JP2008257007A - Photosensitive resin laminate and photosensitive resin printing plate material obtained from same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water developable photosensitive resin laminate applicable to a high-definition circuit printing plate by using a technique for precisely reproducing dense image information with a photosensitive resin printing plate precursor. <P>SOLUTION: (1) The photosensitive resin laminate includes at least a support, an adhesive layer and a photosensitive resin layer, wherein the photosensitive resin layer has a thickness of 10-150 μm and the adhesive layer contains a soluble high molecular compound having the same constitutional unit as the photosensitive resin composition layer. (2) In the photosensitive resin laminate (1), the soluble high molecular compound contained in the adhesive layer is a water- or alcohol-soluble polyamide containing a constitutional unit of 6-nylon. (3) In the photosensitive resin laminate (1) or (2), the photosensitive resin layer contains a benzophenone type ultraviolet absorber. (4) In the photosensitive resin laminate (1) to (3), the adhesive layer has a two-layer structure, in which a polyamide-containing crosslinked adhesive layer is disposed on a polyurethane-based adhesive layer disposed on the support. (5) A photosensitive resin printing plate is obtained from the photosensitive resin laminate (1) to (4). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin laminate used for a photosensitive resin printing plate that accurately reproduces an image. More specifically, the present invention relates to a photosensitive resin laminate for circuit printing and a photosensitive resin printing plate material.

Conventionally, techniques such as inkjet printing, screen printing, and electrostatic printing have been known for circuit printing (see, for example, Patent Documents 1, 2, and 3). However, this conventional technique has problems in terms of manufacturing cost and circuit line width reproducibility. Among other printing methods, letterpress printing has both printing cost and relatively sharp printing, but it is difficult to combine high sensitivity and depth. Application to circuit printing was difficult.
Patent Publication 2004-273205 Patent Publication 2001-14493 Patent Publication No. 6-53635

    The present invention has been made against the background of such prior art problems. That is, an object of the present invention is to provide a photosensitive resin laminate excellent in high-definition circuit printing.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have reached the present invention.
That is, this invention consists of the following structures.

(1) A photosensitive resin laminate comprising at least a support, an adhesive layer and a photosensitive resin layer, wherein the photosensitive resin layer has a thickness of 10 to 150 μm, and the adhesive layer is the same as the photosensitive resin composition layer A photosensitive resin laminate comprising a soluble polymer compound having a structural unit.
(2) The photosensitive resin laminate according to (1), wherein the soluble polymer compound contained in the adhesive layer is a polyamide containing a 6-nylon constituent unit and soluble in alcohol and / or water.
(3) The photosensitive resin laminate according to (1) or (2), wherein the photosensitive resin layer further contains a benzophenone-based ultraviolet absorber.
(4) The photosensitive resin according to (1) to (3), wherein the adhesive layer has a two-layer structure, and a crosslinked adhesive layer containing polyamide is provided on a polyurethane-based adhesive layer provided on a support. Laminated body.
(5) A photosensitive resin printing plate obtained from the photosensitive resin laminate of (1) to (4).

According to the present invention, a dense circuit pattern can be printed.
The effect of light scattering at the inner mass part in the photosensitive resin layer can be reduced, and the formed pattern can be maintained on the support, providing an optimal photosensitive resin original plate for forming high-definition patterns. can do.

  Hereinafter, the present invention will be described in detail.

  In the present invention, the thickness of the photosensitive resin layer is preferably 10 to 150 μm. This is because by reducing the photosensitive resin layer, curing can be performed with a smaller exposure amount than that of a normal resin plate, and relief thickening due to light scattering at the inner mass part in the photosensitive resin layer can be suppressed. Furthermore, it becomes easy to wash the photosensitive resin layer up to the mass part of the adhesive layer at the time of development, and the pattern can be made to exist independently. Further, swelling due to the solvent can be suppressed only to an independent pattern mass portion, and it is expected to improve reproducibility.

  The photosensitive resin layer used in the printing plate of the present invention contains a known soluble polymer compound, a crosslinking agent (also referred to as an ethylenically unsaturated compound), a photoinitiator composition, and an ultraviolet absorber. Furthermore, other additives such as plasticizers, thermal polymerization inhibitors, dyes, pigments, fragrances or antioxidants may be included. The polymer compound used in the present invention is preferably a polymer binder that is soluble in alcohol and / or water. Specifically, polyether amide, polyether ester amide, tertiary nitrogen-containing polyamide, ammonium salt type 3 Examples thereof include polyamides containing quaternary nitrogen atoms, addition polymers of amide compounds having one or more amide bonds and organic diisocyanate compounds, among which polyamides containing tertiary nitrogen atoms and polyamides containing ammonium salt type tertiary nitrogen atoms are preferred.

  Suitable crosslinking agents (ethylenically unsaturated compounds) include dipentaerythritol, pentaerythritol, trimethylolpropane, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, phthalic acid, ethylene oxide adduct, bisphenol A, Diglycidyl ether acrylic acid adduct of bisphenol F, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol penta (meth) Addition product of poly (glycidyl ether) such as acrylate and dipentaerythritol penta (meth) acrylate and (meth) acrylic acid, such as adipic acid Examples include, but are not limited to, polyunsaturated compounds such as a reaction adduct of a polyvalent carboxylic acid and glycidyl (meth) acrylate, an addition reaction product of a polyvalent amine such as propylenediamine and glycidyl (meth) acrylate, and the like. In addition, two or more of these compounds can be used in combination.

  Furthermore, examples of the photoinitiator composition used in the present invention 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 ultraviolet absorber used for this invention is used in order to make the shoulder mass site | part of a relief pattern into an acute angle. As this ultraviolet absorber, a commercially available ultraviolet absorber can be used, and a commercially available fluorescent brightener may be used. Examples include salicylic acids, benzophenones, benzotriazoles, cyanoacrylates and UV absorbers, and these may be used in combination with UV stabilizers, hindered amine light stabilizers, and the like. Specifically, p-benzoquinone, oxybenzone, 4-tert-butyl-4-methoxy-benzoylmethane, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'4,4'-tetra Hydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-benzophenone dimethoxy, 1,4-bis (4-benzoyl-3-hydroxyphenoxy ) -Butane and the like. Among them, benzophenones are preferable, and 2,2′4,4′-tetrahydroxybenzophenone is particularly preferable.

  In the present invention, when a fine pattern is present independently, it is necessary to firmly bond the photosensitive resin layer and the support. Therefore, the adhesive layer used in the present invention has a two-layer structure, and is a multilayer adhesive layer in which a crosslinked adhesive layer (B) containing polyamide is provided on a polyurethane-based adhesive layer (A) provided on a support.

  A known adhesive can be used for the adhesive layer (A). Examples thereof include polyester urethane adhesives and epoxy adhesives obtained by curing soluble polyester with polyvalent isocyanate. Among them, polyester urethane adhesives are preferable because they are excellent in adhesion to photosensitive resins, and among polyester urethane adhesives, an adhesive composed of polyester and isocyanurate type polyisocyanate is more preferable.

  The adhesive layer (B) is composed of an adhesive layer containing a soluble polymer compound having the same structural unit as that of the photosensitive resin layer. The crosslinkable component contained in the adhesive layer (B) is preferably a component that is crosslinked thermally and / or photochemically. Specifically, it is a resin composition having crosslinkability, that is, a crosslinkable composition comprising a soluble polymer compound, a polymerizable unsaturated compound and a polymerization initiator is preferred.

  Soluble polymer compounds used in the present invention include polyamides, polyvinyl alcohols, polyurethanes and the like that are soluble in alcohol and / or water, among which polyamides are preferred. Specific polyamides include polyether amides, polyether ester amides, tertiary nitrogen-containing polyamides, ammonium salt type tertiary nitrogen atom-containing polyamides, addition polymers of amide compounds having one or more amide bonds and organic diisocyanate compounds. Among them, tertiary nitrogen-containing polyamides and ammonium salt type tertiary nitrogen atom-containing polyamides are particularly preferable.

  Furthermore, in this invention, adhesion | attachment with the photosensitive resin layer is strengthened when a polymerizable unsaturated compound bridge | crosslinks by photopolymerization and / or thermal polymerization. Examples of the polymerizable unsaturated compounds include dipentaerythritol, pentaerythritol, trimethylolpropane, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, phthalic acid, ethylene oxide adduct, bisphenol A and bisphenol F diglycidyl ether acrylic. Acid adduct, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol penta ( Addition product of poly (glycidyl ether) such as (meth) acrylate and (meth) acrylic acid, polyvalent carboxylic acid such as adipic acid and glycidyl Examples include, but are not limited to, polyunsaturated compounds such as a reaction adduct with (meth) acrylate, an addition reaction product of polyvalent amine such as propylenediamine and glycidyl (meth) acrylate, and the like. Two or more of these compounds can be used in combination.

  Moreover, in this invention, if a polymerizable unsaturated substance can be bridge | crosslinked, regardless of a method, in order to bridge | crosslink suitably, it bridge | crosslinks by using light and / or heat as a medium. It is preferable to use a known photopolymerization initiator that uses light as a medium. For example, benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzyl ketals such as dimethyl ketal and diethyl ketal, benzophenones, anthraquinones, and diacetyl photoinitiators are preferred. However, two or more types may be used in combination. Furthermore, other minor components can be added to the adhesive layer (B). Examples of the additive include a plasticizer, a dye, a crosslinking agent, an ultraviolet absorber, an antihalation agent, and a surfactant.

  Examples of the support used in the present invention include a plastic film such as a polyester film, a metal plate such as iron, stainless steel, and aluminum, and a metal-deposited film.

  The photosensitive resin laminate (also referred to as a photosensitive resin printing original plate) used in the present invention and circuit printing plate is obtained by any desired method such as hot pressing, casting, melt extrusion, solution casting, etc. It can be set as a photosensitive resin printing original plate having a thickness of sheet.

  Further, a protective layer may be provided in the present invention. As the protective layer, a plastic film is used, and among them, a polyester film having excellent dimensional stability is preferable. In the protective layer, a film-like plastic, for example, a polyester film having a thickness of 125 μm, on which a non-sticky transparent polymer film having a thickness of 1 to 3 μm that can be dispersed or dissolved in a developer is formed. Is used. By laminating a film having this thin film on the photosensitive layer so that the film is in contact with the photosensitive layer, even if the surface adhesiveness of the photosensitive layer is strong, the plastic film is removed before the exposure operation. It can be easily peeled from the photosensitive layer.

  As a method for preparing a printing plate from a photosensitive resin original plate, first, a cover film is peeled off, a 1 to 30 μm spacer is placed on the photosensitive layer, a glass mask having a transparent image portion is overlaid thereon, and from above. When exposure is performed by irradiating actinic rays, the exposed portion is cured and insolubilized. For the actinic ray, a light source such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, or a xenon lamp, usually centered on a wavelength of 300 to 400 nm, is used.

  After the exposure, the non-exposed portion is dissolved and removed using an appropriate solvent, preferably water, particularly neutral water, so that the development is performed quickly in a short time, and a printing plate (relief plate) is obtained. As the developing method, it is preferable to use a spray developing device, a brush developing device, or the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.

[Synthesis of Polyamide 1]
ε-caprolactam 55.0 parts by mass, N, N′-bis (γ-aminopropyl) piperazine adipate 40.0 parts by mass, 1,3-bisaminomethylcyclohexane adipate 7.5 parts by mass and water 100 parts by mass, The reactor was placed in a reactor, sufficiently purged with nitrogen, then sealed and gradually heated. When the internal pressure reached 10 kg / cm 2, water in the reactor was gradually distilled out and returned to normal pressure in 1 hour, and then reacted at normal pressure for 1.0 hour. The maximum polymerization temperature was 220 ° C. The obtained polymer obtained transparent light yellow polyamide 1 having a melting point of 140 ° C. and a specific viscosity of 2.00. This polyamide was soluble in alcohol and acidic water.

[Production of photosensitive resin composition]
After 50.0 parts by mass of the obtained polyamide 1, 50.0 parts by mass of methanol and 10 parts by mass of water were mixed at 60 ° C. for 2 hours in a heating and stirring kettle with stirring to completely dissolve the polymer, 44.0 parts by mass of an acrylic acid adduct of methylolpropane triglycidyl ester, 3 parts by mass of methacrylic acid, 0.1 part by mass of hydroquinone monomethyl ether, 0.02 parts by mass of 2,2'4,4'-tetrahydroxybenzophenone and benzyl 2 parts by mass of dimethyl ketal was added and dissolved for 30 minutes. 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 1 was obtained.

  After 50.0 parts by mass of the obtained polyamide 1, 50.0 parts by mass of methanol and 10 parts by mass of water were mixed at 60 ° C. for 2 hours in a heating and stirring kettle with stirring to completely dissolve the polymer, 44.0 parts by mass of an acrylic acid adduct of methylolpropane triglycidyl ester, 3 parts by mass of methacrylic acid, 0.1 part by mass of hydroquinone monomethyl ether and 2 parts by mass of benzyldimethyl ketal were added and dissolved for 30 minutes. 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 photosensitive resin composition 2 containing no fluid viscous UV absorber was obtained.

[Manufacture of support]
On a chrome-plated steel sheet with a thickness of 200 μm, 100 g of commercially available linear polyester byron RV-30SS (Toyobo) 0.1 g of U-CATSA102 (San Apro Co., Ltd.), Coronate L (Nippon Polyurethane Industry Co., Ltd.) A coating solution obtained by sequentially mixing 10.0 g is applied uniformly using a bar coater, immediately put into a 140 ° C. hot air dryer and dried for 3 minutes to form an adhesive layer 1 having a thickness of about 20 μm. The support body 1 which has was obtained.

  On the support 1 subjected to the treatment of the adhesive layer, 65 parts by mass of ultraamide-IC (manufactured by BASF) as alcohol-soluble nylon, 35 parts by mass of trimethylolpropane triglycidyl ether / triacrylate, 0.3 mass of dimethylbenzyl ketal A 25% methanol solution containing 0.1 part by mass of hydroquinone monomethyl ether was applied using a roll coater, dried for 3 minutes in a hot air dryer at 90 ° C., and immediately placed at 30 cm directly under an 80 w / cm super high pressure mercury lamp. Then, an actinic ray was irradiated in the presence of air for 30 seconds to obtain a support 2 having an adhesive layer 2 having a thickness of about 20 μm.

  Further, 65 parts by mass of polyamide 1, 35 parts by mass of trimethylolpropane triglycidyl ether / triacrylate, 0.3 part by mass of dimethylbenzyl ketal, 0.1 part by mass of hydroquinone monomethyl ether on support 1 subjected to adhesion treatment A 25% methanol solution containing 1% is applied using a roll coater, dried for 3 minutes with a hot air dryer at 90 ° C., and immediately after 30 seconds under an 80 w / cm ultra-high pressure mercury lamp, an actinic ray is applied for 30 seconds in the presence of air. To obtain a support 3 having an adhesive layer 3 having a thickness of about 20 μm.

Examples 1 to 6, Comparative Examples 1 and 2
The obtained photosensitive resin composition 1 between the supports 1 to 3 and a 125 μm-thick polyester film having a coating of 2 μm-thick polyvinyl alcohol (AH-24, manufactured by Nippon Synthetic Chemical Co., Ltd.), 2 is laminated on the photosensitive layer with a laminator so that the coating side is in contact with the photosensitive layer, and the sheet thickness of the total thickness is 950 μm, 570 μm, 520 μm, 500 μm and the photosensitive layer thickness is 480 μm, 100 μm, 50 μm, 30 μm. A functional resin original plate was obtained.

In each photosensitive resin original plate, a glass substrate on which a fine image pattern in which 50 fine lines of 30 μm × 4 cm are arranged at intervals of 100 μm was chrome-deposited was used, and each raw plate was sandwiched with a 25 μm spacer and a glass mask was used. Contact exposure was performed. After exposure, the unexposed portion was washed away by spray development (water pressure 4 kgf / cm ² ), dried by a dryer at 75 ° C. for 10 minutes, and post-exposure was performed.

  The evaluation results are shown in Table 1. In Comparative Example 1, an image pattern was not clearly formed, and in Comparative Example 2, the pattern was washed away by spray development and could not be formed. However, in Examples 1 to 6, it was possible to wash out the unexposed part up to the adhesive layer, and it was possible to make the thin line independently exist. In order to confirm the reproducibility of the image pattern, a sample subjected to Pt deposition at an acceleration voltage of 10 kV was observed with a Hitachi scanning electron microscope S4500. In Examples 1 to 5, it was confirmed that the shoulder mass portion had an acute angle and the reproducibility was good. In Example 6, compared with Examples 1-5, the shoulder part was roundish.

According to the present invention, a dense pattern can be formed, the manufacturing cost can be further reduced, and workability is very easy, so that it is expected to greatly contribute to the industry.

Claims (5)

  A photosensitive resin laminate comprising at least a support, an adhesive layer and a photosensitive resin layer, wherein the photosensitive resin layer has a thickness of 10 to 150 μm, and the adhesive layer has the same structural unit as the photosensitive resin composition layer. A photosensitive resin laminate comprising a soluble polymer compound having the same.   2. The photosensitive resin laminate according to claim 1, wherein the soluble polymer compound contained in the adhesive layer is a polyamide that contains 6-nylon constituent units and is soluble in alcohol and / or water.   The photosensitive resin laminate according to claim 1 or 2, wherein the photosensitive resin layer further contains a benzophenone-based ultraviolet absorber.   The photosensitive resin laminate according to claim 1, wherein the adhesive layer has a two-layer structure, and a crosslinked adhesive layer containing polyamide is provided on a polyurethane-based adhesive layer provided on the support. A photosensitive resin printing plate obtained from the photosensitive resin laminate according to claim 1.