Dry film and method for producing the same

Abstract

To provide a method for producing a dry film in which a protective film and a resin composition layer are adequately brought into close contact with each other regardless of prescription of the resin composition, by a roll-to-roll method.SOLUTION: A method for producing a dry film by a roll-to-roll method includes a step (a) of coating a surface of a first film with a resin composition and obtaining a first laminate, a step (b) of drying the resin composition of the first laminate, and (c) a step of laminating the first laminate and a second film so that the resin composition after the drying and the second film are brought into contact with each other, and obtaining a second laminate, where such a temperature as the first laminate and the second film are laminated in the step (c) is adjusted to 40 to 75°C, and the pressure is adjusted to 0.2 to 0.7 MPa.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a dry film and a method for producing the same. [Background technology]

[0002] Conventionally, dry films (laminated films) have been used as one of the means for forming protective films and insulating layers such as solder resists and interlayer insulating layers provided on printed wiring boards used in electronic devices and the like (for example, Patent Document 1). Dry films have a resin composition layer obtained by applying an appropriate resin composition onto a support film and then drying the resin composition, and are generally distributed on the market in a state in which a protective film is further laminated on the surface opposite to the support film (i.e., the surface of the resin composition layer) in order to protect the resin composition layer. A printed wiring board having the above-mentioned protective film and insulating layer can be manufactured by attaching the resin composition layer of the dry film to a substrate and performing patterning and curing treatment.

[0003] A typical dry film having two films, a protective film and a support film, and a resin composition layer between these films is manufactured by first applying a resin composition onto a support film, then drying in a drying oven to form a dried resin composition (resin composition layer) on the support film, and then laminating a protective film onto the surface of the resin composition layer. Industrially, the dry film is manufactured in a long sheet shape, and is wound up into a roll shape simultaneously with or after the manufacturing. For example, the dry film is manufactured in a long shape with a width of 1 m and a length of 8000 m, and is wound up into a roll shape simultaneously with or after the manufacturing.

[0004] The manufacture and winding of such a dry film is generally carried out by the so-called roll-to-roll method, in which a constant tension is applied to the support film from the unwinding of the support film to the winding of the manufactured dry film, during which the application of the resin composition to the support film and the lamination of a protective film onto the resin composition layer are continuously carried out.

[0005] However, in such a roll-to-roll method, unless the temperature and pressure when laminating the protective film are appropriately adjusted, the protective film is not properly laminated on the resin composition layer (i.e., the protective film does not properly adhere to the resin composition layer). In addition, in the roll-to-roll method, since the support film is wound while tension is applied, if the adhesion between the protective film and the resin composition layer is excessive, the dry film produced will curl in the machine direction in relation to the flexibility of each film and the resin composition layer, resulting in a problem of reduced handleability. Conventionally, it has been reported that such excessive adhesion between the protective film and the resin composition layer can be suppressed by devising the formulation of the resin composition that forms the resin composition layer (for example, Patent Document 2). However, in such a technology, the formulation of the resin composition that forms the resin composition layer is limited, and there were cases where it was not possible to provide a dry film that forms a protective film or an insulating layer having desired properties. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2015-10179 A [Patent Document 2] Patent Publication No. 2022-28036 Summary of the Invention [Problem to be solved by the invention]

[0007] Under these circumstances, a technical problem exists to provide a method for producing a dry film in which a protective film and a resin composition layer are appropriately adhered to each other by a roll-to-roll process, regardless of the formulation of the resin composition.

[0008] Therefore, the present invention has an object to provide a method for producing a dry film in which a protective film and a resin composition layer are appropriately adhered to each other by a roll-to-roll process, regardless of the formulation of the resin composition. Another object of the present invention is to provide a dry film obtained by such a production method. [Means for solving the problem]

[0009] As a result of intensive research, the inventors have found that in a method for producing a dry film including the steps of (a) applying a resin composition to the surface of a first film to obtain a first laminate, (b) drying the resin composition of the first laminate, and (c) laminating the first laminate and a second film so that the dried resin composition and the biaxially oriented polypropylene are in contact with each other to obtain a second laminate, the above-mentioned problems can be solved even when the steps (a) to (c) are performed in a series of roll-to-roll processes by adjusting the temperature at which the first laminate and the second film are laminated in the step (c) to 40 to 75°C and the pressure to 0.2 to 0.7 MPa. The present invention is based on this finding. That is, the gist of the present invention is as follows.

[0010] [1] A method for producing a dry film, comprising the steps of: (a) applying a resin composition to a surface of a first film to obtain a first laminate; (b) drying the resin composition of the first laminate; and (c) a step of laminating the first laminate and a second film so that the dried resin composition is in contact with the second film to obtain a second laminate; Including, In the step (c), the temperature for laminating the first laminate and the second film is 40 to 75° C., and the pressure is 0.2 to 0.7 MPa. The steps (a) to (c) are carried out in a continuous roll-to-roll process. The manufacturing method. [2] The method according to [1], wherein the first film is a polyethylene terephthalate film. [3] The method according to [1] or [2], wherein the second film is a biaxially oriented polypropylene film. [4] The method according to any one of [1] to [3], wherein the thickness of the resin composition after drying in the step (b) is 10 to 200 μm. [5] The method according to any one of [1] to [4], wherein the amount of the solvent contained in the resin composition after drying in the step (b) is 5 mass% or less based on the total mass of the resin composition after drying. [6] A dry film obtained by the manufacturing method according to any one of [1] to [5]. Effect of the Invention

[0011] According to the present invention, it is possible to provide a method for producing a dry film in which a protective film and a resin composition layer are appropriately adhered to each other by a roll-to-roll process, regardless of the formulation of the resin composition.

[0012] [Dry film manufacturing method] According to one aspect of the present invention, there is provided a method for producing a dry film (hereinafter, also referred to as the "production method of the present invention"). The production method of the present invention includes the steps of: (a) applying a resin composition to a surface of a first film to obtain a first laminate; (b) drying the resin composition of the first laminate; and (c) a step of laminating the first laminate and a second film so that the dried resin composition is in contact with the second film to obtain a second laminate; Including, In the step (c), the temperature for laminating the first laminate and the second film is 40 to 75° C., and the pressure is 0.2 to 0.7 MPa. The method is characterized in that the steps (a) to (c) are carried out in a continuous roll-to-roll system. The steps (a) to (c) will be described in detail below.

[0013] <Process (a)> In the step (a), a resin composition is applied to the surface of a first film to obtain a first laminate.

[0014] The first film has the role of supporting the resin composition layer in the dry film obtained by the manufacturing method of the present invention (hereinafter also referred to as the "dry film of the present invention"), i.e., the role of a support film, and the resin composition is applied to the first film and dried to form the resin composition layer.

[0015] The first film can be used without any particular limitation as long as the effects of the present invention are achieved, and examples of the first film include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate, films made of thermoplastic resins such as polyimide films, polyamideimide films, polypropylene films, and polystyrene films, and surface-treated paper. Among these, from the viewpoints of heat resistance, mechanical strength, and handleability, polyester films are preferably used, and PET films are more preferably used. Moreover, these films may be used alone or in combination of two or more to form a laminate.

[0016] The first film may be surface-treated as necessary. The type of surface treatment is not particularly limited, but examples thereof include release treatment, sputtering, and ultra-thin copper foil formation.

[0017] From the viewpoint of improving mechanical strength, the above-mentioned thermoplastic resin film is preferably a film stretched in a uniaxial or biaxial direction.

[0018] The thickness of the first film is not particularly limited as long as the effects of the present invention are achieved, and can be appropriately selected depending on the application of the dry film of the present invention, for example, 10 to 150 μm, preferably 25 to 50 μm. When the thickness of the first film is 25 μm or more, the dry film of the present invention has particularly excellent handleability, and when it is 50 μm or less, the dry film of the present invention is economically excellent during production.

[0019] The method of applying the resin composition onto the first film can be a well-known method for producing a dry film. For example, the resin composition is diluted with a solvent such as an organic solvent as necessary to adjust the viscosity to an appropriate level, and then applied to the first film in a uniform thickness by a coating method such as a slot die coater, MB coater, gravure coater, comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, or spray coater. Among these, a slot die coater, MB coater, or gravure coater is preferably used.

[0020] The viscosity of the resin composition is not particularly limited as long as the effect of the present invention is achieved, and can be appropriately set according to the film thickness after drying of the resin composition. Specifically, when the film thickness after drying of the resin composition is 30 μm or less, the viscosity of the resin composition is preferably adjusted to 200 mPa·s to 1000 mPa·s. When the film thickness after drying of the resin composition is more than 30 μm, the viscosity of the resin composition is preferably adjusted to more than 1000 mPa·s. By setting the resin composition in such a range, the surface of the resin composition applied on the first film can be made in a good condition. The lower the viscosity of the resin composition, the higher the line speed during application can be increased, thereby increasing productivity, but color unevenness is likely to occur during drying. On the other hand, the higher the viscosity of the resin composition, the less likely color unevenness occurs during drying, but if the line speed during application is increased, streaks are likely to occur, so the line speed cannot be increased and productivity decreases. Therefore, the viscosity of the resin composition is appropriately adjusted according to the desired productivity, the allowable degree of color unevenness and streaks, etc.

[0021] There is no particular restriction on the coating thickness of the resin composition, but preferably, the coating thickness of the resin composition is appropriately adjusted so that the coating thickness of the resin composition after drying in the step (b) described below is in the range of 1 to 200 μm. Particularly preferably, the coating thickness of the resin composition is appropriately adjusted so that the coating thickness of the resin composition after drying is in the range of 10 to 200 μm. By making the coating thickness of the resin composition after drying 10 μm or more, not only can the adhesion between the protective film and the resin composition layer in the dry film be made appropriate, but also curl in the machine direction can be suppressed, even when the dry film of the present invention is produced by a roll-to-roll method.

[0022] <Process (b)> In step (b), the resin composition of the first laminate obtained in step (a) is dried to form a layer of the dried resin composition (hereinafter, also simply referred to as a "resin composition layer"). In step (b), the first laminate including the resin composition may be dried as a whole.

[0023] The conditions for drying the resin composition may be well-known and commonly used conditions for producing a dry film. The drying temperature may be, for example, 60 to 150°C. The drying time may be, for example, 10 seconds to 20 minutes, preferably 10 seconds to 2 minutes. In a preferred embodiment, the drying temperature and drying time are set so that the amount of solvent (residual solvent amount) contained in the resin composition after drying (i.e., the resin composition layer) relative to the total mass of the resin composition before drying is preferably 0.3 to 5.0 mass%, particularly preferably 0.5 to 3.0 mass%. By making the amount of residual solvent in the resin composition layer 5 mass% or less, deformation of the resin composition during lamination and protrusion from the first and second films due to insufficient drying of the resin composition layer can be suppressed. In addition, when the amount of residual solvent in the resin composition layer is 5 mass% or less, the dry film of the present invention does not fall under the category of "first-class organic solvent, etc." in Article 1, item 3, subparagraph (c) of the Organic Solvent Poisoning Prevention Regulations, so that the dry film of the present invention can be used without using special equipment, etc. On the other hand, when the amount of the residual solvent in the resin composition layer is 0.3% by mass or more, good adhesion between the resin composition layer and the second film can be achieved when the two are laminated together.

[0024] The resin composition of the first laminate can be dried, for example, using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (a method in which hot air in the dryer is brought into countercurrent contact using a heat source that uses steam for air heating, and a method in which hot air is blown onto a support from a nozzle).

[0025] <Process (c)> In step (c), the laminate on which the resin composition layer is formed in step (b) is laminated with a second film under conditions of a temperature of 40 to 75° C. and a pressure of 0.2 to 0.7 MPa to obtain a second laminate. The laminate and the second film are laminated so that the resin composition layer of the laminate and the second film are in contact with each other (i.e., on the surface of the resin composition layer opposite to the support film).

[0026] The second film has a role of preventing foreign matter such as dust from adhering to the surface of the resin composition layer of the dry film, and a role of preventing physical damage to the surface of the resin composition layer and improving handling when the dry film is slit, i.e., a role of a protective film. In addition, when the dry film of the present invention is laminated by heating or the like so that the resin composition layer side of the dry film is in contact with a base material such as a substrate to be integrally molded, the second film is usually peeled off from the resin composition layer before lamination.

[0027] The second film can be used without any particular limitation as long as the effects of the present invention are achieved, and for example, polypropylene film, polyethylene film, polytetrafluoroethylene film, surface-treated paper, etc. can be used. In the roll-to-roll method, since thermal lamination is performed while applying a certain tension, it is preferable that the film has a small stretch rate. From this viewpoint, among these, polypropylene film is preferably used, and biaxially oriented polypropylene film (OPP) is particularly preferably used from the viewpoints of tear resistance, transparency, and heat resistance.

[0028] The second film preferably has adhesiveness. The adhesiveness of the second film can be appropriately set without any particular limitation as long as the adhesive strength between the resin composition layer and the second film is smaller than the adhesive strength between the resin composition layer and the first film, and the resin composition layer is not peeled off from the first film when the second film is peeled off from the resin composition layer.

[0029] The thickness of the second film is not particularly limited as long as the effects of the present invention are achieved, and can be appropriately selected depending on the application of the dry film of the present invention, and is, for example, 10 to 150 μm.

[0030] In the manufacturing method of the present invention, the above-mentioned steps (a), (b) and (c) are carried out in a series of roll-to-roll processes. The roll-to-roll process generally refers to a manufacturing process in which a substrate wound in a roll shape is unrolled, a layer structure is constructed on the unrolled substrate, and the substrate is wound again in a roll shape. In the manufacturing method of the present invention, the roll-to-roll process means that a first film wound in a roll shape is unrolled (unrolled), a resin composition is applied onto the unrolled first film, dried, a second film is further laminated, and the substrate is wound again in a roll shape. The unrolling method and the winding method are not particularly limited, and the well-known method can be used in the manufacturing method of a dry film using the roll-to-roll process.

[0031] <Resin composition> In the manufacturing method of the present invention, the resin composition applied to the first film to form the resin composition layer can be used without any particular limitation as long as it is a resin composition that can be formed into a film, and the formulation can be appropriately set according to the application of the dry film of the present invention. The components of the resin composition will be described in detail below.

[0032] (Resin component) As the resin component of the resin composition, a thermoplastic resin, a photocurable resin, a thermosetting resin, etc. can be used depending on the application of the dry film of the present invention. These resin components may be used alone or in combination of two or more.

[0033] The thermoplastic resin is not particularly limited as long as the effects of the present invention are achieved, and examples thereof include acrylic resins, phenoxy resins, polyimide resins, polyamideimide resins, polybenzoxazole resins, polyamide resins, polyurethane resins, polyurethaneimide resins, polyurea resins, polysiloxane resins, polyester resins, polyether resins, polyketone resins, and polyetherketone resins.

[0034] The photocurable resin is not particularly limited as long as the effect of the present invention is exhibited, but preferably a carboxyl group-containing resin is used. As the carboxyl group-containing resin, various conventionally known resins having a carboxyl group in the molecule can be used. By including a carboxyl group-containing resin in the resin composition, it is possible to impart alkali developability to the resin composition layer. In particular, from the viewpoint of the photocurability and development resistance of the resin composition, a photosensitive carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is preferred. The ethylenically unsaturated double bond in the molecule constituting the carboxyl group-containing resin is preferably derived from acrylic acid or methacrylic acid or a derivative thereof. When only a carboxyl group-containing resin without an ethylenically unsaturated double bond is used, in order to make the resin composition photocurable, it is necessary to use a compound having a plurality of ethylenically unsaturated groups in the molecule, i.e., a photopolymerizable monomer, which will be described later, in combination. Specific examples of the carboxyl group-containing resin include the following compounds (which may be either oligomers or polymers). The following compounds may be used alone or in combination of two or more.

[0035] (1) Carboxyl group-containing resins obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc.

[0036] (2) Carboxylic acid-containing urethane resins obtained by the polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl-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.

[0037] (3) Carboxylic acid-containing photosensitive urethane resins obtained by polyaddition reaction of diisocyanates with partially acid anhydride-modified products of reaction products of bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins and biphenol type epoxy resins with monocarboxylic acid compounds having ethylenically unsaturated double bonds such as (meth)acrylic acid, carboxyl group-containing dialcohol compounds and diol compounds.

[0038] (4) A photosensitive urethane resin containing a carboxyl group, which is terminated with (meth)acrylation by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as a hydroxyalkyl (meth)acrylate, during the synthesis of the resin (2) or (3) described above.

[0039] (5) A carboxyl group-containing photosensitive urethane resin having a terminal (meth)acryloyl group added during the synthesis of the resin (2) or (3) described above by an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, or the like.

[0040] (6) A carboxyl group-containing photosensitive resin obtained by reacting a difunctional or more polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.

[0041] (7) A carboxyl group-containing photosensitive resin obtained by reacting a multifunctional epoxy resin with the hydroxyl groups of a bifunctional (solid) epoxy resin further epoxidized with epichlorohydrin, with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.

[0042] (8) Carboxyl group-containing polyester resins obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid with a bifunctional oxetane resin and then adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting primary hydroxyl groups.

[0043] (9) A carboxyl group-containing photosensitive 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, adipic acid, or another such polybasic acid anhydride.

[0044] (10) A carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride.

[0045] (11) A carboxyl group-containing photosensitive resin 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, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride.

[0046] (12) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to any one of the resins (1) to (11). In this specification, (meth)acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

[0047] The acid value of the carboxyl group-containing resin is preferably 30 to 150 mgKOH / g, more preferably 50 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is 30 mgKOH / g or more, the alkaline developability of the resin composition layer is improved. On the other hand, when the acid value of the carboxyl group-containing resin is 150 mgKOH / g or less, good pattern drawing of the resin composition layer can be facilitated.

[0048] The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000, more preferably 5,000 to 100,000. By making the weight average molecular weight of the carboxyl group-containing resin 2,000 or more, it is possible to suppress the decrease in moisture resistance of the coating film after exposure of the resin composition and the associated film loss during development, and as a result, it is possible to suppress the decrease in resolution. On the other hand, by making the weight average molecular weight of the carboxyl group-containing resin 150,000 or less, it is possible to improve the developability and storage stability of the resin composition. The weight average molecular weight of the carboxyl group-containing resin can be measured by gel permeation chromatography (GPC).

[0049] Any known thermosetting resin can be used, for example, amino resins such as melamine resin, benzoguanamine resin, melamine derivatives, and benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimide, and carbodiimide resins. Among these, particularly preferably used are thermosetting resins having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio)ether groups) in the molecule. By including a thermosetting resin in the resin composition, it is expected that the heat resistance of the resin composition is improved. The thermosetting resin may be used alone or in combination of two or more types.

[0050] The thermosetting resin having a plurality of cyclic (thio)ether groups in the molecule is a compound having a plurality of 3-, 4-, or 5-membered cyclic (thio)ether groups in the molecule, and examples thereof include a compound having a plurality of epoxy groups in the molecule, i.e., a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, i.e., a polyfunctional oxetane compound, and a compound having a plurality of thioether groups in the molecule, i.e., an episulfide resin.

[0051] Examples of polyfunctional epoxy compounds include epoxidized vegetable oils, bisphenol A type epoxy resins, hydroquinone type epoxy resins, bisphenol type epoxy resins, thioether type epoxy resins, brominated epoxy resins, novolac type epoxy resins, biphenol novolac type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, glycidylamine type epoxy resins, hydantoin type epoxy resins, alicyclic epoxy resins, trihydroxyphenylmethane type epoxy resins, bixylenol type or biphenol type epoxy resins, or mixtures thereof. ;bisphenol S type epoxy resins;bisphenol A novolac type epoxy resins;tetraphenylolethane type epoxy resins;heterocyclic epoxy resins;diglycidyl phthalate resins;tetraglycidylxylenoylethane resins;naphthalene group-containing epoxy resins;epoxy resins having a dicyclopentadiene skeleton;glycidyl methacrylate copolymer epoxy resins;cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resins;epoxy-modified polybutadiene rubber derivatives;CTBN-modified epoxy resins, etc., but are not limited to these.

[0052] Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, and (3-ethyl-3-oxetanyl)methyl acrylate. Examples of the oxetanes include polyfunctional oxetanes such as acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, and their oligomers or copolymers, as well as ethers of oxetane alcohols and novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, or resins having hydroxyl groups such as silsesquioxane. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates.

[0053] Examples of compounds having multiple cyclic thioether groups in the molecule include bisphenol A episulfide resins, etc. Using a similar synthesis method, episulfide resins in which the oxygen atoms of the epoxy groups of novolac epoxy resins are replaced with sulfur atoms can also be used.

[0054] Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds, and methylolurea compounds.

[0055] The isocyanate compound may be a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and adducts, biuret and isocyanurates of the above-mentioned isocyanate compounds.

[0056] The blocked isocyanate compound may be an addition reaction product of an isocyanate compound and an isocyanate blocking agent. Examples of isocyanate compounds that can react with an isocyanate blocking agent include the polyisocyanate compounds described above. Examples of isocyanate blocking agents include phenol-based blocking agents, lactam-based blocking agents, active methylene-based blocking agents, alcohol-based blocking agents, oxime-based blocking agents, mercaptan-based blocking agents, acid amide-based blocking agents, imide-based blocking agents, amine-based blocking agents, imidazole-based blocking agents, and imine-based blocking agents.

[0057] (Photopolymerizable monomer) The resin composition can be mixed with a photopolymerizable monomer as necessary. The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond. The photopolymerizable monomer is effective when a photocurable resin, particularly a carboxyl group-containing non-photosensitive resin having no ethylenically unsaturated double bond, is used as a resin component, since it is necessary to use a photopolymerizable monomer in combination to make the resin composition photocurable.

[0058] Examples of photopolymerizable monomers include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, etc. Specific examples include alkyl acrylates such as 2-ethylhexyl acrylate and cyclohexyl acrylate; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; mono- or diacrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethyl isocyanurate. Polyhydric alcohols such as polyhydric alcohols or their alkylene oxide adducts or ε-caprolactone adducts; phenols such as phenoxy acrylate and bisphenol A diacrylate or their alkylene oxide adducts; glycidyl ether acrylates such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and at least one of the following may be appropriately selected and used: acrylates obtained by directly acrylate aliphaticating polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, and polyester polyols, or urethane acrylate aliphaticating polyols such as melamine acrylates, and methacrylates corresponding to the acrylates. Such photopolymerizable monomers can also be used as reactive diluents. The photopolymerizable monomers may be used alone or in combination of two or more.

[0059] (Photopolymerization initiator) The resin composition may contain a photopolymerization initiator as necessary. In particular, when the resin composition contains the above-mentioned photocurable resin, the resin composition preferably contains a photopolymerization initiator. Any known photopolymerization initiator may be used. The photopolymerization initiator may be used alone or in combination of two or more.

[0060] Specific examples of the photopolymerization initiator 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-trimethylpentane. Bisacylphosphine oxides such as 2,6-dimethoxybenzoyldiphenylphosphine oxide, 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-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloyl monoacylphosphine oxides such as phenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one benzoin, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, and other benzoins; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, and other benzophenones;Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl 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 acetophenones such as thanone and N,N-dimethylaminoacetophenone; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2-amylanthraquinone , 2-aminoanthraquinone, and other anthraquinones; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetylacetone, 1-[4-(phenylthio)phenyl]-, 2 ... oxime esters such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanium, and other titanocenes; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like.

[0061] A photoinitiator assistant or a sensitizer may be used in combination with the above-mentioned photopolymerization initiator. Examples of the photoinitiator assistant or sensitizer include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. In particular, it is preferable to use thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. By including a thioxanthone compound, it is possible to improve the deep curing property. Although these compounds may be used as photopolymerization initiators, it is preferable to use them in combination with a photopolymerization initiator. In addition, the photoinitiator assistant or sensitizer may be used alone or in combination of two or more kinds.

[0062] In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb specific wavelengths, they may have low sensitivity in some cases and function as ultraviolet absorbers. However, they are not used only for the purpose of improving the sensitivity of the composition. If necessary, they can absorb light of a specific wavelength to increase the photoreactivity of the surface, change the line shape and opening of the resist to a vertical, tapered, or reverse tapered shape, and improve the accuracy of the line width and opening diameter.

[0063] (Thermosetting catalyst) The resin composition may contain a thermosetting catalyst as necessary. In particular, when the resin composition contains the above-mentioned thermosetting resin, it is preferable to contain a thermosetting catalyst for curing the resin composition in the resin composition. The thermosetting catalyst contained in the resin composition may be a known curing agent that is generally used to cure the above-mentioned thermosetting resin. Examples of the thermosetting catalyst 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 sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. In addition, examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT 3513N (trade name of dimethylamine-based compound), DBU, DBN, and U-CAT SA 102 (all bicyclic amidine compounds and salts thereof) manufactured by San-Apro Co., Ltd. In particular, the present invention is not limited to these, and any catalyst that promotes the reaction of at least one of an epoxy resin or oxetane compound with a carboxyl group, or at least one of an epoxy group and an oxetanyl group, may be used alone or in combination of two or more types. Also usable are 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. These compounds that also function as adhesion-imparting agents are preferably used in combination with a heat curing catalyst.

[0064] (Filler) The photosensitive resin composition may be blended with a filler as necessary to increase the physical strength and dissolution rate of the coating film. As such a filler, known inorganic or organic fillers may be used, and barium sulfate, spherical silica, hydrotalcite, and talc are particularly preferably used. Furthermore, titanium oxide, metal oxides, and metal hydroxides such as aluminum hydroxide may be used as extender pigment fillers to obtain a white appearance and flame retardancy. The filler may be surface-treated or may not be surface-treated. Moreover, the filler may be used alone or in combination of two or more types.

[0065] (Coloring agent) The resin composition may contain a colorant as required. As the colorant, a commonly used and known colorant such as red, blue, green, yellow, white, black, etc. may be used, and any of a pigment, dye, and colorant may be used.

[0066] Examples of colorants include those having the following Color Index (CI; published by The Society of Dyers and Colourists) numbers:

[0067] Red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Blue colorants include phthalocyanine and anthraquinone, and pigments can be used as pigments. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used. Green colorants include phthalocyanine, anthraquinone, and perylene. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used. Yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. White colorants include rutile or anatase titanium oxide. Examples of black colorants include carbon black, graphite, iron oxide, titanium black, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, molybdenum sulfide, bismuth sulfide, etc. In addition, purple, orange, brown, and other colorants may be added for the purpose of adjusting the color tone.

[0068] (Organic solvent) An organic solvent may be blended into the resin composition for the purpose of adjusting the viscosity during preparation or application to a film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, and γ-butyrolactone; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. Known and commonly used organic solvents can be used. The organic solvent may be used alone or in combination of two or more kinds.

[0069] The amount of the organic solvent is not particularly limited as long as the effects of the present invention are achieved, but is set so that the amount of the solvent (residual solvent amount) contained in the resin composition after drying (i.e., the resin composition layer) relative to the total mass of the resin composition before drying is preferably 0.3 to 5.0 mass%, particularly preferably 0.5 to 3.0 mass%. The amount of the organic solvent can be, for example, more than 0 mass% and 90 mass% or less relative to the total mass of the resin composition.

[0070] (Other Ingredients) In addition to the above-mentioned components, the resin composition may further contain, as necessary, components such as a photoinitiator assistant, a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, a polymerization inhibitor, a copper inhibitor, an antioxidant, an anti-rust agent, a thickener such as organic bentonite or montmorillonite, at least one of silicone-based, fluorine-based, and polymer-based defoamers and leveling agents, imidazole-based, thiazole-based, and triazole-based silane coupling agents, phosphinates, phosphate ester derivatives, and phosphorus compounds such as phosphazene compounds. These may be those known in the field of electronic materials. EXAMPLES

[0071] The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples.

[0072] [Synthesis of carboxyl group-containing resin A] In an autoclave equipped with a thermometer, a nitrogen inlet, an alkylene oxide inlet, and a stirrer, 119.4 parts by mass of a novolac cresol resin (Shonoru (registered trademark) CRG951 manufactured by Aica Kogyo Co., Ltd., OH equivalent: 119.4), 1.19 parts by mass of potassium hydroxide, and 119.4 parts by mass of toluene were charged, and the system was replaced with nitrogen while stirring, and the temperature was raised. Next, 63.8 parts by mass of propylene oxide was gradually added dropwise, and the temperature was raised to 125 to 132°C and 0 to 4.8 kg / cm. 2The mixture was reacted at 100° C. for 16 hours. After that, the mixture was cooled to room temperature, and 1.56 parts by mass of 89% phosphoric acid was added to the reaction solution and mixed to neutralize the potassium hydroxide, thereby obtaining a propylene oxide reaction solution of a novolac cresol resin [solid content: 62.1%; hydroxyl value: 182.2 mg KOH / g (307.9 g / eq.)]. This propylene oxide reaction solution had an average of 1.08 moles of propylene oxide added per equivalent of phenolic hydroxyl group. Next, 293.0 parts by mass of the obtained propylene oxide reaction solution of a novolac cresol resin, 43.2 parts by mass of acrylic acid, 11.53 parts by mass of methanesulfonic acid, 0.18 parts by mass of methylhydroquinone, and 252.9 parts by mass of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and the mixture was reacted at 110° C. for 12 hours while being stirred by blowing air at a rate of 10 ml / min. 12.6 parts by mass of water produced by the reaction was distilled off as an azeotropic mixture with toluene. After that, it was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 parts by mass of 15% aqueous sodium hydroxide solution, and then washed with water. After that, the toluene was replaced with 118.1 parts by mass of diethylene glycol monoethyl ether acetate in an evaporator and distilled off to obtain a novolac-type acrylate resin solution. Next, 332.5 parts by mass of the resulting novolac-type acrylate resin solution and 1.22 parts by mass of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and 60.8 parts by mass of tetrahydrophthalic anhydride were gradually added while blowing air at a rate of 10 ml / min and stirring, and the mixture was reacted at 95 to 101°C for 6 hours, cooled, and then taken out. In this way, a solution of carboxyl group-containing resin A (solid content: 65% by mass, acid value of solid content: 87.7 mgKOH / g) was obtained.

[0073] [Synthesis of carboxyl group-containing resin B] A solution of carboxyl group-containing resin B was obtained in the same manner as in the above-mentioned [Synthesis of carboxyl group-containing resin A], except that the solid content of the solution of the carboxyl group-containing resin was adjusted to 70.6 mass %.

[0074] [Synthesis of carboxyl group-containing resin C] In a reaction vessel equipped with a gas inlet tube, a stirrer, a cooling tube, a thermometer, and a dropping funnel for continuous dropping of an alkali metal hydroxide aqueous solution, 224 parts by mass of 1,5-dihydroxynaphthalene with a hydroxyl group equivalent of 80 g / equivalent and 1075 parts by mass of bisphenol A type epoxy resin (jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 189 g / equivalent) were charged and dissolved at 110 ° C. under a nitrogen atmosphere and stirring. Next, 0.65 parts by mass of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 ° C., and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C., to obtain an epoxy compound (1-a) with an epoxy equivalent of 452 g / equivalent. Thereafter, the temperature in the flask was cooled to 40 ° C., and 1920 parts by mass of epichlorohydrin, 1690 parts by mass of toluene, and 70 parts by mass of tetramethylammonium bromide were added, and the temperature was raised to 45 ° C. under stirring and maintained. Then, 364 parts by mass of 48% sodium hydroxide aqueous solution was continuously dropped over 60 minutes, and the reaction was continued for another 6 hours. After the reaction was completed, most of the excess epichlorohydrin and toluene were recovered by distillation under reduced pressure, and the reaction product containing by-product salt and toluene was dissolved in methyl isobutyl ketone and washed with water. After separating the organic solvent layer and the water layer, methyl isobutyl ketone was distilled off from the organic solvent layer by distillation under reduced pressure to obtain a polynuclear epoxy resin (1-b) with an epoxy equivalent of 277 g / equivalent. In the obtained polynuclear epoxy resin (1-b), approximately 1.59 out of 1.98 alcoholic hydroxyl groups in the epoxy compound (1-a) were epoxidized, calculated from the epoxy equivalent. Therefore, the epoxidation rate of the alcoholic hydroxyl groups was approximately 80%. Next, 277 parts by mass of polynuclear epoxy resin (1-b) was placed in a flask equipped with a stirrer, a cooling tube and a thermometer, 290 parts by mass of carbitol acetate was added, and the mixture was dissolved by heating. 0.46 parts by mass of methylhydroquinone and 1.38 parts by mass of triphenylphosphine were added, and the mixture was heated to 95-105°C, and 72 parts by mass of acrylic acid were gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80-90°C, and 129 parts by mass of tetrahydrophthalic anhydride was added and the mixture was reacted for 8 hours. The reaction was monitored by measuring the oxidation and total oxidation of the reaction solution by potentiometric titration, and the resulting addition rate was used to monitor the reaction, with the end point being a reaction rate of 95% or more.In this way, a solution of carboxyl group-containing resin C (solid content: 62 mass %, acid value of solid content: 100 mgKOH / g) was obtained.

[0075] [Preparation of surface-treated inorganic filler] A surface-treated inorganic filler (solid content: 70% by mass) was obtained by uniformly dispersing 70 g of spherical silica (SFP-30M manufactured by Denka Co., Ltd., average particle size: 600 nm), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.).

[0076] [Preparation of resin composition 1] 154 parts by mass of the solution of the carboxyl group-containing resin A synthesized above as a photocurable resin, 10 parts by mass of Omnirad 819 manufactured by IGM Resins as a photopolymerization initiator, 1 part by mass of UVS-581 manufactured by Air Performance Chemical Co., Ltd. as a sensitizer, 475 parts by mass of the surface-treated inorganic filler prepared above as a filler, 15 parts by mass of DA-600 manufactured by Sanyo Chemical Industries, Ltd. as a photopolymerizable monomer, 57 parts by mass of N-730-A manufactured by DIC Corporation as a thermosetting resin, 25 parts by mass of melamine (solid content: 55% by mass) manufactured by Nissan Chemical Industries, Ltd. as a thermosetting catalyst, 1 part by mass of DICY (solid content: 73% by mass) manufactured by Mitsubishi Chemical Corporation as a thermosetting catalyst, and 10 parts by mass of a mixture of phthalocyanine blue and PIGMENT Yellow 147 (content ratio 57:43, solid content: 10% by mass) as a colorant were blended and premixed with a stirrer, and then kneaded with a three-roll mill to prepare a resin composition 1.

[0077] [Preparation of Resin Composition 2] As a thermosetting resin, 30 parts by mass of YX8000 manufactured by Mitsubishi Chemical Corporation, 70 parts by mass of ST-6100 manufactured by Nippon Steel Chemical & Material Co., Ltd., 100 parts by mass of YX6954BH30 (solid content: 30% by mass) manufactured by Mitsubishi Chemical Corporation as a thermoplastic resin, 2 parts by mass of DICY7 manufactured by Mitsubishi Chemical Corporation as a thermosetting catalyst, 1 part by mass of 2E4MZ manufactured by Shikoku Chemical Industry Co., Ltd., 0.2 parts by mass of MA-100 manufactured by Mitsubishi Chemical Corporation as a colorant, and 50 parts by mass of cyclohexanone as an organic solvent were blended and premixed with a stirrer, and then kneaded with a three-roll mill to prepare resin composition 2.

[0078] [Preparation of Resin Composition 3] As a thermosetting resin, 20 parts by mass of jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation, 30 parts by mass of HP-7200L manufactured by DIC Corporation, 40 parts by mass of N-740 manufactured by DIC Corporation, 500 parts by mass of Teisan Resin SG-P3 manufactured by Nagase ChemteX Corporation as a thermoplastic resin, 30 parts by mass of HF-1 manufactured by UBE Corporation as a thermosetting catalyst, 1 part by mass of 2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd., 1000 parts by mass of FB-7SDX manufactured by Denka Co., Ltd. as a filler, 2 parts by mass of KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent, 30 parts by mass of carbon black as a colorant, and 100 parts by mass of diethylene glycol monoethyl ether acetate as an organic solvent were blended and premixed with a stirrer, and then kneaded with a three-roll mill to prepare a resin composition 3.

[0079] [Preparation of Resin Composition 4] The photocurable resin was 99 parts by mass of the solution of carboxyl group-containing resin B synthesized above, 48 parts by mass of the solution of carboxyl group-containing resin C synthesized above, 10 parts by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator, 15 parts by mass of DPHA manufactured by Nippon Kayaku Co., Ltd. and 5 parts by mass of TMPTA manufactured by Nippon Kayaku Co., Ltd. as photopolymerizable monomers, 14 parts by mass of RE-306 manufactured by Nippon Kayaku Co., Ltd. as a thermosetting resin, and 10 parts by mass of 1,2,4,6-trimethylbenzoyldiphenylphosphine oxide manufactured by Nippon Kayaku Co., Ltd. as a thermosetting resin. Resin composition 4 was prepared by blending 35 parts by mass of YDCN-704P manufactured by Terial Corporation, 0.2 parts by mass of 1B2PZ manufactured by Shikoku Chemical Industry Co., Ltd. as a thermosetting catalyst, 0.5 parts by mass of melamine, 5 parts by mass of BYK-410 manufactured by BYK as a rheology control agent, 1 part by mass of phthalocyanine blue as a colorant, and 11 parts by mass of diethylene glycol monoethyl ether acetate as an organic solvent and premixing the mixture with a stirrer, followed by kneading with a three-roll mill.

[0080] [Preparation of dry film] Using a slot die coater, the resin compositions 1 to 4 prepared above were applied to the surface of the first film, polyethylene terephthalate (PET) film A (Lumirror (registered trademark) T60 manufactured by Toray Industries, Inc., thickness 38 μm), PET film B (Therapeel (registered trademark) HP2 manufactured by Toray Industries, Inc., thickness 38 μm), or PET film C (Toyobo Ester (registered trademark) film E5041 manufactured by Toyobo Co., Ltd.), so that the film thickness after drying was as shown in Table 1, to form a resin composition layer. Next, the PET film to which each resin composition was applied was dried using a hot air circulation drying oven at 60 to 140° C. and 1 to 10 minutes, with the drying conditions appropriately adjusted so that the resin composition layer of the laminate after drying had the residual solvent amount shown in Table 1. Next, the dried laminate and the second film, biaxially oriented polypropylene (OPP) film (Alphan MA-411 manufactured by Oji F-Tex Co., Ltd.), were laminated at the temperature and pressure shown in Table 1 to prepare each dry film of the examples and comparative examples. The resin composition layer of the laminate and the OPP film were laminated by passing the laminate between a stainless steel roll and a laminating roll while adjusting the laminating pressure so that the resin composition layer of the laminate and the roughened surface of the OPP film were in contact with each other. The laminating pressure was adjusted by lifting the laminating roll with an air cylinder.

[0081] The amount of residual solvent in the resin composition of each laminate after lamination with the OPP film was measured according to the following procedure. First, a copper foil was placed on a hot plate heated to 38°C, and the dried laminate was placed on the copper foil so that the resin composition layer of the dried laminate was in contact with the copper foil. Next, pressure was applied by hand from the PET film side to attach the copper foil and the dried laminate. Next, the PET film was peeled off from the dried laminate, and the solvent was completely removed by drying at 100°C for 20 minutes in a hot air circulation dryer. Next, the laminate was left in a desiccator with a humidity of 5% or less for 20 minutes and returned to room temperature. The amount of residual solvent in the resin composition layer was calculated based on the following formula. The results are shown in Table 1.

number

[0082] [Table 1]

[0083] [Evaluation of adhesion of OPP film] The state of adhesion of the OPP film to the resin composition layer in each of the dry films of the Examples and Comparative Examples was evaluated. Specifically, the behavior of the OPP film when each dry film was lifted by hand so that the OPP film side was vertically downward was visually confirmed and evaluated according to the following criteria. The results are shown in Table 1. In addition, in none of the dry films was excessive adhesion between the resin composition layer and the OPP film observed. Good: The OPP film does not fall even when the dry film is lifted, and adhesion is sufficient. ×: When the dry film was lifted, the OPP film fell off, and adhesion was insufficient.

[0084] From the results shown in Table 1, it can be seen that the resin composition layer and the OPP film are appropriately adhered to each other by adjusting the temperature to 40 to 75°C and the pressure to 0.2 to 0.7 MPa when laminating the resin composition layer and the OPP film of the dried laminate, as in the case of each of the dry films of Examples 1 to 10. This result suggests that the dry film can be successfully produced by the roll-to-roll method.

Claims

1. A method for producing a dry film, comprising the steps of: (a) applying a resin composition to a surface of a first film to obtain a first laminate; (b) drying the resin composition of the first laminate; and (c) a step of laminating the first laminate and a second film so that the dried resin composition is in contact with the second film to obtain a second laminate; Including, The temperature for laminating the first laminate and the second film in the step (c) is 40 to 75° C., and the pressure is 0.2 to 0.7 MPa; The steps (a) to (c) are carried out in a continuous roll-to-roll process. The manufacturing method.

2. The method of claim 1 , wherein the first film is a polyethylene terephthalate film.

3. The method of claim 1 wherein the second film is a biaxially oriented polypropylene film.

4. The method according to claim 1, wherein the film thickness of the resin composition after drying in the step (b) is 10 to 200 μm.

5. The method according to claim 1 , wherein the amount of the solvent contained in the resin composition after drying in the step (b) is 5 mass % or less based on the total mass of the resin composition after drying.

6. A dry film obtained by the method according to any one of claims 1 to 5.

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