Laminated film for pattern formation and non-photosensitive screen printing plate and method for manufacturing the same

Abstract

[Problem] To provide a pattern forming laminated film which prevents moisture absorption from the air, unnecessary component from remaining on the surface of a plate film, and tackiness of a photosensitive resin layer. [Means for Solving Problem] The present invention provides a pattern forming laminated film, a non-photosensitive screen printing plate using the pattern forming laminated film, and a method for manufacturing the same, the pattern forming laminated film being characterized by comprising, in order, a support layer, a paste layer, a non-water-soluble polymer layer, and a photosensitive resin layer.

Description

Technical Field

[0001] This invention relates to laminated films for pattern forming and unexposed screen printing plates, as well as methods for manufacturing them. Background Technology

[0002] One method for manufacturing screen printing plates is using a pattern-forming film. Compared to directly coating a photosensitive resin layer, this method has advantages in the following aspects: when transferring the photosensitive resin layer using a pattern-forming film, the photosensitive resin film can be smoothly formed on the screen, and uneven thickness within the plate is suppressed. Therefore, it is possible to produce a high-precision plate with sharp edges after development and minimal uneven ink transfer.

[0003] When using such a pattern-forming film to manufacture a printing plate for screen printing, water, photosensitive resin, etc. are first coated on the screen, the photosensitive resin layer of the pattern-forming film is adhered, and after it is fully dried, the support layer is peeled off, thereby transferring the photosensitive resin layer onto the screen. Then, the photosensitive resin layer is exposed through a pattern mask, and then developed with water, etc., thereby forming a specified pattern on the screen.

[0004] However, the surface of the photosensitive resin layer is often sticky due to its composition, which can cause the following problems: it is difficult to align the pattern mask during exposure, thus hindering uniform and tight adhesion with the pattern mask; or when the pattern mask is peeled off from the photosensitive resin layer after exposure, part of the photosensitive resin layer is damaged and contaminates the pattern mask.

[0005] To prevent these problems, Japanese Patent Application Publication No. 58-60745 and International Publication No. 2013-080958 proposed a pattern-forming laminate in which polyvinyl alcohol and fluorinated compounds are disposed as an intermediate layer between the support layer and the photosensitive resin layer.

[0006] However, since polyvinyl alcohol is a water-soluble polymer, it is believed to absorb moisture from the air, which seems insufficient to suppress the stickiness of the printing plate.

[0007] Furthermore, this intermediate layer is originally a non-photosensitive material and is removed during development. However, due to prolonged contact with the photosensitive resin layer, some photosensitive components migrate to the intermediate layer and become insoluble in the developer during exposure. Therefore, sometimes the intermediate layer components cannot be removed by development, leaving residues on the film surface. Consequently, the originally designed performance of the photosensitive resin cannot be achieved.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 58-60745

[0011] Patent Document 2: International Publication No. 2013-080958 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] According to the present invention, the objective is to prevent the absorption of moisture from the air, prevent unnecessary components from remaining on the surface of the film, suppress the stickiness of the photosensitive resin layer, and improve poor adhesion and workability during exposure.

[0014] Methods for solving problems

[0015] The present invention solves the above-mentioned problems by providing a laminated film for forming a specified pattern.

[0016] Therefore, the pattern-forming laminated film of the present invention is characterized by being composed of a support layer, a paste layer, a water-insoluble polymer layer and a photosensitive resin layer in sequence.

[0017] Such a pattern-forming laminated film of the present invention preferably includes the following embodiment: the above-mentioned photosensitive resin layer is a photosensitive resin that can be developed with neutral water.

[0018] Such a pattern-forming laminated film of the present invention preferably includes the following embodiment: the interlayer adhesion (x) between the support layer and the paste layer, the interlayer adhesion (y) between the paste layer and the non-water-soluble polymer layer, and the interlayer adhesion (z) between the non-water-soluble polymer layer and the photosensitive resin layer are in the following relationship:

[0019] Interlayer adhesion force (x) > Interlayer adhesion force (y)

[0020] Interlayer adhesion (z) > interlayer adhesion (y).

[0021] Such a pattern-forming laminated film of the present invention preferably comprises the following embodiment: a layer in which the interlayer adhesion (y) between the above-mentioned paste layer and the non-water-soluble polymer layer is 0.001 to 1.0 N / 25 mm.

[0022] Such a pattern-forming laminated film of the present invention preferably includes the following embodiment: the haze value of the above-mentioned non-water-soluble polymer layer is 5.0% or less.

[0023] Such a pattern-forming laminated film of the present invention preferably includes the following embodiment: the thickness of the above-mentioned non-water-soluble polymer layer is 1 to 100 μm.

[0024] Such a pattern-forming laminated film of the present invention preferably includes the following embodiment: the above-mentioned photosensitive resin layer includes a photosensitive resin containing the following components (A) and (B),

[0025] Component (A): Polyvinyl alcohol with a saponification degree of 50 mol% or higher.

[0026] Component (B): Diazo resin.

[0027] Such a pattern-forming laminated film of the present invention preferably comprises the following embodiment: the photosensitive resin layer comprises a photosensitive resin containing the following components (A), (C), and (D).

[0028] Component (A): Polyvinyl alcohol with a saponification degree of 50 mol% or higher.

[0029] Component (C): An epoxy compound having at least one epoxy group.

[0030] Component (D): Photoacid generator.

[0031] Such a pattern-forming laminated film of the present invention preferably includes the following embodiment: the above-mentioned photosensitive resin layer includes a photosensitive resin containing the following component (E).

[0032] Component (E): Pyridine with styrene substitution Quinoline substituted with styrene or styrene The degree of saponification of the base is 50 mol% or more of polyvinyl alcohol.

[0033] Such a pattern-forming laminated film of the present invention preferably comprises the following embodiment: the above-mentioned photosensitive resin layer comprises a photosensitive resin further containing the following components (F) and (G),

[0034] Component (F): A free radical polymerizable compound having at least one olefinic unsaturated bond.

[0035] Component (G): Photoradical polymerization initiator.

[0036] Such a pattern-forming laminated film of the present invention preferably includes the following embodiment: the above-mentioned photosensitive resin layer includes a photosensitive resin further comprising the following component (H).

[0037] Composition (H): Aqueous polymer emulsion.

[0038] Such a pattern-forming laminated film of the present invention preferably includes the following embodiment: a protective layer is further laminated on the photosensitive resin layer side of the above-mentioned pattern-forming laminated film.

[0039] Furthermore, the non-photosensitive screen printing plate of the present invention is characterized by comprising:

[0040] A laminated film, which is obtained by removing the support layer and paste layer from the above-mentioned pattern-forming laminated film; and

[0041] A screen, which is laminated on the photosensitive resin layer side of the above-mentioned laminated film.

[0042] Furthermore, the method for manufacturing the non-photosensitive screen printing plate of the present invention is characterized by comprising the following steps (a) and (b):

[0043] Step (a): The step of bonding a screen to the photosensitive resin layer side of the laminated film for forming the above pattern.

[0044] Step (b): Step of peeling the support layer and paste layer from the non-water-soluble polymer layer of the laminated film for pattern formation.

[0045] Furthermore, the screen printing plate of the present invention is characterized in that a latent image is formed and a photosensitive resin layer is developed on an unexposed screen printing plate, wherein the unexposed screen printing plate comprises:

[0046] A laminated film, which is obtained by removing the support layer and paste layer from the above-mentioned pattern-forming laminated film; and

[0047] A screen, which is laminated on the photosensitive resin layer side of the above-mentioned laminated film.

[0048] Furthermore, the method for manufacturing the screen printing plate of the present invention is characterized by including the following steps (a) to (f).

[0049] Step (a): The step of bonding a screen to the photosensitive resin layer side of the laminated film for forming the above pattern.

[0050] Step (b): A step of peeling the support layer and paste layer from the non-water-soluble polymer layer of the laminated film for forming the above pattern.

[0051] Step (c): The step of depositing a pattern mask on the surface of the above-mentioned water-insoluble polymer layer.

[0052] Process (d): The process of forming a latent image on the above-mentioned photosensitive resin layer.

[0053] Process (e): The process of peeling off the above-mentioned non-water-soluble polymer layer.

[0054] Step (f): A step of developing the photosensitive resin layer on which the latent image described above has been formed.

[0055] Furthermore, the photosensitive resist substrate of the present invention is characterized in that it comprises: the above-mentioned pattern forming laminate, and a substrate laminated on the side of the above-mentioned photosensitive resin layer of the pattern forming laminate.

[0056] Invention Effects

[0057] The pattern forming laminate of the present invention has a non-water-soluble polymer layer laminated on the surface of a photosensitive resin layer. Because the surface of the non-water-soluble polymer layer is smooth, it is easy to position the pattern mask on the surface of the non-water-soluble polymer layer.

[0058] Furthermore, due to the high adhesion and uniformity between the pattern mask and the non-water-soluble polymer layer, deformation of the pattern mask can be suppressed. Therefore, extremely accurate exposure of the photosensitive resin layer and formation of the latent image are possible.

[0059] Furthermore, this non-water-soluble polymer layer acts as a protective layer for the photosensitive resin layer, preventing the surrounding environment and deteriorating components from affecting the photosensitive resin layer. For example, it can prevent the photosensitive resin layer from absorbing moisture or prevent the transfer of harmful components from other layers, thus maintaining the original excellent properties of the photosensitive resin for a long time.

[0060] Therefore, the pattern-forming laminated film according to the present invention can be used to obtain a screen printing plate that accurately forms the desired high-precision pattern.

[0061] The pattern forming laminate of the present invention, by having a non-water-soluble polymer layer on the photosensitive resin layer during exposure, eliminates the concerns about moisture absorption and residue in the case of conventional water-soluble polymer layers, and can prevent the pattern mask from being contaminated by the photosensitive resin components.

[0062] Moreover, it can prevent poor adhesion caused by the stickiness of the photosensitive resin layer, and it is easy to align. It also inhibits the adhesion of impurities and makes it easy to remove attached impurities.

[0063] Furthermore, the presence of a polymer layer eliminates concerns about adhesion, thus broadening the design scope of photosensitive materials. Attached Figure Description

[0064] Figure 1 This is a schematic diagram illustrating a preferred non-photosensitive screen printing plate of the present invention.

[0065] Figure 2 This is a schematic diagram illustrating a preferred non-photosensitive screen printing plate of the present invention.

[0066] Figure 3 is a schematic diagram illustrating a preferred method for manufacturing a screen printing plate according to the present invention. Detailed Implementation

[0067] <Laminated film for pattern forming>

[0068] The pattern-forming laminated film of the present invention is characterized in that it is composed of a support layer, a paste layer, a water-insoluble polymer layer and a photosensitive resin layer in sequence.

[0069] The pattern-forming laminate of the present invention comprises: a support layer, a paste layer, a water-insoluble polymer layer, and a photosensitive resin layer. Here, "comprises" refers not only to the case where only the listed layers (i.e., the support layer, paste layer, water-insoluble polymer layer, and photosensitive resin layer) are included, but also to the case where layers or materials other than those listed are included. A protective layer is a representative example of such layers other than those listed.

[0070] The pattern-forming laminate of the present invention can be applied to various printing technologies, particularly screen printing. When applying the pattern-forming laminate of the present invention to such a printing field, firstly, sometimes, the interface between the paste layer and the water-insoluble polymer layer is peeled off, the support layer and the paste layer are removed, and then the water-insoluble polymer layer is peeled off.

[0071] Therefore, as a particularly preferred pattern-forming laminate of the present invention applicable to the field of screen printing, the interlayer adhesion (x) between the support layer and the paste layer, the interlayer adhesion (y) between the paste layer and the non-water-soluble polymer layer, and the interlayer adhesion (z) between the non-water-soluble polymer layer and the photosensitive resin layer can be described as follows.

[0072] Interlayer adhesion force (x) > Interlayer adhesion force (y)

[0073] Interlayer adhesion force (z) > Interlayer adhesion force (y)

[0074] It should be noted that the interlayer adhesive force (x) and interlayer adhesive force (z) can be in the following states: (x) is greater than (z), (x) is less than (z), and (x) is equal to (z).

[0075] <Supporting Layer>

[0076] In this invention, a support layer made of various materials can be used as the support layer. For example, a support layer made of various resin materials can be used, or a support layer made of natural raw materials can also be used.

[0077] Preferred materials include, for example, paper, release paper, polyesters such as polyethylene terephthalate, polymethylpentene, polypropylene, polyolefins such as polyethylene, halogenated vinyl polymers such as polyvinyl fluoride and polyvinyl chloride, polyamides such as nylon, cellulose such as cellophane, polystyrene, acrylic resins, and polyimide films. The support layer can be transparent or opaque. To improve the functionality of the laminated film, release treatment, matte treatment, and easy-to-bond treatment can be applied to one or both sides. For example, through the above treatments, the interlayer adhesion (x) between the support layer and the paste layer can be easily controlled.

[0078] The thickness of the support layer is not particularly limited, but is preferably 10 to 200 μm, and particularly preferably 30 to 125 μm.

[0079] <Paste Layer>

[0080] In this invention, a paste layer made of various materials can be used as the paste layer. That is, there are no particular limitations on the paste material used in the paste layer, and various paste materials can be used.

[0081] As preferred paste materials, various pastes represented by substances such as acrylic (one-component or two-component) adhesives or binders, rubber-based or polyurethane-based adhesives or binders, silicone-based adhesives or binders, and vinyl acetate-based adhesives or binders can be used.

[0082] Furthermore, solvent-free, solvent-based, emulsion-based, thermosetting, UV-curing, EB-curing, and hot-melt types can be used.

[0083] The thickness of the paste layer is not particularly limited, but is preferably 0.5 to 30 μm, and particularly preferably 0.5 to 20 μm.

[0084] The paste layer can be formed by the following methods: after applying the above-mentioned paste material to the support layer by common coating methods such as gravure printing, comma coating, air knife method, scraper method, rod coating, mold coating, and doctor blade method, it is dried and cured by methods such as heat treatment, ultraviolet irradiation treatment, and electron beam irradiation treatment.

[0085] The choice of paste material for forming the paste layer is preferably such that the interlayer adhesion force (y) between the paste layer and the non-water-soluble polymer layer is 0.001 to 1.0 N / 25 mm, and particularly preferably 0.005 to 0.5 N / 25 mm (p-PET). When it is less than 0.001 N / 25 mm, peeling and lifting may occur due to insufficient adhesion to the non-water-soluble polymer layer, which is not preferred. On the other hand, when it is greater than 1.0 N / 25 mm, it is difficult to peel off from the non-water-soluble polymer layer, paste residue may occur after peeling, or the surface contamination may increase, which is also not preferred. The interlayer adhesion force (y) is expressed as the force when peeled at a speed of 300 mm / min at a 180-degree angle after 1 minute at 23°C (according to JIS-Z0237).

[0086] The laminated film for pattern formation of the present invention preferably ensures that, after the support layer and the paste layer are peeled off from the water-insoluble polymer layer, the paste constituting the paste layer does not remain on the surface of the water-insoluble polymer layer. (Using 10cm...) 2When the mass of the paste material is 100, the residual amount of paste on the surface of the non-water-soluble polymer layer after the paste layer is peeled off is preferably 5% or less, more preferably 1% or less, and particularly preferably 0.1% or less.

[0087] <Non-water-soluble polymer layer>

[0088] In the pattern-forming laminated film of the present invention, the resin constituting the photosensitive resin layer is photocured through the non-water-soluble polymer layer.

[0089] The non-water-soluble polymer layer preferably has a low haze value. For example, the haze value is preferably 0.01 to 5.0%, and particularly preferably 0.05 to 3.0%. Here, the haze value is the value measured according to JIS-K7136.

[0090] By keeping the haze value within the preferred range described above, the photosensitive resin layer can be cured well even with low light irradiation, and the photosensitive resin layer can form a highly detailed desired pattern.

[0091] Preferred non-water-soluble polymer layers include, for example, polyesters such as polyethylene terephthalate, polymethylpentene, polypropylene, polyethylene and other polyolefins, halogenated vinyl polymers such as polyfluorinated vinyl polymers such as polyvinyl chloride, polyamides such as nylon, cellulose such as cellophane, polystyrene, acrylic resins, polyimide, polyethersulfone resins and other films.

[0092] When the non-water-soluble polymer layer is within the haze value range, release treatment or easy-bonding treatment can be applied to one or both sides to improve the function of the laminated film. For example, through the above treatment, it is easier to control the interlayer adhesion (y) between the paste layer and the non-water-soluble polymer layer, and the interlayer adhesion (z) between the non-water-soluble polymer layer and the photosensitive resin layer.

[0093] Polyester films and polyolefin films are suitable as particularly preferred non-water-soluble polymer layers. The thickness is preferably 1 to 100 μm.

[0094] <Photosensitive resin layer>

[0095] The photosensitive resin layer of the pattern-forming laminate of the present invention may comprise a resin that can form a latent image by light irradiation and can be developed by neutral water. Preferably, it is a resin that can be used as a solvent to form a coating film.

[0096] Preferred examples of such photosensitive resin layers include the following first, second, and third examples.

[0097] <<First Photosensitive Resin Layer>>

[0098] A first specific example of a photosensitive resin layer comprises a photosensitive resin containing the following components (A) and (B).

[0099] Component (A): Polyvinyl alcohol with a saponification degree of 50 mol% or higher.

[0100] Component (B): Diazo resin.

[0101] Here, "containing" means that in addition to containing the listed components (i.e., containing only components (A) and (B)), it also contains other components besides those listed. Examples of such other components besides those listed are components (F) to (H) (described in detail later).

[0102] Regarding the ratio (mass%) of component (A) to component (B), the ratio of component (A): component (B) is preferably 1:0.005 to 1:0.5, and particularly preferably 1:0.01 to 1:0.2.

[0103] The photosensitive resin containing components (A) and (B) may contain any one or more of components (F) to (H) as needed.

[0104] Ingredient(A)

[0105] Component (A) is polyvinyl alcohol with a saponification degree of 50 mol% or more. The saponification degree is preferably 50-100 mol%, particularly preferably 70-100%, and can also be a copolymer with other vinyl monomers as long as it does not impair water solubility. Its average degree of polymerization is preferably 200-5000, particularly preferably 300-4000. Two or more polyvinyl alcohols with different saponification and polymerization degrees can also be mixed. Furthermore, modified polyvinyl alcohols such as cationic or anionic modifiers can also be used.

[0106] Ingredient (B)

[0107] Component (B) is a diazo resin. Specific examples include: diazo resins containing condensates of p-diazodiphenylamine or 3-methoxy-4-diazodiphenylamine with 4,4′-dimethoxymethyldiphenyl ether, and their sulfate, phosphate, and zinc chloride complex anionic complexes; and diazo resins containing sulfate, phosphate, and zinc chloride complex anionic complexes of condensates of p-diazodiphenylamine or 3-methoxy-4-diazodiphenylamine with paraformaldehyde. Besides p-aminodiphenylamine, water-soluble diazo resins can also be used, formed by condensing diazo compounds of diphenylamines such as 4-amino-4′-methyldiphenylamine, 4-amino-4′-ethyldiphenylamine, 4-amino-4′-methoxydiphenylamine, 4-amino-4′-chlorodiphenylamine, and 4-amino-4′-nitrodiphenylamine with aldehydes such as paraformaldehyde, acetaldehyde, propionaldehyde, and n-butyraldehyde.

[0108] Of particular preference are condensates of diazidodiphenylamine and paraformaldehyde, condensates of 3-methoxy-4-diazodiphenylamine and paraformaldehyde, condensates of diazidodiphenylamine and 4,4′-bismethoxymethyldiphenyl ether, and condensates of 3-methoxy-4-diazodiphenylamine and 4,4′-bismethoxymethyldiphenyl ether.

[0109] The above-mentioned component (B) can be used alone or in combination with two or more components.

[0110] Ingredients(F)

[0111] Component (F) is a free radical polymerizable compound having at least one olefinic unsaturated bond, equivalent to monomers and oligomers as described in the "Photocuring Technology Data Sheet" (Technonnet Co., 2000).

[0112] Specific examples of monofunctional monomers include: 2-ethylhexyl (meth)acrylate, isodecanyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, morpholine ethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, methoxydiethylene (meth)acrylate, methoxytriethylene (meth)acrylate, and so on. Methoxytetraethylene(propylene) glycol acrylate, (meth)acrylate methoxypoly(ethylene(propylene) glycol) acrylate, (meth)acrylate ethoxydiethylene(propylene) glycol acrylate, (meth)acrylate ethoxytriethylene(propylene) glycol acrylate, (meth)acrylate cyclohexyl acrylate, (meth)acrylate tetrahydrofuran acrylate, (meth)acrylate isobornyl acrylate, (meth)acrylate dicyclopentyl acrylate, (meth)acrylate N,N-dimethylaminoethyl acrylate, (meth)acrylate N,N-diethylaminoethyl acrylate, oxide-modified phosphate (meth)acrylate, ω-carboxyl-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, etc.

[0113] Please note that in this specification, "(meth)acrylate" refers to both "methacrylate" and "acrylate", and "ethylene (propylene) glycol" refers to both "ethylene glycol" and "propylene glycol".

[0114] Specific examples of multifunctional monomers having two or more olefinic unsaturated bonds include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide (propane)-modified bisphenol A diacrylate, neopentyl glycol di(meth)acrylate, bis(acryloyloxyneopentyl glycol) adipate, bis(methacryloyloxyneopentyl glycol) adipate, and so on. Chlorohydrin-modified 1,6-hexanediol di(meth)acrylate, neopentyl hydroxypentanoic acid neopentyl glycol di(meth)acrylate, caprolactone-modified neopentyl hydroxypentanoic acid neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane)tri(meth)acrylate Acrylates, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, hydroxypropyl acrylate-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol polypropoxyacrylate, stearic acid-modified pentaerythritol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol... Pentylenetetroxide poly(meth)acrylate, caprolactone-modified dipentaerythritol poly(meth)acrylate, glycerol di(meth)acrylate, epichlorohydrin-modified glycerol tri(meth)acrylate, oxide-modified glycerol tri(meth)acrylate, tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, caprolactone-modified tri(acryloyloxyethyl)isocyanurate, caprolactone-modified tri(methacryloyloxyethyl)isocyanurate, oxide-modified bisphenol (meth)acrylate, etc.

[0115] As oligomers, for example, polyester (meth)acrylate oligomers, bisphenol A type epoxy (meth)acrylates, caprolactone addition (meth)acrylates, phenolic varnish type epoxy (meth)acrylates, cresol varnish type epoxy (meth)acrylates, and other epoxy (meth)acrylates, urethane (meth)acrylates, etc., can be used.

[0116] Furthermore, polyester dendritic macromolecules containing olefinic unsaturated bonds can be used. Specific examples of such polyester dendritic macromolecules containing olefinic unsaturated bonds are described in Japanese Patent Application Publications Nos. 2005-76005, 2005-47979, and 2005-76005.

[0117] The above-mentioned component (F) can be used alone or in combination with two or more components.

[0118] When the total of the above components (A) and (B) is set to 100% by mass, the amount (by mass) of component (F) is preferably 1.0 to 800% by mass, and particularly preferably 10 to 600% by mass.

[0119] Ingredient (G)

[0120] Component (G) is a photopolymerization initiator, which is not particularly limited. For example, it can be benzophenone, bis-N,N-dimethylaminobenzophenone and other benzophenones, thioxanthone, isopropylthioxanthone and other thioxanthones.

[0121] In addition, examples of oil-soluble photoradical polymerization initiators include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and other benzoin and benzoin alkyl ethers; acetophenones, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)one, 1-hydroxycyclohexylphenyl ketone, and other acetophenones; 2-methyl- Aminoacetophenones such as 1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone; thioxanones such as 2,4-dimethylthioxanone, 2,4-diethylthioxanone, 2-chlorothioxanone, isopropylthioxanone, 2,4-diisopropylthioxanone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones or xanthones, etc., can be used alone or in combination of two or more. In addition, known sensitizers such as tertiary amines can be used alone or in combination of two or more.

[0122] The amount (mass%) of component (G) relative to component (F) is preferably 0.1 to 20% by mass, and particularly preferably 0.5 to 10% by mass.

[0123] Component (H)

[0124] Component (H) is an aqueous polymer emulsion, such as: polyvinyl acetate, vinyl acetate / ethylene copolymer, vinyl acetate / acrylate copolymer, (meth)acrylic acid polymer, styrene / butadiene copolymer, methyl methacrylate / butadiene copolymer, acrylonitrile / butadiene copolymer, chloroprene polymer, isoprene polymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, silicone resin, polyethylene, polyurethane, fluoropolymer, etc. Examples of these hydrophobic polymer particles include: polyvinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, vinyl acetate-acrylic acid copolymer emulsion, ethylene-vinyl acetate-acrylic acid terpolymer emulsion, vinyl chloride-vinyl acetate copolymer emulsion, acrylic emulsion, styrene-butadiene latex emulsion, MBR latex emulsion, acrylonitrile-butadiene rubber latex emulsion, chloroprene rubber latex emulsion, vinylidene chloride emulsion, etc. Furthermore, aqueous emulsions of polymers with cross-linked structures obtained by emulsion polymerization of aqueous emulsions prepared from multifunctional (meth)acrylates using thermal polymerization initiators or photopolymerization initiators are suitable. Polyethylene dispersions, polyolefin ionomer dispersions, and urethane ionomer dispersions are useful as synthetic polymer dispersions.

[0125] When the total of the above components (A) and (B) is set to 100% by mass, the presence rate (by mass%) of component (H) is preferably 1 to 1500% by mass, and particularly preferably 10 to 1000% by mass.

[0126] Other ingredients

[0127] In the first photosensitive resin layer, as other components, crosslinking agents, organic or inorganic particles, silane coupling agents, pigments, dyes, thermal polymerization inhibitors, surfactants, defoamers, antioxidants, adhesion promoters, plasticizers, solvents, surface tension modifiers, stabilizers, chain transfer agents, flame retardants, antibacterial agents, preservatives, etc., may be added as needed.

[0128] <<Second Photosensitive Resin Layer>>>

[0129] A second specific example of a photosensitive resin layer comprises a photosensitive resin containing the following components (A), (C) and (D).

[0130] Component (A): Polyvinyl alcohol with a saponification degree of 50 mol% or higher.

[0131] Component (C): An epoxy compound having at least one epoxy group.

[0132] Component (D): Photoacid generator

[0133] Here, "containing" means that in addition to containing the listed components (i.e., containing only components (A), (C), and (D)), it also contains other components besides those listed. Components (F) to (H) can be cited as representative examples of such other components besides those listed.

[0134] Regarding the ratio (mass%) of component (A) to component (C), the ratio of component (A): component (C) is preferably 1:1 to 1:10, and particularly preferably 1:2 to 1:6. The amount (mass%) of component (D) relative to the above-mentioned component (C) is preferably 1 to 20% by mass, and particularly preferably 3 to 10% by mass.

[0135] The photosensitive resin containing the above-mentioned components (A), (C) and (D) may contain any one or more of components (F) to (H) as needed.

[0136] Ingredient(A)

[0137] As component (A) in the second specific example, it can be used in those exemplified as component (A) in the first specific example of the photosensitive resin.

[0138] Ingredient (C)

[0139] Component (C) is a compound having at least one epoxy group.

[0140] Examples of glycidyl ethers with two or more functional groups include: ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, dibromonepentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl terephthalate, diglycidyl phthalate, hydrogenated diglycidyl phthalate, and bisphenol A. PO2mol adducts include diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, etc. Furthermore, examples of alicyclic epoxy compounds include: 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, the adduct of 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate with ε-caprolactone, 1,2,8,9-diepoxylimonene, (3,3′,4,4′-diepoxy)biscyclohexyl, 1,2-epoxy-4-vinylcyclohexane, 1,2-bis(hydroxymethyl)-1-butanol with 1,2-epoxy-4-(2-oxypyrimidine)cyclohexane adduct, tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone, and 3,4-epoxycyclohexylmethyl methacrylate, etc.

[0141] Examples of monofunctional epoxy compounds include: 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol (EO)5 glycidyl ether, p-tert-butylphenyl glycidyl ether, dibromophenyl glycidyl ether, lauryl alcohol (EO)15 glycidyl ether, Cl2 and Cl3 mixed alcohol glycidyl ether, and N-glycidyl phthalimide. If these are used as reactive diluents, high-viscosity or solid epoxy resins can be used. For example, phenolic varnish epoxy resins, cresol varnish epoxy resins, trihydroxyphenylmethane epoxy resins, dicyclopentadiene phenol epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, biphenol epoxy resins, bisphenol A varnish epoxy resins, epoxy resins containing a naphthalene skeleton, heterocyclic epoxy resins, epoxidized polybutadiene, epoxides of styrene-butadiene block copolymers, brominated epoxy resins, biphenyl epoxy resins, and amine epoxy resins can be used.

[0142] Alternatively, compounds having at least one oxobutyl group can be mixed with the aforementioned epoxy compounds.

[0143] Examples of oxetane compounds include those described in J. V. Crivello and H. Sasaki, J. M. Pure Appl. Chem., A30(2&3), 189 (1993) or J. H. Sasaki and V. Crivello, J. M. Pure Appl. Chem., A30(2&3), 915 (1993). Examples include: 3-ethyl-3-hydroxymethyloxetane (oxetane), 2-ethylhexyloxetane, (3-ethyloxetane-3-yl)methyl methacrylate, (3-ethyloxetane-3-yl)methacrylate, 3-ethyl-3-(4-hydroxybutoxymethyl)oxetane and other monofunctional oxetane compounds, xylene dioxetane, 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, 4,4′-bis[(3-ethyl-3-oxetane)methoxymethyl]biphenyl], bis[(3-ethyl-3-oxetane)methyl]isophthalate and other difunctional compounds. Multifunctional oxetane compounds, including pentaerythritol tris(3-ethyl-3-oxetane-butylmethyl) ether, pentaerythritol tetra(3-ethyl-3-oxetane-butylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetane-butylmethyl) ether, dipentaerythritol penta(3-ethyl-3-oxetane-butylmethyl) ether, dipentaerythritol tetra(3-ethyl-3-oxetane-butylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetane-butylmethyl) ether, and bis(trimethylolpropane)tetra(3-ethyl-3-oxetane-butylmethyl) ether.

[0144] The above-mentioned component (C) can be used alone or in combination with two or more components.

[0145] Ingredient (D)

[0146] Component (D) is an acid-generating agent, using a compound used in chemically amplified photoresists or photocationic polymerization (see "Organic Materials for Imaging," edited by the Organic Electronic Materials Research Association, Bunshin Publishing (1993), pp. 187-192"). Specific examples of acid-generating agents include: Cationic compounds, halogenated compounds that produce hydrohalic acids, and sulfonated compounds that produce sulfonic acids.

[0147] Examples of ionic acid generators include: diazo. ammonium, iodine Suede Diceroxide wait Cations of Cl - ,Br - I - ZnCl3 - HSO3 - BF4 - PF6 - AsF6 - SbF6 - CH3SO3 - CF3SO3 - Perfluorobutane sulfonate, perfluorooctane sulfonate, camphor sulfonate, benzene sulfonate, p-toluene sulfonate, 9,10-dimethoxyanthracene-2-sulfonate, cyclohexylaminosulfonate, (C6F5)4B - (C4H9)4B - Wait for the salt.

[0148] As mentioned above Specific examples of cations include: phenyldiazepine. p-Methoxydiazo α-Naphthyldiazo Biphenyldiazo Diphenylamine-4-diazo 3-Methoxydiphenylamine-4-diazo 2,5-Diethoxy-4-methoxybenzoylamide phenyldiazo 2,5-Dipropoxy-4-(4-Tolyl)thiophenyldiazo 4-Methoxydiphenylamine-4-diazo The condensate of 4-diazodiphenylamine and formaldehyde, and 1-methoxyquinoline 1-Ethoxyisoquinoline 1-Benzylmethylpyridine 1-Benzyl-4-benzoylpyridine 1-Benzylquinoline N-substituted benzothiazoles (Refer to Japanese Patent Application Publication No. 5-140143, etc.)

[0149] Examples also include: benzyltriphenylsulfonium, p-methoxyphenyl diphenylsulfonium, bis(p-methoxyphenyl)phenylsulfonium, tri(p-methoxyphenyl)sulfonium, p-phenylthiophenyl diphenylsulfonium, benzyltetramethylenesulfonium, benzoylmethyltetramethylenesulfonium, benzoylmethyldimethylsulfonium, p-methoxyphenyldiethylsulfonium, naphthyldialkylsulfonium (Japanese Patent Application Publication No. 9-118663, Japanese Patent Application Publication No. 5-140209), (2-naphthylcarbonylmethyl)tetramethylenesulfonium, (p-hydroxyphenyl)dimethylsulfonium, (4-hydroxynaphthyl)-dimethylsulfonium, (4,7-dihydroxynaphthyl)-1-dimethylsulfonium, (4,8-dihydroxynaphthyl)-1-dimethylsulfonium, and diphenyliodine. Phenyl(4-methoxyphenyl)iodine Phenylenyl{4-(tert-butyl)phenyl}iodine 4-Bis{4-(tert-butyl)phenyl}iodide bis(4-dodecylphenyl)iodine (4-Methoxyphenyl)(4-Octophenyl)iodine Benzylmethyltriphenyl cyanomethyltriphenyl wait.

[0150] Examples of acid-producing agents that generate hydrohalic acids include: 1-methyl-3,5-bis(trichloromethyl)-triazine, 1-phenyl-3,5-bis(trichloromethyl)-triazine, 1-(4-chlorophenyl)-3,5-bis(trichloromethyl)-triazine, 1-(4-methoxyphenyl)-3,5-bis(trichloromethyl)-triazine, 1-(4-butoxyphenyl)-3,5-bis(trichloromethyl)-triazine, and 1-(3,4-methylenedioxyphenyl) 1-(3,4-Dimethoxyphenyl)-3,5-bis(trichloromethyl)-triazine, 1-(4-methoxynaphthyl-1)-3,5-bis(trichloromethyl)-triazine, 1-{2-(4-methoxyphenyl)vinyl}-3,5-bis(trichloromethyl)-triazine, 1-{2-(2-methoxyphenyl)vinyl}-3,5-bis(trichloromethyl)-triazine, 1-{2-( 3,4-Dimethoxyphenyl)vinyl}-3,5-bis(trichloromethyl)-triazine, 1-{2-(3-chloro-4-methoxyphenyl)vinyl}-3,5-bis(trichloromethyl)-triazine, 1-(biphenyl-1)-3,5-bis(trichloromethyl)-triazine, 1-(4-hydroxybiphenyl-1)-3,5-bis(trichloromethyl)-triazine, 1-(4-methoxybiphenyl-1)-3,5-bis(trichloromethyl)-triazine, 1-(4-methylbiphenyl-1)-3,5-bis(trichloromethyl)-triazine, 1,3,5-tris(trichloromethyl)-triazine, 1,3-dichloro-4-trichloromethylbenzene, 1,1,1-trichloro-{2,2-84-chlorophenyl}ethane, phenyltribromomethyl sulfone, 1-alkenyl-4-methyl-4-trichloromethyl-2,5-cyclohexadiene, 2-tribromoquinoline, 1-alkenyl-2,3-benzo-4,4,5,6-tetrachlorohexene-5, etc.

[0151] Examples of acid-producing agents that generate sulfonic acid include: 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 1-(p-toluenesulfonyloxyimino)-1-phenylacetonitrile, 1-(p-toluenesulfonyloxyimino)-1-phenylacetonitrile, benzoin p-toluenesulfonate, 2-p-toluenesulfonyloxy-2-benzoylpropane, p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, N-trifluoromethanesulfonyloxydiphenylmaleimide, N-p-toluenesulfonyloxysuccinimide, N-camphorsulfonyloxysuccinimide, N-trifluoromethanesulfonyloxysuccinimide, and N-trifluoromethanesulfonyloxysuccinimide. Imides, N-perfluorobutyryloxysuccinimide, N-p-toluenesulfonyloxyphthalimide, N-camphorsulfonyloxyphthalimide, N-trifluoromethanesulfonyloxyphthalimide, N-perfluorobutyryloxyphthalimide, N-p-toluenesulfonyloxy-1,8-naphthoimide, N-camphorsulfonyloxy-1,8-naphthoimide, N-trifluoromethanesulfonyloxy-1,8-naphthoimide, N-perfluorobutyryloxy-1,8-naphthoimide, 1,2,3-tris(p-toluenesulfonyloxy)benzene, bis(phenyl sulfone), bis(phenylsulfonyl)methane, etc.

[0152] Alternatively, the sensitizer can be used in combination with an acid-producing agent, and the desired sensitizer is an electron-donating compound. Examples of sensitizers with this property include: aromatic polycyclic compounds, porphyrin compounds, phthalocyanine compounds, polymethyl methacrylate dye compounds, anthocyanin compounds, coumarin compounds, and thiopyrans. Compounds, pyran Compounds, p-dialkylaminostyrene compounds, thioxanthate compounds, etc., but not limited to these. Most of them are recorded in "The Pigment Handbook" (Kodansha) compiled by Taiga, Hirashima, Matsuoka, and Kitao, "The Pigment Engineering Handbook" compiled by the Color Materials Association, Asakura Shoten (published in 1989), "Dye Catalogue" of the Hayashibara Biochemical Research Institute Photosensitive Pigment Research Institute, etc.

[0153] Ingredients(F)

[0154] As component (F) in the second specific example, it can be used in those exemplified as component (F) in the first specific example of the photosensitive resin.

[0155] When the total of the above components (A), (C) and (D) is set to 100% by mass, the presence rate (by mass%) of component (F) is preferably 1 to 60% by mass, and particularly preferably 5 to 30% by mass.

[0156] Ingredient (G)

[0157] As component (G) in the second specific example, the component (G) exemplified as component (G) in the first specific example of the photosensitive resin can be used.

[0158] The presence rate (mass%) of component (G) relative to component (F) is preferably 0 to 20% by mass, and particularly preferably 0.1 to 10% by mass.

[0159] Component (H)

[0160] As component (H) in the second specific example, it can be used in those exemplified as component (H) in the first specific example of the photosensitive resin.

[0161] When the total of the above components (A), (C) and (D) is set to 100% by mass, the presence rate (by mass%) of component (H) is preferably 0.5 to 200% by mass, and particularly preferably 1 to 100% by mass.

[0162] Other ingredients

[0163] In the second photosensitive resin layer, other components may be used as needed, such as crosslinking agents, organic or inorganic particles, silane coupling agents, pigments, dyes, thermal polymerization inhibitors, surfactants, defoamers, antioxidants, adhesion promoters, plasticizers, solvents, surface tension modifiers, stabilizers, chain transfer agents, flame retardants, antibacterial agents, and preservatives.

[0164] <<Third Photosensitive Resin Layer>>>

[0165] A third specific example of a photosensitive resin layer comprises a photosensitive resin containing the following component (E).

[0166] Component (E): Pyridine with styrene substitution Quinoline substituted with styrene or styrene Polyvinyl alcohol with a saponification degree of 50 mol% or more

[0167] The photosensitive resin containing component (E) may contain any one or more of components (F) to (H) as needed.

[0168] Ingredient (E)

[0169] Component (E) contains pyridine with styrene substitution. Quinoline substituted with styrene or styrene The vinyl acetate polymer saponifier with a saponification degree of 50 mol% or more has photocrosslinking properties. Preferred specific examples include compounds represented by the following general formula (1) or general formula (2).

[0170] [Chemistry 1]

[0171]

[0172] (where R is in the formula) 1 Represents a hydrogen atom, alkyl group, or aralkyl group, which can be substituted with hydroxyl or carbamoyl groups. Furthermore, their carbon-carbon bonds can be separated by an oxygen atom or an unsaturated bond. R 2 Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m is an integer from 1 to 6. n is 0 or 1. X - This refers to halide ions, phosphate ions, methyl sulfate ions, sulfonate ions, free radical polymerizable monomers with anionic dissociation capabilities, or mixtures of these anions.

[0173] As R 1 Alkyl or aralkyl, preferably alkyl or aralkyl with 1 to 10 carbon atoms, particularly preferably with 1 to 7 carbon atoms. As a specific residue (R) 1 Examples of such compounds include: methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl, 3-methoxypropyl, allyl, crotonyl, benzyl, etc. When m exceeds the range of 1 to 6, the photoinsoluble film is prone to swelling, and m is more preferably 1 to 4. n can be 0 or 1.

[0174] As X - Preferably, phosphate ions, methyl sulfate ions, or, as halide ions, Cl- - or Br - As a sulfonate ion, CH3SO3 is preferred. - CH3CH2SO3 - C6H5SO3 - p-CH3C6H4SO3 - Additionally, as X -Examples of free radical polymerizable monomers include those having at least one olefinic unsaturated bond and possessing anionic dissociation capability. Examples of residues possessing anionic dissociation capability include sulfonic acids, carboxylic acids, and phosphoric acids, which can be used as free radical polymerizable monomers with anionic groups by preparing their alkali metal salts or ammonium salts of aliphatic amines. Examples of free radical polymerizable unsaturated groups in monomers used in this context include (meth)acryloyl (hereinafter, (meth)acryloyl refers to both acryloyl and methacryloyl), maleic acid monoester, styryl, allyl, etc. Examples of undissociated acidic monomers include: acrylic acid, methacrylic acid, monomethyl maleate, monoethyl maleate, 2-(meth)acryloyloxyethyl phthalate, 3-(meth)acryloyloxy-2-propyl phthalate, 3-(meth)acryloyloxy-2-propyl phthalate, 2-(meth)acryloyloxyethyl cyclohexane-3-ene-1,2-dicarboxylic acid, 2-(meth)acryloyloxyethyl succinate, and 2-(meth)acryloyloxyethyl cyclohexane-1,2-carboxylic acid. 2-(meth)acryloyloxyethyl maleate, ω-carboxy-polycaprolactone monoacrylate, acrylic acid dimer, 2-(meth)acryloyloxyethyl phosphate, 3-(meth)acryloyloxypropyl phosphate, 2-(meth)acryloyloxy-3-propyl phosphate, ω-(meth)acryloylpolyethyleneoxyethylene phosphate, ω-(meth)acryloylpolypropyleneoxyethylene phosphate, styrene sulfonic acid, N-(2-sulfoethyl)acrylamide, N-(2-sulfoethyl)methylacrylamide, etc., but not limited to these.

[0175] Ingredients(F)

[0176] As component (F) in the third specific example, it can be used in those exemplified as component (F) in the first specific example of the photosensitive resin.

[0177] When the above component (E) is set to 100% by mass, the presence rate (by mass%) of component (F) is preferably 1.0 to 800% by mass, and particularly preferably 10 to 600% by mass.

[0178] Ingredient (G)

[0179] As component (G) in the third specific example, it can be used in those exemplified as component (E) in the first specific example of the photosensitive resin.

[0180] When the above component (F) is set to 100% by mass, the presence rate (by mass%) of component (G) is preferably 0.1 to 20% by mass, and particularly preferably 0.5 to 10% by mass.

[0181] Component (H)

[0182] As component (H) in the third specific example, it can be used in those exemplified as component (H) in the first specific example of the photosensitive resin.

[0183] When the above component (E) is set to 100% by mass, the presence ratio (by mass%) of component (H) is preferably 1 to 1500% by mass, and particularly preferably 10 to 1000% by mass.

[0184] Other ingredients

[0185] In the third photosensitive resin layer, other components may be used as needed, such as crosslinking agents, organic or inorganic particles, silane coupling agents, pigments, dyes, thermal polymerization inhibitors, surfactants, defoamers, antioxidants, adhesion promoters, plasticizers, solvents, surface tension modifiers, stabilizers, chain transfer agents, flame retardants, antibacterial agents, preservatives, etc.

[0186] <Protective Layer>

[0187] The pattern-forming laminate of the present invention may include layers other than a support layer, a paste layer, a water-insoluble polymer layer, and a photosensitive resin layer. A representative example of such other layers is a protective layer.

[0188] This protective layer primarily functions to protect the pattern-forming laminate of the present invention. For example, when this protective layer is disposed on the surface of the photosensitive resin layer, it can prevent damage to the photosensitive resin layer caused by external impacts, pressure, etc., and prevent deterioration caused by moisture, gas, light, etc. The pattern-forming laminate of the present invention is easy to overlap, roll into a roll, and store.

[0189] In this invention, a protective layer made of various materials can be used. For example, a protective layer made of various resin materials can be used, and a protective layer made of natural materials can also be used.

[0190] There are no restrictions on the specific material of the protective layer; for example, the same material as the support layer can be used. The thickness of the protective layer is not particularly limited, but is preferably 1–50 μm.

[0191] When the pattern-forming laminate of the present invention, on which a protective layer is disposed on the surface of the photosensitive layer, is applied, for example, to a screen printing plate, the protective layer is peeled off first compared to the other layers constituting the pattern-forming laminate of the present invention. Therefore, the interlayer adhesion between the protective layer and the photosensitive layer is preferably lower than the other interlayer adhesions (x) to (z) (i.e., lower than the interlayer adhesion (y)). Therefore, release processing can be performed on one or both sides.

[0192] Furthermore, it can be transparent or opaque. Examples include: paper, release paper, polyesters such as polyethylene terephthalate, polymethylpentene, polypropylene, polyolefins such as polyethylene, halogenated vinyl polymers such as polyvinyl fluoride and polyvinyl chloride, polyamides such as nylon, cellulose such as cellophane, polystyrene, acrylic resins, and polyimide films. Additionally, release treatment, matte treatment, and easy-bonding treatment can be applied to one or both sides without sacrificing the lamination function.

[0193] <Unexposed screen printing plate (First unexposed screen printing plate)>

[0194] The first unexposed screen printing plate of the present invention is characterized in that it comprises the above-described pattern forming laminate and a screen laminated on the side of the photosensitive resin layer of the above-described pattern forming laminate.

[0195] Figure 1 This illustrates a preferred example of the first unexposed screen printing plate 8 of the present invention. Figure 1 The preferred non-photosensitive screen printing plate 8 of the present invention shown includes a pattern forming laminate 1 (specifically, a pattern forming laminate 1 consisting of a support layer 2, a paste layer 3, a non-water-soluble polymer layer 4, and a photosensitive resin layer 5 in sequence) and a screen 6 laminated on the photosensitive resin layer 5 side of the pattern forming laminate 1. Here, the screen 6 is attached to the frame material 7 in the same way as a typical screen printing plate.

[0196] <Method for manufacturing an unexposed screen printing plate (first unexposed screen printing plate)>

[0197] The method for manufacturing the unexposed screen printing plate (first unexposed screen printing plate) of the present invention is characterized by comprising the following step (a).

[0198] Step (a): A step of bonding a screen to the photosensitive resin layer side of the laminated film for forming the above pattern.

[0199] According to the manufacturing method of this screen printing plate, for example, it can be manufactured Figure 1 The unexposed screen printing plate 8 is shown.

[0200] In step (a), when the screen 6 is bonded to the photosensitive resin layer 5 side of the pattern forming laminate 1, the following methods are preferred, for example: (1) pre-coating the screen 6 with a photosensitive material (preferably the same or similar to the photosensitive resin forming the photosensitive resin layer 5) or water, thereby bonding the photosensitive resin layer 5 of the pattern forming laminate 1 thereon; (2) overlapping the photosensitive resin layer 5 of the pattern forming laminate 1 on the screen 6, and then coating the overlapping portion with a photosensitive material or water that is the same or similar to the photosensitive resin forming the photosensitive resin layer.

[0201] <Unexposed screen printing plate (Second unexposed screen printing plate)>

[0202] Another preferred embodiment of the second unexposed screen printing plate of the present invention (the second unexposed screen printing plate) is characterized by comprising: a laminated film, which is a laminated film obtained by removing the above-mentioned support layer and paste layer from a pattern forming laminated film; and a screen, which is laminated on the photosensitive resin layer side of the above-mentioned laminated film.

[0203] Figure 2 This illustrates a preferred example of the second unexposed screen printing plate 9 of the present invention.

[0204] Figure 2 The preferred non-photosensitive screen printing plate 9 of the present invention shown includes from Figure 1 The unexposed screen printing plate 8 shown is a pattern forming laminate 1' in which the support layer 2 and paste layer 3 have been removed, and a screen 6 is laminated on the side of the photosensitive resin layer 5 of the laminate 1'.

[0205] <Method for manufacturing an unexposed screen printing plate (second unexposed screen printing plate)>

[0206] The method for manufacturing the unexposed screen printing plate (the second unexposed screen printing plate) of the present invention is characterized by comprising the following steps (a) and (b).

[0207] Step (a): Step of bonding a screen to the photosensitive resin layer side of the laminated film for forming the above pattern.

[0208] Step (b): Step of peeling the support layer and paste layer from the non-water-soluble polymer layer of the laminated film for pattern formation.

[0209] Figure 2 This describes a preferred specific example of an unexposed screen printing plate 9 obtained by such a manufacturing method.

[0210] <Methods for Manufacturing Screen Printing Plates>

[0211] The method for manufacturing the screen printing plate of the present invention is characterized by comprising the following steps (a) to (f):

[0212] Step (a): The step of bonding a screen to the photosensitive resin layer side of the laminated film for forming the above pattern.

[0213] Step (b): A step of peeling the support layer and paste layer from the non-water-soluble polymer layer of the laminated film for forming the above pattern.

[0214] Step (c): The step of depositing a pattern mask on the surface of the above-mentioned water-insoluble polymer layer.

[0215] Process (d): The process of forming a latent image on the above-mentioned photosensitive resin layer.

[0216] Process (e): The process of peeling off the above-mentioned non-water-soluble polymer layer.

[0217] Step (f): A step of developing the photosensitive resin layer on which the latent image described above has been formed.

[0218] Figure 3 is a schematic diagram illustrating the manufacturing method of the screen printing plate of the present invention.

[0219] Figure 3A This describes a summary of step (a) in which the screen 6 is bonded to the photosensitive resin layer 5 side of the laminated film 1 used for pattern formation.

[0220] Figure 3B This section outlines the process (b) of peeling the support layer 2 and paste layer 3 from the non-water-soluble polymer layer 4 of the laminated film 1 used for pattern formation.

[0221] Figure 3C This section outlines the process (c) of depositing a pattern mask 10 on the surface of the aforementioned water-insoluble polymer layer 4.

[0222] Figure 3D This describes a summary of step (d) in which energy lines from the surface of the pattern mask 10 are irradiated onto the photosensitive resin layer 5 to form a latent image α on the photosensitive resin.

[0223] Figure 3E This section outlines the process (e) for peeling off the aforementioned water-insoluble polymer layer 4.

[0224] Figure 3F This describes an outline of the screen printing plate 11 obtained by performing step (f) of developing the photosensitive resin layer 5 on which the latent image α is formed. In this step (f), the photosensitive resin layer 5 on which the latent image α is formed is washed with water (e.g., neutral water), and a developing process is performed, including removing uncured areas of the photosensitive resin layer 5 (i.e., areas where the latent image α is not formed). Then, by drying the developed material, a screen printing plate 11 with a predetermined opening pattern can be obtained.

[0225] The pattern-forming laminated film 1 of the present invention has a water-insoluble polymer layer 3, on which a pattern mask 10 is disposed, and then irradiation with energy lines and formation of a latent image α are performed via the pattern mask 10. The water-insoluble polymer layer 3 prevents the photosensitive resin layer from becoming sticky due to moisture absorption and component migration, thus making it easy to determine the position of the mask pattern 10 on the surface of the water-insoluble polymer layer 3.

[0226] According to the screen printing plate of the present invention, since the surface of the finished printing plate can be processed to be flat, the printing reproducibility is good and the adhesion to the printed object is also good. Therefore, it is possible to suppress ink from flowing to the back of the printing plate and reduce the number of times the printing plate is wiped.

[0227] <Photosensitive Resist Substrate>

[0228] The photosensitive resist substrate of the present invention is characterized in that it comprises: the above-described pattern-forming laminate and a substrate laminated on the side of the above-described pattern-forming laminate of the above-described photosensitive resin layer.

[0229] As a substrate laminated to the photosensitive resin layer, a variety of materials can be used. Examples include: wood, stone, fabric, paper, ceramics, glass, cellulose acetate, polyester, polyolefin, polyimide, synthetic resins such as epoxy resin, glass fiber reinforced resin, metals such as aluminum, copper, nickel, iron, zinc, magnesium, and cobalt, semiconductor materials such as silicon and gallium arsenide germanium, and insulating materials such as silicon nitride and silicon oxide.

[0230] The photosensitive resist substrate of the present invention is a photosensitive resin that can be developed with neutral water, thus eliminating the need for organic solvents or alkaline aqueous solutions as developing solutions. In this respect, it is more environmentally and operationally advantageous than conventional photosensitive resist substrates.

[0231] Besides screen printing, photosensitive resist substrates can be obtained by bonding laminated films for pattern formation onto substrates such as metal or glass. Unlike conventional resins containing organic solvents, this method uses neutral water as the solvent, resulting in lower environmental pollution. Since development can be performed using neutral water without organic solvents or alkaline water, it is advantageous from environmental, operational, and developer storage and disposal perspectives. Furthermore, depending on the substrate, there are substrates that may discolor or deform due to organic solvents or alkalis; the use of neutral water for development broadens the range of substrate choices.

[0232] Example

[0233] <Example 1>

[0234] Pattern Formation Using Laminated Films

[0235] A 75 μm thick polyethylene terephthalate (PET) film was prepared as a support layer. An ethylene-vinyl acetate (EVA) emulsion adhesive was then applied to the film using a bar coater and dried at 100°C for 3 minutes to form a 10 μm thick paste layer. A 6 μm thick PET film was then laminated onto this paste layer using a laminator as a layer composed of a water-insoluble polymer.

[0236] Next, a photosensitive resin 1 containing the above-mentioned components (A), (B), (F), (G), and (H) is coated by a bar coater and heated and dried at 40°C for 30 minutes to form a photosensitive resin layer with a thickness of 20 μm, thereby obtaining a laminated film for pattern formation.

[0237] <Example 2>

[0238] After forming the photosensitive resin layer of Example 1, a polyethylene film with a thickness of 25 μm is laminated on it as a protective layer. Otherwise, the same procedure as in Example 1 is followed to produce a laminated film for pattern formation.

[0239] <Example 3>

[0240] The paste layer uses an acrylic adhesive, and the layer composed of C) non-water-soluble polymer uses a 12 μm thick polyolefin film. Otherwise, the same procedure as in Example 1 is followed to produce a laminated film for patterning.

[0241] <Comparative Example 1>

[0242] Pattern Formation Using Laminated Films

[0243] A 75 μm thick polyethylene terephthalate film was prepared as a support layer. A 5.0% by mass aqueous solution of polyvinyl alcohol (Clare Polyval 95-88 manufactured by Clare Co., Ltd.) was coated onto the film using a bar coater. The film was then heated and dried at 40°C for 30 minutes, thereby forming a 5 μm thick layer composed of a water-soluble polymer. Next, a photosensitive resin 1 containing the aforementioned components (A), (B), (F), (G), and (H) was coated onto the film using a bar coater. The resin was then heated and dried at 40°C for 30 minutes, thereby forming a 20 μm thick photosensitive resin layer, thus obtaining a laminated film for pattern formation.

[0244] <Comparative Example 2>

[0245] As a layer composed of water-soluble polymers, a resin containing fluorine compounds (SP-2050UC diazo resin manufactured by Murakami Co., Ltd.) was used. Otherwise, the same procedure as in Comparative Example 1 was followed to produce a laminated film for pattern formation.

[0246] <Comparative Example 3>

[0247] A polyethylene terephthalate film with a thickness of 75 μm is prepared as a support layer. A photosensitive resin 1 containing the above-mentioned components (A), (B), (F), (G), and (H) is coated on it using a bar coater. The film is then heated and dried at 40°C for 30 minutes to form a photosensitive resin layer with a thickness of 20 μm, thereby obtaining a film for pattern formation.

[0248] <Evaluation Method 1>

[0249] On a polyester fiber mesh fixed to an aluminum frame, a photosensitive resin 1 containing the aforementioned components (A), (B), (F), (G), and (H) is coated using a stainless steel tub, and then bonded to the photosensitive resin layer side of the pattern-forming laminate prepared above. Before bonding the pattern-forming laminate prepared in Example 2, the protective layer is peeled off, and then the photosensitive resin layer side is bonded. After drying at 40°C for 30 minutes, the support layer is peeled off. For the pattern-forming laminates prepared in Examples 1, 2, and 3, the paste layer is peeled off simultaneously with the support layer.

[0250] Next, an overlay pattern mask is applied, a vacuum is created, and a 3kW metal halide lamp is used as the light source. The photosensitive resin layer is exposed at a distance of 1 meter from the light source and for 2 minutes. After removing the pattern mask, the resin layer is developed using tap water. This yields the screen printing plate.

[0251] In Examples 1, 2, and 3, development was performed after removing the non-water-soluble polymer layer before development.

[0252] Surface tack 1

[0253] The pattern masks are evaluated from A to C based on the ease of alignment when overlapping them.

[0254] A: It enables the pattern mask to move smoothly and is easy to align.

[0255] B: The pattern mask cannot be moved smoothly, making alignment difficult.

[0256] C: The pattern mask is stuck to the surface and cannot be aligned.

[0257] Surface adhesion 2

[0258] The ease of peeling off the pattern mask after vacuum exposure is evaluated from A to C.

[0259] A: There is no resistance when peeling off the pattern mask, and it can be easily peeled off.

[0260] B: There is resistance when peeling off the pattern mask, and it cannot be peeled off smoothly.

[0261] C: The pattern mask is stuck to the surface, and part of the surface is damaged.

[0262] Surface condition

[0263] Evaluation is based on the surface condition of the developed screen printing plate, ranging from ○ to ×.

[0264] ○: There is no residue on the surface of the photosensitive resin layer.

[0265] ×: Other components remain on the surface of the photosensitive resin layer.

[0266] The evaluation results are shown in Table 1.

[0267]

[0268] <Example 4>

[0269] Pattern Formation Using Laminated Films

[0270] A 75 μm thick polyethylene terephthalate (PET) film was prepared as a support layer. An organosilicon adhesive was then coated onto the film using a bar coater, and the film was heated and dried at 100°C for 3 minutes to form a 5 μm thick paste layer. Subsequently, a 12 μm thick polyolefin film was laminated onto the paste layer as a layer composed of a water-insoluble polymer using a laminator.

[0271] Next, a photosensitive resin 2 containing the above-mentioned components (E), (F), (G), and (H) is coated by a bar coater and heated and dried at 40°C for 30 minutes to form a photosensitive resin layer with a thickness of 30 μm, thereby obtaining a laminated film for pattern formation.

[0272] <Example 5>

[0273] The paste layer uses an ethylene-vinyl acetate emulsion adhesive, and otherwise the same procedure is followed as in Example 4 to produce a patterned laminate.

[0274] <Example 6>

[0275] The paste layer uses a urethane-based adhesive, and otherwise the same procedure as in Example 4 is followed to produce a patterned laminate.

[0276] <Example 7>

[0277] An acrylic adhesive is used for the paste layer. Otherwise, the same procedure as in Example 4 is followed to produce a laminated film for pattern formation.

[0278] <Comparative Example 4>

[0279] Pattern Formation Using Laminated Films

[0280] As a layer composed of a non-water-soluble polymer, a release film with a single side of a 25 μm thick polyester film subjected to silicone release treatment was used. Otherwise, the same procedure as in Example 4 was followed to fabricate a pattern-forming laminate. The silicone-treated side of the release film was then attached to the photosensitive resin layer side.

[0281] <Comparative Example 5>

[0282] As a support layer, a release film with a single side of a 75 μm thick polyester film subjected to silicone release treatment was used. Otherwise, the same procedure as in Example 5 was followed to fabricate a pattern-forming laminate. The silicone-treated side of the release film was then attached to the paste layer side.

[0283] <Comparative Example 6>

[0284] As a layer composed of a non-water-soluble polymer, an easy-to-adhere film with one side of a 25 μm thick polyester film subjected to corona discharge treatment was used. Otherwise, the same procedure as in Example 6 was followed to fabricate a pattern-forming laminated film. The corona-treated side of the easy-to-adhere film was then attached to the paste layer side.

[0285] <Comparative Example 7>

[0286] The photosensitive resin layer uses the photosensitive resin 3 containing components (A) and (B) (H) as described above. Otherwise, the same procedure as in Example 7 is followed to produce a laminated film for pattern formation.

[0287] <Evaluation Method 2>

[0288] On a polyester fiber mesh fixed to an aluminum frame, a photosensitive resin for pattern forming films is coated using a stainless steel drum, and the photosensitive resin layer of the aforementioned pattern forming laminated film is then bonded to the mesh. The mesh is dried at 40°C for 30 minutes to obtain a test plate.

[0289] After storing at 25°C and 50% humidity for 24 hours, apply transparent tape to the support layer and peel it off by pulling it upwards. Confirm which area of ​​interfaces 1 to 3 peels off.

[0290] Interface 1: Support Layer / Paste Layer

[0291] Interface 2: Paste layer / water-insoluble polymer layer

[0292] Interface 3: Water-insoluble polymer layer / photosensitive resin layer

[0293] ○: Peeling at interface 2, with no residual paste layer on the non-water-soluble polymer layer.

[0294] ×: Stripping the area outside of interface 2.

[0295] The evaluation results are shown in Table 2 below.

[0296]

[0297] <Example 8>

[0298] Pattern Formation Using Laminated Films

[0299] A 75 μm thick polyethylene terephthalate (PET) film was prepared as a support layer. An organosilicon adhesive was then coated onto the film using a bar coater, and the film was heated and dried at 100°C for 3 minutes to form a 3 μm thick paste layer. Subsequently, a 12 μm thick polyolefin film with a haze value of 0.3% was laminated onto the paste layer using a laminator as a layer composed of a water-insoluble polymer.

[0300] Next, a photosensitive resin 4 containing the above-mentioned components (A), (B), (F), and (G) is coated by a bar coater and heated and dried at 40°C for 30 minutes to form a photosensitive resin layer with a thickness of 15 μm, thereby obtaining a laminated film for pattern formation.

[0301] Next, on a stainless steel fiber mesh fixed to an aluminum frame, a photosensitive resin for each pattern-forming film is applied using a stainless steel tub, and the photosensitive resin layer of the aforementioned pattern-forming laminated film is adhered to it. After drying at 40°C for 30 minutes, the support layer and the paste layer are peeled off.

[0302] Next, the pattern mask is superimposed on the non-water-soluble polymer layer, a vacuum is drawn, and a 3kW metal halide lamp is used as the light source. The photosensitive resin layer is exposed under the conditions that the distance between the light source and the surface of the plate is 1m and the irradiation time is 2 minutes, 3 minutes, 4 minutes and 5 minutes respectively.

[0303] Next, the pattern mask is removed, and then the resin layer is developed using tap water. This yields the screen printing plate.

[0304] <Example 9>

[0305] The non-water-soluble polymer layer uses a 50 μm thick, highly transparent polyethylene terephthalate film with a haze value of 1.0%. Otherwise, the same procedure as in Example 8 is followed to obtain the screen printing plate.

[0306] <Example 10>

[0307] The photosensitive resin layer uses photosensitive resin 5 containing the above-mentioned components (A) and (C) and (D). Otherwise, the same procedure as in Example 8 is followed to obtain the screen printing plate.

[0308] <Comparative Example 8>

[0309] The non-water-soluble polymer layer uses a polyolefin film with a thickness of 30 μm and a haze value of 6%. Otherwise, the same procedure as in Example 8 is followed to obtain the screen printing plate.

[0310] <Comparative Example 9>

[0311] The non-water-soluble polymer layer uses a general-purpose polyethylene terephthalate film with a thickness of 25 μm and a haze value of 5.7%. Otherwise, the same procedure as in Example 8 is followed to produce a laminated film for patterning.

[0312] <Comparative Example 10>

[0313] The non-water-soluble polymer layer uses a polyolefin film with a thickness of 125 μm and a haze value of 1.5%. Otherwise, the same procedure as in Example 10 is followed to produce a laminated film for patterning.

[0314] <Evaluation Method 3>

[0315] Use a 100x magnifying glass to examine the pattern on the obtained screen printing plate and determine the sensitivity and resolution.

[0316] Sensitivity: Set the shortest exposure time of step tablet 7 or higher to the sensitivity.

[0317] Resolution: The narrowest width (μm) of L / S that can be resolved by the sensitivity determined above will be used as the resolution.

[0318] The evaluation results are shown in Table 3 below.

[0319]

[0320] Symbol Explanation

[0321] 1: Pattern forming laminate; 2: Support layer; 3: Paste layer; 4: Non-water-soluble polymer layer; 5: Photosensitive resin layer; 6: Screen printing; 7: Frame material; 8: First unexposed screen printing plate; 9: Second unexposed screen printing plate; 1′: Laminated film; 10: Pattern mask; 11: Screen printing plate

Claims

1. A laminated film for pattern formation, characterized in that, It consists of a support layer, a paste layer, a water-insoluble polymer layer, and a photosensitive resin layer, in sequence. The non-water-soluble polymer layer is a film selected from polyester, polyolefin, and halogen-containing vinyl polymers. The thickness of the non-water-soluble polymer layer is 1–100 μm. The photosensitive resin layer is a photosensitive resin that can be developed with neutral water.

2. The pattern-forming laminated film according to claim 1, wherein, The non-water-soluble polymer layer is a membrane selected from polyethylene terephthalate, polypropylene, and polyvinyl chloride.

3. The laminated film for pattern formation according to claim 1, wherein, The interlayer adhesion force x between the support layer and the paste layer, the interlayer adhesion force y between the paste layer and the water-insoluble polymer layer, and the interlayer adhesion force z between the water-insoluble polymer layer and the photosensitive resin layer are related as follows: Interlayer adhesion strength x > interlayer adhesion strength y Interlayer adhesion z > interlayer adhesion y.

4. The laminated film for pattern formation according to claim 1, wherein, The interlayer adhesion y between the paste layer and the non-water-soluble polymer layer is 0.001 to 1.0 N / 25 mm.

5. The pattern-forming laminated film according to claim 1, wherein, The haze value of the non-water-soluble polymer layer is below 5.0%.

6. The laminated film for pattern formation according to claim 1, wherein, The photosensitive resin layer comprises a photosensitive resin containing components (A) and (B) below. Ingredient (A): Polyvinyl alcohol with a saponification degree of 50 mol% or higher. Component (B): Diazo resin.

7. The pattern-forming laminated film according to claim 1, wherein, The photosensitive resin layer comprises a photosensitive resin containing the following components (A), (C), and (D). Ingredient (A): Polyvinyl alcohol with a saponification degree of 50 mol% or higher. Component (C): An epoxy compound having at least one epoxy group. Ingredient (D): Photoacid-producing agent.

8. The laminated film for pattern formation according to claim 1, wherein, The photosensitive resin layer comprises a photosensitive resin containing the following component (E). Component (E): Pyridine with styrene substitution Quinoline substituted with styrene or styrene The base is polyvinyl alcohol with a saponification degree of 50 mol% or more.

9. The pattern-forming laminated film according to claim 6, wherein, The photosensitive resin layer comprises a photosensitive resin that also contains the following components (F) and (G). Component (F): A free radical polymerizable compound having at least one olefinic unsaturated bond. Component (G): Photoradical polymerization initiator.

10. The pattern-forming laminated film according to claim 6, wherein, The photosensitive resin layer comprises a photosensitive resin that also contains the following component (H). Component (H): Aqueous polymer emulsion.

11. The pattern-forming laminated film according to any one of claims 1 to 10, wherein, A protective layer is further laminated on the side of the photosensitive resin layer of the laminated film for pattern formation.

12. A non-photosensitive screen printing plate, characterized in that, Include: A laminated film, which is obtained by removing the support layer and the paste layer from the pattern-forming laminated film according to any one of claims 1 to 10; and A screen, which is laminated on the photosensitive resin layer side of the laminated film.

13. A screen printing plate, characterized in that, A latent image is formed on an unexposed screen printing plate, and a photosensitive resin layer is developed. The unexposed screen printing plate includes: A laminated film, which is obtained by removing the support layer and the paste layer from the pattern-forming laminated film according to any one of claims 1 to 10; and A screen, which is laminated on the photosensitive resin layer side of the laminated film.

14. A photosensitive resist substrate, characterized in that, Include: The pattern-forming laminated film according to any one of claims 1 to 10, and A substrate laminated on the side of the photosensitive resin layer of the pattern-forming laminated film.

Images