JPS6274912A - Photosensitive polymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition which can cure by irradiation with light and gives a resist excellent in releasability, by mixing a thermoplastic polymer binder with a specified addition-polymerizable compound and a photoinitiator (system). CONSTITUTION:100pts.wt. thermoplastic polymer binder (A) obtained by copolymerization with 5-50wt% carboxyl group-containing addition- polymerizable monomer (A) [e.g., poly(methyl methacrylate/acrylic acid) (75/25wt%)] is mixed with 20-200pts.wt. addition-polymerizable compound (B), b.p. >=50 deg.C, containing at least 2pts.wt. unsaturated compound (a), MW of 350-2,000, having at least three unsaturated groups in the molecule and represented by the formula (wherein R1-3 are each H or CH3 and n is 1-6), e.g., glycerylpropoxy trimethacrylate and at least 2pts.wt. compound (b) having at least two addition-polymerizable ethylene groups and at least one phenylene group in the molecule {e.g., 2,2-bis[4-(acryloxy.diethoxy)phenyl]propane} and 0.01-30pts.wt. photoinitiator (system) (C).

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a photosensitive polymer composition that is cured by irradiation with light. More specifically, the present invention relates to a photosensitive polymer composition whose resist removability has been improved in the step of removing a cured resist.

(Prior Art) Photosensitive polymeric compositions are generally applied to substrates such as copper clad laminates or metal surfaces to be subjected to microfabrication by coating lamination, etc. 111? ! When exposed to actinic light, the exposed areas are cured, and the unexposed areas are dissolved and removed with a suitable solvent. Appropriate solvents can be roughly divided into 1, 1.1-
Some use an organic solvent such as trichloroethane, and others use an aqueous solvent such as an aqueous sodium carbonate solution.

In recent years, photosensitive polymer compositions that are developed using aqueous solvents have been increasingly used in view of the work environment, surrounding environment, and manufacturing costs.

However, it is known that the aqueous solvent-developed type is inferior in the removability of the resist after pattern formation by etching or plating, compared to the case of using a conventional photosensitive polymer composition of the solvent-developed type. There is.

In other words, organic solvent development type resist stripping is generally carried out using a solvent such as methylene chloride, and the strips become small pieces, making it easy to clean the product and reducing the possibility of re-adhesion to the product or stripping machine. , the stripping solution can be easily regenerated by filtration. On the other hand, the aqueous solvent-developed type is removed by a heated aqueous sodium hydroxide solution or potassium hydroxide solution, but the peeled pieces do not break into small pieces and form a so-called "seaweed" shape, which causes problems with re-adhesion and regeneration by filtration of the remover. Difficulty in this has become a major problem in the work.

Therefore, there is a desire for a water-based development type photosensitive polymer composition that can be peeled off into small pieces when the resist is peeled off.

(Object of the invention) The present invention solves these problems by using a polyfunctional acrylate or methacrylate having three or more unsaturated groups of a specific structure in the same molecule as a polyfunctional monomer in a photosensitive polymer composition. This solves the problem.

(Structure of the Invention) (a) 5 to 50 weight percent of an addition polymerizable monomer having a carboxyl group is copolymerized to 100 parts by weight of a thermoplastic polymer binder (R in the formula,
(R1 and R3 are hydrogen atoms or methyl groups, and n is an integer of 1 to 6) (1) At least 3 unsaturated groups represented by the formula are present in one molecule.
at least 2 parts by weight of an unsaturated compound with a molecular weight of 350 to 2,000 or more, and 2 parts by weight or more of a compound having at least two addition-polymerizable ethylene groups and at least one phenylene group in the molecule at 50°C at normal pressure. 20 to 200 parts by weight of an addition polymerizable compound having a boiling point of 0.01 to 30 parts by weight of a photoinitiator and/or a photoinitiator system. be.

The thermoplastic polymer binder is an acidic monomer that imparts developability to the binder, that is, a carboxylic acid or acid anhydride having one unsaturated group, such as acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, Propiolic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid half ester, etc., and non-acidic monomers to maintain the resist's plating resistance, etching resistance, flexibility and plasticity when not exposed to light, etc. Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate; esters of vinyl alcohols, such as vinyl-n-butyl ether; deaf or aromatic It is obtained by copolymerizing a polymerizable styrene derivative or styrene substituted in the group ring.

Examples of the unsaturated compound having a molecular weight of 350 to 2,000 having at least three unsaturated groups in one molecule represented by the general formula (1) include glyceryl ethoxy triacrylate, glyceryl propoquine trimethacrylate, glyceryl propoquine triacrylate, and triacrylate. Methylolpropane ethoxy triacrylate, trimethylolpropane propoxy triacrylate, pentaerythritol ethoxy triacrylate, pentaerythritol etquin tetraacrylate, pentaerythritol propoxytetraacrylate, glycerylshedkin triacrylate, glyceryl triethoxy triacrylate, glyceryl dipropoxy triacrylate, Examples include glyceryl dipropoxy trimethacrylate, trimethylolpropane ethoxy triacrylate, trimethylol propane dipropoxy triacrylate, pentaerythritol jepoxy triacrylate, pentaerythritol triepoxy triacrylate, pentaerythritol triepoxy trimethacrylate, etc., but the present invention It is not limited to these. These are 2 to 200 parts by weight per 100 parts by weight of the thermoplastic polymer binder,
It is preferable to use 10 to 100 parts by weight.

Compounds having at least two addition-polymerizable ethylene groups and at least one phenylene group in the molecule include 2.
2bis[4-(methacryloxyjethoxy)phenyl]propane (trademark BPE-20 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
0), 2.2bis[4-(methacryloxy polyethoxy)phenyl]propane (Shin-Nakamura Chemical Industry Co., Ltd. Trademark B)
PE-500, BPE-1300), 2゜2-bis [4
−(acryloxy-jetoxy)phenyl]propane (
Shin-Nakamura Chemical Industry Co., Ltd. trademark A-BPE-4), Viscoat +540 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Viscoat-)
, +3700 (manufactured by Osaka Organic Chemical Industry (Aji)), but is not limited thereto.

These amounts are 2 parts by weight per 100 parts by weight of the thermoplastic polymer binder.
-200 parts by weight, preferably 10 to 100 parts by weight.

As the addition polymerizable compound, in addition to the above-mentioned essential components, the following compounds can also be mixed and used.

For example, styrene compounds such as styrene, methylstyrene, and chlorostyrene, methyl (meth)acrylate (meaning methyl acrylate and methyl methacrylate, hereinafter similarly abbreviated), ethyl (meth)acrylate, n- and i- Propyl (meth)acrylate, n-, 5ec- and t-butyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2
-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate,
Butoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, etc. Functional (meth)acrylate compounds, (meth)acrylonitrile, (meth)acrylamides such as (meth)acrylamide, N-methylol (meth)acrylamide, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene Glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyprolene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, l, 4
- Trifunctional (meth)acrylates such as butanediol di(meth)acrylate, neopentyl glycol')(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, Methylolethanetri (meth)
acrylate, trifunctional or higher functional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, hydrogenated bisphenol A ethylene oxide and/or
or trifunctional (meth)acrylates such as propylene oxide adducts (meth)acrylates, N, N
'-methylenebis(meth)acrylamide, N,
Examples include bisamides such as N'-benzylidene bis(meth)acrylamide.

The invention is not limited to these.

Photoinitiators and/or photoinitiator systems include substituted or unsubstituted polynuclear quinones, such as 2-ethylanthraquinone, 2-tert-butylanthraquinone,
Octamethylanthraquinone, 1゜2-benzanthraquinone, 2.3-benzanthraquinone, 2-phenylanthraquinone, 2゜3-diphenylanthraquinone,
l-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-natsutaquinone,
9゜lO-phenanthraquinone, 2-methyl-1,4-
naphthaquinone, 2.3-dichloronaphthaquinone, 1.4
-dimethylanthraquinone, 2.3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, 7.
8.9.10-Tetrahydrophtacenequinone and the like. Other aromatic ketones include benzophenone, Michler's ketone (4,4'-bis(dimethylamino)benzophenone), 4°4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, and the like. Other examples include benzoin and benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin.
．． 5-triarylimidazole dimer and 2-mercaptobenzoxazole, leuco crystal violet,
Combinations with tris(4-diethylamino-2-methylphenyl)methane and the like can also be used.

In addition, there are substituted or unsubstituted thioxanthone, such as 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-dimethylthioxanthone, and the like.

Furthermore, these thioxanthones and aliphatic or aromatic tertiary amines such as N-methyljetanolamine, P
- Combinations with methylaminobenzoic acid ethyl ester, etc. can also be used, and combinations of thioxanthone and alkylaminobenzophenone, such as Michler's ketone, and combinations of thioxanthone and oxime ester, such as benzophenone oxime acetate, are also effective.

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 0.01 to 30% relative to the thermoplastic polymer binder.
Parts by weight, preferably 0.1-15 parts by weight, can be used.

In the present invention, in addition to the above-mentioned essential elements, stabilizers, dyes, etc. can be added as necessary. Examples of the stabilizer include hydroquinone, hydroquinone monomethyl ether, and t-butylcatechol. These can be added within a range that does not inhibit the photopolymerization reaction. Also,
Plasticizers can also be added to impart appropriate flexibility.

For example, phthalate esters such as diethyl phthalate, dibutyl phthalate, diethyl phthalate, and dioctyl phthalate, fatty acid esters such as dioctyl adipate and diptyl diglycol adipate, phosphoric acid esters such as trimethylphosphine, and sulfonic acids such as toluenesulfonamide. Examples include amides.

(Usage mode of the invention) When the photopolymerizable composition is solvent-free, the photopolymerizable composition is usually printed or coated, and when the photopolymerizable composition is dissolved or dispersed in a solvent, it is coated or coated onto a suitable support. The photopolymer layer can be obtained by impregnation and then evaporation of the solvent. The support in this case may be any support as long as it does not adversely affect the photopolymerization, and examples thereof include various types of Plus Deck, various films, paper, glass, various metals, and ceramic products.

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 when producing a printing plate printed circuit board or the like.

(Mode of carrying out the invention) Next, the present invention will be specifically explained using 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.

Poly(methyl methacrylate-acrylic acid) C75725
Weight%) 50g Glyceryl propoxytriacrylate (GPT^ manufactured by Celanese) 20g 2.2-bis[4-(acryloxy-jetoxy)phenyl]propane (A-BPE-4 manufactured by Shin Nakamura Chemical Co., Ltd.) 10
g2-Chlorthioxanthone 0.4g
N-methyljetanolamine O1g Victoria Blue BlI O,04
g Medimethylluketone 60g Tetrahydrofuran 20g This was coated on a 25 μm thick polyethylene glycol terectalate film support and dried to obtain a photosensitive film.

The thickness of the photosensitive layer was 25 μm. This was laminated using a rubber roll heated to 100° C. on a copper surface whose surface had been previously cleaned with acetone.

This was cut out into a 5 x 5 cm square, and then irradiated with an ultra-high pressure mercury lamp from a height of 50 cm for 10 seconds to cure it.

When this was immersed in 3% sodium hydroxide water heated to 50° C., it was peeled off in 15 seconds and the peeled piece was a thin piece that could be easily filtered.

Next, it was laminated on a copper plate in the same way, and then a strafe step tablet and a line mask for resolution were stacked on top of each other and irradiated in the same way with an ultra-high pressure mercury lamp, and then developed with 1% sodium carbonate water at 30°C, resulting in a good resolution of 40 μm in 8 steps. A resist relief image was obtained.

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

Poly(methyl methacrylate-n-butyl acrylate-methacrylic acid) (45/30/25% by weight) 50g glyceryl propoxy triacrylate (GPTA manufactured by Celanese)
15g2.2-Bis[4-(acryloxy-jethoxy)phenyl]propane (Shin-Nakamura Chemical Industry Co., Ltd. A-BPE-4) 10
gTetraethylene glycol diacrylate 5g2-
Chlorthioxanthone 0.4 g N-methyljetanolamine 0.1 g Victoria Blue BH 0.04 g Methyl ethyl ketone 70 g Tetrahydrofuran 10 g A 25 μm photosensitive layer was obtained in the same manner as in Example 1.

When evaluated in the same manner, it peeled off into small pieces in 40 seconds. Further, a good resist relief image with a resolution of 40 μm was obtained in 8 stages.

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

Poly(methyl methacrylate-acrylic acid) ('1572
5% by weight) 50g trimethylolpropane ethoxytriacrylate tsg2.
2-bis[4-(acryloxyjethoxy)phenyl]propane 10g2-
Chlorthioxanthone 0.4 g N-methyljetanolamine 0.1 g Victoria Blue BHO, 04 g Methyl ethyl ketone 60 g Tetrahydrofuran 20 g The same procedure as in Example 1 was carried out to obtain a 25 μm photosensitive layer.

When evaluated in the same manner, it peeled off into small pieces in 15 seconds.

Further, a good relief image was obtained in 7 stages.

Example 4 A photosensitive polymer composition was obtained by mixing the following components.

Poly(methyl methacrylate-acrylic acid) (75/2
5% by weight) 50g trimethylolpropanepropoxytriacrylate
15g2.2-bis[4-
Acryloxy Shedkin) Phenyl Propane
10g 2-chlorothioxanthone
0,4g N-methyljetanolamine
o, tg Victoria Blue BI
O,04g methyl ethyl ketone
60g tetrahydrofuran 2
This was carried out in the same manner as in Example I to obtain a 25 μm photosensitive layer. When evaluated in the same manner, it peeled off into small pieces in 20 seconds. In addition, a good relief image with a resolution of 50 μm was obtained in 7 stages.

Example 5 A photosensitive polymer composition was obtained by mixing the following components.

Poly(methyl methacrylate-acrylic acid) (75/2
5% by weight) 50g glyceryltriethoxytriacrylate 15g2.2
-Bis[4-acryloxyjethoxy)phenyl]propane 10g2-chlorothioxanthone 0.1g Victoria Blue BI
O,04g methyl ethyl ketone
60g tetrahydrofuran
20g was prepared in the same manner as in Example 1 to give a thickness of 25μm.
A photosensitive layer was obtained. When evaluated in the same manner, it peeled off into small pieces in 20 seconds. In addition, a good relief image with a resolution of 50 μm was obtained with 7 stages.

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

Poly(methyl methacrylate-acrylic acid) (75/25
Weight%) 50g Trimethylolpropane triacrylate 20g2.2
-Bis[4-acryloxyjethoxy)phenyl]propane (A-BPE-4 manufactured by Shin Nakamura Chemical Industry) 10g
2-chlorothioxanthone 0.4gN
- Methyljetanolamine 0.1 g Victoria Blue BH 0.04 g Methyl ethyl ketone 60 g Tetrahydrofuran 20 g This was carried out in the same manner as in Example 1 to obtain a 25 μm photosensitive layer. When evaluated in the same manner, it was found that although it was peeled off in 20 seconds, the peeled pieces did not turn into small pieces and were in a so-called "wakame state", a shape that made filtration difficult.

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

Poly(methyl methacrylate-acrylic acid) (75/2
5% by weight) 50g glyceryl propoxytriacrylate (GPT manufactured by Celanese)
A) 30g 2-chlorothioxanthone 0.4g N-methyljetanolamine 0.1g Victoria Blue B) I
0.04g methyl ethyl ketone
80g tetrahydrofuran
20g was prepared in the same manner as in Example 1, and 25μ
A photosensitive layer of m was obtained. When similarly evaluated, it peeled off in the form of small pieces, but it took 60 seconds to peel off.

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

Poly(methacrylic acid-n-butyl acrylate-methacrylic acid) (45/30/25% by weight) 50 g glyceryl propoxy triacrylate (manufactured by Celanese GP)
TA) 25g 2-chlorothioxanthone 0.4g N-methyljetanolamine 0.1g Victoria Blue BH0,
04 g Methyl ethyl ketone 70 g Tetrahydrofuran 10 g A 25 μm photosensitive layer was obtained in the same manner as in Example 1. When similarly evaluated, it peeled off in the form of small pieces, but it took 90 seconds to peel off.

Claims (1)

[Claims] (a) Based on 100 parts by weight of a thermoplastic polymer binder copolymerized with 5 to 50 weight percent of an addition-polymerizable monomer having a carboxyl group, (b) ▲Mathematical formula, chemical formula , tables, etc. ▼ (In the formula, R_1, R_2, R_3 are hydrogen atoms or methyl groups, and n is an integer of 1 to 6) (I) Having at least 3 or more unsaturated groups represented by the formula in one molecule Contains at least 2 parts by weight of an unsaturated compound with a molecular weight of 350 to 2,000, and 2 parts by weight or more of a compound having at least two addition-polymerizable ethylene groups and at least one phenylene group in the molecule, at a temperature of 50°C or higher at normal pressure. 20 to 200 parts by weight of addition polymerizable compound having a boiling point (c) photoinitiator and/or photoinitiator system 0.01 to 3 parts by weight
A photosensitive polymer composition characterized in that it contains 0 parts by weight.