JPS60208303A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:A composition that is obtained by adding a combination of an amino- containing compound and epoxy-containing compound to a photosensitive resin containing a halogen-containing compound, thus being used in the fields of coating and ink, because of its high photosensitivity and storage storability. CONSTITUTION:The objective composition is composed of (A) 100pts.wt. of a compound having at least one photopolymerizable carbon-carbon double bond in the molecule such as acrylic acid, mathacrylamide, polyhydric alcohol polyacrylate, (B) 10-300pts.wt. of a halogen-containing compound (chlorinated polyethylene or brominated polyphenyl), (C) 1-10pts.wt. of a photopolymerization initiator containing an acyclic amine such as a combination of 4,4-bismethylaminobenzophenone with benzoin and (D) 1-10pts.wt., per 100pts.wt. of component B, of a compound bearing at least one epoxy group in the molecule such as phenyl glycidyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive resin composition that is highly sensitive and has excellent storage stability.

Photosensitive resins are used in a wide range of fields such as paints, inks, and photoresists, and play an important role in saving energy and shortening work time because they harden in a short time when exposed to light. There is a desire to shorten the time. The most common method for accelerating the curing speed of photosensitive adhesives is to use a photopolymerization initiator and a compound containing amino acid as a photopolymerization accelerator.
A method of increasing the sensitivity of F is known.

However, photosensitive 1rl resin 11h containing halogen-containing compounds for the purpose of improving flammability and heat resistance.
What happens when you use the above amino group-containing compound? 8 Likelihood (
(b) Immediately after preparing the fat, the curing speed is 7, but as time passes after preparation, the photoimaging speed decreases and the kneading sensitivity decreases over time, resulting in storage stability of 1. The problem was that it was bad.

Therefore, the present inventors investigated amino 1. (As a result of intensive studies with the aim of improving storage stability when using compounds containing epoxy), discovered that the storage stability was significantly improved, and came up with the present invention.

That is, this invention provides a) a compound having at least one photopolymerizable carbon-carbon double bond in the molecule, b) a photopolymerization initiator system containing a halogen-containing compound, an acyclic amine, and d) a molecule. The present invention relates to a photosensitive resin composition containing as an essential component a compound having at least one epoxy group.

The photosensitive resin composition of the present invention has high sensitivity because it contains an acyclic amine, which is an amino group-containing compound, in the photopolymerization initiator system. Therefore, the rate of photoreactions such as photopolymerization reaction and Y crosslinking reaction is fast. Moreover, because this composition contains a compound having an epoxy group in its molecule as one of its essential components, it is possible to reduce the amount of light observed when using a photopolymerization initiator system containing a halogen-containing compound and an amine group-containing compound together. There is no decrease in reaction rate over time, nor is there a decrease in sensitivity over time, and the high sensitivity described in -1- is stably maintained, and it has excellent kneading storage stability.

The reason why the photosensitive resin composition of the present invention has excellent storage stability as described above by containing a compound having an epoxy group in the molecule is considered to be as follows.

That is, when a halogen-containing compound is contained in the photosensitive resin composition, the halogen-containing compound gradually decomposes to generate hydrogen halide. If the composition does not contain a compound containing an epoxy group in its molecule, this hydrogen halide reacts with the compound containing an amino group to form a quaternary ammonium salt. Therefore, the concentration of the amine group-containing compound in the composition decreases over time, and the sensitivity of the composition decreases accordingly.

However, when the composition described in - is impregnated with a compound having an epoxy group in the molecule, the epoxy group of this compound and the hydrogen halide react with each other, so that the amino group-containing compound and ) The reaction with hydrogen chloride is greatly suppressed.

Therefore, the concentration of the amino group-containing compound in the composition hardly decreases over time, and as a result, the composition can maintain its initial high sensitivity, resulting in excellent storage stability. .

Compounds having at least [flI, preferably two or more] photopolymerizable carbon-carbon double bonds in the molecule of component a used in this invention include acrylic esters, acrylamides, and methacrylic esters. esters, methacrylamides, allyl compounds, vinyl ethers, vinyl ethers, N-vinyl compounds, nutylenes, crotonic acid esters, and the like.

More specifically, compounds having one photopolymerizable carbon-carbon double bond in the molecule include acrylic acid, methacrylic acid, alkyl ester acrylates (e.g. propyl acrylate, butyl acrylate, amyl acrylate,
ethylhexyl acrylate, octyl acrylate, etc.)
, methacrylic acid alkyl esters (e.g. methyl methacrylate, ethyl methacrylate, propyl methacrylate,
isopropyl methacrylate, etc.), acrylamide, N
-alkylacrylamide (alkyl groups include, for example, methyl group, ethyl group, butyl group, isopropyl group, t
-butyl group, ethylhexyl group, etc.), methacrylamide, N-alkyl methacrylamide (alkyl group includes methyl group, ethyl group, isopropyl group, 1-butyl group, ethylhexyl group, etc.), allyl ester (e.g. allyl acetate, allyl caproate, allyl tunoprilate, allyl lau Inonate, allyl palmitate, etc.),
Alkyl vinyl ether octyl vinyl ether, decyl vinyl ether ethylhexyl vinyl ether), vinyl ester (
For example, vinyl butyrate, vinyl IJ methyl acetate, vinyl diethyl acetate, vinyl valeryl-1.
, vinyl caproate), styrene'fR (e.g. styrene, methylstyrene, chloromethylstyrene, alkoxystyrene,) , esul crotonate, hexyl crotonate, isopropyl crotonate, etc.).

Examples of compounds having two or more photopolymerizable carbon-carbon double bonds in the molecule include polyhydric alcohols polyacrylate and polymethacrylate (here, "poly" refers to diacrylate and dimethacrylate). ). 1- As for alcohol,
Polyethylene glycol, Voliv 11 pyrene oxide,
Polybutylene oxide, (β-human 1'xyethoxy)
Benzene, chrycerin, cycloserine, neopentyl glycol, trimethylol pan, triethylol pan, pentaerythritol, dipentaeryth 11
1,--ol, sorbitan, sorbitol, 1,4-butanediol, 1,2,4-butanetriol, 2-butene-1,4-diol, 2-butyl-2-ethylbutenobanediol, 2-butene- 1-4-diol, I+1
Examples include 3-propanediol, triethanolamine, decalinol, 3-chloro-2-propanediol, and the like.

Furthermore, acrylates and methacrylates commercially available under the names of oligoester acrylate, oligoester methacrylate, epoxy acrylate, urethane acrylate, etc. can also be suitably used. As the component a, 71. You can use it alone 2
1Φt': 11 (7 may also be used.

Each b component used in this invention! The halogen-containing compound functions as a twist retardant, an N-, F-plastic agent, a polymer modifier, etc., and also as a binder in the case of 11"5 molecules. As this component, for example, chlorinated polyethylene, chlorinated Polypropylene, comb chloride, polyvinyl chloride, polyvinylidene chloride, bolik ('J) sulfonated ethylene, chlorinated paraffin, monide polyphenyl, chlorinated polyphenyl, perchlorohentane clodecane, tetrabromobutane, hexabromcifu'1 dodecane , tetrabromo bisphenol A, het acid, het acid anhydride, tetrabromo phthalic anhydride, etc. Among these, the l fiii or two species I- can be used.
The blending ratio of the component (1) in 'Good 3, - is usually 10 to 300 mold parts per 100 mold parts of component a in -1,
It is best to set it to the level of the market department. If the ratio of this component 1) is too low, the photosensitive main resin composition will be glazed with 1! G, 1 + J guard j
If properties such as IIIg are not sufficiently imparted and the proportion of sludge is too high, the sensitivity of the composition will decrease, which is undesirable.

The acyclic amine contained in component C in this invention is:
t) An amine without a nitrogen-containing heterocycle in its molecule is conventionally known as a photopolymerization initiator or a photopolymerization accelerator. Examples of the amine include 4,4-bisdimethylaminobenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, 4Φ4'-bisdiethylaminobenzophenone, etinope 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid lauryl, 4- Isopropyl dimethylaminobenzoate, octyl 4-diisopropylaminobenzoate, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, dimethylaminopropylamine, monoethanolamine, ethanolamine, triethanolamine, N-methyljetanolamine, N -N-dimethylcyclohexylamine, NllN
-Dimethylaniline and the like.

Among the above-mentioned non-quadratic amines, there are those which function as a +ff initiator even when they are alone, such as amines having a carbonyl group in the molecule, and such amines have a tI
Although X alone may be used as the C component, it is usually better to use one or more of the above acyclic amines together with one or more of other photopolymerization initiators. The obtained bf is nimble. In such a combination system, the acyclic amine shown in "-" generally functions as a photopolymerization accelerator.

Photopolymerization initiators that can be used in combination with the acyclic amine described in 1. include conventionally known photopolymerization initiators, such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, Benzophenone, anthraquinone, 2-methylanthraquinone, 2-[-butylanthraquinone, 9-10-phenanthrenequinone, diacetyl, benzyl, 2,2-jethoxyacetophenone,
p-t-butyltrichloroacetophenone, 2.4
- Carbonyl compounds such as diethylthioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone are mentioned as suitable ones, and other organic sulfur compounds (arsenic compounds, peroxides, redox compounds, azo compounds, diazo compounds, light A reducing dye or the like may also be used.

When using the above acyclic amine and the above photopolymerization initiator in combination, the ratio of the acyclic amine in the C component is usually 5% by weight or more. If this ratio is too small, the resulting photosensitive resin composition will have low sensitivity, which is not preferable.

The blending ratio of component C in the photosensitive resin composition is usually 01 to 2 parts by weight per 100 parts by weight of component a above.
The amount is preferably about 0 parts by weight, preferably about 1 to 10 parts by weight, and if this ratio is too small, the sensitivity of the composition will become low, which is not preferable. However, if this ratio is too large, it is not preferable because commensurate effects cannot be obtained and the physical properties of the composition after photoreaction deteriorate.

The d component used in this invention, that is, the compound having at least one epoxy group in the molecule, is an epoxy compound derived from a compound having a phenolic hydroxyl group and epichlorohydrin (e.g., phenyl glycidyl ether, bisphenol A dichlorohydrin). glycidyl ether,
bisphenol F diglycidyl ether, etc.), epoxy compounds derived from compounds with alcoholic hydroxyl groups and epichlorohydrin (e.g. 2-ethylhexyl glycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, neo pentyl glycol diglycidyl ether, etc.), epoxy compounds derived from a compound having a carboxyl group and epichlorohydrin (e.g. phthalic acid diglycidyl ether, tetrahydrontal acid diglycidyl ester, etc.), carbon-carbon double bonds. Compounds that are epoxidized with peracetic acid etc. (e.g. epoxidized soybean oil, epoxidized linseed oil, epoxidized polybutadiene, epoxy compounds with a cyclohexene oxide skeleton, etc.), and among these epoxy compounds, One type of these may be used alone or two or more types may be used in combination.

The blending ratio of the component d in the photosensitive resin composition is preferably about 1 to 10 parts by weight per 100 parts by weight of the component b. If this ratio is too small, the storage stability of the above composition will be low, and if it is too high, the physical properties of the composition after photoreaction will deteriorate, which is not preferred.

The photosensitive resin composition of the present invention does not contain the above-mentioned a y d components as essential components, but may contain various additives in addition to these components as necessary. Examples of such additives include various polymers such as polymethyl methacrylate, polyacrylic acid, polymethyl acrylate, polyvinyl acetate, and polyacrylonitrile as binders, as well as paramethoxyphenol, hydroquinone, [-butylcatechol, Thermal polymerization inhibitors such as 206-di-t-butyl-p-cresol, coloring agents such as various dyes and pigments, plasticizers such as dimethyl phthalate, dibutyl phthalate, and triethylene glycol cycaprylate, silica, clay, Examples include fillers such as talc and calcium carbonate, and flame retardants such as antimony trioxide, zirconium hydroxide, ammonium phosphate, and tricresyl phosphate.

Depending on the use of the composition described in item 1, it may contain a solvent such as methyl acetate, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, trichloroethylene, monochlorobenzene, tetrahydrofuran, or ethylene glycol monomethyl ether acetate. It may also be used as a solution.

The photosensitive resin composition of the present invention, which contains each of the components listed in item 1 above, polymerizes or crosslinks in a short time upon irradiation with light. Applications of this composition include photocurable paints and printing inks. This composition is suitable for printing plate materials and 7
It can also be used as an otoresist.

The light source used to polymerize or crosslink the composition described in item 1 is usually a light source containing light with a wavelength in the range of 350 to 500 nm, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp. etc. can be used.

The present invention will be explained by describing examples in ltV, but the invention is not limited to the examples below.

In addition, in the following, parts mean parts by weight.

Example 1 A photosensitive resin composition of the present invention was obtained by blending and uniformly mixing the following components.

Benzophenone 5.0 parts Powdered silica (manufactured by Nippon Aerosil Co., Ltd., part name Aerosil 14-200) 1.0 parts Paramethoxyphenol 01 parts Comparative Example 1 Same as Example 1 except that 10 parts of epoxidized soybean oil was not used. A photosensitive resin composition was obtained.

Comparative Example 2 Exposure was carried out in the same manner as in Example 1 except that 0.5 parts of 4,4'-bisdiethylaminobenzophenone was not used. A 1E resin composition was obtained.

<Test Example 1> In the above Example 1 and Comparative Examples 1 and 2? j) The freshly prepared photosensitive resin composition was applied to a thickness of about 20 μm on each 100 μm thick polyester film, and heated for 20 m using a conveyor-type UV irradiation device (80 W high-pressure mercury lamp, distance from the lamp: 1 l, 110 CFn). Exposure is carried out at a conveyor speed of /min, and it takes 1! for the surface tack to disappear. /I checked the number of shots.

In addition, after storing the photosensitive tree 11 composition described in item 1 at 50'O for 5 weeks, the number of irradiations was examined in the same manner as above.

The results of these measurements are shown in Table 1 below.

Table 1 (Co., Ltd.) No hardening even after 10 passes Example 2 The following components were mixed uniformly while heating at 60 to 70°C, and then cooled to obtain a uniform solution.

Paramethoxyphenol 0.1 part The following components were added to the above homogeneous solution and mixed uniformly to obtain a photosensitive resin composition of the present invention.

2,4-diethylthioxanthone 30 parts Chrycerin diglycidyl ether 1.0 part Comparative Example 3 Glycerin diglycidyl ether i, o parts Total 11J
A photosensitive resin composition was obtained in the same manner as in Example 2 except that T was not used.

Comparative Example 4 The amount of 2,4-diethylthioxanthone used was 60 parts, and the amount of isopropyl dimethylamine benzoate was 3.0 parts.
A photosensitive resin composition was obtained in the same manner as in Example 2, except that no part was used.

Test Example 2 The photosensitive resin compositions immediately obtained in Example 2 and Comparative Examples 3 and 4 above were each coated on aluminum foil-1 to a thickness of 30 μm, and 60 parts were heated using an 8KW ultra-high pressure mercury lamp. The light was irradiated from a distance of m, and the amount of exposure required to eliminate surface tack was measured. The above photosensitive resin composition was dried at 50'O.
After being stored for 5 weeks, the exposure amount was measured in the same manner as described in -1-.

The results of these measurements are shown in Table 2 below.

Table 2 (→Example 3 in which surface tack did not disappear despite exposure at 1,000 mJ/71) A photosensitive resin composition of the present invention was obtained by blending and uniformly mixing the following components.

Benzophenone 30 parts Paramethoxyphenol O' part Methyl ethyl ketone 350 parts Comparative Example 5 A photosensitive resin composition was obtained in the same manner as in Example 3 except that 0.5 parts of ethylene glycol diglycidyl ether was not used.

Comparative Example 6 A photosensitive resin composition was obtained in the same manner as in Example 3 except that 03 parts of 4,4-bisdimethylaminobenzophenone was not used.

<Test Example 3> The photosensitive resin compositions immediately obtained in Example 3 and Comparative Examples 5 and 6 above were applied onto an aluminum plate with a cleaned surface so that the thickness after drying was 20 μm. , 5 at 80°C
A photosensitive layer was formed by drying for a minute. A film for sensitivity measurement (product name: PS Step Guide manufactured by Fuji Photo Film Co., Ltd.) and a patterned negative film were closely attached to the surface of this photosensitive layer, and a 3KW ultra-high pressure mercury lamp was used to expose the film from a distance of 60CrrL.
N light was applied at 0 mJ/cyd. Next, this photosensitive layer was
The film was immersed in 1,1-trichloroethane for 4 minutes and developed, and the step sensitivity was examined using the above film for sensitivity measurement.

Note that this step sensitivity is 15 steps from 1 step to 15 steps.
It is divided into stages, and the density difference between each stage is 0.15, with a larger number indicating higher sensitivity.

Now, place the aluminum plate on which the photosensitive layer was formed in the same manner as above.
After being stored at 0°C for 4 weeks, it was exposed and developed in the same manner as described in Section 1 above, and the step sensitivity was measured.

The above l1i11 determination results were as shown in Table 3 below.

Table 3 (*1) A clear image was obtained (*2) The exposed area swelled and some parts peeled off from the aluminum plate (*3) The exposed area completely dissolved and no pattern could be formed. Example 4 In place of 20 parts of chlorinated rubber, a tetrabromobisphenol A derivative (trade name Firegant 8000 manufactured by Ondai Kasei Co., Ltd.) was used.
) A photosensitive resin composition of the present invention was obtained in the same manner as in Example 2, except that 20 parts of the photosensitive resin composition was used.

Comparative Example 7 A photosensitive resin composition was obtained in the same manner as in Example 4 except that 1.0 part of glycerin diglycidyl ether was not used.

Comparison Example 8 A photosensitive tree 11)i composition was obtained in the same manner as in Example 4 except that 30 parts of isopropyl dimethylaminobenzoate was not used.

(p8. obtained in Example 4 and Comparative Examples 7 and 8 described below.
Regarding the photosensitive resin composition, the amount of exposure required to eliminate surface tack was investigated in the same manner as in Test Example 2.

These results are shown in Table 4 below.

Table 4 (G) Surface tack did not disappear after exposure at 1,000 mJ/Crdt As is clear from the results in item 1-, the photosensitive resin composition of the present invention has high sensitivity and storage stability. You can see that he is also very good at sex.

Patent applicant: Nitto Electric Industry Co., Ltd. Winter 1

Claims (2)

[Claims] (1) a) a compound having at least one photopolymerizable carbon-carbon double bond within the compound, b) a halogen-containing compound, C
d) a photosensitive resin composition comprising, as an essential number, a photopolymerization initiator thread containing an acyclic amine; and d) a compound having at least one epoxy group in the molecule. (2) The photosensitive resin composition according to claim 11, wherein component C contains an acyclic amine as a photopolymerization accelerator.