JP2010085513A - Photosensitive dry film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive dry film achieving fine patterning on a thick film, reducing loss of a coating liquid in a printing method, improving productivity, and having excellent storage stability by using the photosensitive dry film for forming a light-shielding member, which is conventionally carried out by a printing method. <P>SOLUTION: In the photosensitive dry film, a resin layer comprising a black photosensitive resin composition (B) is formed on the uneven surface of a substrate (A) having unevenness on its surface. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive dry film useful for forming a black matrix used in a liquid crystal display or the like, and a light shielding member for a reading lens such as an optical printer or a copying machine.

  In recent years, as electronic devices are required to be miniaturized, it is indispensable to miniaturize members used for them, and at the same time, an image transmission device for a writing optical system such as an optical printer or a reading optical system such as a scanner. For example, higher resolution is required. Conventionally, a refractive index distribution type rod lens array has been used in an imaging optical system used for these. According to the gradient index rod lens array, an erecting equal-magnification imaging optical system can be realized extremely compactly. However, since this lens array is manufactured by arranging a large number of rod lens elements and fixing them with resin, uneven arrangement of the rod lens elements is likely to occur. Such unevenness of the array affects the resolution of the lens array, and stray light or the like is likely to occur in a high-resolution device, causing image unevenness.

  A resin erecting lens array has been developed as a lens array that can suppress the occurrence of such unevenness of alignment. The resin erecting lens array realizes an erecting equal-magnification imaging optical system by laminating two or more flat lens array plates each having a large number of lenses formed on the surface of a transparent substrate. (Refer to Patent Document 1 and Patent Document 2) Such resin erecting lens arrays have been used so far in combination with a liquid crystal display element to form a liquid crystal image on a space or an object. In order to apply the vertical lens array to an optical printer or scanner, it is necessary to improve resolution and transmitted light amount and reduce stray light. Recently, a method of forming a light-shielding partition by a photolithography method using a black photosensitive composition has also been proposed.

  However, in such a composition intended for light shielding, it is necessary to contain a large amount of a light shielding black pigment such as carbon black in order to color the composition black. Therefore, in the photolithography method, if the film thickness of the composition is large, it is difficult for light to reach the deepest part of the film at the time of exposure, and photocurability is insufficient. As a result, undercutting occurred in the development process, and a desired pattern shape could not be obtained, and there were problems such as poor adhesion to the substrate. If the amount of light exposure is increased in order to realize the deepest part curability of the film, there arises a problem that the resolution is lowered. Accordingly, there has been no black photosensitive resin composition that can form a light-shielding member having a thickness of 20 μm or more, no undercut during development, adhesion, and good blackness.

Recently, there has been a report of a black photosensitive resin composition (hereinafter also referred to as a coating solution) having no sufficient undercut and having a sufficient black density for the purpose of solving the above problems (see Patent Document 3). However, since the composition forms a coating film by a printing method, there is a problem that a manufacturing process is high because a drying process is necessary and the printing method itself has a large amount of coating liquid loss. In addition, the coating liquid is an essential component in the composition in order to obtain the deep curing performance of the translucent fine particles, but there is also a problem that the storage stability is poor due to the presence of the translucent fine particles in the composition. It was.
JP 2003-202411 A Japanese Patent Laid-Open No. 2004-070268 JP 2007-322485 A

  Therefore, according to the present invention, fine patterning can be realized even with a thick film by forming a light shielding member using a photosensitive dry film, which has been conventionally performed by a printing method, and there is little coating liquid loss as in the printing method. An object of the present invention is to provide a photosensitive dry film having excellent productivity and excellent storage stability.

  The present invention relates to a photosensitive dry film comprising a resin layer made of a black photosensitive resin composition (B) on an uneven surface of a substrate (A) having an uneven surface.

  Moreover, this invention relates to said photosensitive dry film characterized by the unevenness | corrugation of the surface of a base material (A) being surface roughness (Ra) 0.25-1 micrometer.

  Further, the present invention provides the photosensitive resin according to any one of the above, wherein the irregularities on the surface of the substrate (A) are formed by a resin composition (C) containing a resin curable by heat or light and translucent fine particles. It relates to dry film.

  In the present invention, the black photosensitive resin composition (B) includes a black pigment, a carboxyl group- and ethylenically unsaturated group-containing resin, and a photopolymerization initiator. It relates to dry film.

  In the present invention, any one of the above photosensitive dry films is bonded to an optical member, then exposed by a photomask method or a direct drawing method, the substrate (A) is then peeled off, and further developed to develop a black photosensitive property. The present invention relates to a method for producing a patterned optical article, wherein a pattern is formed on an optical member by removing an uncured portion of the resin composition (B).

  The present invention also relates to a patterned optical article obtained by the above manufacturing method.

  The photosensitive dry film of the present invention is excellent in deep curability and resolution at the time of exposure by using a substrate having irregularities on the surface, does not generate undercut at the time of development, and has high blackness. It has been found that a thick film shading member can be formed. Therefore, it can be suitably used for forming a black matrix used in a liquid crystal display or the like, or a light shielding member for a reading lens such as an optical printer or a copying machine.

  As a result of intensive studies to solve the above problems, the present inventors are characterized in that a resin layer using a black photosensitive resin composition is formed on the uneven surface of a substrate having uneven surfaces. While the photosensitive dry film is excellent in deep part curability and resolution after exposure / development, it has been found that a desired light-shielding member having the same film thickness can be produced at any time by having a composition having no fluidity at room temperature. The present invention will be described in detail below.

The base material (A) having irregularities on the surface of the present invention requires that irregularities be formed on the surface of a sheet such as a plastic film having optical transparency. Further, the irregularities preferably have a surface roughness (Ra) of 0.25 to 1 μm, and more preferably 0.25 to 0.6 μm. When the substrate (A) has irregularities, when the black resin composition is applied to the surface thereof to produce a photosensitive dry film, irregularities are formed on the resin layer. Therefore, even if there are no translucent fine particles in the black resin layer, due to the unevenness of the resin layer, appropriate light scattering occurs when the resin layer is exposed by photolithography, and the light is deepest in the resin layer. A good pattern without undercut can be formed.
In the present invention, the surface roughness (Ra) indicates an arithmetic average roughness defined in JIS B0601 and JIS B0031. A three-dimensional structural analysis microscope (manufactured by ZYGO System Canon Marketing Japan Co., Ltd.) was used to measure the surface roughness of the substrate (A).

  For example, polyester (polypropylene), cellophane, polycarbonate, cellulose acetate, polyethylene, polyvinyl chloride, polystyrene, nylon, polyimide, polyvinylidene chloride, ionomer, etc. Coating resin composition containing translucent fine particles, forming irregularities on plastics film by embossing with a mold, etc., but heat and light curable resin and translucent fine particles It is more preferable to use a resin composition (C) containing

Examples of the resin curable by heat or light that can be contained in the resin composition (C) include polyester resins, epoxy resins, and melamine resins.
The light-transmitting fine particles that can be contained in the resin composition (C) may be any fine particles that can form desired irregularities on the substrate (A) and have light-transmitting properties. Can be used. Examples of the inorganic fine particles include fine particles such as silica. Examples of the organic fine particles include polymer fine particles such as acrylic and styrene. The translucent fine particles contained in the resin composition (C) have an absolute value of the difference in refractive index from the resin component excluding the coloring component for imparting black color from the black photosensitive resin composition (B). 04 is preferable. When the absolute value of the difference in refractive index exceeds 0.04, light diffusion and light attenuation increase, which may lead to deterioration of deep part curability and patterning property. The average particle diameter of the translucent fine particles is preferably 0.1 to 8 μm. If it is out of the range, it may be difficult to form desired irregularities on the substrate (A).

  Moreover, it is preferable that a translucent fine particle is 5-20 weight part among 100 weight part of non volatile matters of a resin composition (C). When the amount is less than 5 parts by weight, it may be difficult to form desired irregularities on the substrate (A). On the other hand, when the amount exceeds 20 parts by weight, light diffusion becomes large, and there is a possibility that pattern formation of the resin layer is deteriorated. The average particle diameter in the present invention is a value measured by Mastersizer 2000 (manufactured by Sysmex Corporation).

  Further, the light-transmitting fine particles are contained in the resin composition (C) so as to be an optical path for curing to a deep portion while suppressing halation without disturbing the progress of light in the base material (A) during exposure. It is preferable that the absolute value of the refractive index difference with the cured product of the resin curable by heat or light is 0 to 0.04. If it is out of the range, the straightness of light is lowered, and the patterning property of the resin layer may be lowered. The light-transmitting fine particles preferably have a refractive index in the range of 1.40 to 1.90, and more preferably have a refractive index in the range of 1.47 to 1.55. Is more preferable. When the resin composition (C) is coated on a plastic film, the coating surface of the plastic film may be subjected to corona treatment, easy adhesion treatment, etc. for improving adhesion.

The black photosensitive resin composition (B) of the present invention preferably contains a black pigment. The black pigment is not particularly limited as long as it has sufficient light shielding properties, and examples thereof include metal oxide, carbon black, lamp black, bone black, graphite, aniline black, cyanine black, and titanium black. Examples of the metal oxide include those containing one or more of oxides such as Fe, Cr, Mn, and Co as a main component, for example, CrO ₃ , Cr ₂ O ₃ , MnO, Mn ₃ O _4. , Mn ₂ O ₃ , MnO ₂ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , CoO, Co ₃ O ₄ , NiO, Cu ₂ O, ZrO ₂ , MoO ₃ , TiO _2, etc. also used composite metal oxides such as _{Mn 2 O 3 · CuO · Fe} 2 O 3, CoO · Cr 2 O 3 · Fe 2 O 3, CuO · Mn 2 O 3 · Cr 2 O 3, CuO · Cr 2 O 3 be able to. Among these, iron oxide is preferable from the viewpoints of printability, embedding property, and bubble removal property. The average particle diameter of the black pigment is preferably 0.001 to 5 μm, more preferably 0.001 to 1 μm from the viewpoint of resolution. If it is out of the range, the formed resin layer may not have a desired resolution. The black pigment is preferably contained in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight in 100 parts by weight of the black photosensitive resin composition (B). When the amount is less than 0.1 part by weight, it may be difficult to obtain blackness with sufficient light shielding properties. On the other hand, when the amount is more than 50 parts by weight, there is a fear that the strength of the coating film is easily lowered.

The black photosensitive resin composition (B) preferably further contains a carboxyl group- and ethylenically unsaturated group-containing resin and a photopolymerization initiator. Moreover, a thermoplastic resin, an ethylenically unsaturated group containing compound, a polymerization inhibitor, etc. can also be included as needed.
As the carboxyl group- and ethylenically unsaturated group-containing resin of the present invention, for example, those synthesized by the following methods (1) to (4) are preferable.
(1) An unsaturated monocarboxylic acid (b) is reacted with a polyfunctional epoxy compound (a) having at least two epoxy groups in one molecule, and a polybasic acid anhydride (c) is further added to the generated hydroxyl group. It was obtained by reacting.
(2) One epoxy group per molecule in a part of the carboxyl group of the copolymer of the unsaturated monocarboxylic acid (b) and the other compound (d) having an ethylenically unsaturated double bond And a compound obtained by reacting a compound (e) having an ethylenically unsaturated double bond.
(3) A copolymer of an unsaturated monocarboxylic acid (b) and another compound (d) having an ethylenically unsaturated double bond, and one epoxy group in one molecule and an ethylenically unsaturated dicarboxylic acid. A compound obtained by reacting a compound (e) having a heavy bond, and reacting a polybasic acid anhydride (c) with the produced hydroxyl group.
(4) A hydroxyalkyl (meth) acrylate is reacted with a copolymer of a polybasic acid anhydride (c) having an unsaturated group and a compound (d) having an ethylenically unsaturated double bond. Can be mentioned. In the present specification, (meth) acrylate is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.

The acid value of the carboxyl group- and ethylenically unsaturated group-containing resin is preferably 50 to 150 mgKOH / g, and more preferably 60 to 120 mgKOH / g. When the acid value is less than 50 mgKOH / g, the developability may be deteriorated. On the other hand, if it exceeds 150 mgKOH / g, the alkali resistance, water resistance, moisture resistance and the like of the cured film may be lowered.
Examples of the polyfunctional epoxy compound (a) having at least two epoxy groups in one molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, water Bisphenol A type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated phenol novolac type epoxy resin, bisphenol A novolak type epoxy resin, trihydroxyphenylmethane Type epoxy resin, tetraphenylolethane type epoxy resin, phenol novolac type epoxy resin containing naphthalene skeleton, phenol novolak type epoxy resin containing dicyclopentadiene skeleton Glycidyl ether compounds such as resins; glycidyl ester compounds such as diglycidyl terephthalate; alicyclic epoxy resins such as EHPE-3150 manufactured by Daicel Chemical Industries; heterocyclic epoxy resins such as triglycidyl isocyanurate; N Epoxy compounds such as glycidylamines such as, N, N ′, N′-tetraglycidylmetaxylenediamine and copolymers of glycidyl (meth) acrylate and a compound having an ethylenically unsaturated double bond can be used. Among these, polyfunctional phenol novolac type epoxy resins that are solid at room temperature (25 ° C.), cresol novolac type epoxy resins, and copolymers of glycidyl (meth) acrylate and compounds having an ethylenically unsaturated double bond are particularly preferable. . These epoxy resins can be used alone or in combination of two or more. In the case of the copolymer of the said glycidyl (meth) acrylate and the compound which has an ethylenically unsaturated double bond, it is preferable that 20-60 mol% of glycidyl (meth) acrylate is contained with respect to a copolymer. When the molar content of glycidyl (meth) acrylate is less than 20 mol%, the amount of unsaturated monocarboxylic acid added may be reduced, and sufficient photocurability may not be obtained. On the other hand, when the molar content of glycidyl (meth) acrylate exceeds 60 mol%, it may be difficult to synthesize the copolymer. Further, in the case of such a copolymer of glycidyl (meth) acrylate and a compound having an ethylenically unsaturated double bond, the weight average molecular weight is 10,000 to 70,000, preferably 15,000 to 60,000. A range of is desirable. When the weight average molecular weight is less than 10,000, the dryness to touch of the coating film may be lowered. On the other hand, when it exceeds 70,000, the developability may be lowered. The weight average molecular weight is measured using a standard polystyrene calibration curve by gel permeation chromatography.

  Examples of the unsaturated monocarboxylic acid (b) include acrylic acid, methacrylic acid, itaconic acid, β-carboxylethyl acrylate, β-carboxylethyl methacrylate, and the like. Among these, acrylic acid or methacrylic acid is particularly preferable from the viewpoint of photosensitivity and storage stability. These unsaturated monocarboxylic acids (b) can be used alone or in admixture of two or more. The amount of these unsaturated monocarboxylic acids added is preferably 0.95 to 1.10 moles per mole of the epoxy group of the polyfunctional epoxy compound (a). When the addition amount of unsaturated monocarboxylic acid is less than 0.95 mol, an unreacted epoxy group remains and the storage stability after addition of the polybasic acid anhydride (c) is lowered, which is not preferable. On the other hand, if it exceeds 1.10 equivalent, unreacted unsaturated monocarboxylic acid remains and the odor becomes strong, which is not preferable.

  Examples of the polybasic acid anhydride (c) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride. Acids, cycloaliphatic dibasic anhydrides such as methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride And aliphatic or aromatic polybasic acid anhydrides such as trimellitic anhydride can be used alone or in combination of two or more. Among these, alicyclic dibasic acid anhydrides are particularly preferable from the viewpoint of developability. The amount of addition of these polybasic acid anhydrides (c) is such that the acid anhydride is 1 mol of the alcoholic hydroxyl group produced by the reaction of the polyfunctional epoxy compound (a) and the unsaturated monocarboxylic acid (b). A ratio of 0.3 to 0.8 mol of the group is suitable, and the addition amount is preferably such that the acid value of the resulting carboxyl group-containing and ethylenically unsaturated group-containing resin is 50 to 150 mgKOH / g.

  Examples of the compound (d) having an ethylenically unsaturated double bond include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, and methacrylic acid esters such as methyl methacrylate. Monomers having aromatic rings such as styrene, α-methylstyrene, hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol (meth) acrylamide, N-methoxymethyl ( Examples of the monomer include N-substituted alkoxyl group-containing monomers such as (meth) acrylamide, and other monomers such as acrylonitrile. These monomers can be used alone or in combination of two or more.

  Examples of the compound (e) having one epoxy group and an ethylenically unsaturated double bond in one molecule include glycidyl acrylate and glycidyl methacrylate, and are used alone or in combination of two or more. can do.

  The black photosensitive resin composition (B) may contain an ethylenically unsaturated compound other than the carboxyl group and ethylenically unsaturated group-containing resin. Specifically, for example, (meth) acrylic acid, methyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, carbitol (meth) acrylate, 2-ethylhexyl (meta ) Acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, styrene, acrylonitrile, N-vinylpyrrolidone, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1.4-butanediol diacrylate, 1.6-hexanediol di (meth) acrylate, 1.9-nonane Low molecular weight ethylenically unsaturated compounds such as diol di (meth) acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, trimellirol propane triacrylate, dipentaerythritol hexaacrylate, (meth) acrylate of phenol alkylene oxide adduct Or epoxy acrylate, urethane acrylate, polyester acrylate, alkyd acrylate, petroleum resin acrylate modified, unsaturated polyester, etc. Such molecular weight of ethylenically unsaturated compounds. One or a mixture of two or more of these is used.

  In addition, it is also preferable to use a resin excellent in compatibility with a carboxyl group-containing and ethylenically unsaturated group-containing resin as a thermoplastic resin as necessary. For example, polyvinyl chloride, poly (meth) acrylic acid, poly (meth) acrylic acid ester, polyvinyl ether, polyvinyl acetal, urethane resin, epoxy resin, poamide resin, diallyl phthalate, ethylene vinyl acetate, styrene resin, epoxy acrylic resin, etc. Although it is mentioned, it is not particularly limited. Moreover, when using the said epoxy resin, it is preferable to use the hardening accelerator of an epoxy resin in order to accelerate | stimulate reaction with the carboxyl group which exists. Specific examples of epoxy resin curing accelerators include 2-methylimidazole, 2-ethyl-3-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl- Imidazole compounds such as 2-ethylimidazole and 1-cyanoethyl-2-undecylimidazole; melamine, guanamine, acetoguanamine, benzoguanamine, ethyldiaminotriazine, 2,4-diaminotriazine, 2,4- Triazine derivatives such as diamino-6-tolyltriazine and 2,4-diamino-6-xylyltriazine; tertiary amines such as trimethylamine, triethanolamine, N, N-dimethyloctylamine, pyridine and m-aminophenol Polyphenols and the like. These curing accelerators can be used alone or in combination.

  Furthermore, in the black photosensitive resin composition (B) of the present invention, if necessary, heat such as known and commonly used thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents, solvents, fillers, and epoxy resins. A hardening agent, a coupling agent, etc. can be added. The black photosensitive resin composition (B) of the present invention preferably contains no translucent fine particles from the viewpoint of storage stability and temporal stability.

  The black photosensitive resin composition (B) of the present invention thus obtained was adjusted for the viscosity by the addition of a diluent (the photopolymerizable monomer or organic solvent as a reactive diluent), and then the knife The composition is applied to the uneven surface of the substrate (A) having unevenness on the surface by a known coating method such as a coating method or a screen coating method, and is temporarily dried at a temperature of about 60 to 120 ° C. as necessary. It is preferable to remove the organic solvent contained in the product, form a resin layer, bond the release film, and produce a photosensitive dry film.

  The photosensitive dry film of the present invention is bonded to an object and exposed by selectively irradiating light through a photomask having a predetermined exposure pattern, or exposed by a direct drawing method using a laser beam or the like, and the substrate (A) After peeling off, the unexposed portion can be developed with an alkaline aqueous solution to form a pattern film. Further, a thick pattern film having a desired film thickness can be formed by laminating a photosensitive dry film and repeating the steps of exposure and development a plurality of times.

  As the light source used in the present invention, ultraviolet light and visible light such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a metal halide lamp are suitable. A laser beam or the like can also be used as a light source. In addition, electron beams, α rays, β rays, γ rays, X-ray neutron rays and the like can be used in combination.

  A method for producing a patterned optical article will be described. When the release film is bonded to the photosensitive dry film of the present invention, after peeling it off, the optical member and the resin layer are bonded so as to contact each other, and then the substrate is formed by a photomask method or a direct drawing method. After exposure from the (A) side, a patterned optical article can be produced by removing the substrate (A) and further removing the uncured portion of the black photosensitive resin composition (B) by development. . The optical member as used in the present invention is, for example, a plastic substrate such as a molded lens assembly or a prism sheet, or a substrate represented by lime soda glass, and a pattern is formed on the substrate. The optical article has a light shielding member.

  Further, a specific example of forming a pattern on a microlens as an optical member will be described below. In the case where a light shielding member is formed on a resin erecting lens array, for example, by photolithography using the photosensitive dry film of the present invention, first, as shown in FIG. 1, a flat plate having a large number of lenses formed on the surface of a transparent substrate A pressure device such as a laminator is brought into close contact so that the lens array of the mold contacts the resin layer of the photosensitive dry film. Next, a photomask is overlaid from the substrate side and exposed. Alternatively, exposure is performed by directly drawing with a laser beam or the like along the concave portion between the lenses. Thereafter, the photomask and the base material (A) are peeled off, and then the unexposed portion is developed with an alkaline aqueous solution to form a light erecting lens in which a light shielding member is formed along the concave portion between the lenses as shown in FIG. An array is obtained. Moreover, a photosensitive dry film is further affixed on the light shielding member, and a light shielding member having a desired height can be formed by repeating the steps of exposure and development a plurality of times. In the present specification, the “height” of the light shielding member refers to the height from the deepest contact portion with the optical member to the uppermost surface of the light shielding member. In the case of a vertical lens array, it refers to the height from the base of the recess 3 to the top surface of the light shielding member 9.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. In the following table, “part” means “part by weight”, and “Mw” means “weight average molecular weight”.

Example 1
HP216 mat coat [mixture of acrylic resin (hydroxyl value 60 acid value 1.5) and melamine resin as resin curable by heat or light, silica as translucent fine particles (average particle size 1.8 μm, refractive index 1. 495), and a resin curable with heat or light and translucent fine particles mixed at 90: 8 (weight ratio). Nonvolatile content: 46%, manufactured by Toyo Ink Co., Ltd.] A mixed solvent consisting of toluene / ethyl acetate / IPA (40/30/30 weight ratio) was added to 100 parts by weight and 1 part by weight of p-toluenesulfonic acid, and the nonvolatile content was 42%. In addition, the resin composition (C) was obtained. In addition, about 100 parts by weight of the resin curable by heat or light, 5 parts by weight of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) was blended, and the cured product was irradiated with an integrated light amount of 500 mJ / cm ² with a high-pressure mercury lamp. It was 1.499 when the refractive index was measured using the Abbe refractometer (Atago Co., Ltd.).

The resin composition (C) was applied to a polyethylene terephthalate film having a thickness of 16 μm (R340 manufactured by Mitsubishi Plastics) with a microgravure coater and dried to obtain a substrate (A) having irregularities on the surface having a thickness of 4 μm. In addition, the unevenness | corrugation of the surface was surface roughness (Ra) 0.30 micrometer.
Next, on the uneven surface of the substrate (A), the black photosensitive resin composition (B) of Formulation Example 1 in Table 1 is added to toluene / methyl ethyl ketone / propylene glycol monomethyl ether (40/40/20 weight ratio). A solution prepared by adding a mixed solvent comprising a non-volatile content of 63% was applied by a knife coating method to a dry film thickness of 30 μm to form a resin layer. Next, a release film (T-100H manufactured by Mitsubishi Plastics) was attached so as to come into contact with the resin layer to obtain a photosensitive dry film. In addition, 5 parts by weight of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) was blended with 100 parts by weight of the composition example 1 in Table 2 excluding the black pigment, and irradiated with an integrated light amount of 500 mJ / cm ² with a high-pressure mercury lamp. It was 1.498 when the refractive index was measured using the Abbe refractometer (Atago Co., Ltd.) about hardened | cured material. ,
Using the obtained photosensitive dry film, the release film was peeled off, laminate transfer was performed on a lime soda glass plate, and physical properties were evaluated.

(Example 2)
Except for increasing the translucent fine particles of the resin composition (C) of Example 1 from 8 parts to 18 parts to create a substrate (A) having irregularities on the surface (film thickness 4 μm, Ra = 0.5 μm) A photosensitive dry film was prepared under the same conditions as in Example 1, and physical properties were evaluated.

(Example 3)
Except for reducing the translucent fine particles of the resin composition (C) of Example 1 from 8 parts to 2 parts to prepare a substrate (A) having irregularities on the surface (film thickness 4 μm, Ra = 0.15 μm) A dry film was prepared under the same conditions as in Example 1, and physical properties were evaluated.

(Comparative Example 1)
A photosensitive dry film was prepared under the same conditions as in Example 1 except that the polyethylene terephthalate film was used as a substrate without using the substrate (A) of Example 1, and physical properties were evaluated.

(Comparative Example 2)
A photosensitive dry film was prepared under the same conditions as in Example 1 except that the polyethylene terephthalate film was used as a base material without using the base material (A) of Example 2, and physical properties were evaluated.

(Comparative Example 3)
A black photosensitive resin composition was prepared by adding a mixed solvent of toluene / methyl ethyl ketone / propylene glycol monomethyl ether (40/40/20 weight ratio) to the black photosensitive resin composition of Formulation Example 2 in Table 1 so that the nonvolatile content was 66%. The physical properties of the product solution prepared were evaluated according to the methods described below.

  The physical properties of the obtained photosensitive dry film and black photosensitive resin composition were evaluated in the following items. The results are summarized in Table 2.

(Patternability evaluation)
The photosensitive dry films of Examples 1 to 3 and Comparative Examples 1 to 2 were uniformly applied to lime soda glass with a pressure laminator (special laminator 800 type manufactured by Taisei Laminator, pasting temperature 25 ° C., linear pressure 0.5 kgf / cm). Then, exposure was performed at three levels of 200, 500, and 1000 mJ / cm ² using an ultrahigh pressure mercury lamp through a negative mask having a line pattern L / S = 80/400 μm. Next, after developing with a 1 wt% sodium carbonate aqueous solution for 30 seconds, the line width of the pattern obtained with three levels of exposure was measured with an optical microscope and evaluated according to the following criteria.
Comparative Example 3 was the same as that of the photosensitive dry film except that the black photosensitive resin composition solution was applied on a lime soda glass so as to have a dry film thickness of 30 μm by a silk screen printer and a resin layer was formed. Evaluation was performed in the same manner as in the case.
The patterning evaluation criteria are as follows.
・ If the line pattern is within ± 10% of the negative mask pattern (80/400 μm), there is no practical problem. Example) 82/397.
X1: Undercut occurred, chipping occurred in the line pattern, and the line pattern could not be measured.
X2: Halation occurred, the line shape was not straight, and the line pattern could not be measured.

(Evaluation of patterning after time)
After preparing the photosensitive dry film, it was stored at a temperature of 7 ° C. for 1 month, returned to room temperature, then subjected to patterning evaluation, and compared with before storage.

From the results of Table 2, Comparative Examples 1 to 3 had poor patterning properties and storage stability.
On the other hand, since Examples 1-3 use the photosensitive dry film using the base material (A) having surface irregularities, no undercut or halation occurs, and even a thick film of 30 μm is good. Both patterning properties and storage stability are compatible.
Therefore, the photosensitive dry film of the present invention can be suitably used for the formation of a black matrix used for a liquid crystal display or the like, or a light shielding member for a reading lens of an optical printer, a copying machine or the like.

Sectional view when exposing by photomask method Sectional drawing of the optical article patterned.

Explanation of symbols

1 lens array plate 2 lens 3 recess 4 uneven surface 5 black photosensitive resin composition 6 photomask 7 light 8 resin formation lens array 9 light shielding member

Claims (6)

  A photosensitive dry film obtained by forming a resin layer made of a black photosensitive resin composition (B) on an uneven surface of a substrate (A) having an uneven surface.   The photosensitive dry film according to claim 1, wherein the unevenness of the surface of the substrate (A) has a surface roughness (Ra) of 0.25 to 1 μm.   3. The photosensitive dry film according to claim 1, wherein the unevenness of the surface of the substrate (A) is formed by a resin composition (C) comprising a resin curable by heat or light and translucent fine particles. .   The photosensitive resin according to any one of claims 1 to 3, wherein the black photosensitive resin composition (B) contains a black pigment, a resin containing a carboxyl group and an ethylenically unsaturated group, and a photopolymerization initiator. Dry film. Bonding the photosensitive dry film according to any one of claims 1 to 4 to an optical member,
Next, after exposure by a photomask method or a direct drawing method, the substrate (A) is peeled off,
Furthermore, the uncured part of a black photosensitive resin composition (B) is removed by image development, and a pattern is formed on the member for optics, The manufacturing method of the patterned optical article characterized by the above-mentioned.   A patterned optical article obtained by the manufacturing method according to claim 5.

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