JPH02221960A - Photosensitive resin composition and photosensitive film - Google Patents

Abstract

PURPOSE:To reduce time required for peeling a hardened film and to solubilize peeled pieces in a peeling solution by mixing a specified phthalate, a compound having a urethane bond and a double bond and a polymer having carboxylic groups with a resin composition. CONSTITUTION:The composition is mixed with A; the phthalate represented by formula I, such as beta-hydroxyethyl-beta'-acryloyloxyethyl phthalate, and B; the compound having at least one urethane bond and a polymerizable double bond, such as the reaction product of diisocyanate and (meth)acrylate, and C; the film-formable polymer having carboxylic groups and polymerizable double bonds, optionally in addition, a compound, such as trimethylolpropane triacrylate, and a photopolymerization initiator or its system in a (A+B)/C weight ratio of (30-100)/100.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photosensitive resin composition, and more specifically, to a novel photosensitive resin composition that can shorten the peeling time of a photocured part and in which the photocured part is soluble in a stripping liquid. The present invention relates to a photosensitive resin composition and a photosensitive film using the same.

[Conventional technology]

Conventionally, printed circuit boards are produced by laminating a photosensitive resin composition onto a copper substrate, exposing it to light in a pattern, removing the unexposed areas with a developer, performing etching or plating to form a pattern, and then curing. It is manufactured by a method in which parts are peeled off and removed from the substrate.

Peeling of the cured film is usually done using an automatic peeling machine, but
If the peeled pieces are large, they will become entangled with the roll of the peeling machine, significantly reducing work efficiency, and if the peeled pieces are too small, they may not be removed by filtration and may re-adhere to the clean substrate. . Therefore, it is desirable that the peeling piece is soluble in the peeling solution.

However, in the case of an alkali-developable photosensitive resin composition, the higher the hydrophilicity of the composition, the shorter the peeling time is and the easier it is for peeling pieces to dissolve. The higher the hydrophilicity, the worse the ability tends to be. Currently, the resist shape,
Although the tenting ability is good, a stripping solution is used that takes a long time to strip, does not dissolve the strips, and has poor workability.

[Problem to be solved by the invention]

An object of the present invention is to solve the problems of the prior art, maintain good resist shape and tenting ability, shorten the peeling time of the cured film, and dissolve peeling pieces in the stripping solution.
An object of the present invention is to provide a photosensitive resin composition with excellent peelability and a photosensitive film using the same.

[Means to solve the problem]

As a result of intensive research on the above-mentioned problem, the present inventors have found that specific photosensitivity obtained by adding a specific ethylenically unsaturated compound to a carboxyl group-containing film-like polymer and a photoinitiator or a photoinitiator system. The inventors have discovered that the cured film of the resin composition can be peeled off in a short time, and the peelable pieces can be dissolved in a peeling liquid, and the present invention has been achieved.

That is, the present invention provides (a) General 24) R1 (wherein R+, R2 and R8 are hydrogen atoms or methyl groups, m and n are integers of O to 3)
(b) a compound having at least one urethane bond and a polymerizable double bond in the molecule;
(C) A photosensitive resin composition containing a carboxyl group-containing film-like polymer and (d) a photoinitiator or photoinitiator system, wherein the total amount of (a) and (g)) is
30 to 10 parts per 1 part of 100 MW of the total amount of the compound having a polymerizable double bond used in the photosensitive resin composition.
The present invention relates to a photosensitive resin composition containing 0 parts by weight and a photosensitive film formed by forming a layer of this photosensitive resin composition on a base film.

Examples of the compound (component (a)) represented by the general formula (I) used in the present invention include β-hydroxyethyl-β1-(meth)acryloyl (meaning methacryloyl or acryloyl, the same hereinafter) oxyethyl Phthalate, β-hydroxyethyl-β1-(meth)acryloyloxyisopropyl phthalate, β-hydroxyisopropyl-β1-(meth)acryloyloxyethylisopropyl phthalate, β-hydroxy-3-
Oxybenthyl β1-(meth)acryloyl-3-oxypentyl phthalate, β-hydroxy-3,6-cyoxynonyl-β1-(meth)acryloyl-3,6-
Examples include cyoxynonyl phthalate. These compounds can be used alone or in combination of two or more.

Compounds having at least one urethane bond and a polymerizable double bond in the molecule used in the present invention (component (b)
)) include diisocyanate-1 and (meth)acrylic esters (meaning methacrylic esters or acrylic esters, hereinafter referred to as urethane acrylates obtained from tolylene diisocyanate and 2-hydroxyethyl acrylate). reaction product with the same);
2゜2.4-) Reaction products of diisocyanates, (meth)acrylic acid esters and diols, such as urethane acrylate consisting of limethylhexamethylene diisocyanate, cyclohexane dimetatool and 2-hydroxyethyl acrylate; 2゜Examples include compounds having a polyvalent isocyanate and an allyl group, such as a reaction product of 2.4-)limethylhexamethylene triisocyanate and allyl alcohol.

In addition to the compounds mentioned above, examples of compounds with polymerizable double bonds include polyhydric alcohols such as α.

Compounds obtained by addition of β-unsaturated carboxylic acids, such as trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate , dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyethylene glycol diacrylate, trimethylolpropane ethoxytetraacrylate, etc.; obtained by adding α,β-unsaturated carboxylic acid to a glycidyl group-containing compound. compounds, such as trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether di(meth)acrylate, etc.; polycarboxylic acids, such as maleic anhydride, and substances having hydroxyl groups and ethylenically unsaturated groups, such as β- Esterified products with hydroxyedyl (meth)acrylate, etc.; alkyl esters of acrylic acid or methacrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, (
Butyl meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. can be used. These compounds may be used alone or in combination of two or more.

The amount of components (a) and (b) used in the present invention is 30 to 100 parts by weight, preferably 30 to 100 parts by weight, based on a total of 1100 parts by weight of the compound having a polymerizable double bond used in the composition. It is used in an amount of 50 to 80 parts by weight. If this amount is less than 30 parts by weight, the peeling time will be long and the peeling pieces will not dissolve in the stripping solution. In addition, the usage ratio of component (a) and component (b) is component (a):component (b) in weight ratio.
is preferably in the range of 1:10 to 10:1(7).

The carboxyl group-containing film l used in the present invention and the property-imparting polymer (component (C)) include, for example, a copolymer of a (meth)acrylic acid alkyl ester and (meth)acrylic acid, and a (meth)acrylic acid alkyl ester. and (meta)
Examples include copolymers of acrylic acid and vinyl monomers that can be copolymerized with these. Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Examples of vinyl monomers copolymerizable with the (meth)acrylic acid alkyl ester and (meth)acrylic acid include tetrahydrofurfuryl (meth)acrylate, dimethylethyl (meth)acrylate, and (meth)acrylate.
Diethyl acrylate, glycidyl methacrylate, 2,2
．． 2-trifluoroethyl (meth)acrylate, 2,
Examples include 2゜3.3-tetrafluoropropyl (meth)acrylate acrylamide, diacetone acrylamide, styrene, vinyltoluene and the like.

The use of component (C) improves coating properties and the film strength of the resulting cured product. The amount used is preferably 50 to 300 parts by weight based on a total of 1100 parts by weight of the compound having a polymerizable double bond.

Photoinitiator or photoinitiator-based compound used in the present invention (
Component (d)) includes, for example, benzophenone, N, N
"-Tetramethyl-4,41-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4
Aromatic ketones such as '-diaminobenzophenone, 4-methoxy-4°-dimethylaminobenzophenone, 2-ethylanthraquinone, and phenanthrenequinone, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether, benzyl dimethyl ketal, benzyl Benzyl ketal such as diethyl ketal, benzoin such as methylbenzoin, ethylbenzoin, 2-(o-chlorophenyl)-4,5
-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5
-diphenylimidazole dimer, 2-(O-methoxyphenyl)-4,5-diphenylimidazole dimer,
2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(P-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-
dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methylmercaptophenyl)-4
, 5-diphenylimidazole dimer, etc.
Examples include triaryl imidazole dimer. The amount used is the total amount of compounds with polymerizable double bonds by weight: 100! It is preferably 0.1 to 50 parts by weight based on it part.

The photosensitive resin composition of the present invention can contain a thermal polymerization inhibitor such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine, and butylcatechol.

The photosensitive resin composition of the present invention may also contain colorants such as dyes and pigments. As the coloring agent, for example, Tsukusin, Auramine Base, Crystal Violet, Victoria Pure Blue, Malachite Green, Methyl Orange, Acid Violet RRH, etc. are used. Furthermore, plasticizers, adhesion promoters, talc, etc. can also be added.

In the photosensitive resin composition of the present invention, the above-mentioned components are dissolved and mixed using, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, methylalconyl, ethyl alcohol, toluene, etc. By doing so, it can be used as a uniform solution. The photosensitive resin composition in the form of a solution can be used by applying it to a substrate such as a copper plate, drying it, and then exposing it to actinic light to photocure it. Alternatively, the composition in solution form is applied onto a base film such as polyethylene terephthalate and dried to form a photosensitive resin composition layer, and the resulting photosensitive film is laminated on a substrate and photocured for use. You can also do that. The active light source used for photocuring has a wavelength of 30
A device that emits light of 0 to 450 nm, such as a mercury vapor arc, a carbon arc, or a xenon arc, is used.

〔Example〕

The present invention will be explained below with reference to Examples.

Examples 1 to 3 and Comparative Examples 1 to 3 Carboxyl group-containing film properties imparting polymer (component (C)
) as methacrylic acid/methyl methacrylate/butyl methacrylate/2-ethylhexyl acrylate copolymer (weight ratio 2515015/20, weight average molecular weight!=
Using 150 g (polymer component 60 g) of 40% by weight methyl cellosolve/toluene (heavy N ratio 6/4) I solution (polymer component 60 g), 0.03 g of malachite green and 1.0 g of leuco crystal violet were added to this solution. og, tribromomethylphenylsulfone 0.5g, methyl ethyl ketone 10g
,) Solution A was obtained by blending 20 g of toluene and 5.0 g of methyl alcohol.

To this solution A, compounds having a polymerizable double bond (components (a), (b), and others) and a photoinitiator or a photoinitiator system (component (component) d))
A solution of the photosensitive resin composition *l *2 *3 *4 *5 *6 β-hydroxyethyl-β1-acryloyloxyethyl phthalate manufactured by Kyoeisha Yushi Co., Ltd., in the general formula (I), m=n= L
Rt % Rz and R, = hydrogen atom Urethane acrylate 2.2-bis(4- (methacryloxypentaethoxyphenyl)propane (manufactured by Shin Nakamura Chemical Co., Ltd.) Trimethylolpropane triacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) Polypropylene glycol diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) Trimethylolpropane ethoxy triacrylate (manufactured by Niyo Kasei Kogyo Co., Ltd.) *7 Benzyl Dimethyl Co., Ltd. (manufactured by Ciba Geigy) Next, this solution was uniformly applied onto a 25 μm thick polyethylene terephthalate film and dried for about 10 minutes in a hot air convection dryer at 100° C. to obtain a photosensitive film. The film thickness of the photosensitive resin composition after drying was 50 μm.

On the other hand, a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., MC
The copper surface of L-E-61) was polished with Scotch Prite Buff Roll (manufactured by Jujutsu 3M, registered trademark), washed with water,
The resulting copper-clad N temporary was dried with an air stream and heated to 60°C, and the photosensitive resin composition layer was laminated on the copper surface while heating to 110°C.

Next, using a negative film on the substrate thus obtained, a 3KW high pressure mercury lamp (manufactured by Oak Seisakusho Co., Ltd., HMW-
201B), exposure was performed at 150 mJ/cd. At this time, in order to evaluate the photosensitivity, a negative film (optical density 0.05
was used as the first step, and a step tablet in which the optical density increased by 0.15 with each step was used.

Then remove the polyethylene terephthalate film,
At 30°C, add 1 uit% sodium carbonate aqueous solution to 50-1
The unexposed areas were removed by spraying for 50 seconds. The number of step tablets of the photocured film formed on the copper-clad laminate was measured to evaluate the photosensitivity of the photosensitive resin composition, and the results are shown in Table 2.

The higher the number of steps on the step tablet, the higher the photosensitivity.

Next, it was treated with a 3% by weight aqueous sodium hydroxide solution at 45°C, the photocured portion was peeled off, and the time required to complete the peeling was measured.The results are shown in Table 2. In addition, the peeled piece was immersed in a 3% by weight sodium hydroxide aqueous solution at a concentration of 0.4 rrr/l, left in a constant temperature bath at 40°C, and the condition of the peeled piece was visually observed every 12 hours. The time for dissolution was determined. The results are shown in Table 2. The shape of the resist was also observed using a scanning electron microscope (Hitachi S-500A), and the case where there was no sidewall cavity in the resist was evaluated as ◯, and the case where there was sidewall cavity was evaluated as ×. The results are shown in Table 2.

Further, a copper clad laminate having 1,419 holes with a hole diameter of 2 uua in advance was laminated, exposed and developed using the above-described method, and the number of tent tears on the holes was visually observed. According to the resin composition and the photosensitive film obtained from the resin composition, it is possible to maintain good resist shape and tenting properties, shorten the peeling time of the cured film, and dissolve peelable pieces in the stripping liquid, so that peeling is easy. It is possible to prevent pieces from re-adhering and improve workability.

Claims (1)

[Claims] 1. (a) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, R_1, R_2 and R_3 are hydrogen atoms or methyl groups, m and n means an integer of 0 to 3), (b) a compound having at least one urethane bond and a polymerizable double bond in the molecule, (c) a carboxyl group-containing film-like polymer, and ( d) A photosensitive resin composition containing a photoinitiator or photoinitiator system, wherein the total amount of (a) and (b) is such that the total amount of polymerizable double bonds used in the photosensitive resin composition is The photosensitive resin composition contains 30 to 100 parts by weight based on 100 parts by weight of the total amount of compounds. 2. A photosensitive film comprising a layer of the photosensitive resin composition according to claim 1 formed on a base film.