JP2000056461A - Antitackifying layer composition and photosensitive resin laminate using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antitackifying layer composition superior in photosensitive characteristics, especially, surface sensitivity by incorporating at least a reactive monomer having water solubility of a specified value or more, and a photoinitiator in a water-soluble polymer. SOLUTION: This antitackifying layer composition contains at least the reactive monomer having water-solubility of >=12% and the photoinitiator in the water-soluble polymer, preferably, having hydroxyl groups in the molecule, embodied by polyvinylalcohol and its derivatives, cellulose derivatives, water-soluble butyral, a copolymer with a compound having a hydroxyl group and the like, and mainly, preferably, saponified products of the ester compounds of polyvinylalcohols. The saponification degree is not limited so far as it is soluble in an aqueous solvent, but it is preferred to be >=70 weight %, especially, >=98 weight %.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an anti-adhesion layer composition and a photosensitive resin laminate using the same. More specifically, when used for an anti-adhesion layer of a photosensitive resin which can be developed with an aqueous system, a photosensitive resin laminate having excellent photosensitive characteristics, particularly excellent surface sensitivity, can be obtained.

[0002]

2. Description of the Related Art Usually, a photosensitive resin plate is obtained by vacuum-contacting the plate surface of a photosensitive resin layer using a negative or positive film original film, and irradiating an actinic ray to partially remove the photosensitive resin layer. After exposure and curing, a method is used in which the original film is peeled off and the unexposed and uncured portions are developed and removed to produce a printing relief. In this plate making method,
The most commonly used method for making the original film of a negative or positive film easily peelable from the surface of the photosensitive resin layer is to provide a thin layer of a polymer with low adhesiveness on the surface of the photosensitive resin layer. Have been. For example, JP-A-51-49803, JP-A-54-68224
JP, JP-A-58-110941, JP-A-57-10741
-208556, JP-A-2-113254, JP-A-4-130325, JP-A-5-727
40, JP-A-5-232708, JP-A-5-232708
-297594, JP-A-5-313375, JP-A-6-324497, JP-A-9-717
No. 65, JP-A-9-138499, JP-A-9
-274322.

[0003] These anti-adhesion layer compositions are used for the purpose of mainly peeling the negative or positive film from the surface of the photosensitive resin layer of the original film, in addition to the photosensitive resin layer. It is also intended to prevent deterioration of characteristics over time. In particular, when the photosensitive resin is of an aqueous development type, polyvinyl alcohol having high oxygen barrier properties is mainly used as the water-soluble polymer of the anti-adhesion layer. However, only the anti-adhesion layer composition using the water-soluble polymer made of polyvinyl alcohol does not sufficiently satisfy the photosensitive characteristics of the photosensitive resin, particularly the characteristics of the surface sensitivity.

[0004]

Therefore, in the present invention, the thin layer of the anti-adhesion layer laminated on the photosensitive resin laminate is non-adhesive, and furthermore, the photosensitive characteristics of the photosensitive resin, especially the characteristics of the surface sensitivity, are sufficiently improved. It is an object to obtain an anti-adhesion layer composition that satisfies the conditions.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on the composition of the anti-adhesion layer and the photosensitive resin laminate using the same, and as a result, finally completed the present invention. It has arrived. That is, the present invention uses an anti-adhesion layer composition characterized in that a water-soluble polymer contains at least a reactive monomer having a solubility in water of 12% or more and a photoinitiator, and the adhesive layer is used. It is a photosensitive resin laminate.

As the water-soluble polymer of the anti-adhesion layer composition of the present invention, those having a hydroxyl group in the molecule are preferable, for example, polyvinyl alcohol and its derivatives, cellulose, water-soluble butyral, and compounds having a hydroxyl group in the molecule. Copolymers and the like, but the anti-adhesion layer composition of the present invention is preferably one obtained mainly by saponifying an ester compound of polyvinyl alcohol,
The saponification degree may be 70% by weight as long as it is soluble in an aqueous solvent.
Or more, and particularly preferably 98% or more.

[0007] The solubility in water in the present invention means the compatibility of the reactive monomer with water. As a measuring method, the reactive monomer is dropped into 100 g of stirring water, and after stirring, stirring is carried out. This is a method in which the solubility in water is determined by stopping and visually determining the presence or absence of phase separation between water and the reactive monomer after 24 hours. If the solubility in water is low, phase separation occurs. The solubility of the reactive monomer in water in the present invention is 12% or more, preferably 20%.
More preferably, 30% or more is desirable. 12 solubility in water
%, Phase separation is unfavorable if used as it is, since the coating property on the cover film becomes poor (repelling).

Specifically, the reactive monomer having a solubility in water of 12% or more used in the present invention includes an anionic group such as a carboxyl group, a phosphate group and a sulfonic acid group, and an amino group in a molecular chain. And ethylenically unsaturated compounds containing a hydrophilic group such as a cationic group such as an imino group, a quaternary ammonium salt, or a tertiary sulfonium salt; a nonionic group such as a hydroxyl group, an ether group or an amide group;
Acrylic acid, (meth) acrylates, polyacrylates (monovalent, divalent, trivalent salts with metal ions),
Propenamide, 2-acrylamido-2-methylpropanesulfonic acid, diethyl glycol (meth) acrylate ethoxylate tetraethylene glycol (meth) acrylate, 2-methoxyethyl (meth) acrylate, glycerin / monoallyl ether, diallyldimethyl Ammonium chloride and the like are mentioned as examples, but are not limited to these. These may be used alone or in combination of two or more.

The content of the reactive monomer having a solubility in water of 12% or more is 0.1% with respect to the water-soluble polymer.
2 to 20% by weight, preferably 0.5 to 15% by weight, particularly 1 to 10% by weight is desirable. If it is less than 0.2% by weight, no improvement in surface sensitivity can be expected. Although the sensitivity is improved, the coatability is poor in a thin layer coating for obtaining a cover film having an anti-adhesion layer, which is not preferable.

The photoinitiator used in the present invention includes, for example, benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzoin alkyl ketals, anthraquinones, and thioxanthones. It can be used after dissolution or already in liquid form, and it is particularly preferable to use a liquid photoinitiator in advance. The compounding amount of the photoinitiator is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

The cover film having the anti-adhesion layer composition of the present invention includes polyethylene terephthalate film, polyethylene film, polypropylene film,
A 0.1 to 10 μm thin layer of the anti-adhesion layer composition is provided on a plastic resin film such as a polystyrene film, and the cover film has dimensional stability and heat resistance,
From the viewpoint of mechanical properties, a polyethylene terephthalate film is preferable, and further, a surface roughness Ra = 0.01 to 5 μm
It is preferable to use an optically etched or sand-matted mat film. The thickness of the matte film is preferably 50 to 175 μm.

The photosensitive resin composition used in the present invention includes: (1) a core phase mainly composed of a non-crosslinkable hydrophobic polymer (A) having a glass transition temperature of 5 ° C. or lower; From a shell phase mainly composed of a hydrophilic polymer, and (3) a matrix phase mainly composed of a mixture of a hydrophobic polymer (B) incompatible with the hydrophobic polymer (A) and a non-gaseous ethylenically unsaturated compound. It is a photosensitive resin composition which is constituted and further contains a photopolymerization initiator. Specifically, the photosensitive resin compositions disclosed in JP-A-3-72353, JP-A-3-171139, JP-A-7-168358 and the like can be used.

The photosensitive resin laminate for a printing plate of the present invention comprises:
At least an adhesive layer, a photosensitive resin layer, an anti-adhesion layer of the present invention and a cover film are formed on a support, and a method for producing the anti-adhesion layer is applied to the cover film in advance, and the adhesive layer is applied to the support in advance. After preparing the applied material, a method of laminating both layer materials around the photosensitive resin composition to a desired thickness and width by a general method such as hot pressing, cast molding, calendering, coating method and the like is adopted. be able to.

The ultraviolet light used for curing the photosensitive resin master using the photosensitive resin laminate obtained by the above method has a wavelength of 150 to 500 mμ, particularly 300 to 40 μm.
A light source having a wavelength range of 0 μm is effective, and the light source used is a low-pressure mercury lamp, a high-pressure mercury lamp, a carbon arc lamp,
Ultraviolet fluorescent lamps, chemical lamps, xenon lamps, zirconium lamps, zirconium lamps and the like are desirable. The printing plate of the present invention is prepared by applying a negative film having a transparent image to the photosensitive resin original plate using the light source, vacuum-contacting the film, irradiating the image with ultraviolet light, and developing a non-image portion that is not exposed with a developing solution. Obtained by using

As the developer, water having a pH of from 5 to 9 including water for daily use can be used, and an alkaline compound such as sodium hydroxide and sodium carbonate, a surfactant, a water-soluble organic solvent and the like can be used as a main component of the water. May be contained. As the above surfactant, sodium alkylnaphthalenesulfonate, sodium alkylbenzenesulfonate, etc. are optimal, and in addition, anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants are used. it can. The developer is preferably used at a temperature of 25 ° C to 50 ° C.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, in order to obtain the anti-adhesion layer composition of the present invention on the cover film, polyvinyl alcohol is used in an amount of 1 to 15% by weight, preferably 2 to 5% by weight, and a hydrophilic group is further added. The content of the ethylenically unsaturated compound is 0.2 to 20% by weight, preferably 1 to 10% by weight, based on the pure content of polyvinyl alcohol, and the photoinitiator is 0.1 to 1% by weight.
It is desirable to contain 0% by weight, preferably 0.5 to 5% by weight. The thickness of the anti-adhesion layer comprising the anti-adhesion layer composition of the present invention is 0.1 to 10 μm after drying, preferably 1.5 to 10 μm.
５5 μm.

Next, as the photosensitive resin composition in the photosensitive resin laminate using the anti-adhesion layer of the present invention, any photosensitive resin composition having a photosensitive resin layer developable with water or an aqueous medium can be applied. For example, Japanese Patent Application Laid-Open Nos.
No. 0-173055, JP-A-63-8648, JP-A-2-175702, JP-A-1-108542, JP-A-4-3162, JP-A-1-219735, JP-A-1-31192, JP-A-2-305805, JP-A-3-228060, JP-A-3-72353, JP-A-3-171139, JP-A-7-168358, and the like include photosensitive resin compositions. An ordinary method is used for the production of the conductive resin laminate, and a usual method can also be used for ultraviolet exposure and development processing in plate making of a photosensitive printing plate.

[0018]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”.
The evaluation method in the examples is based on the method described below. (Photosensitivity) (1) Surface sensitivity (Γ): The photosensitive resin surface is exposed and developed using an inspection negative film (manufactured by Dainippon Screen), and the number of steps of the inspection negative film is measured to determine the surface feeling. did. Γ = maximum number of steps after exposure / development−number of complete curing steps (smaller difference means higher surface sensitivity.) (2) Halftone dot retention (%): 150 in the same evaluation as above
The state of retention of 1 pi 2% of halftone dots was observed and evaluated by%. 1
00% indicates that the halftone dot is retained without being scraped.

Reference Example 1 <Production of hydrophilic polymer> 119.0 parts of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.)
62.0 parts of dimethylolpropionic acid (Yoshimichi Fujii),
29.0 parts of polytetramethylene glycol (G-850, manufactured by Hodogaya Chemical Co., Ltd.) and di-n-dilaurate
5.0 parts of butyltin was dissolved in 300 parts of tetrahydrofuran, and this solution was placed in a 1-liter flask with a stirrer, heated to 65 ° C. while stirring, and the reaction was continued for 2 hours. Acrylonitrile-butadiene oligomer having a terminal amino group in a separate container (Hycar AT
BN 1300 × 16, manufactured by Ube Industries, Ltd.) 184.
A solution prepared by dissolving 0 parts in 270 parts of tetrahydrofuran is
It was added to the above one-liter flask with stirring at room temperature. Tetrahydrofuran was distilled off from the polymer solution under reduced pressure and dried under reduced pressure to obtain a polymer having a number average molecular weight of 6,700. Next, 100 parts of this polymer was dissolved in 100 parts of methyl ethyl ketone, and 4.8 parts of lithium hydroxide were added thereto.
A solution of 100 parts of methanol in 100 parts was added with stirring at room temperature, and the mixture was further stirred for 30 minutes to obtain a hydrophilic polymer.

Reference Example 2 <Production of photosensitive resin composition> Nitrile-butadiene rubber (acrylonitrile 35%) (J) was used as the hydrophobic polymer (A) in 11 parts of the hydrophilic polymer obtained in Reference Example 1 above.
SR N230SH, manufactured by Nippon Synthetic Rubber Co., Ltd.) 38 parts,
Butadiene rubber (JSR) as the hydrophobic polymer (B)
BR02L, 15 parts by Nippon Synthetic Rubber Co., Ltd.), butadiene oligoacrylate (PB-A Kyoeisha Yushi Co., Ltd.)
26 parts, 1,6-hexanediol dimethacrylate 10 parts, benzyl dimethyl ketal 1 as a photoinitiator
And 0.5 part of hydroquinone monomethyl ether as a thermal polymerization inhibitor were kneaded together with 40 parts of toluene and 10 parts of water at 105 ° C. using a heating kneader, and then toluene and water were distilled off under reduced pressure. A film obtained by coating the obtained photosensitive resin composition with a polyester-based adhesive on polyethylene terephthalate having a thickness of 125 μm, and a mat film having a thin layer comprising the anti-adhesion layer composition of the present invention were heat-pressed. 105 ° C, 1
By heating and pressing at a pressure of 00 kg / cm ² for 1 minute, a 2.8 mm thick photosensitive resin laminate was prepared.

Example 1 To 95 parts of pure water, 2.5 parts of cocenol AH-26 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 97 to 99%) was added, and the mixture was stirred at 90 ° C. for 1 hour. Next, after cooling to room temperature, 2.5 parts of 1,2-propylene glycol, 27 parts of diallyldimethylammonium chloride (DADMAC) (manufactured by Daiso Co., Ltd., 65% pure), Dulcure-1
173 (manufactured by MERK) and 0.03 part of Epan 740 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were slowly added under stirring, and the mixture was further stirred for 30 minutes. Next, this solution was reverse-coated at a rate of 6 m / min on a 95 mm thick chemical mat film (TC5002 manufactured by Toyo Cloth) at 105 ° C. × 3.
After drying for a minute, an anti-adhesion layer having a thickness of 2 μm was obtained.

Next, 2.8 mm
After creating a thick photosensitive resin laminate (original plate), peel off the chemical mat film on the original plate, peel off the inspection negative film, and place the inspection negative film on top of it under vacuum and close contact with a high-pressure mercury lamp (Dainippon Screen Co., Ltd.) 25W / m
Exposure at 2. After removing the inspection negative film, the film was immersed in a 40 ° C. aqueous developing solution containing 2 parts by weight of sodium butylnaphthalenesulfonate (Perex NB-L, manufactured by Kao Corporation) and developed with a brush for 15 minutes to give a relief having an image. I got When the photosensitive characteristics were evaluated using this relief,
Δ in the case of 10 minutes of front exposure from the inspection negative film is 1.
5 stages, 100% dot retention of 1501 pi 2%
Met. This evaluation tendency showed the same result for the sample aged for one month.

Example 2 In the same manner as in Example 1, except that 18 parts of glycerin monoallyl ether (manufactured by Daiso Co., purity: 99% or more) was added instead of DADMAC,
As a result of evaluating the anti-adhesion layer, the photosensitive resin laminate, and the plate making, Δ was two steps, and the dot retention of 1501 pi 2% was 100%. The same applies to the evaluation over one month.

Example 3 An anti-adhesion layer, a photosensitive resin laminate and a plate making evaluation were performed in the same manner as in Example 1 except that 0.05 parts of methacrylic acid was added instead of DADMAC. As a result, Γ was 1.3 steps and the dot retention of 1501 pi 2% was 100%. The same applies to the evaluation over one month.

Example 4 The procedure of Example 1 was repeated, except that 0.05 parts of 2-acrylamido-2-methylpropanesulfonic acid was added instead of DADMAC.
As a result of evaluation of the photosensitive resin laminate and plate making, Δ was one step and the dot retention of 1501 pi 2% was 100%. The same applies to the evaluation over one month.

Example 5 An anti-adhesion layer, a photosensitive resin laminate, and a plate making were prepared in the same manner as in Example 1 except that 0.05 parts of dimethylaminoethyl acrylate was added instead of DADMAC. As a result of evaluation, Δ was 150 at 1.3 steps.
The dot retention of 1 pi 2% was 100%. The same applies to the evaluation over one month.

Comparative Example 1 In Example 1, except that DADMAC was not added,
The anti-adhesion layer, the photosensitive resin laminate, and the plate making evaluation were performed in the same manner as in Example 1. As a result, Δ was 3.5 steps, and 1501 pi 2
% Dot retention was 50%.

The results of Examples 1 to 5 and Comparative Example 1 are shown in Table 1.

[Table 1]

[0029]

The photosensitive resin laminate obtained by laminating the anti-adhesion layer composition of the present invention has improved photocurability due to light irradiation on the photosensitive resin surface layer, and as a result, the brush resistance during development is improved. The improvement improves the photosensitive characteristics, particularly the retention of halftone dots, and makes it possible to obtain a clear printed matter having excellent print reproducibility, which greatly contributes to the industry.

Claims (3)

[Claims] 1. An anti-adhesion layer composition comprising a water-soluble polymer containing at least a reactive monomer having a solubility in water of at least 12% and a photoinitiator. 2. The anti-adhesion layer composition according to claim 1, wherein the content of the reactive monomer having a solubility in water of 12% or more is 0.2 to 20% by weight based on the water-soluble polymer. 3. A photosensitive resin laminate having at least a support, a photosensitive resin layer, an anti-adhesion layer and a cover film, wherein the anti-adhesion layer is the anti-adhesion layer composition according to claim 1. Photosensitive resin laminate.