Curable resin composition, curable film using the same, and laminate

Abstract

The curable resin composition of the present invention comprises a monomer having 1 to 6 (meth)acrylamide groups in one molecule and a polymer having (meth)acrylamide groups in one molecule, wherein the total number of (meth)acrylamide groups in one molecule of the monomer that are similar to the (meth)acrylamide groups in the polymer is 2 or less.

Description

Technical Field

[0001] This invention relates to a curable resin composition, and a curable film and laminate using the same. More specifically, it relates to a curable resin composition suitable for manufacturing photosensitive spacers, components of optical sensors (collimator parts, etc.), outer coatings of displays and touch sensors, and the like, and a curable film and laminate using the same. Prior Technology

[0002] In recent years, the applications of curable resin compositions using (meth)acrylates have been expanding, with cured products using these compositions being used in various devices. For example, cured films (organic films) using curable resin compositions can be applied to components of photosensitive spacers or optical sensors (collimators, etc.), as well as outer coatings for displays or touch sensors, among other applications. Furthermore, with the advancement of technology in recent years, the performance requirements for curable resin compositions have become increasingly stringent. For instance, in the case of forming layered curable films, it is important to precisely control the shape of the curable film.

[0003] In recent years, in particular, there has been an increasing demand for so-called thick organic films with a thickness exceeding 10 μm. As an example, negative photosensitive compositions that can be developed even with low-concentration alkaline developing solutions, have excellent environmental resistance, and can be made into thick films can be cited (see Patent Document 1 below). [Previous Technical Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2021-26029 Summary of the Invention

[0005] [The problem the invention aims to solve]

[0006] On the other hand, unique properties are often required for applications involving thick film formation. For example, shrinkage stress is generated during the curing of the resin composition, but if this shrinkage stress is too strong, it can sometimes lead to severe substrate warping or film cracking or crazing. The harmful effects of such shrinkage stress are particularly pronounced when forming hardened films on large glass substrates or when forming thick hardened films. Therefore, there is a strong desire to develop a curable resin composition that can suppress shrinkage stress during the formation of hardened films.

[0007] The purpose of this invention is to solve the above-mentioned problems by providing a curable resin composition capable of suppressing shrinkage stress during the formation of a curable film, a curable film using the same, and a laminate. [Technical means to solve the problem]

[0008] The inventors conducted intensive research to solve the aforementioned problems. Their findings revealed that by combining specific monomers with alkali-soluble polymers, the problems could be solved, thus completing this invention.

[0009] <1> A curable resin composition comprising a monomer having 1 to 6 (meth)acrylic groups in one molecule and a polymer having (meth)acrylic groups in one molecule, and The total number of (meth)acrylyl groups in the monomer molecule described above that are of the same type as the (meth)acrylyl group in the polymer described above is 2 or less. <2> As mentioned above <1> The described curable resin composition comprises the above-mentioned monomers in which the total number of (meth)acrylic groups in one molecule is 1 to 2. <3> As mentioned above <1> or <2> The described curable resin composition, wherein the monomer has only one of acrylonitrile and methacrylonitrile as the (meth)acrylonitrile. <4> As mentioned above <1> to <3> The curable resin composition described in any one of the above-mentioned methods, wherein the total number of (meth)acrylyl groups in 1 molecule of the monomer that are similar to (meth)acrylyl groups in the polymer is 0. <5> As mentioned above <1> to <4> The curable resin composition described in any one of the above claims, wherein the (meth)acrylic acid equivalent in the polymer is 520 or more. <6> As mentioned above <1> to <5> The curable resin composition described in any one of the above-mentioned monomers, wherein the (meth)acrylic equivalent of the monomer is 220 or more. <7> As mentioned above <1> to <6> The curable resin composition described in any one of the above claims, wherein the mass ratio (x:y) of the monomer (x) to the polymer (y) is 30:100 to 160:100. <8> A hardened film, which is made using the method described above. <1> to <7> It is formed from any of the curable resin compositions described in the present invention. <9> As mentioned above <8> The hardened membrane described has a thickness of 10 μm or more. <10> As mentioned above <8> or <9> The recorded hardened film, when heated at 230°C for 30 minutes, produces a curl with a diameter of 9.0 mm or more. <11> A multilayer comprising a substrate and, as described above, formed on the substrate. <8> to <10> The hardened membrane described in any of the records. [Effects of the Invention]

[0010] According to the present invention, a curable resin composition capable of suppressing shrinkage stress during the formation of a curable film, a curable film using the same, and a laminate are provided. Implementation

[0011] The following describes in detail the form in which the present invention is carried out (hereinafter referred to as "this embodiment"). However, the present invention is not limited thereto, and various changes can be made without departing from its spirit. Furthermore, when referred to in this specification as "(meth)acrylic acid", "(meth)acrylate", "(meth)acrylic acid", etc., it is used to mean both acrylonitrile (acrylic) and methacrylic acid (methacrylic).

[0012] Curing Resin Compositions The curable resin composition of this embodiment (hereinafter sometimes simply referred to as "resin composition") comprises a monomer having 1 to 6 (meth)acrylic groups in one molecule and a polymer having (meth)acrylic groups in one molecule, wherein the total number of (meth)acrylic groups in one molecule of the monomer that are similar to the (meth)acrylic groups of the polymer is 2 or less.

[0013] The resin composition according to this embodiment is a resin composition comprising a monomer having 1 to 6 (meth)acrylonitrile groups per molecule (hereinafter sometimes simply referred to as "monomer component") and a polymer having (meth)acrylonitrile groups per molecule (hereinafter sometimes simply referred to as "polymer component"). Furthermore, in the resin composition of this embodiment, the total number of (meth)acrylonitrile groups in one molecule of the monomer that are similar to the (meth)acrylonitrile groups of the polymer is 2 or less.

[0014] The resin composition of this embodiment, by including monomeric and polymeric components that satisfy these necessary conditions, can suppress shrinkage stress during the formation of a hardened film. This suppresses warping of the hardened film that occurs when forming a hardened film on a glass substrate or a thick hardened film. Furthermore, the hardened film obtained from the curable composition of this embodiment exhibits excellent resistance to solvents such as N-methylpyrrolidone (NMP) (hereinafter sometimes referred to as "solvent resistance").

[0015] The reason why the shrinkage stress of the hardened film using the resin composition of this embodiment is suppressed is unclear, but it is speculated that: the monomer component and the polymer component both have (meth)acrylyl groups, and the total number of (meth)acrylyl groups similar to those in the polymer component is 2 or less. Therefore, the degree of reaction between the monomer component and the polymer component based on (meth)acrylyl groups is controlled, and the generation of shrinkage stress during curing is suppressed. On the other hand, it is speculated that, as mentioned above, the curable composition of this embodiment also has excellent solvent resistance, so although the generation of shrinkage stress is suppressed, the curing reaction proceeds sufficiently.

[0016] (Monomer components) The resin composition of this embodiment comprises a monomer having 1 to 6 (meth)acrylonitrile groups per molecule. Furthermore, regarding the aforementioned monomer, the total number of (meth)acrylonitrile groups in one monomer molecule that are similar to the (meth)acrylonitrile groups of the polymer is 2 or less.

[0017] -The number of (meth)acrylic groups contained in one molecule of the monomer component- Here, "monomers having 1 to 6 (meth)acrylic groups in one molecule" means that the total number of (meth)acrylic groups in one molecule of a monomer component is 1 to 6. As a monomer component, a single monomer may be used, or multiple monomers may be used in combination.

[0018] When the resin composition of this embodiment uses only one monomer as a monomer component, the total number of (meth)acrylic groups in one molecule of that monomer component is the same as the number of (meth)acrylic groups in one molecule of the monomer, and the total number of "acrylic groups" and "methacrylic groups" contained in one molecule of the monomer is equivalent to this.

[0019] Furthermore, when the resin composition of this embodiment uses multiple monomer components, the number of (meth)acrylic groups in the monomer components is calculated by multiplying the number of (meth)acrylic groups in each monomer by the mass ratio of each monomer in the total monomer component. This value is obtained by summing these values ​​for each monomer component. The "number of (meth)acrylic groups" of a monomer component can be calculated, for example, as follows. Furthermore, when the monomer component includes monomers having acrylamide and monomers having methacrylic groups, or monomers having both acrylamide and methacrylic groups, for each monomer component, the total number of acrylamide groups and the total number of methacrylic groups are calculated separately, multiplied by the mass ratio of each monomer in the total monomer component, and the sum of these values ​​is the total number.

[0020] The number of acrylonitrile (or methacrylonitrile) in a monomeric component containing multiple monomers (component 1 to component n) = [(Total number of acrylonitrile (or methacryloyl) groups in component 1) × (Ratio of component 1 to all monomeric components)] + [(Total number of acrylonitrile (or methacryloyl) groups in component 2) × (Ratio of component 2 to all monomeric components)] + ... + [(Total number of acrylonitrile (or methacryloyl) groups in component n) × (Ratio of component n to all monomeric components)]

[0021] For example, when the monomer components contain monomer component 1 with 1 acrylonitrile and monomer component 2 with 2 acrylonitrile in a mass ratio of 20 / 80, the number of (meth)acrylonitrile groups in the monomer component is 1×(20 / (20+80))+2×(80 / (20+80))=1.8.

[0022] -The total number of (meth)acrylonitrile groups in one monomer molecule that are of the same class as the (meth)acrylonitrile group in the polymer- Subsequently, regarding "the total number of (meth)acrylyl groups in one monomer molecule that are of the same type as the (meth)acrylyl group in the polymer", when the polymer has an acrylyl group, it refers to the total number of acrylyl groups contained in one monomer molecule; when the polymer has a methacrylyl group, it refers to the total number of methacrylyl groups contained in one monomer molecule; and when the polymer has both acrylyl and methacrylyl groups, it refers to the total number of acrylyl groups and the total number of methacrylyl groups contained in one polymer molecule.

[0023] The number of (meth)acrylonitrile groups in one molecule of the monomer component is 1 to 6. If the number of (meth)acrylonitrile groups in one molecule of the aforementioned monomer component is 0, the reactivity with polymers containing (meth)acrylonitrile groups decreases. Furthermore, if the number of (meth)acrylonitrile groups in one molecule of the aforementioned monomer component exceeds 6, the effect of suppressing shrinkage stress during curing decreases. The number of (meth)acrylonitrile groups in one molecule of the monomer component is not particularly limited, but from the viewpoint of suppressing shrinkage stress during curing, 1 to 4 is preferred, more preferably 1 to 3.5, and even more preferably 1 to 2.

[0024] The total number of (meth)acrylyl groups in monomer 1 molecule of the monomer component that are similar to the (meth)acrylyl group of the polymer is 2 or less. If the total number of (meth)acrylyl groups exceeds 2, the effect of suppressing shrinkage stress during curing is reduced. Furthermore, from the viewpoint of suppressing shrinkage stress during curing, the above total number is preferably 1 or less, and more preferably 0, but there is no particular limitation. Furthermore, from the viewpoint of suppressing shrinkage stress during curing, the monomer component of this embodiment preferably has only one of acrylyl and methacrylyl as a (meth)acrylyl group. For example, when the monomer component has only one of acrylyl and methacrylyl, and the total number of (meth)acrylyl groups in monomer 1 molecule that are similar to the (meth)acrylyl group of the polymer is 0, the polymer component has only methacrylyl or a group that the monomer component does not have among the acrylyl groups.

[0025] From the viewpoint of suppressing shrinkage stress during hardening, the (meth)acrylic equivalent of the monomer component is preferably 220 or more, more preferably 300 or more, and particularly preferably 350 or more. The (meth)acrylic equivalent of the monomer component in the composition can be calculated by dividing (the formula weight of the monomer) by (the base number of (meth)acrylic acid). When multiple monomer components are used, the (meth)acrylic equivalent is set as the value obtained by multiplying the (meth)acrylic equivalent of each monomer by the mass ratio of each monomer in the total monomer component, and is the sum of the values ​​of each monomer component.

[0026] The following compounds can be cited as specific examples of monomeric components. Examples of monomers having one acrylonitrile include: α-(1-sideoxy-2-propen-1-yl)-ω-[4-(1-methyl-1-phenylethyl)phenoxy]poly(oxyethylene), hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, tributyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, isodecanyl acrylate, stearyl acrylate, isobutyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, benzyl acrylate, phenoxyethyl acrylate, ethyl carbitol acrylate, methoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol acrylate, acrylic acid ( 2-Methyl-2-ethyl-1,3-dioxolane-4-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl acrylate, cyclic trimethylolpropane formal acrylate, 3,3,5-trimethylcyclohexyl acrylate, ethoxylated o-phenylphenol acrylate, dicyclopentenyl acrylate, dicyclopentenoxyethyl acrylate, dicyclopentyl acrylate, nonylphenoxy polyethylene glycol acrylate, nonylphenoxy polyethylene glycol acrylate, tetrahydrofuran methanol acrylate polymer, ethoxyethoxyethanol acrylate polymer, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H,1H,5H-octafluoropentyl acrylate, 1H,1H,2H,2H-tridecylfluorooctyl acrylate, etc.

[0027] Examples of monomers having one methacrylic group include: hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, isobutyl methacrylate, tributyl methacrylate, n-octyl methacrylate, isononyl methacrylate, lauryl methacrylate, isodecanyl methacrylate, stearyl methacrylate, isobutyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, ethyl carbitol methacrylate, methoxyethyl methacrylate, and methoxytriethylene glycol methyl methacrylate. Acrylic esters, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, methyl methacrylate (2-methyl-2-ethyl-1,3-dioxolane-4-yl) methacrylate, methyl methacrylate (3-ethyloxetane-3-yl) methacrylate, cyclic trimethylolpropane acetal methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, ethoxylated o-phenylphenol methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentyl methacrylate, nonylphenoxy polyethylene glycol methacrylate, nonylphenoxy polyethylene glycol methacrylate, etc.

[0028] Examples of monomers having two acrylonitrile groups include: bisphenol AEO3.8 molar adduct diacrylate, bisphenol A ethoxylated diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, bisphenol A diglycidyl ether acrylate adduct, diethylene glycol diacrylate, polyethylene glycol #400 diacrylate, polypropylene glycol #400 diacrylate, polypropylene glycol #700 diacrylate, polytetramethylene glycol diacrylate, 1,6-hexanediol acrylate polymer, dialkyldiol diacrylate, etc.

[0029] [Chemistry 1]

[0030] Examples of monomers having two methacrylic groups include: bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, tripropylene glycol dimethacrylate, bisphenol A diglycidyl ether-acrylic acid adduct, diethylene glycol dimethacrylate, polyethylene glycol #400 dimethacrylate, polypropylene glycol #400 dimethacrylate, polypropylene glycol #700 dimethacrylate, polytetramethylene glycol dimethacrylate, etc.

[0031] [Chemistry 2]

[0032] Examples of monomers having three or more acrylonitrile groups include: tri-(2-acryloyloxyethyl) isocyanurate (acryloyl group number: 3), dipentaerythritol hexaacrylate (acryloyl group number: 6), dipentaerythritol pentaacrylate (acryloyl group number: 5), trimethylolpropane triacrylate (acryloyl group number: 3), pentaerythritol tri and tetraacrylate (acryloyl group number: 3~4), pentaerythritol tri and tetraacrylate ethoxylate (acryloyl group number: 3~4), glycerol triacrylate ethoxylate (acryloyl group number: 3), pentaerythritol tetraacrylate propoxylate (acryloyl group number: 4), and di-trimethylolpropane tetraacrylate (acryloyl group number: 4), etc. Examples of monomers having three or more methacrylic groups include: tri-(2-methacryloxyethyl) isocyanurate (methacrylic group number: 3), pentaerythritol hexamethacrylate (methacrylic group number: 5), trimethylolpropane trimethacrylate (methacrylic group number: 3), pentaerythritol tri- and tetramethacrylate (methacrylic group number: 3~4), pentaerythritol tri- and tetramethacrylate ethoxylated (methacrylic group number: 3~4), glycerol trimethacrylate ethoxylated (methacrylic group number: 3), pentaerythritol tetramethacrylate propionate (methacrylic group number: 4), and di-trimethylolpropane tetramethacrylate (methacrylic group number: 4), etc.

[0033] Among the aforementioned monomer components, α-(1-sideoxy-2-propen-1-yl)-ω-[4-(1-methyl-1-phenylethyl)phenoxy]poly(oxyethylene), bisphenol AEO3.8 molar adduct diacrylate, ethoxylated bisphenol A dimethacrylate, tri-(2-acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate are particularly preferred, and even more preferred are bisphenol AEO3.8 molar adduct diacrylate and α-(1-sideoxy-2-propen-1-yl)-ω-[4-(1-methyl-1-phenylethyl)phenoxy]poly(oxyethylene).

[0034] Furthermore, the content of the monomer component in the resin composition of this embodiment is not particularly limited. For example, from the viewpoint of suppressing shrinkage stress during hardening, it is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass, relative to the total solids content in the composition. In this specification, "total solids content" means all components in the resin composition except for the solvent.

[0035] Furthermore, the resin composition of this embodiment may also contain other monomers within a range that does not affect the effects of the present invention. These other monomers may be photopolymerizable monomers used in conventional photosensitive resin compositions. When these other monomers are used together, the content of the monomer component of this embodiment in all monomers is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0036] The mass ratio of polymer component [x] to monomer component [y] in the resin composition of this embodiment [x:y] (= content of monomer component (g): content of polymer component (g)) is not particularly limited. From the viewpoint of suppressing shrinkage stress during curing, it is preferably 30:100 to 160:100, more preferably 40:100 to 100:100, and even more preferably 50:100 to 80:100.

[0037] The mass ratio of polymer component [x] to monomer component [y] can be adjusted by appropriately changing the amount of monomer component or polymer component added. Furthermore, there is no particular limitation on the method for determining the above mass ratio; the polymer component and monomer component contained in the resin composition can be separated by known methods, and the polymer component and monomer component of each specific embodiment can be determined accordingly. For example, a low-polarity solvent (e.g., n-hexane) is used to precipitate the polymer components, separating them from the monomer components (and components containing photopolymerization initiators). Then, the mass of each component after solvent removal is determined, and the content of the polymer and monomer components in each embodiment is analyzed to determine the mass ratio of polymer component [x] to monomer component [y]. Furthermore, if gas chromatography-mass spectrometry (GCMS) or liquid chromatography-mass spectrometry (LCMS) can be used to specifically determine the content of oligomers, photopolymerization initiators, or other additives, then the aforementioned mass ratio can be obtained with high precision through quantitative analysis such as GC or LC.

[0038] (Polymer composition) The resin composition of this embodiment comprises a polymer having a (meth)acrylic group in one molecule. Preferably, an alkali-soluble resin is used as the polymer component of this embodiment. Furthermore, the polymer component of this embodiment preferably has only one of an acrylonitrile and a methacrylic group as the (meth)acrylic group, but this is not particularly limited.

[0039] From the perspective of suppressing shrinkage stress during hardening, the (meth)acrylic equivalent of the polymer component is preferably 520 or more, more preferably 600 or more, and especially preferably 700 or more.

[0040] The polymer component may also have other reactive groups besides (meth)acrylic acid. Examples of other reactive groups include thermally crosslinking groups and photocrosslinking groups, among which thermally crosslinking groups are preferred.

[0041] Furthermore, when the polymer component has thermally crosslinking groups other than (meth)acrylic acid groups, from the viewpoint of suppressing shrinkage stress during hardening, the equivalent amount of thermally crosslinking groups of the polymer component (relative to the total amount of thermally crosslinking groups including (meth)acrylic acid groups) is preferably greater than 520, more preferably greater than 600, and even more preferably greater than 700.

[0042] From the perspective of suppressing the stickiness (adhesion) of the hardened film, or from the perspective of manufacturability during the formation of the hardened film, the weight-average molecular weight of the polymer component is preferably 3,000 to 50,000, more preferably 4,000 to 30,000, and even more preferably 5,000 to 20,000. The molecular weight of the polymer component can be determined by gel permeation chromatography (manufactured by Tosoh Corporation, trade name: HLC-8120, column: G-5000HXL and G-3000HXL 2-linked, detector: RI, mobile phase: tetrahydrofuran).

[0043] The polymer components of this embodiment can be used alone or in combination. The content of alkali-soluble resin in the resin composition of this embodiment is not particularly limited, and can be appropriately determined based on the mass ratio (x:y) of the monomer component (x) to the polymer component (y). From the viewpoint of solubility in the developer solution, for example, when used as a photoresist material, it is preferably 5-80% by mass relative to the total solid content in the composition, more preferably 10-60% by mass, and even more preferably 20-40% by mass.

[0044] The polymer component used in this embodiment can be used without particular limitation, as long as it is a polymer containing a unit structure having a (meth)acrylic group in one molecule. The unit structure used in this embodiment is not particularly limited, and examples include unit structures derived from (meth)acrylic acid, methyl (meth)acrylate, butyl acrylate and other alkyl (meth)acrylates, 2-hydroxyethyl methacrylate, dicyclopentyl methacrylate, benzyl methacrylate and the like.

[0045] Furthermore, regarding the unit structure having a (meth)acrylic group, for example, the unit structure can be prepared by reacting the above-mentioned unit structure with glycidyl methacrylate, 2-acryloxyethyl isocyanate, 2-methacryloxyethyl isocyanate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc.

[0046] Examples of polymer components used in this embodiment include those with the following structures.

[0047] [Chemistry 3]

[0048] (other) The resin composition of this embodiment may contain photopolymerization initiators or microparticles smaller than 100 nm, for example, within the range that does not impair the effect of the resin composition of this embodiment.

[0049] The aforementioned photopolymerization initiators are compounds that do not function as photopolymerization initiators when used alone, but whose ability to enhance photopolymerization initiation is increased when used in combination with photopolymerization initiators. Examples of photopolymerization initiators include tertiary amines such as triethanolamine, which are effective when used in combination with benzophenone.

[0050] Adding microparticles smaller than 100 nm can improve the elastic resilience of the hardened film of the resin composition in this embodiment. There are no particular limitations on the microparticles smaller than 100 nm; examples include Al₂O₃, TiO₂, Fe₂O₃, ZnO, CeO₂, Y₂O₃, Mn₃O₄, and SiO₂. Furthermore, there are no particular limitations on the shape of the microparticles; examples include true spherical, spherical, and polyhedral shapes.

[0051] (Preparation of the resin composition) The resin composition of this embodiment can be prepared by adding, as needed, photopolymerization initiators, solvents, surfactants, leveling agents, chain transfer agents, polymerization inhibitors, viscosity modifiers, etc., in addition to the monomer components and polymer components described above, and then mixing them. The resin composition of this embodiment is not particularly limited and can be a negative photocurable resin.

[0052] -Photopolymerization initiator- The resin composition of this embodiment may contain a photopolymerization initiator. The photopolymerization initiator of this embodiment is not particularly limited, and one having an absorption wavelength of I-ray (365 nm) may be suitable.

[0053] There are no particular limitations on photopolymerization initiators. Examples include: acetophenone, 2,2'-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and other acetophenone derivatives; α-amino ketone photopolymerization initiators such as 2-benzyl-2-dimethylamino-1-(4-hydroxyphenyl)-butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-hydroxy-4-yl-phenyl)-butane-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-hydroxypropane-1-one; or 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], acetonitrile-1-[9-ethyl-6-(2-methyl)-[] ... [9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-1-(O-acetylated oxime), 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n- Butyl-6-(2-ethylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9.H.-carbazole-3-yl]-1-(O-acetylgoxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyran] [9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9.H.-carbazole-3-yl]-1-(O-acetylgoxime), acetone-1-[9-ethyl-6-(2-methyl-4-(2,2-dimethyl-1,3-dioxo)]-1-(O-acetylgoxime), acetone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxo]-1-(O-acetylgoxime)]-1-(O-acetylgoxime) Photopolymerization initiators such as oxime esters like pentylcyclo(methoxybenzoyl)-9,H-carbazole-3-yl]-1-(O-acetylated oxime; or benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bis(dimethylamino)benzophenone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; and benzoin dimethyl ketal. Sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; triterpenoids such as 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine, 2,4-trichloromethyl-(helizoyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; and thiols such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzothiazole.These photopolymerization initiators can be used alone or in combination of two or more.

[0054] The content of the photopolymerization initiator in the resin composition of this embodiment is not particularly limited. For example, from the viewpoint of the curability of the hardened film, it is preferably 0.1 to 10.0% by mass relative to the total solid content in the composition, more preferably 0.5 to 7.5% by mass, and even more preferably 1.0 to 5.0% by mass.

[0055] -solvent- As the solvent mentioned above, any known solvent used in photosensitive resin compositions may be appropriately selected. There are no particular limitations on the solvent; examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMAc), propylene glycol monoethyl ether acetate, and methyl 3-methoxypropionate; ethers such as polyoxyethylene lauryl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and diethylene glycol methyl ethyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; and amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0056] -Surfactants- As the aforementioned surfactant, a known surfactant suitable for use in photosensitive resin compositions may be appropriately selected. Examples of such surfactants include silicone-based surfactants, acrylic-based surfactants, and fluorinated surfactants.

[0057] Hardened membranes and laminates The curing film using the resin composition of this embodiment exhibits suppressed shrinkage stress during curing and minimal warping. Furthermore, by depositing the curing film of this embodiment onto a substrate, a laminate comprising a substrate and a curing film formed on the substrate can be fabricated. The curing film formed using the resin composition of this embodiment also exhibits excellent solvent resistance. Therefore, when forming other organic films on the curing film of this embodiment, for example, it exhibits stronger resistance to the solvents used in forming the organic layer, suppressing film thickness reduction caused by the solvent or defects caused by solvent penetration into the film interface.

[0058] The hardened film and laminate of this embodiment can be formed by forming a coating film containing a resin composition on a substrate, and then exposing and developing the coating film. There is no particular limitation on the exposure method; for example, the resin composition of this embodiment can also be obtained using a projection exposure (lens scanning) method with a multi-lens system. The substrate can be appropriately selected depending on the application of the hardened film; for example, known substrates such as glass plates or polyimide films can be appropriately used.

[0059] Water, organic solvents, and alkaline aqueous solutions can be used appropriately in the above-mentioned development process. Considering environmental impact, it is preferable to use an alkaline aqueous solution. Examples of alkaline aqueous solutions include: aqueous solutions of inorganic salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; and aqueous solutions of organic salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

[0060] When the monomer component and the polymer component of this embodiment have the same type of (meth)acrylic acid group, there is a tendency for the polymer and monomer to react during curing, but this is not particularly limited. On the other hand, when the monomer component and the polymer component of this embodiment have different types of (meth)acrylic acid groups, there is a tendency for the polymers and monomers to react with each other during curing.

[0061] (film thickness) The resin composition of this embodiment is particularly useful for forming thick organic films because the shrinkage stress during the formation of the hardened film is suppressed. For example, the lower limit of the thickness of the hardened film using the resin composition of this embodiment can be set to 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more, depending on the application. Furthermore, the upper limit of the thickness of the hardened film can be set to 100 μm or less, preferably 90 μm or less, and even more preferably 80 μm or less, depending on the application.

[0062] (curly) The shrinkage stress of the hardened film in this embodiment is suppressed during film hardening. For example, the diameter of the curl produced by heating a sample sheet (size 100 mm × 100 mm × thickness 10 μm) at 230°C for 30 minutes is 9.0 mm or more, preferably 15.0 mm or more, and even more preferably 20.0 mm or more. Furthermore, regarding the hardened film of this embodiment, even when a sample sheet (size 100 mm × 100 mm) with a thickness of 20 μm is prepared, the diameter of the curl measured under the same conditions is preferably 9.0 mm or more, and even when a sample sheet (size 100 mm × 100 mm) with a thickness of 30 μm is prepared, the diameter of the curl measured under the same conditions is particularly preferably 9.0 mm or more.

[0063] The larger the diameter of the curl, the more the warping of the hardened film is suppressed. Furthermore, if the curl is 9 mm or more, even when the hardened film is applied to a large substrate (such as a glass plate or polyimide film) of 600 mm × 720 mm or more, the warping of the substrate or the generation of cracks and defects in the hardened film can be effectively suppressed. Furthermore, if the thickness of the hardened film is approximately 1 mm or less, there is a tendency for the curvature to decrease as the thickness of the hardened film increases. The curvature can be measured using the values ​​obtained by the method described in the following examples.

[0064] Purpose of Use The cured and laminated products formed by the resin composition of this embodiment can be suitably used for various applications, especially for optical components or displays using organic films with a thickness of 10 μm or more. Specific applications include, for example, photosensitive spacers, components of optical sensors (collimators, etc.), outer coatings for displays and touch sensors, color filters, etc. [Example]

[0065] The present invention will now be described in more detail using examples and comparative examples. The present invention is not limited to the following examples.

[0066] (Synthesis of Polymer B-1) In a glass flask equipped with a heating-cooling-stirring device, a reflux cooling tube, and a nitrogen inlet tube, propylene glycol monomethyl ether acetate (389.5 g), methacrylic acid (50.0 g), methyl methacrylate (81.4 g), 2-hydroxyethyl methacrylate (90.7 g), and dicyclopentyl methacrylate (51.2 g) were added. While stirring the mixture, aeration was carried out under a nitrogen atmosphere for 1 hour. After nitrogen replacement, 2,2'-azobis(isobutyronitrile) (15.3 g) was added, and the reaction was carried out at 80°C for 8 hours.

[0067] 2-Acryloxyethyl isocyanate (65.6 g) and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxy free radical (0.01 g) were added to the obtained solution, and the reaction was carried out at 60 °C for 9 hours to obtain the target polymer B-1.

[0068] The polymer contains only acrylates as the type of (meth)acrylate. Furthermore, molecular weight determination using GPC (Gel Permeation Chromatography) revealed that polymer B has a weight-average molecular weight (mW) of 12,300, and its acrylonitrile equivalent, calculated based on the added mole ratio, is 728. The structures of the obtained compounds are shown below.

[0069] [Chemistry 4]

[0070] (Synthesis of polymer B-2) In a glass flask equipped with a heating-cooling-stirring device, a reflux cooling tube, and a nitrogen inlet tube, add propylene glycol monomethyl ether acetate (305.1 g), propylene glycol monomethyl ether (138.7 g), methacrylic acid (100.0 g), methyl methacrylate (116.3 g), and butyl acrylate (52.6 g). While stirring the mixture, aeration was carried out under a nitrogen atmosphere for 1 hour. After nitrogen replacement, 46.2 g of 2,2'-azobis(isobutyronitrile) was added, and the mixture was reacted at 80°C for 8 hours.

[0071] Glycidyl methacrylate (66.1 g), dimethyl benzylamine (0.6 g), and butylated hydroxytoluene (0.02 g) were added to the obtained solution, and the mixture was reacted at 100°C for 9 hours to obtain the target polymer B-2.

[0072] The polymer contains only methacrylates. Furthermore, molecular weight determination using GPC showed that polymer B-2 has a weight-average molecular weight (mW) of 7,400, and the methacrylate equivalent calculated based on the added mole ratio is 735. The structures of the obtained compounds are shown below.

[0073] [Chemistry 5]

[0074] (Synthesis of polymer B-3) In a glass flask equipped with a heating-cooling-stirring device, a reflux cooling tube, and a nitrogen inlet tube, propylene glycol monomethyl ether acetate (570.7 g), methacrylic acid (100.0 g), and benzyl methacrylate (245.6 g) were added. While stirring the mixture, aeration was carried out under a nitrogen atmosphere for 1 hour. After nitrogen replacement, 40.4 g of 2,2'-azobis(isobutyronitrile) was added, and the mixture was reacted at 80°C for 8 hours. Glycidyl methacrylate (103.2 g), dimethyl benzylamine (0.6 g), and butylated hydroxytoluene (0.03 g) were added to the obtained solution, and the mixture was reacted at 100°C for 9 hours to obtain the target polymer B-3.

[0075] The polymer contains only methacrylates. Molecular weight was determined using GPC, and the weight-average molecular weight (mW) of polymer B-3 was 10,000. The methacrylate equivalent calculated based on the added mole ratio was 705.

[0076] [Chemistry 6]

[0077] (Synthesis of polymer B-4) Cyclopentanone (371.4 g), methacrylic acid (65.0 g), and dicyclopentyl methacrylate (135.0 g) were added to a glass flask equipped with a heating-cooling-stirring device, a reflux cooling tube, and a nitrogen inlet tube. While stirring the mixture, aeration was carried out under a nitrogen atmosphere for 1 hour. After nitrogen replacement, 16.0 g of 2,2'-azobis(isobutyronitrile) was added, and the reaction was carried out at 80°C for 8 hours. 75.0 g of glycidyl methacrylate, 0.5 g of dimethyl benzylamine, and 0.03 g of 4-methoxyphenol were added to the obtained solution, and the mixture was reacted at 100°C for 19 hours to obtain the target polymer B-4.

[0078] The polymer contains only methacrylates. Molecular weight was determined using GPC, and the weight-average molecular weight (mW) of polymer B-4 was 8,000. The methacrylate equivalent calculated based on the added mole ratio was 523.

[0079] [Chemistry 7]

[0080] (Preparation of the curing resin composition PR-1) Polymer B-1 (100 parts by weight (solid content)), monomer A-1 ((meth)acrylic acid equivalent 354.45) (60 parts by weight (solid content)), photopolymerization initiator (product name: IRGACURE OXE01, manufactured by BASF Japan) (0.8 parts by weight (solid content)), and surfactant (product name: DOWSIL Fz2122, manufactured by Dow Chemical) (0.2 parts by weight) were mixed, and propylene glycol monomethyl ether acetate as an organic solvent was added to achieve a solid content concentration of 40% by weight. The mixture was stirred and then filtered using a membrane filter with a pore size of 5.0 μm to prepare a curable resin composition PR-1.

[0081] (Preparation of curing resin compositions PR-2~PR-18 and curing resin compositions CE-1~CE-2) Curable resin compositions PR-2 to PR-18 and CE-1 to CE-4 were prepared using the types and amounts of polymer components, monomer components, photopolymerization initiators, surfactants, organic solvents and any other components shown in Table 1 below, except that the process was carried out in the same manner as in Example 1.

[0082] The following lists the names of the monomers, photoinitiators, surfactants, and solvents used.

[0083] (monomer) • Monomer (A-1): α-(1-Side-oxy-2-propen-1-yl)-ω-[4-(1-methyl-1-phenylethyl)phenoxy]poly(oxyethylene) (Product name: Viscoat#315, manufactured by Osaka Organic Chemicals Co., Ltd., acrylonitrile equivalent (average) 322.13, number of acrylonitrile groups: 1, number of methacrylonitrile groups: 0)

[0084] [Chemistry 8]

[0085] • Monomer (A-2): Bisphenol A EO3.8 molar adduct diacrylate (Product name: Viscoat#700HV, manufactured by Osaka Organic Chemicals Co., Ltd., acrylonitrile equivalent (average) 338.4, number of acrylonitrile groups: 2, number of methacrylic groups: 0)

[0086] [Chemistry 9]

[0087] • Monomer (A-3): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Product name: ARONIX M-402, manufactured by Toa Synthetic Co., Ltd., acrylonitrile equivalent (average): 99.8, number of acrylonitrile groups (average): 5.6, number of methacrylic groups: 0)

[0088] [Chemistry 10]

[0089] • Monomer (A-4): Tris-(2-Acryloxyethyl) isocyanurate (Product name: NK Ester A-9300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., acrylonitrile equivalent 141.1, number of acrylonitrile groups: 3, number of methacrylonitrile groups: 0)

[0090] [Chemistry 11]

[0091] • Monomer (A-5): Ethylene oxide bisphenol A dimethacrylate (Product name: NK Ester BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., acrylonitrile equivalent (average) 270.3, number of acrylonitrile groups: 0, number of methacrylic groups: 2)

[0092] [Chemistry 12]

[0093] • Monomer (A-6): A mixture of tripentaerythritol acrylate, monopentaerythritol acrylate, dipentaerythritol acrylate, and polypentaerythritol acrylate (Product name: Viscoat#802, manufactured by Osaka Organic Chemicals Co., Ltd., average acrylonitrile equivalent 101.4, number of acrylonitrile groups (average): 6.8, number of methacrylic groups: 0).

[0094] [Chemistry 13]

[0095] (Photopolymerization initiator) • IRGACURE OXE-01 (manufactured by BASF) (surfactants) Silicone-based surfactant (DOESIL Fz2122, manufactured by Dow Chemical Company) (solvent) ·PGMAc: Propylene glycol monomethyl ether acetate •PGM: Propylene Glycol Monomethyl Ether • CPN: Cyclopentanone

[0096] (Curling test) -Preparation of polyimide film for use in curling tests- A polyimide film (product name: Kapton, manufactured by TORAY-DUPONT, 25 μm thick) was cut into 10 cm × 10 cm pieces and taped onto a 10 cm × 10 cm, 0.7 mm thick soda glass substrate to create a coating substrate. Then, using a spin coater, a curable resin composition was coated onto the substrate in 10 μm thicknesses, and the coating was left to stand on a top pin for 5 minutes. Afterward, the film was dried in an oven at 100°C for 2 minutes. Next, it was photocured using an exposure machine (22 mW, 100 mJ). Then, it was developed using a 0.4% (w / w) tetramethylammonium hydroxide aqueous solution, followed by a 30-second rinse with pure water. The resulting exposed and developed film was then heated in an oven at 230°C for 30 minutes to obtain a coated and cured polyimide film for a curl test. The following describes the method for measuring the thickness of hardened films.

[0097] -Curling Test- When the polyimide film with a hardened coating is separated from the glass substrate using a cutting blade, the polyimide film curls up due to the stress of the hardened film itself. At this time, the curled polyimide film is observed from the front side of the curling direction, and the curling diameter is measured using vernier calipers. Specifically, the average of the length of the longest side and the length of the shortest side is defined as the curling diameter, and the average of the values ​​obtained by performing this step twice is defined as the curling diameter of this invention. Furthermore, the lengths of the longest and shortest sides do not include the length of the hardened material and the polyimide film, which is the so-called inner diameter of the curled polyimide film with a hardened coating.

[0098] [Preparation of glass for measuring film thickness with coated and hardened film] The curable resin compositions of each embodiment were coated onto sodium glass measuring 10 cm × 10 cm and 0.7 mm thick to prepare glass coated with a curable film. The amount of curable resin composition applied was set to be the same as that used in preparing the polyimide film coated with a curable film for the curling test described above. Furthermore, the conditions for preparing the curable film were set to be the same as those used when coating the polyimide film with the curable resin composition in the preparation of the polyimide film coated with a curable film for the curling test described above. Subsequently, a portion of the hardened film on the glass substrate coated with the hardened film was peeled off using a razor, and the film thickness was measured using a stylus-type surface shape measuring instrument (product name: P-10, manufactured by KLA-Tencor).

[0099] [Soluble Resistance Test] Add N-methylpyrrolidone (NMP) to a glass petri dish, and immerse the glass coated with the hardened film obtained above in NMP at 25°C (solvent temperature) for 30 minutes. After 30 minutes, the glass coated with the hardened film was removed from the NMP for film thickness measurement, and the film thickness of the hardened film after washing and drying was measured. The film thickness change rate (residual film rate) of the hardened film after the solvent resistance test was calculated as an indicator of solvent resistance.

[0100] Residual film percentage (%) after solvent resistance test = [(Thickness of the hardened film after solvent resistance test) ÷ (Thickness of the hardened film before solvent resistance test))] × 100

[0101] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Curing resin composition (by mass) PR-1 PR-2 PR-3 PR-4 PR-5 PR-6 PR-7 PR-8 PR-9 A ingredient A-1 60 70 80 90 100 160 100 100 100 A-2 - - - - - - - - - A-3 - - - - - - - - - A-4 - - - - - - - - - A-5 - - - - - - - - - Component B B-1 100 100 100 100 100 100 100 - - B-2 - - - - - - - 100 - B-3 - - - - - - - - 100 B-4 - - - - - - - - - Photoinitiator 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 surfactants 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 organic solvents PGMAc PGMAc PGMAc PGMAc PGMAc PGMAc PGMAc PGMAc PGMAc - - - - - - - PGM - Component A reactive base equivalent 322 322 322 322 322 322 322 322 322 Component B reactive base equivalent 728 728 728 728 728 728 728 735 705 Total amount of component A (meth)acrylic acid 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 The total number of (meth)acrylic groups in component A, which is similar to component B. 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Film thickness(um) 10.2 10.3 10.5 10.1 10.2 10.3 13.2 12.5 13.4 Curl diameter (mm) 10.5 11.0 11.3 11.3 11.6 11.3 13.0 18.5 25.0 Solvent resistance (%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 91.0 90.0

[0102] [Table 2] Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Curing resin composition (by mass) PR-10 PR-11 PR-12 PR-13 PR-14 PR-15 PR-16 PR-17 PR-18 A ingredient A-1 - - - - - - - - 55 A-2 60 60 60 60 30 - 80 40 25 A-3 - - - - - - - 40 - A-4 - - - - - - - - - A-5 - - - - - 60 - - - Component B B-1 100 - - - 100 100 - - - B-2 - 100 - - - - 100 100 - B-3 - - 100 - - - - - 100 B-4 - - - 100 - - - - - Photoinitiator 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 surfactants 0.2 0.2 0.2 02 0.2 0.2 0.2 0.2 0.2 organic solvents PGMAc PGMAc PGMAc PGMAc PGMAc PGMAc PGMAc PGMAc PGMAc - PGM - CPN - - PGM PGM - Component A reactive base equivalent 338 338 338 338 338 270 338 222 327 Component B reactive base equivalent 728 735 705 523 728 728 735 735 705 Total amount of component A (meth)acrylic acid 2.0 2.0 2.0 2.0 2.0 2.0 2.0 3.8 1.3 The total number of (meth)acrylic groups in component A, which is similar to component B. 0.0 0.0 0.0 0.0 2.0 0.0 0.0 0.0 0.0 Film thickness(um) 10.2 12.7 13.0 10.3 10.1 10.3 10.8 11.2 13.4 Curl diameter (mm) 9.5 16.5 24.5 14.0 10.5 10.5 21.0 13.5 23.5 Solvent resistance (%) 100.0 94.0 95.0 94.0 100.0 94.0 96.0 100.0 93.0

[0103] [Table 3] Comparative Example 1 Comparative Example 2 Curing resin composition (by mass) CE-1 CE-2 A ingredient A-1 - - A-2 - - A-3 60 - A-4 - - A-5 - - A-6 - 60 Component B B-1 100 100 B-2 - - B-3 - - B-4 - - B-5 - - Photoinitiator 0.8 0.8 surfactants 0.2 0.2 organic solvents PGMAc PGMAc - - Component A reactive base equivalent 100 101 Component B reactive base equivalent 728 728 Total amount of component A (meth)acrylic acid 5.6 6.8 The total number of (meth)acrylic groups in component A, which is similar to component B. 5.0 0.0 Film thickness(um) 10.8 10.3 Curl diameter (mm) 5.9 6.5 Solvent resistance (%) 100.0 100.0

[0104] As shown in the table, the curable resin compositions of the examples can form thick films with a curl diameter of 9.0 mm or more, and the shrinkage stress during film formation is suppressed. Furthermore, the obtained curable films also exhibit excellent solvent resistance. In contrast, it can be seen that although the number of (meth)acrylyl groups in one molecule of monomer is 6 or less, the total number of (meth)acrylyl groups of the same type as the (meth)acrylyl group in the polymer exceeds 2, and the curing resin composition of Comparative Example 1, which uses a monomer with more than 6 (meth)acrylyl groups in one molecule, both have a curl diameter of 9 mm or less, and the shrinkage stress during the formation of the curing film is not sufficiently suppressed.

[0105] The entire system of the invention of Japanese Patent Application No. 2021-106852, filed on June 28, 2021, is incorporated herein by reference. Furthermore, all documents, patent applications, and technical specifications described in this specification are incorporated into this specification by reference to the same extent as those specifically and separately described and incorporated by reference.

Claims

1. A curable resin composition comprising a monomer having 1 to 6 (meth)acrylic groups in one molecule and an alkali-soluble polymer having (meth)acrylic groups in one molecule, wherein the total number of (meth)acrylic groups in one molecule of the monomer that are similar to the (meth)acrylic groups in the polymer is 2 or less, the (meth)acrylic equivalent in the alkali-soluble polymer is 520 to 735 and the weight average molecular weight is 5,000 to 20,000, and the content of the monomer having (meth)acrylic groups in all monomers is 80% by mass or more.

2. The curable resin composition of claim 1, comprising the above monomers having a total of 1 to 2 (meth)acrylic groups in one molecule.

3. The curable resin composition of claim 1, wherein the monomer has only one of acrylonitrile and methacrylonitrile as the (meth)acrylonitrile.

4. The curable resin composition of claim 1, wherein the total number of (meth)acrylyl groups in the monomer 1 molecule that are similar to the (meth)acrylyl group of the polymer is 0.

5. The curable resin composition of claim 1, wherein the (meth)acrylic equivalent of the monomer is 220 or more.

6. The curable resin composition of claim 1, wherein the mass ratio (x:y) of the monomer (x) to the polymer (y) is 30:100 to 160:

100.

7. A curing film formed using a curing resin composition as claimed in any one of claims 1 to 6.

8. The hardened film, as requested in item 7, has a thickness of 10 μm or more.

9. The curing film of claim 7, when heated at 230°C for 30 minutes, has a curl diameter of 9.0 mm or more.

10. A laminate comprising a substrate and a hardened film as claimed in claim 7 formed on the substrate.