JP2006117858A - Photo-sensitive resin composition for forming adhesive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo-sensitive resin composition showing adhesion specifically to a polyester. <P>SOLUTION: The photo-sensitive resin composition for forming an adhesive material comprises a resin (a) having a number average molecular weight of 1,000-500,000 and an organic compound (b) containing a polymerizable unsaturated group and having a number average molecular weight of 100- less than 1,000, and the resin (a) contains a compound containing a carbonate bond and a urethane bond in the main chain in an amount of 20-100 wt% relative to the total amount of the resin (a), and the composition can be cured by light. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition for forming an adhesive material having specific adhesiveness to a polyester film such as polyethylene terephthalate.

Polyester film materials such as polyethylene terephthalate (PET) are widely used as flexible supports. For example, in the printing field, particularly in the flexographic printing field, a PET film having dimensional stability is used in large quantities as a flexible support for forming a printing plate.
When printing using a sheet-like printing plate, when fixing the sheet-like printing plate on the plate cylinder of a printing press, first, double-sided adhesive tape on the plate cylinder or on the cushion layer attached on the plate cylinder Is attached to the printing plate while accurately aligning the printing plate. However, the double-sided adhesive tape used is always sticky and has a high surface tack. Therefore, if dust or dust in the atmosphere adheres to the surface, it cannot be easily removed, and in some cases, the printing plate can be attached with dust or dust attached, causing a reduction in plate thickness accuracy. . A decrease in plate thickness accuracy also leads to a decrease in the quality of printed matter.

In addition, a liquid curable pressure-sensitive adhesive is generally used so as to follow fine irregularities on the surface of the substrate. Furthermore, photosensitive adhesives have been studied because of the ease of moldability that requires a very short time for molding, and are known as photo-curable adhesives. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2001-279218) describes a photocurable pressure-sensitive adhesive composition and a photocurable pressure-sensitive adhesive sheet. In Patent Document 1, a photocationically polymerizable compound is used, and there is a description that always has high adhesiveness. However, there is no description that has adhesiveness specifically to polyester.
It has photo-curing properties, and after photo-curing, the surface of the cured product has a small tack (it does not feel sticky when touched by hand) and can be removed even if dust or dirt adheres to it, but it has strong adhesion to polyester film. There has been no known pressure-sensitive adhesive material having selectivity with respect to a substrate to be bonded.
JP 2001-279218 A

  Providing a photosensitive resin composition for forming an adhesive material having specific adhesiveness to polyester.

  The present inventors have intensively studied and are photosensitive resins containing a resin (a) having a number average molecular weight of 1,000 or more and 500,000 or less and an organic compound (b) having a polymerizable unsaturated group having a number average molecular weight of 100 or more and less than 1,000. It is a resin composition, and the photocured product surface of the photosensitive resin composition in which the resin (a) has a carbonate bond and a urethane bond has a surprisingly strong adhesion to polyester such as PET. The phenomenon was discovered and the present invention was completed.

The present invention is as follows.
1. A photosensitive resin composition comprising a resin (a) having a number average molecular weight of 1,000 to 500,000, and an organic compound (b) having a polymerizable unsaturated group having a number average molecular weight of 100 to less than 1,000, wherein the resin (A) contains a compound having a carbonate bond and a urethane bond in the molecular main chain, containing 20 wt% or more and 100 wt% or less of the total amount of the resin (a), and is photocured. Resin composition.
2. The resin (a) contains a compound having a polyurethane skeleton obtained by a condensation reaction of a polycarbonate diol having a number average molecular weight of 100 or more and 100,000 or less and a diisocyanate compound, and having a polymerizable unsaturated group in the molecule. It is characterized by 1. 2. A photosensitive resin composition for forming an adhesive material according to 1.
3. The organic compound (b) contains a compound having an aromatic functional group and / or an alicyclic functional group in the molecule at 10 wt% to 100 wt% of the total amount of the organic compound (b) 1 . Or 2. 2. A photosensitive resin composition for forming an adhesive material according to 1.

4). 1. The photosensitive resin composition is liquid at 20 ° C. To 3. The photosensitive resin composition for forming an adhesive material according to any one of the above.
5. 1. To 4. It is the adhesive material obtained by photocuring the photosensitive resin composition in any one of these, Comprising: This adhesive material surface shows adhesiveness with respect to a polyester film, and adhesive strength is 150 N / m or more and 10 kN / m or less. An adhesive material characterized by being.
6). 1. To 4. The photosensitive resin composition according to any one of the above is applied to one or both surfaces of a sheet-like support or a cylindrical support to form a photosensitive resin composition layer, and then irradiated with light. A laminate having an adhesive material obtained by photocuring.

7). 5. A cushion layer is provided between the sheet-like support or the cylindrical support and the adhesive material. The laminated body as described in.
8). On the adhesive material, a sheet-like printing original plate or sheet-like printing plate having a polyester film as a support is further pasted so that the polyester material is inside and the adhesive material and the polyester film are in contact with each other. 6). Or 7. The printing base material which has a laminated body of description.
9. 1. To 4. The photosensitive resin composition according to any one of the above is applied to a sheet-like support or a cylindrical support with a film thickness of 0.5 μm or more and 5 mm or less to form a photosensitive resin composition layer. The manufacturing method of the adhesive material characterized by including the process of photocuring by irradiating light to the photosensitive resin composition layer.
10. 8. In the step of photocuring by irradiating with light, irradiating with light in the atmosphere The manufacturing method of the adhesive material of description.
11. 8. A step of adjusting the film thickness of the pressure-sensitive adhesive material by cutting or / and grinding or / and polishing after the photocuring step. Or 10. The manufacturing method of the adhesive material of description.

  ADVANTAGE OF THE INVENTION By this invention, the photosensitive resin composition for adhesive material formation which has adhesiveness specifically with respect to polyester can be provided.

In the following, a more detailed description will be given centering on preferred embodiments of the present invention.
The photosensitive resin composition for forming an adhesive material of the present invention comprises a photosensitive resin composition containing a resin (a) as a polymer component and an organic compound (b) having a polymerizable unsaturated group in the molecule as a monomer component. The resin (a) contains a compound having a carbonate bond and a urethane bond in the molecular main chain of 20 wt% to 100 wt% of the total amount of the resin (a). Preferably they are 40 wt% or more and 100 wt% or less, More preferably, they are 50 wt% or more and 100 wt% or less. If it contains 20 wt% or more and 100 wt% or less, the adhesive material obtained by photocuring this photosensitive resin composition can maintain the effect which has adhesiveness specifically with respect to polyester.

  The resin (a) of the present invention is a compound having a number average molecular weight of 1,000 to 500,000. Moreover, when comprising the photosensitive resin composition, it is preferable to have a polymerizable unsaturated group in a molecule | numerator. A preferable range of the number average molecular weight of the resin (a) is 2000 or more and 300,000 or less, and a more preferable range is 5000 or more and 100,000 or less. If the number average molecular weight of the resin (a) is 1000 or more, the adhesive material produced by photocuring later maintains strength and can withstand repeated use. Further, if the number average molecular weight of the resin (a) is 500,000 or less, the viscosity at the time of molding of the photosensitive resin composition does not increase excessively, and a laminate having a sheet-like or cylindrical adhesive material The body can be made. The number average molecular weight referred to here is a value measured by gel permeation chromatography, calibrated with polystyrene having a known molecular weight, and converted.

  The definition of “polymerizable unsaturated group” in the present invention is a polymerizable unsaturated group involved in a radical or addition polymerization reaction. A particularly preferred resin (a) is a polymer having an average of 0.7 or more polymerizable unsaturated groups per molecule. When the average is 0.7 or more per molecule, the mechanical strength of the adhesive obtained from the photosensitive resin composition of the present invention is excellent. Furthermore, its durability is good, and it can withstand repeated use, which is preferable. Considering the mechanical strength of the adhesive material, the amount of the polymerizable unsaturated group of the resin (a) is more preferably more than 1 per molecule. In the resin (a), the position of the polymerizable unsaturated group is preferably directly bonded to the end of the polymer main chain, the end of the polymer side chain, the polymer main chain, or the side chain. The average number of polymerizable unsaturated groups contained in one molecule of the resin (a) can be obtained by a molecular structure analysis method using a nuclear magnetic resonance spectrum method (NMR method).

  As a method for producing the resin (a), for example, a direct introduction of a polymerizable unsaturated group may be used. Alternatively, a hydroxyl group, an amino group, an epoxy group, a carboxyl group, Can bind to the reactive groups of the above components having a molecular weight of about several thousand having a plurality of reactive groups such as acid anhydride groups, ketone groups, hydrazine residues, isocyanate groups, isothiocyanate groups, cyclic carbonate groups, and alkoxycarbonyl groups. It reacts with a binder having a functional group (for example, a polyisocyanate in the case of a hydroxyl group or an amino group), adjusts the molecular weight, converts to a terminal binding group, and then reacts with this terminal binding group. A method of introducing a polymerizable unsaturated group at the molecular terminal by reacting with an organic compound having a functional group and a polymerizable unsaturated group is preferred.

The compound having a carbonate bond and a urethane bond in the molecular main chain contained in the resin (a) can be easily obtained by subjecting a polycarbonate diol and a diisocyanate compound to a condensation reaction. Moreover, the condensate of polycarbonate diol and diisocyanate may exist in the compound as a block. The number average molecular weight of the polycarbonate diol to be used is preferably 100 or more and 100,000 or less. A more preferable range is 500 or more and 20,000 or less, and further preferably 1000 or more and 10,000 or less. If it is the range of 100 or more and 100,000 or less, a condensation reaction with a diisocyanate compound can be implemented easily.
Examples of the polycarbonate diol include aliphatic polycarbonate diol, aromatic polycarbonate diol, and alicyclic polycarbonate diol. When the flexibility of the adhesive material is required, an aliphatic polycarbonate diol is particularly preferable. Specific examples include 4,6-polycarbonate diol, 5,6-polycarbonate diol, and 8,9-polycarbonate diol. Compounds having different number average molecular weights from Asahi Kasei Chemicals, Kuraray, Daicel, etc. It can be obtained.

  Examples of diisocyanate compounds include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylylene xylene diisocyanate, trimethylhexamethylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and cyclohexylene diisocyanate. Can give.

  Examples of the resin that can be used by mixing with the resin (a) include compounds having a polymerizable unsaturated group in the molecular main chain or side chain, such as polydienes such as polybutadiene and polyisoprene. In addition, a polymer compound having a polymerizable unsaturated group introduced into the molecule by a chemical reaction such as a substitution reaction, elimination reaction, condensation reaction, or addition reaction using a polymer compound having no polymerizable unsaturated group as a starting material. It can also be mentioned. Examples of polymer compounds having no polymerizable unsaturated group include polyolefins such as polyethylene and polypropylene, polyhaloolefins such as polyvinyl chloride and polyvinylidene chloride, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyvinyl acetate, and polyvinyl acetal. In addition to C-C chain polymers such as polyacrylic acid, poly (meth) acrylic acid esters, poly (meth) acrylamide, and polyvinyl ether, polyethers such as polyphenylene ether, polythioethers such as polyphenylene thioether, polyethylene Polymer compounds such as polyesters such as terephthalate, polycarbonates, polyacetals, polyurethanes, polyamides, polyureas, polyimides, polydialkylsiloxanes, etc. It can be the mentioned polymer compound having a hetero atom, a random copolymer synthesized from a plurality of types of monomer components, the block copolymers. Furthermore, it is possible to use a mixture of a plurality of polymer compounds having a polymerizable unsaturated group introduced in the molecule.

  In particular, when applied on a flexible support, in order to obtain flexibility, it is preferable that a part of the resin (a) is a liquid resin having a glass transition temperature of 20 ° C. or less. A liquid resin having a glass transition temperature of 0 ° C. or lower can be used. Examples of such liquid resins include hydrocarbons such as polycarbonate polyurethane, polyethylene, polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated poisoprene, polyesters such as adipate and polycaprolactone, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Such as polyethers such as aliphatic polycarbonates, silicones such as polydimethylsiloxane, polymers of (meth) acrylic acid and / or derivatives thereof, and mixtures and copolymers thereof. A compound having a saturated group can be used. In particular, unsaturated polyurethanes having a polycarbonate skeleton are preferable from the viewpoint of weather resistance. The liquid resin here means a polymer that has the property of being easily deformed by flow and solidified into a deformed shape by cooling. When an external force is applied, the liquid resin is instantly deformed according to the external force. When the external force is removed, the term corresponds to an elastomer having a property of restoring the original shape in a short time. When the resin (a) is a liquid resin at 20 ° C., the photosensitive resin composition is also liquid at 20 ° C.

  The photosensitive resin composition of the present invention, which can obtain good plate thickness accuracy and dimensional accuracy when molded into a sheet or cylinder, has a viscosity at 20 ° C. of 10 Pa · s to 10 kPa · s. preferable. More preferably, it is 50 Pa · s or more and 5 kPa · s or less. If the viscosity is 10 Pa · s or more, the mechanical strength of the produced adhesive material is sufficient, and even when it is molded into a cylindrical shape, the shape can be easily maintained and processed easily. If the viscosity is 10 kPa · s or less, it is easily deformed even at room temperature and easy to process. It is easy to form into a sheet or cylinder and the process is simple. In particular, in order to obtain a cylindrical adhesive layer with high plate thickness accuracy, when the liquid photosensitive resin layer is formed on the cylindrical support, the photosensitive resin composition does not cause a phenomenon such as dripping due to gravity. Thus, the viscosity is preferably 100 Pa · s or more, more preferably 200 Pa · s or more, and still more preferably 500 Pa · s or more. Moreover, when the photosensitive resin composition used by this invention is a liquid especially in 20 degreeC, it is preferable to have thixotropic property. Although the photosensitive resin composition of this invention may contain the volatile solvent component, it is more preferable that a solvent is not included from viewpoints, such as work environment property and the ease of handling.

The organic compound (b) is a compound having a polymerizable unsaturated group having a number average molecular weight of 100 or more and less than 1000. When it is 100 or more and less than 1000, it is easy to dilute with resin (a), and it is difficult to evaporate and vaporize in the molding process. The polymerizable unsaturated group is a polymerizable unsaturated group involved in a radical or addition polymerization reaction as described in the resin (a).
Specific examples of the organic compound (b) include radical reactive compounds such as olefins such as ethylene, propylene, styrene and divinylbenzene, acetylenes, (meth) acrylic acid and derivatives thereof, haloolefins, acrylonitrile and the like. Saturated nitriles, (meth) acrylamide and derivatives thereof, aryl compounds such as aryl alcohol and aryl isocyanate, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid and derivatives thereof, vinyl acetates, N-vinylpyrrolidone, N-vinyl carbazole and the like can be mentioned, and (meth) acrylic acid and derivatives thereof are preferable examples from the viewpoints of the abundance of the types, price, decomposability upon laser light irradiation, and the like. Examples of the derivative of the compound include alicyclic such as cycloalkyl-, bicycloalkyl-, cycloalkene-, bicycloalkene-, aromatic such as benzyl-, phenyl-, phenoxy-, fluorene-, alkyl-, halogen Alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl-, tetrahydrofurfuryl-, allyl-, glycidyl-, alkylene glycol-, polyoxyalkylene glycol-, (alkyl / allyloxy) polyalkylene glycol- and trimethylolpropane Examples thereof include esters of polyhydric alcohols such as polydimethylsiloxane and compounds having a polysiloxane structure such as polydiethylsiloxane. Moreover, you may be a heteroaromatic compound containing elements, such as nitrogen and sulfur.

  In addition, as a compound having an epoxy group that undergoes a ring-opening addition reaction, a compound obtained by reacting a polyol such as various diols or triols with epichlorohydrin, an epoxy compound obtained by reacting a peracid with an ethylene bond in the molecule, etc. Can be mentioned. Specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A Diglycidyl ether, bisphenol A Diglycidyl ether, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate) diol diglycidyl ether, poly (caprolactone) diol di of compounds with addition of lenoxide or propylene oxide Examples thereof include epoxy compounds such as glycidyl ether, epoxy-modified silicone oil (trade name “HF-105” manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

In this invention, the organic compound (b) which has these polymerizable unsaturated groups can select the 1 type (s) or 2 or more types according to the objective. For example, when used as an adhesive for mounting a printing plate, long-chain aliphatic, alicyclic or aromatic derivatives are used as organic compounds in order to suppress swelling with respect to organic solvents such as alcohols and esters that are printing ink solvents. It is preferable to have at least one kind.
In order to increase the mechanical strength of the adhesive obtained from the photosensitive resin composition of the present invention, the organic compound (b) preferably has at least one alicyclic or aromatic derivative. It is preferably 20 wt% or more of the total amount of the organic compound (b), more preferably 50 wt% or more. The aromatic derivative may be an aromatic compound having an element such as nitrogen or sulfur.

In order to increase the rebound resilience of the pressure-sensitive adhesive material, for example, a methacrylic monomer as described in JP-A-7-239548 can be used, or it can be selected using the technical knowledge of known photosensitive resins for printing.
The photosensitive resin composition of the present invention is crosslinked by irradiation with light or an electron beam to exhibit physical properties as a printing original plate, and a polymerization initiator can be added at that time. Polymerization initiators can be selected from those generally used. For example, initiators for radical polymerization, cationic polymerization, anion polymerization, etc., which are exemplified in “Polymer Data Handbook-Basics” edited by the Society of Polymer Science, 1986, published by Baifukan, etc. Can be used. Further, crosslinking by photopolymerization using a photopolymerization initiator is useful as a method for producing a printing original plate with high productivity while maintaining the storage stability of the photosensitive resin composition of the present invention. Known initiators can also be used. As a photopolymerization initiator for inducing a radical polymerization reaction, a hydrogen abstraction type photopolymerization initiator (d) and a decay type photopolymerization initiator (e) are used as particularly effective photopolymerization initiators.

  Although it does not specifically limit as a hydrogen abstraction type photoinitiator (d), It is preferable to use an aromatic ketone. Aromatic ketone is efficiently converted into an excited triplet state by photoexcitation, and a chemical reaction mechanism has been proposed in which this excited triplet state generates a radical by extracting hydrogen from the surrounding medium. The generated radical is considered to be involved in the photocrosslinking reaction. Any compound can be used as the hydrogen abstraction type photopolymerization initiator (d) used in the present invention as long as it is a compound that generates radicals by extracting hydrogen from the surrounding medium through an excited triplet state. Examples of aromatic ketones include benzophenones, Michler ketones, xanthenes, thioxanthones, anthraquinones, and the like. It is preferable to use at least one compound selected from these groups. Benzophenones refer to benzophenone or derivatives thereof, and specifically include 3,3 ', 4,4'-benzophenone tetracarboxylic acid anhydride, 3,3', 4,4'-tetramethoxybenzophenone, and the like. Michler ketones refer to Michler ketone and its derivatives. Xanthenes refer to derivatives substituted with xanthene and an alkyl group, phenyl group, or halogen group. Thioxanthones refer to thioxanthone and derivatives substituted with an alkyl group, a phenyl group, and a halogen group, and examples thereof include ethylthioxanthone, methylthioxanthone, and chlorothioxanthone. Anthraquinones are anthraquinone and derivatives substituted with alkyl groups, phenyl groups, halogen groups, and the like. The addition amount of the hydrogen abstraction type photopolymerization initiator is preferably 0.1 wt% or more and 10 wt% or less, more preferably 0.5 wt% or more and 5 wt% or less of the total amount of the photosensitive resin composition. If the addition amount is within this range, when the photosensitive resin composition is photocured in the air, the curability of the pressure-sensitive adhesive material surface can be sufficiently secured, and the weather resistance can be secured.

  The decay type photopolymerization initiator (e) refers to a compound that generates an active radical by generating a cleavage reaction in the molecule after light absorption, and is not particularly limited. Specific examples include benzoin alkyl ethers, 2,2-dialkoxy-2-phenylacetophenones, acetophenones, acyloxime esters, acylphosphine oxides, azo compounds, organic sulfur compounds, diketones, and the like. It is preferable to use at least one compound selected from these groups. Examples of benzoin alkyl ethers include compounds such as benzoin isopropyl ether and benzoin isobutyl ether. Examples of 2,2-dialkoxy-2-phenylacetophenones include 2,2-dimethoxy-2-phenylacetophenone and 2,2-diethoxy-2-phenylacetophenone. Examples of acetophenones include acetophenone, trichloroacetophenone, 1-hydroxycyclohexylphenylacetophenone, 2,2-diethoxyacetophenone, and the like. Acylphosphine oxides include 2,4,6-trimethyl-benzoyl-diphenylphosphine oxide, bis (2,4,6-trimethyl-benzoyl) -phenylphosphine oxide, bis (2,4,6-trimethyl-benzoyl). -2,4-diisobutoxyphenylphosphine oxide, bis (2,4,6-trimethyl-benzoyl) -2,4-diisopropoxyphenylphosphine oxide, bis (2,4,6-trimethyl-benzoyl) -2, 4-diisopentyloxyphenylphosphine oxide, bis (2,4,6-trimethyl-benzoyl) -2,4-dioctyloxyphenylphosphine oxide, bis (2,6-diethoxy-benzoyl) -2-propoxy-4- Mention methylphenylphosphine oxide, etc. It can be. Examples of acyl oxime esters include 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime. Examples of the azo compound include azobisisobutyronitrile, diazonium compound, and tetrazene compound. Examples of organic sulfur compounds include aromatic thiols, mono and disulfides, thiuram sulfides, dithiocarbamates, S-acyl dithiocarbamates, thiosulfonates, sulfoxides, sulfinates, dithiocarbonates, and the like. Examples of diketones include benzyl and methylbenzoyl formate. The addition amount of the collapsible photopolymerization initiator is preferably 0.1 wt% or more and 10 wt% or less, more preferably 0.3 wt% or more and 3 wt% or less of the total amount of the photosensitive resin composition. When the addition amount is within this range, when the photosensitive resin composition is photocured in the air, the curability inside the adhesive material can be sufficiently secured.

  A compound having a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule can also be used as the photopolymerization initiator. There may be mentioned α-aminoacetophenones. For example, the following general formulas such as 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone The compound shown by (1) can be mentioned.

(In the formula, each R ₂ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. X represents an alkylene group having 1 to 10 carbon atoms.)
The amount of the compound having a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule is 0.1 wt% or more and 10 wt% of the total amount of the photosensitive resin composition. The following is preferable, and more preferably 0.3 wt% or more and 3 wt% or less. If the addition amount is within this range, even if the photosensitive resin composition is photocured in the air, the mechanical properties of the adhesive can be sufficiently ensured.

  A photopolymerization initiator that induces an addition polymerization reaction by absorbing light and generating an acid can also be used. For example, photocationic polymerization initiators such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts, or polymerization initiators that absorb light and generate bases. The addition amount of these photopolymerization initiators is preferably in the range of 0.1 wt% to 10 wt% of the total amount of the photosensitive resin composition.

The ratio of the resin (a) and the organic compound (b) in the photosensitive resin composition of the present invention is usually preferably 5 to 200 parts by mass of the organic compound (b) with respect to 100 parts by mass of the resin (a). The range of 20-100 mass parts is more preferable.
The pressure-sensitive adhesive material is formed by photocrosslinking and curing a photosensitive resin composition. Therefore, a three-dimensional crosslinked structure is formed by the reaction between the polymerizable unsaturated groups of the organic compound (b) or the polymerizable unsaturated group of the resin (a) and the polymerizable unsaturated group of the organic compound (b). It is insolubilized in commonly used ester, ketone, aromatic, ether, alcohol and halogen solvents. This reaction occurs between the organic compounds (b), between the resins (a), or between the resin (a) and the organic compound (b), and the polymerizable unsaturated group is consumed. When the photopolymerization initiator is used for cross-linking and curing, the photopolymerization initiator is decomposed by light. Therefore, the adhesive material is extracted with a solvent and separated by GC-MS (gas chromatography). Method), LC-MS method (method of mass spectrometry of those separated by liquid chromatography), GPC-MS method (method of separation and gel analysis by gel permeation chromatography), LC-NMR method (liquid chromatography) By analyzing the separated product using a nuclear magnetic resonance spectrum, unreacted photopolymerization initiators and decomposition products can be identified. Furthermore, by using the GPC-MS method, LC-MS method, and GPC-NMR method, the unreacted polymer, the unreacted organic compound (b), and the polymerizable unsaturated group in the solvent extract are reacted. The resulting relatively low molecular weight product can also be identified from analysis of the solvent extract. For the high molecular weight component insoluble in the solvent in which the three-dimensional cross-linked structure is formed, by using the pyrolysis GC-MS method, the site formed by the reaction of the polymerizable unsaturated group is formed as a component constituting the high molecular weight body. It is possible to verify whether it exists. For example, it can be estimated from the mass spectrometry spectrum pattern that there is a site where a polymerizable unsaturated group such as a methacrylate group, an acrylate group, or a vinyl group has reacted. The pyrolysis GC-MS method is a method in which a sample is thermally decomposed and a gas component to be generated is separated by gas chromatography and then mass spectrometry is performed. The decomposition product derived from the photopolymerization initiator and the unreacted photopolymerization initiator are detected together with the unreacted polymerizable unsaturated group or the site obtained by the reaction of the polymerizable unsaturated group in the crosslinked cured product. Then, it can be concluded that the photosensitive resin composition was obtained by photocrosslinking and curing.

  A tack tester (manufactured by Toyo Seiki Seisakusho) can be used for measuring the adhesive strength of the adhesive. For example, at 20 ° C., a ring having a PET film having a width of 13 mm and a thickness of 125 μm is brought into contact with the surface of an aluminum ring having a radius of 50 mm and a width of 13 mm on the smooth surface of the adhesive material, and a load of 0.5 kg is applied to the ring. In addition, after leaving for 4 seconds, when the wheel is pulled up at a constant speed of 30 mm per minute and the resistance force when the wheel is separated from the adhesive material surface is read with a push-pull gauge, 150 N / m to 10 kN / m Preferably, it is preferably less than 150 N / m when measured by contacting the aluminum wheel.

  As a method for molding the photosensitive resin composition of the present invention into a sheet or cylinder, an existing resin molding method can be used. For example, a casting method, a method of extruding a resin from a nozzle or a die with a machine such as a pump or an extruder, adjusting a thickness with a blade, adjusting a thickness by calendaring with a roll, a spray method, and the like can be exemplified. In that case, it is also possible to perform molding while heating within a range that does not deteriorate the performance of the resin. Moreover, you may perform a rolling process, a grinding process, etc. as needed. Usually, it is often formed on a sheet-like support made of a material such as PET or nickel, but it may be formed directly on a cylinder of a printing machine. A cylindrical support made of fiber reinforced plastic (FRP), plastic, or metal such as nickel can also be used. The cylindrical support can be hollow with a constant thickness for weight reduction. The role of the sheet-like support or the cylindrical support is to ensure the dimensional stability of the adhesive material.

  Therefore, it is preferable to select one having high dimensional stability. When evaluated using the linear thermal expansion coefficient, a preferable range of linear thermal expansion coefficient is −10 ppm / ° C. to 100 ppm / ° C., and more preferably −10 ppm / ° C. to 70 ppm / ° C. Specific examples of materials include polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylene ether resin, polyphenylene thioether resin, polyethersulfone resin, all Examples thereof include liquid crystal resins composed of aromatic polyester resins, wholly aromatic polyamide resins, and epoxy resins. Further, these resins can be laminated and used. Moreover, a porous sheet, for example, a cloth formed by knitting fibers, a nonwoven fabric, a film in which pores are formed, or the like can be used as the sheet-like support. When a porous sheet is used as the sheet-like support, high adhesiveness is obtained because the pressure-sensitive adhesive layer and the sheet-like support are integrated by photo-curing after impregnating the photosensitive resin composition into the holes. Obtainable. The fibers forming the cloth or nonwoven fabric include glass fibers, alumina fibers, carbon fibers, alumina / silica fibers, boron fibers, high silicon fibers, potassium titanate fibers, inorganic fibers such as sapphire fibers, natural materials such as cotton and hemp Examples include fibers, semi-synthetic fibers such as rayon and acetate, and synthetic fibers such as nylon, polyester, acrylic, vinylon, polyvinyl chloride, polyolefin, polyurethane, polyimide, and aramid. Further, cellulose produced by bacteria is a highly crystalline nanofiber, and is a material capable of producing a thin nonwoven fabric with high dimensional stability.

  In addition, as a method of reducing the linear thermal expansion coefficient of a sheet-like or cylindrical support, a method of adding a filler, a method of impregnating or coating a resin on a mesh cloth such as wholly aromatic polyamide, a glass cloth, etc. Can be mentioned. As the filler, generally used organic fine particles, inorganic fine particles such as metal oxide or metal, organic / inorganic composite fine particles, and the like can be used. In addition, porous fine particles, fine particles having cavities inside, microcapsule particles, and layered compound particles in which a low molecular compound intercalates can be used. In particular, metal oxide fine particles such as alumina, silica, titanium oxide, and zeolite, latex fine particles made of polystyrene / polybutadiene copolymer, natural product-based organic fine particles such as highly crystalline cellulose, and the like are useful.

  By performing physical and chemical treatment on the surface of the sheet-like support or cylindrical support used in the present invention, the adhesiveness with the pressure-sensitive adhesive material can be improved. Examples of the physical treatment method include a sand blast method, a wet blast method for injecting a liquid containing fine particles, a corona discharge treatment method, a plasma treatment method, an ultraviolet ray or vacuum ultraviolet ray irradiation method, and the like. Examples of chemical treatment methods include strong acid / strong alkali treatment methods, oxidant treatment methods, and coupling agent treatment methods.

  The molded photosensitive resin composition layer is cross-linked by light irradiation to form an adhesive material. Further, it can be crosslinked by light irradiation while molding. Examples of the light source used for curing include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a germicidal lamp, a carbon arc lamp, a xenon lamp, and a metal halide lamp. The light applied to the photosensitive resin composition layer preferably has a wavelength of 200 nm to 300 nm. In particular, since many hydrogen abstraction type photopolymerization initiators have strong light absorption in this wavelength region, when having light with a wavelength of 200 nm to 300 nm, the curability of the adhesive material layer surface can be sufficiently secured. . Although the light source used for curing may be one type, the curability of the resin may be improved by curing using two or more types of light sources having different wavelengths, so two or more types of light sources may be used. There is no problem.

The thickness of the adhesive material may be arbitrarily set according to the purpose of use, but is preferably in the range of 0.1 μm to 5 mm. In some cases, a plurality of materials having different compositions may be stacked. Moreover, when laminating | stacking on a sheet form, it can also laminate | stack not only on one side of a sheet-like support body but on both sides. Moreover, you may be the laminated body which laminated | stacked the adhesive material layer of this invention on the single side | surface of a sheet-like support body, and laminated | stacked the double-sided adhesive layer on the opposite surface.
In the present invention, a cushion layer made of an elastomer can be formed below the adhesive material. The cushion layer is preferably an elastomer layer having a Shore A hardness of 10 to 70 degrees. When the Shore A hardness is 10 degrees or more, the print quality can be ensured because the film is appropriately deformed. Moreover, if it is 70 degrees or less, it can play the role as a cushion layer. A more preferable range of Shore A hardness is 10 to 50 degrees.

The cushion layer is not particularly limited, and any cushion layer may be used as long as it has rubber elasticity, such as a thermoplastic elastomer, a photocurable elastomer, and a thermosetting elastomer. It may be a porous elastomer layer having nanometer-level micropores, or an elastomer layer having closed cells or open cells in the layer. In particular, from the viewpoint of processability to a sheet-like or cylindrical printing plate, it is convenient and preferable to use a liquid photosensitive resin composition that is cured by light and to use a material that becomes elastomer after curing.
Specific examples of the thermoplastic elastomer used for the cushion layer include SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene-polyethylene / polybutylene-polystyrene), which are styrenic thermoplastic elastomers, and the like. Olefin-based thermoplastic elastomer, urethane-based thermoplastic elastomer, ester-based thermoplastic elastomer, amide-based thermoplastic elastomer, silicon-based thermoplastic elastomer, fluorine-based thermoplastic elastomer, and the like.

Examples of the photocurable elastomer include those obtained by mixing a photopolymerizable monomer, a plasticizer, a photopolymerization initiator, and the like with the thermoplastic elastomer, and a liquid composition obtained by mixing a photopolymerizable monomer, a photopolymerization initiator, etc. with a plastomer resin. Can be mentioned. In the present invention, unlike the design concept of the photosensitive resin composition, in which the function of forming a fine pattern is an important element, it is not necessary to form a fine pattern using light, and by curing by overall exposure, Since it is sufficient to ensure a certain level of mechanical strength, the degree of freedom in selecting a material is extremely high.
Moreover, non-sulfur cross-linked rubbers such as sulfur cross-linked rubber, organic peroxide, phenol resin initial condensate, quinone dioxime, metal oxide, and thiourea can also be used.
Furthermore, it is also possible to use a three-dimensionally crosslinked elastomer obtained by using a curing agent that reacts with a telechelic liquid rubber.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited by these.
(1) Viscosity The viscosity of the photosensitive resin composition was measured at 20 ° C. using a B type viscometer (B8H type; manufactured by Tokyo Keiki Co., Ltd., Japan).
(2) Measurement of number average molecular weight The number average molecular weight of the resin (a) was determined by conversion with polystyrene having a known molecular weight using a gel permeation chromatography method (GPC method). Using a high-speed GPC device (HLC-8020 manufactured by Tosoh Corporation, Japan) and a polystyrene-filled column (trademark: TSKgel GMHXL; manufactured by Tosoh Corporation, Japan), the measurement was performed with tetrahydrofuran (THF). The column temperature was set to 40 ° C. As a sample to be injected into the GPC apparatus, a THF solution having a resin concentration of 1 wt% was prepared, and the injection amount was 10 μl. As the detector, for the resin (a), an ultraviolet absorption detector was used, and 254 nm light was used as monitor light. The resin (a) used in the examples or comparative examples of the present invention had a polydispersity (Mw / Mn) determined by the GPC method greater than 1.1, and therefore the number average molecular weight determined by the GPC method. Mn was adopted. The molecular weight of the organic compound (b) used was determined from the molecular structure identified by the nuclear magnetic resonance spectrum method in which the observation nucleus is H, because the polydispersity is less than 1.1.

(3) Measurement of the number of polymerizable unsaturated groups The average number of polymerizable unsaturated groups present in the molecule of the synthesized resin (a) was obtained by removing unreacted low-molecular components using liquid chromatography. Thereafter, molecular structure analysis was performed using a nuclear magnetic resonance spectrum method (NMR method).
(4) Surface tack measurement of photocured material The surface tack of the photocured material to the PET film was measured using a tack tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 20 ° C. with a radius of 50 mm and a width on the smooth surface of the photocured material. A ring with a PET film having a width of 13 mm and a thickness of 125 μm is brought into contact with the surface of a 13 mm aluminum ring, a load of 0.5 kg is applied to the ring and left for 4 seconds, and then the ring is moved at a constant speed of 30 mm per minute. The resistance force at the time when the wheel was pulled away from the surface of the photocured material was read with a push-pull gauge. Moreover, the surface tack measurement with respect to aluminum was implemented by removing the said PET film.

(Production Example 1)
A 1 L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Corporation. Trademark “PCDLL4672” (number average molecular weight 1990, OH number 56.4) 447.24 g and tolylene diisocyanate 30 After adding .83 g and reacting at 80 ° C. for about 3 hours, 14.83 g of 2-methacryloyloxyisocyanate is added, and further reacted for about 3 hours, and the terminal is a methacryl group (polymerization within the molecule). A resin (A) having a number average molecular weight of about 10,000 having an average of about 2 unsaturated groups) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

(Production Example 2)
A 1 L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Corporation. Trademark “PCDLL4672” (number average molecular weight 1990, OH number 56.4) 447.24 g and tolylene diisocyanate 30 .83 g was added and reacted at 80 ° C. for about 3 hours. Then, 7.42 g of 2-methacryloyloxyisocyanate was added and further reacted for about 3 hours, and the terminal was a methacrylic group (polymerization within the molecule). A resin (a) having a number average molecular weight of about 10,000 having an average of about 1 unsaturated group per molecule) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

(Examples 1-3)
As resin (a), the resins (a) and (b) prepared in Production Example 1 or 2 were used, and as shown in Table 1, a polymerizable monomer, a photopolymerization initiator, and other additives were added to form a photosensitive resin composition. I made a thing.
The prepared photosensitive resin composition is formed into a 0.5 mm thick sheet on a 125 μm thick PET film, and the surface is coated with a 15 μm thick PET film that has been subjected to release treatment. Was irradiated. The amount of energy irradiated was 2000 mJ / cm ² (value obtained by integrating the illuminance measured with the UV-35-APR filter over time). The lamp illuminance on the irradiated surface was measured using a UV meter (trade name “UV-M02” manufactured by Oak Manufacturing Co., Ltd.). The lamp illuminance measured using a filter (trade name “UV-35-APR filter” manufactured by Oak Manufacturing Co., Ltd.) was ² mW / cm ² .

Table 2 shows the surface tack value of the adhesive material. In any of Examples 1 to 3, no stickiness was felt by touching the surface of the adhesive material with a hand.
As the photopolymerization initiator used, 2,2-dimethoxy-2-phenylacetophenone (DMPAP) was a decay type photopolymerization initiator.
The photosensitive resin compositions of Examples 1 to 3 were all liquid at 20 ° C. The viscosity measured using a B-type viscometer was 100 Pa · s or more and 5 kPa · s or less in any system at 20 ° C.

(Comparative Example 1)
A polybutadiene having a number average molecular weight of about 3000 and having hydroxyl groups at both ends of the molecule was reacted with tolylene diisocyanate to synthesize a polyurethane compound having both ends being isocyanate groups. Furthermore, 2-hydroxyethyl methacrylate was reacted with the obtained polyurethane compound to obtain an unsaturated polyurethane compound having a methacrylate group at the terminal and having a number average molecular weight of 12,000. This compound has a urethane bond in the molecule but no carbonate bond. 16 parts by mass of lauryl methacrylate (molecular weight 245), 4 parts by mass of polypropylene glycol dimethacrylate (number average molecular weight 660), 1,3-butylene glycol dimethacrylate (molecular weight 226) 4 with respect to 100 parts by mass of the obtained unsaturated polyurethane compound Mass parts, 1.5 parts by mass of benzoin isobutyl ether, and 0.01 parts by mass of 2,6-di-tert-butyl-4-methylphenol were mixed to obtain a photosensitive resin composition. The obtained photosensitive resin composition was photocured by the same method as in Example 1 except that it was formed into a sheet having a thickness of 0.5 mm.
The surface tack for aluminum was 360 N / m, and the surface tack for PET was 900 N / m. When the surface of the adhesive material was touched by hand, it was sticky and showed stickiness.

Example 4
The photosensitive resin composition used in Example 1 was applied at a thickness of 1.0 mm using a doctor blade on a fiber reinforced plastic sleeve having an inner diameter of 300 mm and a thickness of 2 mm, and the light of a metal halide lamp was applied in the atmosphere. The photosensitive resin composition layer was cured by irradiation with 2000 mJ / cm ² (value obtained by time integration of illuminance measured with a filter (trade name “UV-35-APR filter” manufactured by Oak Seisakusho)). Then, it grind | polished using the grindstone until thickness became 0.5 mm.
The surface tack for aluminum was 80 N / m and the surface tack for PET was 220 N / m. There was no stickiness as if the surface of the adhesive was touched by hand.
A flexographic printing plate (thickness: 1.27 mm) having a PET support with a thickness of 125 μm as a support is pasted on the obtained adhesive material with the PET inside, and the flexographic printing plate is temporarily fixed without coming off. I was able to.

  The present invention is suitably used as a photosensitive resin composition for forming an adhesive material having specific adhesion to polyester.

Claims (11)

  A photosensitive resin composition comprising a resin (a) having a number average molecular weight of 1,000 to 500,000, and an organic compound (b) having a polymerizable unsaturated group having a number average molecular weight of 100 to less than 1,000, wherein the resin (A) contains a compound having a carbonate bond and a urethane bond in the molecular main chain, containing 20 wt% or more and 100 wt% or less of the total amount of the resin (a), and is photocured. Resin composition.   The resin (a) contains a compound having a polyurethane skeleton obtained by a condensation reaction of a polycarbonate diol having a number average molecular weight of 100 or more and 100,000 or less and a diisocyanate compound, and having a polymerizable unsaturated group in the molecule. The photosensitive resin composition for forming an adhesive material according to claim 1.   The organic compound (b) contains a compound having an aromatic functional group and / or an alicyclic functional group in the molecule in an amount of 10 wt% to 100 wt% of the total amount of the organic compound (b). Item 3. The photosensitive resin composition for forming an adhesive material according to Item 1 or 2.   The photosensitive resin composition for forming an adhesive material according to any one of claims 1 to 3, wherein the photosensitive resin composition is liquid at 20 ° C.   An adhesive material obtained by photocuring the photosensitive resin composition according to any one of claims 1 to 4, wherein the adhesive material surface exhibits adhesiveness to a polyester film, and the adhesive strength is 150 N / m or more. The pressure-sensitive adhesive material is 10 kN / m or less.   After applying the photosensitive resin composition according to any one of claims 1 to 4 on one or both sides of the surface of a sheet-like support or a cylindrical support to form a photosensitive resin composition layer, light A laminate having a pressure-sensitive adhesive material obtained by photo-curing by irradiating with an adhesive.   The laminate according to claim 6, further comprising a cushion layer between the sheet-like support or the cylindrical support and the adhesive material.   On the adhesive material, a sheet-like printing original plate or sheet-like printing plate having a polyester film as a support is further pasted so that the polyester material is inside and the adhesive material and the polyester film are in contact with each other. A printing substrate having the laminate according to claim 6.   The photosensitive resin composition according to any one of claims 1 to 4 is applied on a sheet-like support or a cylindrical support in a film thickness of 0.5 µm to 5 mm to form a photosensitive resin composition layer. The manufacturing method of the adhesive material characterized by including the process of photocuring by irradiating light to the process and the formed photosensitive resin composition layer.   The method for producing a pressure-sensitive adhesive material according to claim 9, wherein in the step of photocuring by irradiating light, light is irradiated in the atmosphere.   The method for producing an adhesive material according to claim 9 or 10, further comprising a step of adjusting the film thickness of the adhesive material by cutting or / and grinding or / and polishing after the photocuring step.