WO2015129443A1

WO2015129443A1 - Curable resin composition and use thereof

Info

Publication number: WO2015129443A1
Application number: PCT/JP2015/053527
Authority: WO
Inventors: 裕己橘; 元秀橋本; 加原　浩二
Original assignee: 株式会社日本触媒
Priority date: 2014-02-26
Filing date: 2015-02-09
Publication date: 2015-09-03
Also published as: TWI608301B; TW201610583A

Abstract

Provided are: a curable resin composition that produces a cured product having extremely high surface hardness, sufficient transparency and excellent adhesiveness; a cured film formed from such cured resin composition; and a member for a display device and a display device with which high performance can be realized as a result of having the cured film. The curable resin composition comprises an alkali-soluble resin and a bifunctional or higher polyfunctional (meth)acrylate compound, wherein: the alkali-soluble resin includes an alkali-soluble resin (A) having a weight-average molecular weight of 5,000 or higher and having ethylenic unsaturated groups in the side chains; the curable resin composition further comprises an epoxy compound and/or maleic acid polymer; and the maleic acid polymer is obtained by polymerization of a monomer component comprising an aromatic vinyl compound and maleic anhydride derivative and/or hydrolysis product thereof.

Description

Curable resin composition and use thereof

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 member for a display device, and a display device.

Application of curable resin compositions that can be cured by heat or active energy rays to components of various display devices represented by, for example, liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. There is. For example, a capacitive touch panel display device generally has a structure in which a transparent conductive film such as ITO is formed on a substrate, and a protective film or insulating film for protecting the transparent conductive film is further formed. In addition to being excellent in adhesion with a transparent conductive film and transparency, component members such as protective films and insulating films are generally required to have high surface hardness in order to reduce external impact. ing. As conventional curable resin compositions, for example, the compositions described in Patent Documents 1 to 7 have been developed.

In recent years, along with the high definition of display devices and the like, it may also be required that the cured product of the curable resin composition exhibits good electrical characteristics. As an indicator of electrical properties, a method of evaluating migration of silver ions between metal wires made of silver or silver alloy is known (see, for example, Patent Document 8). If the migration of silver ions is suppressed, it can be said that the insulation reliability between metal wires is excellent, so it can be judged whether or not the electrical characteristics are good.

Unexamined-Japanese-Patent No. 2004-264686 Unexamined-Japanese-Patent No. 7-209865 JP, 2013-227485, A Japanese Patent Application Laid-Open No. 6-001944 JP 2008-180992 A JP 2000-039713 A JP, 2013-187279, A JP 2013-125797 A

As described above, the cured product of the curable resin composition is required to exhibit excellent adhesion and transparency and to have high surface hardness. Further, depending on the application and the like, good developability and electrical characteristics may be required. And in recent years, with the advancement of technology such as display devices, even higher performance is strongly demanded for each member to be used, but a curable resin composition capable of sufficiently meeting these needs is still Not developed. For example, the composition described in Patent Document 1 has room for devising in terms of surface hardness and electrical properties of a cured product, and the composition described in Patent Document 2 has room for devising in terms of electrical properties. There is concern about coloring due to amide bond. The composition described in Patent Document 3 has room for improvement in terms of electrical characteristics. The compositions of Patent Documents 4 to 7 have room for improvement in terms of the surface hardness of the cured product, and the compositions of Patent Document 7 also have room for devising to further improve the developability.

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

The inventors of the present invention conducted various studies on curable resin compositions, and if the composition contains an alkali-soluble resin and a bifunctional or higher polyfunctional (meth) acrylate compound, it is excellent in photosensitivity and curability. Focused on becoming And, as an alkali-soluble resin, at least an alkali-soluble resin (A) having a predetermined molecular weight and having an ethylenically unsaturated group in a side chain, and further a group consisting of an epoxy compound and a predetermined maleic acid polymer It has been found that when the composition contains at least one selected from the group selected, a cured product having extremely high surface hardness and excellent in transparency and adhesion can be obtained. In particular, when at least the epoxy compound is contained, the surface hardness of the obtained cured product is further improved; and when at least the predetermined maleic acid based polymer is contained, a cured product having extremely excellent electric properties can be obtained. It has also been found that when both the epoxy compound and the predetermined maleic acid-based polymer are contained, a cured product having extremely good electrical properties and further improved surface hardness can be obtained. Moreover, such a curable resin composition is particularly suitable as a resin composition for forming a protective film or an insulating film used for a touch panel display device, a color filter, etc., and a cured film to be formed from this, a display device The inventors have found that the members and the display device can sufficiently cope with the recent demands for high definition and high performance, and have arrived at the present invention in view of the fact that the above-mentioned problems can be clearly solved.

That is, the present invention is a curable resin composition containing an alkali-soluble resin and a polyfunctional (meth) acrylate compound having two or more functional groups, wherein the alkali-soluble resin has a weight average molecular weight of 5000 or more and An alkaline soluble resin (A) having an ethylenically unsaturated group, the curable resin composition further comprises an epoxy compound and / or a maleic acid-based polymer, and the maleic acid-based polymer is an aromatic vinyl It is a curable resin composition obtained by polymerizing a monomer component containing a compound and a maleic anhydride derivative and / or a hydrolyzate thereof.

The present invention is also a cured film formed of the above curable resin composition.
The present invention is also a member for a display device having the above cured film.
The present invention is also a display device having the above cured film.
The present invention will be described in detail below. In addition, the form which combined 2 or 3 or more of each preferable form of this invention described below is also a preferable form of this invention.

[Curable resin composition]
The curable resin composition (also simply referred to as a resin composition) of the present invention is
(1) alkali-soluble resin,
(2) a polyfunctional (meth) acrylate compound having two or more functional groups,
(3) at least one selected from the group consisting of an epoxy compound and a predetermined maleic acid polymer,
And components (1) to (3). As necessary, one or more other components may be further contained. Each component can be used alone or in combination of two or more.
Hereinafter, the bifunctional or higher polyfunctional (meth) acrylate compound is also referred to as a "polyfunctional (meth) acrylate compound".

Here, it can be said that both the epoxy compound and the predetermined maleic acid-based polymer, which are the component (3), are common in that they have “a functional group that causes a dehydration condensation reaction”. That is, the epoxy compound has a hydroxyl group (-OH) or can generate a hydroxyl group (-OH), and the hydroxyl group is, for example, a carboxyl group (-COOH) that can be possessed by the alkali-soluble resin (A). Alternatively, it can be dehydrated and condensed with the metal base. Although it is preferable that a predetermined maleic acid based polymer has a COOR ^b group (R ^b represents a hydrogen atom or a metal atom) in the structure, the COOR ^b group is, for example, an alkali-soluble resin (A) And can be dehydrated and condensed with a hydroxyl group (—OH) that can be possessed by the polyfunctional (meth) acrylate compound. From such a viewpoint, the following curable resin composition is also one of the inventions by the present inventor.
A curable resin composition comprising an alkali soluble resin and a bifunctional or higher polyfunctional (meth) acrylate compound,
The alkali-soluble resin includes an alkali-soluble resin (A) having a weight average molecular weight of 5,000 or more and having an ethylenically unsaturated group in a side chain,
The curable resin composition further includes a compound (X) having a functional group that causes a dehydration condensation reaction,
The compound (X) is an epoxy compound and / or a maleic acid polymer,
The curable resin composition, wherein the maleic acid polymer is obtained by polymerizing a monomer component containing an aromatic vinyl compound and a maleic anhydride derivative and / or a hydrolyzate thereof.

In the present specification, the “solid content total amount” means the total amount of components that form a cured product (components excluding solvents and the like that volatilize when the cured product is formed). Specifically, an alkali-soluble resin (solid content), a polyfunctional (meth) acrylate compound, an epoxy compound (solid content), a maleic acid-based polymer (solid content) prescribed in the present invention, and other cured products are formed. When the component (other polymerizable compound, coupling agent, inorganic fine particle) is included, the total mass of the component and the component is meant.

<Alkali-soluble resin>
The curable resin composition of the present invention contains an alkali soluble resin (A) as an alkali soluble resin. The alkali-soluble resin (A) is one having a weight average molecular weight of 5,000 or more and having an ethylenically unsaturated group in the side chain.
In the present invention, the total amount of such an alkali-soluble resin (A) and a predetermined maleic acid-based polymer contained as necessary is 100% by mass of the total solid content of the curable resin composition. The content is preferably 5% by mass or more, and preferably 70% by mass or less. By being in such a range, the effects of the present invention can be more remarkably exhibited. The amount is more preferably 10 to 65% by mass, still more preferably 15 to 60% by mass, and particularly preferably 15 to 50% by mass.

Here, when the curable resin composition of the present invention contains a maleic acid-based polymer as specified in the present invention, the content is preferably 90 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). It is. This makes it possible to give a cured product which is further excellent in electrical characteristics, adhesion, surface hardness and the like, and also makes the cured product more excellent in light resistance. Thus, a form in which the content of the maleic acid based polymer specified in the present application is 90 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A) is a particularly preferable form of the present invention. More preferably, it is 85 parts by mass or less, still more preferably 80 parts by mass or less. The amount is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more.

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

Although it does not specifically limit as an acid value (AV) of the said alkali-soluble resin (A), For example, it is suitable that they are 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 which is more excellent in developability. More preferably, it is 30 mg KOH / g or more, still more preferably 40 mg KOH / g or more. Moreover, 250 mgKOH / g or less is more preferable, More preferably, it is 230 mgKOH / g or less, Especially preferably, it is 210 mgKOH / g or less. In particular, when it is 210 mg KOH / g or less, the curability of the cured product is better, and for example, the electrical properties are also better. Still more preferably, it is at most 200 mg KOH / g, most preferably at most 150 mg KOH / g.
In the present specification, the acid value of the polymer is determined from the acid value of the solution and the solid content of the solution after the acid value of the polymer solution is measured by the method described in the examples described later. It can be determined by calculating The solid content of the polymer solution can be determined by the method described in the examples described later.

The alkali-soluble resin (A) is a polymer having an ethylenically unsaturated group (i.e., a double bond) in a side chain (this is also referred to as a "side chain double bond-containing polymer"). Preferably, a polymer (also referred to as a base polymer) obtained by polymerizing a monomer component containing a monomer having an acid group and a polymerizable double bond (also referred to as a base polymer) has a functional group capable of binding to an acid group and a polymerizable compound. It is a polymer obtained by reacting a compound having a heavy bond. Each monomer used here can be used alone or in combination of two or more.

Particularly preferred as the alkali-soluble resin (A) is a polymer having a ring structure in the main chain. When a polymer having a ring structure in the main chain is used as the alkali-soluble resin (A), the heat resistance, the surface hardness and the adhesion are excellent, and further, for example, the change with time after exposure to high temperature is further suppressed and various physical properties are further improved. A cured product which can be developed more stably can be obtained. In recent display devices, in order to give various members strength to withstand external impact, tempered glass may be used for the substrate, but a weight having a ring structure in the main chain as the alkali-soluble resin (A) The use of coalescence is very suitable because a cured product which can exhibit excellent adhesion to tempered glass even after high temperature exposure can be obtained.

Therefore, the monomer component forming the above-mentioned base polymer is, together with a monomer having an acid group and a polymerizable double bond, one or two or more monomers capable of introducing a ring structure to the main chain skeleton of the polymer. It is preferable to include species or more. As a monomer capable of introducing a ring structure into the main chain skeleton of the polymer, for example, a monomer having a double bond-containing ring structure in the molecule, or a polymer having a ring structure in the main chain by cyclopolymerization. The monomer etc. which form a union are mentioned.
In addition, the monomer component which forms the said base polymer is also called "a base polymer component."

Examples of the monomer having an acid group and a polymerizable double bond include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; maleic acid, fumaric acid, itacon Unsaturated polyvalent carboxylic acids such as acid, citraconic acid and mesaconic acid; and a chain between an unsaturated group such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate and a carboxyl group Extended unsaturated monocarboxylic acids; unsaturated acid anhydrides such as maleic anhydride and itaconic acid; phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); etc. . Among these, it is preferable to use a carboxylic acid monomer (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) from the viewpoint of versatility, availability and the like. More preferably, unsaturated monocarboxylic acids are used in terms of reactivity, alkali solubility, etc., more preferably (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid), and among them, particularly preferred is Is methacrylic acid.

The content ratio of the monomer having an acid group and a polymerizable double bond in the base polymer component is preferably, for example, 5% by mass or more with respect to 100% by mass of the base polymer component. This makes the alkali solubility more sufficient, and, for example, makes the curable resin composition more useful for applications where developability is required. Moreover, it is preferable that it is 85 mass% or less from the point which can maintain the outstanding external appearance, adhesiveness, etc. of hardened | cured material also after high temperature exposure. More preferably, it is 10 to 80% by mass, and further preferably 15 to 75% by mass.

In addition to the above-mentioned monomer component having an acid group and a polymerizable double bond, the above monomer component contains one or more other radically polymerizable monomers (also referred to as other monomers). It may be included.

As the above-mentioned other monomers, for example, as described above, as a monomer capable of introducing a ring structure into the main chain skeleton of a polymer, a monomer having a double bond-containing ring structure in the molecule, One or more monomers such as monomers forming a polymer having a ring structure in the main chain by cyclopolymerization are preferable. Such monomers include N-substituted maleimide monomers, dialkyl-2,2 '-(oxydimethylene) diacrylate monomers, and α- (unsaturated alkoxyalkyl) acrylate monomers. It is preferred to use at least one selected from the group consisting of the body. Thus, the alkali-soluble resin (A) is an N-substituted maleimide monomer unit, a dialkyl-2,2 '-(oxydimethylene) diacrylate monomer unit, and / or an α- (unsaturated) The form which is a polymer having an alkoxyalkyl) acrylate monomer unit is one of the preferred forms of the present invention.

In particular, a resin containing an N-substituted maleimide monomer unit and / or a dialkyl-2,2 '-(oxydimethylene) diacrylate monomer unit has heat resistance and dispersibility (for example, colorant dispersion) ), Hardness and the like can be further improved. In addition, resins containing α- (unsaturated alkoxyalkyl) acrylate monomer units have performance that contributes to plate making properties such as adhesion, curability, dry resolubility, etc., colorant dispersion, 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, for example, a resin containing a structural unit derived from the monomer by a polymerization reaction or a crosslinking reaction of the monomer.

Examples of the N-substituted maleimide monomer include N-cyclohexyl maleimide, N-phenyl maleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, Nt-butyl maleimide, N-dodecyl maleimide, N-benzyl maleimide, N-naphthyl maleimide and the like can be mentioned, and one or more of these can be used. Among them, N-cyclohexyl maleimide, N-phenyl maleimide, and N-benzyl maleimide are preferable, and N-benzyl maleimide is particularly preferable, from the viewpoint of less coloring and excellent dispersibility.

Examples of the N-benzylmaleimide include: benzylmaleimide; alkyl-substituted benzylmaleimides such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl-substituted benzylmaleimides such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide And halogen-substituted benzyl maleimides such as o-dichlorobenzyl maleimide and p-dichlorobenzyl maleimide.

As the above-mentioned dialkyl-2,2 '-(oxydimethylene) diacrylate monomer, for example, dimethyl-2,2'-[-], from the viewpoint of little coloring and dispersibility, ease of industrial availability, etc. It is preferable to use oxybis (methylene)] bis-2-propenoate and the like.

Examples of the α- (unsaturated alkoxyalkyl) acrylate monomers include α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α-allyloxymethyl. N-propyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, n-amyl α-allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate n -Hexyl, α-allyloxymethyl acrylic acid s-hexene , N-heptyl α-allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, α-allyloxy 2-ethylhexyl methyl acrylate, capryl α-allyloxymethyl acrylate, nonyl α-allyloxymethyl acrylate, decyl α-allyloxymethyl acrylate, undecyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid Lauryl, tridecyl α-allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-alicylic acid Linear saturated hydrocarbon groups such as stearyl yloxy acrylate, nonadecyl α-allyloxy methyl acrylate, eicosyl α-allyloxy methyl acrylate, ceryl α-allyloxy methyl acrylate, melic α-allyloxy methyl acrylate Containing α- (allyloxymethyl) acrylate is preferred. In addition, alkyl- (α-methallyloxymethyl) acrylate monomers and the like are also preferable. Among them, methyl α-allyloxymethyl acrylate (also referred to as α- (allyloxymethyl) methyl acrylate) is particularly preferable.

The α- (unsaturated alkoxyalkyl) acrylate monomer can be produced, for example, by the production method disclosed in WO 2010/114077.

The content ratio of the monomers capable of introducing a ring structure into the main chain skeleton of the above polymer (the ratio of the total of the monomers when two or more are used) is, for example, 1 to 40% % Is preferred. Within this range, it is possible to obtain a cured film having further improved heat resistance, dispersibility, surface hardness and the like. Among them, the content ratio of N-substituted maleimide monomer, dialkyl-2,2 '-(oxydimethylene) diacrylate monomer, and / or α- (unsaturated alkoxyalkyl) acrylate monomer, among others The ratio of the total (when two or more are used) is preferably 1 to 40% by mass with respect to 100% by mass of the base polymer component. When the content of the main chain ring structure derived from these monomer components is increased, the adhesion tends to be improved. Further, when the addition amount of the N-substituted maleimide monomer is further increased, a cured product which is more excellent in terms of hardness is obtained, and a dialkyl-2,2 '-(oxydimethylene) diacrylate monomer is used. As a result, a cured product that is more excellent in heat resistant 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.
As the content ratio of the above N-substituted maleimide monomer, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer, and / or α- (unsaturated alkoxyalkyl) acrylate monomer The amount is preferably 2 to 40% by mass, more preferably 3 to 35% by mass.

As the other monomer, one or more of other (meth) acrylic acid ester-based monomer not corresponding to the above-described monomer, an aromatic vinyl-based monomer, etc. is used. be able to.

The above-mentioned other (meth) acrylic acid ester-based monomers include dialkyl-2, 2'- (oxydimethylene) diacrylate-based monomers, and α- (unsaturated alkoxy alkyl) acrylate-based monomers It means (meth) acrylic acid ester type monomers other than.
Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate (meth ) S-Butyl acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n- (meth) acrylate Hexyl, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, (meth) Isooctyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, Meta) phenyl acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (Meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid glycidyl, (meth) acrylic acid β-methylglycidyl, (meth) acrylic acid β -Ethyl glycidyl, (meth) acrylic acid In addition to xycyclohexyl) methyl, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate and the like, 1,4-dioxaspiro [4,5] deca-2 -Ylmethacrylic acid, (meth) acryloyl morpholine, 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 (meta Acrylate, and the like.

Among the above (meth) acrylic ester monomers, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, (from the viewpoint of excellent heat resistance) It is preferable to use benzyl meta) acrylate and alkoxylated phenylphenol (meth) acrylate. More preferably, methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and / or alkoxylated phenylphenol (meth) acrylate are preferable in terms of excellent heat resistance, adhesion, and developability. To use.

Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methylstyrene and methoxystyrene. Among them, styrene and vinyltoluene are preferable in terms of the heat-resistant colorability and heat-degradability of the resin.

The content ratio of the other (meth) acrylic acid ester-based monomer and / or the aromatic vinyl-based monomer (the ratio of the total thereof when two or more are used) is, for example, 100% by mass of the above-mentioned base polymer component On the other hand, 1 to 80% by mass is preferable. Within this range, a cured product which is more excellent in heat resistant colorability and alkali solubility can be obtained. More preferably, it is 5 to 75% by mass, still more preferably 10 to 70% by mass.

The above-mentioned other monomers are also, for example, (meth) acrylamides exemplified in JP-A-2013-227485 [0051]; macromonomer having (meth) acryloyl group at one end of polymer molecular chain Conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; etc. One or two or more kinds can also be used. The content ratio 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 properties of the cured product, it is preferable that the alkali-soluble resin (A) does not have a hydrophilic group such as a hydroxyl group. However, when the alkali-soluble resin (A) contains a hydroxyl group, the hydroxyl group is preferably a secondary hydroxyl group rather than a primary hydroxyl group. Further, the monomer component copolymerized to obtain the above-mentioned alkali-soluble resin (A) does not contain as much as possible a monomer having a hydrophilic group (for example, a (meth) acrylic acid ester having a hydroxyl group etc.) Is preferred. Specifically, the content ratio of the monomer having a hydrophilic group is preferably 20% by mass or less in 100% by mass 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 a display device screen having a capacitive touch panel is touch-input.
With a capacitive touch panel, when the user's finger contacts the window of the touch panel, a capacitance is formed between the finger and the (transparent) electrode of the touch panel, and the position touched by the change in capacitance accompanying this To detect
Therefore, the performance of the display device can be improved by improving the electrical characteristics of various portions in which the cured film is formed.

As a method of polymerizing the above-mentioned monomer component, methods usually used such as bulk polymerization, solution polymerization, emulsion polymerization and the like can be used, and may be appropriately selected according to the purpose and application. Among them, solution polymerization is preferable because it is industrially advantageous and structural adjustment such as molecular weight is easy. Moreover, although the polymerization mechanism of the said monomer component can use the polymerization method based on mechanisms, such as radical polymerization, anion polymerization, cationic polymerization, coordination polymerization, the polymerization method based on a radical polymerization mechanism is industrially It is preferable because it is also advantageous.

Preferred embodiments of the above polymerization reaction are as described in JP-A-2013-227485, [0053] to [0065]. The polymerization time is preferably 1 to 8 hours, more preferably 1 to 5 hours, and still more preferably 2 to 4 hours.

The alkali-soluble resin (A) is preferably a polymer obtained by reacting a compound having a functional group capable of binding to an acid group and a polymerizable double bond to the base polymer obtained as described above. However, examples of the polymerizable double bond in the compound having a functional group capable of binding to an acid group and a polymerizable double bond include, for example, (meth) acryloyl group, vinyl group, allyl group, methallyl group and the like. As the compound, those having one or more of these are preferable. Among them, a (meth) acryloyl group is preferable in terms of reactivity. Moreover, as a functional group which can be bonded to an acid group, for example, a hydroxy group, an epoxy group, an oxetanyl group, an isocyanate group and the like can be mentioned, and as the compound, those having one or more of these are preferable. . Among them, an epoxy group (including a glycidyl group) is preferable in view of the speed of the modification treatment reaction, the heat resistance and the dispersibility.

Examples of the compound having a functional group capable of binding to the above acid group and a polymerizable double bond include glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, Examples thereof include vinyl benzyl glycidyl ether, allyl glycidyl ether, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinyl cyclohexene oxide and the like, and one or more of these can be used. Among them, it is preferable to use a compound (monomer) having an epoxy group and a (meth) acryloyl group.

The amount (compounding ratio) of the compound having a functional group capable of binding to the above-mentioned acid group and a polymerizable double bond is a monomer having an acid group constituting the base polymer and a polymerizable double bond ( Blending ratio (mass%) of a compound having a functional group capable of binding to an acid group and a polymerizable double bond (hereinafter referred to as “compound y”) added to a carboxylic acid of a monomer x ′ ′) That is, it is determined by “{mol amount of compound y (mol) / mol amount of monomer x (mol)} × {blending ratio of monomer x (% by mass)}” to be 50% by mass or less It is preferable to set. This makes it possible to obtain a cured product with better electrical properties and adhesion. More preferably, the content is less than 50% by mass, whereby a cured product excellent in electrical properties, adhesion, and light adhesion can be obtained. More preferably, it is 45% by mass or less, particularly preferably 40% by mass or less, and most preferably 35% by mass or less. Moreover, it is preferable that it is 5 mass% or more. More preferably, it is 7% by mass or more.
Here, the “blending ratio (mass%) of the monomer x” refers to the blending of the monomer x when the total amount of the base polymer component (monomer component forming the base polymer) is 100 mass%. The amount (mass%) is meant.

For example, GMA (glycidyl methacrylate) is used as a compound (compound y) having a functional group capable of binding to an acid group and a polymerizable double bond, and a monomer having an acid group and a polymerizable double bond (single When MAA (methacrylic acid) is used as the monomer x), “the compounding ratio (mass%) of the compound having a functional group capable of binding to an acid group and a polymerizable double bond” described above is added It means mass% of GMA converted to mass of MAA, and can be determined by "{molar amount of GMA (mol) / molar amount of MAA (mol)} x MAA blending ratio (mass%)". It is preferable that this numerical value is within the above-mentioned preferred range.

The alkali-soluble resin (A) is, for example, the acid group of the base polymer component when reacting the base polymer component with a compound having a functional group capable of binding to an acid group and a polymerizable double bond (preferably A method of making the amount of the carboxyl group in excess of the amount of the functional group capable of binding to the acid group and the compound having the polymerizable double bond; the above-mentioned base polymer component, the functional group capable of binding to the acid group, and polymerization The compound is preferably produced by a method of reacting a compound having a polybasic acid anhydride group after the reaction with a compound having a sexual double bond, and the like; and the like.
Specifically, it is preferable to manufacture by the method described in JP-A-2013-227485 [0069] to [0076].

The alkali-soluble resin (A) preferably has an equivalent amount of an ethylenically unsaturated group, ie, a double bond equivalent of 200 to 10,000. This makes it possible to more fully exhibit the effects of the present invention. Among them, 400 to 5000 is more preferable. Thereby, for example, adhesion and surface hardness are further improved. The lower limit is more preferably 450 or more, particularly preferably 500 or more, and the upper limit is more preferably 4000 or less, still more preferably 3000 or less, particularly preferably 2000 or less, and most preferably 1500 or less. Thus, a form in which the double bond equivalent of the alkali-soluble resin (A) is 500 to 1,500 is also one of the preferred forms of the present invention.

The double bond equivalent is the mass (g) of the solid content of the polymer solution per 1 mol of double bond of the polymer. The weight of the solid content of the polymer solution as referred to herein is, for example, the weight of the above-mentioned base polymer component, the weight of the compound having a functional group capable of binding to an acid group and a polymerizable double bond, and the weight of a chain transfer agent And the sum of It can be determined by dividing the mass of the solid content of the polymer solution by the amount of double bonds of the polymer. The amount of double bonds of the polymer can be determined from the amount of the introduced acid group and the functional group capable of binding and the compound having a polymerizable double bond.

The alkali-soluble resin (A) has a weight average molecular weight of 5,000 or more. Thereby, the developability and surface hardness of a hardened material can be raised. Preferably it is 7,000 or more, more preferably 10,000 or more. The reason is not clear, but when the weight average molecular weight is 10,000 or more, the remaining of the polyfunctional (meth) acrylate compound on the pattern edge during development is more sufficiently suppressed, so the pattern edge is It approaches a right angle (square), that is, the developability is significantly improved. Moreover, when such an alkali-soluble resin (A) is used, the surface hardness of the cured product is further improved, and furthermore, various excellent physical properties can be more stably exhibited even after being exposed to a high temperature environment. it can. More preferably, it is 11000 or more, particularly preferably 11500 or more, and most preferably 12000 or more. Moreover, it is preferable that it is 250,000 or less from a viewpoint of viscosity etc. More preferably, it is 100,000 or less, still more preferably 50,000 or less, particularly preferably 30,000 or less, and most preferably 20,000 or less.
When the alkali-soluble resin has a high molecular weight, the higher the acid value, the easier the development.
In the present specification, the weight average molecular weight can be measured by the method described in the examples described later.

<Maleic acid polymer>
The curable resin composition of the present invention may, if necessary (for example, when used for applications requiring higher surface hardness, electrical properties, etc.), an aromatic vinyl compound, a maleic anhydride derivative, and the like. It is preferable to include a maleic acid-based polymer obtained by polymerizing a monomer component containing at least one of hydrolysates thereof. That is, the curable resin composition of the present invention preferably contains at least an alkali-soluble resin (A), a polyfunctional (meth) acrylate compound, and the maleic acid polymer. As a result, it is possible to provide a cured product having an even more satisfactory surface hardness and an extremely good electrical property.

It is preferable that the said maleic acid type polymer is what shows alkali solubility. Moreover, it is also preferable that it is resin (polymer) which does not have an ethylenically unsaturated group in a side chain.

The monomer component forming the above-mentioned maleic acid-based polymer can be copolymerized with these compounds as needed as long as it contains an aromatic vinyl compound and a maleic anhydride derivative and / or a hydrolyzate thereof It may further contain other monomers. Each of these monomers may be used alone or in combination of two or more. The content of the other monomer is preferably, for example, 10 to 50% by mass in 100% by mass of the total amount of the monomer components.
A commercial item may be used as the above-mentioned maleic acid polymer.

Examples of the aromatic vinyl compounds include styrene; alkyl-substituted styrenes such as methylstyrene (vinyltoluene), ethylstyrene, propylstyrene, isopropylstyrene, butylstyrene, dimethylstyrene, diethylstyrene and the like; methoxystyrene, ethoxystyrene, propoxystyrene And alkoxy substituted styrenes such as butoxystyrene; aromatic group substituted styrenes such as vinylbiphenyl and benzyl styrene; halogen substituted styrenes such as chlorostyrene, fluorostyrene, bromostyrene and chloro-methylstyrene; vinyl benzoic acid and styrene sulfonic acid In addition to styrene compounds such as acid-substituted styrene, vinyl naphthalene, vinyl anthracene and the like can be mentioned. Among these, styrenic compounds are preferable, and styrene is more preferable.

Examples of the above-mentioned maleic anhydride derivative and / or a hydrolyzate thereof include maleic anhydride, itaconic anhydride, alkenyl succinic anhydride, citraconic anhydride, 2,3-dimethyl maleic anhydride and the like. And these hydrolysates. In addition, when the preferable form of a maleic anhydride derivative is represented by a chemical formula, it can represent with the following general formula (a).

In the above formula (a), R ¹ and R ² are the same or different and each represents a hydrogen atom or a hydrocarbon group, or R ¹ and R ² are bonded directly or via a hydrocarbon chain May be The hydrocarbon group is preferably a hydrocarbon group having 1 to 10 carbon atoms, and is preferably an alkyl group or a phenyl group. The carbon number of the alkyl group is more preferably 1 to 6. The hydrocarbon chain is preferably an alkyl chain having 1 to 10 carbon atoms, and more preferably the alkyl chain has 1 to 6 carbon atoms. Particularly preferred as R ¹ and ^{R 2,} it is a form in which both of ^{R 1} and ^{R 2} represents a hydrogen atom.

In the above-mentioned monomer component, the content ratio of the aromatic vinyl compound and the maleic anhydride derivative and / or the hydrolyzate thereof is an aroma relative to the total 100 mol% of the maleic anhydride derivative and / or the hydrolyzate thereof. It is preferable that the amount of the group vinyl compound is 10 to 500 mol%. More preferably, it is 50 to 400 mol%.

The polymerization method of the above-mentioned monomer component is not particularly limited, and may be carried out by an ordinary method. After the polymerization, if necessary, the esterification reaction may be performed using an alcohol or the like, or the neutralization reaction may be performed using a metal salt such as a sodium salt or an ammonium salt.

The structural unit (also referred to as a structural unit (1)) represented by the following formula (1) and the structural unit (structural unit (2) represented by the following formula (2) are particularly preferable as the above-mentioned maleic acid polymer Also referred to as This makes it possible to more fully exhibit the effects of the present invention.

In the formula, A represents a phenyl group which may have a substituent. R ¹ and R ² are the same or different and each represents a hydrogen atom or a hydrocarbon group, or R ¹ and R ² may be bonded directly or via a hydrocarbon chain. R ³ and R ⁴ may be the same or different and each represent an OR ⁵ group or an NR ⁶ R ⁷ group, or R ³ and R ⁴ may be combined to form an anhydrous ring. R ⁵ , R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, a metal atom, or a hydrocarbon group which may have a substituent, an ether bond and / or an ester bond. However, R ³ and R ⁴ do not contain metal atoms at the same time.

In the above formula (1), A represents a phenyl group which may have a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, an aryl group of 6 to 10 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, and the like. 1 type or 2 types or more of are mentioned.

In the above formula (2), R ¹ and R ² are the same as the corresponding symbols in the above formula (a).
Further, in the OR ⁵ group and the NR ⁶ R ⁷ group which R ³ and R ⁴ can represent, R ⁵ , R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, a metal atom or a hydrocarbon group ( However, the hydrocarbon group may have at least one selected from the group consisting of a substituent, an ether bond, and an ester bond).
Examples of the metal atom include alkali metal atoms such as lithium atom, sodium atom and potassium atom; alkaline earth metal atoms such as calcium atom and magnesium atom; transition metal atoms such as iron; Among them, an alkali metal atom or an alkaline earth metal atom is preferable, an alkali metal atom is more preferable, and a sodium atom or a potassium atom is more preferable.
The hydrocarbon group is preferably a hydrocarbon group having 1 to 18 carbon atoms. Moreover, it is preferable that it is an alkyl group or a phenyl group. The carbon number of the alkyl group is preferably 1 to 18, more preferably 1 to 12, and still more preferably 3 to 9. The substituent which the hydrocarbon group may have is as described above for A in the above formula (1), and among them, a halogen atom is preferable.

Particularly preferably, any of R ³ and R ⁴ is a hydroxyl group or a metal neutralization salt thereof as the constituent unit represented by the above formula (2). That is, it is particularly preferable that either of R ³ and R ⁴ is an OR ^b group (R ^b represents a hydrogen atom or a metal atom).
Specifically, for example, one of R ³ and R ^{4 represents} an alkoxy group, that is, an OR ^a group (R ^a represents an alkyl group which may have a substituent), and the other is OR form which represents ^b group (R ^b represents a hydrogen atom or a metal atom); either R ³ or R ⁴ represents an OR ^b group (R ^b represents a hydrogen atom or a metal atom); A form in which one represents an OR ^c group (wherein R ^c represents a hydrocarbon group having 1 to 18 carbon atoms containing an ether bond and may have a substituent).

In the above-mentioned maleic acid polymer, the proportion of the structural units (1) and (2) is preferably 0.1 to 5 mol of the structural unit (1) with respect to 1 mol of the structural unit (2). More preferably, it is 0.5 to 4 moles. The average number of repeating (m) of the structural unit (1) in one molecule of the maleic acid polymer and the structural unit such that the abundance ratio of the structural units (1) and (2) falls within the above range It is preferable to set the average number of repetitions (n) of (2). For example, the number m is preferably 1 to 60, and the number n is preferably 1 to 12, more preferably m is 1 to 48, and n is 1 to 12.

The maleic acid polymer preferably has an acid value (AV) of, for example, 20 mg KOH / g or more and less than 300 mg KOH / g. Thereby, more sufficient alkali solubility is expressed, and it becomes possible to obtain a cured product which is more excellent in developability. More preferably, it is 30 mg KOH / g or more, still more preferably 40 mg KOH / g or more. Further, 290 mg KOH / g or less is more preferable.

The above-mentioned maleic acid polymer preferably has a weight average molecular weight of 100 or more. Thereby, a cured product with higher surface hardness can be obtained. More preferably, it is 1000 or more, still more preferably 5000 or more. Moreover, it is preferable that it is 250,000 or less from a viewpoint of viscosity etc. More preferably, it is 100,000 or less, still more preferably 50,000 or less, particularly preferably 30,000 or less, and most preferably 20,000 or less.

<Epoxy compound>
The curable resin composition of the present invention preferably further contains one or more epoxy compounds, if necessary (for example, when used for applications requiring higher surface hardness, etc.). That is, the curable resin composition of the present invention preferably contains at least an alkali-soluble resin (A), a polyfunctional (meth) acrylate compound, and an epoxy compound. This makes it possible to provide a cured product having an even more sufficient surface hardness.

In the present specification, an epoxy compound means a compound containing an epoxy group. The number of epoxy groups contained in one molecule of epoxy compound may be 1 or 2 or more, but is preferably 2 or more from the viewpoint of obtaining a cured product in a shorter time. 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 enabling the effects of the present invention to be exhibited more sufficiently.

The content of the epoxy compound is preferably such that the total amount of the epoxy compound is 10 to 150 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). This can further improve the surface hardness of the cured product. The amount is more preferably 20 to 100 parts by mass, still more preferably 30 to 80 parts by mass.

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, it is possible to more fully exhibit the function and effect of the present invention. More preferably, it is 150 or more, and from the viewpoint of viscosity, more preferably 100,000 or less, still more preferably 50,000 or less, and particularly preferably 10,000 or less.

The above epoxy compound is not particularly limited as long as it is a compound having an epoxy group in the molecule, but an epoxy compound having an alicyclic structure is particularly preferable. 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 can be further enhanced, and the light resistance of the cured product can be improved. Thus, a form including at least an epoxy compound having an alicyclic structure as the above-mentioned epoxy compound is also one of the preferred forms 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 surface hardness, one having no aromatic ring in the molecule is particularly preferable. . In addition, a group in which an alicyclic structure and an epoxy group are integrated (also referred to as an alicyclic epoxy group), such as an epoxy cyclohexane group or an epoxy group directly or via a hydrocarbon attached to a cyclic aliphatic hydrocarbon The compound to contain is also suitable as an epoxy compound which has alicyclic structure.

Among the epoxy compounds having an alicyclic structure, examples of compounds 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 -Heterocyclic ring-containing epoxy compounds such as 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of butanol, triglycidyl isocyanurate and the like.

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, they are compounds having a glycidyl ether group directly or indirectly bonded 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 (this is also referred to as “aromatic epoxy compound”), and more preferably a glycidyl ether bonded to an aromatic ring It is a hydrogenated product of a compound having a group (this is also referred to as "aromatic glycidyl ether compound"). Specifically, a hydrogenated bisphenol A epoxy compound, a hydrogenated bisphenol S epoxy compound, a hydrogenated bisphenol F epoxy compound, and the like are preferable. Particularly preferred are hydrogenated bisphenol A-type epoxy compounds and hydrogenated bisphenol F-type epoxy compounds.

In the present invention, as the epoxy compound, one or more other epoxy compounds can be used together with or instead of the above-described epoxy compound having an alicyclic structure. Preferably, 50% by mass or more of the epoxy compound having an alicyclic structure is used in 100% by mass of the total amount of epoxy compounds 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.

<Multifunctional (Meth) Acrylate Compound>
The curable resin composition of the present invention contains a bifunctional or higher polyfunctional (meth) acrylate compound.
The bifunctional or higher polyfunctional (meth) acrylate compound is a compound having two or more (meth) acryloyl groups in one molecule, and the presence of such a compound makes the resin composition photosensitive. And it becomes the thing excellent in hardenability and it becomes possible to obtain a hardened film of high hardness.
Here, the (meth) acryloyl group means a methacryloyl group and / or an acryloyl group, but in the present invention, an acryloyl group is preferable from the viewpoint of being more excellent in reactivity. That is, the above-mentioned polyfunctional (meth) acrylate compound is particularly preferably a polyfunctional acrylate compound having two or more acryloyl groups.

Preferably as a functional number of the said polyfunctional (meth) acrylate compound, it is three or more. Thereby, the photosensitivity and the curability can be further enhanced, and the hardness and the transparency of the cured product can be further enhanced. Thus, a form in which the above-mentioned polyfunctional (meth) acrylate compound is a trifunctional or higher polyfunctional (meth) acrylate compound is one of the preferable forms of the present invention. The functionality is more preferably 4 or more, still more preferably 5 or more. Moreover, it is preferable that it is 10 or less from a viewpoint of suppressing a cure shrinkage more, More preferably, it is 8 or less, More preferably, it is 6 or less.
In addition, even if it is a polyfunctional (meth) acrylate compound with few functional numbers, if it is a compound which has fluorene structure, since the hardness of hardened | cured material can be improved more, it is preferable. Therefore, the polyfunctional (meth) acrylate compound is preferably a trifunctional or higher polyfunctional (meth) acrylate compound and / or a polyfunctional (meth) acrylate compound having a fluorene skeleton.

Although the molecular weight of the said polyfunctional (meth) acrylate compound is not specifically limited, From a handling viewpoint, 2000 or less is suitable, for example. More preferably, it is 1000 or less. Moreover, 100 or more is 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, cyclohexane dimethanol Difunctional (meth) acrylates 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, glycerin 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 adducted trimethylolpropane tri (meth) acrylate, ethylene oxide adducted 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 hexamer (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 higher polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate; etc.

In the curable resin composition, the content ratio of the polyfunctional (meth) acrylate compound is 200 parts by mass with respect to 100 parts by mass in total of the alkali-soluble resin (A) and the maleic acid polymer contained as needed. It is preferable that it is less than part. Within this range, a cured product (cured film) which is more excellent in curability can be obtained. More preferably, it is 190 parts by mass or less. Among them, from the viewpoint of improving adhesion, the amount is preferably 180 parts by mass or less, more preferably 170 parts by mass or less, and still more preferably 160 parts by mass or less. Further, from the viewpoint of improving the electrical properties, it is preferably 120 parts by mass or less, more preferably 110 parts by mass or less, still more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, particularly preferably 80 parts by mass The amount is preferably at most 70 parts by mass, most preferably at most parts. Moreover, it is preferable that it is 20 mass parts or more from a viewpoint of improving a developability more. More preferably, it is 25 parts by mass or more.

<Other polymerizable compounds>
The curable resin composition of the present invention may further optionally contain a polymerizable compound (also referred to as another polymerizable compound) other than the above-described polyfunctional (meth) acrylate compound and epoxy compound. Such polymerizable compounds may be used alone or in combination of two or more.
A polymerizable compound is also referred to as a polymerizable monomer, and is a polymerizable unsaturated bond that can be polymerized by irradiation of active energy rays such as free radicals, electromagnetic waves (eg, infrared rays, ultraviolet rays, X-rays, etc.) and electron beams. (Also referred to as a polymerizable unsaturated group); a cationically polymerizable group; a compound having a polymerizable group such as (except for the above-mentioned polyfunctional (meth) acrylate compound and epoxy compound). Preferably, the former is a compound containing a polymerizable unsaturated bond, and in particular, a radically polymerizable compound (radically polymerizable monomer) is preferable.

The polymerizable compound (preferably a radically polymerizable compound) is a monofunctional compound having one polymerizable group in its molecule (also referred to as a monofunctional polymerizable compound) and a polyfunctional compound having two or more It can also be classified as a polyfunctional polymerizable compound (except for those corresponding to the above-mentioned polyfunctional (meth) acrylate compounds), and one or more of these can be used. The molecular weight of the polymerizable compound is not particularly limited, but from the viewpoint of handling, for example, 2000 or less is preferable.

Among the above radically polymerizable compounds, the monofunctional polymerizable compound is not particularly limited, and, for example, (meth) acrylic acid ester monomers; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated groups and Unsaturated monocarboxylic acids whose chain is extended between carboxyl groups; aromatic vinyl monomers; N-substituted maleimide monomers; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; Saturated isocyanates etc. are mentioned. Among these, (meth) acrylic acid ester type monomers are preferable, in other words, monofunctional (meth) acrylate compounds are 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 them, the former is preferable, and in particular, a compound having one (meth) acryloyl group and one aliphatic hydrocarbon group having 5 to 24 carbon atoms in one molecule is preferable. Specific examples of aliphatic hydrocarbon groups include aliphatic saturated hydrocarbon groups (alkyl groups) and aliphatic unsaturated hydrocarbon groups (for example, alkenyl groups). Among them, an aliphatic saturated hydrocarbon group is preferable because a cured product which is further excellent in adhesion and the like can be obtained. Specifically, a group represented by C _n H _{2n + 1} (n = 5 to 24) is preferable.

The carbon number of the aliphatic hydrocarbon group is preferably 5 to 24. By this, the surface hardness of the cured product becomes more sufficient, and the compatibility with other contained components becomes more excellent. The carbon number is preferably 8 or more. Moreover, 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 (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate (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 a linear or branched aliphatic hydrocarbon group such as acrylate, 2-decyltetradecyl (meth) acrylate, 2-decyl tetradecanyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate and the like Compounds; compounds having a cyclic aliphatic hydrocarbon group such as isobornyl (meth) acrylate and adamantyl (meth) acrylate; and the like. Among them, compounds having the above-described aliphatic saturated hydrocarbon group having a preferred carbon number are more preferable.

Among the above-mentioned radically polymerizable compounds, as a polyfunctional polymerizable compound, for example, in addition to the above-mentioned unsaturated polyvalent carboxylic acids and unsaturated acid anhydrides, JP-A-2013-227485 [0097] to [0098] Vinyl ether group-containing (meth) acrylate compounds; polyfunctional allyl ether compounds; allyl group-containing (meth) acrylic esters; polyfunctional (meth) acryloyl group-containing isocyanurates; polyfunctional Also included are allyl group-containing isocyanurates; polyfunctional urethane (meth) acrylates; polyfunctional aromatic vinyls; and the like.

When the said curable resin composition contains the monofunctional (meth) acrylate compound which has a C5-C24 aliphatic hydrocarbon group which is an arbitrary component mentioned above, the content rate will be the solid content of a resin composition The total amount is preferably 3 to 30% by mass in 100% by mass. Thereby, the transparency of the cured product can be further improved, and the adhesion and electrical characteristics can be further improved. More preferably, it is 4% by mass or more, further preferably 5% by mass or more, and more preferably 25% by mass or less, further preferably 20% by mass or less.
When the curable resin composition of the present invention contains a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon group having 5 to 24 carbon atoms in addition to the polyfunctional (meth) acrylate compound, the crosslink density is As the adhesion is further reduced and the adhesion is further improved, the effects of the present invention will be more significantly exhibited.

The content of the other polymerizable monomer other than the monofunctional (meth) acrylate compound having an aliphatic hydrocarbon group having 5 to 24 carbon atoms is, for example, 100% by mass of the total solid content of the curable resin composition. And 10% by mass or less. More preferably, it is 5% by mass or less, still more preferably 1% by mass or less.

<Photoinitiator>
The curable resin composition of the present invention preferably also contains a photopolymerization initiator. This makes it possible to further improve the sensitivity and the curability of the resin composition. Thus, the form in which the above-mentioned curable resin composition further contains a photopolymerization initiator is one of the preferable forms of the present invention. In addition, the curable resin composition of the present invention is preferably a photosensitive resin composition.

The above-mentioned photopolymerization initiator is preferably a radical polymerizable photopolymerization initiator. A radically polymerizable photopolymerization initiator is one that generates a polymerization initiating radical by irradiation of an active energy ray such as an electromagnetic wave or an electron beam, and one or two or more kinds commonly used can be used. . Moreover, you may use together 1 type, or 2 or more types of a photosensitizer, an optical radical polymerization accelerator, etc. as needed. By using a photosensitizer and / or a photo radical polymerization accelerator together with the photopolymerization initiator, the sensitivity and the curability are further improved.

Specific examples of the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE 907”, manufactured by BASF), 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“IRGACURE 369”, manufactured by BASF Corp.), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpho) Amino ketone compounds such as phosphorus-4-yl-phenyl) -butan-1-one (“IRGACURE379”, manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethan-1-one (“IRGACURE 651”, BASF Corporation), phenylglyoxylic acid methyl ester ("DAROCUR MBF", BASF Corporation) Benzyl ketal compounds of the formula: 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE 184”, manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (“DAROCUR1173”, manufactured by BASF Corporation) ), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“IRGACURE 2959”, manufactured by BASF), 2-hydroxy-1- {4 -[4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one ("IRGACURE 127", manufactured by BASF AG), [1-hydroxy-cyclohexyl-phenyl- Ketone + benzophenone] ("IRGACURE 500", manufactured by BASF) Alkyl phenone compounds exemplified in JP-A-2013-227485 [0084] to [0086] other than hydroketone compounds such as; benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethylated triazines Compounds such as halomethylated oxadiazole compounds; biimidazole compounds; oxime ester compounds; titanocene compounds; benzoate compounds; acridine compounds etc .; phosphine oxide compounds; oxime ester compounds; etc. .

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, it is preferable that the said curable resin composition contains an aminoketone type polymerization initiator further. Thereby, the hardness and the developability become more excellent. In addition, 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 it is 2 parts by mass or more with respect to 100 parts by mass of the total solid content of the curable resin composition. Is preferred. This makes it possible to obtain a cured product which is more excellent in adhesion, and peeling is sufficiently suppressed even after high temperature exposure. More preferably, it is 5 parts by mass or more, still more preferably 7 parts by mass or more. Further, in consideration of the balance between the influence of the decomposition product of the photopolymerization initiator, the economy and the like, the content is preferably 35 parts by mass or less. More preferably, it is 25 parts by mass or less.

In the present invention, as described above, it is preferable to use an aminoketone-based polymerization initiator as the polymerization initiator, but in this case, the total amount of the polymerization initiator (ie, aminoketone-based polymerization initiator and other polymerization initiators) The total amount of 100% by mass of the aminoketone-based polymerization initiator is preferably 20% by mass or more. More preferably, it is 30% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more.

Examples of photosensitizers and photoradical polymerization accelerators that may be used in combination with the above-mentioned photopolymerization initiators include, for example, dye-based compounds exemplified in JP-A-2013-227485 [0088]; dialkylaminobenzene-based compounds Mercaptan hydrogen donors, etc. may be mentioned. Further, the content (total amount) of the photosensitizer and / or the radical photopolymerization accelerator may be appropriately set according to the purpose and application, and is not particularly limited, but the curability, the influence of the decomposition product and the economy From the viewpoint of balance of properties, the content is preferably 0.001 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention. More preferably, it is 0.01 to 15 parts by mass, further preferably 0.05 to 10 parts by mass.

<Coupling agent>
The curable resin composition of the present invention preferably also contains a coupling agent. The coupling agent has the property of binding to the oxidized surface of the inorganic substance by hydrolysis reaction or condensation reaction, and by using this property, for example, adhesion to a substrate on which ITO or the like is deposited It is possible to make the sex more fully exhibited. Thus, a form in which the above-mentioned curable resin composition further includes a coupling agent is also one of the preferred forms of the present invention.

Specific examples of the coupling agent include, for example, vinyl group, (meth) acrylic group, epoxy group, amino group, mercapto group, -N = C = O group, -N (R ⁸ ) -C (= O) A coupling agent having a group such as a group (wherein R ⁸ represents a hydrogen atom (H) or any group) is preferred. Among them, those having a vinyl group, a (meth) acryloyl group and / or an epoxy group are preferable. More preferably, it is a (meth) acryloyl group. Also, those having an amino group are suitable. When the curable resin composition of the present invention contains at least an amino group-containing coupling agent, it is possible to give a cured product which can stably exhibit better adhesion even after exposure to a high temperature environment. The cured product has an even higher surface hardness and is particularly excellent in adhesion to tempered glass. Thus, a form in which the above-mentioned coupling agent contains an amino group-containing coupling agent is also one of the preferred forms of the present invention.

The above-mentioned amino group-containing coupling agent is a coupling agent containing one or more amino groups in the molecule. The amino group may be any of a primary amino group (-NH ₂ ), a secondary amino group (-N (H) R ⁹ ), and a tertiary amino group (-NR ¹⁰ R ¹¹ ) ( Here, R ⁹ , R ¹⁰ and R ¹¹ are the same or different and each represent any group / atom other than a hydrogen atom). Among them, those having at least one selected from the group consisting of a primary amino group (—NH ₂ ) and a secondary amino group are preferable, and those having at least a primary amino group are more preferable. By including the coupling agent containing a primary amino group, the adhesion of the cured product is further significantly improved.

The amino group-containing coupling agent also preferably contains silicon, zirconia, titanium and / or aluminum as a central metal. More preferred is one having silicon as a central metal, and even more preferred is a silane coupling agent containing an amino group (also referred to as an amino group-containing silane coupling agent). As a result, it is possible to obtain a cured product having more sufficient surface hardness and adhesion without causing temporal changes in appearance such as discoloration, coloring, and cracks even after high temperature exposure.
In addition, as a coupling agent which has metals other than a silicon as a center metal, a zirco aluminate type coupling agent, a titanate type coupling agent, etc. are mentioned, for example.

The above-mentioned coupling agent also preferably contains, for example, silicon, zirconia, titanium and / or aluminum as a central metal. Among them, one having silicon as a central metal is preferable, and a silane coupling agent is more preferable. By using a silane coupling agent, the adhesion and surface hardness of the cured product can be made more sufficient.

As the silane coupling agent, and one or more groups described above, the alkoxysilane group ^{_{^{(-Si (OR 12) 3-}}} n (R 13) n; OR 12 represents a hydrolyzable group, R ¹² is preferably a hydrocarbon group, and R ¹³ represents a hydrocarbon group, and n is preferably 0, 1 or 2. Among them, it is preferable to use a silane coupling agent having a vinyl group, a (meth) acryloyl group and / or an epoxy group, whereby there is no time-dependent change in appearance such as discoloration, coloring or cracks even after high temperature exposure, It becomes possible to obtain a cured product having more sufficient surface hardness and adhesion.

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, 3- (meth) acryloxypropyltri Examples thereof include methoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane and the like.

Specific examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Examples thereof include glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

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

As a silane coupling agent which has said -N = C = O group, 3-isocyanate propyl triethoxysilane etc. are mentioned, for example, The silane coupling which has -N (R < ⁸ >)-C (= O)-group The agent includes, for example, tris- (trimethoxysilylpropyl) isocyanurate.

Among the above-mentioned silane coupling agents, it is particularly preferable to use a silane coupling agent having a (meth) acryloyl group (also referred to as a (meth) acryloyl group-containing silane coupling agent), whereby the storage stability of the resin composition is obtained. Is better. In addition, the adhesion will be further improved.
In addition, from the viewpoint of improving the storage stability of the resin composition and the adhesion of the cured product, the above-mentioned curable resin composition contains, as a coupling agent, a (meth) acryloyl group-containing silane coupling agent, and an amino group. It is preferable to include a containing coupling agent. Among these, it is more preferable to contain a (meth) acryloyl group-containing silane coupling agent and an amino group-containing silane coupling agent. Thus, the form in which the above-mentioned coupling agent contains a (meth) acryloyl group-containing silane coupling agent and an amino group-containing silane coupling agent is one of the preferable forms of the present invention.

As a coupling agent which has metals other than a silicon as a center metal among the said coupling agents, a zirco aluminate type coupling agent, a titanate type coupling agent, etc. are mentioned, for example.

In the curable resin composition, the content (total content) of the coupling agent is preferably 3% by mass or more in 100% by mass of the total solid content of the curable resin composition. By including 3% by mass or more, it is possible to have sufficient adhesion and surface hardness even after high temperature exposure. More preferably, it is 4 mass% or more, More preferably, it is 5 mass% or more. Moreover, it is preferable that it is 30 mass% or less from a viewpoint of storage stability etc. of a curable resin composition. More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.

Here, when the curable resin composition contains an amino group-containing coupling agent, the content of the amino group-containing coupling agent is 1 to 100% by mass with respect to 100% by mass of the total content of the coupling agent. Is preferred. This further improves the storage stability of the resin composition and the adhesion of the cured product. Further, from the viewpoint of improving the transparency of the cured product, it is more preferably 3 to 90% by mass, still more preferably 5 to 50% by mass, and particularly preferably 8 to 20% by mass.
When an amino group-containing coupling agent and a (meth) acryloyl group-containing coupling agent are used in combination, their mass ratio (amino group-containing coupling agent / (meth) acryloyl group-containing coupling agent) is 3 to It is preferably 90/10 to 97. More preferably, it is 5 to 50/50 to 95, more preferably 8 to 20/80 to 92.

<Fluorine-based additive>
The curable resin composition of the present invention may also contain one or more fluorine-based additives (also referred to as fluorine additives) from the viewpoint of further improving the curability. 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, and, for example, a compound generally used as a fluorine-based surfactant or a fluorine-based surface modifier can be used.

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

It is preferable that the above-mentioned fluorine-based additive further contains 0.01 to 80% by mass of fluorine in 100% by mass of the total amount of the fluorine-based additive. The fluorine content can be quantified, for example, by ion chromatography.

As the above-mentioned fluorine-based additive, although there are nonionic and anionic ones, etc., nonionic ones are preferable from the viewpoint of dispersibility with the resin.

Specific examples of the fluorine-based additive include, for example, perfluorobutane sulfonate (Megaface F-114), perfluoroalkyl group-containing carboxylate (Megaface F-410), perfluoroalkyl ethylene oxide adduct ( Megafuck F-444, EXP TF-2066), perfluoroalkyl group-containing phosphate ester (Megafuck EXP TF-2148), perfluoroalkyl group-containing phosphoric acid ester neutralized amine (Megafuck EXP TF) -2149), fluorine-containing group / hydrophilic group-containing oligomer (Megaface F-430, EXP / TF-1540), fluorine-containing group / lipophilic group-containing oligomer (Megaface F-552, F-554, F-558) , F-561, R-41), fluorine-containing groups, hydrophilic groups, lipophilic groups, Gomer (Megafuck F-477, F-553, F-555, F-556, F-557, F-562, R-40, EXP / TF-1760), fluorine-containing group / hydrophilic group・ Lipophilic group ・ UV reactive group containing oligomer (Megaphorc RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-77) etc. (all are manufactured by DIC Corporation) ). Among them, compounds containing a lipophilic group (fluorinated group / lipophilic group-containing oligomers, fluorine-containing groups / hydrophilic groups / lipophilic group-containing oligomers, fluorine-containing groups / hydrophilic groups / lipophilic groups / UV-reactive group-containing compounds Oligomers are preferred.

The content of the fluorine-based additive may be appropriately set according to the purpose, application, etc., and is not particularly limited, but 0.05 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition. Is preferred. The amount is more preferably 0.1 parts by mass or more, more preferably 5 parts by mass or less, still more preferably 4 parts by mass or less, and particularly preferably 3 parts by mass or less.

<Solvent>
The curable resin composition of the present invention preferably also contains a solvent. The solvent is preferably used as a diluent or the like. That is, specifically, the viscosity is reduced to improve the handleability; the coating film is formed by drying; the dispersion medium of the coloring material; and the like, which is suitably used for the curing resin composition, etc. It is a low viscosity organic solvent capable of dissolving or dispersing each component of

As the above-mentioned solvent, one or two or more normally used solvents can be used, and they may be appropriately selected according to the purpose and application, and are 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 D. Glycol monoethers such as propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, etc. Monoethers, glycols, cyclic ethers, glycol monoethers, glycol ethers, alkyl esters, ketones, aromatic carbons other than tellurium, as exemplified in JP-A-2013-227485 [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 10 to 90% by mass is contained in 100% by mass of the total of the curable resin composition of the present invention Is preferred. More preferably, it is 20 to 80% by mass, particularly preferably 40 to 80% by mass, and most preferably 60 to 80% by mass.

The above-mentioned curable resin composition is further, for example, coloring material (also referred to as coloring agent); dispersing agent; heat resistance improver; leveling agent; developing aid; filler; Thermosetting resins such as phenolic resins and polyvinylphenols; Curing aids such as multifunctional thiol compounds; Plasticizers; Polymerization inhibitors; UV absorbers; Antioxidants; Matting agents; Antifoaming agents; Antistatic agents; Slips Surface modifiers, thixotropic agents, thixotropic aids, quinone diazide compounds, polyhydric phenol compounds, acid generators, etc. may be contained alone or in combination of two or more. For example, when using the said curable resin composition for a color filter use, it is preferable to contain a coloring material.

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

<Method of 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 dispersing the above-mentioned component using various mixers and dispersers. The dispersing step and the mixing step are not particularly limited, and may be performed by a usual method. In addition, it may further include other steps normally performed. When the said curable resin composition contains a color material, it is suitable to manufacture through the dispersion | distribution processing process of a color material.

[Cured film]
Next, a cured film formed using the curable resin composition of the present invention will be described.
The curable resin composition of the present invention can form a cured film by irradiating (exposing) active energy rays. Specifically, for example, the curable resin composition is applied onto a substrate (also referred to as a base material) and dried, and a cured film is formed by irradiating (exposing) an active energy beam on the coated surface. Is preferred. Thus, the cured film formed of the said curable resin composition is also one of this invention. Further, since the above curable resin composition is suitably used as a resist material, a form in which a cured film formed of the above curable resin composition is a cured resist film is also one of preferred embodiments of the present invention. It is one.

The cured film preferably has, for example, a resistance value reduction time of 100 hours or more in the ion migration test. By using such a cured film, the electrical characteristics of the display device member and the like are further improved. The resistance value reduction time is more preferably 150 hours or more, still more preferably 200 hours or more, and particularly preferably 250 hours or more.
An ion migration test can be performed by the method as described in the Example mentioned later.

Here, with a display device member having a cured film with good electrical characteristics, for example, high definition can be achieved when a display device screen having a capacitive touch panel is touch-input. With a capacitive touch panel, when the user's finger contacts the window of the touch panel, a capacitance is formed between the finger and the (transparent) electrode of the touch panel, and the position touched by the change in capacitance accompanying this To detect Therefore, the performance of the display device can be improved by improving the electrical characteristics of various portions in which the cured film is formed.

The substrate on which the curable resin composition is applied (also referred to as a substrate) is not particularly limited. For example, transparent glass substrates such as white plate glass, blue plate glass, silica coated blue plate glass, etc .; polyethylene terephthalate (PET), polyester , Sheets or films made of thermoplastic resins such as polycarbonate, polyolefin, polysulfone, ring-opened polymers of cyclic olefins and hydrogenated products thereof; sheets or films made of thermosetting resins such as epoxy resin, unsaturated polyester resin; aluminum Metal substrate such as plate, copper plate, nickel plate, stainless steel plate; ceramic substrate; semiconductor substrate having photoelectric conversion element; member composed of various materials such as glass substrate (color filter for LCD) provided with color material layer on the surface; Etc. Among them, in view of heat resistance, a glass substrate or a plastic substrate, a sheet or film made of a heat resistant resin is preferable. The substrate is preferably a transparent substrate.

The substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, etc., if necessary, or an inorganic material such as a gas barrier layer or protective film on both sides or one side of the substrate. You may form the coating film of a component or an organic component. Moreover, when using a cured film for members for display apparatuses, it is suitable to form electrodes, such as ITO, in the said board | substrate. The cured film of the present invention is excellent not only in adhesion to the substrate but also in adhesion to an electrode such as an ITO film.

It does not specifically limit as method to apply | coat the said curable resin composition to a board | substrate, For example, spin coating, slit coating, roll coating, a cast coating etc. are mentioned, Any method can also be used preferably.

The coating film may be dried after being applied to the substrate 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 kind of the curing component, the film thickness, the performance of the dryer, etc., but the temperature is usually 50 to 150 ° C. for 10 seconds to 300 seconds. Is preferred.

As a light source of the above-mentioned active energy ray, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, an argon ion laser Laser light sources such as YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, etc. are used. Further, as a method of the exposure machine, a proximity method, a mirror projection method, a stepper method may be mentioned, but a proximity method is preferably used.
In the irradiation step of the active energy ray, depending on the application, the active energy ray may be irradiated through a predetermined mask pattern. In this case, the exposed portion is cured, and the cured portion is insolubilized or poorly dissolved in the developer.

Further, if necessary, after the irradiation process of the active energy ray, a process of developing with a developer to remove the unexposed area and form a pattern (also referred to as a development process) may be performed. Thereby, a patterned cured film can be obtained.
The development processing in the development step can be carried out usually at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, ultrasonic development and the like. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development.

The developer is not particularly limited as long as it dissolves the curable resin composition of the present invention, but an organic solvent or an alkaline aqueous solution is usually used, and a mixture of these may be used.
As an organic solvent suitable as a developing solution, an ether solvent, alcohol solvent, etc. are mentioned, for example. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkylphenyl ethers, aralkyl phenyl ethers, diaromatic ethers And isopropanol, benzyl alcohol and the like.

The alkaline aqueous solution may contain, if necessary, a surfactant, an organic solvent, a buffer, a dye, a pigment and the like in addition to the alkaline agent. Examples of the organic solvent in this case include organic solvents suitable as the above-described developer. As an alkali agent, 1 type, or 2 or more types, such as an inorganic alkali agent which was illustrated by Unexamined-Japanese-Patent No. 2013-227485 [0164]; amines; etc. can be used, For example, as surfactant For example, one or more of nonionic surfactants, anionic surfactants, amphoteric surfactants and the like as exemplified in JP-A-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 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, and a post-heating step (also referred to as a heat treatment step). . By performing such post-treatment, it is possible to further strengthen the hardness and adhesion of the patterned cured film.

Among the post-treatment steps described above, the latter is preferably the heat treatment step, 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 exhibited more sufficiently. Thus, a form in which the cured film is heat-treated at a temperature of 60 ° C. or higher is also one of the preferred forms of the present invention. The temperature of the heat treatment is more preferably 80 ° C. or more, and preferably 300 ° C. or less. Further, the heat treatment time is not particularly limited, but for example, 10 seconds to 300 minutes is preferable.

[Uses of curable resin composition, etc.]
The curable resin composition of the present invention provides a cured product (cured film) having extremely high surface hardness, sufficient adhesion, and high transparency. In particular, when the curable resin composition of the present invention contains a predetermined maleic acid-based polymer, it can give a cured product with good electrical properties, and when it contains an epoxy compound, a cured product having a higher surface hardness. Can be given. Therefore, the cured product (cured film) formed from such a curable resin composition is, for example, ink, printing, as well as components of various display devices such as a liquid crystal display device, a solid-state imaging device, and a touch panel display device. It is preferably used in various applications such as printing plates, printed wiring boards, semiconductor elements, photoresists, various optical members, electric machines and electronic devices. Among them, color filters used in liquid crystal display devices, solid-state imaging devices and the like, and touch panel display devices are suitably used, and particularly, protective films (colors (colors) in these various display devices using the above curable resin composition It is preferable to form a protective film for a filter, a protective film for a touch panel display, and the like, and an insulating film (an insulating film for a touch panel display and the like). As a result, the reliability of the display quality and the imaging quality of various display devices can be sufficiently enhanced to the extent that the demand for higher performance in recent years can be sufficiently addressed. Thus, the embodiment in which the curable resin composition is a curable resin composition for forming a protective film or an insulating film, the embodiment 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 The form which is is also included in the preferred form of the present invention. Further, a cured film formed of the above curable resin composition, a member for a display device having the cured film, and a display device having the cured film are included in the present invention.

The member for a display device and the display device of the present invention have the above-described cured film, but may further include one or more other component members and the like. The cured film formed of the curable resin composition stably has excellent adhesion to a substrate and the like, has high hardness, and also has 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 touch-panel-type display apparatus etc. are suitable. In particular, a capacitive type is preferable as the touch panel type display device.

In addition, the member for display devices 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 be a member (for example, a color filter or the like) that includes the above-mentioned cured film.

Since the curable resin composition of the present invention is configured as described above, it can provide a cured product having sufficient adhesion with extremely high surface hardness and high transparency. Therefore, a member for a display device and a display device having a cured film formed of such a curable resin composition are very useful in the optical field and the electric and electronic fields.

EXAMPLES The present invention will be described in more detail by way of the following examples, but the present invention is not limited to these examples. In addition, unless there is particular notice, "part" shall mean "mass part" and "%" shall mean "mass%", respectively.
In the following synthesis examples and preparation examples, various physical properties and the like were measured as follows.

1. Physical properties of resin solution (alkali-soluble resin)]
(1) Weight average molecular weight (Mw)
The weight average molecular weight was measured by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corp.) and a column TSKgel Super HZM-M (manufactured by Tosoh Corp.) 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, and after about 1 g of acetone was added and dissolved, it was naturally dried at normal temperature. Then, after drying at 140 ° C. for 3 hours using a hot air drier (trade name “PHH-101” manufactured by ESPEC, Inc.), it was allowed to cool in a desiccator and its mass was measured. The solid content concentration (% by mass) of the polymer solution was calculated from the mass loss.

(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 and 10 g of water, and a 0.1 N KOH aqueous solution is used as a titration solution to make an automatic titrator (trade name "COM-555, manufactured by Hiranuma Sangyo Co., Ltd. The acid value of the resin solution was measured, and the acid value per 1 g of solid content was determined from the acid value of the solution and the solid content of the solution.

2. Physical Properties of Coating (Cured Film) (1) Physical Properties of ITO Substrate An ITO substrate having a thickness of 30 nm and ITO (Indium Tin Oxide) deposited thereon was prepared. The obtained resin composition is applied to the ITO substrate 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 (trade name “TOPCON” Exposure was performed at an exposure dose of 60 mJ / cm ² (365 nm illuminance conversion) using TME-150 RNS ′ ′), and heat treatment (230 ° C. for 30 minutes) was performed. Initial physical property evaluation (cross-cut test, pencil hardness test, film color evaluation test) and light resistance evaluation were performed using the obtained coated film as described below.

(1-1) Cross-cut test (adhesion evaluation)
The test was conducted according to JIS-K5400-8.5 (1990), and evaluated according to the following criteria.
○: 10 points according to JIS standard.
× 1: 8 points according to JIS.
× 2: 6 points according to JIS standard.
× 3: 4 points according to JIS standard.
× 4: 2 points according to JIS standard.
× 5: 0 points in JIS standard.

(1-2) Pencil hardness test (hardness evaluation)
The tests were conducted according to JIS-K5600-5-4 (1999), but all the loads were carried out with 500 g of JIS-K5400 (1990) of the old JIS version, and the hardest pencil which did not produce a scar was used as the hardness It was the value of (surface hardness).
The hardness decreases in the order of 3H>2H>H>F>HB>B>2B>3B> 4B.

(1-3) Film Color Evaluation Test The color of the coated film (cured film with a thickness of 1.5 μm) obtained above was visually evaluated. Specifically, the following criteria were evaluated.
○: The cured film is colorless and transparent.
Δ: The cured film is pale white.
X: The cured film is cloudy.

(1-4) Light resistance test The coating film (cured film with a thickness of 1.5 μm) obtained above is set in a machine in the direction in which UV strikes from the glass surface using a xenon weather meter (manufactured by X75SC Suga Test Instruments) 60 W / m ² (300 to 400 nm accumulated light amount), BPT 63 ° C., 50% RH irradiation for 30 h, the test is conducted according to JIS-K 5400-8.5 (1990), and the above-mentioned (1) Evaluation was performed in the same manner as the eye test (adhesion evaluation) criteria.

(2) Electrical characteristics (ion migration test)
Using alkali-free glass, an APC alloy of L / S = 10 mm / 1 mm was vapor deposited by an ion sputtering apparatus (Auto Fine Coater JFC-1600: manufactured by JEOL) to produce a glass substrate with metal wiring provided with a simple wiring.
Next, using the obtained glass substrate, the resin composition obtained in each preparation example is applied by spin coating and heat-treated (80 ° C. for 3 minutes), and then 1 cm of the end portion is masked, 2.0 kW Exposure was performed at an exposure dose of 60 mJ / cm ² (365 nm illuminance conversion) using a UV aligner (trade name "TME-150 RNS" manufactured by TOPCON, equipped with an ultra-high pressure mercury lamp. After alkali development, heat treatment (230 ° C.) 30 minutes) was performed to obtain an insulating substrate with metal wiring.
Next, using a silver paste (Fujikura Kasei XA-910) on the exposed metal substrate of the obtained insulating substrate with metal wiring, and curing it at 150 ° C. for 30 minutes, using the silver paste (XF-910 made by Fujikura Chemical Co., Ltd.) I am connected.
Using this evaluation sample, a voltage of 5 V is applied for a certain period of time under constant temperature and humidity conditions of 80 ° C. and 95% RH, and the time (h) in which the resistance value decreases is an ion migration device (MIG-87: manufactured by IMV) ) Was used.

(3) Evaluation of developability (residue)
The obtained resin composition is applied to a glass substrate by spin coating, heat-treated (80 ° C. for 3 minutes), and then through a photomask provided with a 50 μm line and space opening at a distance of 100 μm from the applied film. Exposure with an exposure dose of 60 mJ / cm ² (365 nm illuminance equivalent) with a UV aligner (trade name "TME-150 RNS" manufactured by TOPCON, equipped with a 2.0 kW ultra-high pressure mercury lamp, The aqueous solution of potassium hydroxide was sprayed for 40 seconds with a spin developing machine to dissolve and remove the unexposed area, and the remaining exposed area was developed by washing with pure water for 10 seconds to evaluate the developability. .
Specifically, the coated film developed through the photomask as described above was evaluated using a surface roughness meter (trade name "VertScan 2.0" manufactured by Ryoka System Co., Ltd.) according to the following criteria.
○: Unexposed area and exposed area are flowing cleanly and without residue.
Fair: some residues can be confirmed in the unexposed area.
X: Many residues can be confirmed in the unexposed area.

(4) Evaluation of Adhesion to Tempered Glass The obtained resin composition is applied to a strengthened glass (Dragon Trail, manufactured by Asahi Glass Co., Ltd.) by a spin coating method and heat-treated (80 ° C. for 3 minutes) to obtain 2.0 kW of super Exposure was performed at a dose of 60 mJ / cm ² (365 nm illuminance conversion) using a UV aligner (trade name "TME-150 RNS" manufactured by TOPCON, Inc.) equipped with a high pressure mercury lamp, and heat treatment (230 ° C for 30 minutes) was performed. . The obtained coated film was evaluated (cross-cut test) after PCT (Pressure Cooker Test) for 3 hours under a water vapor pressure condition of 120 ° C.
Specifically, tests were conducted in accordance with JIS-K5400-8.5 (1990), and evaluated according to the following criteria.
○: 10 points according to JIS standard.
× 1: 8 points according to JIS.
× 2: 6 points according to JIS standard.
× 3: 4 points according to JIS standard.
× 4: 2 points according to JIS standard.
× 5: 0 points in JIS standard.

[Synthesis of resin solution]
Resin solution A (No. A-1 to A-13) was synthesized as the alkali-soluble resin (A) contained in the resin composition.

Synthesis Example 1 (Synthesis of A-1)
456 parts of propylene glycol monomethyl ether (PGME) is charged into a separable flask equipped with a cooling pipe as a reaction tank, heated to 90 ° C. under a nitrogen atmosphere, and then 30 parts of benzylmaleimide (BzMI) as a dropping system 1 and methacrylic acid 180 parts of (MAA), 90 parts of cyclohexyl acrylate (CHA), 30 parts of PGME, 6 parts of Perbutyl O (trade name, manufactured by NOF Corporation), 9 parts of n-dodecyl mercaptan (n-DM) as dropping system 2, 71 parts of PGME Each was continuously supplied over 3 hours. Then, after maintaining the temperature at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and polymerization was continued for 1.5 hours.
Subsequently, 99 parts of glycidyl methacrylate (GMA), 1.2 parts of triethylamine (TEA) as a catalyst, and 0.6 parts of Antege W-400 (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added to this reaction liquid The reaction was continued at 110 ° C. for 2 hours and at 115 ° C. for 4 hours while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%) to obtain a double bond equivalent of 588 g / equivalent of 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 example 2 (synthesis of A-2)
In a separable flask with cooling tube as a reaction vessel, 185 parts of propylene glycol monomethyl ether acetate (PGMEA) and 185 parts of PGME are charged and heated to 90 ° C. under a nitrogen atmosphere, then 25 parts of BzMI and 143 parts of MAA as dropping system 1 Then, 83 parts of CHA, 13 parts of PGMEA, 13 parts of PGME, 5 parts of perbutyl O, 11 parts of n-DM as dropping system 2, 34 parts of PGMEA and 34 parts of PGME were continuously supplied over 3 hours. Then, after maintaining the temperature at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and polymerization was continued for 1.5 hours. Then, 124 parts of GMA, 1.1 parts of TEA as a catalyst, and 0.6 parts of Ange W-400 as a polymerization inhibitor were added to this reaction solution, and 110 ° C. while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%) The reaction was continued for 2 hours at 115 ° C. for 7 hours to obtain a resin solution A-2 having a double bond equivalent of 444 g / equivalent.
Various physical properties of the obtained resin solution A-2 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis example 3 (synthesis of A-3)
90 parts of PGMEA and 90 parts of PGME are charged in a separable flask equipped with a cooling pipe as a reaction tank, heated to 90 ° C. under a nitrogen atmosphere, and then 60 parts of MAA, 76 parts of CHA, 2.7 parts of Perbutyl O as dropping system 1. As a dripping system 2, 5.7 parts of n-DM, 37 parts of PGMEA and 37 parts of PGME were continuously supplied as a dropping system 2 over 3 hours. Then, after maintaining the temperature at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and polymerization was continued for 1.5 hours.
Then, 45 parts of GMA, 0.5 parts of TEA as a catalyst, 0.3 parts of antage W-400 as a polymerization inhibitor are added to this reaction solution, and 110 ° C. while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%) The reaction was continued for 2 hours at 115 ° C. for 4 hours to obtain a double bond equivalent of 593 g / equivalent of a resin solution A-3.
Various physical properties of the obtained resin solution A-3 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 4 (Synthesis of A-4)
382 parts of PGMEA and 95 parts of PGME are charged in a separable flask equipped with a cooling pipe as a reaction tank, and the temperature is raised to 90 ° C. under a nitrogen atmosphere, then 12 parts of BzMI as a dropping system 1, 74 parts of MAA, 170 parts of CHA, 2 45 parts of hydroxyethyl acrylate (HEA), 10 parts of PGMEA, 2 parts of PGME, 6 parts of perbutyl O, 12 parts of n-DM as a dropping system 2, 54 parts of PGMEA and 14 parts of PGME are continuously supplied over 3 hours. Then, after maintaining the temperature at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and polymerization was continued for 1.5 hours.
Then, 25 parts of GMA, 1.0 part of TEA as a catalyst, and 0.5 parts of antage W-400 as a polymerization inhibitor were added to this reaction liquid, and 110 ° C. while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%) The reaction was continued for 2 hours at 115 ° C. for 3 hours to obtain a resin solution A-4 with a double bond equivalent of 1941 g / equivalent.
Various physical properties of the obtained resin solution A-4 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis example 5 (synthesis of A-5)
In a separable flask equipped with a cooling pipe as a reaction vessel, 460 parts of PGME is charged, and the temperature is raised to 90 ° C. under a nitrogen atmosphere, then 30 parts BzMI, 249 parts MAA as a dropping system 1, 21 parts CHA, 30 parts PGME, 6 parts perbutyl O As a dripping system 2, 13 parts of n-DM and 67 parts of PGME were continuously supplied over 3 hours. Then, after maintaining the temperature at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and polymerization was continued for 1.5 hours.
Then, add 125 parts of PGME, 248 parts of GMA, 1.6 parts of TEA as a catalyst, 0.8 parts of Antej W-400 as a polymerization inhibitor to this reaction solution, and bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%) The reaction was continued at 110 ° C. for 2 hours and at 115 ° C. for 10 hours to obtain resin solution A-5 having a double bond equivalent of 323 g / equivalent.
Various physical properties of the obtained resin solution A-5 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 6 (Synthesis of A-6)
As a reaction vessel, 921 parts of PGMEA is charged in a separable flask equipped with a cooling pipe, heated to 90 ° C. under a nitrogen atmosphere, and then, as a dropping system 1, dimethyl-2,2 '-[oxybis (methylene)] bis-2 -102 parts of propenoate (MD), 182 parts of MAA, 175 parts of benzyl methacrylate (BzMA), 51 parts of methyl methacrylate (MMA), 10.2 parts of perbutyl O, 16.8 parts of n-DM as dropping system 2 and 44 parts of PGMEA Was continuously supplied over 150 minutes each. Thereafter, the temperature was raised to 110 ° C., and polymerization was continued for 3 hours.
Next, 210 parts of GMA, 2.2 parts of TEA as a catalyst, 0.2 parts of Antej W-400 as a polymerization inhibitor, and 119 parts of PGMEA are added to this reaction solution, and nitrogen and oxygen mixed gas (oxygen concentration 7%) is bubbled By continuing the reaction at 110 ° C. for 2 hours and at 115 ° C. for 4 hours, a double bond equivalent of 490 g / equivalent of resin solution A-6 was obtained.
Various physical properties of the obtained resin solution A-6 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 7 (Synthesis of A-7)
After charging 921 parts of PGMEA in a separable flask with a condenser as a reaction vessel and raising the temperature to 90 ° C. under a nitrogen atmosphere, 102 parts of methyl α-allyloxymethyl acrylate (AMA) and 182 parts of MAA as dropping system 1 175 parts of BzMA, 51 parts of MMA, 10.2 parts of Perbutyl O, 16.8 parts of n-DM as the dropping system 2 and 44 parts of PGMEA were continuously supplied over 150 minutes. Thereafter, the temperature was raised to 110 ° C., and polymerization was continued for 3 hours.
Next, 210 parts of GMA, 2.2 parts of TEA as a catalyst, 0.2 parts of Antej W-400 as a polymerization inhibitor, and 119 parts of PGMEA are added to this reaction solution, and nitrogen and oxygen mixed gas (oxygen concentration 7%) is bubbled By continuing the reaction at 110 ° C. for 2 hours and at 115 ° C. for 4 hours, a double bond equivalent of 490 g / equivalent of resin solution A-7 was obtained.
Various physical properties of the obtained resin solution A-7 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 8 (synthesis of A-8)
362 parts of PGMEA and 91 parts of PGME are charged in a separable flask equipped with a cooling pipe as a reaction tank, and the temperature is raised to 90 ° C. under a nitrogen atmosphere, and then 30 parts of BzMI, 60 parts of MAA, 210 parts of CHA, 24 parts of PGMEA, 24 parts of PGMEA as a dropping system 1 6 parts of Perbutyl O, 6 parts of n-DM as dropping system 2, 59 parts of PGMEA and 15 parts of PGME were continuously supplied over 3 hours. Then, after maintaining the temperature at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and polymerization was continued for 1.5 hours.
Next, 58 parts of PGMEA, 14 parts of PGME, 50 parts of GMA, 1.1 parts of TEA as a catalyst, 0.5 parts of Ange W-400 as a polymerization inhibitor, and nitrogen and oxygen mixed gas (oxygen concentration 7%) are added to this reaction solution. The reaction was continued at 110 ° C. for 2 hours and at 115 ° C. for 7 hours while bubbling to obtain a resin solution A-8 having a double bond equivalent of 1025 g / equivalent.
Various physical properties of the obtained resin solution A-8 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 9 (synthesis of A-9)
154 parts of PGMEA and 38 parts of PGME are charged in a separable flask with a cooling pipe as a reaction tank and heated to 90 ° C. in a nitrogen atmosphere, and then 51 parts of BzMI, 34 parts of MAA as an dripping system 1, 85 parts of CHA, 41 parts of PGMEA, PGME10 3.4 parts of Perbutyl O, 7.3 parts of n-DM as the dropping system 2, 58 parts of PGMEA and 15 parts of PGME were continuously supplied over 3 hours. Then, after maintaining the temperature at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and polymerization was continued for 1.5 hours.
Next, 38 parts of PGMEA, 10 parts of PGME, 28 parts of GMA, 0.6 parts of TEA as a catalyst, 0.3 parts of Ange W-400 as a polymerization inhibitor, and nitrogen and oxygen mixed gas (oxygen concentration 7%) are added to this reaction solution. The reaction was continued at 110 ° C. for 2 hours and at 115 ° C. for 7 hours while bubbling to obtain a resin solution A-9 having a double bond equivalent of 1045 g / equivalent.
Various physical properties of the obtained resin solution A-9 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Examples 10 to 13 (Synthesis of A-10 to A-13)
Similar to Synthesis Example 1 except that the types of monomers constituting the base polymer, the blending ratio thereof, and the blending ratio of GMA to be added were changed as shown in Table 1 and that the solvent was changed to PGMEA alone. Resin solutions A-10 to A-13 were obtained by the following procedure.
Various physical properties of each of the obtained resin solutions were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Table 1 shows the details of the resin solutions A-1 to A-13.
In addition, the numerical value of each monomer which comprises the base polymer in Table 1 described the mixture ratio (mass%) of each monomer when this monomer total amount is 100 mass%. Further, the numerical value of GMA added to the base polymer is added to the carboxylic acid component of a monomer having an acid group and a polymerizable double bond (in Synthesis Examples 1 to 13, corresponding to MAA or AA). GMA is described as mass% converted to mass of MAA (or AA), “blending ratio in mass conversion of GMA to MAA (or AA) (mass%) = {molar amount of GMA (mol) / MAA (or The molar amount of AA) (mol)} × MAA (or AA) blending ratio (% by mass) ”. For example, in Synthesis Example 1 (A-1), MAA is 60% by mass in the base polymer (100% by mass), and 696 mmol of GMA is added to 60% by mass (2091 mmol) of MAA, The blending ratio of the GMA was defined as "20".

The abbreviations in Table 1 are as follows.
BzMI: benzyl maleimide MD: dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate AMA: α- (allyloxymethyl) methyl acrylate CHA: cyclohexyl acrylate CHMA: cyclohexyl methacrylate BzMA: benzyl methacrylate MAA: methacryl Acid AA: acrylic acid MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate GMA: glycidyl methacrylate AV: acid value Mw: weight average molecular weight of finally obtained polymer NV: solid concentration

[Preparation of resin composition and evaluation test of coating film]
Preparation Example 1 (Resin Composition a-1)
In solid content, 25 parts of resin solution A-10, 35 parts of dipentaerythritol hexaacrylate (DPHA), 10 parts of isobornyl acrylate (IB-XA), 20 parts of SMA 17352 as a maleic acid polymer, coupling 10 parts of KBM 503 as an agent, 20 parts of IRGACURE 907 as a photopolymerization initiator, 0.2 parts of F-554 as a fluorine additive, 0.5 parts of Ange W-400 as a polymerization inhibitor, and a dilution solvent (PGMEA) The mixture was added to a solid content concentration of 25% and stirred to obtain a resin composition a-1.
The physical properties of the coated film (cured film) were evaluated for the obtained resin composition a-1 according to the above-described evaluation method. The results are shown in Table 2.

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

Preparation Example 9 (Resin composition b-1)
In terms of solid content, 25 parts of resin solution A-10, 35 parts of dipentaerythritol hexaacrylate (DPHA), 20 parts of SMA 2625, 10 parts of 2021P, 10 parts of KBM 503, 20 parts of IRGACURE 907, 0 parts of F-554 A resin composition b-1 was obtained by adding 2 parts, 0.5 parts of antage W-400, and further adding a dilution solvent (PGMEA) to a solid content concentration of 25% and stirring.
The physical properties of the coated film (cured film) were evaluated for the obtained resin composition b-1 according to the above-described evaluation method. The results are shown in Table 3.

Preparation Examples 10 to 15
Resin compositions b-2 to b-7 were obtained in the same manner as in Preparation Example 9 using the raw materials shown in the table and at the composition ratio shown in Table 3, respectively. About each of the obtained resin composition, the physical property of the coating film was evaluated in accordance with the evaluation method mentioned above. The results are shown in Table 3.

Preparation Example 16 (Resin Composition c-1)
25 parts of resin solution A-10, 10 parts of isobornyl methacrylate (IB-X), 35 parts of dipentaerythritol hexaacrylate (DPHA), 20 parts of 2021 P, 8 parts of KBM 503, and 2 parts of KBM 903 in terms of solid content 20 parts of IRGACURE 907, 0.2 parts of F-554, 0.5 parts of Ange W-400, and a dilution solvent (PGMEA) to a solid concentration of 25%, and the resin composition is stirred. The object c-1 is obtained.
The physical properties of the coated film (cured film) were evaluated for the obtained resin composition c-1 according to the above-described evaluation method. The results are shown in Table 4.

Preparation Examples 17-19
Resin compositions c-2 to c-4 were obtained in the same manner as in Preparation Example 16 using the raw materials shown in the table at the mixing ratio shown in Table 4. About each of the obtained resin composition, the physical property of the coating film was evaluated in accordance with the evaluation method mentioned above. The results are shown in Table 4.

The abbreviations in Tables 2 to 4 are as follows. The blending amounts of the respective raw materials in Tables 2 to 4 are solid contents. In Tables 2 to 4, the use of a dilution solvent (PGMEA: propylene glycol monomethyl ether acetate) is omitted.
DPHA: dipentaerythritol hexaacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
A-9300: Ethoxylated isocyanurate triacrylate (trade name, Shin-Nakamura Chemical Co., Ltd.)
IB-XA: isobornyl acrylate (trade name “light acrylate IB-XA”, manufactured by Kyoeisha Chemical Ltd. IB-X: isobornyl methacrylate (trade name “light ester IB-X”, manufactured by Kyoeisha Chemical FA-513AS: Dicyclopentanyl acrylate (trade name "Funkry FA-513AS", manufactured by Hitachi Chemical Co., Ltd.)
TMPTA: trimethylolpropane triacrylate NBAC-ST: butyl acetate dispersed silica sol (trade name, manufactured by Nissan Chemical Industries, Ltd.)
SMA 17352: Styrene / maleic anhydride copolymer (Mw by GPC = 7000, styrene / maleic anhydride molar ratio = 1/1) (trade name, manufactured by Kawa Crude Oil Co., Ltd.)
SMA 2625: Styrene / maleic anhydride copolymer (Mw by GPC = 9000, styrene / maleic anhydride molar ratio = 2/1) (trade name, manufactured by Kawa Crude Oil Co., Ltd.)
2021P: 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (trade name "Ceroxide 2021P", manufactured by Daicel Corporation)
YX-8000: Epoxy resin having an alicyclic structure (trade name, manufactured by Japan Epoxy Resins Co., Ltd.)
828 US: Epoxy resin having an aromatic ring (trade name, manufactured by Japan Epoxy Resins Co., Ltd.)
KBM 503: 2-methacryloxypropyl trimethoxysilane (trade name "Shin-Etsu Silicone KBM-503", manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM 903: 3-aminopropyltrimethoxysilane (brand name "Shin-Etsu Silicone KBM-903", manufactured by Shin-Etsu Chemical Co., Ltd.)
IRGACURE 907: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name, manufactured by Ciba Specialty Chemicals)
F-554: Fluorine-containing or lipophilic group-containing oligomer (nonionic, trade name “Megafuck F-554”, manufactured by DIC)
Antage W-400: Phenolic antioxidant (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.)

From Table 2, the following was confirmed.
While the resin compositions a-1 to a-3 and a-6 to a-8 obtained in Preparation Examples 1 to 3 and 6 to 8 all contain a maleic acid polymer, Preparation Examples 4 to The resin compositions a-4 to a-5 obtained in 5 are mainly different from each other in that they do not contain a maleic acid based polymer.
Under these differences, the physical properties of the coated films obtained from the two are compared with each other. With the coated films obtained from the resin compositions a-4 to a-5, the resin compositions a-1 to a-3, a- It was confirmed that the time for decreasing the resistance value, which is an evaluation index of the electrical characteristics, was extremely short as compared with the coated films obtained from 6 to a-8. Also, it was found that the coated films obtained from the resin compositions a-1 to a-3 and a-6 to a-8 were at sufficient levels in terms of transparency, adhesion and surface hardness.
Therefore, it is confirmed that the curable resin composition of the present invention can give a cured product having extremely excellent electric properties and sufficient adhesion, surface hardness and transparency by containing at least a maleic acid based polymer. It was done.

From Table 3, the following was confirmed.
The resin compositions b-1 to b-4 and b-7 obtained in Preparation Examples 9 to 12 and 15 all contain an alkali-soluble resin (A) and a maleic acid polymer and / or an epoxy compound. However, the resin composition b-5 obtained in Preparation Example 13 is mainly different in that a resin A-11 having a weight average molecular weight of less than 5000 is used as an alkali-soluble resin, and the resin composition obtained in Preparation Example 14 is The substance b-6 is mainly different in that a resin A-12 having no ethylenically unsaturated group in the side chain is used as the alkali-soluble resin.
The physical properties of the respective coated films are compared under these differences, and the coated films obtained from the resin compositions b-1 to b-4 and b-7 have a balance among all of the adhesiveness, surface hardness and developability. It was confirmed that it was excellent. Above all, it was confirmed that the coated film obtained from the resin composition b-7 had extremely high surface hardness. On the other hand, the coated film obtained from the resin composition b-5 had insufficient developability, and the coated film obtained from the resin composition b-6 had extremely low surface hardness. In addition, it was found that the coated films obtained from the resin compositions b-1 to b-4 and b-7 had a sufficient level of transparency.
Therefore, the curable resin composition of the present invention has an extremely high surface hardness by containing the alkali-soluble resin (A) and the maleic acid polymer and / or the epoxy compound, and the developability and adhesion are excellent. It was confirmed that an excellent cured product could be provided.

Although not described in Table 3, in order to confirm the electrical properties of the cured product, when the above-described ion migration test was performed using each of the resin compositions b-1 to b-4 and b-7, the resin composition When the resin compositions b-1 to b-4 were used, it was confirmed that the resistance value decrease time was extremely long, that is, the electrical characteristics were excellent as compared with the case where the product b-7 was used. From this point of view, it has been found that it is preferable to include at least a predetermined maleic acid-based polymer from the viewpoint of improving the electrical characteristics.

From Table 4, the following was confirmed.
The resin compositions c-1 to c-4 obtained in Preparation Examples 16 to 19 contain an amino group-containing coupling agent. In this case, it can be seen that the adhesion to tempered glass is extremely high after high temperature exposure.
Therefore, the curable resin composition of the present invention contains at least an amino group-containing coupling agent as a coupling agent, so that the adhesive can be stably developed even after being exposed to a high temperature environment. It was confirmed to give an object.

The alkali-soluble resin (A) contained in the resin compositions c-1, c-2 and c-4 is a resin having a ring structure in its main chain, while the alkali contained in the resin composition c-3 The soluble resin (A) is mainly different from the other in that it has no ring structure in its main chain. When the physical property results of the respective coated films are compared under such a difference, the coated films obtained from the resin compositions c-1, c-2 and c-4 are the coated films obtained from the resin composition c-3. In comparison, it can be seen that the adhesion to tempered glass is higher after high temperature exposure. From this, it was found that it is particularly preferable to use a polymer having a ring structure in the main chain as the alkali-soluble resin (A) in order to exhibit more excellent adhesion (especially adhesion to tempered glass).

Although not described in Table 4, in order to confirm the electrical properties of the cured product, when the above-described ion migration test was performed using resin compositions c-1, c-2 and c-4, respectively, the resin composition When the resin composition c-2 was used, it was confirmed that the resistance value reduction time was extremely long, that is, the electrical properties were excellent, as compared with the case where the object c-1 or c-4 was used. From this point of view, it has been found that it is preferable to include at least a predetermined maleic acid-based polymer from the viewpoint of improving the electrical characteristics.
Although not described in Table 4, the coated films obtained from the resin compositions c-1 to c-4 were at sufficient levels in terms of transparency and surface hardness.

Claims

A curable resin composition comprising an alkali soluble resin and a bifunctional or higher polyfunctional (meth) acrylate compound,
The alkali-soluble resin includes an alkali-soluble resin (A) having a weight average molecular weight of 5,000 or more and having an ethylenically unsaturated group in a side chain,
The curable resin composition further contains an epoxy compound and / or a maleic acid polymer,
A curable resin composition characterized in that the maleic acid polymer is obtained by polymerizing a monomer component containing an aromatic vinyl compound and a maleic anhydride derivative and / or a hydrolyzate thereof. object.
The curable resin composition according to claim 1, wherein the curable resin composition comprises at least an epoxy compound having an alicyclic structure as the epoxy compound.
The said maleic acid polymer has the structural unit represented by following formula (1), and the structural unit represented by following formula (2), The hardenability of Claim 1 or 2 characterized by the above-mentioned. Resin composition.

In the formula, A represents a phenyl group which may have a substituent. R 1 and R 2 are the same or different and each represents a hydrogen atom or a hydrocarbon group, or R 1 and R 2 may be bonded directly or via a hydrocarbon chain. R 3 and R 4 may be the same or different and each represent an OR 5 group or an NR 6 R 7 group, or R 3 and R 4 may be combined to form an anhydrous ring. R 5 , R 6 and R 7 are the same or different and each represents a hydrogen atom, a metal atom, or a hydrocarbon group which may have a substituent, an ether bond and / or an ester bond. However, R 3 and R 4 do not contain metal atoms at the same time.
The curable resin composition according to any one of claims 1 to 3, wherein the content of the maleic acid polymer is 90 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). object.
The curable resin composition according to any one of claims 1 to 4, further comprising a coupling agent.
The curable resin composition according to claim 5, wherein the coupling agent comprises an amino group-containing coupling agent.
The curable resin composition according to claim 5, wherein the coupling agent comprises a (meth) acryloyl group-containing silane coupling agent and an amino group-containing silane coupling agent.
The curable resin composition according to any one of claims 1 to 7, further comprising a photopolymerization initiator.
A cured film comprising the curable resin composition according to any one of claims 1 to 8.
A member for a display device comprising the cured film according to claim 9.
A display device comprising the cured film according to claim 9.