JP2017111196A - Curable resin composition and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition that is excellent especially in light resistance adhesion and gives a cured product having an extremely high surface hardness, a cured film that is formed of such a curable resin composition, and a member for a display and a display that can achieve high performance by including the cured film.SOLUTION: There is provided a curable resin composition that contains an alkali soluble resin including a ring structure in the principal chain, the curable resin composition further containing a coupling agent and a phosphoric ester compound.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition and its use. More specifically, the present invention relates to a curable resin composition useful for constituent members of various display devices, a cured film using the same, a display device member, and a display device.

Various applications of curable resin compositions that can be cured by heat or active energy rays have been studied for components of various display devices represented by liquid crystal display devices, solid-state imaging devices, touch panel display devices, and the like. For example, a capacitive touch panel display device usually has a structure in which a transparent conductive film such as ITO is formed on a substrate, and a protective film or an insulating film for protecting the transparent conductive film is further formed. In addition to excellent adhesion to the transparent conductive film, constituent members such as protective films and insulating films are required to have high surface hardness in order to mitigate external impacts. As conventional curable resin compositions, compositions and the like described in Patent Documents 1 and 2 have been developed.

JP 2011-248274 A Japanese Patent Laying-Open No. 2015-172675

As described above, a cured product of the curable resin composition is required to exhibit excellent adhesion and high surface hardness. In recent years, with the advancement of technologies such as display devices, there has been a strong demand for higher performance for each member used. For example, it is possible to sufficiently suppress changes over time after prolonged light exposure. It is also demanded that various physical properties (adhesion and the like) are stably expressed, that is, excellent in light resistance such as light resistance and adhesion. However, the present situation is that a curable resin composition that can sufficiently meet these demands has not yet been developed. For example, in the compositions described in Patent Documents 1 and 2, the cured product has insufficient surface hardness and light-resistant adhesion, and there is room for improvement in these respects.

This invention is made | formed in view of the said present condition, and it aims at providing the curable resin composition which gives the hardened | cured material which is excellent in light-resistant adhesiveness and has high surface hardness. Another object of the present invention is to provide a cured film formed of such a curable resin composition, and a display device member and a display device that can realize high performance by having the cured film.

The present inventor, while variously examining the curable resin composition, using a polymer having a ring structure in the main chain as an alkali-soluble resin, and a composition containing a coupling agent and a phosphate ester compound, The synergistic effect of these components has been found to provide a composition that gives a cured product that is excellent not only in adhesion but also in light resistance such as light adhesion and having extremely high surface hardness (also referred to as hardness). Moreover, such a curable resin composition is particularly useful as a protective film or a resin composition for forming an insulating film used for a touch panel display device, a color filter, and the like, and a cured film obtained by curing this, It has also been found that the display device member and the display device can sufficiently meet the recent demand for higher performance, and the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.
The coupling agent used in the present invention is a compound containing no phosphorus atom (a phosphorus-free coupling agent). A coupling agent containing a phosphorus atom is not included in the coupling agent used in the present invention.

That is, the present invention is a curable resin composition containing an alkali-soluble resin having a ring structure in the main chain, and further containing a coupling agent and a phosphate ester compound.
The curable resin composition preferably further contains a polyfunctional polymerizable compound.
The curable resin composition preferably further contains a monofunctional polymerizable compound.
The curable resin composition preferably further contains an epoxy compound.

The present invention is also a cured film obtained by curing the curable resin composition.
The present invention is also a member for a display device having the cured film.
The present invention is also a display device having the cured film.

Since the curable resin composition of the present invention is configured as described above, it is particularly excellent in light-resistant adhesion and can provide a cured product having high surface hardness. Accordingly, a cured film, a member for a display device, and a display device obtained by curing such a curable resin composition are extremely useful in the optical field, the electric machine / electronic field, and the like.

Although the preferable form of this invention is demonstrated concretely below, this invention is not limited only to the following description, In the range which does not change the summary of this invention, it can change suitably and can apply. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more also corresponds to the preferable form of this invention.

[Curable resin composition]
The curable resin composition of the present invention (also simply referred to as a resin composition) includes an alkali-soluble resin, a coupling agent, and a phosphate ester compound, and further contains one or two other components as necessary. More than one species may be included. Each component can be used alone or in combination of two or more.

In the present specification, the “total amount of solids” of the resin composition refers to the total amount of components forming the cured product among the components constituting the resin composition, that is, components excluding the solvent that volatilizes when the cured product is formed ( This means the total amount of solid content and non-volatile content. Specifically, when an alkali-soluble resin, a coupling agent, a phosphate ester compound, and other cured product forming components (for example, a polymerizable compound, an epoxy compound, a coloring material, a dispersant, etc.) are included The total solid content mass of the component.

<Alkali-soluble resin>
The curable resin composition of the present invention contains a polymer having a ring structure in the main chain as an alkali-soluble resin. Use of such an alkali-soluble resin is excellent in heat resistance, surface hardness, adhesion, and light-proof adhesion.For example, even after high-temperature exposure or long-time light exposure, changes over time are suppressed and various physical properties are stabilized. A cured product that can be expressed can be provided.

In the resin composition, the total amount of the alkali-soluble resin (the total amount of the polymer having a ring structure in the main chain and other alkali-soluble resins that may be further included as necessary) is the solid content of the resin composition. It is preferably 5% by mass or more and more preferably 70% by mass or less with respect to the total amount of 100% by mass. By being in such a range, it becomes possible to show the effect of the present invention more remarkably. More preferably, it is 10-65 mass%, More preferably, it is 15-60 mass%, Most preferably, it is 15-50 mass%.
In addition, when using together other alkali-soluble resin, it is preferable that the ratio of the polymer which has a ring structure in a principal chain is 50 mass% or more in 100 mass% of total amounts of alkali-soluble resin. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

The alkali-soluble resin may be a resin (polymer) exhibiting alkali solubility, and is preferably a polymer having an acid group in its molecule (also referred to as an acid group-containing polymer). Examples of the acid group include a functional group that neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group, and has only one of these. You may have, and you may have 2 or more types. Among these, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is more preferable.

Although it does not specifically limit as acid value (AV) of the said alkali-soluble resin, For example, it is suitable that it is 20 mgKOH / g or more and less than 300 mgKOH / g. Thereby, more sufficient alkali solubility is expressed, and it becomes possible to obtain a cured product having better developability. More preferably, it is 40 mgKOH / g or more, More preferably, it is 60 mgKOH / g or more. When the acid value is 60 mgKOH / g or more, it is extremely useful for applications in which developability is regarded as important. Most preferably, it is 80 mgKOH / g or more. Further, from the viewpoint of curability, 250 mgKOH / g or less is more preferable, more preferably 230 mgKOH / g or less, particularly preferably 210 mgKOH / g or less, more preferably 200 mgKOH / g or less, and most preferably 150 mgKOH / g or less.
In the present specification, the acid value of the polymer is determined by measuring the acid value of the polymer solution by the method described in the examples described later, and then calculating the acid value per solid content from the acid value of the solution and the solid content of the solution. Can be obtained by calculating. The solid content of the polymer solution can be determined by the method described in Examples described later.

The alkali-soluble resin preferably has a weight average molecular weight of 5000 or more. Thereby, the developability and surface hardness of hardened | cured material can be improved. More preferably, it is 7000 or more, More preferably, it is 10,000 or more. The reason is not clear, but when a polymer having a weight average molecular weight of 10,000 or more is used, the pattern edge is perpendicular (square) because the polymerizable compound is more sufficiently suppressed from remaining on the pattern edge during development. That is, developability is remarkably improved. In addition, when such an alkali-soluble resin is used, the surface hardness of the cured product is further improved, and the heat resistance and the light-resistant adhesion are further improved. More preferably, it is 11000 or more, Especially preferably, it is 11500 or more, Most preferably, it is 12000 or more. Moreover, it is preferable that it is 250,000 or less from viewpoints, such as a viscosity. More preferably, it is 100,000 or less, More preferably, it is 50,000 or less, Especially preferably, it is 30,000 or less, Most preferably, it is 20,000 or less.
In addition, when alkali-soluble resin is high molecular weight, the one where an acid value is higher becomes easy to develop.
In this specification, a weight average molecular weight can be measured by the method as described in the Example mentioned later.

As said alkali-soluble resin, it is preferable that it is a polymer obtained by superposing | polymerizing the monomer component containing the monomer which can introduce | transduce a ring structure into the principal chain skeleton of a polymer, for example. In addition, a polymer obtained by reacting the polymer (also referred to as a base polymer) with a compound having a functional group capable of binding to an acid group and a polymerizable double bond (a polymer having a double bond in the side chain or It may also be referred to as a side chain double bond-containing polymer), and this side chain double bond-containing polymer is also included in the alkali-soluble resin of the present invention. Especially, in this invention, it is especially preferable to use the polymer which does not have a double bond in a side chain (polymer which does not contain a side chain double bond) from a viewpoint of improving light-resistant adhesiveness more.
In addition, the monomer and compound of a raw material can each use 1 type (s) or 2 or more types, and the monomer component (it is also called a monomer composition) which forms a base polymer is also called "base polymer component." Below, the raw material component and polymerization method of alkali-soluble resin are further demonstrated.

-Raw material components (monomers, etc.)-
(I) Monomer capable of introducing a ring structure into the main chain skeleton of the polymer As a monomer capable of introducing a ring structure into the main chain skeleton of the polymer, for example, it has a double bond-containing ring structure in the molecule. Examples thereof include a monomer and a monomer that forms a polymer having a cyclic structure in the main chain by cyclopolymerization. Such a monomer is preferably at least one selected from the group consisting of N-substituted maleimide monomers, acrylic ether dimers, and α- (unsaturated alkoxyalkyl) acrylate monomers. is there. In this case, the alkali-soluble resin is a polymer having an N-substituted maleimide monomer unit, an acrylic ether dimer unit, and / or an α- (unsaturated alkoxyalkyl) acrylate monomer unit.

In particular, a resin (polymer) containing an N-substituted maleimide monomer unit and / or an acrylic ether dimer unit is cured with improved heat resistance, dispersibility (for example, colorant dispersibility), hardness, and the like. It becomes possible to give a film. In addition, resins containing α- (unsaturated alkoxyalkyl) acrylate monomer units can contribute to plate-making properties such as adhesion, curability, and dry redissolvability, colorant dispersibility, heat resistance, and transparency. It is possible to provide a cured film with improved properties and the like.
The resin (polymer) containing the above-mentioned monomer unit means a resin containing a structural unit derived from the monomer by, for example, a monomer polymerization reaction or a crosslinking reaction.

(I-1) N-substituted maleimide monomer As N-substituted maleimide monomers, for example, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N -T-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, p-methylbenzylmaleimide, p-butylbenzylmaleimide, p-hydroxybenzylmaleimide, o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide , P-dichlorobenzylmaleimide, and the like. Among them, N-phenylmaleimide and N-benzylmaleimide are preferable from the viewpoint of transparency, and N-benzylmaleimide is particularly preferable. Examples of N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide; halogen-substituted benzylmaleimide such as o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide; and the like.

(I-2) Acrylic ether dimer As an acrylic ether dimer, for example, the following general formula (1):

(Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or an organic group having 1 to 25 carbon atoms which may have a substituent). is there.

In the general formula (1), R ¹ and R ² may represent a hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent, as the carbon group having 1 to 25 carbon atoms. . For example, a linear or branched alkyl group; an aryl group; an alicyclic group; an alkyl group substituted with alkoxy; an alkyl substituted with an aryl group exemplified in JP2013-061599A [0037] Group; etc. are mentioned. Of these, primary or secondary carbon hydrocarbon groups which are difficult to be removed by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl and the like, are preferable in terms of heat resistance.
Note that R ¹ and R ² may be the same type of organic group or different organic groups.

Among the acrylic ether dimers, dialkyl-2,2 '-(oxydimethylene) diacrylate monomers are preferable. Specifically, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-propyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2 ′-[ Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (stearyl)- , 2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2'- [Oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2,2′- [Oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, Dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) -2 2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′-[oxybis (methylene) )] Bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, and the like.

Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[ Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. From the viewpoints of little coloring, dispersibility, industrial availability, and the like, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate is more preferable.

(I-3) α- (unsaturated alkoxyalkyl) acrylate monomer As the α- (unsaturated alkoxyalkyl) acrylate monomer, for example, alkyl- (α-methallyloxymethyl) acrylate, α -(Allyloxymethyl) acrylate is preferred. Of these, α- (allyloxymethyl) acrylate is more preferable.

Examples of the α- (allyloxymethyl) acrylate include the following general formula (2):

A compound represented by the formula (wherein R ³ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms which may have a substituent) is preferable. In this specification, “α- (allyloxymethyl) acrylate” includes a compound in which R ³ is a hydrogen atom (that is, α-allyloxymethylacrylic acid).

R ³ may be appropriately selected according to the purpose and application, but the organic group having 1 to 30 carbon atoms that R ³ can represent may have a substituent, and 1 to 30 carbon atoms. The hydrocarbon group is preferably. Specifically, for example, a chain saturated hydrocarbon group exemplified in JP2013-061599A [0037]; an alkoxy-substituted chain in which a part of the hydrogen atoms of the chain saturated hydrocarbon group is replaced with an alkoxy group Linear saturated hydrocarbon group; hydroxy-substituted chain saturated hydrocarbon group in which part of chain saturated hydrocarbon group hydrogen atom is replaced with hydroxy group; part of chain saturated hydrocarbon group hydrogen atom is replaced with halogen Halogen-substituted chain saturated hydrocarbon group; chain unsaturated hydrocarbon group, and chain unsaturated hydrocarbon group in which part of the hydrogen atom is replaced with an alkoxy group, hydroxy group or halogen; alicyclic hydrocarbon group And an alicyclic hydrocarbon group in which a part of the hydrogen atom is replaced by an alkoxy group, a hydroxy group or a halogen; an aromatic hydrocarbon group and a part of the hydrogen atom are substituted by an alkoxy group, a hydroxy And aromatic hydrocarbon groups substituted with halogen; and the like. Moreover, arbitrary substituents may be further bonded to these organic groups.

Specific examples of the α- (allyloxymethyl) acrylate include, for example, α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid. n-propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α- N-amyl allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate , Α-allyloxymethyl acrylate s-hexyl, -N-heptyl allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid 2-ethylhexyl, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate, α -Tridecyl allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-allyloxy Contains chain saturated hydrocarbon groups such as stearyl dimethyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate, etc. α- (allyloxymethyl) acrylate is preferred. In addition, compounds exemplified in JP2013-061599A [0037] (for example, alkoxyalkyl-α- (allyloxymethyl) acrylate) are also suitable. Among these, methyl α-allyloxymethyl acrylate (also referred to as α- (allyloxymethyl) methyl acrylate) is particularly preferable.

The α- (unsaturated alkoxyalkyl) acrylate can be produced, for example, by a production method disclosed in International Publication No. 2010/114077.

The content ratio of the monomer capable of introducing a ring structure into the main chain skeleton of the polymer (total ratio when two or more are used) is, for example, 1 with respect to 100% by mass of the base polymer component (total amount). It is preferable that it is -40 mass%. Thereby, light-resistant adhesiveness, heat resistance, dispersibility, surface hardness, etc. can be further improved. In particular, the content ratio of N-substituted maleimide monomer, acrylic ether dimer, and / or α- (unsaturated alkoxyalkyl) acrylate (total ratio when two or more are used) is the above base polymer component. It is preferable that it is 1-40 mass% with respect to 100 mass%. When the content of the main chain ring structure derived from these monomer components increases, the adhesion and light-resistant adhesion tend to be improved. Further, when the addition amount of the N-substituted maleimide monomer is further increased, a cured product having higher hardness can be obtained, and when an acrylic ether dimer is used, a cured product having better heat resistance colorability can be obtained. If the content ratio of the N-substituted maleimide monomer is too large, the development speed may not be more appropriate. The content of the N-substituted maleimide monomer, acrylic ether dimer, and / or α- (unsaturated alkoxyalkyl) acrylate is more preferably 2 to 40% by mass, and still more preferably 3 to 35% by mass. .

(Ii) Monomer Having Acid Group The base polymer component preferably contains a monomer having an acid group in addition to a monomer capable of introducing a ring structure into the main chain skeleton of the polymer.
The monomer having an acid group is a compound having an acid group and a polymerizable double bond in the molecule. For example, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; Unsaturated monocarboxylic acids in which the chain between an unsaturated group and a carboxyl group, such as acid mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryloyloxyethyl); maleic anhydride, itaconic anhydride Unsaturated acid anhydrides such as phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); Among these, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. More preferred are unsaturated monocarboxylic acids in terms of reactivity, alkali solubility, etc., more preferred is (meth) acrylic acid (ie acrylic acid and / or methacrylic acid), and particularly preferred is methacrylic acid. .

The blending ratio of the monomer having an acid group is preferably, for example, 5% by mass or more with respect to 100% by mass of the total amount of the base polymer component. Thereby, the solubility with respect to an alkali becomes more sufficient, and it becomes a more useful resin composition for the use where developability is required. Moreover, it is preferable that it is 85 mass% or less at the point which can maintain the outstanding external appearance, adhesiveness, etc. of hardened | cured material after high temperature exposure or long time light exposure. More preferably, it is 8-80 mass%, More preferably, it is 10-75 mass%.

(Iii) Other monomer The base polymer component may be one kind of another monomer (also referred to as another monomer) that can be copolymerized with at least one of the above-described monomers, if necessary. Or you may contain 2 or more types. Other monomers are not particularly limited. For example, other (meth) acrylic acid ester monomers and aromatic vinyl monomers that do not correspond to the monomers (i) and (ii) above are used. Examples include a polymer.

Specific examples of the other (meth) acrylic acid ester monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid i. -Propyl, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, (meta ) T-amyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Cyclohexylmethyl, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, (meth Stearyl acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxy (meth) acrylate Ethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxy (meth) acrylate Butyl, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acryl Acid β-methylglycidyl, (meth) acrylic acid β-ethylglycidyl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid N, N-dimethylaminoethyl, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, etc. In addition, 1,4-dioxaspiro [4,5] dec-2-ylmethacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1 , 3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3 Dioxolane, alkoxylated phenylphenol (meth) acrylate.

Among the above (meth) acrylic acid ester monomers, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic are excellent in heat resistance and light adhesion. It is preferable to use acid cyclohexyl, benzyl (meth) acrylate, and alkoxylated phenylphenol (meth) acrylate. More preferably, in terms of excellent heat resistance, adhesion, light-resistant adhesion, and developability, methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and / or alkoxylated phenylphenol (Meth) acrylate is used.

Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene, methoxy styrene, and the like. Of these, styrene and vinyltoluene are preferable from the viewpoint of heat resistance coloring property and heat decomposition property of the resin.

The content ratio of the other (meth) acrylic acid ester monomer and / or aromatic vinyl monomer (total ratio when two or more are used) is, for example, 100% by mass of the base polymer component. On the other hand, it is suitable that it is 1-90 mass%. When it is within this range, a cured product that is more excellent in heat-resistant colorability, light-resistant adhesion, and alkali solubility can be obtained. More preferably, it is 5-85 mass%, More preferably, it is 10-85 mass%.

Examples of the other monomer include (meth) acrylamides exemplified in JP2013-227485A [0051]; a macromonomer having a (meth) acryloyl group at one end of a polymer molecular chain. Conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; The content is preferably 20% by mass or less in 100% by mass of the base polymer component.

Here, from the viewpoint of further improving the electrical characteristics of the cured product, it is preferable that the monomer used for obtaining the base polymer does not have a hydroxyl group. That is, it is preferable not to use a hydroxyl group-containing monomer for the polymerization when obtaining the base polymer. Specifically, for example, the proportion of the hydroxyl group-containing monomer is preferably 20% by mass or less with respect to 100% by mass of the total amount of the base polymer component.

Note that with a display device member having a cured product (cured film) with good electrical characteristics, for example, high definition can be achieved when touch-inputting a display device screen having a capacitive touch panel. Capacitance type touch panel is a position where a capacitance is formed between the finger and the (transparent) electrode of the touch panel when the user's finger touches the touch panel window, and the position touched by the change in capacitance accompanying this. Is detected. Therefore, it is possible to improve the performance of the display device by improving the electrical characteristics of various portions where the cured film is formed.

-Polymerization method-
As a method for polymerizing the monomer component, a commonly used technique such as bulk polymerization, solution polymerization, emulsion polymerization or the like can be used, and it may be appropriately selected according to the purpose and application. Among these, solution polymerization is preferred because it is industrially advantageous and structural adjustments such as molecular weight are easy. The polymerization mechanism of the monomer component may be a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization, but the polymerization method based on the radical polymerization mechanism is industrial. Is also preferable.

A preferred form of the polymerization reaction is as described in JP 2013-227485 A [0053] to [0065]. The polymerization time is preferably 1 to 8 hours, more preferably 1 to 5 hours, and further preferably 2 to 4 hours.

The alkali-soluble resin may be a polymer obtained by reacting the base polymer obtained as described above with a compound having a functional group capable of binding to an acid group and a polymerizable double bond. Examples of the polymerizable double bond in the compound having a functional group capable of bonding to a group and a polymerizable double bond include (meth) acryloyl group, vinyl group, allyl group, methallyl group, etc. Those having one or more of these are preferred. Of these, a (meth) acryloyl group is preferable in terms of reactivity. In addition, examples of the functional group capable of binding to an acid group include a hydroxy group, an epoxy group, an oxetanyl group, an isocyanate group, and the like, and those having one or more of these as the compound are suitable. . Of these, epoxy groups (including glycidyl groups) are preferred from the viewpoint of the speed of the modification treatment reaction, heat resistance, and dispersibility.

Examples of the compound having a functional group capable of binding to the acid group and a polymerizable double bond include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, Examples thereof include vinyl benzyl glycidyl ether, allyl glycidyl ether, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide, and the like, and one or more of these can be used. Among these, it is preferable to use a compound (monomer) having an epoxy group and a (meth) acryloyl group. In particular, glycidyl (meth) acrylate and / or (and) having high reactivity and being easy to control, easily available, and capable of introducing not only radical polymerizable double bonds but also hydroxyl groups at the same time. More preferred is (meth) acrylic acid 3,4-epoxycyclohexylmethyl.

The addition amount of the compound having a functional group capable of binding to the acid group and a polymerizable double bond is preferably 2 to 60 mass with respect to 100 mass parts of the total amount of the monomer component (base polymer component) giving the base polymer. Part. When the addition amount of the compound is within this range, the curability is further enhanced, the strength after curing is more sufficient, and the storage stability of the obtained polymer (polymer containing a side chain double bond) is also obtained. Is further improved, and coloring is sufficiently suppressed in the cured product. More preferably, it is 10 parts by mass or more. The upper limit is more preferably 55 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 45 parts by mass or less.

The method of adding a functional group capable of bonding to an acid group and a compound having a polymerizable double bond to a part of the acid group in the base polymer is not particularly limited as long as a known method is adopted. The reaction temperature is preferably, for example, 60 ° C to 140 ° C. It is also preferable to use a known catalyst such as an amine compound such as triethylamine or dimethylbenzylamine; an ammonium salt such as tetraethylammonium chloride; a phosphonium salt such as tetraphenylphosphonium bromide; an amide compound such as dimethylformamide;

As a result of the introduction of the double bond, the double bond equivalent (meaning the resin weight (g) per 1 mol of double bond) of the alkali-soluble resin (polymer containing side chain double bond) obtained is the light-resistant adhesion. From the viewpoint of improvement, it is preferably 3000 or more. More preferably, it is 4000 or more, More preferably, it is 4500 or more. On the other hand, from the viewpoint of improving the surface hardness, it is preferably 200 to 10,000, more preferably 400 to 5000, still more preferably 450 to 4000, particularly preferably 500 to 3000, more preferably 500 to 2000, and most preferably. 500-1500.

The double bond equivalent is a measure of the amount of double bonds contained in the molecule. If the compounds have the same resin weight, the amount of double bonds introduced decreases as the double bond equivalent value increases. . The double bond equivalent can be calculated from the charged amount of a polymer or a compound introducing a double bond. It can also be measured using various analyzes such as titration and elemental analysis, NMR and IR, and differential scanning calorimetry.
In the present specification, the double bond equivalent is determined by the following formula.
Double bond equivalent = (weight of base polymer + weight of compound containing functional group capable of binding to acid group and polymerizable double bond) / (compound containing functional group capable of binding to acid group and polymerizable double bond) Number of moles)

Here, in the present invention, as described above, it is particularly preferable to use a polymer containing no side chain double bond from the viewpoint of further improving the light-resistant adhesion. It is preferable that the ratio of such a side chain double bond-free polymer is 50% by mass or more with respect to 100% by mass of the total amount of the alkali-soluble resin used in the present invention. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

<Coupling agent>
The curable resin composition of the present invention also contains a coupling agent. The coupling agent has a property of binding to an oxidized surface of an inorganic substance through a hydrolysis reaction or a condensation reaction. In the present invention, only by using such a coupling agent and a phosphoric acid ester compound in combination, it is possible to achieve both high hardness and excellent light-resistant adhesion due to its synergistic effect, for example, sufficient change over time even after long-time light exposure. It is possible to suppress adhesion to stable expression of adhesion.

Examples of the coupling agent include a vinyl group, a (meth) acryl group, an epoxy group, an amino group, a mercapto group, a —N═C═O group, a —N (R ⁴ ) —C (═O) — group ( R ⁴ is preferably a coupling agent having a group such as a hydrogen atom (H) or an arbitrary group. Among these, those having a vinyl group, a (meth) acryloyl group and / or an epoxy group are preferable. More preferred is a (meth) acryloyl group. Moreover, what contains silicon, zirconia, titanium, and / or aluminum etc. as a center metal is suitable, and what has silicon as a center metal among these is preferable, More preferably, it is a silane coupling agent. By using a silane coupling agent, the adhesion, light-resistant adhesion and surface hardness of the cured product are further improved.

As the silane coupling agent, and one or more groups described above, the alkoxysilane group _{^{(-Si (OR 5) 3-}} n (R 6) n; OR 5 represents a hydrolyzable group, R ⁵ is preferably a hydrocarbon group, R ⁶ represents a hydrocarbon group, and n is 0, 1 or 2. Among these, it is preferable to use a silane coupling agent having a vinyl group, a (meth) acryloyl group and / or an epoxy group. This makes it possible to more sufficiently suppress changes in various physical properties such as appearance and adhesion even after light exposure for a long time and to obtain a cured product having more sufficient surface hardness.

Examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane.

Examples of the silane coupling agent having a (meth) acryloyl group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyltrimethoxy. Examples thereof include silane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyltriethoxysilane.

Specific examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidyl Sidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

Examples of the silane coupling agent having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropyl. Methyldiethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- ( 2-aminoethyl) aminopropylmethyldiethoxysilane, 3- (2-aminoethyl) aminopropyltriisopropoxysilane, 3- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino)- 2-methylpropyl Limethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl-3 -Aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, bis (3 -Trimethoxysilylpropyl) amine, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine and the like.

The silane coupling agent having an amino group also includes a primary amino group (—NH ₂ ) and a secondary amino group (—N (H) R ⁷ ; where R ⁷ is any group other than a hydrogen atom. -Represents an atom. The thing which has at least 1 sort (s) selected from the group which consists of is preferable, and what has at least a primary amino group is more preferable.

Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

Examples of the silane coupling agent having a —N═C═O group include 3-isocyanatopropyltriethoxysilane and the like, and a silane coupling agent having a —N (R ⁴ ) —C (═O) — group. Examples include tris- (trimethoxysilylpropyl) isocyanurate.

Among the silane coupling agents, a silane coupling agent having a (meth) acryloyl group is particularly preferable, and thereby the storage stability of the resin composition becomes better. Moreover, adhesiveness and light-resistant adhesiveness are also improved.
In addition, as a coupling agent which has metals other than silicon as a central metal, a zirco aluminate coupling agent, a titanate coupling agent, etc. are mentioned, for example.

In the curable resin composition, the content of the coupling agent is preferably 3 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin. Thereby, light-resistant adhesiveness and surface hardness are improved more. More preferably, it is 4 mass parts or more, More preferably, it is 5 mass parts or more. Moreover, it is preferable that it is 100 mass parts or less from a viewpoint of improving developability etc. other than being able to improve light-resistant adhesiveness more even if there is too much quantity. More preferably, it is 80 mass parts or less, More preferably, it is 70 mass parts or less, Especially preferably, it is 60 mass parts or less, Most preferably, it is 50 mass parts or less.

Among the coupling agents, the content of the silane coupling agent having a (meth) acryloyl group is preferably 1 to 100% by mass with respect to 100% by mass of the total amount of the coupling agent. Since the silane coupling agent having a (meth) acryloyl group has high compatibility with a phosphate ester, the effects of the present invention are further exhibited. More preferably, it is 30-100 mass%, More preferably, it is 50-100 mass%, Most preferably, it is 80-100 mass%.

<Phosphate compound>
The curable resin composition of the present invention also contains a phosphate ester compound. The phosphoric acid ester compound has one or more phosphoric acid ester structures (“O═P (OH) ₃ ”) in which _three or more hydrogen atoms of phosphoric acid represented by an organic group are substituted. The structure is not particularly limited as long as it is a compound having a structure, and it is possible to use one or more of monovalent phosphate monoester, divalent phosphate diester, and trivalent phosphate triester. it can. Of these, phosphoric acid monoesters, phosphoric acid diesters or mixtures thereof are preferred.

Although the ester group which the said phosphate ester compound has is not specifically limited, For example, alkyl groups, such as a methyl group, an ethyl group, an octyl group, and 2-ethylhexyl group; Aryl groups, such as a phenyl group, a tolyl group, a naphthyl group; Aralkyl group A group containing a polymerizable double bond such as a (meth) acryloyl group, a vinyl ether group, or a propenyl ether group; Among these, a group containing one or more polymerizable double bonds is preferable from the viewpoint of improving light resistance and hardness. That is, as the phosphoric acid ester compound, a compound having a polymerizable double bond is particularly preferable. Among these, in terms of reactivity, a compound having a (meth) acryloyl group (also referred to as a (meth) acryloyl group-containing phosphate compound) is preferable.

Examples of the (meth) acryloyl group-containing phosphate compound include the following general formula (3):

(In the formula, R ⁸ represents a hydrogen atom or a methyl group. R ⁹ represents an alkylene group having 1 to 4 carbon atoms, and may be linear or branched. X Represents an —OCO (CH ₂ ) _m — group, m represents an integer of 1 to 10, p represents an integer of 0 to 3, a represents an integer of 0 to 3). It is preferable that

In said formula (3), although p represents the integer of 0-3, Preferably it is 0 or 1, More preferably, it is 1. Among them, m in the —OCO (CH ₂ ) _m — group is preferably 2 to 10 because compatibility with other components is improved. More preferably, it is 3-6.
a represents an integer of 0 to 3, and is preferably 1 or 2. In addition, it is also suitable to use together the compound whose a in the said Formula (3) is 1, and the compound whose a is 2 as a phosphate ester compound.

Examples of the compound represented by the general formula (3) include 2- (meth) acryloyloxyethyl acid phosphate, bis [2-((meth) acryloyloxy) ethyl] phosphate, caprolactone-modified bis [2- ( (Meth) acryloyloxyethyl)] phosphate, caprolactone modified [2-((meth) acryloyloxyethyl)] acid phosphate, caprolactone modified bis [2-((meth) acryloyloxymethyl)] phosphate, caprolactone modified bis [2-((Meth) acryloyloxypropyl)] phosphate, caprolactone-modified bis [2-((meth) acryloyloxybutyl)] phosphate, and the like. Examples of commercially available products include KAYAMER series (for example, KAYAMER PM-1, PM-21, PM-2) manufactured by Nippon Kayaku Co., Ltd., and light ester series (for example, light esters P-1M, P-2M) manufactured by Kyoeisha Chemical Co., Ltd. Etc. are suitable.

In the curable resin composition, the content of the phosphate ester compound is preferably 3 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin. Thereby, light-resistant adhesiveness and surface hardness are improved more. More preferably, it is 4 mass parts or more, More preferably, it is 5 mass parts or more. Moreover, even if there is too much quantity, light-resistant adhesiveness may not be improved more, and it is preferable that it is 100 mass parts or less from viewpoints, such as coloring suppression and developability improvement. More preferably, it is 80 mass parts or less, More preferably, it is 60 mass parts or less, Especially preferably, it is 50 mass parts or less, Most preferably, it is 40 mass parts or less.

In the present invention, from the viewpoint of further exerting the effect of the present invention, the mass ratio of the coupling agent to the phosphate ester compound (coupling agent / phosphate ester compound) is 1 to 99/99 to 1. Is preferred. More preferably, it is 20-80 / 80-20, More preferably, it is 40-80 / 60-20, and the light resistance adhesiveness and surface hardness of hardened | cured material improve it notably more in this range. Especially preferably, it is 45-80 / 55-20.

<Polymerizable compound>
The curable resin composition of the present invention preferably also contains a polymerizable compound. The polymerizable compound is also referred to as a polymerizable monomer, and can be polymerized by irradiation with active radicals such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays), electron beams, etc. It is also a compound having a polymerizable group such as a polymerizable unsaturated group); a cationic polymerizable group; etc. (excluding an epoxy compound described later). The former is a compound containing a polymerizable unsaturated bond, and a radical polymerizable compound is particularly preferable.

The polymerizable compound (preferably a radical polymerizable compound) includes a monofunctional compound having one polymerizable group in the molecule (also referred to as a monofunctional polymerizable compound) and a polyfunctional compound having two or more ( (Also referred to as a polyfunctional polymerizable compound), and one or more of these can be used. Although the molecular weight of a polymeric compound is not specifically limited, From the viewpoint of handling, 2000 or less is suitable, for example.

Among the polymerizable compounds, the use of a polyfunctional polymerizable compound can further increase the surface hardness, and the use of a monofunctional polymerizable compound can further improve the light-resistant adhesion. Thus, the form in which the curable resin composition further contains a polyfunctional polymerizable compound and the form in which the curable resin composition further contains a monofunctional polymerizable compound are one of preferred forms of the present invention. . Especially, it is preferable that the resin composition of this invention contains a polyfunctional polymerizable compound and a monofunctional polymerizable compound, and, thereby, both surface hardness and light-resistant adhesiveness can be made compatible at a high level. More preferably, as described later, a polyfunctional (meth) acrylate compound and a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon group having 5 to 24 carbon atoms. Adhesion and light-resistant adhesion are further improved.

The polyfunctional polymerizable compound may have a functional number of 2 or more, preferably 3 or more. Thereby, photosensitivity and sclerosis | hardenability are raised more, and the hardness and transparency of hardened | cured material improve more. More preferably, it is 4 or more, More preferably, it is 5 or more. Further, from the viewpoint of further suppressing curing shrinkage, the functional number is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less. In addition, when it has two or more functional groups, the same functional group may be sufficient, but a different functional group may be sufficient.
Here, even if it is a polyfunctional polymerizable compound with few functional numbers, if it is a compound which has a fluorene skeleton, since the hardness of hardened | cured material can be improved more, it is preferable. Of these, polyfunctional (meth) acrylate compounds having a fluorene skeleton are preferred.

Examples of the polyfunctional polymerizable compound include a polyfunctional (meth) acrylate compound (such as a bifunctional (meth) acrylate compound and a trifunctional or higher polyfunctional (meth) acrylate compound) described below, as well as JP-A-2013-227485. No. [0097] to [0098], polyfunctional vinyl ether compounds; vinyl ether group-containing (meth) acrylate compounds; polyfunctional allyl ether compounds; allyl group-containing (meth) acrylic esters; polyfunctional (meth) Examples also include acryloyl group-containing isocyanurates; polyfunctional allyl group-containing isocyanurates; polyfunctional urethane (meth) acrylates; polyfunctional aromatic vinyls;

Among the polyfunctional polymerizable compounds, it is preferable to use a compound having a (meth) acryloyl group from the viewpoints of reactivity, economy, availability, and the like. That is, a polyfunctional (meth) acrylate compound is preferable, and by including this, the resin composition becomes more excellent in photosensitivity and curability, and a hardened and highly transparent cured product can be obtained. Thus, the form in which the polyfunctional polymerizable compound is a polyfunctional (meth) acrylate compound having two or more functions is a particularly preferred form of the present invention. The preferred range of the functional number is as described above. Therefore, it is more preferable to use a polyfunctional (meth) acrylate compound having three or more functions.

Here, the (meth) acryloyl group means a methacryloyl group and / or an acryloyl group. In the present invention, an acryloyl group is preferable from the viewpoint of excellent reactivity. That is, the polyfunctional (meth) acrylate compound is preferably a polyfunctional acrylate compound having two or more acryloyl groups.

Although the molecular weight of the said polyfunctional (meth) acrylate compound is not specifically limited, For example, 2000 or less is suitable from a viewpoint of handling. More preferably, it is 1000 or less. Moreover, 100 or more are suitable.

Although it does not specifically limit as said polyfunctional (meth) acrylate compound, For example, the following compound etc. are mentioned.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Bifunctional (meta) such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene ) Acrylate compounds;

Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (Meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol Trifunctional or more polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate;

When the curable resin composition of the present invention contains a polyfunctional polymerizable compound (preferably a polyfunctional (meth) acrylate compound), the content is 10 to 300 mass with respect to 100 mass parts of the total amount of the alkali-soluble resin. Part or less. Within this range, a cured product (cured film) that is more excellent in curability and light-resistant adhesion can be obtained, and developability is sufficient. More preferably, it is 20-250 mass parts, More preferably, it is 25-200 mass parts, Most preferably, it is 30-180 mass parts.

The monofunctional polymerizable compound is not particularly limited, and examples thereof include (meth) acrylic acid ester monomers; (meth) acrylamides; unsaturated monocarboxylic acids; and chain extension between an unsaturated group and a carboxyl group. Unsaturated monocarboxylic acids, aromatic vinyl monomers, N-substituted maleimide monomers, conjugated dienes, vinyl esters, vinyl ethers, N-vinyl compounds, unsaturated isocyanates, and the like. . Among these, (meth) acrylic acid ester monomers are preferable. That is, in other words, a monofunctional (meth) acrylate compound is preferable.

Examples of the monofunctional (meth) acrylate compound include monofunctional (meth) acrylate compounds having an aliphatic hydrocarbon group and monofunctional (meth) acrylate compounds having an aromatic ring (aromatic hydrocarbon group). Among these, the former is preferable, and a compound having one (meth) acryloyl group and an aliphatic hydrocarbon group having 5 to 24 carbon atoms in one molecule is particularly preferable. Specific examples of the aliphatic hydrocarbon group include an aliphatic saturated hydrocarbon group (alkyl group) and an aliphatic unsaturated hydrocarbon group (for example, alkenyl group). Among these, an aliphatic saturated hydrocarbon group is preferable because a cured product having further excellent adhesion and light-resistant adhesion can be obtained. Specifically, a group represented by C _n H _{2n + 1} (n = 5 to 24) is preferable.

The aliphatic hydrocarbon group preferably has 5 to 24 carbon atoms. As a result, the surface hardness of the cured product becomes more sufficient, and the compatibility with other components is also improved. More preferably, it is 8 or more as carbon number. Moreover, More preferably, it is 22 or less, More preferably, it is 20 or less.

The monofunctional (meth) acrylate compound having an aliphatic hydrocarbon group is preferably, for example, n-amyl (meth) acrylate, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n-hexyl (meta ) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate (also called lauryl (meth) acrylate) ), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) It has an aliphatic hydrocarbon group consisting of a linear or branched chain such as acrylate, 2-decyltetradecyl (meth) acrylate, 2-decyltetradecanyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate and the like. Compounds; compounds having an aliphatic hydrocarbon group having a cyclic structure such as isobornyl (meth) acrylate and adamantyl (meth) acrylate; and the like. Among these, compounds having an aliphatic saturated hydrocarbon group having a preferable carbon number described above are more preferable.

When the curable resin composition of the present invention contains a monofunctional polymerizable compound (preferably a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon group having 5 to 24 carbon atoms), the content ratio thereof is the above alkali-soluble property. It is preferable that it is 10-300 mass parts or less with respect to 100 mass parts of total amounts of resin. Within this range, a cured product (cured film) that is more excellent in curability and light-resistant adhesion can be obtained, and developability is sufficient. More preferably, it is 20-250 mass parts, More preferably, it is 25-200 mass parts, Most preferably, it is 30-180 mass parts.

When the curable resin composition of the present invention contains both a monofunctional polymerizable compound and a polyfunctional polymerizable compound, from the viewpoint of more exerting the effects of the present invention, the monofunctional polymerizable with respect to the total amount of 100% by mass. It is preferable that the mass ratio of a compound is 10-90 mass%. More preferably, it is 20-80 mass%, More preferably, it is 30-50 mass%.

In addition, the content ratio of other polymerizable compounds other than the polyfunctional (meth) acrylate compound and the monofunctional (meth) acrylate compound having an aliphatic hydrocarbon group having 5 to 24 carbon atoms is more sufficient for the effects of the present invention. From the viewpoint of making it possible to exhibit it, it is preferable that it is 10% by mass or less in a total amount of 100% by mass of the polymerizable compound. More preferably, it is 5 mass% or less, More preferably, it is 1 mass% or less.

<Epoxy compound>
The curable resin composition of the present invention preferably contains one or more epoxy compounds. This makes it possible to obtain a cured product that is superior in surface hardness and light-resistant adhesion. The epoxy compound means a compound containing an epoxy group, and the number of epoxy groups contained in one molecule of the compound may be 1 or 2 or more, preferably from the viewpoint of obtaining a cured product in a shorter time. 2 or more. That is, the epoxy compound is preferably a polyfunctional epoxy compound. The epoxy compound is also particularly preferably an epoxy resin from the viewpoint of more fully exhibiting the effects of the present invention.

The epoxy compound preferably has a weight average molecular weight of 100 or more and 250,000 or less. By using such an epoxy compound, the effects of the present invention can be more fully exhibited. More preferably, it is 150 or more, and from the viewpoint of viscosity, it is more preferably 100,000 or less, still more preferably 50,000 or less, and particularly preferably 10,000 or less.

Although it will not specifically limit if it is a compound which has an epoxy group in a molecule | numerator as said epoxy compound, The epoxy compound which has an alicyclic structure is especially suitable. When the resin composition of the present invention contains at least an epoxy compound having an alicyclic structure, the surface hardness of the cured product is further improved and the light resistance is also improved. As described above, a form including at least an epoxy compound having an alicyclic structure as the epoxy compound is also a preferred form of the present invention.

The epoxy compound having an alicyclic structure is a compound having an alicyclic structure and an epoxy group in the molecule, but from the viewpoint of improving the surface hardness, those having no aromatic ring in the molecule are particularly suitable. . In addition, a group (also referred to as an alicyclic epoxy group) in which an alicyclic structure and an epoxy group are integrated, such as an epoxycyclohexane group or an epoxy group added directly or via a hydrocarbon to a cyclic aliphatic hydrocarbon. The compound to be contained is also suitable as an epoxy compound having an alicyclic structure.

Among the epoxy compounds having an alicyclic structure, examples of the compound containing an alicyclic epoxy group include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, epsilon-caprolactone modified-3, In addition to compounds having an epoxycyclohexane group such as 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate, 2,2-bis (hydroxymethyl) -1 -Heterocycle-containing epoxy compounds such as 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of butanol and triglycidyl isocyanurate.

The epoxy compound having an alicyclic structure is also preferably a compound having an epoxy group directly or indirectly bonded to a saturated aliphatic cyclic hydrocarbon skeleton. More preferably, it is a compound having a glycidyl ether group bonded directly or indirectly to a saturated aliphatic cyclic hydrocarbon skeleton. Such an epoxy compound is preferably a hydrogenated product of a compound having an epoxy group bonded to an aromatic ring (also referred to as an aromatic epoxy compound), more preferably a glycidyl ether group bonded to an aromatic ring. It is a hydrogenated product of a compound having this (also referred to as an aromatic glycidyl ether compound). Specifically, hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, and the like are preferable. Particularly preferred are hydrogenated bisphenol A type epoxy compounds and hydrogenated bisphenol F type epoxy compounds.

The content of the epoxy compound is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. Thereby, the surface hardness and light-resistant adhesiveness of hardened | cured material improve further. More preferably, it is 20-100 mass parts, More preferably, it is 30-80 mass parts.

In the present invention, as the epoxy compound, one or more other epoxy compounds may be used together with or instead of the epoxy compound having the alicyclic structure described above. Preferably, 50 mass% or more of the epoxy compound having an alicyclic structure is used out of 100 mass% of the total amount of the epoxy compound used in the resin composition of the present invention. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

<Photopolymerization initiator>
It is preferable that the curable resin composition of the present invention also contains a photopolymerization initiator. Thereby, the sclerosis | hardenability and sensitivity of a resin composition improve more. Thus, the form in which the said curable resin composition further contains a photoinitiator is one of the suitable forms of this invention. Moreover, it is preferable that the curable resin composition of this invention is a photosensitive resin composition.

The photopolymerization initiator is preferably a radical polymerizable photopolymerization initiator. A radical polymerizable photopolymerization initiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam, and one or more commonly used ones can be used. . Moreover, you may use together 1 type (s) or 2 or more types of photosensitizers, radical photopolymerization promoters, etc. as needed. Sensitivity and curability are further improved by using a photosensitizer and / or a radical photopolymerization accelerator in combination with the photopolymerization initiator.

Specific examples of the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE907”, manufactured by BASF), 2-benzyl. 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“IRGACURE369”, manufactured by BASF), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morphol Aminoketone compounds such as phospho-4-yl-phenyl) -butan-1-one (“IRGACURE379”, manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethane-1-one (“IRGACURE651”, BASF), phenylglyoxylic acid methyl ester ("DAROCUR MBF", manufactured by BASF), etc. 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE184”, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (“DAROCUR1173”, manufactured by BASF) ), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“IRGACURE2959”, manufactured by BASF), 2-hydroxy-1- {4 -[4- (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (“IRGACURE127”, manufactured by BASF), [1-hydroxy-cyclohexyl-phenyl- Ketone + Benzophenone] ("IRGACURE500", manufactured by BASF) In addition to the above-mentioned hydroketone compounds, alkylphenone compounds, benzophenone compounds, benzoin compounds, thioxanthone compounds, halomethylated triazine compounds exemplified in JP2013-227485A [0084] to [0086] Halomethylated oxadiazole compounds; biimidazole compounds; oxime ester compounds; titanocene compounds; benzoate ester compounds; acridine compounds and the like; phosphine oxide compounds; oxime ester compounds;

Among the photopolymerization initiators, it is particularly preferable to use at least an aminoketone compound (also referred to as an aminoketone polymerization initiator). That is, the curable resin composition preferably further contains an aminoketone polymerization initiator. Thereby, hardness and developability become more excellent. It is also preferable to use a hydroketone compound (also referred to as a hydroketone polymerization initiator) or a benzyl ketal compound (also referred to as a benzyl ketal polymerization initiator).

The content of the photopolymerization initiator may be appropriately set according to the purpose, application, etc., and is not particularly limited, but is 0.1% by mass or more with respect to 100% by mass of the total solid content of the curable resin composition. Preferably it is. Thereby, it becomes possible to fully exhibit the effect of this invention. More preferably, it is 0.5 mass% or more, More preferably, it is 1 mass% or more. Further, considering the balance between the influence of the decomposition product of the photopolymerization initiator, economy, etc., it is preferably 35% by mass or less. More preferably, it is 25 mass% or less.

In the present invention, as described above, it is preferable to use an aminoketone polymerization initiator as the polymerization initiator. In this case, the total amount of the polymerization initiator (that is, the aminoketone polymerization initiator and other polymerization initiators) The aminoketone polymerization initiator is preferably 20% by mass or more with respect to 100% by mass of the total amount). More preferably, it is 30 mass% or more, More preferably, it is 50 mass% or more, Most preferably, it is 55 mass% or more.

Examples of the photosensitizer and photoradical polymerization accelerator that may be used in combination with the photopolymerization initiator include dye-based compounds and dialkylaminobenzene-based compounds exemplified in JP2013-227485A [0088]. Mercaptan hydrogen donors; and the like. In addition, the content (total amount) of the photosensitizer and / or photoradical polymerization accelerator may be appropriately set according to the purpose and application, and is not particularly limited. From the viewpoint of balance of properties, it is preferably 0.001 to 20% by mass with respect to 100% by mass of the total solid content of the curable resin composition of the present invention. More preferably, it is 0.01-15 mass%, More preferably, it is 0.05-10 mass%.

<Fluorine-based additive>
The curable resin composition of the present invention preferably also contains a fluorine-based additive (also referred to as a fluorine additive) from the viewpoint of improving curability and surface smoothness. The fluorine-based additive also has a function as a leveling agent.

The fluorine-based additive is a compound having a fluorine atom in the structure. For example, a compound that is usually used as a fluorine-based surfactant or a fluorine-based surface modifier can be used.

The fluorine-based additive is soluble in various organic solvents (for example, ether solvents, ester solvents, ketone solvents, alcohol solvents, etc.) from the viewpoint that it is preferable not to separate components in the curable resin composition. Those having a high value are more preferably used. Specifically, for example, those having an HLB value (hydrophilic / lipophilic balance) in the range of 0 to 16 are suitable. The HLB value is more preferably 1-13.
The HLB value is obtained by, for example, the Griffin method or the Davis method.

The fluorine-containing additive preferably further contains 0.01 to 80% by mass of fluorine in a total amount of 100% by mass of the fluorine-based additive. The fluorine content can be quantified by, for example, ion chromatography.

The fluorine-based additive also includes nonionic and anionic ones, and nonionic ones are preferable from the viewpoint of dispersibility with the resin and the like.

Specific examples of the fluorine-based additive include perfluorobutane sulfonate (Megafac F-114), perfluoroalkyl group-containing carboxylates (Megafac F-410), perfluoroalkylethylene oxide adducts ( Mega-Fuck F-444, EXP.TF-2066), perfluoroalkyl group-containing phosphate ester (Mega-Fact EXP.TF-2148), perfluoroalkyl group-containing phosphate ester-type neutralized amine (MegaFack EXP.TF) -2149), fluorine-containing group / hydrophilic group-containing oligomer (Megafac F-430, EXP • TF-1540), fluorine-containing group / lipophilic group-containing oligomer (Megafac F-552, F-554, F-558) F-561, R-41), fluorine-containing group / hydrophilic group / lipophilic group-containing o Gomer (Megafuck F-477, F-553, F-555, F-556, F-557, F-559, F-562, R-40, EXP / TF-1760), fluorine-containing group / hydrophilic group -Oligophilic group / UV-reactive group-containing oligomer (Megafac RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-77), etc. ). Among them, compounds containing lipophilic groups (containing fluorine-containing groups / lipophilic group-containing oligomers, fluorine-containing groups / hydrophilic groups / lipophilic group-containing oligomers, fluorine-containing groups / hydrophilic groups / lipophilic groups / UV-reactive groups) Oligomer) is preferred.

The content of the fluorine-based additive may be appropriately set according to the purpose, application, etc., and is not particularly limited, but is 0.05 to 10% by mass with respect to 100% by mass of the total solid content of the curable resin composition. It is preferable that More preferably, it is 0.1 mass% or more, More preferably, it is 5 mass% or less, More preferably, it is 4 mass% or less, Most preferably, it is 3 mass% or less.

<Solvent>
The curable resin composition of the present invention preferably also contains a solvent.
A solvent is preferably used as a diluent or the like. Specifically, the viscosity is lowered and the handling property is improved; the coating film is formed by drying; the coloring material is used as a dispersion medium; and the like in the curable resin composition. It is a low-viscosity organic solvent that can dissolve or disperse each component.

The solvent may be appropriately selected according to the purpose and application, and is not particularly limited. For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Ethylene glycol ethers such as propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate and 3-methoxybutyl acetate In addition to ters, monoalcohols; glycols; cyclic ethers; glycol monoethers; glycol ethers; alkyl esters; ketones; aromatic carbonization exemplified in JP2013-227485A [0092] Hydrogens; aliphatic hydrocarbons; amides; and the like.

The amount of the solvent used may be appropriately set according to the purpose and application, and is not particularly limited, but is 10 to 90% by mass in the total amount of 100% by mass of the curable resin composition of the present invention. It is preferable. More preferably, it is 20-80 mass%, Most preferably, it is 40-80 mass%, Most preferably, it is 60-80 mass%.

The curable resin composition further has, for example, a coloring material (also referred to as a colorant); a dispersant; a heat resistance improver; a leveling agent; a development aid; a filler; Thermosetting resins such as phenolic resins and polyvinylphenols; Curing aids such as polyfunctional thiol compounds; Plasticizers; Polymerization inhibitors; Ultraviolet absorbers; Antioxidants; Matting agents; Antifoaming agents; 1 type, or 2 or more types, such as an agent; surface modifier; thixotropic agent; thixotropic agent; quinonediazide compound; polyhydric phenol compound; For example, when using the said curable resin composition for a color filter use, it is preferable that a coloring material is included.

From the viewpoint of further improving the electrical characteristics, the curable resin composition of the present invention preferably contains as little inorganic particles as possible, such as silica fine particles. Specifically, the content ratio of the inorganic fine particles is preferably 3% by mass or less in the total solid content of 100% by mass of the curable resin composition. More preferably, it is 1 mass% or less, More preferably, it is 0 mass%, that is, it is substantially free of inorganic fine particles.

<Method for producing curable resin composition>
It does not specifically limit as a manufacturing method of the curable resin composition of this invention, For example, it can prepare by mixing and disperse | distributing the containing component mentioned above using various mixers and dispersers. The dispersion step and the mixing step are not particularly limited, and may be performed by a normal method. Further, it may further include other steps that are normally performed. When the said curable resin composition contains a color material, it is suitable to manufacture through the dispersion | distribution process process of a color material.

[Curing film]
Next, the cured film formed by curing the curable resin composition of the present invention will be described.
The curable resin composition of the present invention can give a cured film by irradiation (exposure) with an active energy ray. Specifically, for example, the curable resin composition is applied onto a substrate (also referred to as a base material) and dried, and the applied surface is irradiated (exposed) with an active energy ray to form a cured film. It is preferable. A cured film formed by curing the curable resin composition as described above is also one aspect of the present invention. Moreover, since the said curable resin composition is used suitably as a resist material, the form whose cured film formed by hardening | curing the said curable resin composition is a resist cured film is also a suitable form of this invention. .

The substrate (also referred to as a base material) to which the curable resin composition is applied is not particularly limited. For example, a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass; polyethylene terephthalate (PET), polyester, Sheets or films made of thermoplastic resins such as polycarbonate, polyolefin, polysulfone, cyclic olefin ring-opening polymers and hydrogenated products thereof; sheets or films made of thermosetting resins such as epoxy resins and unsaturated polyester resins; aluminum plates Metal substrate such as copper plate, nickel plate, stainless steel plate; ceramic substrate; semiconductor substrate having photoelectric conversion element; member made of various materials such as glass substrate (color filter for LCD) having a color material layer on the surface; etc. Is mentioned. Especially, the sheet | seat or film which consists of heat resistant resin among a glass substrate and a plastic substrate from a heat resistant point is preferable. The substrate is preferably a transparent substrate.

If necessary, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, etc., and an inorganic component such as a gas barrier layer or a protective film on both sides or one side of the substrate. Or you may form the coating film of an organic component. Moreover, when using a cured film for the member for display apparatuses, it is suitable to form electrodes, such as ITO, on the said board | substrate. In addition, the cured film of this invention is excellent also in not only a board | substrate but adhesiveness with electrodes, such as an ITO film | membrane, and light-resistant adhesiveness.

The method for applying the curable resin composition to the substrate is not particularly limited, and examples thereof include spin coating, slit coating, roll coating, and cast coating, and any method can be preferably used.

The coating film after being applied to the substrate can be dried using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but are usually performed at a temperature of 50 to 150 ° C. for 10 seconds to 300 seconds. Is preferred.

Examples of the light source of the active energy beam include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a lamp light source such as a carbon arc, a fluorescent lamp, an argon ion laser. Laser light sources such as YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser are used. Further, examples of the exposure system include a proximity system, a mirror projection system, and a stepper system, but the proximity system is preferably used.
In the irradiation process of the active energy beam, the active energy beam may be irradiated through a predetermined mask pattern depending on the application. In this case, the exposed portion is cured, and the cured portion is insolubilized or hardly soluble in the developer.

Further, if necessary, after the step of irradiating with the active energy beam, a step of developing with a developer to remove an unexposed portion and forming a pattern (also referred to as a developing step) may be performed. Thereby, a patterned cured film can be obtained.
The development treatment in the development step can be usually performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development. In addition, when using alkaline aqueous solution as a developing solution, it is preferable to wash | clean with water after image development.

The developer is not particularly limited as long as it dissolves the curable resin composition of the present invention. Usually, an organic solvent or an alkaline aqueous solution is used, and a mixture thereof may be used.
Examples of the organic solvent suitable as the developer include ether solvents and alcohol solvents. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkyl phenyl ethers, aralkyl phenyl ethers, diaromatic ethers , Isopropanol, benzyl alcohol and the like.

In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary. Examples of the organic solvent in this case include organic solvents suitable as the developer described above. As the alkali agent, for example, one or more of inorganic alkali agents, amines, and the like exemplified in JP2013-227485A [0164] can be used. For example, 1 type, or 2 or more types, such as a nonionic surfactant; anionic surfactant; amphoteric surfactant, etc. which were illustrated by Unexamined-Japanese-Patent No. 2013-227485 [0165] can be used.

Further, if necessary, a post-curing step (also referred to as post-baking or post-treatment step) may be performed. The post-curing step includes, for example, a post-heating step (also referred to as a heat treatment step) in addition to a step of exposing with a light amount of, for example, 0.5 to 5 J / cm ² using a light source such as a high-pressure mercury lamp. . By performing such post-treatment, it becomes possible to further strengthen the hardness and adhesion of the patterned cured film.

Among the post-treatment steps described above, the latter heat treatment step is preferred, and the temperature at that time is preferably 60 ° C. or higher. By performing the heat treatment step in this temperature range, the reactive compound is decomposed, and the effects of the present invention can be more fully exhibited. More preferably, it is 80 degreeC or more, and it is preferable to set it as 300 degrees C or less. Moreover, although heat processing time is not specifically limited, For example, it is preferable that it is 10 seconds-300 minutes.

[Uses of curable resin composition]
The curable resin composition of the present invention is particularly excellent in adhesion and light-proof adhesion, and gives a cured product having high surface hardness. Therefore, a cured product (cured film) obtained by curing such a curable resin composition is, for example, a liquid crystal display device, a solid-state imaging device, a component of various display devices such as a touch panel display device, ink, It is preferably used for various applications such as various optical members such as printing plates, printed wiring boards, semiconductor elements, and photoresists, electric machines and electronic devices. Especially, it is suitable to use for the color filter used for a liquid crystal display device, a solid-state image sensor, etc., and a touch-panel type display device, Especially the protective film (color color) in these various display devices using the said curable resin composition. It is preferable to form a protective film for a filter, a protective film for a touch panel display device, or an insulating film (such as an insulating film for a touch panel display device). As a result, the reliability of display quality and imaging quality of various display devices can be sufficiently increased to the extent that it can sufficiently meet the recent demand for higher performance. Thus, the form in which the curable resin composition is a curable resin composition for forming a protective film or an insulating film, the form in which the cured film is a protective film or an insulating film, and the cured film is a cured film for a touch panel These forms are also included in the preferred forms of the present invention. Moreover, the cured film formed with the said curable resin composition, the member for display apparatuses which has this cured film, and the display apparatus which has this cured film are contained in this invention.

The member for a display device and the display device of the present invention have the cured film, but may further include one or more other constituent members. A cured film formed by curing the curable resin composition is excellent in adhesion to a substrate and the like and light-resistant adhesion, and has high hardness and high transparency. Therefore, it is very useful as a protective film or an insulating film in various display devices. Although it does not specifically limit as a display apparatus, For example, a liquid crystal display device, a solid-state image sensor, a touchscreen display apparatus etc. are suitable. As the touch panel display device, a capacitance type device is particularly preferable.
The display device member may be a film-like single layer or multilayer member composed of the cured film, or a member in which another layer is combined with the single layer or multilayer member. It may also be a member (for example, a color filter) that includes the cured film in its configuration.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
In the following synthesis examples and preparation examples, various physical properties and the like were measured or evaluated as follows.

1. Physical properties of resin solution (alkali-soluble resin) (1) Weight average molecular weight (Mw)
Weight average molecular weight was measured by a GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corporation) and column TSKgel SuperHZM-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent.

(2) Solid content concentration (NV)
About 0.3 g of the polymer solution (resin solution) was weighed into an aluminum cup, dissolved by adding about 1 g of acetone, and then naturally dried at room temperature. Then, using a hot air dryer (trade name “PHH-101” manufactured by ESPEC CORP.), It was dried at 140 ° C. for 3 hours, allowed to cool in a desiccator, and mass was measured. From the mass reduction amount, the solid content concentration (% by mass) of the polymer solution was calculated.

(3) Acid value (AV)
1.5 g of the resin solution is precisely weighed and dissolved in a mixed solvent of 90 g of acetone / 10 g of water, and 0.1 T KOH aqueous solution is used as a titrant. )), The acid value of the resin solution was measured, and the acid value per gram of the solid content was determined from the acid value of the solution and the solid content of the solution.

2. Physical properties of coated film (cured film) (1) Hardness and light-resistant adhesive glass An ITO substrate was prepared by depositing ITO (Indium Tin Oxide) with a thickness of 30 nm. The resin composition obtained on this ITO substrate was applied by spin coating, heat-treated (80 ° C. for 3 minutes), and then a UV aligner equipped with a 2.0 kW ultra-high pressure mercury lamp (made by TOPCON, trade name “ TME-150RNS ”) was exposed at an exposure amount of 60 mJ / cm ² (in terms of 365 nm illuminance), followed by heat treatment (230 ° C. for 30 minutes). Using the coating film thus obtained, the following hardness test and light resistance adhesion test were performed.

(1-1) Hardness test (hardness evaluation)
The test was conducted in accordance with JIS-K5600-5-4 (1999), but all loads were applied at 500 g of the old JIS version of JIS-K5400 (1990). The value was (surface hardness).
The hardness decreases in the order of 3H>2H>H>F>HB>B>2B>3B> 4B.

(1-2) Light Resistance Adhesion Test Using a xenon weather meter (X25, manufactured by Suga Test Instruments Co., Ltd.) on the coating film obtained as described above, a test light of 300 nm to 700 nm is applied to the machine from the glass surface. Then, exposure was performed for a predetermined time (24 hours, 48 hours, and 96 hours) with an exposure amount of 320 W / m ² (300 to 400 nm integrated light amount). About the coating film after each time progress, the cross cut test according to JIS-K5400-8.5 (1990) was performed, and the following reference | standard evaluated.
○: 8 or 10 points according to JIS standards.
Δ: 4 or 6 points according to JIS standards.
X: 0 or 2 points according to JIS standards.

(2) Evaluation of developability (residue) After applying the obtained resin composition to a glass substrate by a spin coat method and heat-treating (80 ° C. for 3 minutes), a 50 μm line-and-space at a distance of 100 μm from the coating film. With a UV aligner (trade name “TME-150RNS”, manufactured by TOPCON) equipped with a 2.0 kW ultrahigh pressure mercury lamp through a photomask provided with an opening, the exposure amount is 60 mJ / cm ² (365 nm illuminance conversion). Develop by exposing to light and spraying a 0.05% aqueous potassium hydroxide solution with a spin developer for 40 seconds to dissolve and remove the unexposed areas and washing the remaining exposed areas with pure water for 10 seconds. Then, developability was evaluated.
Specifically, the coating film developed through the photomask as described above was evaluated with a surface roughness meter (manufactured by Ryoka System Co., Ltd., trade name “VertScan 2.0”) according to the following criteria.
○: The unexposed and exposed areas are flowing cleanly and without residue.
Δ: A little residue can be confirmed in the unexposed area.
X: Many residues can be confirmed in an unexposed part.

(Synthesis of resin solution)
Resin solution A (No. A-1 to A-4) was synthesized as the alkali-soluble resin (A) contained in the resin composition.

Synthesis Example 1 (Synthesis of A-1)
A separable flask with a cooling tube as a reaction vessel was charged with 190 parts of propylene glycol monomethyl ether acetate (PGMEA) and 48 parts of propylene glycol monomethyl ether (PGME), and the temperature was raised to 90 ° C. in a nitrogen atmosphere. 1, 17 parts of benzylmaleimide (BzMI), 20 parts of methyl methacrylate (MMA), 14 parts of methacrylic acid (MAA), 119 parts of cyclohexyl methacrylate (CHMA), 14 parts of PGMEA, 3 parts of PGME, t-butylperoxy-2-ethylhexano 3 parts of art (trade name “Perbutyl O”, manufactured by NOF Corporation), 3 parts of n-dodecyl mercaptan (n-DM), 49 parts of PGMEA and 12 parts of PGMEA are continuously supplied over 3 hours as the dropping system 2 did. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and polymerization was continued for 1.5 hours to obtain a resin solution A-1.
Various physical properties (weight average molecular weight Mw, solid content concentration NV, and acid value AV per solid content) of the obtained resin solution A-1 were measured. The results are shown in Table 1.

Synthesis Examples 2 to 4 (Synthesis of A-2 to A-4)
Resin solutions A-2 to A-4 were obtained in the same manner as in Synthesis Example 1 except that the blending ratio of each monomer constituting the resin solution was changed to the ratio described in Table 1.

Synthesis Example 5 (Synthesis of A-5)
A base polymer was obtained by carrying out the same polymerization as in Synthesis Example 1 except that the blending ratio of each monomer was changed to the ratio shown in Table 1.
Next, 16.5 parts of glycidyl methacrylate (GMA), 0.4 parts of triethylamine (TEA) as a catalyst, and 0.2 parts of Antage W-400 as a polymerization inhibitor are added to 100 parts of the base polymer thus obtained. Then, while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%), the reaction was continued at 110 ° C. for 2 hours and 115 ° C. for 7 hours to obtain a resin solution A-5 having a double bond equivalent of 1019 g / equivalent. .

Table 1 shows details of the resin solutions A-1 to A-5.
In Table 1, the numerical values of the monomers constituting the base polymer of the resin solutions (polymers) A-1 to A-4 and the resin solution A-5 are based on the total amount of the monomers being 100% by mass. The blending ratio (mass%) of each monomer was described. The amount of GMA means the amount (parts) of GMA added to 100 parts of the total amount of monomer components forming the base polymer.

Abbreviations in Table 1 are as follows.
BzMI: benzyl maleimide CHMA: cyclohexyl methacrylate MAA: methacrylic acid MMA: methyl methacrylate AV: acid value Mw: weight average molecular weight NV of finally obtained polymer NV: solid content concentration

[Preparation of resin composition and evaluation test of coating film]
Example 1 (resin composition B-1)
In terms of solid content, 20 parts of resin solution A-2, 32 parts of dipentaerythritol hexaacrylate, 5 parts of KBM503, 5 parts of PM-21, 10 parts of 2021P, 28 parts of IB-XA, Antage W-400 0.5 part, 0.2 part F-554, 20 parts IRGACURE907, and further adding a diluent solvent (PGMEA) to a solid content concentration of 25% and stirring to obtain a resin composition B-1 It was.
About the obtained resin composition B-1, the physical property of the coating film (cured film) was evaluated according to the evaluation method mentioned above. The results are shown in Table 2.

Examples 2-4, Comparative Examples 1-4
Resin compositions B-2 to B-8 were obtained in the same manner as in Example 1 using the raw materials shown in the table at the mixing ratios shown in Table 2. About each of the obtained resin composition, the physical property of the coating film was evaluated according to the evaluation method mentioned above. The results are shown in Table 2.

Abbreviations in Table 2 are as follows. The amount of each raw material in Table 2 is the solid content. In Table 2, the use of a diluting solvent (PGMEA: propylene glycol monomethyl ether acetate) is omitted.
KBM503: 3-methacryloxypropyltrimethoxysilane (trade name “Shin-Etsu Silicone KBM-503”, manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM903: 3-Aminocypropyltrimethoxysilane (trade name “Shin-Etsu Silicone KBM-903”, manufactured by Shin-Etsu Chemical Co., Ltd.)
PM-21: Phosphate ester (trade name “KAYAMER PM-21”, manufactured by Nippon Kayaku Co., Ltd.)
DPE-6A: Dipentaerythritol hexaacrylate (trade name “Light acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.)
IB-XA: Isobornyl acrylate (trade name “Light Acrylate IB-XA”, manufactured by Kyoeisha Chemical Co., Ltd.)
2021P: 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (trade name “Celoxide 2021P”, manufactured by Daicel Corporation)
W-400: Phenolic antioxidant (trade name “ANTAGE W-400”, manufactured by Kawaguchi Chemical Co., Ltd.)
F-554: Fluorine-containing / lipophilic group-containing oligomer (nonionic, trade name “Megafac F-554”, manufactured by DIC Corporation)
IRGACURE907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name, manufactured by BASF)

From Table 2, the following was confirmed.
Resin compositions B-1 to B-4 obtained in Examples 1 to 4 all include an alkali-soluble resin having a ring structure in the main chain, a coupling agent, and a phosphate ester compound, while being comparative examples. The resin compositions B-5, B-6, and B-8 obtained in 1, 2, and 4 are mainly different in that they do not contain a phosphate ester, and the resin composition B-7 obtained in Comparative Example 3 is a silane. The main difference is that it does not contain a coupling agent. Under such differences, when comparing the physical property results of the coating films obtained from the respective resin compositions, the coating films obtained from the resin compositions B-1 to B-4 are the resin compositions B-5 and B-6. The film was remarkably excellent in light-resistant adhesion as compared with the coating film obtained from B-8, and had sufficient adhesion even after long-time light exposure for 48 hours and further 96 hours. It was also confirmed that the surface hardness was remarkably higher than that of the coating film obtained from the resin composition B-7. Moreover, it turned out that the coating film obtained from resin composition B-1-B-4 was excellent also in developability also in the practical level, and also excellent in transparency.

Here, when the same evaluation test as described above was performed on the coating film obtained using an alkali-soluble resin having no ring structure in the main chain instead of the resin solutions A-1 to A-4, the coating film was It was confirmed that both the hardness and the light-resistant adhesion were inferior to the coating films obtained from the resin compositions B-1 to B-4. Therefore, it has been found that the use of an alkali-soluble resin having a ring structure in the main chain is essential for exerting the effects of the present invention.

The coating film obtained from the resin compositions B-1 to B-4 (using the resin solutions A-2 to A-4) also uses the resin solution A-1 instead of the resin solutions A-2 to A-4. It was also confirmed that the developability was superior to the obtained coating film. Therefore, it has been found that the use of an alkali-soluble resin having an acid value of 60 mgKOH / g or more is particularly useful for applications in which developability is regarded as important.

Claims (7)

A curable resin composition comprising an alkali-soluble resin having a ring structure in the main chain,
Furthermore, a curable resin composition comprising a coupling agent and a phosphate ester compound. Furthermore, a polyfunctional polymerizable compound is contained, The curable resin composition of Claim 1 characterized by the above-mentioned. The curable resin composition according to claim 1, further comprising a monofunctional polymerizable compound. Furthermore, an epoxy compound is included, The curable resin composition in any one of Claims 1-3 characterized by the above-mentioned. A cured film obtained by curing the curable resin composition according to claim 1. A member for a display device, comprising the cured film according to claim 5. A display device comprising the cured film according to claim 5.