JP6000576B2 - Original printing - Google Patents

Description

  The present invention relates to a printing original plate. The present invention also relates to a support substrate for a printing original plate.

  As printing methods, letterpress printing and intaglio printing, which are methods for printing a printing plate with a three-dimensional shape, are known. In letterpress printing, printing is performed by applying ink to the convex portions of the printing plate. In intaglio printing, printing is performed by applying ink to the concave portions of the printing plate.

Among printing plates used for letterpress printing, in particular, flexographic printing plates used for flexographic printing, which is a type of letterpress printing, generally have a photosensitive resin layer laminated on a polyester film as a support. Yes.
A method for producing a flexographic printing plate by making a photosensitive resin plate using the photosensitive resin layer is as follows.
First, UV exposure is performed on the entire surface of the photosensitive resin layer through the polyester film (back exposure) to provide a thin uniform cured layer. Next, a negative film is disposed on the photosensitive resin layer, image exposure (relief exposure) is performed on the photosensitive resin layer through the negative film, and the photosensitive resin layer is photocured according to the pattern of the transparent image carrier. Thereafter, the unexposed portion (that is, the portion that has not been photocured) in the photosensitive resin layer is washed with a developing solution to form a desired image, that is, a relief image, and is made as a photosensitive resin plate and printed. Get a version.

The printing plate obtained as described above is used by being fixed to a plate cylinder of a printing press with a double-sided tape or the like. However, when the printing plate is passed between the plate cylinder and the impression cylinder of the printing press, the photosensitive resin layer may be peeled off from the polyester film due to the shearing stress, and printing may have to be interrupted. It was. Further, when the printing plate is removed from the plate cylinder at the end of printing, the photosensitive resin layer and the polyester film may be peeled off, and the printing plate may be damaged and cannot be reused.
From these viewpoints, it is necessary that the polyester film and the photosensitive resin layer are firmly bonded, and the adhesive force is 580N when the polyester film and the photosensitive resin layer are forcibly peeled at a peeling angle of 180 °. / Cm or more is preferable.

In view of the above-mentioned present situation, there is a demand for a printing plate in which a photosensitive resin layer and a polyester film are firmly bonded and both do not easily peel off. However, since the photosensitive resin layer and the polyester film differ greatly in properties such as polarity, it has been difficult to firmly bond them.
In a printing plate that is a laminate in which a photosensitive resin layer and a polyester film are laminated via an adhesive layer, the composition of the photosensitive resin layer may affect the adhesiveness of the adhesive layer. .

  For example, in Patent Document 1 and Patent Document 2, an adhesive layer containing a photosensitive resin layer having a specific photosensitive resin composition and a reaction product of a polyol having a polyester structure and / or a polyurethane structure and a polyfunctional isocyanate is provided. Combining is disclosed.

  Patent Document 3 discloses an underlayer made of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 11 to 50% by mass. Patent Document 4 discloses an adhesive layer for bonding the photosensitive resin layer and the support.

  Patent Document 5 discloses a photosensitive resin plate material in which a synthetic rubber-based photosensitive resin layer is provided on a base material via a photopolymerizable adhesive. Patent Documents 6 and 7 disclose a support for a photosensitive resin plate composed of multiple layers.

JP 2000-155410 A JP 2001-264959 A JP 2004-109443 A International Publication No. 2004/104701 Pamphlet JP 2008-191638 A JP-A-1-283557 JP-A-5-313377

However, Patent Documents 1 and 2 disclose that an adhesive composition exhibiting good adhesive force on a photosensitive resin layer made of a photosensitive resin composition that does not contain a specific ethylenically unsaturated compound in the photosensitive resin composition. Not mentioned.
Patent Documents 3 and 4 do not describe the tackiness of the adhesive layer.
Moreover, in patent document 5, since the photopolymerizable adhesive was used, there existed a problem that handling of the base material (support body) which apply | coated the adhesive bond layer became complicated. Furthermore, there is no description regarding silica particles.
Patent Documents 6 and 7 have no description regarding the use of a thermoplastic elastomer for the adhesive layer. Patent Document 6 describes that powdered silica is added to the adhesive layer, but there is no description regarding silica particles and adhesive strength. Further, Patent Document 7 also describes adding silica to an adhesive as an antiblocking agent, but there is no description regarding the use of a thermoplastic elastomer as an adhesive component and silica and adhesive strength.

  The problem to be solved by the present invention is to provide a printing original plate in which a polyester film and a photosensitive resin layer are firmly bonded and dust can be prevented from adhering to the adhesive layer.

  In order to solve the above problems, the present inventors have made extensive studies on the composition of the adhesive layer applied on the polyester film, and as a result, surprisingly, the silica particles that have been known to have an effect of reducing tackiness. In order to improve the tackiness, by adding to the adhesive layer, where it is common knowledge to improve tackiness, by finding the contradictory effects of reducing tackiness and improving adhesive strength, It has been found that the above-mentioned problems can be solved by finding that dust adhesion to the agent layer can be reduced, and the present invention has been achieved.

That is, the present invention is as follows.
[1]
A printing original plate in which at least an adhesive layer (B) and a photosensitive resin layer (C) are sequentially laminated on a polyester film (A),
The adhesive layer (B) is at least one thermoplastic elastomer (b-1) composed of at least one monovinyl substituted aromatic hydrocarbon and at least one conjugated diene, and at least one silica. A printing original plate containing particles (b-2).
[2]
The printing original plate as described in [1], wherein the silica particles (b-2) are subjected to a hydrophobic treatment.
[3]
The printing original plate as described in [1] or [2], wherein the silica particles (b-2) have an average particle diameter of 1 to 10 μm.
[4]
The printing original plate [5] according to any one of [1] to [3], wherein the adhesive layer (B) further contains at least one polyester resin.
The printing original plate in any one of [1]-[4] in which a thermoplastic elastomer (b-1) contains a styrene-butadiene block copolymer and / or a styrene-isoprene block copolymer.
[6]
The printing original plate according to any one of [1] to [5], wherein the polyester film (A) has at least an undercoat layer (D) on a surface on which the adhesive layer (B) is laminated.
[7]
The photosensitive resin layer (C) is at least one thermoplastic elastomer comprising at least one monovinyl-substituted aromatic hydrocarbon and at least one conjugated diene, at least one ethylenically unsaturated compound, And the printing original plate in any one of [1]-[6] containing at least 1 or more types of photoinitiator.
[8]
A support substrate for a printing original plate in which an adhesive layer (B) is laminated on a polyester film (A),
The adhesive layer (B) is at least one thermoplastic elastomer (b-1) composed of at least one monovinyl substituted aromatic hydrocarbon and at least one conjugated diene, and at least one silica. A support base material for a printing original plate containing particles (b-2).

  ADVANTAGE OF THE INVENTION According to this invention, the polyester film and the photosensitive resin layer can adhere | attach firmly, and the printing original plate which can suppress adhesion of refuse to an adhesive bond layer can be provided.

  Hereinafter, modes for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The printing original plate in this embodiment is formed by sequentially laminating at least an adhesive layer (B) and a photosensitive resin layer (C) on a polyester film (A), and the adhesive layer (B) has at least one kind. At least one thermoplastic elastomer (b-1) comprising at least one monovinyl-substituted aromatic hydrocarbon and at least one conjugated diene, and at least one silica particle (b-2).
The printing original plate of this embodiment can be used as a printing plate that can be printed by applying a three-dimensional shape. Further, by containing at least one kind of silica particles (b-2) in the adhesive layer, the polyester film and the photosensitive resin layer are firmly bonded. This is preferable in that the properties are not impaired.

(Polyester film (A))
Examples of the polyester for forming the polyester film (A) include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Among these, polyethylene terephthalate is preferable from the viewpoints of mechanical characteristics, processing characteristics, cost, and the like.
The polyester film (A) may be subjected to corona treatment, plasma treatment, flame treatment, alkali chemical treatment, or the like, as necessary.

The polyester film (A) has a layer (hereinafter sometimes simply referred to as “undercoat layer”) applied for the purpose of improving adhesion, and this undercoat layer is usually about 0.001 to 1 μm. It is provided by coating with a thickness. The polyester film having an undercoat layer is preferably produced by a so-called in-line process in which the undercoat layer is applied in the process of producing a biaxially stretched film.
The presence or absence of these undercoat layers can be examined by a known technique such as infrared absorption spectrum measurement or measurement by electron spectroscopy. Furthermore, the presence or absence of the undercoat layer can also be examined by irradiating the polyester film with an ion beam, decomposing the polyester film surface, and examining the decomposition product.
From the viewpoint of obtaining better adhesive strength, a polymer of (meth) acrylate is preferable as the main component constituting the undercoat layer. Examples of such a polymer include polymers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and copolymers thereof. Etc. If necessary, these (co) polymers can be used as a copolymer with (meth) acrylic acid, styrene, acrylonitrile, vinyl chloride or the like.

As the other component of the undercoat layer, a compound having a urethane bond is preferable, and a compound having a urethane bond obtained from an isocyanate compound having one or more aromatic rings is more preferable. Examples of such a compound include a reaction product of a compound having active hydrogen and an isocyanate compound having an aromatic ring.
Examples of the compound having active hydrogen include ethylene glycol, 1,4-butanediol, neopentyl glycol, and diols such as polyether diols composed of polyethers thereof. Moreover, a polyester compound etc. can also be used as a compound which has active hydrogen. Examples of the polyester compound include dicarboxylic acid components such as terephthalic acid and isophthalic acid, and alcohol components such as condensates such as ethylene glycol, 1,4-butanediol and polyether polyol compounds thereof. It is done.
Examples of the isocyanate compound having an aromatic ring include toluene diisocyanate and 4,4-diphenylenemethane diisocyanate.

The thickness of the polyester film (A) is preferably 30 to 300 μm, more preferably 75 to 200 μm.
When the thickness is 30 μm or more, the strength required as a support in the printing original plate can be imparted, and when it is 300 μm or less, flexibility as the printing plate can be imparted, and also suitable from the viewpoint of cost. It is.

(Adhesive layer (B))
The adhesive layer (B) laminated on the polyester film (A) contains at least one kind of thermoplastic elastomer (b-1) and at least one kind of silica particles (b-2). The thermoplastic elastomer (b-1) is a thermoplastic elastomer comprising at least one kind of monovinyl-substituted aromatic hydrocarbon and at least one kind of conjugated diene.
In the present embodiment, “containing at least one or more types” means that one type of the contained components is included, and may include one type or two or more types.

Examples of the monovinyl-substituted aromatic hydrocarbon constituting the thermoplastic elastomer (b-1) include styrene, t-butylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-dimethyl-p-aminoethylstyrene. N, N-diethyl-p-aminoethylstyrene, vinylpyridine, p-methylstyrene, p-methoxystyrene, tertiary butylstyrene, α-methylstyrene, 1,1-diphenylethylene, and the like. Among these, styrene is preferable from the viewpoint of the lamination property of the adhesive layer.
Monovinyl substituted aromatic hydrocarbons can be used alone or in combination of two or more.

Examples of the conjugated diene constituting the thermoplastic elastomer (b-1) include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, Examples include 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, and the like.
Conjugated dienes can be used alone or in combination of two or more.

Examples of the thermoplastic elastomer (b-1) include a first polymer block mainly composed of at least one monovinyl aromatic hydrocarbon unit and a second polymer block mainly composed of at least one conjugated diene unit. Specifically, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-ethylene / propylene block copolymer, styrene-ethylene / butylene block Examples thereof include styrene-butadiene block copolymers and styrene-isoprene block copolymers (styrene-butadiene block copolymers and styrene-isoprene block copolymers).
A thermoplastic elastomer (b-1) can be used individually or in combination of 2 or more types.
The conjugated diene unit may be a hydrogenated conjugated diene hydrogenated unit, and a styrene-ethylene / butylene block copolymer or styrene-ethylene / propylene block copolymer in which the conjugated diene unit is completely hydrogenated. Etc. or may be used in combination.

In the present embodiment, “mainly” means that 50% by mass or more is contained in the copolymer block, preferably 80% by mass or more, and more preferably 90% by mass or more. .
The monovinyl aromatic hydrocarbon units in the copolymer block may be uniformly distributed or non-uniformly (for example, tapered). A plurality of uniformly distributed portions and / or non-uniformly distributed portions may coexist in each copolymer block.

Examples of the block copolymer comprising a monovinyl-substituted reporting group hydrocarbon and a conjugated diene include, for example, a linear block copolymer represented by the following general formula group (I) or a general formula group (II) below. The linear block copolymer or the radial block copolymer is included.
(AB) n, A- (BA) n, A- (BA) n-B, B- (AB) n. (I)
[(AB) k] m-X, [(AB) k-A] mX, [(BA) k] mX, [(BA) kB] m- X (II)
In the general formula group, A represents a polymer block mainly composed of monovinyl-substituted aromatic hydrocarbon units, and B represents a polymer block mainly composed of conjugated diene units or conjugated diene hydrogenated units.
X is an m-valent group, for example, silicon tetrachloride, tin tetrachloride, epoxidized soybean oil, polyhalogenated hydrocarbon compound, carboxylic acid ester compound, polyvinyl compound, bisphenol type epoxy compound, alkoxysilane compound, A residue of a coupling agent such as a halogenated silane compound or an ester compound or a residue of an initiator such as a polyfunctional organolithium compound is shown.
n, k, and m show an integer greater than or equal to 1, for example, 1-5.

The vinyl content in the total amount of conjugated dienes of the polymer block mainly composed of conjugated diene units, for example, the content of 1,2-butadiene or 3,4-isoprene is not particularly limited.
Further, the method for hydrogenating conjugated diene units is not particularly limited.

In the thermoplastic elastomer (b-1), the copolymerization ratio (mass ratio: monovinyl substituted aromatic hydrocarbon / conjugated diene) of the monovinyl substituted aromatic hydrocarbon and the conjugated diene is preferably from the viewpoint of adhesiveness of the adhesive layer. Is 20/80 to 80/20, more preferably 30/70 to 80/20.
When the mass ratio of the monovinyl-substituted aromatic hydrocarbon is 20 or more, the adhesiveness with the polyester film can be enhanced, and when it is 80 or less, the adhesiveness with the photosensitive resin layer can be enhanced.

  In the thermoplastic elastomer (b-1), other functional groups may be introduced, chemical modification such as hydrogenation may be made, or other components may be copolymerized as necessary. .

The number average molecular weight (Mn) of the thermoplastic elastomer (b-1) is preferably 20,000 to 300,000, more preferably 50,000 to 200,000, from the viewpoint of viscosity at room temperature.
The number average molecular weight (Mn) is a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  The content of the thermoplastic elastomer (b-1) in the adhesive layer (B) is preferably 10 to 90% by mass, more preferably, based on the entire adhesive layer (B) from the viewpoint of adhesive strength. 30 to 80% by mass.

For the adhesive layer, as the thermoplastic elastomer, a polyurethane-based thermoplastic elastomer other than the thermoplastic elastomer (b-1), a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, a fluorine-based thermoplastic An elastomer, a silicon-based thermoplastic elastomer, or the like may be used.
These thermoplastic elastomers can be used alone or in combination of two or more.

The silica particles (b-2) mean particles mainly composed of silicon dioxide (SiO ₂ ) and silicon dioxide hydrate (SiO ₂ .nH ₂ O). The main component means that SiO ₂ and SiO ₂ · nH ₂ O are 80% by mass or more in the particles.
Silica particles are produced using silica sand as a raw material, and can be obtained by a wet method in which sodium silicate is reacted with an acid, or a dry method in which silicon tetrachloride is decomposed by heating. Commercially available silica particles can be used as the silica particles (b-1).
Silica particles (b-2) can be used alone or in combination of two or more.

By bringing the silica particles into contact with an organic compound, the organic compound can be irreversibly adsorbed and surface-treated. Moreover, the surface-treated silica can be obtained by putting the precipitated silicic acid obtained by the wet method into a Henschel mixer, spraying and mixing oil. The surface-treated silica particles thus obtained are preferred from the viewpoint of adhesive strength.
Examples of the organic compound used for the surface treatment include hydrocarbon, halogenated hydrocarbon, alcohol, ether, acetal, ketone, aldehyde, ester, polyhydric alcohol, polyhydric alcohol derivative, carboxylic acid, carboxylic anhydride, and phenol. , Nitrogen-containing compounds, fluorine compounds, organosilicon compounds, and the like.
The organic compounds to be adsorbed can be used alone or in combination of two or more.
In addition, as the organic compound used for the surface treatment, a silicon compound such as silicon oil can be used.
In the present embodiment, the surface treatment with an organic compound on silica particles is referred to as “hydrophobic treatment”.
Examples of the silicone oil used for the hydrophobic treatment include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil.
Silicon oils can be used alone or in combination of two or more.

Specific examples of silica particles that have been subjected to hydrophobic treatment include silo hobic grade (manufactured by Fuji Silysia Chemical), Nipsil SS series, S series (manufactured by Tosoh Silica), and Sunsphere ET series (manufactured by AGC S-Itech) ), AEROSIL R series (manufactured by Nippon Aerosil Co., Ltd.) and the like.
Hydrophobic-treated silica particles can be used alone or in combination of two or more.

The average particle diameter of the silica particles (b-2) is preferably 1 to 10 μm or less, more preferably 2 to 5 μm, from the viewpoints of adhesiveness and uniformity.
A known method can be used as a method for measuring the average particle size, and examples thereof include a laser analysis method and a centrifugal precipitation method. The average particle size in this embodiment is an average particle size measured by a wet laser diffraction method. Means.

The content of the silica particles (b-2) is preferably 10 to 90% by mass and more preferably 20 to 70% by mass with respect to the entire adhesive layer (B) from the viewpoint of adhesive strength.
By using the silica particles (b-2) within the above range, the adhesive layer has a low tack on the surface of the adhesive and is excellent in handling, and adheres to the photosensitive resin layer after application of the adhesive layer. It is possible to prevent dust from adhering to the agent layer and to reduce the defective product rate.

An auxiliary additive component may be contained in the adhesive layer (B) as necessary as long as the effects of the present embodiment are not impaired.
Examples of the auxiliary additive component include a crosslinking agent, a plasticizer, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a dye, and a pigment agent. Among these, a crosslinking agent is preferable from the viewpoint of resistance to the solvent used in the ink.
Auxiliary additive components can be used alone or in combination of two or more.

  Examples of the crosslinking agent include polyisocyanate and polyol, photopolymerization initiator and ethylenically unsaturated compound. The addition of a crosslinking agent is preferred because the strength of the adhesive layer is increased and the breakage in the adhesive layer is eliminated.

Examples of the polyisocyanate include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and the like.
As the polyisocyanate, a compound obtained by addition reaction with a polyfunctional alcohol such as bentaerystol or trimethylolpropane under the condition that the polyisocyanate is excessive in terms of functional group equivalent can also be used.
Polyisocyanate can be used individually or in combination of 2 or more types.

Examples of the polyol include aliphatic glycol, alicyclic glycol, ether bond-containing glycol, liquid rubber oligomer having a hydroxyl group in the molecule, polyester resin (polyester polyol), carbonate polyol, caprolactone polyol, and the like. Especially, in order to improve adhesiveness with a polyester film, it is preferable to add a polyester resin.
Polyols can be used alone or in combination of two or more.

As a polyester resin, glass transition temperature becomes like this. Preferably it is 35-150 degreeC, More preferably, it is 60-120 degreeC. When the glass transition temperature is 35 ° C. or higher, the adhesiveness with the polyester film can be increased, and when the glass transition temperature is 150 ° C. or lower, the adhesiveness by bonding with the photosensitive resin layer can be increased. The glass transition temperature that can be determined is determined by suggested scanning calorimetry.

  The polyester structure of the polyester resin is a structure constituted by a polycondensation reaction with a polybasic acid under an excess of polyhydric alcohol components, and a polyester polyol having an acid value of 5 or less is preferable.

Examples of the polybasic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid; oxalic acid, (anhydrous) succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane Saturated dicarboxylic acids such as diacids, hydrogenated dimer acids, fumaric acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, (anhydrous) citraconic acid, aliphatic dicarboxylic acids such as unsaturated dicarboxylic acids such as dimer acid; 1 , 4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid, and aliphatic dicarboxylic acids such as tetrahydrodicarboxylic acid.
Furthermore, 5-sodium sulfoisophthalic acid, 5-hydroxyisophthalic acid, etc. can be used as needed.
Polybasic acids can be used alone or in combination of two or more.

Examples of the polyhydric alcohol include an aliphatic glycol having 2 to 12 carbon atoms, an alicyclic glycol having 6 to 12 carbon atoms, and an ether bond-containing glycol.
Polyhydric alcohols can be used alone or in combination of two or more.

Examples of the aliphatic glycol having 2 to 12 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1 , 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol and the like.
Examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and the like.
Examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol, and glycols obtained by adding ethylene oxide or propylene oxide to a phenolic hydroxyl group of bisphenol, for example, 2,2-bis (4 -Hydroxyethoxyphenyl) propane and the like. Polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can be used as necessary.

  Specifically, as the polyester resin, Chemit K1294, K-1089 (manufactured by Toray Fine Chemical Co., Ltd.), Nichigo Polyester TP series, LP series (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Byron 240, GK360 (manufactured by Toyobo Co., Ltd.) And Esper 9940 (manufactured by Hitachi Chemical Co., Ltd.).

  The content of the polyester resin is preferably 50% by mass or less with respect to the entire adhesive layer (B) from the viewpoint of adhesive strength with the photosensitive resin layer.

Examples of the ethylenically unsaturated compound include olefins such as ethylene, propylene, vinyltoluene, styrene, and divinylbenzene; acetylenes; (meth) acrylic acid and / or derivatives thereof; haloolefins; unsaturated nitriles such as acrylonitrile (Meth) acrylamide and / or derivatives thereof; unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid and derivatives thereof; vinyl acetates; N-vinylpyrrolidone; N-vinylcarbazole; N-substituted maleimide compounds Etc. Among these, (meth) acrylic acid and / or a derivative thereof is preferable from the viewpoint of abundant variety.
An ethylenically unsaturated compound can be used individually or in combination of 2 or more types.

  Examples of the derivative include an alicyclic compound having a cycloalkyl group, a bicycloalkyl group, a cycloalkenyl group, a bicycloalkenyl group, a benzyl group, a phenyl group, a phenoxy group, a naphthalene skeleton, an anthracene skeleton, a biphenyl skeleton, a phenanthrene skeleton. , Aromatic compounds having a fluorene skeleton, etc., alkyl groups, halogenated alkyl groups, alkoxyalkyl groups, hydroxyalkyl groups, aminoalkyl groups, compounds having glycidyl groups, alkylene glycols, polyoxyalkylene glycols, polyalkylene glycols and trialkyls. Examples thereof include ester compounds with polyhydric alcohols such as methylolpropane, and compounds having a polysiloxane structure such as polydimethylsiloxane and polydiethylsiloxane. Moreover, the heteroaromatic compound containing elements, such as nitrogen and sulfur, may be sufficient.

Examples of (meth) acrylic acid and / or derivatives thereof include di (meth) acrylates of alkanediols such as hexanediol and nonanediol; diethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, and butylene glycol. (Meth) acrylate; trimethylolpropane tri (meth) acrylate; dimethyloltricyclodecane di (meth) acrylate; isobornyl (meth) acrylate; phenoxypolyethylene glycol (meth) acrylate; pentaerythritol tetra (meth) acrylate It is done.
The ethylenically unsaturated compound may have a hydroxyl group in the molecule, and as a derivative of (meth) acrylic acid, for example, 2-hydroxy-3-phenoxypropyl (meth) acrylate (a monomer represented by the following formula 1 ), 2- (meth) acryloyloxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycidyl Examples include adducts of ether with (meth) acrylic acid. In addition, the ethylenically unsaturated compound may have a bisphenol skeleton in the molecule, and as a derivative of (meth) acrylic acid, for example, bisphenol A propylene oxide adduct diglycidyl ether (meth) acrylic acid adduct, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylic acid adduct, bisphenol F ethylene oxide-modified di (meth) acrylate, and the like.
(Meth) acrylic acid and / or derivatives thereof can be used alone or in combination of two or more.

As the photopolymerization initiator, those usually used in the field of resin materials or rubber materials can be used. For example, benzophenone, 4,4-bis (diethylamino) benzophenone, 3,3 ′, 4,4 ′ -Benzophenones such as benzophenone tetracarboxylic anhydride and 3,3 ', 4,4'-tetramethoxybenzophenone; anthraquinones such as t-butylanthraquinone and 2-ethylanthraquinone; 2,4-diethylthioxanthone, isopropylthioxanthone, Thioxanthones such as 2,4-dichlorothioxanthone; Michler ketone; diethoxyacetophenone, 2,2-dimethoxy-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxy Cyclo Hexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one, 2- Acetophenones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and trichloroacetophenone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. Sill phosphine oxides; methylbenzoyl formate; 1,7-bis acridinyl heptane; 9-phenyl acridine; azobisisobutyronitrile, diazonium compounds, azo compounds such as tetrazene compounds.
A photoinitiator can be used individually or in combination of 2 or more types.

As the plasticizer, those usually used in the field of resin materials or rubber materials can be used. For example, liquid rubbers such as liquid polybutadiene rubber and liquid isoprene rubber; hydrocarbon oils such as naphthene oil and paraffin oil; Liquid conjugated diene rubber mainly composed of diene such as liquid acrylonitrile-butadiene copolymer, liquid styrene-butadiene copolymer; polystyrene having a number average molecular weight of 2000 or less; sebacic acid ester, phthalic acid ester, etc. It may have a hydroxyl group or a carboxyl group. These may be provided with a photopolymerizable reactive group such as a (meth) acryloyl group.
A plasticizer can be used individually or in combination of 2 or more types.

As the polymerization inhibitor (antioxidant), those usually used in the field of resin materials or rubber materials can be used, and examples thereof include phenol-based materials and phosphite-based materials.
Examples of phenolic materials include vitamin E, tetrakis- (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate) methane, 2,5-di-t- Butyl hydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis- (6-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-butylphenol) ), Octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 4,4′-thiobis- (6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, pentaerythritol tetrakis (3-laurylthiopropionate), pentaerythritol Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,6-di- (t-butyl) -4-methylphenol, 2,2′-methylenebis- (6- t-butyl-p-cresol), 1,3,5-tris (3,5-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.
Examples of phosphite materials include 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, and triphenyl. Phosphite, Tris (nonylphenyl) phosphite, Tris (2-ethylhexyl) phosphite, Trisdecylphosphite, Tris (tridecyl) phosphite, Diphenylmono (2-ethylhexyl) phosphite, Diphenylmonodecylphosphite, Didecyl Monophenyl phosphite, diphenyl mono (tridecyl) phosphite, dilauryl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaeryth Ritol tetraphosphite, tetra (tridecyl) -4,4′-isopropylidene diphenyl diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, hydrogenated bisphenol A / pentaerythritol phosphite Examples thereof include phytopolymer, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-3-methylphenyl) pentaerythritol diphosphite, and the like.
The polymerization inhibitor and the antioxidant can be used alone or in combination of two or more.

As the ultraviolet absorber, those usually used in the field of resin materials or rubber materials can be used, and benzophenone-based, salicylate-based, benzotriazole-based, acrylonitrile-based, metal complex-based compounds, hindered amine-based compounds, etc. For example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5) -di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-ethoxy-2'-ethyloxalic acid bisanilide, 2,2'-dihydroxy-4-methoxybenzophenone, etc. Is mentioned.
An ultraviolet absorber can be used individually or in combination of 2 or more types.

As the dye, those usually used in the field of resin materials or rubber materials can be used, and examples thereof include water-soluble basic dyes, acid dyes, direct dyes, and the like. Examples thereof include dyes, oil-soluble dyes, and disperse dyes. Of these, anthraquinone-based, indigoid-based, and azo-structured dyes are preferable, and azo-based oil-soluble dyes are more preferable.
The dyes can be used alone or in combination of two or more.

As the pigment, those usually used in the field of resin materials or rubber materials can be used. For example, natural pigments, synthetic inorganic pigments, synthetic organic pigments and the like can be mentioned. Examples include triphenylmethane-based, quinoline-based, anthraquinone-based, and phthalocyanine-based pigments.
The pigments can be used alone or in combination of two or more.

The thickness of the adhesive layer is preferably 1 to 500 μm, more preferably 10 to 100 μm.
When the thickness is 1 μm or more, sufficient adhesive force can be imparted, and it is preferably 500 μm or less from the viewpoint of cost.

The method for laminating the adhesive layer (B) on the polyester film (A) is not particularly limited, and examples thereof include a method of applying by a general coating method.
Specifically, each component of the adhesive layer is mixed and dissolved and dispersed in a solvent such as toluene and methyl ethyl ketone, and a polyester film (using a rotary coater such as a bar coater, gravure coater, die coater, etc. Apply to A). Thereafter, the film is dried at 80 to 100 ° C. for several tens of seconds to several minutes to form an adhesive layer (B).
A solvent can be used individually or in combination of 2 or more types.
When polyisocyanate is used as a crosslinking agent in the adhesive layer (B), it is preferably left at 40 to 50 ° C. for several days in order to further promote the urethane forming reaction between the polyisocyanate and the polyfunctional alcohol.

In this embodiment, the support base material for printing original plates by which the adhesive bond layer (B) was laminated | stacked on the polyester film (A) is provided.
Furthermore, it can be set as the printing original plate as a laminated body by laminating | stacking the photosensitive resin layer (C) on an adhesive bond layer (B).

(Photosensitive resin layer (C))
The photosensitive resin layer (C) is subjected to image exposure (relief exposure), and the photosensitive resin layer is photocured according to the pattern of the negative film, and the unexposed portion of the photosensitive resin layer (that is, photocured). This is a layer in which a desired image, that is, a relief image, is formed by washing the unexposed portion with a developing solution.
The photosensitive resin layer (C) is made of a photosensitive resin that can be subjected to image exposure (relief exposure).

  The photosensitive resin is at least one thermoplastic elastomer composed of at least one monovinyl substituted aromatic hydrocarbon and at least one conjugated diene, at least one ethylenically unsaturated compound, and at least one. Contains the above photopolymerization initiator.

As the thermoplastic elastomer in the photosensitive resin, the thermoplastic elastomer described as the thermoplastic elastomer (b-1) can be used.
For the photosensitive resin, as the thermoplastic elastomer, polyurethane-based thermoplastic elastomers other than the thermoplastic elastomer (b-1), polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, fluorine-based resins. Thermoplastic elastomers, silicon-based thermoplastic elastomers, and the like may be used.
These thermoplastic elastomers can be used alone or in combination of two or more.
The thermoplastic elastomer (b-1) used for the adhesive layer (B) and the thermoplastic elastomer used for the photosensitive resin layer (C) may be the same or different.

  As the thermoplastic elastomer used for the photosensitive resin, styrene is preferable as the monovinyl-substituted aromatic hydrocarbon from the viewpoint that the printing original plate can be molded smoothly at a relatively low temperature, and the abrasion resistance of the printing plate finally obtained is high. From the viewpoint, the conjugated diene is preferably butadiene.

The number average molecular weight (Mn) of the thermoplastic elastomer is preferably 20,000 to 250,000, more preferably 30,000 to 200,000, more preferably, from the viewpoint of ensuring the cold flow resistance of the resin relief printing original plate. Is 40,000 to 150,000.
The number average molecular weight (Mn) is a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  The content of the thermoplastic elastomer is preferably 40% by mass to 90% by mass with respect to the entire photosensitive resin, that is, when the total amount is 100% by mass, from the viewpoint of printing durability of the printing plate, More preferably, it is 50 mass%-75 mass%.

As an ethylenically unsaturated compound, the ethylenically unsaturated compound described as a component in the said adhesive bond layer (B) can be used.
These ethylenically unsaturated compounds can be used alone or in combination of two or more.
The ethylenically unsaturated compound used for the adhesive layer (B) and the ethylenically unsaturated compound used for the photosensitive resin layer (C) may be the same or different.

The number average molecular weight (Mn) of the ethylenically unsaturated compound is preferably 100 or more from the viewpoint of securing non-volatility, and preferably less than 1000, more preferably from the viewpoint of compatibility with other components such as a polymer. Is 200 or more and 800 or less. The ethylenically unsaturated compound is preferably an organic compound having a polymerizable unsaturated group.
The number average molecular weight (Mn) is a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  From the viewpoint of printing durability of the printing plate, the content of the ethylenically unsaturated compound is preferably 2% by mass to 50% by mass, more preferably 2% by mass when the total amount of the photosensitive resin is 100% by mass. % To 30% by mass.

A photopolymerization initiator is a compound that absorbs light energy and generates radicals. A photopolymerization initiator, a hydrogen abstraction type photopolymerization initiator, a site that functions as a hydrogen abstraction type photopolymerization initiator and decay. And compounds having a site functioning as a type photopolymerization initiator in the same molecule. As the photopolymerization initiator, a compound having a carbonyl group is preferable, and an aromatic carbonyl compound is more preferable.
As a photoinitiator, the photoinitiator described as a component in the said adhesive bond layer can be used.
A photoinitiator can be used individually or in combination of 2 or more types.
The photopolymerization initiator used for the adhesive layer (B) and the photopolymerization initiator used for the photosensitive resin layer (C) may be the same or different.

  From the viewpoint of printing durability of the printing plate, the content of the photopolymerization initiator is preferably 0.1% by mass to 10% by mass and more preferably 0 when the total amount of the photosensitive resin is 100% by mass. .5 mass% to 5 mass%.

The photosensitive resin layer (C) may contain an auxiliary additive component as necessary as long as the effects in the present embodiment are not impaired.
Examples of auxiliary additives include polar group-containing polymers, plasticizers, polymerization inhibitors, antioxidants, ultraviolet absorbers, and dyes and pigments as coloring means for improving visibility.
As an auxiliary additive component used for the photosensitive resin (C), each component used for the adhesive layer (B) can be used.
Auxiliary additive components can be used alone or in combination of two or more.
The auxiliary additive component used for the adhesive layer (B) and the auxiliary additive component used for the photosensitive resin layer (C) may be the same or different.

The auxiliary additive component different from each component used for the adhesive layer (B) will be described. Examples of the polar group-containing polymer include hydrophilic groups such as a carboxyl group, an amino group, a hydroxyl group, a phosphate group, and a sulfonate group. And water-soluble or water-dispersible copolymers having polar groups such as groups and salts thereof.
Specific examples of the polar group-containing polymer include carboxyl group-containing NBR (nitrile rubber), carboxyl group-containing SBR (styrene butadiene rubber), a polymer of an aliphatic conjugated diene having a carboxyl group, a phosphate group, or a carboxyl group. Examples thereof include an emulsion polymer of an ethylenically unsaturated compound, a sulfonic acid group-containing polyurethane, and a carboxyl group-containing butadiene latex.
From the viewpoint of obtaining high resolution in the target printing plate, carboxyl group-containing butadiene latex is preferred.
A polar group containing polymer can be used individually or in combination of 2 or more types.

  The addition amount of all auxiliary additive components is preferably 0% by mass to 50% by mass, more preferably 15% by mass to 50% by mass, when the total amount of the photosensitive resin is 100% by mass.

The photosensitive resin layer (C) can be prepared by various methods. For example, each component used as a raw material for the photosensitive resin layer is mixed and dissolved and dispersed in an appropriate solvent such as chloroform, tetrachloroethylene, methyl ethyl ketone, toluene, etc., and cast into a mold to evaporate the solvent. The plate-like photosensitive resin layer (C) can be used as it is. Moreover, it can knead | mix with a kneader or a roll mill, without using a solvent, and can also shape | mold into the plate shape of desired thickness with an extruder, an injection molding machine, a press etc., and can also be set as the photosensitive resin layer (C).
The photosensitive resin layer (C) may have adhesiveness at room temperature depending on its composition. Therefore, if necessary, in order to improve the contact property with the transparent image carrier that is overlaid upon the plate making, and at the same time, to improve the peelability of the transparent image carrier, on the surface of the photosensitive resin layer (C), A thin film (cover sheet) may be laminated. This cover sheet is obtained from polyethylene, polypropylene, polyester, polystyrene or the like. The cover sheet may be removed before the transparent image carrier is attached. In that case, it is more preferable to provide the following protective layer.

In order to improve the contact with the transparent image carrier, a solvent-soluble thin flexible protective layer (hereinafter sometimes simply referred to as “protective layer”) may be provided instead of the above (for example, Japanese Patent Publication No. 5-13305).
The protective layer is provided as follows, for example.
Solvent-soluble polyamide, partially saponified polyvinyl acetate, cellulose ester, etc. are dissolved in a solvent such as toluene or isopropyl alcohol, and the resulting solution is directly coated on the surface of the photosensitive resin layer (C) to form a protective layer. Form.

  Further, the obtained solution is coated on a cover sheet such as a polyester film or polypropylene film to form a protective layer, and then the cover sheet provided with the protective layer is laminated or press-bonded to the surface of the photosensitive resin layer. Then, the protective layer may be transferred. The protective layer is exposed by attaching a transparent image carrier on the protective layer, and then removed by dissolution or the like when the unexposed portion of the photosensitive resin is washed out.

  Instead of the protective layer, an ultraviolet shielding layer containing an infrared sensitive substance may be used, and this ultraviolet shielding layer may be used as a transparent image carrier by direct drawing with an infrared laser. Also in this case, when the exposure is completed and unexposed portions are washed out, the ultraviolet shielding layer is removed at the same time.

  After forming the photosensitive resin layer (C) on the adhesive layer (B) laminated on the polyester film (A), that is, on the support substrate, the polyester film is laminated by using a roll or the like. The photosensitive resin layer (C) is brought into close contact with the film (A) through the adhesive layer (B) to form a printing original plate. After laminating, a printing original plate with better thickness accuracy can be obtained by further heat-pressing.

A printing plate can be made using the obtained printing original plate. An example of the plate making method is shown below.
Exposure is performed through the polyester film (A) of the printing original plate, the photosensitive resin layer (C) is photocured, and a thin uniform cured layer is provided (back exposure). Next, a transparent image carrier such as polyester is partially formed on the photosensitive resin layer (C), and image exposure is performed on the photosensitive resin layer (C) through the transparent image carrier, according to the pattern of the transparent image carrier. The photosensitive resin is cured (relief exposure). Thereafter, a portion of the photosensitive resin layer (C) that is not exposed (that is, a portion that is not photocured) is washed with a developing solution to form a desired image, that is, a relief image, thereby obtaining a printing plate. it can.

  Examples of the light source used for photocuring the photosensitive resin layer (C) include a high-pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, and sunlight.

In the case of exposure, in order to make the polyester film (A) more firmly adhere to the photosensitive resin layer (C), or to make the relief image more stable against the stress at the time of washing out the unexposed part. Therefore, back exposure is preferably performed from the polyester film (A) side.
Either the exposure from the transparent image carrier or the exposure from the polyester film (A) side may be performed first, but from the viewpoint of image reproducibility, the exposure from the polyester film (A) side is performed first. It is preferable.

Examples of the developing solution used when the photosensitive resin layer (C) is exposed through a transparent image carrier to form an image and then an unexposed portion is washed out are, for example, 1,1,1-trichloroethane, tetrachloroethylene, etc. Chlorinated organic solvents; ester solvents such as heptyl acetate and 3-methoxybutyl acetate; hydrocarbon solvents such as petroleum fractions, toluene and decalin.
As the developing solution, in addition to the above solvent, a mixed solution in which an alcohol solvent such as propanol, butanol, or pentanol is further mixed can be used.
As the developing solution, an aqueous developer can be used. Examples of the aqueous developer include water / alcohol solutions of nonionic, anionic, cationic, and amphoteric surfactants.
Surfactants can be used alone or in combination of two or more.

Examples of the anionic surfactant include a linear alkylbenzene sulfonate having an alkyl having an average carbon number of 8 to 16, an α-olefin sulfonate having an average carbon number of 10 to 20, an alkyl group, or an alkenyl group having a carbon number. 4-10 dialkyl sulfosuccinates, sulfonates of fatty acid lower alkyl esters, alkyl sulfates having an average carbon number of 10-20, linear or branched alkyl or alkenyl groups having an average carbon number of 10-20 , Alkyl ether sulfates added with 0.5 to 8 moles of ethylene oxide on average, saturated or unsaturated fatty acid salts with an average carbon number of 10 to 22 and the like.
Examples of the cationic surfactant include alkylamine salts, alkylamine ethylene oxide adducts, alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, sapamine-type quaternary ammonium salts, and pyridium salts.
Nonionic surfactants include, for example, polyethylene glycol type higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, fatty acid alkylene oxide adducts, polyhydric alcohol fatty acid ester alkylene oxide adducts, and higher alkylamine alkylene oxide adducts. , Fatty acid amide alkylene oxide adduct, fat and oil alkylene oxide adduct, and polypropylene glycol alkylene oxide adduct, polyhydric alcohol type glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid Examples include esters, alkyl ethers of polyhydric alcohols, and fatty acid amides of alkanolamines.
Examples of amphoteric surfactants include sodium laurylaminopropionate and lauryl dimethyl betaine.

  The concentration of the surfactant in the developing solution is not particularly limited, but is preferably 0.5 to 10% by mass with respect to the total amount of the developing solution.

In addition to the surfactant, the aqueous developer may contain a development aid such as a development accelerator or a pH adjuster, if necessary.
The unexposed portion can be washed out by spraying from a nozzle or brushing with a brush. After the washing, post-exposure may be performed through a rinse washing and drying process.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, the measuring method used for evaluation of an Example and a comparative example is as follows.

[Measurement of adhesive strength]
The printing plate was cut into a width of 1 cm and a length of 15 cm, and left for one day in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50%. Thereafter, the photosensitive resin layer and the polyester film were forcibly peeled from one end by about 5 cm. The opposite side of the peeled polyester film and the metal plate are attached using a double-sided tape (manufactured by 3M, “Scotch ST-416”), autograph (manufactured by Shimadzu Corporation, “autograph AG-X”) Then, a peel test was performed from a portion where the film was forcibly peeled at a speed of 50 mm / min at 180 °, and the adhesive force was measured.

[Adhesive layer dust]
The obtained printing plate was cut into 30 cm × 30 cm and visually inspected, and dust adhering to the adhesive layer was confirmed using waste fibers and dust having a long side of 1 mm or more as dust.

Example 1
(1-1) Preparation of photosensitive resin layer Photosensitive resin 1 and photosensitive resin 2 were obtained by kneading with a kneader with the composition shown in Table 1.
The obtained photosensitive resin 1 or 2 is sandwiched between a polyester film treated with silicon and a polyethylene terephthalate film having a polyamide film, and 1.96 × 10 4 minutes at 130 ° C. using a 1.5 mm spacer. Pressure molding was performed by applying a pressure of ⁷ Pa. It was 1.5 mm when the thickness of the obtained photosensitive resin layer was measured.
(1-2) Preparation of supporting substrate To a stainless steel 200 L reaction vessel equipped with a stirrer, 118 L of water and 500 mL of sodium silicate aqueous solution (2.5 mol / L, Na ₂ O.3.3SiO ₂ ) were added and stirred. While heating to 90 ° C. While maintaining the obtained aqueous solution at 90 ° C., a sodium silicate aqueous solution was added dropwise at a flow rate of 500 mL / min, and sulfuric acid (18 mol / L) was added dropwise at a flow rate of 20 mL / min. The dropping was stopped at 120 minutes, and the SiO ₂ concentration in the reaction solution at this time was 50 g / L.
Subsequently, only sulfuric acid was added dropwise at the same flow rate to pH 2.5 to obtain a precipitated silicic acid slurry. The obtained precipitated silicic acid slurry was washed with water, then dried until the water content became 5%, pulverized with a mill, and passed through a classifier to obtain silica particles having an average particle diameter of 2.5 μm. 1 kg of the silica particles thus obtained was put into a Henschel mixer, and 50 g of dimethyl silicone oil was sprayed and mixed for 5 minutes. This mixture was placed in a nest heater and subjected to heat treatment at 280 ° C. for 3 hours to obtain silica particles 1 subjected to hydrophobic treatment.
As an adhesive layer, 18 parts by mass of a styrene-butadiene copolymer (Asahi Kasei Chemicals, “Tufprene (registered trademark) 912”), 53 parts by mass of a styrene-isoprene copolymer (Clayton Polymer Japan, “KRATON (registered trademark) D1112”) Part, 14.5 parts by mass of silica particles 1 were dispersed in 400 parts by mass of a mixed solution of toluene / methyl ethyl ketone (volume ratio 1/1). 7.0 parts by mass of α, ω-polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., “NISSO-PB (registered trademark) G-1000”), 8.5 mass of adduct of tolylene diisocyanate (3 mol) of trimethylolpropane (1 mol) The parts were further mixed and dissolved.
This 20% solid content solution was applied to a polyester film having an undercoat layer with a knife coater so as to have a thickness of 20 μm to form an adhesive layer, and allowed to stand at 40 ° C. for 72 hours. A support substrate 1 having an adhesive layer was obtained.
(1-3) Preparation of printing original plate The silicon-treated polyester film is peeled off from the photosensitive resin layer, placed on a stainless steel plate heated to 130 ° C., and each photosensitive resin layer made of photosensitive resin 1 or 2 is heated. did. Lamination is performed so that the adhesive layer of the supporting substrate 1 is in contact with the heated photosensitive resin layer, and a printing original plate 1-1 using the photosensitive resin 1 and a printing original plate 1-2 using the photosensitive resin 2 are obtained. It was.
(1-4) Preparation of printing plate The obtained printing original plate 1-1 or 1-2 is subjected to ultraviolet fluorescence having a central wavelength of 370 nm on "AFP (registered trademark) -1500" (manufactured by Asahi Kasei E-materials). Using a lamp, 100 mJ / cm ² of back exposure was performed from the polyester film side, and 6000 mJ / cm ² of image exposure was performed through the transparent image carrier. At this time, the exposure intensity was measured with a UV illuminometer (manufactured by Oak Manufacturing Co., Ltd., “MO-2 type”) using a UV-35 filter. Next, a mixed solution of tetrachloroethylene / n-butanol (volume ratio 3/1) was used as a developing solution, developed with “AFP (registered trademark) -1500” (manufactured by Asahi Kasei E-Materials), and dried at 60 ° C. for 2 hours. Thereafter, post-exposure was performed to obtain a printing plate 1-1 and a printing plate 1-2 each having a three-dimensional shape.
Since the transparent image carrier used was a negative type, a relief type printing plate in which ink adhered to the convex part was obtained.

When the adhesive strength of the obtained printing plate was measured, it was 5.9 N / cm or more as shown in Table 2 regardless of which of the photosensitive resins 1 and 2 was used.
Further, no dust adhered to the adhesive layer of any of the obtained printing plates, and a good printing plate could be obtained.
Using the obtained printing plate, printing on a polyethylene film was performed using an ink containing about 25% by volume of an acetate ester. In order to remove the printing plate after the printing is finished and fixed with double-sided tape from the plate cylinder without peeling off the layer, the photosensitive resin layer has a strong force on the photosensitive resin layer. Even when was added, the photosensitive resin layer was firmly adhered to the polyester film, and the printing plate was not damaged.

(Example 2)
(2-1) Preparation of Support Substrate As an adhesive layer, 36 parts by mass of a styrene-butadiene copolymer (Asahi Kasei Chemicals, “Tufprene (registered trademark) 912”), a styrene-isoprene copolymer (Clayton Polymer Japan, “ KRATON (registered trademark) D1112 ") 53 parts by mass, hydrophobically treated silica particles (manufactured by Tosoh Silica Co., Ltd.," Nipsil (registered trademark) SS-50G ", average particle size 1.3 µm) 13.5 parts by mass, saturated 35 parts by mass of a copolyester resin (“Chemit (registered trademark) K1294” manufactured by Toray Fine Chemical Co., Ltd.) was dispersed in 400 parts by mass of a mixed solution of toluene / methyl ethyl ketone (volume ratio 1: 1). α, ω-polybutadiene glycol (Nippon Soda Co., Ltd., “NISSO-PB (registered trademark) G-1000”) 6.7 parts by mass, trimethylolpropane (1 mol) tolylene diisocyanate (3 mol) adduct 8.5 mass The parts were further mixed and dissolved.
This 20% solid content solution was applied to a polyester film having an undercoat layer using a knife coater so as to have a thickness of 20 μm to form an adhesive layer, which was allowed to stand at 40 ° C. for 72 hours. 2 was obtained.
(2-2) Preparation of printing plate In the same manner as in Example 1 except that the supporting substrate 2 was used, a printing original plate 2-1 laminated with a photosensitive resin 1 and a printing original plate 2 laminated with a photosensitive resin 2 -2 was obtained.
Subsequently, printing plates 2-1 and 2-2 were obtained in the same manner as in Example 1.

In the obtained printing plate, an attempt was made to forcibly peel off in order to measure the adhesive force. However, as shown in Table 2, the photosensitive resin 1 or 2 was used regardless of whether the photosensitive resin 1 or 2 was used. The layer did not peel from the printing plate.
Further, no dust adhered to the adhesive layer of any of the obtained printing plates, and a good printing plate could be obtained.
Using the obtained printing plate, printing on a polyethylene film was performed using an ink containing about 25% by volume of an acetate ester. In order to remove the printing plate after the printing is finished and fixed with double-sided tape from the plate cylinder without peeling off the layer, the photosensitive resin layer has a strong force on the photosensitive resin layer. Even when was added, the photosensitive resin layer was firmly adhered to the polyester film, and the printing plate was not damaged.

(Example 3)
(3-1) Preparation of Support Base Material As an adhesive layer, 36 parts by mass of styrene-butadiene copolymer (manufactured by Asahi Kasei Chemicals Co., Ltd., “Tufprene (registered trademark) A”), silica particles not subjected to hydrophobic treatment (manufactured by Fuji Silysia Co., Ltd.) , 13.5 parts by mass of “Silicia 350”, average particle size 3.9 μm), 35 parts by mass of saturated polyester resin (manufactured by Nippon Synthetic Chemical Industry, “Polyester (registered trademark) TP220”), toluene / methyl ethyl ketone (volume) The mixture was dispersed in 400 parts by mass of a mixed solution having a ratio of 1/1). α, ω-polybutadiene glycol (Nippon Soda Co., Ltd., trade name “NISSO-PB (registered trademark) G-1000”) 6.7 parts by mass, trimethylolpropane (1 mol) tolylene diisocyanate (3 mol) adduct 8.5 The mass part was further mixed and dissolved.
This 20% solid content solution was applied to a corona-treated polyester film using a knife coater so as to have a thickness of 20 μm to form an adhesive layer, which was allowed to stand at 40 ° C. for 72 hours. Material 3 was obtained.
(3-2) Preparation of printing plate In the same manner as in Example 1 except that the supporting substrate 3 was used, a printing original plate 3-1 on which the photosensitive resin 1 was laminated, and a printing original plate 3 on which the photosensitive resin 2 was laminated. -2 was obtained.
Subsequently, printing plates 3-1 and 3-2 were obtained in the same manner as in Example 1.

When the adhesive strength of the obtained printing plate was measured, it was 5.9 N / cm or more as shown in Table 2 regardless of which of the photosensitive resins 1 and 2 was used.
Further, no dust adhered to the adhesive layer of any of the obtained printing plates, and a good printing plate could be obtained.
Using the obtained printing plate, printing on a polyethylene film was performed using an ink containing about 25% by volume of an acetate ester. In order to remove the printing plate after the printing is finished and fixed with double-sided tape from the plate cylinder without peeling off the layer, the photosensitive resin layer has a strong force on the photosensitive resin layer. Even when was added, the photosensitive resin layer was firmly adhered to the polyester film, and the printing plate was not damaged.

Example 4
(4-1) Preparation of Adhesive Layer As an adhesive layer, 36 parts by mass of a styrene-butadiene copolymer (Asahi Kasei Chemicals, “Asafucrex 810”) and hydrophobically treated silica particles (Fuji Silysia, “Silo Ho” BICK (registered trademark) 200 ") 13.5 parts by mass, saturated copolymer polyester resin (Toray Fine Chemical Co., Ltd.," Chemit (registered trademark) K1294 ") 35 parts by mass, toluene / methyl ethyl ketone (volume ratio 1/1) In 400 parts by mass of the mixed solution. α, ω-polybutadiene glycol (Nippon Soda Co., Ltd., “NISSO-PB (registered trademark) G-1000”) 6.7 parts by mass, trimethylolpropane (1 mol) tolylene diisocyanate (3 mol) adduct 8.5 mass The parts were further mixed and dissolved.
This 20% solid content solution was applied to a polyester film having an undercoat layer using a knife coater so as to have a thickness of 20 μm to form an adhesive layer, which was allowed to stand at 40 ° C. for 72 hours. 4 was obtained.
(4-2) Preparation of printing plate In the same manner as in Example 1 except that the supporting substrate 4 was used, the printing original plate 4-1 on which the photosensitive resin 1 was laminated, and the printing original plate 4 on which the photosensitive resin 2 was laminated. -2 was obtained.
Subsequently, printing plates 4-1 and 4-2 were obtained in the same manner as in Example 1.

In the obtained printing plate, an attempt was made to forcibly peel to measure the adhesive force. However, as shown in Table 2, the photosensitive resin layer was used regardless of which of the photosensitive resins 1 and 2 was used. Did not peel from the printing plate.
Further, no dust adhered to the adhesive layer of any of the obtained printing plates, and a good printing plate could be obtained.
Using the obtained printing plate, printing on a polyethylene film was performed using an ink containing about 25% by volume of an acetate ester. In order to remove the printing plate after the printing is finished and fixed with double-sided tape from the plate cylinder without peeling off the layer, the photosensitive resin layer has a strong force on the photosensitive resin layer. Even when was added, the photosensitive resin layer was firmly adhered to the polyester film, and the printing plate was not damaged.

(Example 5)
(5-1) Preparation of Adhesive Layer As an adhesive layer, 55 parts by mass of styrene-butadiene copolymer (manufactured by Asahi Kasei Chemicals Corporation, “Tufprene (registered trademark) 912”), paraffin oil (average carbon number 33, average molecular weight 470, (Density 0.868 at 15 ° C.) 28 parts by mass, 2.5 parts by mass of 1,9-nonanediol diacrylate, 1.5 parts by mass of 2,2-dimethoxy-phenylacetophenone, 3 parts by mass of the monomer represented by the following formula 1 In addition, 10 parts by mass of silica particles that were not subjected to hydrophobic treatment (manufactured by Fuji Silysia Co., Ltd., “Silysia 350”, average particle diameter: 3.9 μm) were dissolved in toluene to obtain a 25% solids solution.
The 25% solid content solution was applied to a polyester film having an undercoat layer using a knife coater so as to have a thickness of 25 μm.
Formula 1:
_{CH 2 = CH-CO-O} -CH 2 CH (OH) CH 2 -O-C 6 H 5
(5-2) Preparation of printing plate In the same manner as in Example 1 except that the supporting substrate 5 was used, a printing original plate 5-1 in which the photosensitive resin 1 was laminated, and a printing original plate 5 in which the photosensitive resin 2 was laminated. -2 was obtained.
Subsequently, printing plates 5-1 and 5-2 were obtained in the same manner as in Example 1.

When the adhesive strength of the obtained printing plate was measured, it was 5.9 N / cm or more as shown in Table 2 regardless of which of the photosensitive resins 1 and 2 was used.
Further, no dust adhered to the adhesive layer of any of the obtained printing plates, and a good printing plate could be obtained.
Using the obtained printing plate, printing on a polyethylene film was performed using an ink containing about 25% by volume of an acetate ester. In order to remove the printing plate after the printing is finished and fixed with double-sided tape from the plate cylinder without peeling off the layer, the photosensitive resin layer has a strong force on the photosensitive resin layer. Even when was added, the photosensitive resin layer was firmly adhered to the polyester film, and the printing plate was not damaged.

(Comparative Example 1)
(6-1) Preparation of Support Substrate As an adhesive layer, 43 parts by mass of a styrene-butadiene copolymer (Asahi Kasei Chemicals, “Asafu Clex 810”), a saturated copolymerized polyester resin (Toray Fine Chemical Co., Ltd., “Chemit (registered) (Trademark) K1294 ") 40 parts by mass was dispersed in 400 parts by mass of a mixed solution of toluene / methyl ethyl ketone (volume ratio 1/1). 7 parts by mass of α, ω-polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., “NISSO-PB (registered trademark) G-1000”) and 10 parts by mass of a tolylene diisocyanate (3 mol) adduct of trimethylolpropane (1 mol) are further mixed. And dissolved.
This 20% solid content solution was applied to a polyester film having an undercoat layer using a knife coater so as to have a thickness of 20 μm to form an adhesive layer, which was allowed to stand at 40 ° C. for 72 hours. 6 was obtained.
(6-2) Preparation of printing plate In the same manner as in Example 1 except that the supporting substrate 6 was used, a printing original plate 6-1 in which the photosensitive resin 1 was laminated, and a printing original plate 6 in which the photosensitive resin 2 was laminated. -2 was obtained.
Subsequently, printing plates 6-1 and 6-2 were obtained in the same manner as in Example 1.

When the adhesive strength of the obtained printing plate was measured, as shown in Table 2, it was less than 5.9 N / cm regardless of which of the photosensitive resins 1 and 2 was used.
Further, it can be seen that 0.1 mm × 3 mm fibrous dust adhered to the printing plate 6-1 and 2 to the printing plate 6-2 on the adhesive layer of the obtained printing plate. Was a dent in the photosensitive resin.
Using the obtained printing plate, printing on a polyethylene film was performed using an ink containing about 25% by volume of an acetate ester. Although the layer did not peel off, in order to remove the printing plate after the printing was finished and fixed with the double-sided tape from the plate cylinder, when I tried to peel it off with the cured resin layer part, the photosensitive resin was Since it peeled from the polyester film, it could not be used for the next printing. Further, when the printed material was observed by paying attention to the portion where dust adhered to the adhesive layer, the recessed portion was printed, and a good printed material could not be obtained.

(Comparative Example 2)
(7-1) Preparation of Support Substrate Hydrophobized silica particles (manufactured by Tosoh Silica Co., Ltd., “Nippil (registered trademark) SS-50G”) 13.5 parts by mass, saturated copolyester resin as an adhesive layer 71 parts by mass (“Chemit (registered trademark) K1294” manufactured by Toray Fine Chemical Co., Ltd.) was dispersed in 400 parts by mass of a mixed solution of toluene / methyl ethyl ketone (volume ratio 1/1). 6.7 parts by mass of α, ω-polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., “NISSO-PB (registered trademark) G-1000”), 8.8 mass of adduct of tolylene diisocyanate (3 mol) of trimethylolpropane (1 mol) The parts were further mixed and dissolved.
This 20% solid content solution was applied to a polyester film having an undercoat layer using a knife coater so as to have a thickness of 20 μm to form an adhesive layer, which was allowed to stand at 40 ° C. for 72 hours. 7 was obtained.
(7-2) Preparation of printing plate In the same manner as in Example 1 except that the supporting substrate 7 was used, a printing original plate 7-1 on which the photosensitive resin 1 was laminated, and a printing original plate 7 on which the photosensitive resin 2 was laminated. -2 was obtained.
Subsequently, printing plates 7-1 and 7-2 were obtained in the same manner as in Example 1.

When the adhesive strength of the obtained printing plate was measured, it was less than 5.9 N / cm as shown in Table 2 regardless of which of the photosensitive resins 1 and 2 was used.
There was no adhesion of dust to the adhesive layer of the obtained printing plate.
Using the obtained printing plate, printing on a polyethylene film was performed using an ink containing about 25% by volume of an acetate ester. The layer did not peel off, but in order to remove the printing plate that had been printed and fixed with double-sided tape from the plate cylinder, the photosensitive resin layer part was peeled off and the photosensitive resin was removed. Since the layer peeled from the polyester film, it could not be used for the next printing.

(Comparative Example 3)
(8-1) Preparation of Adhesive Layer As an adhesive layer, 55 parts by mass of styrene-butadiene copolymer (Asahi Kasei Chemicals, “Tufprene 912”), paraffin oil (average carbon number 33, average molecular weight 470, density at 15 ° C. 0.868) 38 parts by mass, 2.5 parts by mass of 1,9-nonanediol diacrylate, 1.5 parts by mass of 2,2-dimethoxy-phenylacetophenone, and 3 parts by mass of the monomer represented by the above formula 1 in toluene Dissolved to give a 25% solids solution.
Using a knife coater, the support substrate 8 was obtained by applying the polyester film used in (1-2) to a thickness of 25 μm.
(8-2) Preparation of printing plate In the same manner as in Example 1 except that the supporting substrate 8 was used, a printing original plate 8-1 on which the photosensitive resin 1 was laminated, and a printing original plate 8 on which the photosensitive resin 2 was laminated. -2 was obtained.
Subsequently, a printing plate 8-1 and a printing plate 8-2 were obtained in the same manner as in Example 1.

When the adhesive strength of the obtained printing plate was measured, as shown in Table 2, it was 5.9 N / cm or more regardless of which of the photosensitive resins 1 and 2 was used.
In addition, it was found that four 0.1 mm × 3 mm fibrous dust adhered to the printing plate 8-1 and four to the printing plate 8-2 on the adhesive layer of the obtained printing plate. The portion was a recessed portion in the photosensitive resin.
Using the obtained printing plate, printing on a polyethylene film was performed using an ink containing about 25% by volume of an acetate ester. In order to remove the printing plate after the printing is finished and fixed with double-sided tape from the plate cylinder without peeling off the layer, the photosensitive resin layer has a strong force on the photosensitive resin layer. Even when was added, the photosensitive resin layer was firmly adhered to the polyester film, and the printing plate was not damaged. However, when the printed material was observed by paying attention to the part where dust adhered to the adhesive layer, the recessed portion was printed, and a good printed material could not be obtained.

  The printing original plate of the present invention can be effectively used in flexographic printing because the polyester film and the photosensitive resin layer are firmly bonded, and dust can be prevented from adhering to the adhesive layer.

Claims (8)

A printing original plate used for letterpress printing in which at least an adhesive layer (B) and a photosensitive resin layer (C) are sequentially laminated on a polyester film (A),
The adhesive layer (B) is at least one thermoplastic elastomer (b-1) composed of at least one monovinyl substituted aromatic hydrocarbon and at least one conjugated diene, and at least one silica. A printing original plate containing particles (b-2).   The printing original plate according to claim 1, wherein the silica particles (b-2) are subjected to a hydrophobic treatment.   The printing original plate of Claim 1 or 2 whose average particle diameter of a silica particle (b-2) is 1-10 micrometers.   The printing original plate as described in any one of Claims 1-3 in which an adhesive bond layer (B) further contains at least 1 or more types of polyester resin.   The printing original plate as described in any one of Claims 1-4 in which a thermoplastic elastomer (b-1) contains a styrene-butadiene block copolymer and / or a styrene-isoprene block copolymer.   The printing original plate as described in any one of Claims 1-5 in which a polyester film (A) has an undercoat layer (D) at least in the surface which laminates | stacks an adhesive bond layer (B).   The photosensitive resin layer (C) is at least one thermoplastic elastomer comprising at least one monovinyl-substituted aromatic hydrocarbon and at least one conjugated diene, at least one ethylenically unsaturated compound, The printing original plate as described in any one of Claims 1-6 containing at least 1 or more types of photoinitiators. A support base material for a printing original plate used for letterpress printing in which an adhesive layer (B) is laminated on a polyester film (A),
The adhesive layer (B) is at least one thermoplastic elastomer (b-1) composed of at least one monovinyl substituted aromatic hydrocarbon and at least one conjugated diene, and at least one silica. A support base material for a printing original plate containing particles (b-2).