WO2023276911A1

WO2023276911A1 - Curable resin composition, cured film obtained therefrom, and layered product

Info

Publication number: WO2023276911A1
Application number: PCT/JP2022/025437
Authority: WO
Inventors: 茂樹阿波
Original assignee: 大阪有機化学工業株式会社
Priority date: 2021-06-28
Filing date: 2022-06-27
Publication date: 2023-01-05
Also published as: KR20240018633A; CN117500855A; TW202307042A; JPWO2023276911A1

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 the same, and laminate

TECHNICAL FIELD The present invention relates to a curable resin composition, and a cured film and laminate using the same, and specifically, photospacers, members of optical sensors (collimator portions, etc.), overcoat layers of displays and touch sensors, and the like. It relates to a curable resin composition suitable for the production of, and a cured film and laminate using the same.

In recent years, the use of curable resin compositions using (meth)acrylates has expanded, and cured products using these compositions are used in various devices. For example, a cured film (organic film) using a curable resin composition can be applied to a wide variety of applications, including photo spacers, optical sensor members (collimator parts, etc.), and overcoat layers for displays and touch sensors. . In addition, with the development of technology in recent years, the demand for the performance of curable resin compositions is increasing more and more. For example, when forming a layered cured film, it is important to precisely control the shape of the cured film. It has become to.

Especially in recent years, there has been an increasing demand for so-called thick organic films exceeding 10 μm in thickness. Such examples include, for example, a negative photosensitive composition that can be developed even with a low-concentration alkaline developer, has excellent environmental resistance, and can be formed into a thick film (see the following patents: Reference 1).

Japanese Patent Application Laid-Open No. 2021-26029

On the other hand, unique characteristics are often required for thick film formation applications. For example, shrinkage stress is generated when the resin composition is cured, and if the shrinkage stress is too strong, a phenomenon such as a large warpage of the substrate or cracks or fissures in the film may occur. The adverse effects of these shrinkage stresses are particularly noticeable when a cured film is formed on a large glass substrate or when a thick cured film is formed. Therefore, development of a curable resin composition capable of suppressing shrinkage stress during the formation of a cured film is earnestly desired.

In order to solve the above-mentioned problems, the present invention aims to provide a curable resin composition capable of suppressing shrinkage stress during the formation of a cured film, a cured film using the same, and a laminate. .

The inventors diligently studied to solve the above problems. As a result, the inventors have found that the above-described problems can be achieved by combining a specific monomer and an alkali-soluble polymer, and have completed the present invention.

<1> a monomer having 1 to 6 (meth)acrylic groups in one molecule;
A curable resin composition containing a polymer having a (meth) acrylic group in one molecule,
The curable resin composition, wherein the total number of (meth)acrylic groups of the same type as the (meth)acrylic groups of the polymer is 2 or less in one molecule of the monomer.
<2> The curable resin composition according to <1>, comprising the monomer having 1 to 2 (meth)acrylic groups in total per molecule.
<3> The curable resin composition according to <1> or <2>, wherein the monomer has only one of an acrylic group and a methacrylic group as the (meth)acrylic group.
<4> The curability according to any one of <1> to <3>, wherein the total number of (meth)acrylic groups of the same type as the (meth)acrylic groups of the polymer in one molecule of the monomer is 0. Resin composition.
<5> The curable resin composition according to any one of <1> to <4>, wherein the polymer has a (meth)acrylic equivalent of 520 or more.
<6> The curable resin composition according to any one of <1> to <5>, wherein the (meth)acrylic equivalent of the monomer is 220 or more.
<7> Any one of <1> to <6>, wherein the mass ratio (x:y) between the monomer (x) and the polymer (y) is 30:100 to 160:100. A curable resin composition.
<8> A cured film formed using the curable resin composition according to any one of <1> to <7>.
<9> The cured film according to <8>, having a thickness of 10 μm or more.
<10> The cured film according to <8> or <9> above, wherein the curl generated by heating at 230° C. for 30 minutes has a curl diameter of 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.

According to the present invention, it is possible to provide a curable resin composition capable of suppressing shrinkage stress during the formation of a cured film, a cured film using the same, and a laminate.

Hereinafter, the form for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. However, the present invention is not limited to this, and various modifications are possible without departing from the scope of the invention. In the present specification, the terms "(meth)acrylic group", "(meth)acrylate", "(meth)acrylic acid", etc. include both an acrylic group (acryloyl group) and a methacrylic group (methacryloyl group). used with meaning.

<<Curable resin composition>>
The curable resin composition of the present embodiment (hereinafter sometimes simply referred to as "resin composition") includes a monomer having 1 to 6 (meth)acrylic groups in one molecule, and A curable resin composition comprising a polymer having a (meth)acrylic group, wherein the total number of (meth)acrylic groups of the same type as the (meth)acrylic groups of the polymer in one molecule of the monomer is 2 or less. be.

According to the resin composition of the present embodiment, a monomer having 1 to 6 (meth)acrylic groups in one molecule (hereinafter sometimes referred to as "monomer component") and a (meth) ) a polymer having an acrylic group (hereinafter sometimes referred to as “polymer component”). Furthermore, in the resin composition of the present embodiment, the total number of (meth)acrylic groups of the same type as the (meth)acrylic groups of the polymer is 2 or less in one molecule of the monomer.

By containing a monomer component and a polymer component that satisfy these requirements, the resin composition of the present embodiment can suppress shrinkage stress during the formation of a cured film. As a result, it is possible to suppress the occurrence of warpage of the cured film that occurs when forming a cured film on a glass substrate or when forming a thick cured film. In addition, the cured film obtained from the curable composition of the present embodiment has excellent resistance to solvents such as N-methylpyrrolidone (NMP) (hereinafter sometimes referred to as "solvent resistance").

The reason why the shrinkage stress is suppressed in the cured film using the resin composition of the present embodiment is unknown, but while the monomer component has a (meth) acrylic group like the polymer component, and the (meth) Since the total number of (meth)acrylic groups of the same type as acrylic groups is 2 or less, the degree of reaction between the monomer component and the polymer component by the (meth)acrylic groups is controlled, and the occurrence of shrinkage stress during curing is suppressed. It is assumed that there are On the other hand, since the curable composition of the present embodiment is also excellent in solvent resistance as described above, it is presumed that the curing reaction proceeds sufficiently while the generation of shrinkage stress is suppressed.

(monomer component)
The resin composition of this embodiment contains a monomer having 1 to 6 (meth)acrylic groups in one molecule. In addition, the total number of (meth)acrylic groups of the same kind as the (meth)acrylic groups of the polymer in one molecule of the monomer is 2 or less.

-Number of (meth)acrylic groups contained in one molecule of the monomer component-
Here, "a monomer having 1 to 6 (meth)acrylic groups in one molecule" means that the total number of (meth)acrylic groups contained in one molecule of the monomer component is 1 to 6. means. 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 the present embodiment uses a single monomer as a monomer component, the total number of (meth)acrylic groups in one molecule of the monomer component is the (meth)acrylic group in one molecule of the monomer. ), and corresponds to the total number of “acryl groups” and “methacryl groups” contained in one molecule of the monomer.

Further, when the resin composition of the present embodiment uses a plurality of types of monomer components, the number of (meth)acrylic groups of the monomer components is the number of (meth)acrylic groups possessed by each monomer in the total monomer components of each monomer. It is the value calculated by multiplying the mass ratio, and it is the total number of this value for each monomer component. The "number of (meth)acrylic groups" of the monomer component can be calculated, for example, as follows. In addition, when the monomer component contains a monomer containing an acrylic group and a monomer containing a methacrylic group, or a monomer containing both an acrylic group and a methacrylic group, the total number of acrylic groups and the total number of methacrylic groups for each monomer component are Each value calculated by multiplying the mass ratio of each monomer in the total monomer component is calculated separately, and the total value is the total number.

Number of acrylic groups (or methacrylic groups) of monomer components containing multiple monomers (component 1 to component n) =
[(total number of acrylic groups (or methacrylic groups) of component 1) × (ratio of component 1 to the total monomer components)) + [(total number of acrylic groups (or methacrylic groups) of component 2) × (monomer component of component 2 Ratio to the whole)) + ... + [(Total number of acrylic groups (or methacrylic groups) of component n) × (Ratio of component n to the total monomer components))

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

-The total number of (meth)acrylic groups of the same type as the (meth)acrylic groups of the polymer in one molecule of the monomer-
Next, "the total number of (meth)acrylic groups of the same kind as the (meth)acrylic groups of the polymer in one molecule of the monomer" is the acrylic group contained in one molecule of the monomer component when the polymer has an acrylic group. The total number of groups, the total number of methacrylic groups contained in one molecule of the monomer component when the polymer has methacrylic groups, and the total number of methacrylic groups contained in one molecule of the polymer component when the polymer has both acrylic groups and methacrylic groups. refers to the total number of acrylic groups and the total number of methacrylic groups.

The number of (meth)acrylic groups in one molecule of the monomer component is 1-6. When the number of (meth)acrylic groups in one molecule of the monomer component is 0, the reactivity with polymers having (meth)acrylic groups may decrease. Further, when the number of (meth)acrylic groups in one molecule of the monomer component exceeds 6, the effect of suppressing shrinkage stress during curing is reduced. The number of (meth)acrylic 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. 1 to 2 are more preferred.

The total number of (meth)acrylic groups of the same type as the (meth)acrylic groups of the polymer in one monomer molecule of the monomer component is 2 or less. If the total number of (meth)acrylic groups exceeds 2, the effect of suppressing shrinkage stress during curing is reduced. Although not particularly limited, the total number is preferably 1 or less, more preferably 0, from the viewpoint of the effect of suppressing shrinkage stress during curing. Furthermore, the monomer component of the present embodiment preferably has only one of an acrylic group and a methacrylic group as the (meth)acrylic group from the viewpoint of the effect of suppressing shrinkage stress during curing. For example, when the monomer component has only one of an acrylic group and a methacrylic group, and the total number of (meth)acrylic groups of the same type as the (meth)acrylic groups of the polymer in one molecule of the monomer is 0 , the polymer component will have only methacrylic groups or acrylic groups, whichever group the monomer component does not have.

The (meth)acrylic equivalent of the monomer component is preferably 220 or more, more preferably 300 or more, and particularly preferably 350 or more, from the viewpoint of the effect of suppressing shrinkage stress during curing. The (meth)acrylic equivalent of the monomer component in the composition can be calculated by (formula weight of monomer)/(number of (meth)acrylic groups). When using multiple monomer components, the (meth)acrylic equivalent is a value calculated by multiplying the (meth)acrylic equivalent of each monomer by the mass ratio of each monomer in the total monomer components, and summing this value for each monomer component value.

Specific examples of monomer components include the following compounds.
Monomers having one acrylic group include α-(1-oxo-2-propen-1-yl)-ω-[4-(1-methyl-1-phenylethyl)phenoxy]poly(oxyethylene), hydroxy ethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, isodecyl acrylate, stearyl acrylate, isobornyl 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, (2-methyl-2-ethyl-1 ,3-dioxolan-4-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl acrylate, cyclic trimethylolpropane formal acrylate, 3,3,5-trimethylcyclohexyl acrylate, ethoxylated-o-phenylphenol acrylate , dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, nonylphenoxypolyethylene glycol acrylate, nonylphenoxypolyethylene glycol acrylate, tetrahydrofurfuryl alcohol multimeric acrylic acid ester, ethoxyethoxyethanol multimeric acrylic acid ester, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H,1H,5H-octafluoropentyl acrylate, 1H,1H,2H,2H-tridecafluorooctyl acrylate, etc. mentioned.

Monomers having one methacrylic group include hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, isononyl methacrylate, lauryl methacrylate, isodecyl methacrylate, and stearyl methacrylate. , isobornyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, ethylcarbitol methacrylate, methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethyleneglycol methacrylate, methoxypolyethyleneglycol methacrylate , (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl methacrylate, (3-ethyloxetan-3-yl)methyl methacrylate, cyclic trimethylolpropane formal methacrylate, 3,3,5-trimethyl Cyclohexyl methacrylate, ethoxylated-o-phenylphenol methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, nonylphenoxy polyethylene glycol methacrylate, nonylphenoxy polyethylene glycol methacrylate, and the like.

Examples of monomers having two acrylic groups include the following bisphenol AEO 3.8 mol adduct diacrylate, the following ethoxylated bisphenol A diacrylate, 1,4-butanediol diacrylate, 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 acrylic acid polymer ester, dioxane glycol diacrylate, and the like can be mentioned.

Monomers having two methacrylic groups include the following ethoxylated bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, and 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, and the like.

Monomers having 3 or more acrylic groups include tris-(2-acryloyloxyethyl) isocyanurate (number of acrylic groups: 3), dipentaerythritol hexaacrylate (number of acrylic groups: 6), dipentaerythritol pentaacrylate (number of acrylic groups: 5 ), trimethylolpropane triacrylate (acrylic group number: 3), pentaerythritol tri- and tetraacrylate (acrylic group number: 3-4), ethoxylated pentaerythritol tri- and tetraacrylate (acrylic group number: 3-4), ethoxylated glycerin triacrylate Acrylate (number of acrylic groups: 3), propoxylated pentaerythritol tetraacrylate (number of acrylic groups: 4), ditrimethylolpropane tetraacrylate (number of acrylic groups: 4), and the like.
Monomers having 3 or more methacrylic groups include tris-(2-methacryloyloxyethyl) isocyanurate (number of methacrylic groups: 3), dipentaerythritol hexamethacrylate (number of methacrylic groups: 5), trimethylolpropane trimethacrylate (number of methacrylic groups: 3 ), pentaerythritol tri- and tetramethacrylate (number of methacrylic groups: 3-4), ethoxylated pentaerythritol tri- and tetramethacrylate (number of methacrylic groups: 3-4), ethoxylated glycerin trimethacrylate (number of methacrylic groups: 3), propoxylated pentaerythritol Examples include tetramethacrylate (number of methacrylic groups: 4), ditrimethylolpropane tetramethacrylate (number of methacrylic groups: 4), and the like.

Among the monomer components, α-(1-oxo-2-propen-1-yl)-ω-[4-(1-methyl-1-phenylethyl)phenoxy]poly(oxyethylene), bisphenol AEO 3.8 molar adduct diacrylate, ethoxylated bisphenol A dimethacrylate, tris-(2-acryloxyethyl)isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate are preferred, bisphenol AEO 3.8 molar adduct diacrylate, α -(1-oxo-2-propen-1-yl)-ω-[4-(1-methyl-1-phenylethyl)phenoxy]poly(oxyethylene) is more preferred.

In addition, the content of the monomer component in the present embodiment in the resin composition is not particularly limited, but for example, from the viewpoint of suppressing shrinkage stress during curing, the total solid content in the composition is 5 to 60. % by mass is preferable, 10 to 50% by mass is more preferable, and 20 to 40% by mass is particularly preferable. The term "total solids" used throughout this specification means all components other than the solvent in the resin composition.

In addition, the resin composition of the present embodiment may contain other monomers within a range that does not affect the effects of the present invention. As the other monomer, a photopolymerizable monomer used in a general photosensitive resin composition can be used. When other monomers are used in combination, the content of the monomer component in the present embodiment is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more, in all monomers.

In the resin composition of the present embodiment, the mass ratio [x:y] between the polymer component [x] and the monomer component [y] (= content of monomer component (g): content of polymer component (g)) is , Although not particularly limited, from the viewpoint of the effect of suppressing shrinkage stress during curing, 30: 100 to 160: 100 is preferable, 40: 100 to 100: 100 is more preferable, and 50: 100 to 80: 100 is preferable. Especially preferred.

The mass ratio between the polymer component [x] and the monomer component [y] can be adjusted by appropriately changing the charged amount of the monomer component and the polymer component. In addition, although the method for measuring the mass ratio is not particularly limited, the polymer component and the monomer component contained in the resin composition are separated by a known means, and the polymer component and the monomer component of the present embodiment are specified respectively. can be measured by
For example, the polymer component is precipitated with a solvent having a low polarity (for example, normal hexane), separated from the monomer (including the photopolymerization initiator) component, then the mass excluding the solvent in each component is determined, and each The mass ratio of the polymer component [x] to the monomer component [y] can be obtained by analyzing the contents of the polymer component and the monomer component in this embodiment. At this time, if the content of oligomers, photoinitiators and other additives can be specified by gas chromatography mass spectrometry (GCMS) or liquid chromatography mass spectrometry (LCMS), gas chromatography (GC), liquid chromatography A highly accurate mass ratio can be obtained by quantitative analysis such as (LC).

(polymer component)
The resin composition of this embodiment contains a polymer having a (meth)acrylic group in one molecule. As the polymer component in this embodiment, it is preferable to use an alkali-soluble resin. Although not particularly limited, the polymer component in the present embodiment preferably has only one of an acrylic group and a methacrylic group as the (meth)acrylic group.

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

The polymer component may have reactive groups other than (meth)acrylic groups. Other reactive groups include, for example, a thermally crosslinkable group and a photocrosslinkable group, and among these, it is preferable to have a thermally crosslinkable group as the other reactive group.

In addition, when the polymer component has a thermally crosslinkable group other than the (meth)acrylic group, the thermally crosslinkable group equivalent of the polymer component (equivalent to the total amount of the thermally crosslinkable group including the (meth)acrylic group) is also From the viewpoint of suppressing shrinkage stress during curing, it is preferably more than 520, more preferably 600 or more, and particularly preferably 700 or more.

The weight average molecular weight of the polymer component is preferably 3,000 to 50,000, preferably 4,000 to 30, from the viewpoint of suppressing stickiness (tack) of the cured film and from the viewpoint of manufacturability when forming the cured film. ,000 is more preferred, and 5,000 to 20,000 is particularly preferred. Molecular weight measurement of the polymer component is performed by gel permeation chromatography (manufactured by Tosoh Corporation, product number: HLC-8120, column: two connections of G-5000HXL and G-3000HXL, detector: RI, mobile phase: tetrahydrofuran). be able to.

The polymer component in this embodiment may be used alone or in combination. The content of the alkali-soluble resin in the resin composition of the present embodiment is not particularly limited. Although it can be determined, for example, from the viewpoint of solubility in a developer when used as a photoresist material, the total solid content in the composition is preferably 5 to 80% by mass, and 10 to 60 % by mass is more preferred, and 20 to 40% by mass is particularly preferred.

As the polymer component in the present embodiment, any polymer containing a unit structure having a (meth)acrylic group in one molecule can be used without any particular limitation. The unit structure in the present embodiment is not particularly limited, but examples include (meth)acrylic acid; alkyl (meth)acrylates such as methyl (meth)acrylate and butyl acrylate; 2-hydroxyethyl methacrylate; dicyclopentanyl methacrylate ; unit structures derived from benzyl methacrylate and the like.

Further, the unit structure having a (meth)acrylic group includes, for example, glycidyl methacrylate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxy A unit structure having a (meth)acrylic group can be obtained by reacting with cyclohexylmethyl methacrylate or the like.

Examples of the polymer component in this embodiment include those having the following structures.

(others)
The resin composition of the present embodiment may contain, for example, a photopolymerization initiation aid, fine particles of 100 nm or less, and the like, as long as the effects of the resin composition of the present embodiment are not impaired.

The photopolymerization initiation aid is a compound that does not function as a photopolymerization initiator by itself, but increases the ability of the photopolymerization initiator when used in combination with the photopolymerization initiator. Examples of photopolymerization initiation aids include tertiary amines such as triethanolamine, which are effective when used in combination with benzophenone.

Addition of fine particles of 100 nm or less can improve the elastic recovery rate of the cured film of the resin composition of the present embodiment. Fine particles of 100 nm or less are not particularly limited, but examples thereof include Al ₂ O ₃ , TiO ₂ , Fe ₂ O ₃ , ZnO, CeO ₂ , Y ₂ O ₃ , Mn ₃ O ₄ and SiO ₂ . Also, the shape of the fine particles is not particularly limited, but examples include spherical, spherical, and polyhedral shapes.

(Preparation of resin composition)
In addition to the above-described monomer components and polymer components, the resin composition of the present embodiment may optionally contain a photopolymerization initiator, a solvent, a surfactant, a leveling agent, a chain transfer agent, a polymerization inhibitor, and a viscosity modifier. , etc., and mixed. Although not particularly limited, the resin composition of the present embodiment can be a negative photocurable resin.

- Photoinitiator -
The resin composition in this embodiment can contain a photopolymerization initiator. Although not particularly limited, as the photopolymerization initiator in the present embodiment, one having an absorption wavelength in the i-line (365 nm) can be preferably used.

Examples of photopolymerization initiators include, but are not limited to, acetophenone, 2,2′-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p- Acetophenones such as tert-butylacetophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-( α-aminoketone-based photopolymerization initiators such as 4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -yl]-1-(O-acetyloxime), 1-[9-ethyl-6-benzoyl-9. H. -carbazol-3-yl]-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9. H. -carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9. H. -carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9. H. -carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9. H. -carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl }-9. H. -Carbazol-3-yl]-1-(O-acetyloxime) and other oxime ester photopolymerization initiators, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone and other benzophenones; benzyl, Benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropyl sulfur compounds such as thioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone; 2,4-trichloromethyl-(4′-methoxyphenyl)- 6-triazine, 2,4-trichloromethyl-(4′-methoxynaphthyl)-6-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4′-methoxy styryl)-6-triazine and other triazines; azobisisobutyronitrile, benzoyl peroxide, cumene peroxide and other organic peroxides, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc. and the like. One of these photopolymerization initiators may be used alone, or two or more thereof may be used in combination.

The content of the photopolymerization initiator in the resin composition of the present embodiment is not particularly limited. 0% by mass is preferred, 0.5 to 7.5% by mass is more preferred, and 1.0 to 5.0% by mass is particularly preferred.

-solvent-
As the solvent, a known solvent used in photosensitive resin compositions can be appropriately selected and used. Examples of solvents include, but are not limited to, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMAc ), esters such as propylene glycol monoethyl ether acetate and methyl-3-methoxypropionate, and 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.

-Surfactant-
As the surfactant, a known surfactant used in photosensitive resin compositions can be appropriately selected and used. Examples of the surfactant include silicone-based surfactants, acrylic surfactants, fluorine-based surfactants, and the like.

<<Cured film and laminate>>
A cured film using the resin composition of the present embodiment has reduced shrinkage stress during curing and is less warped. Further, by providing the cured film of the present embodiment on a substrate, it is possible to obtain a laminate including the substrate and the cured film formed on the substrate. Since the cured film formed using the resin composition of the present embodiment is also excellent in solvent resistance, for example, when forming another organic film on the cured film of the present embodiment, when forming the organic layer It has strong resistance to the solvent used, and can suppress the decrease in film thickness due to the influence of the solvent and the generation of defects due to penetration of the solvent at the film interface.

The cured film and laminate of this embodiment can be formed by forming a coating film containing a resin composition on a substrate, and exposing and developing the coating film. The exposure method is not particularly limited, but the resin composition of the present embodiment can also be employed, for example, in a projection exposure (lens scan) method using a multi-lens system. The substrate can be appropriately selected according to the use of the cured film, and for example, known substrates such as glass plates and polyimide films can be appropriately used.

For the development, water, an organic solvent, an alkaline aqueous solution, or the like can be used as appropriate. Considering the load on the environment, etc., it is preferable to use an alkaline aqueous solution. Examples of the alkaline aqueous solution 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 hydroxytetramethylammonium and hydroxytetraethylammonium.

Although not particularly limited, when the monomer component in the present embodiment and the polymer component in the present embodiment have the same (meth)acrylic group, the polymer and the monomer tend to react during curing. . On the other hand, when the monomer component in this embodiment and the polymer component in this embodiment have different (meth)acrylic groups, the polymers tend to react with each other and the monomers tend to react with each other during curing.

(film thickness)
Since the resin composition of the present embodiment has suppressed shrinkage stress during the formation of a cured film, it can be used particularly useful for forming a thick organic film. For example, the lower limit of the thickness of the cured film using the resin composition of the present embodiment is preferably 10 µm or more, more preferably 20 µm or more, and particularly preferably 30 µm or more, depending on the application. The upper limit of the thickness of the cured film can be 100 µm or less, preferably 90 µm or less, more preferably 80 µm or less, depending on the application.

(curl)
The cured film in the present embodiment has a suppressed shrinkage stress during film curing. It can be 0 mm or more, preferably 15.0 mm or more, more preferably 20.0 mm or more. In addition, even when the cured film in the present embodiment is a 20 μm thick sample piece (size 100 mm × 100 mm), it is preferable that the curl diameter measured under the same conditions is 9.0 mm or more. Even in the case of a sample piece having a thickness of 30 μm (size of 100 mm×100 mm), it is particularly preferable that the curl diameter measured under the same conditions is 9.0 mm or more.

The larger the curl diameter, the more suppressed the warpage of the cured film. Further, when the curl is 9 mm or more, for example, even when a cured film is provided on a large substrate of 600 mm × 720 mm or more (for example, a glass plate, a polyimide film, etc.), the substrate may warp or the cured film may be damaged. It is possible to effectively suppress the occurrence of cracks, chipping, and the like.
When the thickness of the cured film is approximately 1 mm or less, the curl tends to decrease as the thickness of the cured film increases. For the curl, a numerical value measured by the method described in Examples below can be used.

"Use applications"
Cured products and laminates formed from the resin composition of the present embodiment can be suitably used in various applications, particularly optical members and display applications in which an organic film of 10 μm or more is used. Specific uses include, for example, photospacers, members of optical sensors (collimators, etc.), overcoat layers of displays and touch sensors, and color filters.

Hereinafter, the present invention will be described more specifically using examples and comparative examples. The present invention is by no means limited by the following examples.

(Synthesis of polymer B-1)
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 dicyclopentanyl methacrylate (51.2 g) were charged.
After bubbling these mixtures under a nitrogen atmosphere for 1 hour while stirring and purging with nitrogen, 2,2′-azobis(isobutyrotril) (15.3 g) was further added and reacted at 80° C. for 8 hours.

2-Acryloyloxyethyl isocyanate (65.6 g) and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl (0.01 g) were added to the resulting solution and reacted at 60° C. for 9 hours. to obtain the desired polymer B-1.

The type of (meth)acrylate that the polymer had was only acrylate. Moreover, as a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of Polymer B was 12,300, and the acrylic equivalent calculated from the charge molar ratio was 728.
The structure of the obtained compound is shown below.

(Synthesis of polymer B-2)
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) were charged.
The mixture was bubbled for 1 hour under a nitrogen atmosphere while being stirred, and after purging with nitrogen, 2,2′-azobis(isobutyrotril) (46.2 g) was added and reacted at 80° C. for 8 hours.

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

The type of (meth)acrylate contained in the polymer was only methacrylate. Further, as a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of polymer B-2 was 7,400, and the methacrylic equivalent calculated from the charging molar ratio was 735.
The structure of the obtained compound is shown below.

(Synthesis of polymer B-3)
Propylene glycol monomethyl ether acetate (570.7 g), methacrylic acid (100.0 g), and benzyl methacrylate (245.6 g) were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. .
The mixture was bubbled for 1 hour under a nitrogen atmosphere while being stirred, and after purging with nitrogen, 2,2′-azobis(isobutyrotril) (40.4 g) was added and reacted at 80° C. 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 desired polymer B-3.

The type of (meth)acrylate possessed by the polymer was only methacrylate. As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of Polymer B-3 was 10,000, and the methacrylic equivalent calculated from the charging molar ratio was 705.

(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 condenser, and a nitrogen inlet tube. I prepared.
The mixture was bubbled for 1 hour under a nitrogen atmosphere while being stirred, and the mixture was replaced with nitrogen.
75.0 g of glycidyl methacrylate, 0.5 g of dimethylbenzylamine and 0.03 g of 4-methoxyphenol were added to the obtained solution and reacted at 100° C. for 19 hours to obtain the desired polymer B-4.

The type of (meth)acrylate possessed by the polymer was only methacrylate. As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of the polymer B-4 was 8,000, and the methacrylic equivalent calculated from the charging molar ratio was 523.

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

(Preparation of curable resin compositions PR-2 to PR-18 and curable resin compositions CE-1 to CE-2)
In the same manner as in Example 1 except that the types and amounts of polymer components, monomer components, photopolymerization initiators, surfactants, organic solvents and optional components shown in Table 1 below were used, a curable resin composition PR- 2 to PR-18, and CE-1 to CE-4 were prepared.

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

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

- Monomer (A-2):
Bisphenol A EO 3.8 mol adduct diacrylate (product name: Viscoat #700HV, manufactured by Osaka Organic Chemical Industry Co., Ltd., acrylic equivalent (average value) 338.4, number of acrylic groups: 2, number of methacrylic groups: 0 )

- Monomer (A-3):
A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (product name: Aronix M-402, manufactured by Toagosei Co., Ltd., acrylic equivalent (average value) 99.8, number of acrylic groups (average value): 5. 6, number of methacrylic groups: 0)

- Monomer (A-4):
Tris-(2-acryloxyethyl) isocyanurate (product name: NK Ester A-9300, Shin-Nakamura Chemical Co., Ltd., acrylic equivalent 141.1, number of acrylic groups: 3, number of methacrylic groups: 0)

- Monomer (A-5):
Ethoxylated bisphenol A dimethacrylate (product name: NK Ester BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd., acrylic equivalent (average value) 270.3, number of acrylic groups: 0, number of methacrylic groups: 2)

- Monomer (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 acrylic equivalent 101.4, number of acrylic groups (average value) : 6.8, number of methacrylic groups: 0)

(Photoinitiator)
・ IRGACURE OXE-01 (manufactured by BASF Corporation)
(Surfactant)
- Silicone surfactant (DOESIL Fz2122, manufactured by Dow Chemical Company)
(solvent)
・PGMAc: propylene glycol monomethyl ether acetate ・PGM: propylene glycol monomethyl ether ・CPN: cyclopentanone

(Curl test)
-Preparation of cured film-coated polyimide film for curl test-
A 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 attached with a tape on a soda glass having a size of 10 cm × 10 cm and a thickness of 0.7 mm. A substrate for coating was produced. Then, a curable resin composition was applied using a spin coater so that the dry film thickness was 10 μm, and left to stand on a pin for 5 minutes. After that, the film was dried by heating in an oven at 100° C. for 2 minutes. Then, exposure was performed using an exposure machine (22 mW, 100 mJ) and photocuring was performed. Further, development was performed using a tetramethylammonium hydroxide aqueous solution having a concentration of 0.4% by mass, followed by rinsing with pure water for 30 seconds. The obtained film after exposure and development was heated in an oven at 230° C. for 30 minutes to obtain a cured film-coated polyimide film for curl test. A method for measuring the film thickness of the cured film will be described later.

-Curl test-
When the obtained cured film-coated polyimide 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 side in the winding direction, and the curl diameter was measured with a vernier caliper. Specifically, the average value of the length of the longest side and the length of the shortest side was taken as the curl diameter, and the average value of the values obtained by doing this twice was taken as the curl diameter in the present invention. The length of the longest side and the length of the shortest side are lengths that do not include the cured product and the polyimide film, and are, so to speak, the inner diameter of the curled cured film-coated polyimide film.

[Preparation of cured film coated glass for film thickness measurement]
The curable resin composition of each example was applied onto a soda glass having a size of 10 cm×10 cm and a thickness of 0.7 mm to prepare a cured film-coated glass. At this time, the coating amount of the curable resin composition was the same as in the preparation of the cured film-coated polyimide film for the curl test. Further, the cured film was prepared under the same conditions as those for coating the curable resin composition on the polyimide film in the preparation of the cured film-coated polyimide film for the curl test.
Then, part of the cured film on the cured film-coated glass substrate for film thickness measurement was peeled off with a razor and measured with a stylus surface profiler (product name: P-10, manufactured by KLA-Tencor). , the film thickness of the cured film was measured.

[Solvent resistance test]
N-methylpyrrolidone (NMP) was placed in a glass petri dish, and the cured film-coated glass for film thickness measurement obtained above was immersed in NMP at 25° C. (solvent temperature) for 30 minutes.
After 30 minutes had passed, the cured film-coated glass 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. The film thickness change rate (remaining film rate) of the cured film after the solvent resistance test was calculated according to the following and used as a guideline for solvent resistance.

Remaining 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

As shown in the results in the table, the curable resin compositions of Examples can form thick films, and all of them have a curl diameter of 9.0 mm or more, and contraction stress during the formation of a cured film is suppressed. rice field. Moreover, the solvent resistance of the resulting cured film was also excellent.
On the other hand, the number of (meth)acrylic groups in one molecule of the monomer is 6 or less, but the total number of (meth)acrylic groups of the same type as the (meth)acrylic groups of the polymer exceeds 2. Curing of Comparative Example 1 The curable resin composition and the curable resin composition of Comparative Example 2 using a monomer having more than 6 (meth)acrylic groups in one molecule both have a curl diameter of 9 mm or less, and the cured film It can be seen that the shrinkage stress during formation is not sufficiently suppressed.

The disclosure of Japanese Patent Application No. 2021-106852 filed on June 28, 2021 is incorporated herein by reference in its entirety.
In addition, all publications, patent applications and technical standards mentioned in the specification shall be referred to to the same extent as if each individual publication, patent application or technical standard were specifically and individually noted to be incorporated by reference. , incorporated herein by reference.

Claims

A monomer having 1 to 6 (meth)acrylic groups in one molecule;
A curable resin composition containing a polymer having a (meth) acrylic group in one molecule,
The curable resin composition, wherein the total number of (meth)acrylic groups of the same type as the (meth)acrylic groups of the polymer is 2 or less in one molecule of the monomer.
The curable resin composition according to claim 1, comprising the monomer having 1 to 2 total (meth)acrylic groups in one molecule.
The curable resin composition according to claim 1, wherein the monomer has only one of an acrylic group and a methacrylic group as the (meth)acrylic group.
The curable resin composition according to claim 1, wherein the total number of (meth)acrylic groups of the same type as the (meth)acrylic groups of the polymer in one molecule of the monomer is 0.
The curable resin composition according to claim 1, wherein the polymer has a (meth)acrylic equivalent of 520 or more.
The curable resin composition according to claim 1, wherein the (meth)acrylic equivalent of the monomer is 220 or more.
The curable resin composition according to claim 1, wherein the mass ratio (x:y) of said monomer (x) and said polymer (y) is 30:100 to 160:100.
A cured film formed using the curable resin composition according to any one of claims 1 to 7.
The cured film according to claim 8, which has a film thickness of 10 μm or more.
The cured film according to claim 8, wherein the diameter of the curl generated 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.