JP2930153B2 - 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 fine powder of a polymer comprising a fluorine-containing alkylene group or a polymer containing a fluorine-containing alkyl group in a side chain, or at least one of these fine particles with water and / or a solvent. A dispersion, and (B) polyvinyl alcohol or polyvinyl alcohol
Alcohol and a water-dispersible polymer, and (C) one or more
A fluorine compound having an ethylenically unsaturated group on the above ,
(D) a photopolymerization initiator; and (E) a diamine for the component (B).
A photo-crosslinking agent comprising an azo resin and / or a dichromate
And used as an aqueous liquid . In addition,
Other photosensitive resin compositions for screen printing plate production according to Ming
Is at least (A) a fluorine-containing alkylene group.
Polymer or an alkyl group containing fluorine in the side chain.
Polymer fine powder or at least one of these
And / or (B) styrylpyrene
Having a lydinium group and / or a styrylquinolinium group
Polyvinyl alcohol or the polyvinyl alcohol and
And a water-dispersible polymer, and (C) one or more ethylenic compounds
A fluorine compound having an unsaturated group, and (D) a photopolymerization initiator
And used as an aqueous liquid.

As the polymer comprising a fluorine-containing alkylene group or the polymer having a fluorine-containing alkyl group in the side chain in the component (A), for example, a fluoroethylene resin, a difluoroethylene resin, a trifluoride ethylene resin,
Preferred are a fluoroethylene resin, a tetrafluoroethylene-ethylene copolymer resin, a tetrafluoroethylene-6-propylene copolymer resin, a perfluoroalkoxy resin, a vinylidene fluoride resin, ethylene trifluoride chloride and the like. These may be used alone or in combination. In addition, the polymer may be used directly as a fine powder in the production of the composition, or may be in a state of a water and / or solvent dispersion in advance.

The component (A) is preferably used in a range of 1 to 50 parts by weight as a pure component based on 100 parts by weight of the component (B) (converted to a resin pure component of 30% by weight). If the amount used is less than 1 part by weight, sufficient printability cannot be obtained,
If it exceeds 50 parts by weight, the adhesion to the screen after plate making is reduced.

The polyvinyl alcohol in the component (B) includes not only partially or completely saponified products of a homopolymer of vinyl acetate or a copolymer of a monomer copolymerizable with vinyl acetate, but also those of formaldehyde. Although it may be modified by acetalization such as hydration, butyralization, etc., partially saponified polyvinyl alcohol having a vinyl alcohol content of 70 to 99 mol% in terms of a polymerizable 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.

[0011]

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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.)

[0013]

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[0014]

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[0015]

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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 in the component (B) is used to improve the water resistance of the cured product of the resin composition and the adhesion to the screen and to give it a high resolution. 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. These water-dispersible polymers may contain a styrylpyridinium group, a styrylquinolinium group, or the like as described above as a photodimerization component.

The ethylenically unsaturated group in component (C)
As the fluorine compound, for example, a photoactive compound such as fluorine-containing (meth) acrylate can be used, and in particular, trifluoroethyl (meth) acrylate, 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 component (C) contains
As the ethylenically unsaturated compound, for example, a photoactive monomer such as (meth) acrylic monomer, vinyl acetate, (meth) acrylamide, N-methylolacrylamide, and N-alkyl (meth) acrylamide is used in combination.
Possible , especially pentaerythritol tetra (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, dibromoneopentyl glycol (meth) acrylate and the like are preferred.

Next, as the photopolymerization initiator in the component (D), 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 the range of 0.1 to 15% by weight based on the photoactive unsaturated compound of the component (C).

The component (C) and the component (D) are used as the total amount of the component (B) of polyvinyl alcohol or
1 to 200 parts by weight per 100 parts by weight of the polyvinyl alcohol and the water-dispersible polymer (converted to a resin pure content of 30% by weight)
It is preferred to use in the range of 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. .

According to another aspect of the present invention, the photosensitive resin composition according to the present invention further comprises a diazo resin and / or a dichromate as the (E) photocrosslinking agent for the component (B). You may go out.

As the photocrosslinking agent in the component (E) ,
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 ingredients
(E) is preferably used in a range of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B), and the amount used is less than 0.1 part by weight. In such a case, a cured product having excellent water resistance cannot be obtained, and if it exceeds 10 parts by weight, the adhesion to a screen during water development decreases.

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

[0024]

When making a screen printing plate using the photosensitive resin composition obtained by the above-mentioned formulation, the photosensitive resin composition is converted to an aqueous liquid, for example, by using a bucket or the like to have a film thickness of usually 1 to 1000 μm. Apply to the screen so that
Drying with hot air to produce a screen photosensitive plate, and exposing the obtained screen photosensitive plate through a negative film,
Subsequently, by washing and developing with water or the like, only the unexposed portions of the resin composition are removed and the insolubilized exposed portions remain, and a screen printing plate is obtained.

As another plate making means, the photosensitive resin composition is uniformly applied as an aqueous liquid on a plastic film of polycarbonate, polyester, polyethylene, polyvinyl chloride or the like, dried and dried. A photosensitive film having a thickness of preferably in the range of 1 to 1000 μm is prepared, and the photosensitive layer of the obtained photosensitive film is treated with water, a mixed solvent of water and isopropyl alcohol or another aqueous organic solvent, or the present invention. Is transferred to a screen mesh on which the photosensitive resin composition according to the above is applied in advance, exposed and developed in a conventional manner to obtain a screen printing plate. This method is called the direct method,
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 can be obtained. 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.

[0026]

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 vacuum-adhered to the photosensitive film of the screen photosensitive plate, 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 1 100 parts of a 15% aqueous solution of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 88 mol% was added to polyfluorocarbon TFE F.
-104 (tetrafluoroethylene resin, manufactured by Daikin Industries, Ltd.)
And dispersed with a ball mill or the like, and then mixed with 45 parts of a polyvinyl acetate emulsion liquid (resin concentration: 50%) ,
Perfluorooctyl was added to 100 parts of the obtained mixed resin liquid.
15 parts of ethyl acrylate, trimethylol proppant
5 parts of acrylate and benzoin-isobutylate
Add 2 parts of the mixture with stirring and add diazo resin
One part was 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.

The printing plate of Example 1 and the printing of Comparative Example 1
Using the plate, plus fine PER-77B (etch
Printing on the copper surface of the substrate with
As a result, the printing plate of Example 1 was replaced with the printing plate of Comparative Example 1.
Compared to less bleeding, a good good solvent resistance and water resistance
Indicated.

[0031]

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.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/04 G03F 7/04 7/12 7/12 Examiner Yoshiko Maeda (56) References JP-A-60-10245 (JP, A) JP-A-3-75653 (JP, A) JP-A-62-250440 (JP, A) JP-A-57-177143 (JP, A) JP-A-4-344647 (JP, A) JP-A-4 −369652 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/038 G03F 7/004 G03F 7/021 G03F 7/027 G03F 7/032 G03F 7/04 G03F 7 / 12

Claims (4)

(57) [Claims] 1. A fine powder of a polymer comprising at least (A) a fluorine-containing alkylene group or a polymer containing a fluorine-containing alkyl group in a side chain, or a dispersion of at least one of these in water and / or a solvent. , (B)
Polyvinyl alcohol or polyvinyl alcohol and water
A dispersible polymer, and (C) one or more ethylenically unsaturated
A fluorine compound having a sum group , (D) a photopolymerization initiator,
(E) a diazo resin and / or heavy duty component (B)
Contains photo-crosslinking agent consisting of romate and used as aqueous liquid
A photosensitive resin composition for producing a screen printing plate . 2. An alkylene containing at least (A) fluorine.
Polymer consisting of an alkyl group or an alkyl group containing fluorine
Fine powder of a polymer containing
One of which is a water and / or solvent dispersion, and (B)
Styrylpyridinium group and / or styrylquinolinium
Polyvinyl alcohol having a rubber group or the polyvinyl alcohol
Alcohol and a water-dispersible polymer, and (C) one or more
A fluorine compound having an ethylenically unsaturated group, and (D) light
A photosensitive resin composition for producing a screen printing plate , comprising a polymerization initiator and used as an aqueous liquid . 3. The photosensitive resin according to claim 1 or 2.
Apply the composition on a plastic film and dry
A photosensitive film for producing screen printing plates. 4. The photosensitive resin according to claim 1 or claim 2.
The composition is manufactured using the photosensitive film according to claim 3.
Plated screen printing plate.