WO2012090896A1

WO2012090896A1 - Photosensitive resin laminate

Info

Publication number: WO2012090896A1
Application number: PCT/JP2011/079995
Authority: WO
Inventors: 弘倫米倉; 渉川島
Original assignee: 東洋紡績株式会社
Priority date: 2010-12-27
Filing date: 2011-12-26
Publication date: 2012-07-05
Also published as: JPWO2012090896A1; JP5311247B2

Abstract

Provided are: a photosensitive resin laminate, in which a metal plate is used as a support, and which does not undergo the reduction in yield that is caused by adhered materials on the metal plate and enables the production of printing original plates with improved productivity; and a photosensitive resin laminate which can be checked easily and automatically by an optical device and has excellent plate checking performance. A first embodiment of the present invention is a photosensitive resin laminate comprising at least a metallic support, an adhesive layer and a photosensitive resin layer, wherein the adhesive layer comprises a binder component and at least one inorganic pigment, and wherein the photosensitive resin laminate is characterized in that the ratio of the content of the inorganic pigment to the solid content in the adhesive layer is 10-50 wt% and the adhesive layer has a thickness of 6 μm or more. A second embodiment of the present invention is a photosensitive resin laminate comprising at least a metallic support, an adhesive layer and a photosensitive resin layer, wherein the adhesive layer comprises a binder component and at least one inorganic pigment, and wherein the photosensitive resin laminate is characterized in that the ratio of the content of the inorganic pigment to the solid content in the adhesive layer is 6-50 wt%, the adhesive layer cannot transmit light, and the surface of the adhesive layer, which is exposed completely by developing, has a specular gloss of 80 or more.

Description

Photosensitive resin laminate

This invention relates to the photosensitive resin laminated body which suppresses the fall of the yield resulting from the deposit | attachment which exists in a metal plate, and improves the productivity of a printing original plate. The present invention also relates to a photosensitive resin laminate that is easy for automatic plate inspection using an optical instrument and excellent in plate inspection properties, and can be used as a relief plate material or an intaglio plate material.

The photosensitive resin laminate generally has a support, an adhesive layer, and a photosensitive resin layer, and is further provided with an anti-adhesion layer for the purpose of preventing adhesion on the surface of the photosensitive resin layer, and further a cover film is laminated thereon. It is common that As a method for producing such a photosensitive resin laminate, an anti-adhesion layer is applied to a cover film in advance, and an adhesive layer is applied to a support, and then both layers centering on the photosensitive resin layer are prepared. In general, a material is obtained by laminating a material to a desired thickness and width by hot pressing, cast molding, calendering, coating method or the like.

As a plate making process for forming an image using the photosensitive resin laminate (original), first set the photosensitive resin laminate cut to the required size on the image exposure machine stand, and after peeling the cover film on the raw plate upper layer, Place original film (negative film) in vacuum contact, and then irradiate actinic rays to expose and cure part of photosensitive resin layer, then peel off original film and remove unexposed / uncured part with developer A method of obtaining a printing plate by doing so is generally employed.

In the exposure process of the photosensitive resin layer, the actinic ray that has passed through the photosensitive resin layer is reflected by the base substrate and acts again on the photosensitive resin layer, thereby affecting the reactivity of the photosensitive resin layer and relief. A phenomenon called halation occurs that degrades the resolution of the image. In order to reduce halation, it is known to add an antihalation agent to the adhesive layer (see Patent Documents 1 and 2). As the antihalation agent, a dye having strong absorption mainly in the wavelength region of actinic rays is used.

On the surface of a metal plate such as a steel plate used for the support of the photosensitive resin laminate, there are not a few deposits such as chromium having a diameter of about 1 mm due to non-uniform surface treatment. When a metal plate is used as a support, this deposit exhibits the same effect as an antihalation agent, resulting in non-uniform halation and a marked deterioration in fine points and line retention. For this reason, a plate using a laminate having a deposit on the metal support becomes a defective product. If even one deposit is present in the plate, the entire plate becomes a defective product. Therefore, the yield deteriorates as the size of one photosensitive resin laminate increases, resulting in poor productivity. Met.

On the other hand, it was necessary to inspect whether the photosensitive resin laminate before plate making and the printing plate obtained through the plate making process accurately reproduce a fine pattern for precision instruments before use. Conventionally, as a technique for providing a photosensitive resin laminate having an excellent plate inspection property, a method for improving plate inspection from a cover film material by incorporating a photobleachable dye in an anti-adhesion layer on a photosensitive layer is known. (See Patent Document 3). However, in this method, the anti-adhesion layer is washed away during the development process, and the finished state of the plate cannot be confirmed.

Further, it is known that a dye composed of a phthalocyanine complex is contained in an adhesive layer on a support (see Patent Document 4). As a result, when exposed through the original drawing film, the exposed portion and the non-exposed portion can be visually discriminated, and the finished state of the plate after development can be confirmed, resulting in excellent plate inspection.

However, in order to satisfy the recent demand for higher performance of the photosensitive printing plate, that is, the improvement of the halftone gradation and the reproducibility of fine lines and independent points, the adhesive layer after development as well as the resolution of the plate And a photosensitive resin laminate capable of discriminating fine defects in the photosensitive layer. In visual inspection, there are not only limitations on observation of fine lines, independent points and halftone dots after plate making, but there are also problems in terms of efficiency such as the speed and reproducibility of plate inspection. For this reason, automatic detection of defects by plate inspection using an optical instrument has been demanded.

In the case of a support capable of transmitting light, for example, a film having a transparent support, plate inspection by an optical instrument using transmitted light and automatic detection of defects are being studied. However, when a support that cannot transmit light, for example, a metal support such as a steel plate, is used, strong reflected light from the surface of the support is generated. Since the metal plate is usually subjected to fine surface processing, irregular reflection occurs, which hinders plate inspection when inspecting for the presence of a relief-shaped defect. In addition, when there is a washing-out failure in the developing process, adhesion of unexposed resin, and unevenness of the surface of the adhesive layer, it is difficult to automatically detect defects using an optical device.

JP-A-6-342213 JP 2007-108476 A Japanese Patent Laid-Open No. 62-229127 JP 2001-154367 A

The present invention has been made to solve such problems of the prior art. That is, an object of the present invention is to suppress the yield reduction due to the deposits present on the metal plate and improve the productivity of the printing original plate in the photosensitive resin laminate (original plate) using the metal plate as the support. There is. It is another object of the present invention to provide a photosensitive resin laminate that is easy to perform automatic plate inspection using an optical instrument and that is excellent in plate inspection.

As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by the following means, and have completed the present invention. That is, the present invention comprises the following configurations (1) to (9).
(1) A photosensitive resin laminate including at least a metal support, an adhesive layer, and a photosensitive resin layer, the adhesive layer containing a binder component and at least one inorganic pigment, wherein the solid content of the adhesive layer The photosensitive resin laminate is characterized in that the ratio of the inorganic pigment to 10 to 50% by weight and the thickness of the adhesive layer is 6 μm or more.
(2) The photosensitive resin laminate according to (1), wherein the inorganic pigment is an achromatic inorganic pigment.
(3) The photosensitive resin laminate according to (1), wherein the inorganic pigment is titanium oxide, barium titanate, or carbon black.
(4) The photosensitive resin laminate according to any one of (1) to (3), wherein the adhesive layer is thermosetting.
(5) A photosensitive resin laminate including at least a metal support, an adhesive layer, and a photosensitive resin layer, the adhesive layer containing a binder component and at least one inorganic pigment, wherein the solid content of the adhesive layer The inorganic pigment is 6 to 50% by weight, the adhesive layer is light transmission-inhibiting, and the specular gloss of the surface of the adhesive layer completely exposed by development is 80 or more. Photosensitive resin laminate.
(6) The photosensitive resin laminate according to (5), wherein the inorganic pigment is titanium oxide.
(7) The photosensitive resin laminate according to (5) or (6), wherein the adhesive layer contains a leveling agent.
(8) The photosensitive resin laminate according to any one of (5) to (7), wherein the binder component contains a polyester resin and / or a polyurethane resin.
(9) The photosensitive resin laminate according to any one of (5) to (8), wherein the adhesive layer has a light transmittance of 1% or less at a wavelength of 450 nm.

The photosensitive resin laminate of the present invention has an adhesive layer that has a high concealability to the deposit on the metal support by containing a specific amount of inorganic pigment, and has an adhesive force applicable to printing. For this reason, it has the durability that the support and the photosensitive resin layer are not peeled off during printing plate preparation and printing, and also suppresses the occurrence of defective products by suppressing the influence of deposits adhering to the metal plate can do. Moreover, since the photosensitive resin laminated body of this invention has light transmission inhibitory property, it can observe the surface shape of the photosensitive resin laminated body easily before and behind exposure and image development. In addition, since the surface of the adhesive layer exposed after development is smooth and excellent in light transmission suppression, it is possible to quickly and accurately perform defect inspection and surface observation with optical equipment on the surface of the photosensitive resin laminate after development. . For this reason, it is easy to automate the plate inspection.

2 is an example of a micrograph of the photosensitive resin laminate in Example 1. FIG. 2 is an example of a photomicrograph of a photosensitive resin laminate in Comparative Example 1. 5 is an example of a photomicrograph of a photosensitive resin laminate in Comparative Example 2.

Hereinafter, the photosensitive resin laminate of the present invention will be described based on two embodiments.

(First embodiment)
The photosensitive resin laminate of the first embodiment of the present invention includes at least a metal support, an adhesive layer, and a photosensitive resin layer. The adhesive layer contains a binder component and at least one inorganic pigment. The ratio of the inorganic pigment to the solid content is 10 to 50% by weight, and the thickness of the adhesive layer is 6 μm or more.

The photosensitive resin layer preferably contains a known polymer binder, an ethylenically unsaturated compound, a photopolymerization initiator composition, and an ultraviolet absorber. In addition, other additives such as plasticizers, thermal polymerization inhibitors, dyes, pigments, perfumes or antioxidants may be included. The polymer binder is preferably one that can be dissolved or dispersed in water or a mixture of water and alcohol. Specifically, a polyether amide (for example, JP-A-55-79437), a polyether ester amide (for example, a special compound) Kokai 58-113537, etc.), tertiary nitrogen-containing polyamides (for example, JP-A-50-76055), ammonium salt type tertiary nitrogen atom-containing polyamides (for example, JP-A-53-36555), amide bonds Addition polymer of amide compound having one or more and organic diisocyanate compound (for example, JP-A-58-140737), addition polymer of diamine having no amide bond and organic diisocyanate compound (for example, JP-A-4-97154) Among them, among them, tertiary nitrogen atom-containing polyamides and ammonium salts Tertiary nitrogen atom-containing polyamide are preferable.

Ethylenically unsaturated compounds include diglycidyl ether acrylic acid adducts of bisphenol A and bisphenol F, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate and other polyglycidyl ethers and (meth) acrylic acid addition reaction products, polycarboxylic acid such as adipic acid and glycidyl Examples include, but are not limited to, polyunsaturated compounds such as addition reaction products with (meth) acrylates, addition reaction products of polyvalent amines such as propylene diamine and glycidyl (meth) acrylate. Ku, can also be used by mixing these compounds two or more.

Examples of the photopolymerization initiator composition include benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzyl alkyl ketals, anthraquinones, thioxanthones, and the like. Specifically, benzophenone, chlorobenzophenone, benzoin, acetophenone, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl diisopropyl ketal, anthraquinone, 2-ethylanthraquinone 2-methylanthraquinone, 2-allylanthraquinone, 2-chloroanthraquinone, thioxanthone, 2-chlorothioxanthone and the like.

The photosensitive resin layer may contain an ultraviolet absorber in order to make the shoulder portion of the relief pattern an acute angle. A conventionally well-known thing can be used as a ultraviolet absorber, and what is known as a fluorescent whitening agent may be used. Examples of the ultraviolet absorber include salicylic acids, benzophenones, benzotriazoles, and cyanoacrylates. Specifically, p-benzoquinone, oxybenzone, 4-tert-butyl-4-methoxy-benzoylmethane, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′- Tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2′-dihydroxy-4,4′-benzophenone dimethoxy, 1,4-bis (4-benzoyl-3-hydroxy) Phenoxy) -butane and the like, and these may be used alone or in combination of two or more.

The adhesive layer contains a binder component and at least one inorganic pigment. The adhesive layer may be formed from one layer or a plurality of layers. As the binder component contained in the adhesive layer, a known thermosetting adhesive or elastomeric adhesive can be used. Specifically, adhesives such as urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane resin, polyester resin, nitrile rubber, polystyrene-polyisoprene copolymer resin, polystyrene-polybutadiene copolymer resin, etc. These may be used alone or in combination. Among these, a polyurethane-based adhesive is preferable because it is excellent in bonding with a photosensitive resin, and an adhesive composed of a polyester polyol and an isocyanurate type polyvalent isocyanate is more preferable.

The inorganic pigment contained in the adhesive layer gives high concealment to the deposit on the support. Inorganic pigments include titanium oxide, zinc oxide, iron oxide, chromium oxide, cobalt blue, alumina white, viridian, zinc sulfide, lipotone, cadmium yellow, cadmium red, chrome lead, molybdate orange, dinchloromate, strontium chromate, Examples include white carbon, clay, talc, ultramarine, barite powder, calcium carbonate, lead white, bitumen, manganese violet, and carbon black. In particular, inorganic pigments such as achromatic colors (white, black) such as titanium oxide, barium titanate, and carbon black are preferable because of high concealability. Further, from the viewpoint of concealability and dispersibility, the particle size of the inorganic pigment is preferably 2 μm or less, and more preferably 1 μm or less. The added amount of the inorganic pigment is 10 to 50% by weight, more preferably 12 to 45% by weight, based on the solid content of the adhesive layer. If the addition amount is too small, the deposit cannot be concealed, and if the addition amount is too large, the adhesion performance tends to be lowered.

An inorganic pigment cannot be dissolved unlike a dye that is soluble in a solvent. Therefore, in order to form a uniform adhesive layer, it is necessary to uniformly disperse it in a binder component. For example, a pigment-containing adhesive in which a pigment is uniformly dispersed can be produced by kneading and dispersing a composition comprising a polymer resin, a solvent, and a pigment as a binder by a method such as a three-roller or a dispersing machine. .

A known catalyst, solvent, dispersant, leveling agent, or antifoaming agent may be added to the adhesive forming the adhesive layer. Furthermore, by adding the aforementioned ultraviolet absorber, it may be possible to appropriately prevent halation and improve the reproducibility of the pattern.

The thickness of the adhesive layer is 6 μm or more, preferably 8 μm or more. If the adhesive layer is too thin, it becomes difficult to combine the concealability of the deposit and the adhesive performance. The upper limit of the thickness of the adhesive layer is practically about 50 μm.

The support is made of metal. In particular, known metal materials such as an aluminum plate, a nickel plate, a steel plate, and a steel foil that are excellent in dimensional stability, heat resistance, and mechanical properties are preferably used.

When using a negative when producing a relief, a known negative adhesion preventing layer may be provided to prevent the photosensitive resin and the negative from sticking. In order to prevent external damage, a known cover film may be provided.

(Second embodiment)
The photosensitive resin laminate of the second embodiment of the present invention includes at least a metal support, an adhesive layer, and a photosensitive resin layer, the adhesive layer contains a binder component and at least one inorganic pigment, The ratio of the inorganic pigment to the solid content is 6 to 50% by weight, the adhesive layer is light transmission-inhibiting, and the specular gloss of the surface of the adhesive layer completely exposed by development is 80 or more. To do.

The photosensitive resin layer preferably contains a photosensitive resin that is developed by any method including water development, aqueous medium development, solvent development, and thermal development. As the photosensitive resin layer, those described in the first embodiment can be preferably used.

The adhesive layer is present between the metal support and the photosensitive resin layer, and has a role of bonding both. The adhesive layer may be formed from one layer or a plurality of layers. The thickness of the adhesive layer is usually 5 to 100 μm, preferably 10 to 50 μm.

The adhesive layer preferably contains a binder component and at least one pigment, and further contains a leveling agent and a curing agent. However, when the adhesive layer is composed of a plurality of layers, it is not necessary that all the individual layers contain both the binder component and the inorganic pigment, and if the entire adhesive layer has a layer containing both the binder component and the inorganic pigment, Good.

As the binder component contained in the adhesive layer, those described in the first embodiment can be preferably used.

The adhesive layer is light transmission inhibitory. The light transmission suppressing property is preferably such that the light transmission of the adhesive layer at a wavelength of 450 nm is 1% or less. The light transmission inhibiting property can be imparted by blending a specific amount of inorganic pigment into the adhesive layer. As the inorganic pigment, those described in the first embodiment are preferably used. Titanium oxide is particularly preferable in that the adhesive layer firmly maintains the adhesive force between the metal support and the photosensitive resin layer and is excellent in light transmission suppression. The concentration of the inorganic pigment necessary for exhibiting the light transmission inhibitory property in the adhesive layer varies depending on the type of the pigment and cannot be specified unconditionally, but it is 6% by weight or more, preferably 7% by weight or more, more preferably the solid content of the adhesive layer. Is 8% by weight or more. On the other hand, from the viewpoint of adhesiveness, the concentration of the inorganic pigment is 50% by weight or less, preferably 25% by weight or less, more preferably 20% by weight or less, based on the solid content of the adhesive layer. In the case where the adhesive layer is composed of a plurality of layers, it is not always necessary that all layers contain a pigment, and it is not necessary that all layers have light transmission inhibiting properties. What is necessary is just the light transmission inhibitory property in the whole contact bonding layer.

If there are unevenness or bubbles on the surface of the adhesive layer, it will be difficult to automatically detect defects using optical equipment. If the surface of the adhesive layer having unevenness or bubbles on the surface is low, the specular gloss is low, and if it is smooth, the specular gloss is high. For this reason, the specular gloss of the adhesive layer is significant as an index of the smoothness of the surface of the adhesive layer. If the specular gloss is 80 or more, automatic detection of defects by an optical instrument is easy.

In forming the adhesive layer, it is preferable to add a leveling agent and a solvent to the adhesive. Thereby, unevenness on the surface of the adhesive layer and bubble mixing can be suppressed, and it becomes easy to form a smooth surface. A leveling agent and a solvent can be freely selected from conventionally known ones. In order to form a smooth surface of the adhesive layer, a leveling agent may be added in advance in the composition, and examples of high leveling properties include acrylic, vinyl, fluorine, and silicone. Preferred examples of the leveling agent include a fluorine-based leveling agent Megafac F-443, F-444, F-445, F-470, F-479, F-482, F-484, F-554 (Dainippon Ink Chemical Co., Ltd.) Manufactured by Kogyo Co., Ltd.), silicone leveling agents KP-323, KP-326, KP-341, KP-104, KP-110, KP-112 (manufactured by Shin-Etsu Silicone), Polyflow KL-401, Polyflow KL-402, Polyflow KL-403, polyflow KL-404, polymer leveling agent polyflow WS, polyflow WS30, polyflow WS314 (manufactured by Kyoeisha Chemical Co., Ltd.) can be mentioned. Some of these leveling agents may also act as antifoaming agents. Preferable examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, methyl ethyl ketone and the like, and may be a single solvent or a mixed solvent.

The adhesive layer preferably contains a curing agent in terms of adhesion to the metal support and the photosensitive resin layer, and durability to ink when used for printing. The curing agent can be freely selected from conventionally known ones. A combination using a polyester resin as the binder component and a polyvalent isocyanate as the curing agent is preferable because of excellent adhesion to the photosensitive resin, and isocyanurate type polyvalent isocyanate is particularly preferable as the curing agent.

A curing accelerator may be added to the adhesive layer. The curing accelerator is preferably added for the purpose of efficiently reacting the above curing agent, and Ucat-SA (manufactured by San Apro) is particularly preferable. The curing accelerator is preferably diluted with various solvents, and dioxane is particularly preferable as the solvent to be used.

As in the first embodiment, an ultraviolet absorber may be added to the adhesive layer. Since the adhesive layer has light transmission inhibiting properties, halation is unlikely to occur, but the antihalation effect may be further enhanced.

In order to form the adhesive layer, it is preferable to use a method in which an adhesive containing essential components of the adhesive layer is applied to the support. The method for producing the adhesive used for forming the adhesive layer is not particularly limited. For example, it can be prepared by kneading and dispersing a pigment, a binder component, a solvent, a leveling agent and the like by a method such as a three-roller or a disperser. .

As the support, those excellent in dimensional stability, heat resistance and mechanical properties are good, and metal materials such as aluminum plate, nickel plate, steel plate and steel foil are used. Usually, the metal plate as a support is surface-treated like dull skin / bright skin, and the surface shape is slightly roughened. Moreover, it is necessary to prevent the reflected light on a support body, both when the surface shape of the metal is roughened and when it is not roughened. In the present invention, by including a pigment having a high shielding property in the adhesive layer, it becomes possible to suppress light transmission with respect to the gloss of the metal surface, and the state of the adhesive layer coating surface can be inspected by an optical instrument. Become.

The photosensitive resin laminate may be applied to any development method of thermal development, solvent development, aqueous medium development or water development, and a method of washing out an exposed portion by brush development or spray development may be applied. preferable. Examples of the photosensitive resin composition that can be developed with water or an aqueous medium include JP-A-60-21451, JP-A-2-175702, JP-A-4-3162, JP-A-2-305805, Examples thereof include various photosensitive resin compositions described in JP-A-3-228060, JP-A-10-339951, and the like.

The photosensitive resin laminate is produced by laminating, casting, or extruding a photosensitive resin layer on a support coated with an adhesive layer. Moreover, in order to make plate-making easy, you may laminate | stack a well-known adhesion prevention layer and a protective cover film. A printing plate can be obtained by exposing and developing from the photosensitive resin laminate obtained in the above step using a negative film having a photosensitive property evaluation pattern. The photosensitive resin layer is preferably laminated so as to have a thickness of 20 to 1000 μm, preferably 30 to 500 μm.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, although the quantity of each component is shown by the part, these represent a weight part.

Examples 1A-7A
(Preparation of photosensitive resin composition)
55.0 parts of ε-caprolactam, 40.0 parts of N, N′-bis (γ-aminopropyl) piperazine adipate, 7.5 parts of 1,3-bisaminomethylcyclohexane adipate and 100 parts of water are placed in a reactor. After sufficient nitrogen substitution, the mixture was sealed and gradually heated. When the internal pressure reaches 10 kg / cm ² , the water in the reactor is gradually distilled out to return to normal pressure in 1 hour, and then reacted at normal pressure for 1.0 hour to obtain a transparent light yellow polyamide. It was.

Trimethylolpropane triglycidyl ester was prepared by mixing 50.0 parts of the obtained polyamide, 50.0 parts of methanol and 10 parts of water in a heated dissolution tank with stirring at 60 ° C. for 2 hours to completely dissolve the polymer. 44.0 parts of an acrylic acid adduct, 3 parts of methacrylic acid, 0.1 part of hydroquinone monomethyl ether, 0.02 part of 2,2 ′, 4,4′-tetrahydroxybenzophenone and 2 parts of benzyldimethyl ketal were added. Stir for 30 minutes to dissolve. Next, the temperature was gradually raised to distill methanol and water, and the mixture was concentrated until the temperature in the kettle reached 110 ° C. At this stage, a fluid and viscous photosensitive resin composition was obtained.

(Preparation of support with laminated adhesive layer)
Byron 20SS and Byron 63SS (both made by Toyobo) as binder components, TIPAQUE CR-93 (made by Ishihara Sangyo), titanium oxide as inorganic pigment, and high purity perovskite (made by Sakai Chemical Industry), barium titanate ), Carbon black MA100R (manufactured by Mitsubishi Chemical) or talc MICROACE (manufactured by Nippon Talc), U-CAT SA102 (manufactured by Soda Pot) as a catalyst, and a desmodule comprising an isocyanate group-containing compound as a binder component HLBA (manufactured by Nippon Polyurethane Industry) was sequentially kneaded to obtain an adhesive composition. This adhesive composition was uniformly applied on a chrome-plated steel plate having a thickness of 200 μm as a support and containing a deposit having a diameter of several millimeters using various bar coaters, and immediately 140 ° C. And dried for 3 minutes to prepare a support on which an adhesive layer having a film thickness of 10 μm, 15 μm, or 20 μm was laminated. The compositions of the adhesive layers of Examples 1A to 7A are shown in Table 1.

(Preparation of photosensitive resin laminate)
A laminator is used between the support on which the adhesive layer is laminated and a 125 μm thick polyester film having a 2 μm thick polyvinyl alcohol AH-26 (manufactured by Nippon Synthetic Chemical) as a negative adhesion preventing layer. The photosensitive resin was laminated to prepare a sheet-like photosensitive resin laminate having a total thickness of 1075 μm that can be used with a letter press. The polyester film was used in such a direction that the polyvinyl alcohol film was on the photosensitive resin layer side.

Comparative Examples 1A-6A
In the adhesive layer of the above-described example, NUbian BLACK PC-0850 (made by Orient Chemical Industries) as a dye or FA-48 (made by SINLOIHICOLOR) as an organic fluorescent pigment is used instead of the inorganic pigment (Comparative Examples 1A and 2A) ) Or an inorganic pigment, titanium oxide (TIPAQUE CR-93 (manufactured by Ishihara Sangyo)) (Comparative Examples 3A to 5A), and a photosensitive resin laminate was prepared in the same manner as in the above Examples. Further, in place of the adhesive layer, NUBIAN BLACK PC-0850 alone, which is a dye, was applied, and a sheet-like photosensitive resin laminate was also produced in the same manner as in the above Example (Comparative Example 6A). Table 1 shows the compositions of the adhesive layers of Comparative Examples 1A to 6A.

(Performance evaluation)
The photosensitive resin laminates of Examples 1A to 7A and Comparative Examples 1A to 6A were evaluated by the following methods, and the evaluation results are shown in Table 2.

1. Concealing property The photosensitive resin laminate was visually observed, and it was confirmed according to the following criteria whether or not deposits having a diameter of about 1 mm could be detected.
○: The adhered matter was completely detected visually.
(Triangle | delta): The deposit | attachment was not fully detectable visually.
X: No deposits could be detected visually.

2. Relief shape A relief was prepared using the photosensitive resin laminates of Examples and Comparative Examples under the conditions for reproducing 50 μm fine lines, and used for observation of relief shapes, printing tests, and the like. Use an ultra-high pressure mercury lamp (Oak Manufacturing Co., Ltd.) for exposure, and develop with 25 ° C water using JOW-A2-PD (Nippon Denki Seiki Co., Ltd.) which is an automatic brush developer. went. The shape of the obtained relief was observed with a microscope and evaluated according to the following criteria.
○: The relief was not thin.
X: The relief was thin.

3. Adhesiveness Using the photosensitive resin laminates of Examples and Comparative Examples, reliefs were produced under the conditions of reproducing 50 μm fine lines, and printing was performed 200 shots with a letter press printer. Evaluation of adhesiveness was performed according to the following criteria.
○: Relief was not lost even after printing 200 shots.
(Triangle | delta): The relief was missing by the end of 200 shot printing.
X: The support and the adhesive layer were peeled off during the relief preparation.

4). Relief reproducibility Using the photosensitive resin laminates of Examples and Comparative Examples, reliefs were produced under the conditions of reproducing 50 μm fine lines, and the relief shape was evaluated using a laser microscope (Keyence Corporation) according to the following criteria.
○: The thin line was not twisted.
Δ: The thin line was twisted.
X: The support and the adhesive layer were peeled off during the relief preparation.

Examples 1B-5B, Comparative Examples 1B-5B
(Preparation of adhesives AJ)
41 parts Byron 20SS (solid content 30% by weight, manufactured by Toyobo) and 25 parts Byron 63SS (solid content 30% by weight, manufactured by Toyobo) as binder components, 20 parts methyl ethyl ketone as solvent, and 2.9 parts oxidation as pigment Titanium, 0.1 part KP-341 (manufactured by Shin-Etsu Silicone) as leveling agent, 0.20 part Ucat-SA (solid content 0.18 part, manufactured by San Apro) as a curing accelerator, 0.80 part as a solvent Dioxane and 10 parts of desmodule HL BA (manufactured by Sumika Bayer Urethane Co., Ltd.) as a curing agent were put in a container and kneaded for 30 minutes using a stirrer to obtain an adhesive A. Adhesives BJ were prepared in the same manner as Adhesive A according to the formulation in Table 3.

(Preparation of laminate of adhesive layer and metal support)
For the photosensitive resin laminates of Examples 1B to 5B and Comparative Examples 1B to 5B, adhesives A to J shown in Table 3 were applied to bright skin-treated steel sheets having a thickness of 175 μm. Next, this coated steel sheet was placed in a hot air dryer set at 100 ° C. for 2 minutes, and the coating film was heated and dried to obtain a laminate of an adhesive layer / metal support having an adhesive layer having a thickness of 15 μm.

(Preparation of photosensitive resin composition)
Put 55.0 parts of ε-caprolactam, 40.0 parts of N, N-bis (γ-aminopropyl) piperazine adipate, 7.5 parts of 1,3-bisaminomethylcyclohexane adipate and 100 parts of water into the reactor, and After nitrogen replacement, the mixture was sealed and gradually heated. When the internal pressure reaches 10 kg / cm ² , the water in the reactor is gradually distilled out, returned to normal pressure in 1 hour, then reacted at normal pressure for 1.0 hour, Obtained.

Subsequently, 50.0 parts of the obtained polyamide, 50.0 parts of methanol, and 10.0 parts of water were mixed in a heat-dissolved kettle with stirring at 60 ° C. for 2 hours to completely dissolve the polymer, 44.0 parts of an acrylic acid adduct of trimethylolpropane triglycidyl ester, 3 parts of methacrylic acid, 0.1 part of hydroquinone monomethyl ether, 0.02 part of 2,2 ′, 4,4′-tetrahydroxybenzophenone and benzylmethyl ketal 2 parts were added and stirred for 30 minutes to dissolve. Next, the temperature was gradually raised to distill methanol and water, and the mixture was concentrated until the temperature in the kettle reached 110 ° C. to obtain a fluid and viscous photosensitive resin composition.

(Preparation of photosensitive resin laminate)
A photosensitive resin laminate was prepared by laminating the photosensitive resin composition with a laminate of the adhesive layer / metal support and a cover film. This laminate can be used as a sheet-shaped photosensitive resin original plate having a total thickness of 1075 μm that can be used in a letter press printer.

(Production of adhesive layer-exposed photosensitive resin laminate)
Using the automatic brush developer JOW-A2-PD (manufactured by JEOL Ltd.) without peeling off the cover film of the photosensitive resin laminate obtained above and exposing the exposed photosensitive resin layer Development was performed with water at 25 ° C. When the photosensitive resin is left unwashed by development and the adhesive layer on the metal support side is completely exposed, it is removed from the automatic brush developer, dried at 60 ° C. for 10 minutes, and exposed to adhesive layer. A resin laminate was obtained.

The photosensitive resin laminates of Examples 1B to 5B and Comparative Examples 1B to 5B were evaluated by the following methods, and the results are shown in Table 4.

(Light transmission suppression of adhesive layer and surface irregularities / bubbles)
Using a laser microscope (VY-9500, an ultra-deep color 3D shape measurement microscope manufactured by KEYENCE), a photosensitive resin laminate with an adhesive layer exposed using a standard objective lens with a magnification of 20 times in both the laser microscope mode and the optical microscope mode. Observed. Surface observation was performed in both laser microscope mode and optical microscope mode. Regarding light transmission inhibition, the case where the metallic luster and diffuse reflection derived from the support were suppressed and the surface observation was not hindered was judged as ◯, and the case where there was a hindrance was judged as x. For those having good light transmission inhibiting properties, surface irregularities and bubbles were further observed, and those where neither irregularities nor bubbles were observed were judged as ◯, and those where irregularities or bubbles were observed were judged as x. Examples of surface observation in the optical microscope mode are shown in FIGS.

(Light transmittance of adhesive layer)
Adhesives A to G were applied to a transparent film to form an adhesive layer / film laminate having a dry film thickness of 15 μm. The light transmittance of the adhesive layer / film laminate at a wavelength of 450 nm was measured with a spectrophotometer (manufactured by Horiba Seisakusho Co., Ltd.) and used as an indicator of the light transmission inhibitory property of the adhesive layer.

(Specular gloss of adhesive layer surface)
Based on JIS Z 8741-1997 (Specular Gloss Measurement Method), using a gloss meter Glass Meter VG2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the surface gloss of the adhesive layer exposed photosensitive resin laminate was measured. It was measured.

(Adhesive strength of support and photosensitive resin layer)
For the photosensitive resin laminate, the adhesive strength was measured in order to examine the adhesive strength between the support and the photosensitive resin layer. Below, the preparation methods of a measurement object sample are described. A photosensitive resin laminate was prepared by cutting out a 5 × 16 cm square of an adhesive layer previously coated on a metal support, laminating the photosensitive resin cut out in a 7 × 10 cm square at the center and pressing it. The pressing conditions were a pressure of 30 kg / cm ² , a temperature of 100 ° C., and a pressing time of 20 seconds. The adhesive strength measurement was performed about the sample which carried out the water development after drying the produced photosensitive resin laminated body, and dried it. Adhesive strength of the photosensitive resin layer was peeled from the sample with a peel accuracy of 90 ° and a pulling speed of 50 mm / min. Tensilon (RTC-1210A manufactured by ORIENTEC) was used, and a load cell rated at 100 kgf was used. The measured value was used. Practically, the adhesive force is desirably 3 kg / cm or more, so 3 kg / cm or more was indicated as ≧ 3.0, and less than 3 kg / cm was indicated as <3.0.

(Print life)
Using the photosensitive resin laminate, a relief was produced under the condition of reproducing 50 μm fine lines, and printing was performed 2000 shots with a letter press printer. The printing durability was evaluated according to the following criteria.
○: No peeling occurred between the support and the adhesive layer even after the end of 2000 shot printing.
X: Peeling occurred entirely or partially between the support and the adhesive layer by the end of 2000 shot printing.

The photosensitive resin laminates and adhesive layer / film laminates of Examples 1B to 5B and Comparative Examples 1B to 5B were prepared and subjected to various evaluations as described above. The results are shown in Table 4.

The photosensitive resin laminate of the present invention can suppress the occurrence of defective products of the photosensitive resin laminate by suppressing the influence of the adhered metal plate used for the support, and as a result, the photosensitive resin laminate The productivity of the body can be improved. In addition, the photosensitive resin laminate of the present invention can easily observe the surface shape of the photosensitive resin laminate before and after exposure and development, and the surface of the photosensitive resin laminate can be observed with an optical device. It is possible to quickly and accurately perform defect inspection and surface observation, and it is also easy to automate plate inspection. Plate inspection using an optical instrument can obtain a higher detection sensitivity than visual inspection, and is particularly suitable for the production process of a printing original plate used in the production process of precision instruments. In addition, automation of plate inspection can be expected to improve the production efficiency of the plate manufacturing process.

1: Adhesive layer exposed part 2: Support exposed part

Claims

An inorganic pigment for the solid content of the adhesive layer, comprising at least a metal support, an adhesive layer, and a photosensitive resin layer, wherein the adhesive layer contains a binder component and at least one inorganic pigment. The photosensitive resin laminate is characterized in that the ratio is 10 to 50% by weight and the thickness of the adhesive layer is 6 μm or more.
The photosensitive resin laminate according to claim 1, wherein the inorganic pigment is an achromatic inorganic pigment.
2. The photosensitive resin laminate according to claim 1, wherein the inorganic pigment is titanium oxide, barium titanate, or carbon black.
The photosensitive resin laminate according to any one of claims 1 to 3, wherein the adhesive layer is thermosetting.
An inorganic pigment for the solid content of the adhesive layer, comprising at least a metal support, an adhesive layer, and a photosensitive resin layer, wherein the adhesive layer contains a binder component and at least one inorganic pigment. A photosensitive resin, wherein the adhesive layer has a light transmission-inhibiting property, and the specular gloss of the surface of the adhesive layer completely exposed by development is 80 or more Laminated body.
The photosensitive resin laminate according to claim 5, wherein the inorganic pigment is titanium oxide.
The photosensitive resin laminate according to claim 5 or 6, wherein the adhesive layer contains a leveling agent.
The photosensitive resin laminate according to any one of claims 5 to 7, wherein the binder component contains a polyester resin and / or a polyurethane resin.
9. The photosensitive resin laminate according to claim 5, wherein the adhesive layer has a light transmittance of 1% or less at a wavelength of 450 nm.