JPH08202030A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE: To provide a photosensitive resin composition capable of obtaining a hardened film superior in water resistance and accordingly an image film superior in resolution, solvent resistance, water resistance, and abrasion resistance. CONSTITUTION: A dispersoid comprising a water-insoluble or water-difficultly- soluble compound having photoactive ethylenically unsaturated groups containing an oil-soluble photopolymerization initiator is dispersed in a dispersion medium comprising at least one kind of hydrophobic polymer emulsion selected from an aqueous emulsion of a hydrophobic polymer having a protective colloid of a partially saponified vinyl acetate polymer having a saponification degree of 70-99molar % and containing a water-soluble photopolymerization initiator, and an aqueous emulsion of a hydrophobic polymer having a protective colloid of a partially saponified vinyl acetate polymer having a saponification degree of 70-99%and having a photocrosslinkable group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive resin composition. The present invention relates to a photosensitive resin composition for producing a printing plate, particularly a screen printing plate, which can form an image having excellent resolution, solvent resistance, water resistance and abrasion resistance.

[0002]

2. Description of the Related Art A conventional water-developable printing plate, particularly a photosensitive resin composition for producing a screen printing plate, contains a water-soluble polymer such as partially saponified vinyl acetate polymer or a surfactant as a protective colloid. A photosensitive resin composition prepared by adding a water-soluble photocrosslinking agent such as a diazo compound to a mixture of an aqueous emulsion of a hydrophobic polymer and an aqueous solution of a water-soluble polymer such as a partially saponified vinyl acetate polymer is widely used. There is.

However, in such a conventional photosensitive resin composition, the solvent resistance of the hydrophobic polymer itself is not sufficient, and therefore the cured product obtained does not have low solvent resistance. Therefore, the amount of the water-soluble polymer is increased, and as a result, the water resistance is reduced, etc., so that an image excellent in resolution, solvent resistance, water resistance and abrasion resistance can be obtained. There is a problem that there is no.

Therefore, as a means for solving the above problems, a mixture of a water-soluble photo-crosslinking agent and a partially saponified vinyl acetate polymer or the photo-crosslinking property itself as disclosed in JP-B-4-19543 is used. A water-insoluble or sparingly water-soluble photoactive ethylene-based polymer containing a photopolymerization initiator in a dispersion medium composed of an aqueous liquid containing a partially saponified vinyl acetate polymer having a photocrosslinkable group and a hydrophobic polymer A photosensitive resin composition in which a dispersoid composed of a compound having an unsaturated group is dispersed has been reported.

However, even in such a composition,
In order to stably disperse a dispersoid containing a water-insoluble or sparingly water-soluble photoactive ethylenically unsaturated group-containing photopolymerization initiator in a dispersion medium as described above, a relatively large number of partial kens Since it requires a modified vinyl acetate polymer, it is not possible to prevent deterioration of water resistance of the resulting cured product, so that the image tends to swell during water development, and thus it is difficult to form a good image film. Is. On the other hand, if the compounding amount of the partially saponified vinyl acetate polymer in the photosensitive resin composition is reduced in order to prevent a decrease in water resistance, the water-developability and dispersion stability of the photosensitive resin composition decrease. Problems such as poor storage stability tend to occur.

[0006]

SUMMARY OF THE INVENTION The present invention solves the problems of the prior art as described above and provides a cured film having excellent water resistance. Therefore, the resolution, solvent resistance, water resistance and resistance after development are improved. An object of the present invention is to provide a photosensitive resin composition capable of obtaining an image film excellent in abrasion resistance.

[0007]

In order to solve the above-mentioned problems, the present invention contains a water-soluble photocrosslinking agent and has a saponification degree of 70-9.
An aqueous emulsion of a hydrophobic polymer having 9 mol% partially saponified vinyl acetate polymer as a protective colloid and a partially saponified vinyl acetate polymer having a saponification degree of 70 to 99 mol% having a photocrosslinkable group as a protective colloid. Water-insoluble or sparingly water-soluble photoactive ethylenically unsaturated group containing an oil-soluble photopolymerization initiator in a dispersion medium composed of at least one hydrophobic polymer emulsion selected from aqueous emulsions of hydrophobic polymers Disclosed is a photosensitive resin composition, in which a dispersoid composed of a compound having is dispersed.

The present inventors have an aqueous emulsion of a hydrophobic polymer having a partially saponified vinyl acetate polymer as a protective colloid containing a water-soluble photocrosslinking agent or a photocrosslinkable group,
Therefore, in a dispersion medium composed of an aqueous emulsion of a hydrophobic polymer having a partially cross-linked saponified vinyl acetate polymer having photocrosslinkability as a protective colloid, a water-insoluble or poorly water-soluble emulsion containing an oil-soluble photopolymerization initiator is used. The inventors have found that the above object can be achieved by dispersing a dispersoid composed of a compound having a photoactive ethylenically unsaturated group, and have completed the present invention.

Unlike the conventional photosensitive resin composition, the composition of the present invention does not contain a water-soluble polymer such as a partially saponified polyvinyl acetate polymer in a free state. The film has sufficient water resistance, so that a high-resolution image can be easily formed, and the image film obtained after development is excellent in solvent resistance, water resistance and abrasion resistance. The advantage is that

The reason why the above-mentioned excellent performance can be obtained by the photosensitive resin composition of the present invention is considered as follows. That is, an aqueous emulsion of a hydrophobic polymer having a partially saponified vinyl acetate polymer as a protective colloid is used as a dispersion medium, and an oil-soluble photopolymerization initiator is contained in this as a water-insoluble or sparingly water-soluble photoactive ethylenic unsaturated compound. When a compound having a group is dispersed, it can be stably dispersed without adding a water-soluble polymer such as a partially saponified vinyl acetate polymer, and the partially saponified acetic acid used as a protective colloid. Since the vinyl polymer is integrated with the hydrophobic polymer, the water resistance of the resulting photosensitive resin composition may be superior to that obtained by adding the water-soluble polymer to the dispersion medium. Seem.

The photosensitive resin composition of the present invention contains, as its first component, an aqueous emulsion of a hydrophobic polymer having a partially saponified vinyl acetate polymer having a saponification degree of 70 to 99 mol% as a protective colloid. . This protective colloid is a partially saponified vinyl acetate polymer having a saponification degree of 70 to 99 mol%. The degree of saponification of the partially saponified vinyl acetate polymer makes the resulting photosensitive resin composition water-developable and has good water resistance and solvent resistance of the film after photocuring. Therefore, it is necessary to be 70 to 99 mol%. For the same reason, the degree of polymerization is 500 to 3
It is preferably in the range of 000.

Further, as the protective colloid, a derivative of a partially saponified vinyl acetate polymer having a reactive unsaturated group as disclosed in JP-A-63-81101 can also be used. Then, using the above protective colloid, the compound having an ethylenically unsaturated group is subjected to emulsion polymerization or suspension polymerization in water according to a conventional method to give a saponification degree of 7
An aqueous emulsion of a hydrophobic polymer grafted with a protective colloid consisting of 0-99 mol% partially saponified vinyl acetate polymer can be obtained.

If desired, together with the partially saponified vinyl acetate polymer, other water-soluble polymers such as gelatin, casein, collagen, starch, starch derivatives, arabic gum, methylcellulose, carboxymethylcellulose, polyacrylamide, polyacrylic acid, You may use water-soluble nylon etc. together. The partially saponified vinyl acetate polymer which is the protective colloid is preferably present in an amount of 15 to 75% by weight of solids in the hydrophobic polymer emulsion. If this amount is less than 15% by weight, the redissolvability of the resulting photosensitive resin composition is insufficient, water development becomes difficult, and a good image may not be formed. On the other hand, when the content is more than 75% by weight, the protective colloid during polymerization becomes excessive, and the partially saponified vinyl acetate polymer not grafted to the particles of the hydrophobic polymer remains as the protective colloid. The resulting photosensitive resin composition has low water resistance, and it may not be possible to obtain a good image.

Here, the compound having an ethylenically unsaturated group is a compound having one or two or more ethylenically unsaturated groups in the molecule, and examples thereof include methyl acrylate, ethyl acrylate and butyl acrylate. Acrylic acid-2-
Acrylic acid alkyl esters such as ethylhexyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid alkyl esters such as 2-ethylhexyl methacrylate, epoxy acrylates or methacrylates, urethane acrylates or methacrylates, polyether acrylates Alternatively, methacrylates, polyester acrylates or methacrylates, acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, allyl acrylate, allyl methacrylate, itaconic acid, acrylamide, methacrylamide, dimethylaminoethyl acrylate, dimethylaminomethacrylate. Ethyl, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-methylol Acrylamide, N- methylol methacrylamide, acrylonitrile, styrene, alpha-methyl styrene, vinyl acetate, vinyl toluene, vinyl pyridine, 2-hydroxy-3-phenoxypropyl acrylate, p- nonyl phenoxyethyl acrylate,
1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, 3-butylene glycol dimethacrylate, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2,2-bis [4-
(Methacryloxypolyethoxy) phenyl] propane, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, dipentaerythritol hexaacrylate, butadiene, isoprene, chloroprene, vinyl chloride, vinyl bromide, vinylidene chloride, Examples thereof include vinylidene fluoride. These can be used alone or in combination of two or more.

Further, as the polymerization initiator useful for the polymerization of the above-mentioned compound having an ethylenically unsaturated group, for example, benzoyl peroxide, cumene hydroxyperoxide, succinic acid peroxide, lauroyl peroxide, hydrogen peroxide, etc. Peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-aminodipropane) dihydrochloride, etc. Azo compounds, persulfate compounds such as ammonium persulfate and potassium persulfate, perchloric acid compounds, and redox such as combinations of the persulfate compounds with reducing sulfoxy compounds or combinations of perchloric acid compounds with reducing sulfoxy compounds System catalysts, which may be used alone or in combination of two or more. .

Further, as disclosed in Japanese Patent Application No. 4-178633, a light absorbing agent such as a pigment, a dye or an ultraviolet absorbing agent may be contained in the above-mentioned compound having ethylenic unsaturation. An emulsion of a hydrophobic polymer having a partially saponified vinyl acetate polymer used as a protective colloid for use in the present invention has a photocrosslinkable group, and therefore has a photocrosslinkability by itself and has a saponification degree of 70 to 99 mol%. An emulsion of a hydrophobic polymer having the partially saponified vinyl acetate polymer as the protective colloid is preferable. As an example of such a polymer, a vinyl alcohol unit in a partially saponified vinyl acetate polymer, which is a protective colloid of a hydrophobic polymer emulsion, is added to the following general formula (I).

[0017]

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[0018]

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[0019]

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Represents one member selected from the group represented by
Is an integer of 1 to 6, n is 0 or 1, and in the formulas (II) and (III), R ₁ is a hydrogen atom, an unsubstituted alkyl group, an aralkyl group, a hydroxyl group, a carbamoyl group, A styrylpyridinium group and a styryl each represented by at least one member selected from an ether bond and an unsaturated bond, R ₂ represents at least one member selected from a hydrogen atom and a lower alkyl group, and X ⁻ represents an anion. There is one in which at least one photosensitive unit selected from a quinylium group is introduced by a conventional method.

The introduction ratio of the photosensitive unit is preferably in the range of 0.1 to 60 mol% of the vinyl alcohol unit contained in the vinyl constitutional unit of the partially saponified vinyl acetate polymer, and 0.4 to 10 More preferably, it is in the range of mol%. Introduction rate of photosensitive unit is 0.1 mol%
If it is less, the resulting composition may have insufficient photosensitivity, and if it is more than 60 mol%, there is no particular improvement in the photosensitivity. May be possible.

These hydrophobic polymer emulsions containing these partially saponified vinyl acetate polymers as protective colloids can be used alone or in combination of two or more.
The second component of the photosensitive resin composition of the present invention is a water-insoluble or sparingly water-soluble photoactive ethylenically unsaturated group-containing compound containing an oil-soluble photopolymerization initiator. This component is a compound in which an oil-soluble photopolymerization initiator is contained in a compound having a water-insoluble or sparingly water-soluble and photoactive ethylenically unsaturated group (hereinafter, generically referred to as "ethylenically unsaturated compound"). is there.

Examples of ethylenically unsaturated compounds useful in this second component include ethylene as described above as being useful in preparing emulsions of hydrophobic polymers with partially saponified vinyl acetate polymers as protective colloids. The compound which has a system unsaturated group can be mentioned. These ethylenically unsaturated compounds can be used alone or in combination of two or more.

As the oil-soluble photopolymerization initiator, a substance usually used for photopolymerization of an ethylenically unsaturated compound, that is, a substance which easily generates radicals under light irradiation can be used. The photopolymerization initiator is preferably 0.1 to 1 with respect to 100 parts by weight of the ethylenically unsaturated compound.
It is preferable to use 5 parts by weight, more preferably 0.3 to 10 parts by weight.

The ethylenically unsaturated compound containing an oil-soluble photopolymerization initiator is a hydrophobic polymer emulsion having a partially saponified vinyl acetate polymer as a protective colloid and having a solid content of 100.
The amount is preferably 5 to 1000 parts by weight, more preferably 10 to 500 parts by weight, based on parts by weight. If the amount of the ethylenically unsaturated compound containing the oil-soluble photopolymerization initiator is too small, the cured product of the photosensitive resin composition obtained has insufficient water resistance, and the photosensitive resin composition obtained when used in excess is used. The developability of the product is deteriorated, and problems such as separation and precipitation of the ethylenically unsaturated compound on the film obtained by coating and drying this composition are likely to occur.

A water-soluble photocrosslinking agent is used as the third component. When a partially saponified vinyl acetate polymer, which is a protective colloid of the hydrophobic polymer emulsion in the photosensitive resin composition of the present invention, having no photocrosslinkable group is used, a water-soluble photocrosslinking agent is used. Must be used.
This water-soluble photocrosslinking agent is contained in water which is a dispersion medium of the hydrophobic polymer emulsion, and when the photosensitive resin composition is exposed and cured, it is partially saponified as a protective colloid of the hydrophobic polymer emulsion. Photocrosslinking vinyl acetate polymer,
Let it cure.

Examples of useful water-soluble photocrosslinking agents include diazo compounds, and examples of such compounds include:
Mention may be made of anion complex diazo compounds such as sulfates, phosphates and zinc chloride complex salts of p-diazodiphenylamine-formaldehyde condensate.
These diazo compounds may be used alone or in combination of two or more, and are used for 100 parts by weight of partially saponified vinyl acetate polymer which is a protective colloid of the hydrophobic polymer emulsion in the photosensitive resin composition. It is preferably used in an amount in the range of 2 to 20 parts by weight. If the amount of the diazo compound is less than 2 parts by weight, the cured product of the photosensitive resin composition may have insufficient water resistance, and if it is used in excess of 20 parts by weight, the storage stability of the photosensitive resin composition may decrease. .

In the photosensitive resin composition of the present invention, the water-soluble photocrosslinking agent is used even when the partially saponified vinyl acetate polymer which is a protective colloid of the hydrophobic polymer emulsion has a photocrosslinkable group. It may be added, and in such a case, a cured film having more excellent water resistance can be obtained, which may be preferable. The photosensitive resin composition of the present invention essentially consists of the above-mentioned components, but the additives usually contained in this type of photosensitive resin composition, for example, an emulsion stabilizer, an antifoaming agent, an anti-repellent agent, and an antiseptic agent. Agents, thermal polymerization inhibitors, colorants such as dyes and pigments, and the like can be optionally contained.

The photosensitive resin composition of the present invention can be prepared, for example, by the following operation. That is, a hydrophobic polymer having a partially saponified vinyl acetate polymer dispersed in water as a protective colloid or a partially saponified vinyl acetate polymer having a photocrosslinkable group previously introduced by a conventional method as a protective colloid is used as a protective colloid. An ethylenically unsaturated compound containing an oil-soluble photopolymerization initiator is added to an emulsion composed of a combination or both of these hydrophobic polymers and emulsified and dispersed. If necessary, an emulsion stabilizer, a defoaming agent, an anti-repellent agent, an antiseptic agent, a thermal polymerization inhibitor, a coloring agent such as a dye or a pigment, and the like are optionally added and mixed. Then, finally, a water-soluble photocrosslinking agent dissolved in a small amount of water is added and mixed.

From the viewpoint of the storage stability of the photosensitive resin composition, the water-soluble photocrosslinking agent is preferably added immediately before using the composition. The obtained photosensitive resin composition of the present invention is, for example, 1 to 5 on an arbitrary support such as a screen mesh, a glass substrate, a metal plate, a synthetic resin plate and a semiconductor plate.
It is used by coating so as to have a dry film thickness of 00 μm and drying.

The photosensitive material is brought into close contact with a mask such as a negative film or a positive film, and exposed through a light source such as a xenon lamp, a metal halide lamp or an ultrahigh pressure mercury lamp through the mask. Then, the non-exposed portion is removed by spray development using a developing solution such as water or a water / organic solvent mixture, or immersion development. An image is thus formed and used as various printing plates or resist films.

[0032]

EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 Operation (1) 60 parts by weight of butyl acrylate, 15 parts by weight of 2-ethylhexyl acrylate, 25 parts by weight of ethylene glycol dimethacrylate and 2,2'- as a thermal polymerization initiator.
0.5 parts by weight of azobisisobutyronitrile were mixed and dissolved, and 100 parts by weight of a 18% aqueous solution of a partially saponified vinyl acetate polymer having an average degree of polymerization of 1400 and a degree of saponification of 88 mol% as a protective colloid and ion-exchanged water 95 Suspension polymerization was carried out by a conventional method using 0.8 parts by weight, the solid content concentration was 40% by weight, and the ratio of the protective colloid (partially saponified vinyl acetate polymer) in the solid content was 15% by weight. A hydrophobic polymer emulsion containing a partially saponified vinyl acetate polymer as a protective colloid (hereinafter referred to as "Em-1") was obtained.

Operation (2) Photopolymerization initiator Irugacure 651 (trademark of Ciba Geigy)
Ethylenically unsaturated compound containing 5 parts by weight, 45 parts by weight of 2,2'-bis (4-acryloxydiethoxyphenyl) propane and 55 parts by weight of tripropylene glycol diacrylate, and dissolving them to contain a photopolymerization initiator. (Hereinafter, referred to as “AO-1”).

Then, 240 parts by weight of the above "Em-1" whose solid content concentration was adjusted to 30% by weight was added to the above "AO-1".
After mixing 20 parts by weight, the mixture was emulsified to obtain an emulsion. To this, 20% by weight of a diazo compound consisting of a condensate of p-diazodiphenylamine and formaldehyde
A photosensitive resin composition was obtained by mixing 8 parts by weight of an aqueous solution and 3 parts by weight of a blue pigment (EM color Blue2G: trade name of Dainichiseika Kogyo Co., Ltd.) dispersed in water.

Operation (3) The obtained photosensitive resin composition was applied to a 250-mesh nylon screen fixed to an aluminum frame using a stainless steel bucket. This coating step and drying step 3
Repeated 5 times to obtain a photosensitive coating film having a thickness of 70 μm (including the thickness of the screen).

A positive film was brought into close contact with this photosensitive coating film and exposed for 3 minutes from a distance of 1 m with a 3 kW ultra-high pressure mercury lamp. Then, it was immersed in water for 1 minute to swell it, and further spray-developed with water to obtain a screen printing plate.
The image of the obtained screen printing plate showed little swelling with water, no film filming of the image caused by water swelling was observed, and a 30 μm line-and-space pattern was well resolved.

The screen printing plate was rubbed 300 times with a bleaching cloth impregnated with a mixed solvent of water / acetone = 30/70 (weight ratio) under a load of 1 kg, and the image film was worn and damaged. As a result of observing
It was less than μm and no damage was observed. Comparative Example 1 Operation (1) 60 parts by weight of butyl acrylate, 15 parts by weight of 2-ethylhexyl acrylate, 25 parts by weight of ethylene glycol dimethacrylate and 2,2'- as a thermal polymerization initiator.
0.5 parts by weight of azobisisobutylnitrile was mixed and dissolved, and as a protective colloid, 62 parts by weight of an 18% aqueous solution of a partially saponified vinyl acetate polymer having an average degree of polymerization of 1400 and a degree of saponification of 88 mol% and ion-exchanged water 85.6. Suspension polymerization is carried out by a conventional method using parts by weight, and the solid content is 45% by weight, and the proportion of protective colloid (partially saponified vinyl acetate polymer) in the solid content is 10% by weight. A hydrophobic polymer emulsion (hereinafter referred to as "Em-2") using the coalesced as a protective colloid was obtained.

Operation (2) The above-mentioned "Em-2" 2 in which the solid content concentration was adjusted to 30% by weight.
40 parts by weight and the same "AO-as used in Example 1
20 parts by weight of 1 "were mixed and then emulsified to obtain an emulsion. To this, 8 parts by weight of a 20% by weight aqueous solution of a diazo compound consisting of a condensate of p-diazodiphenylamine and formaldehyde and a blue pigment (EM
Color Blue 2G: 3 parts by weight of Dainichiseika Kogyo Co., Ltd. was mixed to obtain a photosensitive resin composition.

Operation (3) Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain a screen printing plate. This photosensitive resin composition was obtained despite being composed of a hydrophobic polymer emulsion containing a partially saponified vinyl acetate polymer as a protective colloid and an ethylenically unsaturated compound containing a photopolymerization initiator. Due to lack of developability, the screen printing plate could not form a good image because the uncured photosensitive resin composition that was originally dissolved and should be washed away remained in the unexposed area. It is considered that this is because the re-solubility was poor due to too little protective colloid in the hydrophobic polymer emulsion.

Comparative Example 2 Operation (1) The operation (1) of Comparative Example 1 was repeated to obtain "Em-2". Operation (2) The "Em-2" 2 with the solid content concentration adjusted to 30% by weight
27 parts by weight, average degree of polymerization 1700, degree of saponification 88 mol%
10% by weight aqueous solution of partially saponified vinyl acetate polymer 40
Parts by weight and the same "AO-1" 2 used in Example 1
An emulsified liquid was obtained by mixing 0 parts by weight and then emulsifying. To this, 8 parts by weight of a 20% by weight aqueous solution of a diazo compound consisting of a condensate of p-diazodiphenylamine and formaldehyde and a blue pigment (EM color
Blue2G: 3 parts by weight of Dainichiseika Kogyo Co., Ltd. was mixed to obtain a photosensitive resin composition.

Operation (3) Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain a screen printing plate. This photosensitive resin composition comprises the following components: [emulsion resin content (hydrophobic polymer emulsion solid content minus protective colloid) and partially saponified vinyl acetate polymer (including hydrophobic polymer emulsion protective colloid portion). Although the weight ratio with the ethylenically unsaturated compound containing a photopolymerization initiator] is the same as that of Example 1, the image of the obtained screen printing plate has a film tension due to water swelling, The 30 μm line-and-space pattern could not be well resolved.

The screen printing plate was rubbed 300 times back and forth with a bleaching cloth impregnated with a mixed solvent of water / acetone = 30/70 (weight ratio) at a load of 1 kg, and the image film was worn and damaged. As a result of observing
It was ˜3 μm, and breakage was recognized in the edge portion of the image. Example 2 Operation (1) 60 parts by weight of butyl acrylate, 15 parts by weight of 2-ethylhexyl acrylate, 25 parts by weight of ethylene glycol dimethacrylate and 2,2'- as a thermal polymerization initiator.
Azobisisobutyronitrile (0.5 parts by weight) was mixed and dissolved, and as a protective colloid, 140 parts by weight of an 18% aqueous solution of a partially saponified vinyl acetate polymer having an average degree of polymerization of 1400 and a degree of saponification of 88 mol% and ion-exchanged water 109. Suspension polymerization is carried out by a conventional method using parts by weight, the solid content concentration is 36% by weight, and the proportion of protective colloid (partially saponified vinyl acetate polymer) in the solid content is 20% by weight. A hydrophobic polymer emulsion (hereinafter referred to as "Em-3") using a saponified vinyl acetate polymer as a protective colloid was obtained.

Operation (2) The above-mentioned "Em-3" 3 in which the solid content concentration was adjusted to 30% by weight.
30 parts by weight and the same "AO-as used in Example 1
30 parts by weight of 1 "were mixed and then emulsified to obtain an emulsion. To this, 10 parts by weight of a 20% by weight aqueous solution of a diazo compound consisting of a condensate of p-diazodiphenylamine and formaldehyde and a blue pigment (E
M color Blue 2G: 4 parts by weight of Dainichiseika Kogyo Co., Ltd. was mixed to obtain a photosensitive resin composition.

Operation (3) Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain a screen printing plate. The image of the obtained screen printing plate showed little swelling with water, no film filming of the image caused by water swelling was observed, and a 30 μm line-and-space pattern was well resolved.

The screen printing plate was rubbed 300 times back and forth with a bleaching cloth impregnated with a mixed solvent of water / acetone = 30/70 (weight ratio) under a load of 1 kg, and the image film was worn and damaged. As a result of observing
It was less than μm and no damage was observed. Comparative Example 3 Operation (1) The operation (1) of Example 1 was repeated to obtain “Em-1”.

Operation (2) The above-mentioned "Em-1" 3 in which the solid content concentration was adjusted to 30% by weight.
13 parts by weight, average degree of polymerization 1700, degree of saponification 88 mol%
10% by weight aqueous solution of partially saponified vinyl acetate polymer 60
Parts by weight and "AO-1" 3 as used in Example 1
An emulsified liquid was obtained by mixing 0 parts by weight and then emulsifying. To this, 10 parts by weight of a 20% by weight aqueous solution of a diazo compound consisting of a condensate of p-diazodiphenylamine and formaldehyde and 3 parts by weight of a blue pigment (EM color Blue 2G: trade name of Dainichiseika Kogyo Co., Ltd.) dispersed in water. By mixing, a photosensitive resin composition was obtained.

Operation (3) Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain a screen printing plate. This photosensitive resin composition comprises the following components: [emulsion resin content (hydrophobic polymer emulsion solid content minus protective colloid) and partially saponified vinyl acetate polymer (including hydrophobic polymer emulsion protective colloid portion). Although the weight ratio with the ethylenically unsaturated compound containing a photopolymerization initiator] is the same as that of Example 2, the image of the obtained screen printing plate has a film tension due to water swelling, The 30 μm line-and-space pattern could not be well resolved.

The screen printing plate was rubbed 300 times back and forth with a load of 1 kg using a bleaching cloth impregnated with a mixed solvent of water / acetone = 30/70 (weight ratio), and the image film was worn and damaged. As a result of observing
It was ˜3 μm, and breakage was recognized in the edge portion of the image. Example 3 Operation (1) 60 parts by weight of butyl acrylate, 15 parts by weight of 2-ethylhexyl acrylate, 25 parts by weight of ethylene glycol dimethacrylate and 2,2'- as a thermal polymerization initiator.
Azobisisobutyronitrile (0.5 parts by weight) was mixed and dissolved, and as a protective colloid, 250 parts by weight of an 18% aqueous solution of a partially saponified vinyl acetate polymer having an average degree of polymerization of 1400 and a degree of saponification of 88 mol% and ion-exchanged water 53 Suspension polymerization was carried out by a conventional method using 0.7 parts by weight, the solid content concentration was 36% by weight, and the proportion of protective colloid (partially saponified vinyl acetate polymer) in the solid content was 30% by weight. A hydrophobic polymer emulsion (hereinafter, referred to as “Em-4”) using a partially saponified vinyl acetate polymer as a protective colloid was obtained.

Operation (2) The above-mentioned "Em-4" 2 in which the solid content concentration was adjusted to 30% by weight.
40 parts by weight and the same "AO-as used in Example 1
1 "50 parts by weight were mixed and then emulsified to obtain an emulsion. To this, 8 parts by weight of a 20% by weight aqueous solution of a diazo compound consisting of a condensate of p-diazodiphenylamine and formaldehyde and a blue pigment (EM
Color Blue 2G: 3 parts by weight of Dainichiseika Kogyo Co., Ltd. was mixed to obtain a photosensitive resin composition.

Operation (3) Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain a screen printing plate. The image of the obtained screen printing plate showed little swelling with water, no film filming of the image caused by water swelling was observed, and a 30 μm line-and-space pattern was well resolved.

The screen printing plate was rubbed 300 times back and forth with a bleaching cloth impregnated with a mixed solvent of water / acetone = 30/70 (weight ratio) under a load of 1 kg, and the image film was worn and damaged. As a result of observing
It was less than μm and no damage was observed. Comparative Example 4 Operation (1) The operation (1) of Example 1 was repeated to obtain “Em-1”.

Operation (2) The above-mentioned "Em-1" 2 whose solid content concentration was adjusted to 30% by weight
00 parts by weight, average degree of polymerization 1700, degree of saponification 88 mol%
10% by weight aqueous solution of partially saponified vinyl acetate polymer 16
0 parts by weight and the same "AO-1" as used in Example 1
An emulsion was obtained by mixing 60 parts by weight and then emulsifying. To this, 20% by weight of a diazo compound consisting of a condensate of p-diazodiphenylamine and formaldehyde
A photosensitive resin composition was obtained by mixing 10 parts by weight of an aqueous solution and 3.6 parts by weight of a blue pigment (EM color Blue 2G: trade name of Dainichiseika Kogyo Co., Ltd.) dispersed in water.

Operation (3) Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain a screen printing plate. This photosensitive resin composition comprises the following components: [emulsion resin content (hydrophobic polymer emulsion solid content minus protective colloid) and partially saponified vinyl acetate polymer (including hydrophobic polymer emulsion protective colloid portion). Although the weight ratio with the ethylenically unsaturated compound containing a photopolymerization initiator] is the same as that of Example 3, the image of the obtained screen printing plate has a film tension due to water swelling, The 30 μm line-and-space pattern could not be well resolved.

The screen printing plate was rubbed 300 times with a load of 1 kg using a bleaching cloth impregnated with a mixed solvent of water / acetone = 30/70 (weight ratio), and the image film was worn and damaged. As a result of observing
It was ˜3 μm, and breakage was recognized in the edge portion of the image. Example 4 Operation (1) Hydrophobic polymer emulsion "Em-4" using the partially saponified vinyl acetate polymer obtained in Example 3 as a protective colloid.
To 200 parts by weight, 2.7 parts by weight of N-methyl-4- (p-formylstyryl) pyridinium methosulfate was added and condensed by a conventional method to adjust the solid content concentration to a solid content concentration of 3
A hydrophobic polymer emulsion containing 6% by weight of a partially saponified vinyl acetate polymer having a degree of saponification of 70 to 99 mol% and containing a photocrosslinkable group having photocrosslinkability by itself as a protective colloid (hereinafter, referred to as "Em-4S") was obtained.

Operation (2) The above-mentioned "Em-4" 2 in which the solid content concentration was adjusted to 30% by weight.
40 parts by weight and the same "AO-as used in Example 1
1 "50 parts by weight were mixed and then emulsified to obtain an emulsion. In addition to this, a blue pigment dispersed in water (EM color
Blue2G: 3 parts by weight of Dainichiseika Kogyo Co., Ltd. was mixed to obtain a photosensitive resin composition.

Operation (3) Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain a screen printing plate. The image of the obtained screen printing plate showed little swelling with water, no film filming of the image caused by water swelling was observed, and a 30 μm line-and-space pattern was well resolved.

Further, this screen printing plate was rubbed 300 times back and forth with a load of 1 kg using a bleaching cloth impregnated with a mixed solvent of water / acetone = 30/70 (weight ratio), and the image film was worn and damaged. As a result of observing
It was less than μm and no damage was observed. Comparative Example 5 Operation (1) Hydrophobic polymer emulsion "Em-1" using the partially saponified vinyl acetate polymer obtained in Example 1 as a protective colloid.
To 200 parts by weight, 1.5 parts by weight of N-methyl-4- (p-formylstyryl) pyridinium methosulfate was added and condensed by a conventional method to adjust the solid content concentration to a solid content concentration of 4
A hydrophobic polymer emulsion containing 0% by weight of a partially saponified vinyl acetate polymer having a saponification degree of 70 to 99 mol% and containing a photocrosslinkable group having photocrosslinkability by itself as a protective colloid (hereinafter, referred to as "Em-1S") was obtained.

Next, the average degree of polymerization is 1700 and the degree of saponification is 8
To 500 parts by weight of a 14% aqueous solution of 8 mol% partially saponified vinyl acetate polymer, 8.4 parts by weight of N-methyl-4- (p-formylstyryl) pyridinium methosulfate was added and condensed by a conventional method to give a solid. Adjust the concentration so that the solid concentration is 1
A partially saponified vinyl acetate polymer containing a photocrosslinkable group having a photocrosslinkability of 0% by weight (hereinafter, referred to as "P
VA-1S ") was obtained.

Operation (2) The above-mentioned "Em-1S" in which the solid content concentration is adjusted to 35% by weight.
200 parts by weight, 160 parts by weight of a 10% by weight aqueous solution of "PVA-1S" and the same "AO-" used in Example 1
60 parts by weight of 1 "were mixed and then emulsified to obtain an emulsion. In addition to this, a blue pigment dispersed in water (EM color
Blue2G: 3.6 parts by weight of Dainichiseika Kogyo Co., Ltd. was mixed to obtain a photosensitive resin composition.

Operation (3) Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain a screen printing plate. This photosensitive resin composition comprises the following components: [emulsion resin content (hydrophobic polymer emulsion solid content minus protective colloid) and partially saponified vinyl acetate polymer (including hydrophobic polymer emulsion protective colloid portion). Although the weight ratio with the ethylenically unsaturated compound containing a photopolymerization initiator] is the same as that of Example 4, the image of the obtained screen printing plate has a film tension due to water swelling, The 30 μm line-and-space pattern could not be well resolved.

The screen printing plate was rubbed 300 times back and forth with a bleaching cloth impregnated with a mixed solvent of water / acetone = 30/70 (weight ratio) under a load of 1 kg, and the image film was worn and damaged. As a result of observing
It was ˜3 μm, and breakage was recognized in the edge portion of the image. Example 5 Operation (1) 60 parts by weight of phenoxyethyl acrylate, 15 parts by weight of 1,6-hexanediol diacrylate, 25 parts by weight of trimethylolpropane triacrylate and 2,2'-azobisisobutylnitrile as a thermal polymerization initiator. 0.5 parts by weight were mixed and dissolved, and as a protective colloid, 1675 parts by weight of an 18% aqueous solution of a partially saponified vinyl acetate polymer having an average degree of polymerization of 1400 and a degree of saponification of 88 mol% and 235 parts by weight of deionized water were used. Suspension polymerization is carried out by a conventional method, the solid content concentration is 20% by weight, and the proportion of protective colloid (partially saponified vinyl acetate polymer) in the solid content is 75% by weight. Hydrophobic polymer emulsion (hereinafter referred to as "Em-
5 ").

Operation (2) 500 parts by weight of "Em-5" and 150 parts by weight of "AO-1" used in Example 1 were mixed and then emulsified and dispersed to obtain an emulsion. To this, 12 parts by weight of a 20% by weight aqueous solution of a diazo compound consisting of a condensate of p-diazodiphenylamine and formaldehyde and a blue pigment dispersed in water (EM Color Blue 2G: Dainichiseika Kogyo Co., Ltd.) 3.6 parts by weight The parts were mixed to obtain a photosensitive resin composition.

Operation (3) Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain a screen printing plate. The image of the obtained screen printing plate showed little swelling with water, no film filming of the image caused by water swelling was observed, and a 30 μm line-and-space pattern was well resolved.

The screen printing plate was rubbed 300 times back and forth with a load of 1 kg using a bleaching cloth impregnated with a mixed solvent of water / acetone = 30/70 (weight ratio), and the image film was worn and damaged. As a result of observing
It was less than μm and no damage was observed. Comparative Example 6 Operation (1) 60 parts by weight of butyl acrylate, 15 parts by weight of 2-ethylhexyl acrylate, 25 parts by weight of ethylene glycol dimethacrylate and 2,2 'as a thermal polymerization initiator.
-Azobisisobutylnitrile (0.5 parts by weight) is mixed and dissolved, and as a protective colloid, 2230 parts by weight of an 18% aqueous solution of a partially saponified vinyl acetate polymer having an average degree of polymerization of 1400 and a degree of saponification of 88 mol% and 362 parts by weight of deionized water. Part is used to carry out suspension polymerization by a conventional method, the solid content concentration is 18% by weight, and the proportion of protective colloid (partially saponified vinyl acetate polymer) in the solid content is 80% by weight. A hydrophobic polymer emulsion (hereinafter referred to as "Em-6") using a modified vinyl acetate polymer as a protective colloid was obtained.

Operation (2) 556 parts by weight of "Em-6" having a solid content of 18% by weight and the same "AO-1" 167 as used in Example 1
After mixing parts by weight, the mixture was emulsified and dispersed to obtain an emulsion. To this, 20% by weight of a diazo compound consisting of a condensate of p-diazodiphenylamine and formaldehyde
A photosensitive resin composition was obtained by mixing 12 parts by weight of the aqueous solution and 3.6 parts by weight of a blue pigment (EM color Blue2G: trade name of Dainichiseika Kogyo Co., Ltd.) dispersed in water.

Operation (3) Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain a screen printing plate. This photosensitive resin composition was obtained despite being composed of a hydrophobic polymer emulsion containing a partially saponified vinyl acetate polymer as a protective colloid and an ethylenically unsaturated compound containing a photopolymerization initiator. The image of the screen printing plate had a film swelling due to water swelling, and could not well resolve a line and space pattern of 30 μm.

The screen printing plate was rubbed 300 times back and forth with a bleaching cloth impregnated with a mixed solvent of water / acetone = 30/70 (weight ratio) under a load of 1 kg, and the image film was worn and damaged. As a result of observing
It was ˜3 μm, and breakage was recognized in the edge portion of the image. This is because the amount of protective colloid in the hydrophobic polymer emulsion is too large, and partially saponified vinyl acetate polymer that is not grafted to the particles of the hydrophobic polymer remains as a protective colloid and a good image is formed. It is thought to be due to the disappearance.

[0068]

EFFECT OF THE INVENTION According to the photosensitive resin composition of the present invention, the cured film obtained has sufficient water resistance, so that a high-resolution image can be easily formed, and the cured film can be obtained after development. The image film obtained has the particular advantage of being excellent in solvent resistance, water resistance and abrasion resistance.

Claims (4)

[Claims] 1. A saponification degree of 70 to 70 including a water-soluble photocrosslinking agent.
An aqueous emulsion of a hydrophobic polymer having 99 mol% partially saponified vinyl acetate polymer as a protective colloid and a partially saponified vinyl acetate polymer having a degree of saponification of 70 to 99 mol% having a photocrosslinkable group as a protective colloid. Water-insoluble or sparingly water-soluble photoactive ethylenically unsaturated group containing an oil-soluble photopolymerization initiator in a dispersion medium composed of at least one hydrophobic polymer emulsion selected from aqueous emulsions of hydrophobic polymers A photosensitive resin composition, in which a dispersoid composed of a compound having: is dispersed. 2. The photosensitive resin composition according to claim 1, wherein the partially saponified vinyl acetate copolymer, which is a protective colloid, is present in an amount of 15 to 75% by weight of solids in the hydrophobic polymer emulsion. . 3. A styrylpyridinium group and a styrylquininium group in which the photocrosslinkable group of the partially saponified vinyl acetate polymer having a photocrosslinkable group is present as a side chain of the partially saponified vinyl acetate polymer. The photosensitive resin composition according to claim 1, which is at least one selected from the group consisting of: 4. The photosensitive resin composition according to claim 1, wherein the water-soluble photocrosslinking agent is a diazo compound.