JP2930152B2 - Photosensitive resin composition for producing screen printing plate, photosensitive film, and screen printing plate made by using them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to screen printing plate manufacturing.
The present invention relates to a photosensitive resin composition for use , a photosensitive film, and a screen printing plate made by using them.

[0002]

2. Description of the Related Art Screen printing has features such as easy plate making and printing, high image accuracy, few restrictions on a printing medium, and a large thickness of printed ink. Therefore, it is used in a variety of fields as compared with other printing methods, and its application range is expanding and demand is rapidly increasing.

[0003] Conventionally, as a photosensitive film material for screen printing plate production, an aqueous solution of a mixed emulsion of polyvinyl alcohol and polyvinyl acetate to which ammonium dichromate or a diazo resin has been added as a photosensitive agent, a styrylpyridinium group, a styrylquinolate. Photosensitive resin using a photoinsoluble resin which is a polyvinyl alcohol derivative containing an ammonium group, etc., and a compound having an ethylenically unsaturated group for improving resolution, water resistance and solvent resistance. Various photosensitive resin compositions comprising an initiator and a mixture of a compound having an ethylenically unsaturated group and a photoinitiator in a polymer soluble and soluble in an organic solvent and water-soluble are known. Some of them have excellent performance in terms of friction resistance (printing resistance), water resistance and solvent resistance during printing. There. However, screen printing plates made using such a photosensitive resin composition have excellent resolution and solvent resistance, but may cause ink bleeding when printing fine lines or printing on uneven surfaces. At present, defective products are easily generated due to stains of the printing plate due to the back circumference, and it is difficult to reduce the defective products.

On the other hand, Japanese Patent Application Laid-Open No. 02-144537 discloses that a water-repellent and oil-repellent property is imparted by adding an alcohol-soluble fluorine-based surfactant compound to a photosensitive resin composition, and the ink bleeds during printing. There is disclosed a technique for preventing the printing plate from being stained by the back and surroundings. But,
With this photosensitive resin composition, the problems of ink bleeding and printing plate stains are reduced, but on the other hand, poor compatibility of the resin composition, poor adhesion of the photosensitive material to gauze, and shortened life of the screen printing plate, etc. Becomes noticeable.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to prevent the printing plate from being stained due to ink bleeding or back-around, to print ultra-fine lines, and to print well on uneven surfaces. It is another object of the present invention to provide a plate making technique that enables the printing plate to have a longer life. Another object of the present invention is to provide a novel water-developable photosensitive resin composition for producing a screen printing plate , a photosensitive film and a plate made using the photosensitive film, in order to realize the plate-making technology. An object of the present invention is to provide a screen printing plate having printability, solvent resistance, water resistance and printing resistance.

[0006]

A screen according to the present invention.
The photosensitive resin composition for producing a printing plate comprises at least (A) a fluorine compound having an ethylenically unsaturated group or a fluorine compound having an ethylenically unsaturated group and a compound having another ethylenically unsaturated group; A photopolymerization initiator, and (C)
Polyvinyl alcohol or polyvinyl alcohol and water
A dispersible polymer, a diazo resin for the component (C) and
And / or a photo-crosslinking agent comprising dichromate,
It is a water developable type used as a liquid. In addition,
Other photosensitive resin compositions for screen printing plate production according to Ming
Is a fluorine-containing compound having at least (A) an ethylenically unsaturated group.
Compounds or fluorine compounds having ethylenically unsaturated groups
And another compound having an ethylenically unsaturated group, and (B)
A photopolymerization initiator and (C) polyvinyl alcohol or poly (C)
Including vinyl alcohol and a water-dispersible polymer,
The polyvinyl alcohol in the component (C) is a styrene
A rupyridinium group and / or a styrylquinolinium group
It has water developability and is used as an aqueous liquid.

As the fluorine compound having an ethylenically unsaturated group in the component (A), for example, a photoactive compound such as a fluorine-containing (meth) acrylate can be used. In particular, trifluoroethyl (meth) acrylate, 2,2,2 3,
3-tetrafluoropropyl (meth) acrylate,
2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate and the like are preferred.

The other compound having an ethylenically unsaturated group which can be used in combination with the fluorine compound is 1 or 2
Those having the above ethylenically unsaturated group, for example, photoactive monomers such as (meth) acrylic monomers, vinyl acetate, (meth) acrylamide, N-methylolacrylamide, and N-alkyl (meth) acrylamide can be used. Particularly, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, dibromoneopentyl glycol (meth) acrylate and the like are preferable.

Next, as the photopolymerization initiator in the component (B), almost all of those used for photopolymerization of the above-mentioned photoactive unsaturated compound can be used. For example, benzoin alkyl ether, Michler's ketone , Ditertiary butyl peroxide, 4'-isopropyl-2-
Under light irradiation, anthraquinone derivatives such as hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, benzyldimethylketal, tribromoacetophenone, or tert-butylanthraquinone, and thioxanthone derivatives such as chlorothioxanthone A substance that easily generates radicals can be used. These photopolymerization initiators are preferably used in an amount of 0.1 to 15% by weight based on the photoactive unsaturated compound of the component (A).

Further, the polyvinyl alcohol in the component (C) includes not only partially or completely saponified polymers of vinyl acetate homopolymers or copolymers of monomers copolymerizable with vinyl acetate, but also The formalization,
Although it may be modified by acetalization such as butyralization, partially saponified polyvinyl alcohol having a vinyl alcohol content of 70 to 99 mol% in terms of a polymerized monomer is particularly preferable.

According to one aspect of the present invention, the polyvinyl alcohol, it contains styryl pyridinium group, a styryl Luchino Li sulfonium group or the like as an optical dimerization component. Here, the styrylpyridinium group and the styrylquinolinium group each have a structural unit represented by the following general formula.

[0012]

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(Wherein, R represents a hydrogen atom, a halogen, a lower alkyl group or an alkoxy group, m represents an integer of 1 to 6, n represents 0 or 1, and A represents Wherein R _{1 in} Chemical Formulas 2 to 4 represents a hydrogen atom, an alkyl group or an aralkyl group, which may include a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond; R ₂ represents a hydrogen atom or a lower alkyl group, B represents a linear or branched alkylene group having 1 to 6 carbon atoms, and X ⁻ represents an anion.)

[0014]

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[0015]

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[0016]

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The content of the styrylpyridinium group and styrylquinolinium group is preferably in the range of 0.1 to 6.0 mol% based on the polymerization monomer of polyvinyl alcohol. If the content is less than 0.1 mol%, the photosensitivity may be insufficient, and if it exceeds 6.0 mol%, the viscosity may increase significantly and the photoconductor may become unusable.

The water-dispersible polymer as the component (C) is intended to improve the water resistance of the cured product of the resin composition, the adhesion to the screen, and impart high resolution to it. Vinyl emulsion, acrylic resin emulsion, ethylene-vinyl acetate resin emulsion, ethylene-acryl resin emulsion, SB
R latex, silicone resin emulsion, vinyl chloride resin emulsion, vinylidene chloride resin emulsion and the like can be used, and polyvinyl acetate emulsion and ethylene-vinyl acetate resin emulsion are particularly preferable. Further, these water-dispersible polymers may contain a styrylpyridinium group, a styrylquinolinium group, or the like as described above as a photodimerizing component.

According to another aspect of the present invention, the photosensitive resin composition according to the present invention contains a diazo resin and / or a dichromate as a photocrosslinking agent for the component (C) .

As a photocrosslinking agent for the component (C),
For example, ammonium bichromate, potassium dichromate,
A diazo resin of an anion complex, such as a dichromate such as sodium dichromate, a sulfate, a phosphate, and a double salt of zinc chloride of p-diazodiphenylamine-paraformaldehyde condensate can be used. These photocrosslinking agents have a total amount of component (A), component (B) and component (C) of 1
It is preferable to use 0.1 to 10 parts by weight with respect to 00 parts by weight. If the amount is less than 0.1 part by weight, a cured product excellent in water resistance cannot be obtained, and it is 10 parts by weight. When the amount exceeds the part, the adhesion to the screen during water development is reduced.

The component (A) and the component (B) are combined in a total amount of 100 parts by weight of the component (C) (resin pure content of 30%).
(In terms of% by weight) in the range of 1 to 200 parts by weight. If the total amount is less than 1 part by weight, sufficient printability cannot be obtained, and if it exceeds 200 parts by weight, the unsaturated compound may separate and precipitate on a film obtained by coating and drying the resin composition. .

The photosensitive resin composition according to the present invention may optionally contain additives usually used in this kind of photosensitive resin composition in addition to the above-mentioned components. Examples include polymerization inhibitors, emulsion stabilizers, coloring agents such as dyes and pigments, defoamers, and small amounts of organic solvents.

[0023]

In making a screen printing plate using the photosensitive resin composition obtained by the above-mentioned formulation, the photosensitive resin composition is converted into an aqueous liquid, for example, by using a bucket or the like to obtain a required film.
It is applied to a screen so as to be thick , dried by warm air to produce a screen photosensitive plate, and the obtained screen photosensitive plate is exposed through a negative film, and then washed and developed with water or the like, and then developed. Only the unexposed portions of the resin composition are removed, and the insolubilized exposed portions remain, so that a screen printing plate is obtained.

As another plate-making means, the photosensitive resin composition is uniformly coated as an aqueous liquid on a plastic film of polycarbonate, polyester, polyethylene, polyvinyl chloride or the like, dried and dried. To produce a photosensitive film having a thickness in the required range, the photosensitive layer of the obtained photosensitive film, water, a mixed solvent of water and isopropyl alcohol and other aqueous organic solvents, or the photosensitive according to the present invention The screen printing plate is obtained by transferring to a screen mesh on which the conductive resin composition has been applied in advance, exposing and developing in the usual manner. This method is called a direct method, and the operation is simpler than a general method of repeatedly applying the same photosensitive resin composition on a screen mesh, and a screen printing plate excellent in smoothness and printing characteristics is obtained. can get. The photosensitive resin composition according to the present invention can also be suitably used in the direct method, and imparts the desired excellent performance to the resulting screen printing plate.

[0025]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In addition, "%" and "part" described below are all based on weight.

Comparative Example 1 A photosensitive agent was used as a photosensitive agent in a mixed resin solution of 100 parts of a 15% aqueous solution of polyvinyl alcohol having a degree of polymerization of 1700 and a saponification degree of 88 mol% and 45 parts of a polyvinyl acetate emulsion (resin concentration: 50%). An aqueous photosensitive solution (photosensitive resin composition) was obtained by dissolving and mixing 1.2 parts of the diazo resin. Using this photosensitive liquid, application and drying (30 to 40 ° C.) were repeated three times with a bucket on a 230-mesh polyester screen to obtain a photosensitive film having a thickness of 15 μm (not including the screen thickness) firmly adhered to the screen. Was.

A positive film for printed wiring was adhered to the photosensitive film of the screen photosensitive plate in vacuum and exposed to a 4 KW ultra-high pressure mercury lamp (manufactured by Oak) from a distance of 1 m for 2 minutes. Then, after removing the positive film, immersing in water at 20 ° C. for 2 minutes, shower-washing with water at 20 ° C. for 2 minutes to wash off unexposed portions, and drying to prepare a screen printing plate having a fine line of 100 μm. did.

Example 1 15 parts of perfluorooctylethyl acrylate, 5 parts of trimethylolpropane triacrylate and 2 parts of benzoin-isobutyl ether were added to 100 parts of a mixed resin solution of the polyvinyl alcohol and polyvinyl acetate emulsions of Comparative Example 1. Was added with stirring, and 1 part of a diazo resin was further dissolved and mixed to obtain an aqueous photosensitive solution. Using this photosensitive liquid, a screen printing plate having a fine line of 100 μm was produced in the same process as in Comparative Example 1.

Using the printing plate of Example 1 and the printing plate of Comparative Example 1, printing was performed on the copper surface of the substrate with Plusfine PER-77B (etching resist, manufactured by Ryo Kagaku Kogyo Co., Ltd.). The printing plate oozed out around 50 shots, whereas the printing plate of Example 1 was 100
There was no blurring or blurring even with shots, and good printability was exhibited.

Example 2 100 parts of a 15% aqueous solution of polyvinyl alcohol having a polymerization degree of 2400 and a saponification degree of 88% and 70 parts of a polyacrylate resin emulsion (resin concentration: 50%) were mixed with 6 parts of benzyldimethyl ketal. And 54 parts of octafluoropentyl acrylate were added with stirring, and 2 parts of a diazo resin were dissolved and mixed to obtain an aqueous photosensitive solution.

Using this photosensitive solution, a screen printing plate was prepared in the same process as in Comparative Example 1. As a result, bleeding was small, and good solvent resistance and water resistance were exhibited.

Example 3 N-methyl-4- (p) was added to polyvinyl alcohol having a polymerization degree of 1700 and a saponification degree of 88 mol% by acetalization.
19 parts of perfluorooctylethyl acrylate obtained by dissolving 3 parts of benzoin ethyl ether in 100 parts of a 10% aqueous solution of a styrylpyridinium group-added polymer obtained by adding 1.3 mol% of -formylstyryl) pyridinium methosulfate, 19 parts of trimethylolpropane A mixed solution of 1 part of triacrylate was added with stirring, and 30 parts of polyvinyl acetate emulsion (solid content: 50%) was further mixed to obtain an aqueous photosensitive solution. Comparative Example 1 using this photosensitive liquid
In the same manner as in the above, a screen printing plate for a solder mask was produced.

Using this printing plate, Plus Fine P
When printing was performed on a substrate with SR-310 (G-46) (solder resist, manufactured by Ryo Kagaku Kogyo Co., Ltd.), the printing plate of the comparative example bleed out around 50 shots.
Bleed at 00 shots, no blurring, showing good printability.

Example 4 100 parts of the photosensitive solution obtained in Example 1 was diluted with 50 parts of water.
Leave overnight to degas. This photosensitive solution is applied to a uniform thickness on a polyester film using a roll coater,
It dried and the photosensitive film was produced. After cutting this photosensitive film according to the size of the screen, the photosensitive layer is pressed from the outside of the screen frame on an undried screen to which the photosensitive liquid has been uniformly applied in advance,
A screen laminate having the photosensitive layer completely adhered was obtained.

After this screen laminate was dried and the polyester film was peeled off, a positive film was adhered and baked in accordance with a conventional method and washed out and developed to obtain a screen printing plate having good performance.

Example 5 100 parts of the photosensitive solution obtained in Example 3 was diluted with 50 parts of water.
When a screen printing plate was prepared by the same steps as in Example 4 , good performance was obtained.

[0037]

As described above, according to the present invention, a novel water developable photosensitive resin composition for producing a screen printing plate ,
Photosensitive films and screen printing plates with good printing suitability, solvent resistance, water resistance and printing resistance made by using them can be obtained. As a result, printing of ultra-fine lines and good printing on uneven surfaces are possible, and the life of the printing plate is improved.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/12 G03F 7/12 Examiner Yoshiko Maeda (56) References JP-A-60-10245 (JP, A) JP-A-59 -107343 (JP, A) JP-A-61-2248 (JP, A) JP 2-48104 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/038 G03F 7/004 G03F 7/021 G03F 7/027 G03F 7/04 G03F 7/12

Claims (4)

(57) [Claims] 1. A fluorine compound having at least (A) an ethylenically unsaturated group, a fluorine compound having an ethylenically unsaturated group, and a compound having another ethylenically unsaturated group, (B) a photopolymerization initiator, (C) polyvinyl alcohol or polyvinyl alcohol and a water-dispersible polymer;
Diazo resin and / or dichromic acid for component (C)
Contains a photo-crosslinking agent consisting of a salt and is used as an aqueous liquid
A water-developable photosensitive resin composition for producing screen printing plates . 2. The method according to claim 1, wherein at least (A) the ethylenically unsaturated group is
Fluorine compounds or fluorine-containing compounds having ethylenically unsaturated groups.
Compounds and other compounds having an ethylenically unsaturated group
And (B) a photopolymerization initiator, and (C) a polyvinyl alcohol.
Water or polyvinyl alcohol and a water-dispersible polymer.
In addition, the polyvinyl alcohol in the component (C)
Is a styrylpyridinium group and / or styrylquinolyl
A water-developable photosensitive resin composition for producing a screen printing plate , having an aluminum group and used as an aqueous liquid . 3. A photosensitive film for producing a screen printing plate, comprising applying the photosensitive resin composition according to claim 1 on a plastic film and drying. 4. The method of claim 1 or claim 2 photosensitive resin composition according or claim 3 photosensitive film screen printing plate made by using the description.