JPS6224240A - Photopolymerizable composition having high sensitivity - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable composition having high sensitivity and superior stability by combinedly using a specified org. peroxide and a photosensitizer as a photopolymn. initiator. CONSTITUTION:This photopolymerizable composition contains a compound having an ethylenic unsatd. double bond and a photopolymn. initiator consisting of a polyperoxy-ester having a benzophenone group represented by formula I and 4, 4'-bis(dialkylamino)benzophenone represented by formula II. The com pound represented by the formula I may be 3, 3', 4, 4'-tetra-(tert- butylperoxycarbonyl)benzophenone. 4, 4'-Bis(dimethylamino)benzophenone or 4, 4'-bis(diethylamino)benzophenone is preferably used as the compound represented by the formula II. The compounds represented by the formulae I, II are preferable used by 1-30pts.wt. each per 100pts.wt. compound having an ethylenic unsatd. double bond.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a highly sensitive photopolymerizable composition. This composition has a wide range of uses when applied to various substrates, and as a material for forming image areas such as printing plate materials, contact films for plate making, masking films, Blue 7 paper, a-films, and photoresists.

[Conventional technology]

Conventionally, as a means of increasing the sensitivity of photopolymerizable compositions to light, there has been a method of adding benzophenone K 4.4'-bis(dimethylamine)benzophenone (commonly known as q (larzketone)) (for example, rUV by Kiyomi Kato and Shoji Nakahara). "Introduction to Curing Technology" P65, Kobunshi Publishing Association (II984)) and the method of adding organic peroxide to this (Japanese Patent Laid-Open No. 60-35725)
Although the effect on the polymerization rate is certainly recognized, the sensitivity obtained in the former is not sufficient for use in 7-otoresists and other applications, and the latter does not require the amount of organic material necessary to obtain high sensitivity. When a peroxide is used, the stability over time (hereinafter simply referred to as stability) including the thermal stability of the photosensitive resin liquid and the applied film is not sufficient.

[Problem that the invention seeks to solve]

Sensitivity is the most important property in photopolymerizable compositions;
In addition, when considering work efficiency, the appearance of products with higher sensitivity is currently awaited.

In addition, if the one-day stability of the photopolymerizable composition is insufficient, when the drying temperature after applying the photosensitive liquid is high, the exposure time will not be constant, which may cause variations in quality, resulting in poor reproducibility. A so-called "capri" phenomenon occurs in which a clear image cannot be obtained.

An object of the present invention is to obtain a photopolymerizable composition which is highly sensitive and has improved stability of a photosensitive solution and a coated film.

[Means for Solving the Problems] The present inventors have proposed a method of using a specific organic peroxide in combination with a photosensitizer as a photopolymerization initiator), a highly sensitive and highly stable light source. The present invention was achieved by discovering that a polymerizable composition can be obtained.

That is, the present invention provides an ethylenically uncelled double bond (II
) A highly sensitive photopolymerizable composition containing a photopolymerization initiator consisting of 4,4'-bis(dialkylamino)benzophenone represented by:

General formula (I) General formula (II) The compound having an ethylenically unsaturated double bond used in the present invention may be any compound that can be polymerized with a photopolymerization initiator, such as acrylic acid, methacrylic acid, itaconic acid, etc. , maleic acid and its anhydride, phthalic acid and its anhydride, fumaric acid and other unsaturated acids, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, glycidyl (meth)acrylate , hydroxyethyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, pentaerythritol tri(meth)acrylate, trinoterol propane tri(meth)acrylate, ethylene glycol di(meth)acrylate
Unsaturated acid esters such as acrylate, propylene glycol di(meth)acrylate, styrene, acrylamide, 7/IJ lonitrile, N-vinylpyrrolidone, vinyl acetate, and various unsaturated polyesters, unsaturated polyethers, unsaturated Polyurethane or epoxy group-containing L(')7/1JLz-1i''*'1m etc.d!69
0 F Also, examples of the benzophenone group-containing polyhydric peroxyester Gaya koji represented by the general formula (I) 1 used as a photopolymerization initiator in the present invention include 3.3', 4°4'-tetra-
(tert-butylperoxycarboel)benzophenol/,
3. 4,4'-tetra(tertiary amylperoxycarbonyl)benzophenone, 313'14t4'-tetra(tertiary hexylperoxycarbonyl)benzophenone, 3.3', 4,4'-tetra(tertiary octylperoxycarbonyl) oxycarbonyl)benzophenone, 3.3', 4.
Examples include 4'-tetra(ridenruberoxycarbonyl)benzophenone%313', 4.4'-tetra(p-ingrovircumylperoxycarbonyl)benzophenone, and the like.

Examples of the compound represented by the general formula (II) used in the present invention include 4,4'-bis(dimethylamino)benzo7dinone, 441-bis(diethylamino)benzophenone, and 4,4'-bis(cytaclohexylamino). Examples include benzophenone, 4,4'-bis(diethylamino in dihydro)benzophenone, and the like. Among these, 4,4'-bis(dimethylaζ))benzophenone and 4,4'-bis(diethylaζ))benzophenone are particularly preferred.

The blending ratio of each of the above components is 0.01 to 1 part by weight of the compound represented by -Sterka-1 and general formula (II) per 100 parts by weight of the compound having an ethylenically unsaturated double bond.
00 parts by weight, preferably 0.1 to 30 parts by weight, particularly preferably 1 to 30 parts by weight.

Also, the compound represented by the general formula (II)) and the compound represented by the general formula (II)
The compounding ratio of compound (b) shown is that a and b are 1=1 by weight.
0 to 10:1 is preferred.

A photopolymerizable composition with excellent performance cannot be obtained outside the range of the above-mentioned blending amount and blending ratio.

The photopolymerizable composition of the present invention has as an essential component a compound having an ethylenically unsaturated double bond that is polymerizable with the photopolymerization initiator, but may optionally include a binder resin, a polymerization inhibitor, a dye, etc. can be used by appropriately blending them.

Binder resin is used as a coating film forming aid for printing plate materials and photoresists for the purpose of improving physical properties, and is usually used in an amount of 50 to 500 parts by weight per 100 parts by weight of a compound having an ethylenically unsaturated double bond. It is preferable to use about 1 part. Examples of binder resins include (meth)acrylic acid ester resins, vinyl pyrrolidone resins, vinyl alcohol resins, etc., regardless of whether the resin contains a polymeric group or not.

Examples of polymerization inhibitors include p-methoxyphenol and hydroquinone, and examples of dyes include brilliant green, ethyl violet, eosin, and Eris Shikun B.

The photopolymerizable composition of the present invention is used as a photosensitive resin sheet by coating it on various substrates.
Dilute it approximately 5 to 100 times with a solvent such as methyl cellosolve, and apply it uniformly to a thickness of 0.5 to 50μ on the substrate using a method such as spin coating, roll mart, or barcode. use

The photosensitive resin sheet thus obtained undergoes a photopolymerization reaction by being irradiated with actinic light such as ultraviolet rays, and when developed, a predetermined image can be obtained.

〔Effect of the invention〕

The photopolymerizable composition of the present invention uses a combination of the compound represented by the general formula (I) and the compound represented by the general formula (g) as a photopolymerization initiator, so that it is different from the conventional photopolymerizable composition. ] also has extremely high sensitivity and excellent stability. Therefore, it can be used in many photopolymerization reactions and can be applied to many fields such as 10%-type image forming materials, photocurable resins, paints, and printing inks.

〔Example〕

The present invention will be explained in more detail below with reference to Examples and Comparative Examples. Parts in the examples indicate parts by weight.

Examples 1 to 2 and Comparative Examples 1 to 3 A photosensitive liquid was prepared by uniformly mixing photopolymerizable compositions having the following composition.

These photosensitive solutions are anodized with a grained grain;
It was coated onto a rim plate using a whirler so that the dry film thickness was 2 μm, and dried at 40° C. for 5 minutes to obtain a photosensitive substrate.

・Epoxy acrylate 100 parts (EM-800 manufactured by Shishi Nakamura Kagaku Koka) ・Poly(butyl acrylate/ethyl acrylate/methacrylic acid)
100 parts (mole ratio 50/4G/10. molecular weight io million)・3. 3', 4. 4'-teto2-(tert-butylperoxycarbonyl)benzophenone/4.4'-bis(diethylamino)benzophenone (
(hereinafter referred to as EMK) -ter-e benzophenone (hereinafter referred to as BP)
1a1F) -17 parts 1,800 parts of methyl cellosolve A step tablet (12 manufactured by Kodak ■) was stacked on this photosensitive substrate and vacuum-adhered.
6G (1.5 with a 2fJI+ ultra-high pressure mercury lamp from a distance of m)
After exposure for seconds, development is performed with a commercially available alkaline IA solution (DN-3C water-diluted product manufactured by Fuji Photo Film ■), and the number of steps in the exposed area is determined by visual judgment using the step tablet obtained after drying. Sensitivity.

The results are shown in Table IK. Note that the number of steps indicates high sensitivity, such as thick %/%11, and if there is a difference of two steps, the sensitivity is doubled.

Next, the photosensitive substrate before exposure was left for 48 hours in a heat insulating base at 55° C., and the stability was examined by performing post-exposure development in the same manner as above.9. The results are shown in Table 1. Note that here, "normal" indicates that development can be performed normally after exposure, and "impossible" indicates that "capri" appears and normal development is impossible.

! ! l I can't get a rate image. The umbrella skewer is not exposed to light at all.

! As is clear from the results of Il, the products of the present invention that use BTTB and EMK in combination have higher sensitivity and better stability than the comparative examples. It is clear from Comparative Examples 1 and 2 that the present invention is based on the synergistic effect of BTTB and EMK, but in addition, Example 11C
However, by using a small value of 8 parts of IITTB, which has a benzophenone group and a peroxy group in the same molecule, for the EMKS moiety, it was possible to achieve a better result than when a total of 34 parts of BP and PBIF were used separately in Comparative Example 3. The outstanding synergistic effect is also demonstrated by the significantly superior performance obtained.

Example 3 and Comparative Examples 4 to 5 A photosensitive solution having the following composition was prepared according to Example 1.1.
Coated paper (Made by SaniI!Oyashi ■, pearl coat φ10)
A photosensitive sheet was obtained by uniformly coating the film on the surface of the photosensitive film 0) using a 1-per-tar so that the dry coating thickness was 1 μm, and drying. Using this photosensitive sheet, the initial sensitivity and stability were examined in the same manner as in Example 1, except that current gRK water was used. The results are shown in Table 2.

・100 parts of B/querythritol triacrylate ・100 parts of poly-N-vinylpyrrolidone (11,360,000 molecules) - BTT
I-4,4'-bis(dimetelaono)benzophenone (hereinafter referred to as MK) shown in B H2 ・BP ・II BIF ・Methyl cellosolve 50001 Table 2 From the results in Table 2, it can be seen that the products of the present invention are better than those of the comparative example. It is clear that υ has high sensitivity and excellent stability.

Example 4 and Comparative Example 6 A photosensitive solution having the following composition was prepared according to Example IK, and a steel plate polished to a near mirror surface (Japan Test Panel Industry ■) was prepared.
Co., Ltd., JI8H3100 (CIlooP)) using a rotary coater so that the dry coating thickness was 5IwsK.
A photosensitive copper plate was obtained by coating and drying. Using this photosensitive copper plate, isopropanol/water (heavy) is used for development.
Initial sensitivity and stability were investigated in the same manner as in Example 1 except that an i ratio of 50150 J was used. Table 3 shows the results.
Shown below.

・50 parts of trimethylolpropane triacrylate ・150 parts of poly(methyl methacrylate/methacrylic acid) (hetyl ratio 5G150, molecular weight 80,000) ・3.3', 4.4'-tetra (@3 to medium silperoxycarbonyl) Benzophenone (hereinafter referred to as BTTH) Part shown in Table 3・KMK・BP @PBIF・Ether violet 2I・p-
Diphenol in meth 0.11・Methyl ethyl ketone 500#・Isopropatool 500# Table 3 From the results in Table 3, it is clear that the product of the present invention has higher sensitivity and better stability than the comparative example. .

Claims (1)

[Scope of Claims] A compound having an ethylenically unsaturated double bond, a polyvalent benzophenone group-containing peroxyester represented by the following general formula (I), and a 4,4'-bis( A highly sensitive photopolymerizable composition containing a photopolymerization initiator consisting of dialkylamino)benzopheenone. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 and R_1' each have 4 to 8 carbon atoms.
or a tertiary aralkyl group having 9 to 12 carbon atoms; R_2 and R_2' are each a hydrogen atom or a tertiary alkoxy group having 4 to 8 carbon atoms; or a tertiary aralkyl group having 9 to 12 carbon atoms;
represents a tertiary aralkyloxy group of 12. General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... (II) However, R represents an alkyl group, cycloalkyl group, or hydroxyalkyl group having 1 to 6 carbon atoms.