JPH1124276A - Photosensitive resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photosensitive resin laminate having both excellent adhesion to a different kind of material (elasticity reinforcing agent) and light fastness and adapted to a flexographic printing improved in plate making operation efficiency, environmental load and sensitivity to storage place for plates. SOLUTION: This photosensitive resin laminate is obtained by laminating at least a releasing layer and an adhesive layer, and the photosensitive resin layer in this order on a support and this adhesive layer is composed of an adhesive composition comprising a thermoplastic elastomer and a polyester copolymer, in this photosensitive resin laminate comprises an elasticity reinforcing material layer and an adhesive layer and the photosensitive resin layer the adhesive layer is composed of the adhesive composition containing the thermoplastic elastomer and the polyester copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based developable photosensitive resin laminate. More particularly, the present invention relates to a water-based developable photosensitive resin laminate comprising an adhesive composition having excellent adhesion to different materials (elastic reinforcing materials) and light resistance.

[0002]

2. Description of the Related Art Usually, a photosensitive resin laminate for flexographic printing comprises a support on which a photosensitive resin layer having a suitable elasticity is laminated, such as a film, an envelope, a label, or the like.
It is used as a relief material for printing on materials to be printed such as paper bags, heavy bags, wrapping paper, corrugated balls, and paper containers.

[0003] In particular, in the case of printing on heavy bags, wrapping paper, corrugated balls, etc., the photosensitive resin layer is generally thickened because the surface smoothness of the material to be printed is poor and the followability of ink is poor. For example, for plate materials such as heavy bags and corrugated balls, usually 4 mm or more,
Most are used as a plate thickness of about 7 mm. But,
In order to obtain the plate thickness only with the photosensitive resin layer, there are many problems such as economical production, fatigue of the developing solution at the time of development, and the like. The remaining 4 mm is supplied as a printing plate material having a total thickness of about 7 mm by bonding a different kind of material to the photosensitive resin layer.

On the other hand, a photosensitive flexographic plate material which can be developed with a halogen-based organic solvent has conventionally been used. The photosensitive resin plate material is a laminate mainly composed of a layer of a photosensitive elastomer composition. When the laminate is used to adhere to a different kind of material, generally, after removing the support, an ultraviolet exposing machine is used. And a method of dissolving or swelling the layer of the photosensitive elastomer composition with an organic solvent to adhere to a different kind of material. At this time, the dissolved photosensitive elastomer layer functions as an adhesive layer, but as a rubber component of the photosensitive elastomer layer, it has excellent physical adhesiveness due to its good adhesive strength and cohesive strength, and is different from a different material. There is almost no problem such as delamination at the interface of. Furthermore, even after the photosensitive resin comprising the photosensitive elastomer composition and the dissimilar material are adhered to each other, a part of the organic solvent may be partially exposed to the photosensitive elastomer layer at the time of development processing for producing a relief (printing plate) using an organic solvent. By soaking, the adhesiveness is further improved.

Meanwhile, in accordance with recent environmental regulations, a photosensitive flexographic printing plate material which can be developed with water instead of the above-described flexographic printing plate material which can be developed with a halogen-based organic solvent, for example, Japanese Patent Application Laid-Open Nos. Showa 60-173055
JP-A-63-8648, JP-A-1-108542
JP-A-2-175702, JP-A-4-3162
JP-A-1-219735, JP-A-2-30580
5, JP-A-3-228060, JP-A-6-2896
No. 10, plate materials using a photosensitive resin composition disclosed in JP-A-7-114180 and the like are being used.

In the case of these photosensitive flexographic printing plate materials which can be developed with an aqueous system, the structure of the photosensitive resin composition has a phase separation structure or a structure similar thereto in order to enable development with an aqueous developing solution. These, when trying to adhere to a different material in the same manner using the organic solvent using a water-based developable photosensitive flexographic plate material, the solubility of the photosensitive resin composition in the organic solvent and Inadequate swelling,
Even if dissolved and swollen, the photosensitive resin composition has a phase-separated structure, so there is no adhesiveness and cohesive force,
Or, because of insufficient properties, sufficient adhesion between the photosensitive resin and the dissimilar material could not be obtained, and the material could not withstand practical use.

Therefore, as a method of bonding such a photosensitive flexographic plate material to a different material (elastic reinforcing material),
A method using a double-sided adhesive tape, a method using an adhesive, a method in which a photocurable composition is interposed between a photosensitive flexographic plate and a rubber sheet material, and the photosensitive flexographic plate is bonded by exposure (Japanese Patent Publication No. No. 16997), a method of removing the support, exposing it to the back, and bonding with a good solvent (Japanese Patent Publication No. 4-68620), and a method of treating the surface to be bonded with an organic active halogen-containing compound and bonding it (Japanese Patent Publication No. Hei 5-5). -5
No. 6374), a photosensitive flexographic plate in which an adhesive composition comprising a block copolymer and a reactive monomer is provided below a water-based developable photosensitive resin (JP-A-8-29736).
No. 9) is disclosed.

[0008] However, the above method is not sufficient in adhesiveness, and particularly when a different material whose surface is polished is used, it does not adhere sufficiently to the polished surface, so that it is easy to peel off during printing and is expensive. In the method, drying is required to obtain adhesiveness, a long time is required, a solvent in the adhesive is evaporated, and a curl is generated due to evaporation of the solvent. Defects such as adhesion only to the photosensitive resin and not to the photosensitive resin, or vice versa, so that many layers need to be coated, which changes the thickness and affects printability. There is. In the method, photocuring adhesion may not be sufficient depending on the characteristics of the photosensitive flexographic plate, which is not common. In the method, the substrate is removed, exposed to air, and then exposed to light, thereby insufficiently polymerizing the photosensitive resin plate, improving the solubility in an organic solvent, and bonding the film. When it is applied to a printing plate, there is a disadvantage that if it is polymerized, the solubility is further reduced and adhesiveness cannot be obtained. According to the method, when an organic active halogen-containing compound is applied to a flexographic printing plate that can be developed with an aqueous system, adhesiveness is obtained, but the stability of the compound is poor. In the method, although a certain degree of adhesiveness can be obtained by providing a single adhesive composition similar to the photosensitive resin composition, the place where the printing plate is placed because the adhesive composition is inherently easily deteriorated by light and has poor light resistance. It is limited, and furthermore, there is a possibility that the adhesiveness may decrease over time.

[0009]

Accordingly, the present invention has been made in view of such circumstances, and is particularly effective when applied to a water-based developable flexographic printing plate. It is an object of the present invention to provide a photosensitive resin laminate that is easy in adhesive workability and excellent in adhesiveness and light resistance.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that an adhesive composition comprising a thermoplastic elastomer and a copolymerized polyester resin is used as a support and a photosensitive resin. The present inventors have found that a photosensitive resin laminate obtained by interposing and laminating / integrating between them has excellent adhesiveness and light resistance, and has finally completed the present invention. That is, the present invention provides (1) a support, a release layer,
A photosensitive resin laminate comprising an adhesive layer and a photosensitive resin layer, wherein the adhesive layer is an adhesive composition containing a thermoplastic elastomer and a copolymerized polyester resin. And (2) a photosensitive resin laminate comprising an elastic reinforcing material layer, an adhesive layer, and a photosensitive resin layer in order from the lower layer, wherein the adhesive layer is a thermoplastic elastomer.
And a photosensitive resin laminate comprising an adhesive composition containing a copolymerized polyester resin.

In the present invention, the term "elastic reinforcing material" refers to an elastic reinforcing material used for improving printability or obtaining economical efficiency due to poor surface smoothness of a printing material and poor ink followability. The material is not particularly limited, and examples thereof include a rubber sheet material such as raw rubber, vulcanized rubber and synthetic rubber, a soft salt sheet material, and a porous cushion material such as urethane foam. .

In the present invention, the term "adhesiveness" means that when a photosensitive flexographic printing plate material and a dissimilar material are adhered by any method and then developed using a developing machine for producing a relief, a rotary brush or a press-fit is used. Characteristics that are not affected by pressure and are not separated between the photosensitive flexographic plate material and dissimilar materials. Also, when a certain number of copies are printed using this relief, they do not peel and do not affect printability. The adhesive composition does not deteriorate even when exposed to ultraviolet light, and does not cause any problem in adhesiveness (light resistance). Characteristics.

Next, the adhesive layer in the present invention contains a thermoplastic elastomer and a copolyester resin. First, as the thermoplastic elastomer, for example, polystyrene polymer block, polyethylene terephthalate, polytriethylene Polyester polymer blocks represented by methylene terephthalate, polytetramethylene terephthalate, etc .; conjugated diene compound blocks represented by polybutadiene, polyisoprene, polychloroprene, etc .; and aliphatic polyesters such as polycaprolactone. Elastomers such as coalesced blocks, polymer blocks of aliphatic polyethers such as poly (diethylene glycol, triethylene glycol, and tetraethylene glycol), ethylene / propylene copolymer blocks, and ethylene / acrylic acid copolymer blocks Block copolymers and the like, and furthermore, styrene-butadiene random copolymers composed of styrene and butadiene monomer units, acrylonitrile-butadiene random copolymers composed of acrylonitrile and butadiene monomer units, and the like. Elastomer-like random copolymers and the like can be mentioned. Other examples include polybutadiene, polyisoprene, natural polyisoprene, and the like, and these may be used alone or in combination.

The structure of the block copolymer comprising the hard segment A and the soft segment B is not particularly limited. For example, a diblock of the general formula AB, a triblock of ABA, (A -B) n multi-blocks, (A-
B) n · X star type block (n is an integer of 1 to 10)
Among these, in the present invention, a polystyrene block copolymer having a styrene content of 15% or more is preferable, and specifically, styrene.
Butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer, hydrogenated styrene /
Butadiene / styrene block copolymer, styrene / ethylene / butylene / styrene block copolymer, styrene / ethylene / propylene / styrene block copolymer, epoxy-modified styrene / butadiene / styrene block copolymer, and the like. It is preferable to use them alone or in combination.

[0015] The other component of the adhesive layer, a copolyester, is blended in order to improve the adhesiveness and light resistance of the adhesive composition. It is blended in order to provide flexibility that can be easily wound around the plate cylinder. In the present invention, the glass transition temperature is 60 ° C. or less, preferably 3 ° C.
A copolymer polyester resin having a temperature of 0 ° C. or lower, particularly preferably 20 ° C. or lower is used, and the acid component is mainly 70 to 100% by mole of an aromatic dicarboxylic acid, preferably 80 to 100% by mole, and the other dicarboxylic acid is 0 to 30% by mole. Mol%, 25 to 100 mol% of an alkylene glycol having 3 to 10 carbon atoms in the main chain of the glycol component has a glass transition temperature of 60 ° C.
The following copolymerized polyester resin (A) is used, and more preferably, a curing agent (B) capable of reacting therewith is used as (A)
/ (B) = 95/5 to 60/40 (weight ratio).

Examples of the aromatic dicarboxylic acid constituting the copolymerized polyester resin (A) include isophthalic acid, orthophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid. Of these, isophthalic acid and orthophthalic acid are exemplified. It is preferable to use them alone or in combination from the viewpoint of light resistance.

Other dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclohexane. Examples thereof include alicyclic dicarboxylic acids such as dicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. If necessary, polycarboxylic acids such as trimellitic anhydride and pyromellitic anhydride may be used in combination.

Next, the main chain carbon number of the glycol component is 3 to 1
The alkylene glycol of 0 is specifically 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol. , 2,2-
Diethyl-1,3-propanediol, 2-butyl-2
-Ethyl-1,3-propanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol and the like. Can be Particularly preferably, 1,6-hexanediol,
1,5-pentanediol, neopentyl glycol,
3-methyl-1,5-pentanediol, more preferably 1,6-hexanediol and neopentyl glycol. Further, a polyhydric polyol such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol may be used in combination.

As the other components, metal salts such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid and 5 [4-sulfophenoxy] isophthalic acid or 2-sulfo-1,4- Butanediol,
A dicarboxylic acid or glycol containing a sulfonic acid metal base such as a metal salt such as 2,5-dimethyl-3-sulfo-2,5-hexanediol is used in an amount of 5 mol% or less of the total acid or glycol component. You may.

Next, the copolymerized polyester resin (A)
May be used by blending a curing agent (B) that can react with (A). In this case, the blending ratio of (A) and (B) is (A) / (B) = 95/5 to 5. 60/40 (weight ratio), preferably (A) / (B) = 90/10 to 70/3
0. When (A) is more than 95, the light fastness effect is reduced, and when (A) is less than 60, workability is undesirably reduced.

The curing agent (B) which can react with the copolymerized polyester resin (A) includes an isocyanate compound,
Examples thereof include an alkyl etherified aminoformaldehyde resin, an epoxy compound, and the like. Particularly preferred is an isocyanate compound. Specific examples thereof include aromatic and fatty acid diisocyanates, and tri- or higher polyisocyanates. Diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess amounts of these isocyanate compounds and ethylene glycol, propylene glycol, tri Low molecular activities such as methylolpropane, glycerin, sorbitol, ethylenediamine Hydrogen compound or various polyester polyols, polyether polyols, include terminal isocyanate group-containing compounds obtained by reacting such polymer active hydrogen compound polyamides.

The amount of the copolymerized polyester resin used in the present invention is 0.5 to 50% by weight, preferably 5 to 3% by weight.
It is desirable to add 0% by weight, especially 5 to 20% by weight.
If the blending amount of the copolymerized polyester resin is more than 50% by weight, tackiness is generated, and it may not be possible to adhere to a guide roll or the like when producing a photosensitive resin laminate, which may not be produced.

In addition, the adhesive composition of the present invention has a colorant at a concentration that does not hinder polymerization of the photosensitive resin (polymerization for forming a floor of a printing plate) in order to improve plate inspection. May be blended. As specific examples, color index NO (hereinafter referred to as CI) 109, CI 502
05, CI50315, CI50320, CI4259
5, CI45210, CI45160, CI4251
0, CI44090 and the like.

As the support for the photosensitive resin laminate of the present invention, a polyethylene phthalate film is optimal in view of dimensional stability, heat resistance and mechanical performance, but polyethylene, polypropylene, polystyrene and other materials are also available. Can be used. In addition, since there is an operation of peeling off the support of the photosensitive resin laminate during plate making, it is necessary to provide a release layer on the support in order to facilitate the operation. This release layer is provided with a thin layer of a release agent, and has a thickness of 0.1
-2.0μ, preferably 0.1-0.5μ, and generally about 0.1-0.3μ is employed. As the release agent, silicone resin, alkyd resin, acrylic / silicone copolymer resin, other fluorine-based resin, olefin-based (wax), etc. are used. It is preferable from the viewpoint of properties.

As a method for obtaining a support having an adhesive layer of the photosensitive resin laminate of the present invention, an adhesive comprising a thermoplastic elastomer and a copolymerized polyester resin on a support having a thin layer of a release agent in advance is used. A coating solution obtained by dissolving the composition with an organic solvent is applied to a comma coater, a bar coater, and a reverse slot.
It can be obtained by coating and drying using a coating machine such as a rucotor. Until the photosensitive resin and the support are laminated, it is preferable to cover with a separate material to protect the adhesive layer. As the separating material, polyethylene, release paper or the like is usually used, and preferably, embossed polyethylene is preferred from the viewpoint of handleability, release property and the like.

The organic solvent for dissolving the adhesive composition is not particularly restricted but includes, for example, hydrocarbons such as toluene, cyclohexane, benzene and xylene, 1,1,1-trichloroethane and tetrachloride. Halogenated hydrocarbons such as carbon, chloroform and chlorobenzene,
General-purpose organic solvents such as ethers such as dioxane, ketones such as methyl ethyl ketone, and esters such as ethyl acetate can be used. Among these organic solvents, it is preferable to use toluene from an environmental point of view. The concentration of the coating solution dissolved in these organic solvents depends on the type of coating machine and the thickness of the obtained adhesive layer, but is usually used in the range of 10% by weight to 50% by weight. .

The thickness of the adhesive layer used in the present invention is:
It is 10 µ to 150 µ, preferably 30 µ to 90 µ, more preferably 40 µ to 60 µ. When the thickness is less than 10 μm, the adhesiveness with a different material having good flatness is good, but when a different material whose surface is polished is used, the concave portion of the polished surface may not be sufficiently filled with the adhesive layer, and the adhesive may vary. On the other hand, if it exceeds 150 μm, there are problems in the production process such as the occurrence of uneven thickness in production coating and the occurrence of pinholes, which is not preferable.

As a method for obtaining the photosensitive resin laminate of the present invention, a support having the above-mentioned adhesive layer and a cover film having an anti-adhesion layer are prepared in advance, and then the photosensitive resin composition is prepared. A method of laminating to a desired thickness and width by a general method such as hot pressing, calendering, roll pressing and the like can be adopted.

The cover film having the anti-adhesion layer is a cover film having a non-adhesion layer,
Specific examples of the non-adhesive layer include a resin such as a polyamide, polyvinyl alcohol, cellulose ethylene oxide, polymer electrolyte, or nylon resin, which is approximately 1.5 μm A cover film having a 5 μ thick anti-adhesion layer can be used.

Next, the photosensitive resin composition used in the photosensitive resin laminate of the present invention is not particularly limited according to the intended use, and any photosensitive resin composition that can be developed with water can be used. May be. For example, JP-A-60-2
No. 11451, JP-A-60-173055 and JP-A-6
JP-A-3-8648, JP-A-1-108542, JP-A-1-108542
JP-A-2197354, JP-A-2-175702, JP-A-3-228060, JP-A-4-3162, JP-A-6-289610, JP-A-7-114180, and the like. can do.

Here, the aqueous development means a development which can be carried out with water or an aqueous solution containing water.
An aqueous solution containing a surfactant, examples of the surfactant include anionic surfactants such as sodium alkyl benzene sulfonate, nonionic surfactants, cationic surfactants, amphoteric surfactants, and sodium nitrile. An aqueous solution containing an alkaline compound, an aqueous solution containing alcohols such as methyl alcohol and ethyl alcohol, etc., can be used to dissolve or swell the photosensitive resin composition;
They can be used alone or in combination. The development temperature when developing with such water or an aqueous solution containing water is about 25.
It is preferable that it is 0 degreeC-50 degreeC.

The ultraviolet light used for curing the photosensitive resin laminate obtained in the present invention is 150 to 500.
It is effective to use a light source having a wavelength range of 300 μm, particularly a wavelength range of 300 to 400 μm. The light source used is a low-pressure mercury lamp, a high-pressure mercury lamp, a carbon arc lamp, a chemical lamp,
Xenon lamps and the like are preferred.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a photosensitive resin laminate comprising at least a support, a release layer, an adhesive layer and a photosensitive resin layer in order from the lower layer. A photosensitive resin laminate bonded to a different material (elastic reinforcing material such as rubber sheet material, soft salt sheet, etc.) having a thickness of 4 mm for use in corrugated balls, heavy bags, etc. is supplied for printing. In this case, first, the floor is formed by exposing the back surface of the photosensitive resin laminate with an exposing machine having ultraviolet rays. At this time, with the support of the photosensitive resin laminate attached,
Alternatively, exposure may be performed after peeling. Next, by peeling the support together with the release layer, the adhesive layer is exposed and an arbitrary solvent is applied to either the surface of the adhesive layer or the elastic reinforcing material. Load and bond. Further, a negative film having a transparent image is exposed to an image using the ultraviolet exposure apparatus, and the non-image portion which is not exposed is removed with the developing solution to prepare a relief (printing plate). -Supply to printing, etc. It is generally desirable that these manufactured relays be kept in a room where ultraviolet rays are cut off. However, at present, they are exposed to ultraviolet rays, and after these relays are left for several years, they are used again. That is the reality.

[0034]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”. The evaluation in the examples is based on the method described below. (1) Adhesion strength test: The adhesion between the photosensitive resin laminate and the elastic reinforcing material was determined by the following test method. JIS-K
The adhesive strength per inch was determined using a tensile tester (manufactured by Toyo Boldwin Co., Ltd.) according to 6301.
The higher the value of the adhesive strength, the better the adhesiveness. (2) Bending test: What was obtained by bonding the photosensitive resin laminate and the elastic reinforcing material was bent at about 180 degrees, and it was visually determined whether or not the bonded side surface peeled off. Those that do not peel off even when bent are indicated by ○, and those that peel off are indicated by x. (3) PCT test (accelerated test): Using a PCT tester (manufactured by Hirayama), a test was repeated 10 times at 0 ° C. to 50 ° C. in units of 1 day, and it was visually determined whether or not the adhered side face was separated. Those that do not peel are indicated by ○, and those that do peel are indicated by x. (4) Light fastness test: In accordance with JIS-K6301,
The adhesive layer surface of the photosensitive resin laminate was irradiated with an accelerated light resistance tester QUV (manufactured by Q. PANEL) for 240 hours to observe the state of cracks. Those without any cracks are indicated by ○, and those with some cracks are indicated by x. Further, this test piece was adhered to a rubber sheet, bent 180 degrees, and it was visually determined whether or not the adhered side face was peeled off. (5) Curling test: It was visually determined whether the test piece was curled (deformed).な い indicates no curl, and x indicates a little curl.

Reference Example 1 200 parts of a block copolymer composed of polystyrene / polyisoprene / polystyrene [Clayton D-1107 manufactured by Ciel Japan Co., Ltd.] and a copolymerized polyester resin [Vylon GK-170 manufactured by Toyobo Co., Ltd., Tg 11 ° C. ) 20
Was dissolved in 513.4 parts of toluene in a 1-liter flask equipped with a stirrer to prepare a coating solution having a solid content of 30%. Next, a 10 layer having a thin layer of silicon resin prepared in advance is prepared.
Bar on polyethylene terephthalate film of 0μ thickness
The support was dried under a drying condition of 80 ° C. using a coater to obtain a support having an adhesive layer having a thickness of 50 μm (hereinafter referred to as an adhesive film). Then, it was covered with an embossed polyethylene film (separate material) to protect the adhesive layer.

REFERENCE EXAMPLE 2 In Reference Example 1, the copolymerized polyester resin [Vylon GK-170, manufactured by Toyobo Co., Ltd.] was used instead of the copolymerized polyester resin (Vylon GK-170, Tg11 ° C., manufactured by Toyobo Co., Ltd.).
(K-390, Tg 6 ° C.) except that an adhesive film having an adhesive layer having a thickness of 50 μm was produced in the same manner as in Reference Example 1, and the adhesive layer was similarly protected with a separate material.

Reference Example 3 In Reference Example 2, a block copolymer comprising polystyrene, polyisoprene, and polystyrene was used.
Block copolymer composed of polybutadiene / polystyrene (Creton D-KX40 manufactured by Ciel Japan KK)
Except having changed to 5), it carried out similarly to Reference Example 2, and carried out 50 micrometer.
An adhesive film having an adhesive layer having a thickness was prepared, and the adhesive layer was similarly protected with a separate material.

Reference Example 4 In Reference Example 1, without blending a copolymerized polyester,
All references are provided except that 120 parts of a block copolymer composed of polystyrene / polyisoprene / polystyrene (Creton D-1107 manufactured by Ciel Japan Co., Ltd.) is dissolved in 280 parts of toluene to prepare a coating solution having a solid content of 30%. Coating and drying were performed in the same manner as in Example 1 to prepare an adhesive film having an adhesive layer having a thickness of 50 μm, and the adhesive layer was similarly protected with a separate material.

Reference Example 5 In Reference Example 3, without blending the copolymerized polyester,
120 parts of a block copolymer (Creton D-KX405 manufactured by Ciel Japan Co., Ltd.) composed of polystyrene / polybutadiene / polystyrene is used in an amount of 270 parts of toluene and 1.6 parts.
Coating and drying were performed in the same manner as in Reference Example 3 except that a coating solution having a solid content of 30% was prepared by dissolving in 10 parts of hexanediol dimethacrylate to prepare an adhesive film having an adhesive layer having a thickness of 50 μm. Similarly, the adhesive layer was protected by a separate material.

Reference Example 6 A photosensitive resin composition was prepared by the following method.
Hexamethylene diisocyanate 21.8 parts, dimethylolpropionic acid 15.4 parts, polytetramethylene glycol (PG-100 manufactured by Nippon Polyurethane Industry Co., Ltd.)
7.6 parts, and n-butyltin dilaurate 1.0
A solution prepared by dissolving the above solution in 300 parts of tetrahydrofuran was placed in a 1-liter flask equipped with a stirrer, and the flask was heated to 65 ° C. while stirring was continued to continue the reaction for 3 hours. In another container, an acrylonitrile-butadiene oligomer having a terminal amino group (Hycar ATBNX 1300X1
A solution prepared by dissolving 55.3 parts of 6 Ube Industries, Ltd. in 100 parts of methyl ethyl ketone was added to the above flask while stirring at room temperature. The obtained polymer solution was dried under reduced pressure to remove tetrahydrofuran and methyl ethyl ketone, thereby obtaining a polymer having a number average molecular weight of 21,000. Next, 100 parts of the polymer was added to methyl ethyl ketone 10
A solution prepared by dissolving 4.8 parts of lithium hydroxide in 100 parts of methyl alcohol was added to the solution dissolved in 0 parts while stirring at room temperature, and the mixture was further stirred for 30 minutes to obtain a hydrophilic polymer [1]. I got

10 parts of the above-mentioned hydrophilic polymer [1], 45 parts of chlorinated polyethylene (H-135 manufactured by Osaka Soda Co., Ltd.) as the hydrophobic polymer, and styrene-butadiene rubber (J
SR1507 Nippon Synthetic Rubber Co., Ltd. 15 parts, butadiene oligoacrylate (PB-A Kyoeisha Yushi Co., Ltd.)
28.5 parts, 1 part of benzyl dimethyl ketal (Irgacure 651 manufactured by Ciba Geigy Co., Ltd.) and 0.5 part of hydroquinone monomethyl ether in toluene 40
And 10 parts of water, kneaded and dissolved at 105 ° C. using a heating kneader, and defoamed to obtain a photosensitive resin composition.

Example 1 An adhesive film having a thickness of 50 μm comprising the adhesive composition obtained in Reference Example 1, the photosensitive resin composition obtained in Reference Example 6, and a 2 μm thick polyvinyl alcohol prepared in advance were prepared.
Using a cover film having an anti-adhesion layer made of a metal-based material and simultaneously shaping it while peeling the separator material under heating at 100 ° C. on a roll press machine adjusted to a total thickness of 3 mm. Then, a photosensitive resin laminate for flexographic printing having a thickness of 3 mm comprising a support, a release layer, an adhesive layer, a photosensitive resin layer, an anti-adhesion layer and a cover film was obtained in this order from the bottom.

Next, with the support of the photosensitive resin laminate for flexographic printing attached, an ultraviolet light exposure machine (P-113-D manufactured by Dainippon Screen, illuminance 150 W / m ² ) was used. A floor was formed by back exposure for one minute to prepare a photosensitive resin plate. Next, the support having a release layer of the photosensitive resin plate was peeled off to expose the adhesive layer of Reference Example 1, while a rubber sheet material (Kleha Elastomer (R) having a thickness of 4 mm was used as an elastic reinforcing material. After toluene was applied to TW-2) manufactured by Co., Ltd., the adhesive layer and the rubber sheet material were overlapped so as to be in contact with each other, and were laminated under a load that did not deform the photosensitive resin plate. After confirming that the toluene had evaporated, the photosensitive resin plate having the rubber sheet material was washed for about 180 hours.
Observation of the side surfaces of the photosensitive resin plate and the rubber sheet material after bending the sheet revealed that the sheet was not peeled off when bent.
Further, after the photosensitive resin plate was cured by exposure to light for 8 minutes using an ultraviolet exposure device, the adhesive strength was determined using an adhesive strength tester. As a result, the adhesive strength was 1.3 kgf / inch. On the other hand, when the adhesive layer of the photosensitive resin laminate composed of the adhesive composition of Example 1 was exposed to light and treated in a light resistance test to observe the crack state of the adhesive layer, no crack was observed. Further, when this test piece was bonded to a rubber sheet material and subjected to a bending test in the same manner as described above, no peeling occurred.

Next, the cover film on the photosensitive resin plate having the rubber sheet material was peeled off, and the original film was placed thereon and brought into close contact with each other by vacuum. After that, the original film was removed by exposing to an ultraviolet light for 8 minutes, and then the alkylnaphthalene was removed. Developing with a brush for 15 minutes at 40 ° C. in neutral water containing 2% by weight of sodium sulfonate gave a printing relief. The obtained lily
The curl did not generate curl, and even when it was bent, it did not peel off with the rubber sheet material. Also, there was no peeling in the PCT test using this test piece. Next, when printing was performed with a model printing machine using a water-based flexographic ink for corrugated balls (LOXSG manufactured by Toyo Ink), printing was performed without peeling off the rubber sheet material or relief during printing. There was no particular problem with gender.

Example 2 The procedure of Example 1 was repeated except that the adhesive layer obtained in Reference Example 2 was changed to 3 m.
A m-thick photosensitive resin laminate for flexographic printing was produced.
Next, in the same manner as in Example 1, a photosensitive resin plate having a rubber sheet was adhered to a 4 mm-thick rubber sheet. When the bending test was performed in the same manner as in Example 1, the side surface did not peel off, and the adhesive strength test in the same manner as in Example 1 showed 1.4 kgf / inch. Next, in the same manner as in Example 1, there was no peeling in the light resistance test, the curl test after preparing the relief, and the PCT test, and there was no particular problem in printing with a model printing machine. Table 1 shows the evaluation results.

Example 3 The procedure of Example 1 was repeated, except that the adhesive layer obtained in Reference Example 3 was replaced with the adhesive layer of 3 m.
A m-thick photosensitive resin laminate for flexographic printing was produced.
Then, a rubber screen having a thickness of 4 mm was formed in the same manner as in Example 1.
To make a photosensitive resin plate. Table 1 shows the evaluation results of the bending test, the adhesive strength test, the light resistance test, the PCT test, and the like performed in the same manner as in Example 1.

Comparative Example 1 A 3 mm-thick photosensitive film for flexographic printing was prepared in the same manner as in Example 1 except that a 100 μm thick polyethylene terephthalate film support having no adhesive layer was used. A resin laminate was produced. Next, back exposure was performed using an ultraviolet light exposure machine in the same manner as in Example 1, the support was peeled off to expose the photosensitive resin laminate, and then a 4 mm-thick rubber sheet material and toluene were applied. When the photosensitive resin plate and the rubber sheet material were easily peeled off in a bending test when the sheets were overlapped with each other and applied with a load, they were not subjected to a printing test.

COMPARATIVE EXAMPLE 2 The procedure of Example 1 was repeated, except that the adhesive layer obtained in Reference Example 4 was used as the adhesive layer. Photosensitive resin layer and cover
A 3 mm thick photosensitive resin laminate for flexographic printing made of a film was produced. Next, the support was exposed to ultraviolet light from the back surface in the same manner as in Example 1, and the support was peeled off to expose the adhesive layer surface. Then, a rubber sheet material having a thickness of 4 mm was adhered while applying toluene. . When a bending test was performed on the obtained photosensitive resin plate, no side was peeled off. The adhesive strength was determined by an adhesive strength test to be 0.9 kgf / inch. on the other hand,
When a light resistance test was performed on the adhesive layer in the same manner as in Example 1, a crack was generated in the adhesive layer and the adhesive layer could be easily peeled off from the photosensitive resin. Using this test piece and bonding it to a rubber sheet material in the same manner as described above and conducting a bending test, it was observed that the overall adhesive strength was reduced and the side face was easily peeled off. Then, it was confirmed that the adhesion was reduced. Using this test piece, a relief was prepared and printed in the same manner as in Example 1. When several copies were printed, the rubber sheet material and the relief were separated.

Comparative Example 3 The procedure of Example 1 was repeated, except that the adhesive layer obtained in Reference Example 5 was used as the adhesive layer. Photosensitive resin layer and cover
A 3 mm thick photosensitive resin laminate for flexographic printing made of a film was produced. Next, the support was exposed to ultraviolet light from the back surface in the same manner as in Example 1, and the support was peeled off to expose the adhesive layer surface. Then, a rubber sheet material having a thickness of 4 mm was adhered while applying toluene. . When a bending test was performed on the obtained photosensitive resin plate, no side was peeled off. The adhesive strength was determined by an adhesive strength test to be 0.6 kgf / inch. on the other hand,
When a light resistance test was performed on the adhesive layer in the same manner as in Example 1, a crack was generated in the adhesive layer and the adhesive layer could be easily peeled off from the photosensitive resin. Using this test piece, a bending test was performed by bonding it to a rubber sheet material in the same manner as described above. As a result, it was observed that the overall bonding strength was reduced and the side surface was easily peeled off. could not.

Comparative Example 4 A rubber sheet material having a thickness of 4 mm (T Kleha Elastomer Co., Ltd.)
W-2) on a 100 μm thick polyethylene terephthalate film support coated with a brush using a commercially available adhesive (vinylol 2006, modified by nitrile rubber manufactured by Showa Polymer Co., Ltd.) and siliconized beforehand 3 m laminated by a hot press using the photosensitive resin composition obtained in Reference Example 3
The photosensitive resin laminate for flexographic printing having a thickness of m was exposed to light and the support was peeled off, and the surface of the photosensitive resin surface exposed was bonded using a rubber roll. Then, the adhesive strength was determined by an adhesive strength test in the same manner as in Example 1.
When a bending test was performed at 0 gf / inch, the film was easily peeled off and was not subjected to a printing test.

Reference Example 7 The results of Examples 1 to 3 and Comparative Examples 1 to 4 are shown in Table 1 below.

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[Table 1]

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The photosensitive resin laminate of the present invention having the above-mentioned structure is useful when a flexographic printing plate comprising a water-based developable photosensitive resin composition is developed for corrugated ball printing and double bag printing. It is an adhesive composition that is not only workable, environmentally friendly, but also does not affect the adhesiveness even when exposed to ultraviolet rays such as sunlight.
It is a great contribution to the plate making and printing industries.

Claims (2)

[Claims] (1) a support, a release layer,
A photosensitive resin laminate comprising an adhesive layer and a photosensitive resin layer, wherein the adhesive layer comprises an adhesive composition containing a thermoplastic elastomer and a copolymerized polyester resin. . 2. A photosensitive resin laminate comprising an elastic reinforcing material layer, an adhesive layer, and a photosensitive resin layer in order from at least a lower layer, wherein the adhesive layer contains a thermoplastic elastomer and a copolymerized polyester resin. A photosensitive resin laminate comprising a composition.