JPH11170437A - Multi-layer elastic reinforcing material and manufacture of photosensitive resin laminated body using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a multi-layer elastic reinforcing material having excellent light resistance and adhesion to different types of materials (elastic bodies), and a photosensitive resin laminated body appropriate for flexographic printing, where workabrlity, environmental characteristics, and printing plate-placing characteristics in plate-making processes are improved. SOLUTION: (1) A multi-layer elastic reinforcing material is composed of at least an elastic body layer and an adhering layer, where the adhering layer is composed of an adherent composition containing a thermoplastic elastomer and/or copolymer polyester resin. (2) In manufacture of a photosensitive resin laminated body composed of at least an elastic body layer, an adhering layer, and a photosensitive resin layer, the adhering layer of the multi-layer elastic reinforcing material (1) and the photosensitive resin layer are laminated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a multilayer elastic reinforcing material and a method for producing a photosensitive resin laminate using the same.
More specifically, the present invention relates to a multilayer elastic reinforcement made of an adhesive composition having excellent adhesion to different materials (elastic bodies) 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, which is conventionally used, is a laminate mainly composed of a layer of a photosensitive elastomer composition. When bonding with materials,
In general, after the support is removed, back exposure is performed using an ultraviolet exposure machine, and the layer of the photosensitive elastomer composition is dissolved or swelled with an organic solvent to adhere to a different 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 adhesive strength and cohesive strength, so that it has excellent physical adhesiveness, and is made of a different material. There is almost no problem such as delamination at the interface with. 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.

With the recent environmental regulations, instead of the above-mentioned flexographic printing plate material which can be developed with a halogen-based organic solvent, a water-based developable photosensitive flexographic printing plate material, for example,
JP-A-60-21145, JP-A-60-17305
5, JP-A-63-8648, JP-A-1-108854
No. 2, 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 adhering such a photosensitive flexographic plate material and a different material (elastic body), 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 printing plate and a rubber sheet material to bond the photosensitive flexographic printing plate by exposure (Japanese Patent Publication No. 60-16997). Production method of bonding with solvent
No. 68620), a method in which the surface to be bonded is treated with an organic active halogen-containing compound and bonded (Japanese Patent Publication No. 5-5637).
No. 4), 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-8-297369).
Are disclosed.

However, in the above method, the adhesiveness is not sufficient, and particularly when an elastic body whose surface is polished is used, the elastic body does not sufficiently adhere to the polished surface, so that it is easily peeled off at the time of printing.
It is also expensive. In the method, drying is required for a long time in order to obtain adhesiveness, a curl is generated due to evaporation of a solvent in the adhesive, and particularly, depending on the type of adhesive, only different kinds of materials are adhered to each other to obtain photosensitive properties. Does not adhere to resin,
Or, conversely, there are drawbacks such as the necessity of coating several layers, which fluctuates the thickness and affects printability. In the method, photocuring adhesion may not be sufficient depending on the characteristics of the photosensitive flexographic plate, which is not common. The method is a production method in which the polymerization of the photosensitive resin plate is insufficient by removing the support and exposed to air, followed by exposure, thereby improving the solubility in an organic solvent and bonding.
When applied to a flexographic printing plate which can be developed in an aqueous system, there is a drawback 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 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 an elastic reinforcing material for obtaining a photosensitive resin laminate which is easy in bonding workability and excellent in adhesion 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 finally completed the present invention. That is, the present invention provides (1) a multilayer elastic reinforcing material comprising at least an elastic layer and an adhesive layer, wherein the adhesive layer comprises an adhesive composition containing a thermoplastic elastomer and / or a copolyester resin. The method for producing a multilayer elastic reinforcing material according to claim 1 and (2) a photosensitive resin laminate comprising at least an elastic layer, an adhesive layer, and a photosensitive resin layer, wherein the adhesive layer and the photosensitive material in the multilayer elastic reinforcing material according to claim 1 are manufactured. A method for producing a photosensitive resin laminate, comprising laminating a photosensitive resin layer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the elastic body is not particularly limited. For example, rubber sheet materials such as raw rubber, vulcanized rubber, and synthetic rubber, soft salt sheet material, urethane foam And the like.
The dimensional accuracy of the elastic body is 10 m in the width direction.
m to 0 mm / m, preferably 5 mm to 0 mm / m, particularly 3 mm to 0 mm / m, and a length direction of 50 mm to 0 mm.
mm / 3 m, preferably 30 mm to 0 mm / 3 m, particularly preferably 20 mm to 0 mm / 3 m.

Next, the adhesive layer in the present invention refers to a rotating brush or an indentation pressure when a photosensitive resin layer and an elastic body are adhered to each other and then developed using a developing machine for producing a relief. It is not peeled off by the elastic body from the photosensitive resin layer, is not peeled off when a certain number of copies are printed using this relief, does not affect printability, and is exposed to ultraviolet rays such as sunlight. The adhesive composition has the characteristics that it does not cause deterioration in adhesion without light deterioration (light resistance), and that it maintains its adhesion without peeling even after several years of printing. Is what it is.

The adhesive layer in the present invention contains a thermoplastic elastomer or a thermoplastic elastomer and a copolymerized polyester resin. First, as the thermoplastic elastomer, for example, a polystyrene polymer block, polyethylene terephthalate Polyester polymer blocks represented by polybutene, polytrimethylene terephthalate, polytetramethylene terephthalate, etc .; conjugated diene compound blocks represented by polybutadiene, polyisoprene, polychloroprene, etc .; polycaprolactone, etc. Aliphatic polyester polymer block,
Poly (diethylene glycol, triethylene glycol)
, Tetraethylene glycol) and other elastomeric block copolymers such as ethylene-propylene copolymer block, ethylene-acrylic acid copolymer block, and the like. Elastomer-like random copolymers such as a styrene / butadiene random copolymer composed of styrene and butadiene monomer units, and an acrylonitrile / butadiene random copolymer composed of acrylonitrile and butadiene monomer units are exemplified. 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.

Next, the copolymerized polyester to be added to the adhesive layer as required is to improve the adhesiveness and the light resistance, and is further wound around the plate cylinder at the time of printing and dimensional stability. It is blended to provide easy flexibility. In the present invention, a copolymerized polyester resin having a glass transition temperature of 60 ° C. or lower, preferably 30 ° C. or lower, particularly preferably 20 ° C. or lower is used, and the acid component is mainly an aromatic dicarboxylic acid 70 to 100.
The glass transition temperature is 60 ° C. or lower, which is composed of 0 to 30% by mole, preferably 80 to 100% by mole, 0 to 30% by mole of other dicarboxylic acid, and 25 to 100% by mole of alkylene glycol having 3 to 10 carbon atoms in the glycol component. Is used. More preferably, a curing agent (B) capable of reacting therewith is used as (A) / (B) = 95/5.
A copolymerized polyester resin blended at a ratio of ６０60/40 (weight ratio) is used.

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.

Next, as a method for obtaining the multilayer elastic reinforcing material of the present invention, a coating solution obtained by dissolving an adhesive composition containing a thermoplastic elastomer and / or a copolymerized polyester resin in an organic solvent is used. , Bar coater, river
It can be obtained by coating and drying on an elastic body using a coating machine such as a roll coater. Until the photosensitive resin and the multilayer elastic reinforcing material are laminated, it is preferable to cover with a separate material in order 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 μm to 150 μm, preferably 30 μm to 90 μm, more preferably 40 μm to 60 μm. The thickness of the adhesive layer is 10
When the particle size is less than μ, the adhesion to the elastic body having good flatness is good, but when the elastic body whose surface is polished is used, the adhesive layer may not be sufficiently filled in the concave portion of the polished surface, and the adhesion 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.

Next, as a method for obtaining the photosensitive resin laminate of the present invention, a normal support, a support of a photosensitive resin plate having a photosensitive resin layer, is held, or the support is peeled off. After that, if necessary, the floor of the photosensitive resin layer is formed by irradiating ultraviolet rays, and an arbitrary organic solvent is applied to the adhesive layer of the multilayer elastic reinforcing material of the present invention to develop the adhesiveness. The photosensitive resin laminate of the present invention can be obtained by leaving the resin layer in close contact with and adhering to the resin layer until the organic solvent evaporates.

The cover film having an 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 depending on the intended use, and any photosensitive resin composition which 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.

As a method for producing a relief (printing plate) using the photosensitive resin laminate of the present invention having the above structure, a usual method can be employed. For example, the top cover film is peeled off, A negative film is applied to the protective layer and image-exposed using the ultraviolet exposure device. Non-image portions that are not exposed are removed with the developing solution.
(Printing plate). In addition, it is generally desirable that these manufactured reliefs be kept in a room where ultraviolet rays are cut, but at present, they are exposed to ultraviolet rays,
Further, it is a fact that these relays are used again after being left for several years.

[0033]

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.
In addition, it shows that adhesiveness is excellent, so that the value of adhesive strength is large. (2) Dimensional stability: It was visually determined whether or not the relief after development processing was curled (deformed). (3) Light fastness test: Accelerated test for a specific time using an accelerated light fastness tester QUV (manufactured by Q. PANEL) in accordance with JIS-K6301 to determine the crack state between the photosensitive resin layer and the multilayer elastic reinforcing material. Observed. Those having a specific time of 120 hours and no cracks were usually rated as good, and those of 240 hours without cracks were rated as good.

Example 1 200 parts of a block copolymer composed of polystyrene / polyisoprene / polystyrene [Creton D-1107 manufactured by Ciel Japan Co., Ltd.] was dissolved in 300 parts of toluene in a 1 liter flask equipped with a stirrer and solidified. A coating solution of 40% was prepared. Next, using the coating solution, a thickness of 4 mm
Vulcanized rubber sheet (TW manufactured by Kureha Elastomer Co., Ltd.)
In -2), a multilayer elastic reinforcing material having an adhesive layer was prepared by coating with a bar coater adjusted so that the thickness after drying became 50 μm. The adhesive layer was covered with an embossed polyethylene film (separate material) to protect the adhesive layer.

Example 2 A multilayer elastic reinforcing material was obtained in the same manner as in Example 1 except that a coating liquid to be used as an adhesive layer was produced as follows. Block copolymer consisting of polystyrene / polyisoprene / polystyrene in 330 parts of toluene [Creton D-1107 manufactured by Ciel Japan Co., Ltd.] 2
00 parts and 20 parts of a copolymerized polyester resin (Vylon GK-170, manufactured by Toyobo Co., Ltd., Tg 11 ° C.) were dissolved in a 1-liter flask equipped with a stirrer to prepare a coating solution having a solid content of 40%.

Example 3 A multilayer elastic reinforcing material was obtained in the same manner as in Example 1, except that a coating liquid to be used as an adhesive layer was produced as follows. Block copolymer of polystyrene / polybutadiene / polystyrene in 300 parts of toluene (Creton D-KX405 manufactured by Ciel Japan Co., Ltd.)
200 parts were dissolved in a 1-liter flask equipped with a stirrer to prepare a coating solution having a solid content of 40%.

Reference Example 1 A photosensitive flexographic printing plate (raw plate) was prepared in the following manner.
Was prepared. Hexamethylene diisocyanate 21.8
Parts, 15.5 parts of dimethylolpropionic acid, 7.6 parts of polytetramethylene glycol (manufactured by Nippon Polyurethane Industry Co., Ltd., PG-100), and 1.0 part of n-butyltin dilaurate in 300 parts of tetrahydrofuran Was added to a 1-liter flask equipped with a stirrer, and the flask was heated to 60 ° 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 ATBNX1
A solution prepared by dissolving 55.3 parts of 300 × 16 (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, a solution of 4.8 parts of lithium hydroxide dissolved in 100 parts of methyl alcohol is added to a solution of 100 parts of the polymer dissolved in 100 parts of methyl ethyl ketone while stirring at room temperature, and further stirred for 30 minutes. As a result, a hydrophilic polymer [1] was obtained.

10 parts of the above hydrophilic polymer [1], 45 parts of chlorinated polyethylene (H-135 manufactured by Osaka Soda Co., Ltd.) as a 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, disperse and disperse the mixture in a heating kneader.
After kneading and dissolving at 05 ° C. and removing the solution, a photosensitive resin composition was obtained.

Next, a 125 μm polyethylene terephthalate film coated with a release agent prepared in advance and 2
A photosensitive resin composition was heated on a roll press machine adjusted to a total thickness of 3 mm using a cover film having an anti-adhesive layer made of a polyvinyl alcohol-based film having a thickness of 100 μm at a temperature of 100 ° C. The photosensitive resin plate (flexible printing plate) for flexographic printing was obtained by molding mainly the product.

Example 4 From the back side of the photosensitive flexographic printing plate (raw plate) obtained in Reference Example 1, an ultraviolet exposure machine (P-113 manufactured by Dainippon Screen) was used.
-D, illuminance 150W / m ² ) back exposure for 1 minute-
Was formed. Further, after peeling off the back-exposed support of the photosensitive flexographic printing plate and exposing the photosensitive resin layer formed on the floor, the separating material in the multilayer elastic reinforcing material obtained in Example 1 was peeled off. Then, the photosensitive resin layer was adhered by applying a load such that the photosensitive resin layer was not deformed and adhered to the surface of the adhesive layer while applying the toluene using toluene. After confirming that the toluene was evaporated, the photosensitive resin laminate was bent at 180 degrees and the side surfaces of the photosensitive resin layer and the multilayer rubber substrate were observed. Further, after the photosensitive resin layer was cured by exposing the surface to light for 8 minutes using an ultraviolet exposure machine, the adhesive strength was determined using an adhesive strength tester.
/ Inch.

Next, the cover film of the separately prepared photosensitive resin laminate was peeled off, the original film was placed and adhered in vacuum, and the original film was removed by exposing to an ultraviolet light for 8 minutes with an ultraviolet light exposure machine, and then the alkyl naphthalene sulfonate was removed. Developing with a brush in neutral water containing 2% by weight at 40 ° C. for 15 minutes to produce a printing relief having a relief depth of 1 mm. The obtained relief had no curl and did not peel off between the relief and the multilayer elastic reinforcing material when bent. Next, printing was performed with a model printing machine using a water-based flexographic ink for corrugated balls (LOSXG manufactured by Toyo Ink), and good printability was obtained without any particular problem in printability.

Example 5 The multilayer elastic reinforcing material obtained in Example 2 and the photosensitive flexographic printing plate obtained in Reference Example 1 were adhered to the multilayer elastic reinforcing material in the same manner as in Example 4 to obtain a photosensitive material. A conductive resin laminate was produced. When the adhesive strength of the obtained photosensitive resin laminate was determined, it was 1.2 kgf / inch. Next, Example 4
When a printing relief was produced in the same manner as described above, no curl was generated. Further, when a light resistance test was performed, peeling between the adhesive layer and the photosensitive resin layer on the multilayer elastic reinforcing material, cracks and the like occurred. No phenomenon was observed. Further, when printing was performed in the same manner as in Example 4, good printed matter was obtained without any particular problem.

Comparative Example 1 Using the photosensitive flexographic printing plate obtained in Reference Example 1, an elastic body having no adhesive layer was obtained in the same manner as in Example 4 to obtain a photosensitive resin laminate. The adhesive strength between the photosensitive flexographic printing plate and the elastic body is only 30 gf / inch,
It was easily peeled off when bent at 80 degrees, and was not subjected to a printing test.

Comparative Example 2 A commercially available adhesive (vinylol 2006, modified by nitrile rubber manufactured by Showa Polymer Co., Ltd.) was applied to an elastic body (rubber substrate) having a thickness of 4 mm.
Was applied on the elastic body with a brush, and a photosensitive resin laminate was obtained in the same manner as in Example 4. When the adhesive strength was determined in the same manner as in Example 4, the adhesive strength was found to be only 30 gf / inch. The adhesive was easily peeled off when bent at 180 degrees, and was not subjected to a printing test.

Example 6 The multilayer elastic reinforcing material obtained in Example 3 and the photosensitive flexographic printing plate obtained in Reference Example 1 were adhered to the multilayer elastic reinforcing material in the same manner as in Example 4 to obtain a photosensitive material. A conductive resin laminate was produced. When the adhesive strength of the obtained photosensitive resin laminate was measured, it was 0.9 kgf / inch. Next, Example 4
When a printing relief was prepared in the same manner as in Example 1, no curl was generated. When printing was performed in the same manner as in Example 4, good printed matter was obtained without any particular problem.

Reference Example 2 The results of Examples 4 to 6 and Comparative Examples 1 and 2 are shown in Table 1 below.

[0047]

[Table 1]

[0048]

The multilayer elastic reinforcing material of the present invention having the above-mentioned structure has excellent adhesiveness, dimensional stability, light resistance, and the like. It is suitable for an original plate for flexographic printing which can be developed, and is useful when developed for corrugated ball printing, double bag printing, etc., and greatly contributes to the plate making industry and printing industry.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03F 7/11 503 G03F 7/11 503

Claims (2)

[Claims] 1. A multilayer elastic reinforcing material comprising at least an elastic layer and an adhesive layer, wherein the adhesive layer comprises an adhesive composition containing a thermoplastic elastomer and / or a copolyester resin. Multilayer elastic reinforcement. 2. A method for manufacturing a photosensitive resin laminate comprising at least an elastic layer, an adhesive layer and a photosensitive resin layer, wherein the adhesive layer and the photosensitive resin layer of the multilayer elastic reinforcing material according to claim 1 are bonded to each other. A method for producing a photosensitive resin laminate, comprising: