JPS6310681A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which gives a photo-setting film easily peelable with an alkaline liquid and is useful for use as, e.g., photoresist, by mixing a specified thermoplastic high-molecular binder, an addition-polymerizable compound, and a photo-initiator. CONSTITUTION:A thermoplastic high-molecular binder (A) is obtained by the copolymerization of 4-40wt% addition-polymerizable monomer (a) having COOH groups (e.g., methacrylic acid), at least 5wt% nonacidic addition-polymerizable monomer (b) of formula I (wherein R1 is H or CH3; R2 is 1-50C alkylene; R3 is H, 1-5C alkyl or halogen; n is 1-20), and a nonacidic addition- polymerizable monomer (c) having values 'Q' and 'e' that satisfy the relation of formula II [wherein QA and eA are the values 'Q' and 'e' of component (a), respectively; QC and eC are the values 'Q' and 'e of component (c), respectively] (e.g., methyl methacrylate). 100pts.wt. component A is mixed with 10-200 pts.wt. addition-polymerizable compound (B) of formula III (wherein R4-6 and R9-11 are each R1; R7-8 are each H or halogen; n and m are each a positive number and n+m=2-20) and 0.01-30pts.wt. photo-initiator (C) (e.g., 2- chlorothioxanthone).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photosensitive polymer composition that is cured by irradiation with light and developable with an alkaline aqueous solution. More specifically, the present invention relates to a photosensitive polymer composition with improved resistance to treatments such as etching and plating after development.

(Prior art and problems) The photopolymerized cured product is applied to a substrate, such as a copper-clad laminated board, or a metal surface to be processed, by coating or laminating, and then exposed to active light. The exposed areas are cured, and the unexposed areas are dissolved and removed with a solvent having appropriate solubility. Solvents can be broadly divided into 1.

1, 1-? 11 volumes of J chloroethane, etc. (
Some use water-based solvents, while others use water-based solvents such as sodium carbonate solution.

In recent years, photosensitive polymer compositions that are developed using aqueous solvents have been increasingly used from the viewpoint of working environment, surrounding environment, and manufacturing cost.

However, compared to the case of using conventional organic solvent type photopolymerizable curable compositions, there are many restrictions on etching and plating processes, which often causes problems during use.

Particularly in the case of alkaline processing liquids, their use is severely limited because they basically use acidic thermoplastic polymer binders.

However, it is resistant to these alkaline processing solutions.

When such a thermoplastic polymer binder is used, the final peeling of the cured film with an alkaline solution requires a long time or is completely impossible.

(Means for Solving the Problems) As a result of intensive studies by the present inventors to solve such problems, an addition polymerizable compound obtained by copolymerizing an addition polymerizable monomer having a specific structure was developed. The inventors have discovered that both resistance and releasability can be satisfied by combining a type of thermoplastic polymer binder with an addition polymerizable compound having a specific structure, and have thus arrived at the present invention.

That is, the present invention comprises (1) an addition polymerization monomer having a carboxyl group (A
Thermoplastic polymer bond formed by copolymerizing 4 to 40% by weight of the following non-acidic addition polymerization monomer (B) and at least 5% by weight or more of the following non-acidic addition polymerization monomer (C) agent.

Non-acidic addition polymerization monomer (B): CH. = C (I) (夙 is a hydrogen atom or a methyl group, generally is an alkylene group with 1 to 5 carbon atoms, bird is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, a halogen atom, n is 1 to 20 ) Non-acidic addition polymerization monomer (C): At least one non-acidic addition polymerization monomer having a Q value and an e value satisfying the following formula (n) (■, A, eA are addition polymerization monomers Q value and e value of body (A.), QC%eC is ・λ value and e value of addition polymerizable monomer (C)) (2)/y is at least an addition polymerizable compound represented by the following formula 1m) -C-C-CH,! , m) ('R1, he, su, general, formula, 已, is a hydrogen atom or a methyl group, milk, general is a hydrogen atom, halogen atoms n and m are n +
m = positive integer of 2 to 20) (3) The present invention relates to a photosensitive heavy-containing composition characterized in that it contains at least one photoinitiator.

First, the thermoplastic polymer binder used in the present invention will be explained in detail. In the addition-polymerizable compound type photopolymerizable curable composition according to the present invention, the resistance of the resist film largely depends on the properties of the polymer and binder. Acid injection addition polymerization having carboquine/L/ groups in the copolymer forming the polymeric binder of the present invention.

The polymer tA) imparts developability to the copolymer, and its proportion in the copolymer composition is in the range of 4 to 40 percent by weight.

The appropriate ratio varies depending on the type of developer; for example, it is 4 to 15% by weight for a so-called semi-aqueous solution development type containing f-honeytin glycol mo/7"f, renity, etc., and 15% for a completely aqueous solution development type. A range of 40% by weight can be used as a tentative guideline.

Of course, the optimum copolymerization rate of acidic addition polymerizable monomers, whether semi-aqueous or fully aqueous, varies depending on the developer and development conditions.

In the present invention, the addition polymerization monomer (9) having a carboxyl group is preferably methacrylic acid or a mixture of methacrylic acid and acrylic acid. O Since such acidic addition polymerization monomers are copolymerized, the essential The thermoplastic polymeric binder swells and dissolves in alkaline liquid. Therefore, it is essential to copolymerize a non-acidic addition monomer in order to impart resistance.

In particular, non-acidic addition polymerization monomer (2), which is an acrylic ester or methacrylic ester having a specific structure, is effective as a material that improves resistance to alkaline aqueous solutions.

Examples of these include 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, 2-phenoxypropyl acrylate, 3-phenoxypropyl acrylate, phenoxydiethyl acrylate, phenoxytriethoxy acrylate, and phenoxy acrylate. Dipropoquine, P-chlorophenoxyethyl acrylate, P-methylphenoxyethyl acrylate, methacrylic acid 2
- Phenoxypropyl, methacrylic acid, 3-phenoxypropyl, phenoxyjethoxy meccrylate, phenoxytriethoxy methacrylate, phenoxydiproboxy methacrylate, P methacrylate.

Examples include, but are not limited to, -chlorophenoxyethyl, P-methylphenoxyethyl methacrylate, and the like. These non-acidic addition polymerization monomers (B) must be contained in the copolymer in an amount of at least 5% by weight or more.

The non-acidic addition polymerization monomer (C) is the addition polymerization monomer (B)
Together with this, it serves as a component that imparts resistance, but in addition, it also plays a role in controlling the glass transition point (Tg) of the copolymer. A suitable copolymer Tg is between 40°C and 120°C, 40°C.
If the photosensitive layer is sandwiched between a support film and a protective film and used as a "dry film" at temperatures below 120°C, the "cold flow J" phenomenon occurs, where the photosensitive layer flows over time, and above 120°C, the photosensitive layer will dry out. adhesion is significantly impaired.

Furthermore, the non-acidic addition polymerization monomer (C) should be a copolymer in which the acidic addition polymerization monobase (3) is polymerized as uniformly within and between molecules as possible. If the acid injection addition polymerization monomer is not uniformly distributed, the development of the hard one-layer product will be severe, and if it is too large, the copolymer during polymerization will be Precipitation of the copolymer occurs when the coating solution is mixed. This = non-acid injectable "XJ polymerized AI body t(y
)Ima acid Note 7 ■Polymerized phosphor (determined according to the sum).

For example, as polymerized monoxide (A), Metaclear L/acid, Q
, A=2340, e, =0.6s o ), then m p li /L/methyl acid (g, .=
0.740. eC=0.400, (-eA(eA-
eo))=2.95). In this case, n-butyacrylate (-eAc", y-eqH-6
, 11), methacrylic acid and phosphoric acid were rapidly consumed during polymerization, resulting in non-uniform copolymerization.

7. In some cases, precipitation may occur. However, when using the 2-D acid polymerized monomer (A) in the present invention, the non-acidic addition-polymerized monomer (C) The above +[
) define the formula! -1,7).

Examples of the compound represented by the formula (4-methacryloxyshedquinphenyl)propane, 2,2-bis(4-methacryloxybentaethoxypheny)V)
Propane, λ2-binu(4-acryloxydideropoquinphenyl)propane, 2.2-bis(4-7cryloxy9en/I/)propane, 2.2-bis(4-methacryloxydipropoxyphenyl) Propane, 2,2-bis(4
Examples include, but are not limited to, -methacryloxybentapropoxypheni/L/)propane. These may be used singly or in combination. These amounts range from 5 to 100 parts by weight of the thermoplastic polymer binder.
It is particularly preferred to use 10 to 80 parts by weight. It is also possible to add other addition polymerizable compounds as required.

Photoinitiators that can be used in the compositions of the present invention include the following.

That is, substituted or unsubstituted polynuclear quinones, for example 2
-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1.2-benzanthraquinone, 2.3-benzanthraquinone,
2-phenylanthraquinone, 2.3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1.4-natsutaquinone, 9.10-phenylanthraquinone, 2-methy/I/-1 , 4-naphthaquinone, 2,3-dichloronaphthaquinone, 1,4-dimethylanthraquinone, 2,3-
Examples include dimethylanthraquinone, 3-chloro-2-methylanthraquinone, and 7,8,9,10-tetrahydrophtacenequinone di. Other aromatic ketones, e.g.
Benzophenone, Michler'r)n(4゜4'-bis(
dimethylamino)benzophenone),” it, 4
/-bis(diethylamine)benzophenone], 4-methoxy-4/-dimethylaminobenzophenone, and the like. Other examples include benzoin and benzoin ethers such as evabenzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin. Furthermore, 2.4.5-) Realyl imidazole dimer, 2-mercaptobenzoxazole, and leuco crystal violet.

Tris(4-diethylamine-2-methylphenyl) can also be used.

In addition, substituted or unsubstituted thioxanthone compounds, such as 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2.

Examples include 4-dimethylthioxanthone. Furthermore, these thioxanthones and a tertiary or aromatic amine such as N-methyljetanolamine,
Combinations with P-dimethylaminobenzoic acid ethyl ester, etc. can also be used, and combinations of thioxanthone and alkylaminobenzophine such as Michler's ketone, and combination of thioxanthone and oxime ester such as benzophenone oxime acetate are also effective. It is. These addition polymerization initiators that can be activated by light may be used alone or in combination.

Note that the present invention is not limited to these.

These are α based on 100 parts by weight of the thermoplastic polymer binder.
Preferably 01 to 30 parts by weight.

is 0. It can be used in an amount of 1 to 15 parts by weight.

In the present invention, in addition to the above-mentioned essential elements, stabilizers, dyes, etc. can be added as necessary. Stable.

Examples of the agent include hydroquinone, hydroquinone monomethyl ether, and t-butylcatechol. These can be added within a range that does not inhibit the photopolymerization reaction. Additionally, a plasticizer can be added to impart appropriate flexibility and flexibility.

For example, lids such as diethyl phthalate, dibutyl phthalate, diethyl phthalate, dioctyl phthalate, etc.
I/acid esters, fatty acid esters such as dioctyl adipate and dibutyl diglycol adipate, phosphoric acid esters such as trimethylphosphine, and nurphonic acid amides such as luenesulfonic acid amide.

Additionally, dyes may be added to facilitate visual identification of the photosensitive layer. For example, Crystal Bioleft, Malachite Green, Victoria Blue, Methylenebu A/
- etc. can be mentioned.

In the present invention, when the photopolymerizable curable composition is solvent-free, it is usually coated on a suitable support using a printing method or a coating method, and when it is dissolved or dispersed in a solvent, it is coated on a suitable support, and then the solvent is applied. A photopolymer layer can be obtained by evaporation. Particularly when used as a "dry film", polyester film is preferred among various plastic films.

(Effects of the Invention) According to the present invention, a photocured film can be obtained that is easier to peel off with an alkaline liquid than in the past. Details will be explained using examples.

Such photopolymer layers are cured by light from a suitable light source, such as a low-pressure mercury lamp or an ultra-high pressure mercury lamp. The composition of the present invention can be used as a photopolymer or photoresist for producing metal IJ-F images, printed wiring boards, and the like.

(Example) Next, the present invention will be specifically explained with reference to Examples. Note that the present invention is not limited in any way to the embodiments.

Example 1 A photosensitive polymer composition was obtained by mixing the following components.

0 g 2-chlorothioxanthone 1 g N-methyljetanolamine α19 triab
Le - α
059 Methyl Keton
709 Tetrahydrofuran 1 '09 This? A polyethylene film having a thickness of 25 .mu.m was coated on top of a polyethylene film 1:-rethene phthalate film 7, and dried at 75' to obtain a photosensitive film.The military strength of the photosensitive layer was 50 Pm.

this? A polished copper clad laminate was laminated using a rubber roller heated at 100°C.

1self, ′; good and bad: each Bakun mask? On top of that, put 2>W J:) 1 from a distance of 50cm with the Choryo water gate light
After irradiation and faecification, a cylindrical relief image was obtained on the copper-clad laminate when developed with a 30'C01% Sochi sodium aqueous solution.

Next, when the copper was etched with an alkali etchant, a good printed wiring board was obtained.

Next, in order to peel off the cured film, it was immersed in a 3% sodium hydroxide aqueous solution at 50°C, and it was completely peeled off in about 1 minute and 30 seconds.

Example 2 A photosensitive polymer composition was obtained by mixing the following components.

0 g trimethylolpropane acrylate 5 g 2.2 bis(4-acryloquine diethoxyphenyl)fluoride 5 g 2-chlorochloride 1 g N-methyljetanolamine 0.1 g Victoria Blue
α05q Methyl Niti p Ketone
709 Tetrahydrofuran 10% was coated on a 25 μm thick polyethylene glycol terephthalate film support and dried at 75° C. to obtain a photosensitive film. The thickness of the photosensitive layer was 50 μm. This was laminated onto a polished copper-clad laminate using a rubber roller heated to 100°C.

A wiring circuit pattern mask was placed thereon, irradiated and cured, and then developed with a 1% aqueous sodium carbonate solution at 30°C to obtain a resin relief image on the copper clad laminate.

Next, copper was etched using an alkaline etchant, and a good printed wiring board was obtained.

Next, to peel off the cured film, add 3% hydric acid (Hina) I at 50°C.
When immersed in a Jium aqueous solution, it was completely peeled off in about 2 minutes.

Example 3 A photosensitive polymer composition was obtained by mixing the following components.

0 q Trimethylolpropane triacrylate 15 15 g ' Benzophenone L59 Michler's ketone α 15 g Bitriafyl -
α 059 Methyl ethyl ketone 709 Tetrahydrofuran 10 g Evaluation was made in the same manner as in Example 1, but a good printed wiring board was obtained and the cured film was completely peeled off in about 2 minutes.

Comparative example 1 A photosensitive polymer composition was obtained by mixing the following components.

Trimethylolpropane triacrylate 2-chlorothioxanthone 19N-methyljetanolamine α19 triafil -
α 05
g methyl ethyl ketone
709 Tetrahydrofuran 109 Although it was evaluated in the same manner as in Example 1, the cured film could not be affected by alkalinity and a good printed wiring board could not be obtained.

Comparative example 2 The following components were mixed to obtain a photoreflective polymeric material.

50 trimethylolpropane triacrylate 2-chlorothioxanthone 1gN-methyljetanolamine 0.19 triable -
α 05 g
Methi, lunithylkaton 70cutitrahydrofuran 197Evaluation was carried out in the same manner as in Example 1. A7 Recarie・I chant 0 flights・It takes about 4 minutes to remove the eyebrows of Hif Patent applicant Daicel Chemical Industries, Ltd. Yoshihito*mzu Yuba wrote a procedural amendment (voluntary) Showa November 1961 β Commissioner of the Patent Office Black 1) Mr. Akio °-'1, Description of the case 1988 Patent Application No. 146512 2, Name of the invention Photosensitive polymer composition 3, Person making the amendment Relationship with the case Patent Applicant Address 1 Teppocho, Sakai City, Osaka Name (290) Daicel Chemical Industries, Ltd. Representative Yoshifumi Kubota 4, Agent 3-8-1 Kasumigaseki, Chiyoda-ku, Tokyo Toranomon Mitsui Building Daicel Chemical Industries, Ltd. Company Patent Department Phone (507) 3246

Claims (1)

[Scope of Claims] 1 Main components: (1) 4 to 40 weight percent of an addition polymer monomer (A) having a carboxyl group and at least 5 weight percent of the following non-acidic addition polymer monomer (B). A thermoplastic polymer binder obtained by copolymerizing the following non-acidic addition polymerization monomer (C). Non-acidic addition polymerization monomer (B): At least one acrylic ester or methacrylic ester monomer represented by the following general formula (I)▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R_1 is Hydrogen atom or methyl group, R_2 has 1 carbon number
5 alkylene group, R_3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, n is 1 to 20
(an integer up to) Non-acidic addition polymerization monomer (C): At least one non-acidic addition polymerization monomer that has a Q value and ■ value that satisfy the following formula (II)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (Q_A, ■_A are the Q value and ■ value of the addition polymerization monomer (A), Q_C, ■_C are the Q value and ■ value of the addition polymerization monomer (C)) (2) At least the following formula Addition polymerizable compound represented by (III) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (III) (R_4, R_5, R_6, R_9, R_1_0, R_
(1_1 is a hydrogen atom or a methyl group, R_7 and R_8 are hydrogen atoms or halogen atoms, n and m are positive integers such that n+m=2 to 20) (3) Contains at least one photoinitiator A photosensitive polymer composition characterized by: 2 100 parts by weight of a thermoplastic polymer binder as the main component,
Addition polymerizable compound 10-200 parts by weight, photoinitiator 0.0
1 to 30 parts by weight of the photosensitive polymer composition according to claim 1. 3. The photosensitive polymer composition according to claim 2, wherein the addition polymerization monomer (A) having a carboxyl group is methacrylic acid alone or a mixture of methacrylic acid and acrylic acid.