TW202307042A - Curable resin composition, cured film obtained therefrom, and layered product - Google Patents

Abstract

A curable resin composition comprising a monomer having one to six (meth)acryl groups in the molecule and a polymer having a (meth)acryl group in the molecule, wherein the total number of (meth)acryl groups in the monomer molecule which are the same as the (meth)acryl group of the polymer is 2 or less.

Description

Curable resin composition, cured film using same, and laminate

The present invention relates to a curable resin composition, a cured film using the same, and a laminate. Specifically, it relates to a member (collimator section, etc.) suitable for manufacturing photosensitive spacers and optical sensors, Curable resin composition for outer coating of displays and touch sensors, etc., and cured films and laminates using the same.

In recent years, the use of curable resin compositions using (meth)acrylates is expanding, and cured products using the compositions are used in various devices. For example, a cured film (organic film) using a curable resin composition can be applied to a photosensitive spacer or a member of an optical sensor (collimator section, etc.), and an outer cover of a display or a touch sensor, etc. Various uses. Also, with the development of technology in recent years, the performance of curable resin compositions is increasingly required. For example, when forming a layered cured film, it is important to precisely control the shape of the cured film.

In particular, in recent years, there has been an increasing demand for so-called thick organic films having a thickness exceeding 10 μm. As such an example, a negative-type photosensitive composition capable of developing even with a low-concentration alkaline developer, excellent in environmental resistance, and capable of thickening the film can be mentioned (see Patent Document 1 below). [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2021-26029

[Problem to be solved by the invention]

On the other hand, unique characteristics are often required for thick film formation applications. For example, shrinkage stress occurs when the resin composition is hardened, but if the shrinkage stress is too strong, the phenomenon of severe warping of the substrate or cracks or fissures of the film may occur. The harm of these shrinkage stresses is particularly remarkable when forming a cured film on a large glass substrate or forming a thick cured film. Therefore, development of a curable resin composition capable of suppressing shrinkage stress at the time of cured film formation has been earnestly desired.

An object of the present invention is to provide a curable resin composition capable of suppressing shrinkage stress during formation of a cured film, a cured film using the same, and a laminate in order to solve the above problems. [Technical means to solve the problem]

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems. As a result, they found that the above-mentioned problems can be achieved by combining a specific monomer with an alkali-soluble polymer, and completed the present invention.

<1> A curable resin composition comprising a monomer having 1 to 6 (meth)acryl groups in one molecule and a polymer having (meth)acryl groups in one molecule ,and The total number of (meth)acryl groups similar to the (meth)acryl groups of the polymer in one molecule of the monomer is 2 or less. <2> The curable resin composition as described in said <1> which contains the said monomer whose total number of (meth)acryloyl groups in 1 molecule is 1-2. <3> The curable resin composition according to the above <1> or <2>, wherein the monomer has only one of an acryl group and a methacryl group as the (meth)acryl group. <4> The curable resin composition according to any one of the above <1> to <3>, wherein the (meth)acryloyl group of the above-mentioned polymer in one molecule of the above-mentioned monomer is (methyl) The total number of acryl groups is 0. <5> The curable resin composition according to any one of the above <1> to <4>, wherein the (meth)acryl equivalent weight in the polymer is 520 or more. <6> The curable resin composition according to any one of <1> to <5> above, wherein the (meth)acryl equivalent weight in the monomer is 220 or more. <7> The curable resin composition according to any one of <1> to <6> above, wherein the mass ratio (x:y) of the monomer (x) to the polymer (y) is 30:100 ~160:100. <8> A cured film formed using the curable resin composition described in any one of <1> to <7> above. <9> The cured film according to the above <8>, which has a film thickness of 10 μm or more. <10> The cured film according to the above <8> or <9>, wherein the diameter of the curl produced by heating at 230° C. for 30 minutes is 9.0 mm or more. <11> A laminate comprising a substrate and the cured film according to any one of <8> to <10> formed on the substrate. [Effect of Invention]

According to the present invention, a curable resin composition capable of suppressing shrinkage stress during formation of a cured film, a cured film using the same, and a laminate can be provided.

Hereinafter, the mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. However, this invention is not limited to this, Various changes are possible in the range which does not deviate from the summary. In addition, when referring to "(meth)acryl", "(meth)acrylate", "(meth)acrylic acid" and the like in this specification, acryl (acryl) and methacryl are included. It is used in the meaning of both methacryl (methacryl) and the like.

"Hardening Resin Composition" The curable resin composition of this embodiment (hereinafter sometimes simply referred to as "resin composition") contains a monomer having 1 to 6 (meth)acryl groups in 1 molecule, and a monomer having ( In the case of a meth)acryl group polymer, the total number of (meth)acryl groups of the same type as the (meth)acryl group of the above polymer in one molecule of the above monomer is 2 or less.

The resin composition according to this embodiment contains a monomer having 1 to 6 (meth)acryl groups in one molecule (hereinafter sometimes referred to simply as "monomer component"), and a monomer having ( A resin composition of a meth)acryl-based polymer (hereinafter sometimes simply referred to as "polymer component"). Furthermore, in the resin composition of this embodiment, the total number of (meth)acryl groups similar to the (meth)acryl group of the said polymer in 1 molecule of the said monomer is 2 or less.

The resin composition of this embodiment can suppress the shrinkage stress at the time of cured film formation by containing the monomer component and polymer component which satisfy these requirements. Thereby, warpage of the cured film which occurs when forming a cured film or a thick cured film on a glass substrate can be suppressed. In addition, the cured film obtained from the curable composition of the present embodiment is excellent in resistance to solvents such as N-methylpyrrolidone (NMP) (hereinafter may be referred to as "solvent resistance").

The reason why the shrinkage stress of the cured film using the resin composition of this embodiment is suppressed is unknown, but it is speculated as follows: the monomer component has a (meth)acryloyl group similarly to the polymer component, and the polymer component ( The total number of (meth)acryl groups of the same type as the meth)acryl group is 2 or less, so the degree of reaction between the monomer component and the polymer component based on the (meth)acryl group is controlled, and the shrinkage stress during hardening production is suppressed. On the other hand, it is presumed that the curable composition of the present embodiment is also excellent in solvent resistance as described above, so that the curing reaction proceeds sufficiently although the generation of shrinkage stress is suppressed.

(monomer component) The resin composition of this embodiment contains the monomer which has 1-6 (meth)acryloyl groups in 1 molecule. In addition, regarding the above-mentioned monomer, the total number of (meth)acryloyl groups of the same type as the (meth)acryloyl group of the polymer in one molecule of the monomer is 2 or less.

-Number of (meth)acryl groups contained in one molecule of the monomer component- Here, "a monomer having 1 to 6 (meth)acryl groups in 1 molecule" means that the total number of (meth)acryl groups contained in 1 molecule of the monomer component is 1 to 6 . As the monomer component, only a single monomer may be used, or a plurality of monomers may be used in combination.

When the resin composition of this embodiment uses one type of monomer alone as a monomer component, the total number of (meth)acryl groups in one molecule of the monomer component is the same as that of the monomer in one molecule. The number of (meth)acryl groups to have is the same, and the total number of "acryl groups" and "methacryl groups" contained in one molecule of the monomer corresponds to this.

Also, when the resin composition of this embodiment uses a plurality of monomer components, the number of (meth)acryl groups in the monomer components is equal to the number of (meth)acryl groups that each monomer has. The value calculated by multiplying the mass ratio of each monomer in the whole monomer component is the value obtained by summing up the values of each monomer component. "The number of (meth)acryloyl groups" of a monomer component can be calculated as follows, for example. Furthermore, when the monomer component contains a monomer having an acryl group and a monomer having a methacryl group, or a monomer having both an acryl group and a methacryl group, each monomer For body composition, respectively calculate the total acryl group number and the total methacryl group number multiplied by the mass ratio of each monomer in the monomer composition as a whole, and the total value is the total.

The number of acryl groups (or methacryl groups) in monomer components comprising multiple monomers (component 1 to component n) = [(The total number of acryl groups (or methacryl groups) in component 1) x (the ratio of component 1 to the total monomer components)] + [(acryl groups (or methacryl groups) in component 2) total)×(ratio of component 2 to the whole monomer component)]+・・・・+[(total number of acryl (or methacryl) of component n)×(component n relative to monomer Ratio of all ingredients)]

For example, when the monomer component contains monomer component 1 having one acryl group and monomer component 2 having two acryl groups at a mass ratio of 20/80, the (meth)acrylic content of the monomer component The number of acyl groups is 1×(20/(20+80))+2×(80/(20+80))=1.8.

-The total number of (meth)acryl groups of the same type as the (meth)acryl groups of the polymer in one molecule of the monomer- Next, "the total number of (meth)acryl groups of the same type as the (meth)acryl groups of the polymer in one molecule of the monomer" refers to the number of monomer components when the polymer has an acryl group. The total number of acryl groups contained in one molecule refers to the total number of methacryl groups contained in one molecule of the monomer component when the polymer has a methacryl group. In the case of both the acryl group and the methacryl group, it refers to the total number of acryl groups and the total number of methacryl groups contained in one molecule of the polymer component.

The number of (meth)acryloyl groups in 1 molecule of a monomer component is 1-6. When the number of (meth)acryl groups in 1 molecule of the said monomer component is 0, the reactivity with the polymer which has a (meth)acryl group may fall. Also, when the number of (meth)acryloyl groups in one molecule of the monomer component exceeds 6, the effect of suppressing shrinkage stress during curing decreases. The number of (meth)acryloyl groups in one molecule of the monomer component is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3.5 from the viewpoint of the effect of suppressing shrinkage stress during curing. , and more preferably 1-2.

The total number of (meth)acryl groups of the same type as the (meth)acryl groups of the polymer in one molecule of the monomer of the monomer component is 2 or less. If the total number of the (meth)acryl groups exceeds 2, the effect of suppressing the shrinkage stress during curing decreases. Moreover, from the viewpoint of the suppression effect of the shrinkage stress during curing, the above total number is preferably 1 or less, more preferably 0, but it is not particularly limited. Furthermore, from the viewpoint of the effect of suppressing shrinkage stress during curing, it is preferable that the monomer component of this embodiment has only either one of an acryl group and a methacryl group as a (meth)acryl group. . For example, if the monomer component has only one of acryl group and methacryl group, and the (meth)acryl group in one molecule of the monomer is the same as the (meth)acryl group of the polymer When the total number is 0, the polymer component has only a methacryl group or a group that the monomer component of the acryl group does not have.

From the viewpoint of the effect of suppressing shrinkage stress during curing, the (meth)acryl equivalent weight of the monomer component is preferably 220 or more, more preferably 300 or more, particularly preferably 350 or more. The (meth)acryl equivalent of the monomer component in the composition can be calculated by (the formula weight of the monomer) ÷ (the (meth)acryl group number). When multiple monomer components are used, the (meth)acryl equivalent is the value calculated by multiplying the (meth)acryl equivalent of each monomer by the mass ratio of each monomer in the total monomer components , is the value obtained by summing up the values of each monomer component.

Specific examples of monomer components include the following compounds. Examples of monomers having one acryl group include: α-(1-oxo-2-propen-1-yl)-ω-[4-(1-methyl-1-phenylethyl) )phenoxy]poly(ethylene oxide), hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-octyl acrylate, isononyl acrylate, Lauryl Acrylate, Isodecyl Acrylate, Stearyl Acrylate, Iso-Furyl Acrylate, Tetrahydrofurfuryl Acrylate, Tetrahydrofurfuryl Acrylate, Cyclohexyl Acrylate, Benzyl Acrylate, Phenoxyethyl Acrylate, Ethyl Acrylate Carbitol acrylate, methoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol acrylate, acrylic acid (2-methyl- 2-Ethyl-1,3-dioxolan-4-yl)methyl ester, (3-ethyloxetan-3-yl)methyl acrylate, cyclic trimethylolpropane formal acrylic acid ester, 3,3,5-trimethylcyclohexyl acrylate, ethoxylated o-phenylphenol acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentyl acrylate, nonylbenzene Oxypolyethylene glycol acrylate, nonylphenoxy polyethylene glycol acrylate, tetrahydrofuran methanol acrylate polymer, ethoxyethoxyethanol acrylate polymer, 2,2,2-triacrylate Fluoroethyl ester, 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate, etc.

Examples of monomers having one methacryl group include: hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, isobutyl methacrylate, methacrylic acid Tertiary butyl ester, n-octyl methacrylate, isononyl methacrylate, lauryl methacrylate, isodecyl methacrylate, stearyl methacrylate, iso-thiol methacrylate, methacrylic acid Tetrahydrofurfuryl, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, ethyl carbitol methacrylate, methoxymethacrylate ethyl ethyl ester, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, methacrylic acid (2-methyl-2 -Ethyl-1,3-dioxolan-4-yl)methyl ester, (3-ethyloxetan-3-yl)methyl methacrylate, cyclic trimethylolpropane formal Methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, ethoxylated o-phenylphenol methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxy methacrylate Ethyl ester, dicyclopentyl methacrylate, nonylphenoxy polyethylene glycol methacrylate, nonylphenoxy polyethylene glycol methacrylate, etc.

Examples of monomers having two acryl groups include the following bisphenol AEO3.8 molar adduct diacrylate, the following ethoxylated bisphenol A diacrylate, 1,4-butanediol diacrylate, Acrylates, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, bisphenol A diglycidyl ether acrylic acid adduct, diethylene glycol diacrylate , Polyethylene Glycol #400 Diacrylate, Polypropylene Glycol #400 Diacrylate, Polypropylene Glycol #700 Diacrylate, Polytetramethylene Glycol Diacrylate, 1,6-Hexanediol Polymer Acrylate , Dioxanediol diacrylate, etc.

[chemical 1]

Examples of monomers having two methacryl groups include the following ethoxylated bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, and 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.

[Chem 2]

Examples of monomers having three or more acryl groups include tris-(2-acryloxyethyl) isocyanurate (number of acryl groups: 3), dipentaerythritol hexaacrylate (number of acryl groups: 6), dipentaerythritol pentaacrylate (acryl group number: 5), trimethylolpropane triacrylate (acryl group number: 3), pentaerythritol tri- and tetraacrylate (acryl group number: 3-4), ethoxylated Pentaerythritol tri- and tetraacrylate (acryl group: 3-4), ethoxylated glycerin triacrylate (acryl group: 3), propoxylated pentaerythritol tetraacrylate (acryl group: 4), di-trimethylol Propane tetraacrylate (number of acryl groups: 4), etc. Examples of monomers having three or more methacryl groups include tris-(2-methacryloxyethyl) isocyanurate (number of methacryl groups: 3), dipentaerythritol hexamethyl Acrylate (number of methacryl groups: 5), trimethylolpropane trimethacrylate (number of methacryl groups: 3), pentaerythritol tri- and tetramethacrylate (number of methacryl groups: 3~ 4), ethoxylated pentaerythritol tri- and tetramethacrylate (number of methacryl groups: 3 to 4), ethoxylated glycerin trimethacrylate (number of methacryl groups: 3), propoxylated pentaerythritol tetramethacrylate Esters (number of methacryl groups: 4), di-trimethylolpropane tetramethacrylate (number of methacryl groups: 4), and the like.

Among the above-mentioned monomer components, α-(1-oxo-2-propen-1-yl)-ω-[4-(1-methyl-1-phenylethyl)phenoxy is especially preferred ] poly(ethylene oxide), bisphenol AEO3.8 molar adduct diacrylate, ethoxylated bisphenol A dimethacrylate, tris-(2-acryloxyethyl)isocyanurate, diacrylate Pentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and then preferably bisphenol AEO3.8 mole adduct diacrylate, α-(1-side oxy-2-propen-1-yl)-ω-[ 4-(1-Methyl-1-phenylethyl)phenoxy]poly(oxyethylene).

Also, the content of the monomer component of the present embodiment in the resin composition 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, particularly preferably 20 to 40% by mass. In this specification, "total solid content" means all the components in the resin composition except the solvent.

Moreover, the resin composition of this embodiment may contain other monomers in the range which does not impair the effect of this invention. As said other monomer, the photopolymerizable monomer used for a normal photosensitive resin composition can be used. When the other monomers described above are used in combination, the content of the monomer components of the present embodiment in all monomers is preferably at least 50% by mass, more preferably at least 80% by mass, and most preferably at least 90% by mass.

The mass ratio [x:y] of the polymer component [x] to the monomer component [y] (=monomer component content (g):polymer component content (g)) of the resin composition of this embodiment is equal to It is not particularly limited, but from the viewpoint of the effect of suppressing shrinkage stress during hardening, it is preferably 30:100 to 160:100, more preferably 40:100 to 100:100, and most preferably 50:100 to 80: 100.

The mass ratio of the polymer component [x] to the monomer component [y] can be adjusted by appropriately changing the addition amount of the monomer component or the polymer component. Also, the measurement method of the above-mentioned mass ratio is not particularly limited, and the polymer component and the monomer component contained in the resin composition can be separated by a known method, and the polymer component and the monomer component of each embodiment of the present invention can be specified, and by This is measured. For example, using a low-polarity solvent (such as n-hexane) to separate out the polymer components and separate them from the monomer (and photopolymerization initiator) components, and then grasp the quality of each component after removing the solvent, and to The content of the polymer component and the monomer component of each embodiment was analyzed to obtain the mass ratio of the polymer component [x] to the monomer component [y]. At this time, if the content of oligomers or photopolymerization initiators or other additives can be specified by gas chromatography mass spectrometry (GCMS) or liquid chromatography mass spectrometry (LCMS), then it can be obtained by Quantitative analysis such as gas chromatography (GC) and liquid chromatography (LC) can obtain the above-mentioned mass ratio with high precision.

(polymer composition) The resin composition of this embodiment contains the polymer which has a (meth)acryl group in 1 molecule. It is preferable to use an alkali-soluble resin as a polymer component of this embodiment. Moreover, although it is preferable that the polymer component of this embodiment has only any one of an acryl group and a methacryl group as a (meth)acryl group, it does not specifically limit.

From the viewpoint of the effect of suppressing shrinkage stress during curing, the (meth)acryl equivalent weight of the polymer component is preferably 520 or more, more preferably 600 or more, and particularly preferably 700 or more.

The polymer component may also have other reactive groups than (meth)acryl groups. As another reactive group, a thermal crosslinkable group, a photocrosslinkable group, etc. are mentioned, for example, Among them, it is preferable to have a thermal crosslinkable group as another reactive group.

Also, when the polymer component has a thermally crosslinkable group other than the (meth)acryl group, from the viewpoint of suppressing shrinkage stress during curing, the thermally crosslinkable group equivalent of the polymer component ( The equivalent to the total amount of thermally crosslinkable groups including (meth)acryloyl groups) is also preferably more than 520, more preferably 600 or more, particularly preferably 700 or more.

The weight average molecular weight of the polymer component is preferably from 3,000 to 50,000, more preferably from 4,000 to 30,000 from the viewpoint of suppressing stickiness (adhesion) of the cured film, or from the viewpoint of manufacturability when forming a cured film. 5,000 to 20,000. The molecular weight of the polymer component can be determined by gel permeation chromatography (manufactured by Tosoh Co., Ltd., product number: HLC-8120, column: 2 connections of G-5000HXL and G-3000HXL, detector: RI, mobile phase : tetrahydrofuran) to carry out.

The polymer component of this embodiment may be used individually, and may combine plural types. The content of the alkali-soluble resin in the resin composition of the present 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) described above. For example, From the viewpoint of solubility in a developer when used as a photoresist, etc., it is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, relative to the total solid content in the composition , preferably 20 to 40% by mass.

The polymer component of the present embodiment can be used without particular limitation as long as it is a polymer including a unit structure having a (meth)acryl group in 1 molecule. The unit structure of the present embodiment is not particularly limited, and examples thereof include alkyl (meth)acrylates derived from (meth)acrylic acid, methyl (meth)acrylate, and butyl acrylate, and methacrylic acid- Unit structure of 2-hydroxyethyl ester, dicyclopentyl methacrylate, benzyl methacrylate, etc.

Also, regarding the unit structure having a (meth)acryl group, for example, by combining the above unit structure with glycidyl methacrylate, 2-acryloxyethyl isocyanate, 2-methyl isocyanate Acryloxyethyl ester, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, etc. react to form a unit structure with (meth)acryl group.

As a polymer component of this embodiment, the thing of the following structure is mentioned, for example.

[Chem 3]

(other) The resin composition of this embodiment may contain, for example, a photopolymerization initiation aid, fine particles of 100 nm or less, and the like within a range that does not hinder the effect of the resin composition of this embodiment.

The said photopolymerization start aid is a compound which does not function as a photopolymerization initiator alone, but increases the ability of a photopolymerization initiator by using it in combination with a photopolymerization initiator. As a photopolymerization start adjuvant, tertiary amines, such as triethanolamine which are effective when used together with benzophenone, are mentioned, for example.

The elastic recovery rate of the cured film of the resin composition of this embodiment can be improved by adding fine particles of 100 nm or less. It does not specifically limit as _a fine particle of 100 nm or less, For example, _Al2O3 , _{TiO2 , Fe2O3 ,} ZnO, _{CeO2 , Y2O3} , _Mn3O4 , _SiO2 etc. are mentioned. Also, the shape of the microparticles is not particularly limited, and examples thereof include spherical, spherical, and polyhedral shapes.

(Preparation of resin composition) The resin composition of this embodiment can be obtained by adding photopolymerization initiators, solvents, surfactants, leveling agents, chain transfer agents, polymerization inhibitors, viscosity Adjusters and the like are mixed and prepared. The resin composition of this embodiment is not particularly limited, and may be a negative-type photocurable resin.

-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) can be used suitably.

The photopolymerization initiator is not particularly limited, and examples thereof include: acetophenone, 2,2'-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, Dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone and other acetophenones; 2-benzyl-2-dimethylamino-1-(4-𠰌linylphenyl)- Butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-𠰌olin-4-yl-phenyl)-butane-1-one, 2- α-amino ketone photopolymerization initiators such as methyl-1-(4-methylthiophenyl)-2-𠰌linylpropan-1-one; or 1,2-octanedione 1-[4 -(phenylthio)-2-(O-benzoyl oxime)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- Base]-1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9.H.-carbazol-3-yl]-octane-1-ketoxime- O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazol-3-yl]-ethane-1-ketoxime-O-benzene Formate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazol-3-yl]-ethane-1-ketoxime-O-benzoyl Acid ester, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9.H.-carbazol-3-yl]-1-(O- Acetyl oxime), Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9.H.-carbazol-3-yl] -1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzoyl)-9.H.-carbazole-3 -yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-di Oxime ester photopolymerization initiators such as oxolanyl)methoxybenzoyl}-9.H.-carbazol-3-yl]-1-(O-acetyl oxime); or diphenyl Methanone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone and other benzophenones; benzoyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl Benzoin ethers such as ethers; benzoyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropyl Sulfur compounds such as thioxanthone; 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone and other anthraquinones; 2,4-trichloromethane Base-(4'-methoxyphenyl)-6-trichloromethyl, 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-trichloromethyl, 2,4-trichloromethyl Base-(sunflower base)-6-trisyl, 2,4-trichloromethyl-(4'-methoxystyryl)-6-tristyryl, etc.; azobisisobutyronitrile, peroxide Organic peroxides such as benzoyl oxide and cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, etc. These photopolymerization initiators may be used individually by 1 type, and may use 2 or more types together.

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 cured film, it is preferably 0.1 to 10.0 with respect to the total solid content in the composition. % by mass, more preferably 0.5 to 7.5% by mass, particularly preferably 1.0 to 5.0% by mass.

-Solvent- As said solvent, the well-known solvent used for a photosensitive resin composition can be selected suitably and used. The solvent is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; or ethyl acetate, butyl acetate, ethyl lactate, γ- Butyrolactone, propylene glycol monomethyl ether acetate (PGMAc), propylene glycol monoethyl ether acetate, 3-methoxymethyl propionate and other esters; or polyoxyethylene lauryl ether, ethylene glycol monomethyl ether, di Ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and diethylene glycol methyl ethyl ether; or aromatic hydrocarbons such as benzene, toluene, and xylene; or dimethylformamide, dimethylethyl ether, etc. Amides such as amides and N-methylpyrrolidone, etc.

-Surfactant- As said surfactant, the well-known surfactant used for a photosensitive resin composition can be selected suitably and used. As said surfactant, a silicone type surfactant, an acryl type surfactant, a fluorine type surfactant, etc. are mentioned, for example.

"Cured film and laminate" The cured film using the resin composition of this embodiment suppresses generation of shrinkage stress at the time of curing, and has little warping. Moreover, by providing the cured film of this embodiment on a board|substrate, the laminated body provided with a board|substrate and the cured film formed on a board|substrate can be made. The cured film formed using the resin composition of this embodiment is also excellent in solvent resistance. Therefore, for example, when another organic film is formed on the cured film of this embodiment, the solvent used for forming the organic layer is not stable. The tolerance is strong, which can suppress the reduction of film thickness caused by the influence of the solvent or the generation of defects caused by the infiltration of solvent in the film interface.

The cured film and laminated body of this embodiment can be formed by forming the coating film containing a resin composition on a board|substrate, exposing and developing the said coating film. It does not specifically limit as an exposure method, For example, the projection exposure (lens scanning) method using a multi-lens system can also be employ|adopted for the resin composition of this embodiment. As said board|substrate, it can select suitably according to the use of a cured film, For example, a well-known board|substrate, such as a glass plate and a polyimide film, can be used suitably.

Water, an organic solvent, an alkaline aqueous solution, etc. can be used suitably for the said image development. In consideration of the load on the environment, etc., it is preferable to use an alkaline aqueous solution. As the alkaline aqueous solution, for example, aqueous solutions of inorganic salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; aqueous solutions of organic salts such as hydroxytetramethylammonium and hydroxytetraethylammonium, can be used.

When the monomer component of this embodiment has the same type of (meth)acryl group as the polymer component of this embodiment, the polymer tends to react with the monomer during curing, but it is not particularly limited. On the other hand, when the monomer component of this embodiment and the polymer component of this embodiment have different (meth)acryl groups, there is a tendency for polymers and monomers to react during curing.

(film thickness) Since the resin composition of this embodiment suppresses the shrinkage stress at the time of forming a cured film, it can be usefully used especially for the formation of the organic film of a thick film. For example, the lower limit of the thickness of the cured film using the resin composition of this embodiment can be set to preferably 10 μm or more, further preferably 20 μm or more, and most preferably 30 μm or more depending on the application. Also, the upper limit of the thickness of the cured film can be set to 100 μm or less, preferably 90 μm or less, more preferably 80 μm or less depending on the application.

(curly) The shrinkage stress of the cured film of this embodiment is suppressed when the film is hardened. For example, the diameter of the curl produced by heating the sample piece (size 100 mm×100 mm×thickness 10 μm) at 230°C for 30 minutes can be 9.0 mm or more, preferably 15.0 mm or more, further preferably 20.0 mm or more. Also, regarding the cured film of this embodiment, even when a sample piece (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. Above, even in the case of making a sample piece with a thickness of 30 μm (size 100 mm×100 mm), the diameter of the curl measured under the same conditions is preferably 9.0 mm or more.

The larger the diameter of the above-mentioned curl, the more suppressed the curvature of the cured film is. In addition, if the above-mentioned curl is 9 mm or more, for example, even when a cured film is provided on a large substrate (such as a glass plate or polyimide film, etc.) of 600 mm×720 mm or more, it can be effectively suppressed. Warpage of the substrate or cracks and defects in the hardened film. In addition, when the thickness of the cured film is approximately 1 mm or less, the larger the thickness of the cured film, the smaller the curl tends to be. The value measured by the method described in the following Example can be used for the said curl.

"Purpose of Use" Cured products and laminates formed from the resin composition of this embodiment can be suitably used for various applications, especially optical members and displays using an organic film having a thickness of 10 μm or more. Specific uses include, for example, photosensitive spacers, members of optical sensors (collimator portions, etc.), displays and touch sensor outer coatings, color filters, and the like. [Example]

Hereinafter, the present invention will be described more specifically using examples and comparative examples. The present invention is not limited by the following examples.

(Synthesis of Polymer B-1) Add propylene glycol monomethyl ether acetate (389.5 g), methacrylic acid (50.0 g), methyl methacrylate (81.4 g ), 2-hydroxyethyl methacrylate (90.7 g), dicyclopentyl methacrylate (51.2 g). After blowing these mixtures under a nitrogen atmosphere for 1 hour and replacing them with nitrogen, 2,2'-azobis(isobutyronitrile) (15.3 g) was further added and reacted at 80° C. for 8 hours.

Add 2-acryloxyethyl isocyanate (65.6 g), 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl free radical to the obtained solution (0.01 g), reacted at 60° C. for 9 hours to obtain the target polymer B-1.

The type of (meth)acrylate contained in this polymer is only acrylate. Also, the molecular weight was measured by GPC (Gel Permeation Chromatography), and the weight average molecular weight (mW) of polymer B was 12,300, and the acryl equivalent calculated from the added molar ratio was 728. The structures of the obtained compounds are shown below.

[chemical 4]

(Synthesis of Polymer B-2) Add propylene glycol monomethyl ether acetate (305.1 g), propylene glycol monomethyl ether (138.7 g), and methacrylic acid (100.0 g) to a glass flask equipped with a heating and cooling-stirring device, a reflux cooling tube, and a nitrogen gas introduction tube. , methyl methacrylate (116.3 g), butyl acrylate (52.6 g). Stirring these mixtures was carried out under a nitrogen atmosphere for 1 hour, and after replacing with nitrogen, 2,2'- azobis(isobutyronitrile) (46.2 g) was added and it was made to react at 80 degreeC for 8 hours.

Glycidyl methacrylate (66.1 g), dimethylbenzylamine (0.6 g), and dibutylhydroxytoluene (0.02 g) were added to the obtained solution, and reacted at 100° C. for 9 hours to obtain the target Polymer B-2.

The kind of (meth)acrylic acid ester which this polymer has is methacrylic acid ester only. Moreover, when the molecular weight was measured by GPC, the weight average molecular weight (mW) of polymer B-2 was 7,400, and the methacryl equivalent calculated from the addition molar ratio was 735. The structures of the obtained compounds are shown below.

[chemical 5]

(Synthesis of Polymer B-3) Add propylene glycol monomethyl ether acetate (570.7 g), methacrylic acid (100.0 g), benzyl methacrylate (245.6 g ). Stirring these mixtures was carried out under a nitrogen atmosphere for 1 hour, and after replacing with nitrogen, 2,2'- azobis(isobutyronitrile) (40.4 g) was added and it was made to react at 80 degreeC for 8 hours. Glycidyl methacrylate (103.2 g), dimethylbenzylamine (0.6 g), and dibutylhydroxytoluene (0.03 g) were added to the obtained solution, and reacted at 100° C. for 9 hours to obtain the target Polymer B-3.

The type of (meth)acrylate contained in this polymer is only methacrylate. The molecular weight was measured by GPC. As a result, the weight average molecular weight (mW) of polymer B-3 was 10,000, and the methacryl equivalent calculated from the added molar ratio was 705.

[chemical 6]

(Synthesis of Polymer B-4) Cyclopentanone (371.4 g), methacrylic acid (65.0 g), and dicyclopentanyl methacrylate (135.0 g) were placed in a glass flask equipped with a heating-cooling-stirring device, a reflux cooling tube, and a nitrogen gas introduction tube. Stirring these mixtures was carried out under a nitrogen atmosphere for 1 hour, and after nitrogen substitution, 16.0 g of 2,2'- azobis(isobutyronitrile) was added, and it was made to react at 80 degreeC for 8 hours. Add 75.0 g of glycidyl methacrylate, 0.5 g of dimethylbenzylamine, and 0.03 g of 4-methoxyphenol to the obtained solution, and react at 100°C for 19 hours to obtain the target polymer B-4 .

The type of (meth)acrylate contained in this polymer is only methacrylate. The molecular weight was measured by GPC. As a result, the weight average molecular weight (mW) of polymer B-4 was 8,000, and the methacryl equivalent calculated from the added molar ratio was 523.

[chemical 7]

(Preparation of curable resin composition PR-1) Polymer B-1 (100 parts by mass (solid content)), monomer A-1 ((meth)acrylic acid equivalent 354.45) (60 parts by mass (solid content)), photopolymerization initiator (product Name: IRGACURE OXE01, manufactured by BASF Japan Co., Ltd.) (0.8 parts by mass (solid content)), surfactant (product name: DOWSIL Fz2122, manufactured by Dow Chemical Co., Ltd.) (0.2 parts by mass), and mixed as solids Propylene glycol monomethyl ether acetate as an organic solvent was added so that the component concentration became 40% by mass. After these mixtures were stirred, they were filtered through a membrane filter with a pore diameter of 5.0 μm to prepare curable resin composition PR-1.

(Preparation of curable resin compositions PR-2 to PR-18, and curable resin compositions CE-1 to CE-2) The polymer component, the monomer component, the photopolymerization initiator, the surfactant, the organic solvent, and the optional components of the type and amount shown in the following Table 1 were used, and the operation was carried out in the same manner as in Example 1. , and prepared curable resin compositions PR-2 to PR-18, and CE-1 to CE-4.

The names of monomers, photoinitiators, surfactants, and solvents used are shown below.

(monomer) ・Single unit (A-1): α-(1-oxo-2-propen-1-yl)-ω-[4-(1-methyl-1-phenylethyl)phenoxy]poly(oxyethylene) (product name: Viscoat #315, manufactured by Osaka Organic Chemical Industry Co., Ltd., acryl equivalent (average value) 322.13, number of acryl groups: 1, number of methacryl groups: 0)

[chemical 8]

・Single unit (A-2): Bisphenol A EO3.8 molar adduct diacrylate (product name: Viscoat#700HV, manufactured by Osaka Organic Chemical Industry Co., Ltd., acryl equivalent (average value) 338.4, number of acryl groups: 2, methyl Number of acryl groups: 0)

[chemical 9]

・Single unit (A-3): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (product name: ARONIX M-402, manufactured by Toagosei Co., Ltd., acryl equivalent (average) 99.8, number of acryl groups (average): 5.6, Number of methacryl groups: 0)

[chemical 10]

・Single unit (A-4): Tris-(2-acryloxyethyl) isocyanurate (product name: NK Ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd., acryl equivalent: 141.1, number of acryl groups: 3, methyl Number of acryl groups: 0)

[chemical 11]

・Single unit (A-5): Ethoxylated bisphenol A dimethacrylate (product name: NK Ester BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd., acryl equivalent (average value) 270.3, number of acryl groups: 0, methacryl Number of bases: 2)

[chemical 12]

・Single unit (A-6): A mixture of tripentaerythritol acrylate, mono- and dipentaerythritol acrylate, and polypentaerythritol acrylate (product name: Viscoat #802, manufactured by Osaka Organic Chemical Industry Co., Ltd., average acryl equivalent weight 101.4, number of acryl groups (average) : 6.8, the number of methacryl groups: 0)

[chemical 13]

(photopolymerization initiator) ・IRGACURE OXE-01 (manufactured by BASF Co., Ltd.) (surfactant) ・Silicone-based surfactant (DOESIL Fz2122, manufactured by Dow Chemical) (solvent) ・PGMAc: Propylene glycol monomethyl ether acetate ・PGM: Propylene Glycol Monomethyl Ether ・CPN: Cyclopentanone

(curl test) -Manufacture of Polyimide Film Coated with Cured Film for Curl Test- Polyimide film (product name: Kapton, manufactured by TORAY-DUPONT Co., Ltd., thickness 25 μm) was cut into a size of 10 cm×10 cm, and it was pasted on a sodium foil with a size of 10 cm×10 cm and a thickness of 0.7 mm. on the glass to make a substrate for coating. Then, using a spin coater, the curable resin composition was applied so that the dry film thickness became 10 micrometers, respectively, and it left still for 5 minutes on the ejector pin. Thereafter, the film was dried by heating in an oven at 100° C. for 2 minutes. Next, exposure (22 mW, 100 mJ) was performed using an exposure machine to perform photocuring. Furthermore, it developed using the tetramethylammonium hydroxide aqueous solution of the density|concentration of 0.4 mass %, and rinsed with pure water for 30 second after that. The obtained exposed and developed film was heated in an oven at 230° C. for 30 minutes to obtain a polyimide film coated with a cured film for a curl test. The following is a method for measuring the film thickness of the cured film.

-Curl test- When the obtained polyimide film coated with the cured film was separated from the glass substrate with a cutter knife, the polyimide film was wound up due to the stress of the cured film itself. At this time, the curled polyimide film was observed from the positive side in the winding direction, and the diameter of the curl was measured with a vernier caliper. Specifically, the average value of the length of the longest side and the length of the shortest side is set as the curl diameter, and the average value of the values obtained twice is set as the curl diameter of the present invention. Furthermore, the length of the longest side and the length of the shortest side do not include the length of the cured product and the polyimide film, that is, the inner diameter of the polyimide film of the so-called curled coating cured film.

[Manufacture of glass coated with cured film for film thickness measurement] The curable resin composition of each example was coated on a soda glass with a size of 10 cm×10 cm and a thickness of 0.7 mm to produce glass coated with a cured film. At this time, the coating amount of the curable resin composition was set to be the same as that at the time of preparation of the polyimide film of the coated cured film for the above-mentioned curl test. Furthermore, the production conditions of the cured film were set to the same conditions as when the curable resin composition was coated on the polyimide film in the production of the polyimide film of the coating cured film for the above-mentioned curl test, and then cured. Membrane production. Then, a part of the cured film on the glass substrate coated with the cured film was peeled off by a razor to measure the obtained film thickness, and was measured by a stylus surface shape measuring device (product name: P-10, KLA-Tencor Co., Ltd. Manufacturing) to measure the film thickness of the cured film.

[Solvent resistance test] N-methylpyrrolidone (NMP) was added to a glass petri dish, and the glass coated with a hardened film for film thickness measurement obtained above was immersed in NMP at 25° C. (solvent temperature) for 30 minutes. After 30 minutes, the glass coated with the cured film for film thickness measurement was taken out from the NMP, and the film thickness of the cured film after washing with water and drying was measured. Calculate the film thickness change rate (residual film rate) of the cured film after the solvent resistance test according to the following, and use it as an index of solvent resistance.

Residual film rate after solvent resistance test (%) = [(film thickness of cured film after solvent resistance test)÷(film thickness of cured film before solvent resistance test))]×100

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Curable resin composition (mass ratio) PR-1 PR-2 PR-3 PR-4 PR-5 PR-6 PR-7 PR-8 PR-9 A component A-1 60 70 80 90 100 160 100 100 100 A-2 - - - - - - - - - A-3 - - - - - - - - - A-4 - - - - - - - - - A-5 - - - - - - - - - B component 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 Surfactant 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 - Reactive group equivalent of A component 322 322 322 322 322 322 322 322 322 Reactive group equivalent of B component 728 728 728 728 728 728 728 735 705 The total number of (meth)acryl groups in component A 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 The total number of (meth)acryl groups in component A of the same type as 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 Curling 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

[Table 2] Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Curable resin composition (mass ratio) PR-10 PR-11 PR-12 PR-13 PR-14 PR-15 PR-16 PR-17 PR-18 A component A-1 - - - - - - - - 55 A-2 60 60 60 60 30 - 80 40 25 A-3 - - - - - - - 40 - A-4 - - - - - - - - - A-5 - - - - - 60 - - - B component 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 Surfactant 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 - Reactive group equivalent of A component 338 338 338 338 338 270 338 222 327 Reactive group equivalent of B component 728 735 705 523 728 728 735 735 705 The total number of (meth)acryl groups in component A 2.0 2.0 2.0 2.0 2.0 2.0 2.0 3.8 1.3 The total number of (meth)acryl groups in component A of the same type as 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 Curling 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

[table 3] Comparative example 1 Comparative example 2 Curable resin composition (mass ratio) CE-1 CE-2 A component A-1 - - A-2 - - A-3 60 - A-4 - - A-5 - - A-6 - 60 B component B-1 100 100 B-2 - - B-3 - - B-4 - - B-5 - - Photoinitiator 0.8 0.8 Surfactant 0.2 0.2 Organic solvents PGMAc PGMAc - - Reactive group equivalent of A component 100 101 Reactive group equivalent of B component 728 728 The total number of (meth)acryl groups in component A 5.6 6.8 The total number of (meth)acryl groups in component A of the same type as component B 5.0 0.0 Film thickness (um) 10.8 10.3 Curling diameter(mm) 5.9 6.5 Solvent resistance (%) 100.0 100.0

As shown in the results in the table, the curable resin compositions of the examples can form thick films, and the curl diameters are all 9.0 mm or more, and the shrinkage stress during the formation of the cured films is suppressed. Moreover, the solvent resistance of the obtained cured film was also excellent. On the other hand, it can be seen that although the number of (meth)acryl groups in one molecule of the monomer is 6 or less, the total number of (meth)acryl groups similar to the (meth)acryl groups of the polymer exceeds Both the curable resin composition of Comparative Example 1 of 2 and the curable resin composition of Comparative Example 2 using a monomer having more than 6 (meth)acryl groups in one molecule have a curl diameter of 9 mm Next, the shrinkage stress at the time of forming the cured film was not sufficiently suppressed.

The entirety of the invention of Japanese Patent Application No. 2021-106852 filed on June 28, 2021 is incorporated by reference into this specification. In addition, all documents, patent applications, and technical specifications described in this specification are incorporated by reference into this specification to the same extent as if each document, patent application, and technical specification were specifically and individually stated to be incorporated by reference. middle.

Claims (11)

A curable resin composition comprising a monomer having 1 to 6 (meth)acryl groups in one molecule, and A polymer having a (meth)acryl group in one molecule, and The total number of (meth)acryl groups similar to the (meth)acryl groups of the polymer in one molecule of the monomer is 2 or less. The curable resin composition according to claim 1, which comprises the above-mentioned monomer whose total number of (meth)acryloyl groups in one molecule is 1-2. The curable resin composition according to claim 1, wherein the above-mentioned monomer has only any one of an acryl group and a methacryl group as the above-mentioned (meth)acryl group. The curable resin composition according to claim 1, wherein the total number of (meth)acryl groups similar to the (meth)acryl groups of the polymer in one molecule of the above-mentioned monomer is zero. The curable resin composition according to claim 1, wherein the (meth)acryl equivalent weight in the polymer is 520 or more. The curable resin composition according to claim 1, wherein the equivalent weight of (meth)acryl in the above-mentioned monomers is 220 or more. The curable resin composition according to claim 1, wherein the mass ratio (x:y) of the above-mentioned monomer (x) to the above-mentioned polymer (y) is 30:100-160:100. A cured film formed using the curable resin composition according to any one of claims 1 to 7. The hardened film as claimed in item 8 has a film thickness of 10 μm or more. For the cured film according to claim 8, the diameter of the curl produced by heating at 230° C. for 30 minutes is 9.0 mm or more. A laminate comprising a substrate and the cured film according to claim 8 formed on the substrate.