a current density of 2.0 A / dm ² at room temperature for 10 minutes.

<Criterion for tape peeling> a There is no peeling of the resist.

(b) On both sides of the image, portions having a width of 100 μm or less and a length of 1 mm or less peeled off gradually.

c On both sides of the image, portions having a width of 100 μm or more and a length of 1 mm or more peeled off gradually.

d Almost all resist was peeled off.

Examples 2 to 3 Evaluations were performed in the same manner as in Example 1 except that the compositions shown in Table 1 were used. Table 2 shows the results.

Comparative Examples 1-3 Evaluations were made in the same manner as in Example 1 except that the compositions shown in Table 1 were used. Table 2 shows the results.

[Effects of the Invention] The photopolymerizable composition and the photopolymerizable laminate of the present invention have sufficient durability in each of the steps of etching, tenting, and plating, and particularly have excellent resistance in the plating step. Is shown. The peelability is good, and the cured film is rich in flexibility.
Further, the photopolymerizable composition and the photopolymerizable laminate of the present invention,
It has the characteristics required for alkali development and is useful as a resist for producing printed circuit boards.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03F 7/027 G03F 7/033

Claims (4)

(57) [Claims] (1) The carboxyl group content is determined by acid equivalent.
Linear polymer with 100-600, weight average molecular weight of 20,000-500,000
(B) a photopolymerizable unsaturated compound containing both an ethylene glycol chain and a propylene glycol chain in a molecule of a bisphenol A-based acrylate monomer or a methacrylate ester monomer; (C) a photopolymerizable composition comprising 0.01 to 30% by weight of a photopolymerization initiator. (2) The carboxyl group content is determined by acid equivalent.
Linear polymer with 100-600, weight average molecular weight of 20,000-500,000
(B) 5 to 93% by weight of a photopolymerizable unsaturated compound represented by the following formula (I): (Wherein, R ₁ and R ₂ are H or CH ₃ , which may be the same or different. A and B are each represented by —CH (C
H ₃ ) CH ₂ — or —CH ₂ CH ₂ —, which are different. m ₁ + m ₂ is 6 to 12, n ₁ + n ₂ is 6 to 12, and m ₁ , m ₂ ,
n ₁ and n ₂ are positive integers. ) And (c) a photopolymerizable composition comprising 0.01 to 30% by weight of a photopolymerization initiator. 3. A photopolymerizable laminate comprising a photopolymerizable layer and a support layer, wherein the photopolymerizable layer comprises: (a) a carboxyl group content of 100 to 600 in acid equivalent and a weight average molecular weight of 20,000 to 50; (B) a photopolymerizable unsaturated polymer containing both ethylene glycol and propylene glycol chains in the molecule of a bisphenol A-based acrylate or methacrylate monomer A photopolymerizable laminate comprising a composition containing 5 to 93% by weight of a compound and (c) 0.01 to 30% by weight of a photopolymerization initiator. 4. A photopolymerizable laminate comprising a photopolymerizable layer and a support layer, wherein the photopolymerizable layer comprises: (a) a carboxyl group content of 100 to 600 in acid equivalent, and a weight average molecular weight of 20,000 to 50. (B) 5 to 93% by weight of a photopolymerizable unsaturated compound represented by the following formula (I): (Wherein, R ₁ and R ₂ are H or CH ₃ , which may be the same or different. A and B are each represented by —CH (C
H ₃ ) CH ₂ — or —CH ₂ CH ₂ —, which are different. m ₁ + m ₂ is 6 to 12, n ₁ + n ₂ is 6 to 12, and m ₁ , m ₂ ,
n ₁ and n ₂ are positive integers. And (c) a photopolymerizable laminate comprising a composition containing 0.01 to 30% by weight of a photopolymerization initiator.