Photosensitive resin composition for sandblasting and photosensitive film for sandblasting

Abstract

The present invention addresses the aforementioned problem by providing a photosensitive resin composition for sandblasting that is resistant to clouding and exhibits good developability, as well as a photosensitive film. The present invention solves this problem by providing a photosensitive resin composition for sandblasting and a photosensitive film having a photosensitive resin layer containing the photosensitive resin composition. The photosensitive resin composition for sandblasting contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a urethane (meth)acrylate, and (D) an acid-modified epoxy (meth)acrylate, and (E) an alicyclic (meth)acrylate, or (A) an alkali-soluble resin is a copolymer obtained by copolymerizing (i) a styrene derivative, (ii) acrylic acid, and (iv) monomers having olefinic unsaturated groups other than styrene derivatives and acrylic acid.

Description

[0001] This application is a divisional application. Its parent application has the application number 202180039789.X, the application date 2021.6.1, and the invention title: Photosensitive resin composition for sandblasting and photosensitive film for sandblasting. Technical Field

[0002] This invention relates to a photosensitive resin composition for sandblasting and a photosensitive film for sandblasting.

[0003] The following are examples of abbreviations.

[0004] Photosensitive resin composition: Photosensitive resin composition for sandblasting;

[0005] Photosensitive film: Photosensitive film for sandblasting. Background Technology

[0006] Previously, sandblasting was used to process materials such as glass, stone, metal, plastic, and ceramics to create raised surfaces. Now, a photosensitive resin layer patterned using photolithography or similar methods is used as a mask on the material being processed. Then, an abrasive is blown onto the surface to selectively cut the non-mask areas, thus performing sandblasting.

[0007] Examples of photosensitive films used as mask materials for sandblasting include photosensitive films on a support such as a polyester film with a photosensitive resin layer. The photosensitive resin composition for the sandblasting photosensitive film is generally a negative photosensitive resin composition comprising an alkali-soluble resin, a urethane (meth)acrylate, and a photopolymerization initiator. The alkali-soluble resin can be a cellulose derivative or an acrylic resin containing a carboxyl group (see, for example, Patent Documents 1-8).

[0008] Patent document 8 discloses a photosensitive resin composition for sandblasting comprising an alkali-soluble resin, a photopolymerization initiator, a urethane (meth)acrylate, and an epoxy (meth)acrylate, wherein the epoxy (meth)acrylate may include acid-modified epoxy (meth)acrylate.

[0009] To improve the sandblasting resistance of this photosensitive resin composition, the elasticity of the cured film must be increased; therefore, the amount of urethane (meth)acrylate must be maximized. However, if the amount of urethane (meth)acrylate is increased, the urethane (meth)acrylate, which has poor compatibility with alkali-soluble resins, will separate from the alkali-soluble resins over time, resulting in a cloudy photosensitive resin layer and deterioration of the solubility of unexposed areas during the development step.

[0010] Furthermore, increasing the amount of urethane (meth)acrylate increases the adhesion of the photosensitive resin layer in the pre-curing stage, preventing it from peeling off from the support and making it more difficult to transfer the photosensitive resin layer to the substrate. Therefore, the amount of urethane (meth)acrylate must be reduced at the expense of sandblasting resistance.

[0011] One document proposes a method for forming a release layer between a support and a photosensitive resin layer. By including an alkali-soluble resin and using the same components as the alkali-soluble resin used in the photosensitive resin layer, the release layer reduces the likelihood of wrinkling defects in the photosensitive resin layer during coating. The release layer also reduces the peeling force on the support, allowing for easier peeling of the support (see, for example, Patent Documents 9 and 10).

[0012] However, if the release layer and the alkali-soluble resin layer of the photosensitive resin layer are designed to have the same composition, after several months or more, the release layer and the photosensitive resin layer will fuse together, making the support difficult to peel off. Furthermore, during development after exposure, when the unexposed part of the photosensitive resin layer and the release layer are removed at the same time, the surface of the exposed part of the photosensitive resin layer will swell, resulting in a deterioration in clarity.

[0013] Existing technical documents

[0014] Patent documents

[0015] Patent Document 1: Japanese Patent No. 3449572

[0016] Patent Document 2: Japanese Patent No. 3846958

[0017] Patent Document 3: Japanese Patent Application Publication No. 10-69851

[0018] Patent Document 4: Japanese Patent Application Publication No. 2012-27357

[0019] Patent Document 5: Japanese Patent Application Publication No. 2013-156306

[0020] Patent Document 6: International Publication No. 2014 / 200028

[0021] Patent Document 7: Japanese Patent Publication No. 2005-537514

[0022] Patent Document 8: Japanese Patent Application Publication No. 2017-126053

[0023] Patent Document 9: Japanese Patent Application Publication No. 2012-27357

[0024] Patent Document 10: Japanese Patent Application Publication No. 2021-17004 Summary of the Invention

[0025] The problem that the invention aims to solve

[0026] The objective of this invention is to design a photosensitive resin composition for sandblasting containing an alkali-soluble resin and a urethane (meth)acrylate, such that the alkali-soluble resin and the urethane (meth)acrylate have good compatibility, and the photosensitive resin layer containing the photosensitive resin composition for sandblasting is not prone to clouding, so as to provide a photosensitive film for sandblasting with good developability.

[0027] Another objective of this invention is to provide a photosensitive film for sandblasting, which, even after time has passed since its manufacture, does not easily fuse the release layer and the photosensitive resin layer, allows the support to be easily peeled off, and prevents the surface of the photosensitive resin layer from swelling during development.

[0028] Methods for solving problems

[0029] The above-mentioned problems can be solved through the following methods.

[0030] <1> A photosensitive resin composition for sandblasting, characterized in that,

[0031] It contains at least (A) alkali-soluble resin, (B) photopolymerization initiator, (C) urethane (meth)acrylate, and (D) acid-modified epoxy (meth)acrylate, and

[0032] Further contains (E) alicyclic (meth)acrylate,

[0033] The content of (E) alicyclic methacrylate is 5 to 15% by mass relative to the total amount of (A) alkali-soluble resin, (B) photopolymerization initiator, (C) urethane (meth)acrylate, (D) acid-modified epoxy (meth)acrylate and (E) alicyclic (meth)acrylate.

[0034] <2> A photosensitive resin composition for sandblasting, characterized in that it contains at least (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a urethane (meth)acrylate, and (D) an acid-modified epoxy (meth)acrylate.

[0035] (A) The alkali-soluble resin is a copolymer obtained by copolymerizing (i) styrene derivatives, (ii) acrylic acid, and (iv) monomers other than styrene derivatives and acrylic acid that have olefinic unsaturated groups.

[0036] The total amount of (i) styrene derivatives, (ii) acrylic acid, and (iv) monomers having olefinic unsaturated groups other than styrene derivatives and acrylic acid is 10 to 60% by mass and (ii) acrylic acid is 20 to 50% by mass relative to (i) styrene derivatives, (ii) acrylic acid.

[0037] <3> As mentioned above <2> The photosensitive resin composition for sandblasting described herein, wherein (A) the alkali-soluble resin has a mass-average molecular weight of 10,000 to 50,000.

[0038] <4> A photosensitive film for sandblasting, comprising a photosensitive resin layer containing a photosensitive resin composition for sandblasting on a support, characterized in that the photosensitive resin composition is as described above. <1> ~ <3> The photosensitive resin composition for sandblasting described in any one of the following.

[0039] <5> A photosensitive film for sandblasting, comprising a support, a release layer, a photosensitive resin layer, and a protective film stacked sequentially, characterized in that...

[0040] The release layer contains (A') an alkali-soluble resin, and the photosensitive resin layer contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) a urethane (meth)acrylate.

[0041] The alkali-soluble resin of the release layer (A') is a copolymer obtained by copolymerizing (iii) methacrylic acid with (v) monomers other than methacrylic acid that have olefinic unsaturated groups.

[0042] The (A) alkali-soluble resin of the photosensitive resin layer is a copolymer obtained by copolymerizing (i) a styrene derivative, (ii) acrylic acid, and (iv) monomers other than styrene derivatives and acrylic acid that have olefinic unsaturated groups.

[0043] The following are the above <1> The photosensitive resin composition for sandblasting is referred to as "photosensitive resin composition for sandblasting". <1> "or "photosensitive resin composition" <1> The situation described above <2> and <3> The same applies to the photosensitive resin composition for sandblasting.

[0044] In addition, there are the above-mentioned <4> The photosensitive film used for sandblasting is called "photosensitive film for sandblasting". <4> "or "photosensitive film" <4> The situation described above <5> The same applies to the photosensitive film used for sandblasting.

[0045] Invention Effects

[0046] Photosensitive resin composition for sandblasting <1> By containing (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a urethane (meth)acrylate, and (D) an acid-modified epoxy (meth)acrylate, and further containing (E) an alicyclic (meth)acrylate, a photosensitive resin composition for sandblasting can be achieved, which exhibits good compatibility between (A) the alkali-soluble resin and (C) the urethane (meth)acrylate. <1> In the photosensitive resin layer, (A) alkali-soluble resin and (C) urethane (meth)acrylate are not easily separated over time, thus containing a photosensitive resin composition for sandblasting. <1> In a photosensitive film for sandblasting with a photosensitive resin layer, the photosensitive resin layer is less prone to clouding, and the dissolution of the unexposed parts during the development step is less likely to deteriorate.

[0047] Photosensitive resin composition for sandblasting <2> A photosensitive resin composition for sandblasting is obtained by copolymerizing (i) a alkali-soluble resin, (ii) a photopolymerization initiator, (C) a urethane (meth)acrylate, and (D) an acid-modified epoxy (meth)acrylate, wherein (A) the alkali-soluble resin is a copolymer obtained by copolymerizing (i) a styrene derivative, (ii) acrylic acid, and (iv) monomers having olefinic unsaturated groups other than the styrene derivative and acrylic acid, wherein, relative to the total amount of (i) the styrene derivative, (ii) the acrylic acid, and (iv) the monomers having olefinic unsaturated groups other than the styrene derivative and acrylic acid, (i) the styrene derivative is 10-60% by mass and (ii) the acrylic acid is 20-50% by mass. This composition achieves good compatibility between (A) the alkali-soluble resin and (C) the urethane (meth)acrylate. <2> In the photosensitive resin layer, (A) alkali-soluble resin and (C) urethane (meth)acrylate do not easily separate over time, thus containing a photosensitive resin composition for sandblasting. <2> In a photosensitive film for sandblasting with a photosensitive resin layer, the photosensitive resin layer is less prone to clouding, and the dissolution of the unexposed parts during the development step is less likely to deteriorate.

[0048] Photosensitive film for sandblasting <5> By making the (A') alkali-soluble resin of the release layer different from the (A) alkali-soluble resin of the photosensitive resin layer, the release layer and the photosensitive resin layer do not easily fuse even after time has passed since the photosensitive film was made. Because the release layer is not photosensitive and has the property of dissolving in the developer, if the release layer and the photosensitive resin layer fuse, the surface of the photosensitive resin layer will become difficult to cure and easily swell due to the developer. In this invention, the release layer and the photosensitive resin layer do not easily fuse, therefore the surface of the photosensitive resin layer does not easily swell during development. Furthermore, the alkali-soluble resin of the release layer (A') is a copolymer with higher release properties obtained by copolymerizing (iii) methacrylic acid with (v) monomers having olefinic unsaturated groups other than methacrylic acid. The alkali-soluble resin of the photosensitive resin layer (A) is a copolymer obtained by copolymerizing (i) styrene derivatives, (ii) acrylic acid, and (iv) monomers having olefinic unsaturated groups other than styrene derivatives and acrylic acid. Because (ii) acrylic acid participates in the polymerization, the softening point is low, thus improving sandblasting resistance. In addition, because (i) styrene derivatives participate in the polymerization, the compatibility with (C) urethane (meth)acrylate is high, and the effect of not easily separating phases can also be achieved. Attached Figure Description

[0049] Figure 1 This is a cross-sectional schematic diagram showing the composition of the photosensitive film used for sandblasting.

[0050] Figure 2 This is a cross-sectional schematic diagram showing the composition of the photosensitive film used for sandblasting.

[0051] Explanation of reference numerals in the attached figures

[0052] 1 Support, 2 Release layer, 3 Photosensitive resin layer, 4 Protective film. Detailed Implementation

[0053] The present invention will be described in detail below.

[0054] The following are examples of abbreviations.

[0055] Component (A'): (A') Alkali-soluble resin;

[0056] Component (A): (A) Alkali-soluble resin;

[0057] Component (B): (B) Photopolymerization initiator;

[0058] Ingredient (C): (C) carbamate (meth)acrylate;

[0059] Ingredient (D): (D) Acid-modified epoxy (meth)acrylate;

[0060] Ingredient (E): (E) alicyclic (meth)acrylate;

[0061] Monomer (iv): (iv) Monomers having olefinic unsaturated groups, excluding styrene derivatives and acrylic acid;

[0062] Monomer (v): (v) Monomers other than methacrylic acid that have olefinic unsaturated groups.

[0063] In this invention, "alkali-soluble" in "alkali-soluble resin" means that when the resin is made into a film and immersed in a 1% (by mass) sodium carbonate aqueous solution at 25°C for 10 minutes, a film thickness of 0.01 μm or more dissolves. Component (A) specifically refers to a resin containing acidic groups.

[0064] Photosensitive resin composition <1> It contains (A) alkali-soluble resin, (B) photopolymerization initiator, (C) urethane (meth)acrylate, (D) acid-modified epoxy (meth)acrylate and (E) alicyclic (meth)acrylate.

[0065] Photosensitive resin composition <1> In the example of component (A), alkali-soluble cellulose derivatives and acrylic resins containing carboxyl groups can be listed.

[0066] Photosensitive resin composition <1> Among them, alkali-soluble cellulose derivatives include cellulose acetate phthalate, hydroxypropyl methylcellulose phthalate, hydroxypropyl methylcellulose acetate phthalate, and hydroxypropyl methylcellulose acetate succinate.

[0067] Photosensitive resin composition <1> Among acrylic resins containing carboxyl groups, examples include acrylic polymers formed by copolymerizing (meth)acrylates as the main component with olefinically unsaturated carboxylic acids. Additionally, other copolymerizable monomers (besides (meth)acrylates and olefinically unsaturated carboxylic acids) containing olefinically unsaturated groups can also participate in the copolymerization.

[0068] Photosensitive resin composition <1> Examples of (meth)acrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, lauryl methacrylate, tetrahydrofurfuryl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2-(diethylamino)ethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and 2,2,3,3-tetrafluoropropyl methacrylate.

[0069] Photosensitive resin composition <1> In this process, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid are suitable as olefinic unsaturated carboxylic acids, while dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, their anhydrides, and / or half-esters can also be used. Among these, acrylic acid and methacrylic acid are particularly preferred.

[0070] Photosensitive resin composition <1> Among other copolymerizable monomers with olefinic unsaturated groups, examples include styrene, α-methylstyrene, 4-methylstyrene, 3-methylstyrene, 2-methylstyrene, 4-ethylstyrene, 3-ethylstyrene, 2-ethylstyrene, 4-methoxystyrene, 3-methoxystyrene, 2-methoxystyrene, 4-ethoxystyrene, 3-ethoxystyrene, 2-ethoxystyrene, 4-chlorostyrene, 3-chlorostyrene, 2-chlorostyrene, 4-bromostyrene, 3-bromostyrene, 2-bromostyrene, (meth)acrylonitrile, (meth)acrylamide, diacetone (meth)acrylamide, vinyl acetate, vinyl-n-butyl ether, etc.

[0071] Photosensitive resin composition <1> In this study, the acid value (JIS-K0070:1992) of component (A) is preferably 30–500 mg KOH / g, and more preferably 100–300 mg KOH / g. When the acid value is below 30 mg KOH / g, the alkaline development time becomes longer; conversely, if it exceeds 500 mg KOH / g, the sandblasting resistance decreases.

[0072] Photosensitive resin composition <1> In this composition, the mass-average molecular weight of component (A) is preferably 10,000 to 200,000, and more preferably 10,000 to 150,000. When the mass-average molecular weight is less than 10,000, it becomes difficult to achieve the desired effect in the photosensitive resin composition. <1> On the one hand, if the concentration exceeds 200,000, the solubility in alkaline developing solution deteriorates.

[0073] Photosensitive resin composition <1> In this context, component (E) refers to compounds with an alicyclic structure, possessing one or more (meth)acryloyl groups, and a double bond equivalent of less than 300 g / eq. Examples include tricyclodecanediethanol di(meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, and dicyclopentenoxyethyl (meth)acrylate. These can be used alone or in combination of two or more.

[0074] Photosensitive resin composition <2> The product contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a urethane (meth)acrylate, and (D) an acid-modified epoxy (meth)acrylate. Furthermore, (A) the alkali-soluble resin is a copolymer obtained by copolymerizing (i) a styrene derivative, (ii) acrylic acid, and (iv) monomers having olefinic unsaturated groups other than the styrene derivative and acrylic acid. Relative to the total amount of (i) the styrene derivative, (ii) the acrylic acid, and (iv) the monomers having olefinic unsaturated groups other than the styrene derivative and acrylic acid, (i) the styrene derivative is 10–60% by mass, more preferably 30–55% by mass. (ii) the acrylic acid is 20–50% by mass, more preferably 25–40% by mass.

[0075] In component (A), "alkali-soluble" means that when the target resin is made into a film and immersed in a 1% (w / w) sodium carbonate aqueous solution at 25°C for 10 minutes, a film thickness of 0.01 μm or more dissolves. Component (A) specifically includes resins containing acidic groups and having an acid value of 40 mg KOH / g or higher. Specifically, acidic groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and phosphate groups. In photosensitive resin compositions... <2> In this process, (ii) acrylic acid with carboxyl groups is used as the copolymer component of component (A).

[0076] Photosensitive resin composition <2> In this context, (i) styrene derivatives can include styrene, α-methylstyrene, 4-methylstyrene, 3-methylstyrene, 2-methylstyrene, 4-ethylstyrene, 3-ethylstyrene, 2-ethylstyrene, 4-methoxystyrene, 3-methoxystyrene, 2-methoxystyrene, 4-ethoxystyrene, 3-ethoxystyrene, 2-ethoxystyrene, 4-chlorostyrene, 3-chlorostyrene, 2-chlorostyrene, 4-bromostyrene, 3-bromostyrene, 2-bromostyrene, etc. By including (i) styrene derivatives as copolymer components of component (A), the compatibility of urethane (meth)acrylates increases, and component (A) and component (C) are less likely to separate over time.

[0077] Furthermore, in component (A), an acidic group is necessary to impart alkali solubility in the photosensitive resin composition. <2> In this formulation, component (A) contains (ii) acrylic acid as a copolymer component with an acidic group. By including (ii) acrylic acid, compatibility with (C) urethane (meth)acrylate is not compromised, and solubility in alkaline developing solutions is imparted during development.

[0078] Photosensitive resin composition <2> In (iv) monomers having olefinic unsaturated groups other than styrene derivatives and acrylic acid, examples include (meth)acrylates and copolymerizable monomers having olefinic unsaturated groups other than (meth)acrylates. These may be used alone or in combination of two or more.

[0079] Photosensitive resin composition <2> Examples of the aforementioned (meth)acrylates include, for instance, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate. Methyl (meth)acrylate and n-butyl (meth)acrylate are particularly preferred.

[0080] Photosensitive resin composition <2> Among them, monomers with olefinic unsaturated groups that are copolymerizable other than the aforementioned (meth)acrylates can be exemplified by, for example, (meth)acrylonitrile, (meth)acrylamide, diacetone (meth)acrylamide, vinyl acetate, vinyl n-butyl ether, etc.

[0081] Photosensitive resin composition <2> In this process, the acid value (JIS-K0070:1992) of component (A) is preferably 40 mg KOH / g or higher, more preferably 40–500 mg KOH / g, and even more preferably 100–400 mg KOH / g. When the acid value is below 40 mg KOH / g, the alkaline development time tends to be longer; on the other hand, if it exceeds 500 mg KOH / g, the sandblasting resistance decreases.

[0082] In addition, photosensitive resin composition <2> In this composition, the mass-average molecular weight of component (A) is preferably 10,000 to 100,000, and more preferably 10,000 to 50,000. When the mass-average molecular weight is less than 10,000, it becomes difficult to achieve the desired effect in the photosensitive resin composition. <2> On the one hand, if the concentration exceeds 100,000, the solubility in alkaline developing solutions tends to deteriorate.

[0083] Photosensitive resin composition <1> and <2> In the text, as component (B), examples include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Mischel ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, and other aromatic ketones; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and other quinones. Classes include: benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and other benzoin ether compounds; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; biphenylyl dimethyl ketal and other biphenylyl derivatives; 2,4,5-triaryl imidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer; acridine derivatives such as 9-phenylacridinium and 1,7-bis(9,9'-acridyl)heptane; N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds, etc. In the aforementioned 2,4,5-triarylimidazol dimers, the aromatic groups of the two 2,4,5-triarylimidazolium compounds can have the same substituent to form symmetrical compounds, or they can have different substituents to form asymmetrical compounds. Additionally, thioxanthone compounds can be combined with tertiary amine compounds, as in the combination of diethylthioxanthone and dimethylaminobenzoic acid. These can be used alone or in combination of two or more.

[0084] Photosensitive resin composition <1> and <2> In the example, component (C) may include (a) compounds with terminal isocyanate groups formed by the reaction of (b) polyisocyanates with (a) compounds having multiple hydroxyl groups, and (c) products formed by the reaction of (meth)acrylates having hydroxyl groups.

[0085] Examples of compounds having multiple hydroxyl groups (a) include polyesters, polyethers, etc.

[0086] Examples of the aforementioned polyesters include polyesters obtained by ring-opening polymerization of lactones, polycarbonates, and polyesters obtained by condensation reactions of alkyl glycols such as tetramethylene glycol, diethylene glycol, triethylene glycol, and dipropylene glycol with dicarboxylic acids such as maleic acid, fumaric acid, glutaric acid, and adipic acid.

[0087] Specifically, examples of the aforementioned lactones include δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, α,α-dimethyl-β-propiolactone, and β,β-dimethyl-β-propiolactone.

[0088] Specifically, examples of polycarbonates mentioned above include reaction products of diols such as bisphenol A, hydroquinone, and dihydroxycyclohexanone with carbonyl compounds such as diphenyl carbonate, carbonyl chloride, and succinic anhydride.

[0089] Specifically, examples of the aforementioned polyethers include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and polypentamethylene ether glycol.

[0090] The compound with multiple hydroxyl groups in (a) above is preferably tetramethylene glycol or polytetramethylene ether glycol. In this case, sandblasting resistance and clarity are further improved.

[0091] As for the polyisocyanates mentioned in (b), specifically, examples include dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate, nonamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, isophorone diisocyanate, and other aliphatic or alicyclic diisocyanates. These compounds can be used alone or in mixtures of two or more.

[0092] As for the hydroxyl-containing (meth)acrylates mentioned in (c) above, specific examples include methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc., and also compounds formed by adding 1 to 10 mol of ε-caprolactone to these. In particular, 4-hydroxybutyl acrylate is preferred among the hydroxyl-containing (meth)acrylates in (c) as it further improves sandblasting resistance and clarity.

[0093] Photosensitive resin composition <1> and <2> In this mixture, component (C) may contain a carboxyl group. The presence of a carboxyl group tends to improve the solubility in the developer. Component (C) containing a carboxyl group can be obtained by initially reacting a diisocyanate with a diol compound containing a carboxyl group, leaving isocyanate groups at both ends, and then reacting the terminal isocyanate groups of the reaction product with a (meth)acrylate containing a hydroxyl group.

[0094] Photosensitive resin composition <1> and <2> In the formulation, component (D) can include at least one compound formed by reacting (d) an epoxy resin, at least one compound selected from the group consisting of acrylic acid and methacrylic acid, and (e) at least one compound selected from the group consisting of compounds containing carboxylic acids and anhydrides of carboxylic acid compounds. This compound can be synthesized, for example, by imparting at least one compound selected from the group consisting of acrylic acid and methacrylic acid to the epoxy resin (d) and further imparting compound (e). Comparing acrylic acid and methacrylic acid, acrylic acid is preferred due to its good sandblasting resistance.

[0095] Examples of (d) epoxy resins include linear phenolic resins, linear cresol phenolic resins, bisphenol A resins, bisphenol F resins, triphenol resins, tetraphenol resins, phenol-phenylenediamine resins, glycidyl ether resins, or these halogenated epoxy resins.

[0096] Compounds containing carboxylic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, methylendomethylene tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, and benzophenonetetracarboxylic acid. Anhydrides of these carboxylic acid-containing compounds can be listed as an example.

[0097] Photosensitive resin composition <1> and <2> In this process, the acid value of component (D) affects the alkaline development speed, the resist peeling speed, and the softness of the photosensitive resin layer. An acid value of 40–120 mg KOH / g is preferred. If the acid value is below 40 mg KOH / g, the alkaline development time tends to be longer; on the other hand, if it exceeds 120 mg KOH / g, the adhesion to the substrate being treated deteriorates.

[0098] In addition, photosensitive resin composition <1> and <2> In this composition, the mass-average molecular weight of component (D) is preferably between 3,000 and 15,000. When the mass-average molecular weight is less than 3,000, it becomes difficult to achieve the desired effect on the photosensitive resin composition before curing. <1> and <2> The formation of a film-like state. On the other hand, if it exceeds 15,000, there is a tendency for the solubility in alkaline developer to deteriorate.

[0099] In photosensitive resin composition <1> The product may also contain other components besides those listed in (A) to (E) as needed. Examples of such components include crosslinking monomers (component (X)), sensitizers, heat-resistant polymerization inhibitors, plasticizers, colorants (dyes, pigments), photochromic agents, heat-resistant colorants, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, peel accelerators, antioxidants, fragrances, thermosetting agents, water-resistant agents, and oil-resistant agents, each comprising approximately 0.01 to 20% by mass. These components may be used individually or in combination of two or more.

[0100] Photosensitive resin composition <1> In this process, the content of component (A) relative to the total amount of components (A), (B), (C), (D), and (E) is preferably 30–50% by mass, and more preferably 35–45% by mass. If the content of component (A) is less than 30% by mass, the film-forming properties deteriorate, and the alkaline developability decreases. If the content of component (A) exceeds 50% by mass, the sandblasting resistance decreases.

[0101] Photosensitive resin composition <1> In this composition, the content of component (B) relative to the total amount of components (A), (B), (C), (D), and (E) is preferably 0.5 to 4% by mass, and more preferably 1 to 3% by mass. When the content of component (B) is less than 0.5% by mass, there is a tendency for decreased sensitivity. On the other hand, if it exceeds 4% by mass, component (B) becomes difficult to incorporate into the photosensitive resin composition. <1> It tends to dissolve in water.

[0102] Photosensitive resin composition <1> In this process, the content of component (C) relative to the total amount of components (A), (B), (C), (D), and (E) is preferably 30–50% by mass, and more preferably 35–45% by mass. When the content of component (C) is less than 30% by mass, there is a tendency for reduced sandblasting resistance and insufficient photosensitivity. On the other hand, if it exceeds 50% by mass, there is a tendency for excessive increase in the adhesion of the film surface.

[0103] Photosensitive resin composition <1> In this process, the content of component (D) relative to the total amount of components (A), (B), (C), (D), and (E) is preferably 5-30% by mass, and more preferably 5-15% by mass. If the content of component (E) is less than 5% by mass, the clarity may decrease; if it exceeds 30% by mass, the adhesion of the film surface may increase excessively, and the sandblasting resistance may decrease.

[0104] Photosensitive resin composition <1> In this composition, the content of component (E) is 5-15% by mass relative to the total amount of components (A), (B), (C), (D), and (E), with 5-10% by mass being more preferred. When the content of component (E) is less than 5% by mass, a photosensitive resin composition is obtained. <1> The compatibility between the (A) alkali-soluble resin and (C) urethane (meth)acrylate contained in the film tends to deteriorate. On the other hand, if it exceeds 15% by mass, there is a tendency for excessive increase in the adhesion of the film surface and a decrease in sandblasting resistance.

[0105] In photosensitive resin composition <2> The product may also contain ingredients other than those listed in (A) to (D) as needed. These ingredients may include polymerizable monomers, sensitizers, heat-resistant polymerization inhibitors, plasticizers, colorants (dyes, pigments), photochromic agents, heat-resistant colorants, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, peel accelerators, antioxidants, fragrances, thermosetting agents, water-resistant agents, and oil-resistant agents, each comprising approximately 0.01 to 20% by mass. These ingredients may be used individually or in combination of two or more.

[0106] Photosensitive resin composition <2> In this formulation, the content of component (A) relative to the total amount of components (A), (B), (C), and (D) is preferably 35–60% by mass, and more preferably 35–50% by mass. If the content of component (A) is less than 35% by mass, the compatibility with urethane acrylate (C) decreases, and the alkaline developability decreases. If the content of component (A) exceeds 60% by mass, the sandblasting resistance decreases.

[0107] Photosensitive resin composition <2> In this composition, the content of component (B) relative to the total amount of components (A), (B), (C), and (D) is preferably 0.5 to 4% by mass, and more preferably 1 to 3% by mass. When the content of component (B) is less than 0.5% by mass, there is a tendency for decreased sensitivity. On the other hand, if it exceeds 4% by mass, component (B) becomes difficult to incorporate into the photosensitive resin composition. <2> It tends to dissolve in water.

[0108] Photosensitive resin composition <2> In this process, the content of component (C) relative to the total amount of components (A), (B), (C), and (D) is preferably 30–60% by mass, and more preferably 35–50% by mass. When the content of component (C) is less than 30% by mass, there is a tendency for reduced sandblasting resistance and insufficient photosensitivity. On the other hand, if it exceeds 60% by mass, there is a tendency for excessive increase in the adhesion of the film surface.

[0109] Photosensitive resin composition <2> In this process, the content of component (D) relative to the total amount of components (A), (B), (C), and (D) is preferably 5 to 30% by mass, and more preferably 5 to 15% by mass. If the content of component (E) is less than 5% by mass, the clarity will decrease; if it exceeds 30% by mass, the adhesion of the film surface will increase excessively, and the sandblasting resistance will decrease.

[0110] Regarding photosensitive films <4> The feature is that the support 1 has a photosensitive resin layer 3 containing a photosensitive resin composition, wherein the photosensitive resin composition is a photosensitive resin composition. <1> ~ <3> Either of them. As a photosensitive film. <4> Examples include: Figure 1 As shown, a photosensitive film is formed by sequentially stacking a support 1, a photosensitive resin layer 3, and a protective film 4. Other examples include... Figure 2 As shown, a photosensitive film is formed by sequentially stacking a support 1, a release layer 2, a photosensitive resin layer 3, and a protective film 4. Figure 1 and 2 The photosensitive film in the film may also be without a protective film.

[0111] Photosensitive film <5> ,like Figure 2 As shown, it is a photosensitive film consisting of a support 1, a release layer 2, a photosensitive resin layer 3 containing a photosensitive resin composition, and a protective film 4, which are stacked in sequence.

[0112] Photosensitive film <4> and <5> In this process, the support 1 is preferably a transparent film through which active rays can pass. Regarding the thickness of the support 1, from the viewpoint of minimizing light refraction, a thinner film is preferred; from the viewpoint of excellent coating stability, a thicker film is preferred, but a thickness of 10–100 μm is preferred. Examples of transparent films for the support 1 include polyethylene terephthalate and polycarbonate.

[0113] Photosensitive film <4> In this process, the release layer 2 may include polyvinyl alcohol, alkali-soluble resin, a mixture of alkali-soluble resin and urethane (meth)acrylate, a mixture of alkali-soluble resin and epoxy (meth)acrylate, or a mixture of alkali-soluble resin, urethane (meth)acrylate, and epoxy (meth)acrylate. The release layer 2 may or may not be endowed with photopolymerizability. However, from the viewpoint that it can be removed by alkali development, it is more preferable that it is not endowed with photopolymerizability.

[0114] Photosensitive film <4> and <5> In this process, the protective film 4 only needs to be peelable from the uncured photosensitive resin layer 3 or the photosensitive resin layer 3 cured by exposure, and a resin with high release properties can be used. Examples of such films include polyethylene and polypropylene. Other examples include films coated with release agents such as silicone, and films that have undergone corona discharge treatment.

[0115] Photosensitive film <4> In this process, the thickness of the photosensitive resin layer 3 is preferably 10–150 μm, and more preferably 20–120 μm. Photosensitive film <5> In this process, the thickness of the photosensitive resin layer 3 is preferably 10–150 μm, and more preferably 30–120 μm. If the photosensitive resin layer 3 is too thick, problems such as reduced clarity, high cost, and edge blending may easily occur. Conversely, if the photosensitive resin layer 3 is too thin, the sandblasting resistance may be reduced.

[0116] Sandblasting treatment using a photosensitive film for sandblasting includes both direct and indirect methods. Materials that can be treated include glass, stone, metal, plastic, and ceramics.

[0117] The direct method first removes the protective film 4 of the photosensitive film. Next, using a laminator or similar device, the photosensitive resin layer 3 is brought into contact with the substrate for adhesion. Then, after exposing the photosensitive resin layer 3 to the support 1 side through a mask with an embossed image, the support 1 is peeled off from the interface between the release layer 2 and the support 1. Alternatively, to reduce light refraction and ensure high clarity, the photosensitive resin layer 3 is exposed to the embossed image through a mask after peeling off the support 1. [The last sentence appears to be incomplete and possibly refers to a separate process: "On the photosensitive film..."] <5> In this case, exposure occurs from the side of the release layer 2. The exposed portion of the photosensitive resin layer 3 will cure due to polymerization. At this time, on the photosensitive film... <5> In this case, release layer 2 is non-photosensitive and therefore will not cure. Next, the non-exposed areas of photosensitive resin layer 3 are developed by rinsing with developer and then washed with water to obtain a resist image. On the photosensitive film... <5> In this case, development is achieved by rinsing the non-exposed areas of the release layer 2 and the photosensitive resin layer 3 with a developer solution, followed by water washing to obtain a resist image. Next, sandblasting is performed to process the substrate.

[0118] Indirect methods are mostly used when the object being processed is curved or three-dimensional, when the photosensitive film cannot pass through the laminating rollers, or when exposure cannot be performed in a tight seal. First, the photosensitive film is exposed through a mask film with a raised image, held between the support 1 and the mask 2. Then, the support 1 is peeled off. <5> In this case, the separation occurs at the interface between the release layer 2 and the support 1. Furthermore, for applications requiring high clarity, to reduce light refraction, after the support 1 is removed, the photosensitive resin layer 3 is exposed through a mask film with an embossed image. The photosensitive film... <5> In this case, exposure occurs from the side of the release layer 2. The exposed portion of the photosensitive resin layer 3 will cure due to polymerization. At this time, on the photosensitive film... <5> In this case, release layer 2 is non-photosensitive and therefore will not cure. Next, the non-exposed areas of photosensitive resin layer 3 are developed by rinsing with developer and then washed with water. On the photosensitive film... <5> In this case, development is performed by rinsing the non-exposed areas of the release layer 2 and the photosensitive resin layer 3 with a developer solution, followed by water washing. This forms a resist image on the protective film 4, created from the exposed areas of the photosensitive resin layer 3. The resist image is then adhered to the substrate using a water-based adhesive or similar method. Next, the protective film 4 is peeled off, leaving the resist image on the substrate. Finally, sandblasting is performed to process the substrate.

[0119] Regarding photosensitive films <5> The characteristic is that it is a photosensitive film in which a support 1, a release layer 2, a photosensitive resin layer 3, and a protective film 4 are sequentially stacked. The release layer 2 contains (A') an alkali-soluble resin, and the photosensitive resin layer 3 contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) a urethane (meth)acrylate. The (A') alkali-soluble resin of the release layer 2 is a copolymer obtained by copolymerizing (iii) methacrylic acid with (v) a monomer having an olefinic unsaturated group other than methacrylic acid. The (A) alkali-soluble resin of the photosensitive resin layer 3 is a copolymer obtained by copolymerizing (i) a styrene derivative, (ii) acrylic acid, and (iv) a monomer having an olefinic unsaturated group other than styrene derivative and acrylic acid.

[0120] In photosensitive film <5> In this process, release layer 2 contains (A') an alkali-soluble resin. Component (A') of release layer 2 is a copolymer obtained by copolymerizing (iii) methacrylic acid with (v) monomers having olefinic unsaturated groups other than methacrylic acid. By polymerizing (iii) methacrylic acid, release layer 2 exhibits excellent mold release properties.

[0121] Photosensitive film <5> In this context, monomers (v) having olefinically unsaturated groups other than methacrylic acid can be listed as examples of compositions with photosensitive resins. <2> The monomers described in (iv) are the same monomers as the compounds exemplified therein.

[0122] Photosensitive film <5> In this process, the acid value of component (A') is preferably 30–500 mg KOH / g, and more preferably 100–300 mg KOH / g. If the acid value is below 30 mg KOH / g, the development time becomes excessively long; conversely, if it exceeds 500 mg KOH / g, the glass transition temperature (Tg) becomes high, making the release layer 2 prone to cracking. Furthermore, the mass-average molecular weight of component (A') is preferably 10,000–200,000, and more preferably 10,000–150,000. If the mass-average molecular weight is below 10,000, it becomes difficult to form a film on the release layer 2; conversely, if it exceeds 200,000, the solubility in the developer deteriorates.

[0123] Photosensitive film <5> In this process, the release layer 2 may also contain component (C). Component (C) may include photosensitive resin compositions. <1> and <2> The compounds described in the document.

[0124] Photosensitive film <5> In this process, the thickness of the release layer 2 is preferably 0.5 to 15 μm, and more preferably 1 to 10 μm. If the release layer 2 is too thick, there is a tendency for reduced clarity and increased cost. Conversely, if the release layer 2 is too thin, the peelability will be reduced.

[0125] Photosensitive film <5> In addition, the release layer 2 may also contain components other than those mentioned above (A') and (C), as needed. These components may include polymerizable monomers, solvents, plasticizers, colorants (dyes, pigments), defoamers, leveling agents, antioxidants, etc., each containing approximately 0.01 to 20% by mass. These components may be used individually or in combination of two or more.

[0126] Photosensitive film <5> In the photosensitive resin layer 3, there are at least (A) alkali-soluble resin, (B) photopolymerization initiator, and (C) urethane (meth) acrylate.

[0127] Component (A) of the photosensitive resin layer 3 is a copolymer obtained by copolymerizing (i) a styrene derivative, (ii) acrylic acid, and (iv) monomers other than the styrene derivative and acrylic acid that have olefinic unsaturated groups. Because (ii) acrylic acid participates in the polymerization, its softening point is low, thus improving its sandblasting resistance. Furthermore, because (i) the styrene derivative participates in the polymerization, it has high compatibility with component (C) and also achieves a resistance to phase separation.

[0128] Photosensitive film for sandblasting <5> In this invention, because the (A') alkali-soluble resin of the release layer 2 is different from the (A) alkali-soluble resin of the photosensitive resin layer 3, the release layer 2 and the photosensitive resin layer 3 do not easily fuse after the photosensitive film is made, even over time. Since the release layer 2 is not photosensitive and has the property of dissolving in the developing solution, if the release layer 2 and the photosensitive resin layer 3 fuse, the surface of the photosensitive resin layer 3 becomes difficult to solidify and easily swells due to the developing solution. In this invention, the release layer 2 and the photosensitive resin layer 3 do not easily fuse, therefore the surface of the photosensitive resin layer 3 does not easily swell during development.

[0129] As a photosensitive film <5> (i) Styrene derivatives, such as photosensitive resin compositions, are examples. <2> The derivatives described therein.

[0130] Photosensitive film <5> In this context, monomers (iv) of component (A) can be exemplified by compounds listed in monomers (v) of component (A') (i.e., compounds that react with the photosensitive resin composition). <2> (The monomer (iv) described herein is the same substance as the compound exemplified.) The monomer (iv) of component (A) may be the same as or different from the monomer (v) of component (A').

[0131] Photosensitive film <5> In this process, the acid value of component (A) is preferably 30-500 mg KOH / g, and more preferably 200-400 mg KOH / g. When the acid value of component (A) is less than 30 mg KOH / g, the development time becomes longer; on the other hand, if it exceeds 500 mg KOH / g, the adhesion to the treated object deteriorates.

[0132] Photosensitive film <5> In this process, the mass-average molecular weight of component (A) is preferably 10,000 to 200,000, and more preferably 10,000 to 150,000. If the mass-average molecular weight of component (A) is less than 10,000, it may be difficult to form a film on the photosensitive resin layer 3. On the other hand, if it exceeds 200,000, the solubility in the developer may deteriorate.

[0133] Photosensitive resin composition <5> Among them, as component (B), photosensitive resin compositions can be listed. <1> and <2> The photopolymerization initiator described in the document.

[0134] Photosensitive film <5> In this context, the component (C) of the photosensitive resin layer 3 may be one of the compounds listed in the component (C) of the release layer 2. When the release layer 2 contains component (C), the component (C) of the photosensitive resin layer 3 may be the same as or different from the component (C) of the release layer 2.

[0135] Photosensitive film <5> In the photosensitive resin layer 3, other than components (A) to (C) mentioned above may be included as needed. These components may include polymerizable monomers, solvents, heat-resistant polymerization inhibitors, plasticizers, colorants (dyes, pigments), photochromic agents, light-reducing agents, heat-resistant photochromic agents, fillers, defoamers, flame retardants, adhesion promoters, leveling agents, peel accelerators, antioxidants, fragrances, thermosetting agents, water-resistant agents, and oil-resistant agents, each comprising approximately 0.01 to 20% by mass. These components may be used individually or in combination of two or more.

[0136] Photosensitive film <5> In this context, the polymerizable monomer refers to a compound other than component (C) that has at least one polymerizable olefinic unsaturated group within its molecule. Examples include compounds obtained by reacting polyols with α,β-unsaturated carboxylic acids; bisphenol A-based (meth)acrylates; compounds obtained by reacting compounds containing glycidyl groups with α,β-unsaturated carboxylic acids; nonylphenoxy polyethylene oxide acrylates; phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate and β-hydroxyalkyl-β'-(meth)acryloyloxyalkyl-o-phthalate; alkyl (meth)acrylates; and EO and PO-modified nonylphenyl (meth)acrylates. Here, EO and PO represent ethylene oxide and propylene oxide, respectively. EO-modified compounds have an ethylene oxide block structure, and PO-modified compounds have a propylene oxide block structure.

[0137] In addition, photosensitive film <5> In this process, the aforementioned polymerizable monomer may also be a compound having three or more polymerizable olefinic unsaturated groups within its molecule. Examples of photopolymerizable compounds having three or more polymerizable olefinic unsaturated groups within their molecule include compounds containing at least one of the following: trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and trimethylolpropane triglycidyl ether tri(meth)acrylate.

[0138] Photosensitive film <5> In this process, the aforementioned polymerizable monomers may be used alone or in combination of two or more.

[0139] Photosensitive film <5> In the photosensitive resin layer 3, the content of component (A) relative to the total amount of components (A), (B), and (C) is preferably 20-70% by mass, and more preferably 35-50% by mass. If the content of component (A) is less than 20% by mass, the compatibility with urethane acrylate (C) decreases, resulting in reduced developability. If the content of component (A) exceeds 70% by mass, the sandblasting resistance decreases.

[0140] Photosensitive film <5> In this composition, the content of component (B) relative to the total amount of components (A), (B), and (C) is preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass. When the content of component (B) is less than 0.1% by mass, there is a tendency for decreased sensitivity. On the other hand, if it exceeds 10% by mass, component (B) becomes difficult to dissolve in the photosensitive resin composition.

[0141] Photosensitive film <5> In the photosensitive resin layer 3, the content of component (C) relative to the total amount of components (A), (B), and (C) is preferably 25-75% by mass, and more preferably 35-60% by mass. When the content of component (C) is less than 25% by mass, there is a tendency for reduced sandblasting resistance and insufficient photosensitivity. On the other hand, if it exceeds 75% by mass, there is a tendency for excessive increase in the adhesion of the film surface.

[0142] Example

[0143] The present invention will be further described in detail below through embodiments, but the present invention is not limited to these embodiments.

[0144] (Examples 1-4, Comparative Examples 1-4)

[0145] The components shown in Table 1 were mixed to obtain a coating solution of the photosensitive resin composition. The content of each component in Table 1 is expressed in parts by mass. Using a coating rod, the obtained coating solution was applied to a polyethylene terephthalate (PET) film (carrier film, trade name: R310, 16 μm thick, manufactured by Mitsubishi Chemical), and dried at 90°C for 8 minutes to remove the solvent, resulting in a photosensitive resin layer (40 μm thick) containing the photosensitive resin composition on one side of the PET film. A polyethylene film (protective film, trade name: GF1, 30 μm thick, manufactured by Tamagotchi) was then attached to the photosensitive resin layer to produce a photosensitive film. The prepared film was stored at room temperature for 10 days before being used for subsequent evaluation.

[0146]

[0147] In Table 1, each component is described below. In addition, Table 1 also reveals the content of component (E) (the content of component (E) relative to the total amount of components (A), (B), (C), (D) and (E)) [mass %].

[0148] <Ingredients (A)>

[0149] (A) A copolymer resin (weight average molecular weight 30,000) formed by copolymerizing methyl methacrylate / n-butyl acrylate / methacrylic acid in a mass ratio of 64 / 15 / 21.

[0150] <Ingredient (B)>

[0151] (B-1)2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer

[0152] (B-2)4,4'-bis(diethylamino)benzophenone

[0153] <Ingredient (C)>

[0154] (C-2) KAYARAD (Registered Trademark) UXF-4001-M35 (Trade Name, Nippon Kayaku Co., Ltd., 65% Solid Content)

[0155] <Ingredient (D)>

[0156] (D)KAYARAD (Registered Trademark) UXE-3024 (Trade Name, Nippon Kayaku Co., Ltd., 65% Solid Content)

[0157] <Ingredient (E)>

[0158] (E-1)NK Ester A-DCP (trade name, manufactured by Shin-Nakamura Chemical Industry, tricyclodecanediethanol diacrylate)

[0159] (E-2) Light Acrylate IB-XA (trade name, manufactured by Kyoei Chemicals, isobornyl acrylate)

[0160] <Ingredient (X)>

[0161] (X-1)NK Ester 9G (trade name, manufactured by Shin-Nakamura Chemical Industry, polyethylene glycol dimethacrylate)

[0162] (X-2)NK Ester BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Industry, ethoxylated bisphenol A dimethacrylate)

[0163] After being stored at room temperature for 10 days, the state of the photosensitive film was visually observed. The results showed that the photosensitive resin layers of Examples 1-4 and Comparative Example 4 did not exhibit any cloudiness and were transparent. On the other hand, the photosensitive resin layers of Comparative Examples 1-3 were generally cloudy.

[0164] After peeling off the polyethylene film, the photosensitive films of Examples 1-4 and Comparative Examples 1-4 were attached to a 100×100mm, 1.5mm thick glass substrate (borosilicate glass) with the photosensitive resin layer in contact with the glass substrate (the substrate being processed). Next, the photosensitive resin layer was exposed using active radiation through a photomask with a hole pattern of 60μm diameter and 100μm spacing. Then, the PET film was peeled off, and alkaline development was performed using a 1.0% (w / w) sodium carbonate aqueous solution to remove the unexposed photosensitive resin layer. At this point, the unexposed photosensitive resin layer of Examples 1-4 and Comparative Example 4 was completely dissolved, forming an opening according to the 60μm hole pattern. On the other hand, the unexposed photosensitive resin layer of Comparative Examples 1-3 was not dissolved, and an opening could not be formed according to the hole pattern, therefore subsequent evaluation could not be performed.

[0165] Next, using a SiC abrasive (manufactured by Naniwa Abrasive Industry, trade name: GC Micro Powder #1200) to sandblast a glass substrate for 20 minutes (blasting pressure: 0.2 MPa), through which a photosensitive resin layer with a 60 μm hole pattern was formed, pits were created on the glass substrate. In Examples 1, 2, and 4, where the content of component (E) was 5–10% by mass, the opening diameter of the hole pattern in the photosensitive resin layer increased by 0.5–1.5 μm compared to before sandblasting. On the other hand, in Example 3, the opening diameter of the hole pattern increased by 2–4 μm. The photosensitive resin layer in Examples 1, 2, and 4 showed less wear and excellent sandblasting resistance. In Comparative Example 4, the hole pattern was severely cut during the sandblasting process, exposing part of the covered glass substrate, resulting in low sandblasting resistance.

[0166] (Examples 5-10, Comparative Examples 5-8)

[0167] The components shown in Table 2 were copolymerized to obtain (A) alkali-soluble resins of grades (A-1) to (A-10). Furthermore, the content of each component in Table 2 is expressed in parts by mass. Table 2 also lists the acid value and mass-average molecular weight of the (A) alkali-soluble resins.

[0168] The components shown in Table 3 were mixed to obtain a coating solution of the photosensitive resin composition. Furthermore, the unit of content for each component in Table 3 is [parts by mass]. Using a coating rod, the obtained coating solution was applied to a PET film (carrier film, trade name: R310, 16 μm thick, manufactured by Mitsubishi Chemical), dried at 90°C for 8 minutes to remove the solvent components, resulting in a photosensitive resin layer (50 μm thick) containing the photosensitive resin composition on one side of the PET film. A polyethylene film (protective film, trade name: GF1, 100 μm thick, manufactured by TAMAPOLY) was attached to the photosensitive resin layer to produce a photosensitive film. The prepared film was stored at room temperature for 10 days before being used for subsequent evaluation.

[0169]

[0170]

[0171] The components in Table 3 are as follows.

[0172] <Ingredient (B)>

[0173] (B-1)2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer

[0174] (B-2)4,4'-bis(diethylamino)benzophenone

[0175] <Ingredient (C)>

[0176] (C-2) KAYARAD (Registered Trademark) UXF-4001-M35 (Trade Name, Nippon Kayaku Co., Ltd., Solid Content 65% by Weight)

[0177] <Ingredient (D)>

[0178] (D)KAYARAD (registered trademark) UXE-3024 (trade name, Nippon Kayaku Co., Ltd., solid content 65% by weight)

[0179] After being stored at room temperature for 10 days, the state of the photosensitive film was visually observed. As a result, the photosensitive resin layers of Examples 5-10 and Comparative Examples 6 and 8 did not show any cloudiness and were transparent. On the other hand, the photosensitive resin layers of Comparative Examples 5 and 7 showed an overall cloudiness.

[0180] After peeling off the polyethylene film, the photosensitive films of Examples 5-10 and Comparative Examples 5-8 were attached to a 100×100 mm, 1.5 mm thick glass substrate (borosilicate glass) with the photosensitive resin layer in contact with the glass substrate (the object being treated). Next, the photosensitive resin layer was exposed using active rays through a photomask with a hole pattern of 60 μm diameter and 100 μm spacing. Then, the PET film was peeled off, and alkaline development was performed using a 1.0% by mass sodium carbonate aqueous solution to remove the photosensitive resin layer from the unexposed areas. At this point, the photosensitive resin layer in the unexposed areas of Examples 5-9 was completely dissolved, forming openings according to the 60 μm hole pattern. Although the photosensitive resin layer in the unexposed areas of Example 10 was completely dissolved, development took more than twice as long as in Examples 5-9. On the other hand, the photosensitive resin layer in the unexposed areas of Comparative Examples 5 and 7 was not dissolved, and openings could not be formed according to the hole pattern, thus preventing subsequent evaluation. Comparative Example 6 required a long development time, and a large amount of development residue was observed at the bottom of the hole pattern. Compared with Examples 5-9, Comparative Example 8 had a shorter development time, but the resulting pattern floated off the substrate and had poor adhesion; therefore, no further evaluation was conducted.

[0181] Next, using a SiC abrasive (manufactured by Naniwa Abrasive Industry, trade name: GC Micro Powder #1200) to sandblast a glass substrate for 20 minutes (blasting pressure: 0.2 MPa), through which a photosensitive resin layer with a 60 μm pore pattern was formed, pits were created on the glass substrate. In Examples 5-10 and Comparative Example 6, the opening diameter of the pore pattern in the photosensitive resin layer increased by 0.5-1.5 μm compared to before sandblasting. Compared to Examples 5-10, Comparative Example 6 was affected by developing residue, resulting in uneven pit shapes on the glass substrate.

[0182] (Examples 11-14, Comparative Examples 9 and 10)

[0183] The components shown in Table 4 were copolymerized to synthesize alkali-soluble resins (A'-1), (A'-2), (A-1), (A-2), and (A-3). Furthermore, the content of each component in Table 4 is expressed in parts by mass. Table 4 also lists the acid value (JIS K0070:1992) and mass-average molecular weight of the alkali-soluble resins.

[0184] Furthermore, “n-butyl acrylate” and “methyl methacrylate” in Table 4 conform to either monomer (iv) or monomer (v).

[0185] [Table 4]

[0186]

[0187] Next, the components shown in Table 5 were mixed to obtain the coating solution (W-Z) for release layer 2. Furthermore, the unit of content for each component in Table 5 is [parts by mass]. The obtained coating solution was applied to a PET film (support 1, trade name: R310, 16 μm thick, manufactured by Mitsubishi Chemical) using a wire rod, and dried at 80°C for 4 minutes to remove the solvent components, resulting in release layer 2 (dry film thickness: 4 μm) on one side of support 1.

[0188]

[0189] Next, the components of the photosensitive resin layer 3 shown in Table 6 are mixed to obtain a coating solution for the photosensitive resin layer 3. Furthermore, the unit of content for each component in Table 6 is [parts by mass]. Next, the coating solution for the photosensitive resin layer is applied to the release layer 2 of the support 1, which has been coated with the release layer 2, corresponding to the release layer 2 in Table 6. After drying at 90°C for 8 minutes, the solvent components are removed, resulting in the photosensitive resin layer 3 (50 μm thick). A polyethylene film (covering film 4, trade name: GF1, 100 μm thick, manufactured by TAMAPOLY) is attached to the surface of the photosensitive resin layer 3 to produce a photosensitive film for sandblasting.

[0190] [Table 6]

[0191]

[0192] The components in Tables 5 and 6 are as follows.

[0193] <Ingredient (B)>

[0194] (B-1)2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer

[0195] (B-2)4,4'-bis(diethylamino)benzophenone

[0196] <Ingredient (C)>

[0197] (C-1)UV3300B (trade name, manufactured by Mitsubishi Chemical)

[0198] (C-2) KAYARAD (Registered Trademark) UXF-4001-M35 (Trade Name, Nippon Kayaku Co., Ltd., Solid Content 65% by Weight)

[0199] TMP-A (trade name, manufactured by Kyoei Chemical, trimethylolpropane triacrylate)

[0200] After storing the photosensitive films for sandblasting from Examples 11-14 and Comparative Examples 9 and 10 at room temperature for one month, the cover film 4 of the photosensitive film for sandblasting was peeled off and attached to a 3 mm thick glass substrate. Next, exposure was performed through a photomask. Then, the support 1 was peeled off. As a result, in Examples 11-14, the support 1 could be easily peeled off. While it could be peeled off in Comparative Examples 9 and 10, a larger peeling force was required compared to Examples 11-14.

[0201] Next, development was performed using a developer (1.0% by mass sodium carbonate aqueous solution) to remove the unexposed portions of the photosensitive resin layer 3. At this point, the unexposed portions of the photosensitive resin layer 3 in Examples 11-14 were completely dissolved in the developer, forming openings according to a 60 μm hole pattern. Furthermore, after development, the surface of the exposed portions of the photosensitive resin layer 3 was smooth and did not swell, resulting in a good resist image. In Comparative Examples 9 and 10, the surface of the exposed portions of the photosensitive resin layer 3 became uneven, and swelling occurred in the exposed portions of the photosensitive resin layer 3. Additionally, openings could not be formed according to the 60 μm hole pattern, resulting in a poor resist image and low clarity.

[0202] Next, using a SiC abrasive (manufactured by Naniwa Abrasive Industry, trade name: GC Micro Powder #1200) to sandblast the glass substrate for 20 minutes (blasting pressure: 0.2 MPa) through the resist image (exposed area of ​​photosensitive resin layer 3) with a 60 μm hole pattern, recesses were formed on the glass substrate. Sandblasting was successfully performed in Examples 11-14. In Comparative Examples 9 and 10, the resist image did not form openings according to the 60 μm pattern, making sandblasting impossible.

[0203] Industrial availability

[0204] The photosensitive resin composition and photosensitive film of the present invention are applicable to processing using sandblasting.

Claims

1. A photosensitive resin composition for sandblasting, characterized in that, It contains at least A. alkali-soluble resin, B. photopolymerization initiator, C. urethane (meth) acrylate, and D. acid-modified epoxy (meth) acrylate. A. Alkali-soluble resin is a copolymer obtained by copolymerizing i. styrene derivatives, ii. acrylic acid, and iv. monomers other than styrene derivatives and acrylic acid that have olefinically unsaturated groups. The total amount of i styrene derivatives, ii acrylic acid, and iv monomers with olefinic unsaturated groups other than styrene derivatives and acrylic acid is 10% to 60% by mass for i styrene derivatives and ii acrylic acid, and 20% to 50% by mass for ii acrylic acid.

2. The photosensitive resin composition for sandblasting as described in claim 1, wherein, The acid value of alkali-soluble resins based on JIS-K0070:1992 is 40 mg KOH / g to 500 mg KOH / g.

3. The photosensitive resin composition for sandblasting as described in claim 1, wherein, The mass-average molecular weight of alkali-soluble resin A is 10,000 to 50,000.

4. A photosensitive film for sandblasting, comprising a photosensitive resin layer containing a photosensitive resin composition for sandblasting on a support, characterized in that, The photosensitive resin composition is the photosensitive resin composition for sandblasting as described in any one of claims 1 to 3.

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