Laminates, pattern formation methods, cured products, and electronic components

Abstract

To provide a laminate having a resin layer with good uniformity of film thickness. [Solution] The laminate comprises a first film and a resin layer disposed on one surface of the first film. The first film has an arithmetic mean roughness Ra of 0.10 μm or more and 0.22 μm or less on the surface on which the resin layer is disposed, and a glossiness Gs(60°) of 60 or less on the surface on which the resin layer is disposed.

Description

[Technical Field]

[0001] The present invention relates to laminates, pattern forming methods, cured products, and electronic components. [Background technology]

[0002] A technique is known for forming an insulating film called solder resist, which is provided on a printed circuit board, using a dry film composed of a photosensitive resin layer and a support film. Generally, dry films are manufactured by coating a photosensitive resin composition onto a support film, but the thickness of the photosensitive resin layer may be uneven. For example, Patent Document 1 proposes a technique to suppress variations in the thickness of the photosensitive resin layer by adjusting the contact angle between the support film and the photosensitive resin composition. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2023 / 145974 [Overview of the project] [Problems that the invention aims to solve]

[0004] One aspect of the present invention aims to provide a laminate having a resin layer with good uniformity of film thickness. [Means for solving the problem]

[0005] The specific means for solving the aforementioned problems are as follows: [1] comprising a first film and a resin layer disposed on one surface of the first film, The first film has an arithmetic mean roughness Ra of 0.10 μm or more and 0.22 μm or less on the surface on which the resin layer is arranged. A laminate in which the glossiness Gs(60°) on the surface on which the resin layer is arranged is 60 or less.

[0006] [2] The laminate according to [1], wherein the first film has a contact angle with water on the surface on which the resin layer is arranged, which is 90° or less at 20°C.

[0007] [3] The first film is a laminate according to [1] or [2], comprising a filler.

[0008] [4] The laminate according to any one of [1] to [3], wherein the first film comprises a substrate and a mat layer disposed on the substrate and containing a filler, and the resin layer is disposed on the mat layer.

[0009] [5] The laminate according to [4], further comprising a release agent as the mat layer.

[0010] [6] The laminate according to any one of [1] to [5], wherein the resin layer is photosensitive.

[0011] [7] The laminate according to claim 6 is bonded to the substrate with the resin layer facing the substrate, Exposing the resin layer through the first film of the laminate, A pattern forming method comprising removing the first film and forming a pattern on the substrate that includes the cured resin layer.

[0012] [8] [7] Cured material included in the pattern formed by the pattern forming method described above.

[0013] Electronic components containing the cured products described in [9] and [8]. [Effects of the Invention]

[0014] According to one aspect of the present invention, it is possible to provide a laminate having a resin layer with good uniformity of film thickness. [Modes for carrying out the invention]

[0015] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved. Furthermore, the content of each component in a composition means the total amount of multiple substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component exist in the composition. In addition, the upper and lower limits of the numerical ranges described herein can be arbitrarily selected and combined from the numerical values ​​exemplified as numerical ranges. In this specification, (meth)acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions. Furthermore, solid content means the residue remaining after removing volatile components (e.g., organic solvents) from the composition or its components. Embodiments of the present invention will now be described in detail. However, the embodiments shown below are examples of laminates, pattern forming methods, cured products, and electronic components that embody the technical concept of the present invention, and the present invention is not limited to the laminates, pattern forming methods, cured products, and electronic components shown below.

[0016] Laminate The laminate comprises a first film (also called a support film) and a resin layer disposed on one surface of the first film. The first film has an arithmetic mean roughness Ra of 0.10 μm or more and 0.22 μm or less on the surface on which the resin layer is disposed. The first film also has a glossiness Gs(60°) of 60 or less on the surface on which the resin layer is disposed. The laminate may be a dry film capable of forming a solder resist with a matte surface by arranging a resin layer on a substrate and curing it. Alternatively, the laminate may be a dry film capable of forming a solder resist with high resolution and a matte surface by arranging a photosensitive resin layer on a substrate and exposing and developing it.

[0017] Here, the solder resist having a matte finish on the surface means a solder resist with a roughened surface. By roughening the surface of the solder resist, the solder adhesion resistance during solder reflow is improved, and the wiring concealment property is also improved. Furthermore, in the roughened solder resist, the glossiness is moderately suppressed, good designability is obtained, scratches are less noticeable, and it has usefulness in quality control. In the support film of the dry film used when forming a solder resist with a roughened surface, a release treatment may be applied to the surface where the resin layer is disposed. Therefore, the wettability during the formation of the resin layer is low, and it may be difficult to form a resin layer with a uniform film thickness. In the laminate of the present embodiment, the arithmetic mean roughness Ra on the surface where the resin layer of the first film (support film) is disposed is 0.10 μm or more and 0.22 μm or less, and the glossiness Gs (60°) on the surface where the resin layer is disposed is 60 or less. Thus, the wettability during the formation of the resin layer is good, and when applying the composition for forming the resin layer, an increase in the film thickness at the left and right ends with respect to the application direction (so-called ear height) is suppressed, and a resin layer having a uniform film thickness can be formed. Thereby, when the laminate is wound into a roll shape, a roll body with a good winding state can be formed. Also, excellent resolution can be achieved when exposing the photosensitive resin layer. Generally, when the arithmetic mean roughness Ra of the support film surface is large, the wettability with respect to the composition for forming the resin layer tends to improve, but the resolution during exposure tends to decrease. Also, when the arithmetic mean roughness Ra of the support film surface is constant, when the glossiness increases, the wettability with respect to the composition for forming the resin layer tends to decrease. In the present embodiment, by appropriately controlling and combining the arithmetic mean roughness Ra and the glossiness Gs (60°), wettability and resolution can be made compatible at a high level.

[0018] The laminate includes a resin layer having good film thickness uniformity. The film thickness uniformity of the resin layer can be evaluated, for example, when forming the resin layer by applying a composition for forming the resin layer, by comparing the film thicknesses at the left and right ends with respect to the coating direction and the film thickness near the center. For example, when the wettability of the composition for forming the resin layer of the first film on which the resin layer is provided is insufficient, the film thicknesses at the left and right ends with respect to the coating direction tend to increase more than the film thickness near the center. Specifically, for example, the value obtained by dividing the value obtained by subtracting the film thickness near the center from the film thicknesses at the left and right ends with respect to the coating direction by the film thickness near the center may be 20% or less, preferably 10% or less.

[0019] The first film may have an arithmetic mean roughness Ra on the surface where the resin layer is disposed, for example, of 0.10 μm or more and 0.22 μm or less, preferably 0.15 μm or more and 0.20 μm or less. When the arithmetic mean roughness Ra is 0.10 μm or more, the wettability during resin layer formation tends to be good. Also, when it is 0.22 μm or less, the resolution tends to be better. The arithmetic mean roughness Ra of the first film is measured in accordance with JIS B0601:1994. Specifically, for example, as the arithmetic mean value of the surface roughnesses at 10 locations measured in the shape measurement mode using a shape measurement laser microscope (for example, VX-100, manufactured by Keyence Corporation) corresponding to the non-contact measurement method, the arithmetic mean roughness Ra is calculated.

[0020] The first film may have a glossiness Gs(60°) on the surface where the resin layer is disposed, for example, of 60 or less, preferably 50 or less, 40 or less, or 35 or less, and 8 or more, or 12 or more. When the glossiness Gs(60°) is 60 or less, the wettability during resin layer formation tends to be better. The glossiness Gs(60°) of the first film is measured as the specular glossiness in accordance with JIS Z8741:1997 under the condition that both the incident angle and the light receiving angle are 60°. Specifically, the glossiness Gs(60°) can be measured using a digital variable angle gloss meter (for example, Micro-Tri-Gloss, manufactured by BYK Gardener).

[0021] The first film may have a contact angle with water at the surface on which the resin layer is placed, for example, 90° or less at 20°C. Preferably, the contact angle of the first film with water may be 80° or less, or 75° or less, or for example, 60° or more, preferably 65° or more. When the contact angle of the first film with water is 90° or less, the wettability during resin layer formation tends to be better. The contact angle of the first film with water is measured in accordance with JIS R3257:1999. Specifically, at 20°C, ion-exchanged water with a water content of 0.7 μS / cm or less is dropped onto 10 arbitrary locations on the first film, and the contact angle of the droplets formed is measured, and the contact angle is calculated as the arithmetic mean. The contact angle can be measured using a contact angle meter (e.g., DropMaster DM-300: manufactured by Kyowa Interface Science Co., Ltd.) and analysis software (e.g., Interface Measurement and Analysis Integrated System FAMAS: manufactured by Kyowa Interface Science Co., Ltd.).

[0022] The first film may be composed of a resin. The resin constituting the first film may be a light-transmitting resin commonly used in optical applications. Specifically, examples include alkyl poly(meth)acrylate, polyethylene, polypropylene, polystyrene, polycarbonate, aromatic or aliphatic polyamide, polyester, polyimide, etc. The resin constituting the first film may preferably contain at least polyester, and may be a resin mainly composed of polyester. Here, "mainly composed of polyester" means that the polyester content in the resin is 50% by mass or more, preferably 80% by mass or more.

[0023] Polyester is a resin obtained by the condensation polymerization of monomer compositions mainly composed of dicarboxylic acids and diols. Here, "mainly" means that the total content of dicarboxylic acids and diols is 50 mol% or more.

[0024] The dicarboxylic acid may be an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, and 4,4'-diphenylsulfondicarboxylic acid. Examples of aliphatic dicarboxylic acids include adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Preferably, the dicarboxylic acid is an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid. These dicarboxylic acids may be used individually, in combination of two or more, or partially with oxyacids such as hydroxybenzoic acid.

[0025] Examples of diol components include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, and 2,2-bis(4-hydroxyethoxyphenyl)propane. Ethylene glycol is preferably used as the diol. These diols may be used individually or in combination of two or more.

[0026] Preferably, the polyesters include polyethylene terephthalate, copolymers of ethylene terephthalate and ethylene isophthalate, polyethylene naphthalate and its copolymers, polybutylene terephthalate and its copolymers, polybutylene naphthalate and its copolymers, polyhexamethylene terephthalate and its copolymers, polyhexamethylene naphthalate and its copolymers, and preferably contain at least polyethylene terephthalate. These polyesters may be used as homopolymers, or as copolymers or blends, to the extent that the effects of the present invention are not impaired. The resin constituting the first film may be obtained by acquisition or other means, or may be manufactured by known manufacturing methods.

[0027] The first film and the resin film described later may be films obtained by stretching the above-mentioned resin-containing film in one or two axial directions, from the viewpoint of improving mechanical strength.

[0028] The first film may contain a filler. By including a filler, the arithmetic mean roughness and glossiness on the surface on which the resin layer of the first film is placed can be easily adjusted to a desired range. The filler may be included in the resin constituting the first film in a kneaded state, or a matte layer containing the filler may be placed on a resin film that serves as a base material to constitute the first film containing the filler.

[0029] The filler contained in the first film may be inorganic or organic particles. Examples of inorganic particles include silicon dioxide (silica), barium sulfate, titanium dioxide, alumina, talc, Neuburg clay, clay, boehmite, magnesium carbonate, calcium carbonate, aluminum hydroxide, silicon nitride, aluminum nitride, and calcium zirconate. Examples of organic particles include silicone resin, melamine resin, acrylic resin, urea resin, polystyrene resin, styrene-acrylic copolymer, polyethylene resin, polycarbonate resin, and benzoguanamine resin. The average primary particle size of the filler may be, for example, 0.1 μm or more and 10 μm or less. Here, the average primary particle size refers to the arithmetic mean of the particle size of 10 randomly selected particles measured from scanning electron microscope images after the particles contained in the first film have been dispersed in a solvent by ultrasound, the aggregates have been released, and the solvent has been removed by drying.

[0030] By appropriately adjusting the average primary particle size, content, etc., of the filler contained in the first film, a first film having a desired arithmetic mean roughness and gloss can be constructed. For example, the arithmetic mean roughness and gloss can be increased by increasing the average primary particle size of the filler or by increasing the content of the filler. Furthermore, if the first film has a matte layer, the arithmetic mean roughness and gloss can be increased by increasing the content of the filler in the matte layer, reducing the thickness of the matte layer, or increasing the average primary particle size of the filler.

[0031] The first film may comprise a resin film (substrate) and a mat layer disposed on the resin film and containing a filler. The resin constituting the resin film is as previously described. The mat layer may contain a cured product of a curable resin in addition to the filler. The curable resin may contain, for example, melamine. Here, melamine refers to a resin formed by the addition condensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde, but the concept also includes methylolmelamine, which is the initial reaction product of melamine and formaldehyde, and alkylated methylolmelamine, which is its alkylated product. Modified melamines such as methylated methylolmelamine, propylated methylolmelamine, butylated methylolmelamine, and isobutylated methylolmelamine are also included as melamine. Melamine-modified products such as melamine (meth)acrylate are also included. In addition to melamine, the curable resin may further contain other resins such as acrylic resin, epoxy resin, alkyd resin, and polyester resin. The curable resin may be acrylic melamine, a mixture of melamine and acrylic resin; alkyd melamine, a mixture of melamine and alkyd resin; polyester melamine, a mixture of melamine and polyester resin; epoxy melamine, a mixture of melamine and epoxy resin; and so on. From the viewpoint of impact resistance, the curable resin may contain at least one of acrylic melamine and epoxy melamine, and may contain at least acrylic melamine. The acrylic melamine may contain an acrylic polyol as the acrylic resin, and the acrylic polyol may be a copolymer containing substructures derived from alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate.

[0032] A mat layer containing a filler can be formed by applying a mat layer composition, which includes a filler, a curable resin, and a liquid medium as needed, onto a resin film and curing it. The filler content in the mat layer composition may be, for example, 20 to 200 parts by mass, preferably 30 to 120 parts by mass, per 100 parts by mass of curable resin.

[0033] The first film may have a release treatment applied to at least the surface on which the resin layer is placed. The release treatment can be carried out by applying and drying a coating solution, prepared by dissolving or dispersing a release agent such as waxes, silicone wax, or silicone resin in a suitable solvent, to the surface of the first film using known means such as a roll coating method, a spray coating method, gravure printing, or screen printing. These release agents may also be contained in a mat layer containing a filler.

[0034] The release agent may contain at least waxes and may contain at least one compound selected from the group consisting of higher fatty acids, higher fatty acid amides, higher fatty acid esters, and hydroxy fatty acid esters.

[0035] If the mat layer contains a release agent, the content of the release agent, as its solid content, may be, for example, in the range of 0.5% to 40% by mass, preferably in the range of 1% to 20% by mass, and more preferably in the range of 5% to 10% by mass, relative to the solid content of the curable resin. By specifying the content of the release agent, a thermosetting release coating agent with excellent release properties can be obtained. In particular, the content of at least one compound selected from the group consisting of higher fatty acids, higher fatty acid amides, higher fatty acid esters, and hydroxy fatty acid esters, relative to the total solid content of the thermosetting release coating agent, may be, for example, 0.1% to 20% by mass, and preferably 5% to 10% by mass.

[0036] The average thickness of the first film may be, for example, 10 μm or more and 100 μm or less, preferably 20 μm or more, or 80 μm or less. The average thickness of the first film is calculated as the arithmetic mean of measuring the thickness at any 10 locations. Furthermore, if the first film includes a resin film and a mat layer, the average thickness of the resin film may be, for example, 10 μm or more and 100 μm or less, preferably 20 μm or more, or 80 μm or less. In addition, the average thickness of the mat layer may be, for example, 0.1 μm or more and 10 μm or less, preferably 1 μm or more, or 8 μm or less. The average thickness of the mat layer is calculated by subtracting the average thickness of the resin film from the average thickness of the first film, and the average thickness of the resin film is calculated as the arithmetic mean of measuring the thickness at any 10 locations on the resin film before the mat layer is formed.

[0037] The resin layer on one surface of the first film of the laminate may be a thermosetting resin layer or a photosensitive resin layer. If the resin layer is a thermosetting resin layer, a cured resin layer (e.g., solder resist) can be formed on the printed circuit board by placing the resin layer on the printed circuit board and heat-treating it. If the resin layer is a photosensitive resin layer, a patterned curable resin layer can be formed by placing the resin layer on the printed circuit board, exposing it to light, and developing it. Any curable resin composition, such as conventionally known solder resist inks, can be used without limitation to form the resin layer. Below, as one embodiment, an example of a curable resin composition that can be preferably used to form a photosensitive resin laminate will be described.

[0038] When a photosensitive curable resin composition is constructed, it may contain, for example, a carboxyl group-containing resin, a photopolymerizable compound, and a photocuring catalyst. The components constituting the curable resin composition will be described below.

[0039] The carboxyl group-containing resin is a component that polymerizes or crosslinks and hardens upon light irradiation, and its alkali-developable properties allow for the formation of a cured resin layer (e.g., solder resist) with a desired pattern through exposure and development. Various conventionally known photosensitive resins having carboxyl groups in their molecules can be suitably used as the carboxyl group-containing resin. By including the carboxyl group-containing resin in the curable resin composition, alkali-developable properties can be imparted to the resin layer formed from the curable resin composition. From the viewpoint of photocurability, the carboxyl group-containing resin preferably has an ethylenically unsaturated double bond in its molecule in addition to the carboxyl group. Furthermore, the photosensitive resin layer may contain a carboxyl group-containing resin without an ethylenically unsaturated double bond and a photopolymerizable compound. Examples of photopolymerizable compounds include compounds having an ethylenically unsaturated double bond, and may be compounds derived from (meth)acrylic acid or its derivatives.

[0040] Specific examples of carboxyl group-containing resins include the following compounds (which may be either oligomers or polymers):

[0041] (1) Carboxylate-containing resins obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene.

[0042] (2) Carboxyloid-containing urethane resins obtained by polyaddition reactions of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.

[0043] (3) Diisocyanates and bifunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin, and monocarboxylic acid compounds having ethylenically unsaturated double bonds such as (meth)acrylic acid, partially acid anhydride modified products, carboxyl group-containing dialcohol compounds and diol compounds obtained by polyaddition reactions.

[0044] (4) A carboxyl group-containing urethane resin obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, during the synthesis of the resin described in (2) or (3) above, and then (meth)acrylicating the terminal (meth) resin.

[0045] (5) A carboxyl group-containing urethane resin in which a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule is added to the resin of (2) or (3) above during synthesis and (meth)acrylicated at the terminal.

[0046] (6) A carboxyl group-containing resin obtained by reacting a bifunctional or polyfunctional epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chain.

[0047] (7) A carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin, in which the hydroxyl groups of a bifunctional epoxy resin are further epoxidized with epichlorohydrin, with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.

[0048] (8) A carboxyl group-containing polyester resin obtained by reacting a bifunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid, and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting primary hydroxyl group.

[0049] (9) A carboxyl group-containing resin obtained by reacting an epoxy compound having multiple epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl group of the resulting reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.

[0050] (10) A carboxyl group-containing resin obtained by reacting a reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0051] (11) A carboxyl group-containing resin obtained by reacting a reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0052] (12) A carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to any of the resins described in (1) to (11).

[0053] The acid value of the carboxyl group-containing resin may be, for example, 5 mg KOH / g or more and 150 mg KOH / g or less. If the acid value of the carboxyl group-containing resin is 5 mg KOH / g or more, the developability is further improved. Also, if the acid value is 150 mg KOH / g or less, the resolution is further improved. Preferably, the acid value of the carboxyl group-containing resin may be 10 mg KOH / g or more and 130 mg KOH / g or less. Note that the acid value of the carboxyl group-containing resin is a value measured in accordance with JIS K5601-1-2-1:1999.

[0054] The weight-average molecular weight of the carboxyl group-containing resin may vary depending on the resin skeleton, and may be, for example, between 2,000 and 150,000. A weight-average molecular weight of 2,000 or more can further improve the touch-drying properties and resolution of the coated film. Furthermore, a weight-average molecular weight of 150,000 or less can further improve developability and storage stability. The weight-average molecular weight of the carboxyl group-containing resin is preferably between 5,000 and 100,000. The weight-average molecular weight can be measured by gel permeation chromatography (GPC).

[0055] The content of the carboxyl group-containing resin may be, for example, 3% by mass or more and 60% by mass or less, based on the solid content in the photosensitive resin layer, and preferably 3% by mass or more and 55% by mass or less. If the content is 3% by mass or more, the strength of the cured product is further improved. If the content is 60% by mass or less, the viscosity becomes appropriate and the adhesion of the photosensitive resin layer is further improved.

[0056] The photosensitive resin layer may further contain a photopolymerizable compound. The photopolymerizable compound may be any compound having an ethylenically unsaturated double bond. Examples of photopolymerizable compounds include well-known and conventional photopolymerizable polymers, photopolymerizable oligomers, and photopolymerizable monomers, and mixtures thereof may also be used. Because the photopolymerizable compound has an ethylenically unsaturated double bond, it helps to insolubilize the cured resin layer, which has been cured by irradiation with active energy rays, in an alkaline aqueous solution.

[0057] Examples of photopolymerizable oligomers include unsaturated polyester oligomers and (meth)acrylate oligomers. Examples of (meth)acrylate oligomers include epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and bisphenol-type epoxy (meth)acrylate, as well as urethane (meth)acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and polybutadiene-modified (meth)acrylate. Examples of photopolymerizable monomers include alkyl(meth)acrylates such as 2-ethylhexyl(meth)acrylate and cyclohexyl(meth)acrylate; hydroxyalkyl(meth)acrylates such as 2-hydroxyethyl(meth)acrylate and 2-hydroxypropyl(meth)acrylate; mono- or di(meth)acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and Examples include polyhydric (meth)acrylates derived from polyhydric alcohols such as hydroxyethyl isocyanurate or their ethylene oxide or propylene oxide adducts; (meth)acrylates derived from ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth)acrylate and polyethoxydi(meth)acrylate of bisphenol A; (meth)acrylates derived from glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine (meth)acrylate. Photopolymerizable compounds may be used individually or in combination of two or more.

[0058] The content of the photopolymerizable compound in the photosensitive resin layer may be, for example, 5 parts by mass or more and 100 parts by mass or less, preferably 5 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the total amount of carboxyl group-containing resin. If the content is within the above range, the resolution and the strength of the cured product can be further improved.

[0059] The photosensitive resin layer may further contain a photopolymerization initiator as a photocuring catalyst. There are no particular restrictions on the photopolymerization initiator, and known and commonly used ones can be used.

[0060] Examples of photopolymerization initiators include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Bisacylphosphine oxides such as bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, and isopropyl pivaloylphenylphosphine ester. Monoacylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; acylphosphineates such as ethyl(2,4,6-trimethylbenzoyl)phenylphosphine; 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-H Hydroxyacetophenones such as droxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michlar's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone;Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl)]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, etc.; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl Thioxanthones such as thioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoate ethyl ester; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime); bis(η; 5Examples of photopolymerization initiators include titanosenes such as -2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1H-pyrrole-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, and tetramethylthiuram disulfide. The photopolymerization initiator may be used alone or in combination of two or more. Among the above, it is preferable to include at least one of bisacylphosphine oxides, monoacylphosphine oxides, and acylphosphines.

[0061] The content of the photopolymerization initiator in the photosensitive resin layer may be, for example, 1 to 30 parts by mass, preferably 2 to 25 parts by mass, per 100 parts by mass of the total amount of carboxyl group-containing resin. If the content is within the above range, the curability of the photosensitive resin layer will be improved, and the resolution will be even better.

[0062] The photosensitive resin layer may further contain a thermosetting resin. Examples of thermosetting resins include well-known and commonly used ones such as isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy resins, oxetane compounds, and episulfide resins. Among these, epoxy resins are preferred thermosetting resins.

[0063] Specific examples of epoxy resins include, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone-modified epoxy resin, and ε-caprolactone-modified epoxy resin. Thermosetting resins may be used individually or in combination of two or more types.

[0064] The content of the thermosetting resin in the photosensitive resin layer may be, for example, 5 to 150 parts by mass, preferably 10 to 80 parts by mass, based on 100 parts by mass of the total amount of carboxyl group-containing resin. If the content is within the above range, the solder heat resistance of the cured product will be better, and the various properties, especially the insulation reliability, when used as a solder resist for printed circuit boards will also be better.

[0065] If the photosensitive resin layer contains a thermosetting resin, it may further contain a thermosetting catalyst. By including a thermosetting catalyst, the thermosetting reaction can be accelerated, and properties such as adhesion, chemical resistance, and heat resistance can be further improved. Examples of such thermosetting catalysts include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacate dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2E4MZ, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all trade names for imidazole compounds) manufactured by Shikoku Chemicals, Inc., and U-CAT(registered trademark) 3503N and U-CAT3502T (both trade names for dimethylamine blocked isocyanate compounds), DBU, DBN, U-CATSA102, and U-CAT5002 (all bicyclic amidine compounds and their salts) manufactured by Sunapro Co., Ltd. Furthermore, s-triazine derivatives such as guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2,4-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-s-triazine isocyanuric acid adduct may also be used, and preferably these compounds that also function as adhesion imparters may be used in combination with the thermosetting catalyst. The thermosetting catalyst may be used alone or in combination of two or more types.

[0066] The content of the thermosetting catalyst in the photosensitive resin layer may be, for example, 0.1 parts by mass or more and 20 parts by mass or less, preferably 0.5 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of the total amount of thermosetting resin.

[0067] A photosensitive resin layer can be formed by applying a photosensitive resin composition containing the above-mentioned components onto a first film. The photosensitive resin composition forming the photosensitive resin layer may contain an organic solvent. By including an organic solvent, the above-mentioned components can be uniformly dissolved or dispersed, and the viscosity can be adjusted to a level suitable for application. Examples of organic solvents include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, chloroform, and methylene chloride. The content of the organic solvent in the photosensitive resin composition can be appropriately set according to the desired viscosity.

[0068] The photosensitive resin layer may further contain other additives besides the components mentioned above, as long as they do not impair the effects of the present invention. Examples of additives include known inorganic fillers, organic fillers such as silicone powder, nylon powder, and fluorine powder, well-known and conventional thickeners such as fine silica, organic bentonite, and montmorillonite, compounds having polar groups such as carboxyl groups, hydroxyl groups, and acid esters, copolymers containing acid groups, wetting and dispersing agents such as hydroxyl group-containing polycarboxylic acid esters, defoaming agents and / or leveling agents such as silicone-based, fluorine-based, and polymer-based agents, and fiber reinforcing materials such as glass fibers, carbon fibers, and boron nitride fibers. Furthermore, if necessary, it may also contain well-known and conventional adhesion promoters, ultraviolet absorbers, polymerization inhibitors, silane coupling agents such as imidazole-based, thiazole-based, and triazole-based agents, plasticizers, foaming agents, flame retardants, antistatic agents, anti-aging agents, antibacterial and antifungal agents, colorants, antioxidants, and the like.

[0069] The photosensitive resin composition is obtained by dissolving or dispersing each of the above-mentioned components using a mixer, such as a disper, kneader, three-roll mill, or bead mill. The obtained photosensitive resin composition can be applied to a first film, and a laminate can be prepared by removing at least a portion of the organic solvent as needed to form a photosensitive resin layer. The viscosity of the photosensitive resin composition may be, for example, 0.01 Pa·s to 100 Pa·s at 25°C, preferably 0.1 Pa·s or more, or 10 Pa·s or less. The surface tension of the photosensitive resin composition may be, for example, 20 mN / m to 50 mN / m at 20°C, preferably 30 mN / m or more, or 45 mN / m or less.

[0070] The photosensitive resin layer can be formed by applying a photosensitive resin composition to a substantially uniform thickness using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc., and then drying it. The drying conditions are usually 30°C to 150°C for 0.5 to 30 minutes. There are no particular restrictions on the coated film thickness, but generally, the film thickness after drying is appropriately selected within the range of, for example, 0.5 μm to 200 μm, preferably 1 μm to 150 μm.

[0071] The laminate may further include a second film on the side of the resin layer opposite to the first film. The addition of the second film prevents dust and other debris from adhering to the surface of the resin layer and improves handling.

[0072] As the second film (also called a protective film), for example, polyester film, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc., can be used. It is preferable to select a material for the second film such that the adhesive strength between the second film and the resin layer is less than the adhesive strength between the first film and the resin layer. Furthermore, to facilitate the peeling of the second film when using the laminate, a release treatment may be applied to the surface of the second film that is in contact with the resin layer.

[0073] The thickness of the second film is not particularly limited, but is generally selected appropriately depending on the application, within the range of 5 μm to 150 μm.

[0074] Pattern formation method A pattern of cured material can be formed on a substrate using the laminate described above. The pattern formation method includes bonding the laminate to the substrate with the resin layer facing the substrate, exposing the resin layer through a first film of the laminate, removing the first film and developing the laminate to form a pattern including a cured resin layer on the substrate, and curing the patterned cured resin layer by light irradiation, heat, or both to form a cured material.

[0075] As substrates, in addition to pre-circuited printed circuit boards and flexible printed circuit boards, all grades (FR-4, etc.) of copper-clad laminates, polyimide films, PET films, glass substrates, ceramic substrates, wafers, etc. can be used, as well as composite materials such as paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / nonwoven fabric-epoxy resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, etc.

[0076] A pattern formation method using a laminate comprising a second film will be described. First, i) the second film is peeled off from the laminate to expose the resin layer, ii) the resin layer of the laminate is placed facing the substrate and bonded to the substrate, iii) exposure is performed on the first film of the laminate, iv) the first film is removed and developed to form a patterned cured resin layer on the substrate, and v) the patterned cured resin layer is further cured by light irradiation, heat, or both to form a cured product. A patterned cured product is formed on the substrate as a result.

[0077] To bond the resin layer of the laminate to the substrate, it is sufficient that the substrate and the resin layer of the laminate are in close contact, and there are no particular limitations, but it is preferable to bond them under pressure and heat using a vacuum laminator or the like. By using such a vacuum laminator, the resin layer adheres closely to the circuit board, so there is no inclusion of air bubbles, and the ability to fill holes in the substrate surface is also improved. The pressurizing conditions are preferably 0.1 MPa to about 2.0 MPa, and the heating conditions are preferably 40°C to 200°C.

[0078] Exposure (irradiation with active energy rays) is performed on the first film of the laminate. In this process, only the exposed resin layer hardens. The exposure process is not particularly limited; for example, it may be selectively exposed with active energy rays through a photomask with a desired pattern formed on it using a contact (or non-contact) method, or the desired pattern may be exposed with active energy rays using a direct writing device.

[0079] The exposure machine used for active energy ray irradiation can be any device capable of irradiating active energy rays that include at least active energy rays (light) in the range of 350 nm to 450 nm, and is equipped with high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, etc. Furthermore, a direct writing device (for example, a laser direct imaging device that directly draws images with a laser using CAD data from a computer) can also be used. The laser light source for the direct writing device can be either a gas laser or a solid-state laser. The laser light source only needs to be capable of irradiating laser light that includes light in the range of 350 nm to 450 nm, and may also be capable of irradiating laser light with a maximum wavelength in the range of 350 nm to 410 nm. The exposure amount for image formation varies depending on the film thickness, etc., but is generally 20 mJ / cm². 2 More than 800mJ / cm 2 Preferably 20 mJ / cm² 2 More than 600mJ / cm 2 It can be within a certain range. Furthermore, exposure may be performed using either parallel or scattered light.

[0080] After exposure, the first film is peeled off and developed to form a patterned cured resin layer on the substrate. The development process is not particularly limited, and methods such as dipping, showering, spraying, and brushing can be used. As the developer, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines, or organic solvents such as 1,1,1-trichloroethane can be used.

[0081] Next, the patterned cured resin layer is cured by irradiation with active energy rays (light), heat, or both to form a cured product. This step is called main curing or additional curing, and it promotes the polymerization of unreacted monomers in the exposed cured resin layer, and further, it can thermally cure the carboxyl group-containing photosensitive resin and the thermosetting resin (e.g., epoxy resin) to reduce the amount of remaining carboxyl groups. Irradiation with active energy rays can be carried out in the same manner as the exposure described above, but it is preferable to carry it out under conditions with a stronger irradiation energy than that used during exposure. For example, 500 mJ / cm². 2 More than 3000mJ / cm 2 The following conditions may be met. Furthermore, thermal curing can be carried out under heating conditions of 100°C to 200°C for approximately 20 to 90 minutes. It is preferable to perform thermal curing after photocuring. Performing photocuring first suppresses the flow of the resin even during thermal curing.

[0082] In the pattern formation method, the first film has a predetermined arithmetic mean roughness Ra, which allows for the formation of a pattern with excellent resolution even when exposure is performed through the first film. The resolution of the formed pattern may be such that, for example, the aperture diameter of the opening formed in an 80 μm diameter SRO pattern is 75 μm or more and 85 μm or less.

[0083] cured product The cured product is included in the pattern formed by the pattern forming method described above. The cured product may be a cured product of a photosensitive resin layer, and may be a cured product with a roughened surface and a matte finish.

[0084] Electronic components In one embodiment, the present invention may include electronic components having a cured product. Here, "electronic component" means a component used in an electronic circuit, and includes active components such as printed circuit boards, especially flexible printed circuit boards, transistors, light-emitting diodes, and laser diodes, as well as passive components such as resistors, capacitors, inductors, and connectors. The cured resin layer is suitable as a solder resist for these components.

[0085] In other aspects, the present invention also includes the use of the laminate (dry film) in a pattern forming method for forming a pattern including a cured resin layer on a substrate, the laminate (dry film) used in the pattern forming method, the use of the laminate (dry film) in the manufacture of a cured product included in a pattern formed by the pattern forming method, the laminate (dry film) used in the manufacture of a cured product included in a pattern formed by the pattern forming method, the use of the laminate (dry film) in the manufacture of an electronic component including the cured product, and the laminate (dry film) used in the manufacture of an electronic component including the cured product. [Examples]

[0086] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0087] [Synthesis Example 1] Preparation of Acrylic Polyol (A) In a reaction vessel equipped with a stirrer, thermometer, and reflux condenser, 150 parts by mass of xylene were charged, and the reaction temperature was raised to 105°C while blowing nitrogen gas into the xylene. Next, a mixture of 87.5 parts by mass of methyl methacrylate, 12.5 parts by mass of 2-hydroxyethyl methacrylate, and 0.5 parts by mass of perbutyl O was added dropwise over 5 hours while maintaining the reaction temperature at 105°C. Subsequently, the mixture was diluted with methyl ethyl ketone to obtain an acrylic polyol (A) solution with a solid content of 45% by mass. The obtained methyl methacrylate / 2-hydroxyethyl acrylate-based acrylic polyol (A) had a hydroxyl value of 60 mgKOH / g, a glass transition temperature of 98°C, and a weight-average molecular weight of 34,000.

[0088] [Manufacturing Example 1] 177.8 parts by mass (45% solids) of the acrylic polyol (A) solution obtained above, 20 parts by mass of Cymel 303LF (trade name, manufactured by Ornex Japan Co., Ltd., full ether type methylated melamine resin, 100% solids) as a crosslinking agent, 100 parts by mass of Techpolymer SSX-101 (trade name, manufactured by Sekisui Chemical Co., Ltd., resin-based filler, volume average particle size D50 = 1.5 μm) as a filler (particle), and 7.0 parts by mass (100% solids) of stearic acid as a release agent were mixed and stirred to form the main component.

[0089] p-toluenesulfonic acid (100% solids by mass) was diluted with propylene glycol monomethyl ether acetate to a solids content of 22% by mass to prepare a curing agent. The main component and the curing agent were mixed in a mass ratio of 100:10.4, and diluted with 50 parts by mass of toluene for every 100 parts by mass of the total main component and curing agent to prepare a coating liquid for mat layer formation.

[0090] Support film 1 of manufacturing example 1 was produced by coating a resin film (T60, manufactured by Toray Industries, Inc., average thickness 38 μm) with a bar coater using a roll-to-roll method to achieve an average film thickness of 2 μm after drying, and then drying at 100°C for 30 seconds, 140°C for 30 seconds, and 100°C for 20 seconds to form a mat layer on the resin film.

[0091] [Manufacturing Example 2] Support film 2 for manufacturing example 2 was prepared in the same manner as in manufacturing example 1, except that 30 parts by mass of FB-3SDC (product name, manufactured by Denka Co., Ltd., silica filler, volume average particle size D50 = 3.1 μm) were used as filler, and the average thickness of the mat layer was set to 4 μm.

[0092] [Manufacturing Example 3] Support film 3 for Production Example 3 was prepared in the same manner as in Production Example 1, except that 25 parts by mass of ACEMATT OK-607 (trade name, manufactured by Evonik, silica filler, volume average particle size D50 = 4.4 μm) was used as the filler, the amount of release agent added was 15 parts by mass, and the average thickness of the mat layer was 5 μm.

[0093] As support film 4, a polyethylene terephthalate film PTHA (product name, manufactured by Unitika Ltd., average thickness 25 μm) with filler mixed in was prepared.

[0094] Evaluation of surface roughness For support films 1 to 3, the surface roughness of the support film was measured on the surface where the matte layer was formed, and for support film 4, it was measured on one surface, in accordance with JIS B0601-1994. Specifically, a shape-measuring laser microscope (VX-100, manufactured by Keyence Corporation) was used for measurement in shape-measuring mode. The measurement method involved launching the observation application (VK-H1XV), placing the sample to be measured on the XY stage, and focusing with a 100x objective lens in shape-measuring mode using autofocus. The Z-axis was controlled as needed to adjust the focus to the optimal position. Observation images were acquired in either automatic or manual measurement mode. Next, the analysis application (VK-H1XA) was launched and measurement was started. As for the measurement conditions, the evaluation range was the entire field of view, and the surface roughness Ra values ​​were measured at 10 equally spaced locations from the center of the sample outwards, and the arithmetic mean of these values ​​was taken as the arithmetic mean roughness Ra. The results are shown in Table 2.

[0095] Glossiness evaluation For support films 1 to 3, the glossiness Gs(60°) of the support film was measured on the surface where the matte layer was formed, and for support film 4, it was measured on one surface, in accordance with JIS Z 8741-1997. Specifically, the glossiness Gs(60°) of the support film surface was measured using a digital angle-bending gloss meter (Micro-Tri-Gloss, BYK Gardener). Five measurements were taken, and the arithmetic mean of the measured values ​​was taken as the glossiness Gs(60°) of the support film. The results are shown in Table 2.

[0096] Evaluation of contact angle For support films 1 to 3, the contact angle with water was measured on the surface where the mat layer was formed, and for support film 4, it was measured on one surface using a DropMaster DM300 contact angle meter and a FAMAS interface measurement and analysis integrated system (both manufactured by Kyowa Interface Science Co., Ltd.). Specifically, the contact angle with water was measured at 10 arbitrary locations on each support film as follows, and the arithmetic mean of the measured values ​​was taken as the contact angle with water for each support film. The results are shown in Table 2.

[0097] The interface measurement and analysis integrated system was started, and the CA / PD controller was launched. At that time, "Standard" was selected for "Field of View" on the controller screen. Next, water was placed in a plastic syringe, a stainless steel needle (gauge 22) was attached to the tip, and the water was dropped onto the evaluation surface. During the dropping process, it was confirmed that the camera attached to the contact angle meter was in focus. Immediately after dropping the water, the "Measure" button on the controller screen was pressed to start the measurement. The water used for the measurement was: pure water The treated water was prepared using a device (Purelight PRO-0250-003 manufactured by Organo Corporation) and was ion-exchanged water with a water quality of 0.7 μS / cm or less. The water drop volume was 2 μL, the measurement temperature was 20°C, and the lens field of view was set to standard.

[0098] [Synthesis Example 2] Preparation of Carboxylic Acid-Containing Resin Varnish Into an autoclave equipped with a thermometer, a nitrogen introduction device also serving as an alkylene oxide introduction device, and a stirring device, 119.4 g of a novolac-type cresol resin (manufactured by Aica Kogyo Co., Ltd., trade name "Shonol CRG951", OH equivalent: 119.4), 1.19 g of potassium hydroxide, and 119.4 g of toluene were charged. While stirring, the system was purged with nitrogen and heated to raise the temperature. Next, 63.8 g of propylene oxide was gradually dropped in, and the reaction was carried out at a temperature of 125 °C to 132 °C and a pressure of 0 kg / cm 2 to 4.8 kg / cm 2 for 16 hours. After that, 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution cooled to room temperature to neutralize potassium hydroxide, and a propylene oxide reaction solution of a novolac-type cresol resin with a non-volatile content of 62.1% and a hydroxyl value of 182.2 g / eq was obtained. This was such that an average of 1.08 moles of alkylene oxide was added per equivalent of phenolic hydroxyl group. Next, 293.0 g of the obtained propylene oxide reaction solution of the novolac-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube. Air was blown in at a rate of 10 ml / min, and the reaction was carried out at 110 °C for 12 hours while stirring. The water generated by the reaction was distilled off as an azeotropic mixture with toluene, and 12.6 g of water was distilled off. After that, it was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Then, while distilling off toluene by replacing it with 118.1 g of diethylene glycol monoethyl ether acetate using an evaporator, a novolac-type acrylate resin solution was obtained. Next, 332.5 g of the obtained novolac-type acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube. Air was blown in at a rate of 10 ml / min, and while stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added, and the reaction was carried out at 95 °C to 101 °C for 6 hours. In this way, a carboxyl group-containing resin varnish with a solid content acid value of 88 mgKOH / g, a solid content of 65%, and a weight average molecular weight of 2,000 was obtained.

[0099] Preparation of photosensitive resin composition The components, including the carboxyl group-containing resin varnish obtained as described above, were blended in the amounts (parts by mass, solid content) shown in Table 1 below. After pre-mixing with a stirrer, the mixture was kneaded in a three-roll mill to prepare a photosensitive resin composition. The obtained photosensitive resin composition was diluted with propylene glycol monomethyl ether acetate to obtain a coating solution of the photosensitive resin composition, with a viscosity of 200 mPa·s as measured by a rotary viscometer (25°C, 5 rpm).

[0100] [Table 1]

[0101] The components listed in Table 1 are as follows: Photopolymerizable compound: Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA Thermosetting resin 1: Bisphenol A type epoxy resin, manufactured by DIC Corporation, EPICLON840-S Thermosetting resin 2: Biphenol novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd. (NC-3000H) Photopolymerization initiator: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, manufactured by BASF Japan Ltd., IRGACURE OXE02 Barium sulfate: Manufactured by Sakai Chemical Industry Co., Ltd., B-30 Spherical silica: AdmaFine SO-E2, manufactured by Admatex Co., Ltd. Melamine: Manufactured by Nissan Chemical Corporation Coloring agent 1: CIPigment Yellow 147 Colorant 2:CIPigment Blue 15:3 Solvent: Diethylene glycol monoethyl ether acetate

[0102] Examples 1 to 2, Comparative Examples 1 to 2 The coating solution of the photosensitive resin composition obtained above was applied to the matte layers of support films 1 to 3, or to support film 4, using an applicator to a coating thickness of approximately 50 μm, forming a resin layer with a drying thickness of 20 μm, thereby creating a laminate.

[0103] Wettability evaluation After applying a photosensitive resin coating solution to each support film to a thickness of approximately 50 μm, the state of the coating layer was observed after 30 seconds. The ratio (%) obtained by subtracting the film thickness near the center from the film thickness at the left and right edges relative to the coating direction, and dividing this value by the film thickness near the center, was calculated and evaluated according to the evaluation criteria below. The results are shown in Table 2.

[0104] Evaluation Criteria A: It was less than 20%. B: It was 20% or more.

[0105] Resolution evaluation The copper foil surface of an FR-4 copper-clad laminate (100mm x 150mm x 0.8mmt, copper foil on both sides, copper foil thickness 18μm on both sides) was chemically polished at an etching rate of 1μm using a CZ-8101B manufactured by MEC Corporation. The resin layers of each laminate obtained in the examples and comparative examples were then bonded to the chemically polished copper foil surface so that they were in contact with it. Next, a two-chamber vacuum laminator (CVP-300 manufactured by Nikko Materials Co., Ltd.) was used, with the first chamber conditions set to a temperature of 80°C, a pressure of 0.4MPa, and a time of 30 seconds, and the second chamber conditions set to a temperature of 80°C and a pressure of 8kgf / cm². 2 The copper-clad laminate and the laminate were laminated for 60 seconds, and the integrated exposure was 250 mJ / cm using a direct imaging exposure machine (light source: high-pressure mercury lamp). 2A φ80 μm SRO (solder resist aperture) pattern was exposed from the first film side. Then, the first film of the laminate was peeled off and developed with 1% sodium carbonate at 30°C for 90 seconds. After that, the uncured resin layer was removed and patterning was performed. Subsequently, the patterned resin composition was irradiated with an exposure dose of 1000 mJ / cm2 in a UV conveyor furnace equipped with a high-pressure mercury lamp, and then heated at 150°C for 60 minutes to form an additionally cured film, thereby preparing a test substrate. The aperture diameter was measured by observing the aperture at a magnification of 800x using a scanning electron microscope (SEM; JEOL Ltd. JSM6610LV), and evaluated according to the evaluation criteria below. The aperture diameter was measured at 10 arbitrary locations on the SRO pattern film, and the arithmetic mean was taken as the aperture diameter. The results are shown in Table 2.

[0106] Evaluation Criteria A: The aperture diameter was between 75 μm and 85 μm. B: The aperture diameter was less than 75 μm.

[0107] Matte finish evaluation The reflected image of the fluorescent lamp projected onto the cured resin layer was visually observed and evaluated according to the evaluation criteria below. The results are shown in Table 2.

[0108] Evaluation Criteria A: The reflected image of the fluorescent light could not be identified. B: I could vaguely see the reflected image of the fluorescent light. C: The reflected image of the fluorescent light was clearly visible.

[0109] [Table 2]

[0110] By setting the arithmetic mean roughness Ra of the surface on which the resin layer of the first film is placed to 0.10 μm or more and 0.22 μm or less, and the glossiness Gs(60°) to 60 or less, a laminate with a resin layer having good film thickness uniformity can be constructed. Furthermore, the cured product formed using the laminate has a roughened surface and exhibits a good matte finish.

Claims

1. The invention comprises a first film and a resin layer disposed on one surface of the first film, The first film has an arithmetic mean roughness Ra of 0.10 μm or more and 0.22 μm or less on the surface where the resin layer is arranged. A laminate in which the glossiness Gs (60°) on the surface on which the resin layer is arranged is 60 or less.

2. The laminate according to claim 1, wherein the first film has a contact angle with water on the surface on which the resin layer is arranged, which is 90° or less at 20°C.

3. The laminate according to claim 1, wherein the first film comprises a filler.

4. The laminate according to claim 1, wherein the first film comprises a base material and a mat layer disposed on the base material and containing a filler, and the resin layer is disposed on the mat layer.

5. The laminate according to claim 4, wherein the mat layer further comprises a release agent.

6. The laminate according to any one of claims 1 to 5, wherein the resin layer is photosensitive.

7. The laminate according to claim 6 is bonded to the substrate with the resin layer facing the substrate, Exposing the resin layer through the first film of the laminate, A pattern forming method comprising removing the first film and forming a pattern on the substrate that includes the cured resin layer.

8. A cured product included in a pattern formed by the pattern forming method described in claim 7.

9. An electronic component comprising the cured product described in claim 8.

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