JP2015174948A - Curable resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a curable resin composition that can achieve both good adhesion and electrical characteristic and yet can produce a cured product having sufficient surface hardness and transparency; also a cured film formed by said curable resin composition; and a display device member and a display device that can realize high definition by having said cured film.SOLUTION: Provided is a curable resin composition comprising an alkali-soluble resin having a degree of dispersion (Mw/Mn) of 2.0 to 3.5, and a polyfunctional (meth)acrylate compound having 3 or more functionalities.

Description

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

Various applications of curable resin compositions that can be cured by heat or active energy rays have been studied, for example, as components of various display devices such as liquid crystal display devices, solid-state imaging devices, touch panel display devices, and the like. Yes. For example, a capacitive touch panel display generally has a structure in which a transparent conductive film such as ITO is formed on a substrate, and a protective film or an insulating film for protecting the transparent conductive film is formed. In general, constituent members such as a protective film and an insulating film are required to have high adhesion, durability, and surface hardness with a transparent conductive film. Recently, as display devices have higher definition, improvement in electrical characteristics has been demanded. Regarding conventional curable resin compositions, for example, Patent Document 1 discloses a photosensitive resin composition containing a binder polymer having a degree of dispersion of 2.5 to 6.0 and a photopolymerizable compound having a specific structure. Is disclosed. Patent Document 2 discloses a method for producing a photoresist polymer having a narrow molecular weight distribution.

By the way, as an index of electrical characteristics, a technique for evaluating migration of silver ions between metal wirings made of silver or a silver alloy is known (see, for example, Patent Document 3). If migration of silver ions is suppressed, it can be said that the insulation reliability between metal assignments is excellent, and therefore it can be determined whether or not the electrical characteristics are good.

Japanese Patent No. 4900514 JP 2009-249425 A JP2013-125797A

As described above, cured products of curable resin compositions represented by protective films and insulating films in various display devices are required to have excellent adhesion and surface hardness and good electrical characteristics. It has been. In recent years, along with the higher definition of display devices and the like, there has been a strong demand for higher performance for each member used. The current situation is that it is not possible to fully meet the demands of For example, the composition described in Patent Document 1 has room for improvement in terms of the surface hardness of the cured product. Patent Document 2 describes a method for producing a polymer having a molecular weight distribution (Mw / Mn) as narrow as 1.1 to 2.1. Usually, a polymer having a very narrow molecular weight distribution is obtained. However, there is room for improvement in terms of production method, such as using a special apparatus during synthesis or increasing the dropping speed. Patent Document 2 discloses, as Comparative Examples 1 and 2, an example in which a polymer having a molecular weight distribution (Mw / Mn) of 2.2 to 2.6 was obtained. A cured product excellent in hardness, electrical characteristics, etc. cannot be obtained.

The present invention has been made in view of the above-described present situation, and provides a curable resin composition capable of providing a cured product having both good adhesion and electrical characteristics and sufficient surface hardness and transparency. The purpose is to do. Another object of the present invention is to provide a cured film formed of such a curable resin composition, and a display device member and a display device that can realize high definition by having the cured film.

As a result of various studies on the curable resin composition, the inventors of the present invention have excellent photosensitivity and curability if the composition contains an alkali-soluble resin and a bifunctional or higher polyfunctional (meth) acrylate compound. Focused on becoming. And as an alkali-soluble resin, a resin having a degree of dispersion (Mw / Mn) in a predetermined range is used as an essential component, and as a polyfunctional (meth) acrylate compound, a compound having a functionality of 3 or more is used as an appropriate component. It has been found that a cured film with a proper density can be obtained. This cured film can achieve both good adhesion and electrical characteristics, and also has sufficient surface hardness and transparency. In addition, such a curable resin composition is particularly suitable as a protective film or a resin composition for forming an insulating film used for a touch panel display device, a color filter, and the like. As a result, it has been found that the structural members and the display device have excellent electrical characteristics enough to meet the demand for higher definition in recent years, and that the above problems can be solved brilliantly. did.

That is, the present invention is a curable resin composition containing an alkali-soluble resin having a dispersity (Mw / Mn) of 2.0 to 3.5 and a trifunctional or higher polyfunctional (meth) acrylate compound.
The present invention is also a cured film formed from the curable resin composition.
The present invention is also a member for a display device having the cured film.
The present invention is also a display device having the cured film.
The present invention is described in detail below. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.

[Curable resin composition]
The curable resin composition of the present invention (also simply referred to as a resin composition) includes an alkali-soluble resin having a dispersity (Mw / Mn) of 2.0 to 3.5, and a polyfunctional (meth) acrylate having three or more functions. Each of the components can be used alone or in combination of two or more. Moreover, you may contain 1 type, or 2 or more types of another component as needed.
Hereinafter, an alkali-soluble resin having a dispersity (Mw / Mn) of 2.0 to 3.5 is also referred to as “alkali-soluble resin (i)”, and a trifunctional or higher polyfunctional (meth) acrylate compound is referred to as “polyfunctional”. Also referred to as “(meth) acrylate compound”.

In the present specification, the “total amount of solids” means the total amount of components that form a cured product (components other than the solvent that volatilizes when the cured product is formed). Specifically, it means the total mass of the alkali-soluble resin, the polyfunctional (meth) acrylate compound, and, when further containing other polymerizable monomer, coupling agent and / or inorganic fine particles, the component. .

<Alkali-soluble resin>
The curable resin composition of the present invention includes at least an alkali-soluble resin (i) having a dispersity (Mw / Mn) of 2.0 to 3.5 as an alkali-soluble resin. The total amount of such an alkali-soluble resin (the total amount of the alkali-soluble resin (i) and other alkali-soluble resins that may further be included as necessary) is 100% by mass of the total solid content of the curable resin composition. It is preferable that it is 5 mass% or more with respect to 70 mass% or less. By being in such a range, it becomes possible to show the effect of the present invention more remarkably. More preferably, it is 10-65 mass%, More preferably, it is 15-60 mass%, Most preferably, it is 15-50 mass%.

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

The alkali-soluble resin (i) has a dispersity (Mw / Mn) of 2.0 to 3.5. If the dispersity is outside this range, the electrical characteristics are not good, and the effects of the present invention cannot be exhibited. Moreover, when this upper limit is exceeded, the storage stability of a resin composition may not become more sufficient. The lower limit of the dispersity is preferably 2.1 or more, more preferably 2.2 or more, still more preferably 2.3 or more, particularly preferably 2.4 or more, and most preferably 2.5 or more. The upper limit of the dispersity is preferably 3.4 or less, more preferably 3.3 or less, still more preferably 3.2 or less, particularly preferably 3.1 or less, and most preferably 3.0 or less.
In the present specification, the degree of dispersion is also referred to as molecular weight distribution, and means a value determined by “weight average molecular weight (Mw) / number average molecular weight (Mn)”. A weight average molecular weight (Mw) and a number average molecular weight (Mn) can be measured by the method as described in the Example mentioned later.

The alkali-soluble resin (i) preferably has a weight average molecular weight of 7000 or more, more preferably 10,000 or more. The reason is not clear, but if a polymer having a weight average molecular weight of 10,000 or more is used, it is sufficiently suppressed that the polyfunctional (meth) acrylate compound remains on the pattern edge during development. Square), that is, developability is remarkably improved. Further, when such an alkali-soluble resin (i) is used, the surface hardness of the cured product is further improved, and 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, Especially preferably, it is 11500 or more, Most preferably, it is 12000 or more. Moreover, it is preferable that it is 250,000 or less from viewpoints, such as a viscosity. More preferably, it is 100,000 or less, More preferably, it is 50,000 or less, Especially preferably, it is 30,000 or less, Most preferably, it is 20,000 or less.
In addition, when the said alkali-soluble resin is high molecular weight, the one where an acid value is higher becomes easy to develop.

Although it does not specifically limit as acid value (AV) of the said alkali-soluble resin (i), 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 having better developability. Moreover, the dispersity of alkali-soluble resin (i) can be more controlled as an acid value is less than 300 mgKOH / g. More preferably, it is 30 mgKOH / g or more, More preferably, it is 40 mgKOH / g or more. Moreover, 250 mgKOH / g or less is more preferable, More preferably, it is 230 mgKOH / g or less, Most preferably, it is 210 mgKOH / g or less. In particular, when it is 210 mgKOH / g or less, the electrical properties of the cured product become better. More preferably, it is 200 mgKOH / g or less, Most preferably, it is 150 mgKOH / g or less.
In the present specification, the acid value of the polymer is determined by measuring the acid value of the polymer solution by the method described in the examples described later, and then calculating the acid value per solid content from the acid value of the solution and the solid content of the solution. Can be obtained by calculating. The solid content of the polymer solution can be determined by the method described in Examples described later.

From the viewpoint of improving curability, the alkali-soluble resin (i) is a polymer having an ethylenically unsaturated group (that is, a double bond) in the side chain (also referred to as a “side chain double bond-containing polymer”). ) Is preferable. More preferably, a polymer obtained by polymerizing a monomer component including 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 polymerizability. It is a polymer obtained by reacting a compound having a double bond. Each monomer used here can be used alone or in combination of two or more.

The alkali-soluble resin (i) is particularly preferably 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 (i), it is excellent in heat resistance, surface hardness, and adhesion, and moreover, for example, changes over time after high temperature exposure are further suppressed, and various physical properties are further improved. A cured product that can be expressed more stably can be obtained. Thus, the form in which the alkali-soluble resin having a dispersity of 2.0 to 3.5 is a polymer having a ring structure in the main chain is also a preferred form of the present invention. Therefore, the monomer component that forms the base polymer includes one or two monomers capable of introducing a ring structure into the main chain skeleton of the polymer, together with a monomer having an acid group and a polymerizable double bond. It is preferable to include more than one species. Examples of the monomer capable of introducing a ring structure into the main chain skeleton of the polymer include a monomer having a double bond-containing ring structure in the molecule and a polymer having a ring structure in the main chain by cyclization polymerization. Examples thereof include monomers that form a coalescence.

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 vinyl benzoic acid; maleic acid, fumaric acid, and itacon. Unsaturated polyvalent carboxylic acids such as acid, citraconic acid, and mesaconic acid; a chain between unsaturated groups such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate and carboxyl groups Unsaturated monocarboxylic acids extended; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; phosphate group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); . Among these, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. More 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 these, particularly preferable Is methacrylic acid.

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

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

As the other monomer, for example, as described above, as a monomer capable of introducing a ring structure into the main chain skeleton of the polymer, a monomer having a double bond-containing ring structure in the molecule, One type or two or more types of monomers that form a polymer having a cyclic structure in the main chain by cyclopolymerization are suitable. Such monomers include the group consisting of N-substituted maleimide monomers, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers, and α- (unsaturated alkoxyalkyl) acrylates. It is preferable to use at least one selected from the above. Thus, the alkali-soluble resin (i) is an N-substituted maleimide monomer unit, a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer unit, and / or 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, resins containing N-substituted maleimide monomer units and / or dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer units have heat resistance and dispersibility (for example, colorant dispersibility). ), A cured film with improved hardness and the like can be provided.
The resin (polymer) containing the above-mentioned monomer unit means a resin containing a structural unit derived from the monomer by, for example, a monomer polymerization reaction or a crosslinking reaction.

In the monomer component, examples of the N-substituted maleimide monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, and Nt-butylmaleimide. , N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide and the like, and one or more of these can be used. Among these, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable because of little coloring and excellent dispersibility.

Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide , Halogen-substituted benzylmaleimides such as o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide.

Examples of the dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer include, for example, dimethyl-2,2 ′-[, from the viewpoints of little coloring, dispersibility, industrial availability, and the like. It is preferable to use oxybis (methylene)] bis-2-propenoate or the like.

Examples of the α- (unsaturated alkoxyalkyl) acrylate include α-allyloxymethyl acrylic acid, α-allyloxymethyl acrylate methyl, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl acrylate n- Propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α-allyloxy N-amyl methyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate, α -Allyloxymethyl acrylate s-hexyl, α Allyloxymethyl acrylate n-heptyl, α-allyloxymethyl acrylate n-octyl, α-allyloxymethyl acrylate s-octyl, α-allyloxymethyl acrylate t-octyl, α-allyloxymethyl acrylate 2 -Ethylhexyl, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate, α-allyloxymethyl acrylate Tridecyl allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-allyloxy Chain saturated hydrocarbon group-containing α such as stearyl methyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate -(Allyloxymethyl) acrylate is preferred. In addition, alkyl- (α-methallyloxymethyl) acrylate monomers and the like are also preferable. Among these, methyl α-allyloxymethyl acrylate (also referred to as α- (allyloxymethyl) methyl acrylate) is particularly preferable.

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

The content ratio of the monomer capable of introducing a ring structure into the main chain skeleton of the polymer (total ratio when two or more are used) is, for example, 1 to 40 mass with respect to 100 mass% of the base polymer component. % Is preferred. When it is within this range, it becomes possible to obtain a cured film having further improved heat resistance, dispersibility, surface hardness, and the like. In particular, the content ratio of N-substituted maleimide monomer, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer, and / or α- (unsaturated alkoxyalkyl) acrylate (two or more types) When used, the total ratio) is preferably 1 to 40% by mass with respect to 100% by mass of the base polymer component (monomer component forming the base polymer). When the content of the main chain ring structure derived from these monomer components increases, the adhesion tends to be improved. Further, when the addition amount of the N-substituted maleimide monomer is further increased, a cured product that is superior in terms of hardness can be obtained, and a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer is used. By this, the cured | curing material which is more excellent in the point of heat-resistant coloring property is obtained. If the content ratio of the N-substituted maleimide monomer is too large, the development speed may not be more appropriate.
The content ratio of the N-substituted maleimide monomer, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer, and / or α- (unsaturated alkoxyalkyl) acrylate is more preferably 2 to 2. It is 40 mass%, More preferably, it is 3-35 mass%.

As said other monomer, 1 type (s) or 2 or more types, such as other (meth) acrylic acid ester monomer which does not correspond to the monomer mentioned above, and an aromatic vinyl monomer, are used. be able to.

The other (meth) acrylic acid ester monomers are dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers and (meta) other than α- (unsaturated alkoxyalkyl) acrylates. ) Acrylic acid ester monomer.
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, Phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 2-methoxyethyl, (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 (3,4- Xylcyclohexyl) methyl, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, etc., 1,4-dioxaspiro [4,5] deca-2 -Ylmethacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2 -Methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl -1,3-dioxolane, alkoxylated phenylphenol (meta Acrylate, and the like.

Among the above (meth) acrylate monomers, (meth) methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, ( It is also suitable to use benzyl (meth) acrylate and alkoxylated phenylphenol (meth) acrylate. More preferably, in terms of excellent heat resistance, adhesion, and developability, methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and / or alkoxylated phenylphenol (meth) acrylate Is to use.

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

The content ratio of the (meth) acrylic acid ester monomer and / or aromatic vinyl monomer (total ratio when two or more are used) is, for example, 100% by mass of the base polymer component. It is suitable that it is 1-80 mass%. When it is in this range, a cured product that is more excellent in heat-resistant colorability and alkali solubility can be obtained. More preferably, it is 5-75 mass%, More preferably, it is 10-70 mass%.

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

Here, from the viewpoint of further improving the electrical characteristics of the cured product, it is preferable that the alkali-soluble resin (i) does not have a hydrophilic group such as a hydroxyl group. Therefore, the monomer component copolymerized to obtain the alkali-soluble resin (i) contains as little as possible a monomer having a hydrophilic group (for example, a (meth) acrylic acid ester having a hydroxyl group). It is preferable. 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. More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less.

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

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

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

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

The amount of the compound having a functional group capable of binding to the acid group and a polymerizable double bond is, for example, 1 to 100 parts by mass of the base polymer component (total amount of monomer components constituting the base polymer). The amount is preferably 50 parts by mass. More preferably, it is 5-45 mass parts.

The amount of the compound having a functional group capable of binding to the acid group and a polymerizable double bond (mixing ratio) is also determined by the monomer having an acid group and a polymerizable double bond constituting the base polymer (this is referred to as “ The compounding 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 the carboxylic acid of “monomer x” That is, it is obtained by “{molar amount of compound y (mol) / molar amount of monomer x (mol)} × {mixing ratio of monomer x (mass%)}”, and is 50 mass% or less. It is preferable to set to. Thereby, the hardened | cured material with more favorable electrical characteristics can be obtained. More preferably, it is less than 50% by mass, whereby a cured product having more excellent electrical characteristics and light resistance can be obtained. More preferably, it is 45 mass% or less, Most preferably, it is 40 mass% or less, Most preferably, it is 35 mass% or less. Moreover, it is suitable that it is 5 mass% or more. More preferably, it is 7 mass% or more.
In addition, for example, GMA (glycidyl methacrylate) is used as a compound having a functional group capable of bonding to an acid group and a polymerizable double bond (compound y), and a monomer (single monomer having an acid group and a polymerizable double bond). When MAA (methacrylic acid) is used as the monomer x), the above-mentioned “mixing ratio (mass%) of the compound having a functional group capable of binding to an acid group and a polymerizable double bond” (mass%) ”is added. This means mass% in terms of MAA mass in terms of GMA, and is determined by “{GMA molar amount (mol) / MAA molar amount (mol)} × MAA blending ratio (mass%)”. It is preferable that this numerical value is within the above preferable range.

When the alkali-soluble resin (i) is reacted with, for example, the base polymer component and a compound having a functional group capable of binding to an acid group and a polymerizable double bond, the acid group (preferably Is a method in which the amount of the carboxyl group) exceeds the amount of the functional group capable of binding to the acid group and the compound having a polymerizable double bond; the above-mentioned base polymer component, the functional group capable of binding to the acid group and polymerization It is preferable to produce using a technique such as a method of reacting a compound having a polybasic acid anhydride group after reacting with a compound having an ionic double bond.

The step of reacting the base polymer component (preferably a polymer having a carboxyl group) with a compound having a functional group capable of binding to an acid group and a polymerizable double bond ensures a good reaction rate and is a gel. In order to prevent the formation, it is preferably carried out in a temperature range of 50 to 160 ° C. More preferably, it is 70-140 degreeC, More preferably, it is 90-130 degreeC. Moreover, in order to improve reaction rate, the basic catalyst and acidic catalyst for esterification or transesterification normally used can be used as a catalyst. Among them, it is preferable to use a basic catalyst because side reactions are reduced.

Examples of the basic catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tri-n-octylamine, and tetramethylethylenediamine; tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, and n-dodecyltrimethyl. Quaternary ammonium salts such as ammonium chloride; urea compounds such as tetramethylurea; alkylguanidines such as tetramethylguanidine; amide compounds such as dimethylformamide and dimethylacetamide; tertiary phosphines such as triphenylphosphine and tributylphosphine; tetraphenylphosphonium Quaternary phosphonium salts such as bromide and benzyltriphenylphosphonium bromide; It is possible to have. Of these, dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferable in terms of reactivity, handling properties, and halogen-free properties.

The catalyst is used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass as a total of the base polymer component and the compound having a functional group capable of binding to an acid group and a polymerizable double bond group. It is preferable. More preferably, it is 0.1-3 mass parts.

The step of reacting the base polymer component with a compound having a functional group capable of binding to an acid group and a polymerizable double bond also adds a polymerization inhibitor to prevent gelation, It is preferably carried out in the presence. As the molecular oxygen-containing gas, air or oxygen gas diluted with an inert gas such as nitrogen is usually used and blown into the reaction vessel.

As the polymerization inhibitor, a commonly used polymerization inhibitor for radically polymerizable monomers can be used. For example, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, methoquinone, 6-t-butyl. -2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), etc. Phenolic inhibitors, organic acid copper salts, phenothiazines and the like, and one or more of these can be used. Among them, a phenol-based inhibitor is preferable in terms of low coloration and ability to prevent polymerization, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol), methoquinone, 6-t- Butyl-2,4-xylenol and 2,6-di-t-butylphenol are more preferable.

The amount of the polymerization inhibitor used is a functional group capable of bonding with the base polymer component and the acid group from the viewpoint of ensuring sufficient polymerization prevention effect and curability when the curable resin composition is used. And it is preferable that it is 0.001-1 mass part with respect to 100 mass parts of total amounts with the compound which has a polymerizable double bond. More preferably, it is 0.01-0.5 mass part.

Examples of the compound having a polybasic acid anhydride group include succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride. Acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, anhydrous Examples include pyromellitic acid, and one or more of these can be used.

The alkali-soluble resin (i) preferably has an ethylenically unsaturated group equivalent, that is, a double bond equivalent of 200 to 10,000. Thereby, it becomes possible to fully exhibit the effect of this invention. Especially, it is more preferable that it is 400-5000 from a viewpoint of an electrical property improvement. 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, the form in which the double bond equivalent of the alkali-soluble resin (i) is 500 to 1500 is also a preferred form of the present invention.

The double bond equivalent is the mass (g) of the solid content of the polymer solution per 1 mol of the double bond of the polymer. The mass of the solid content of the polymer solution here means the mass of the base polymer component, the mass of the compound having a functional group capable of binding to an acid group and a polymerizable double bond group, and the mass of a chain transfer agent. Is the total. It can be determined by dividing the mass of the solid content of the polymer solution by the double bond amount of the polymer. The double bond amount of the polymer can be determined from the amount of the charged acid group and the compound having a functional group capable of bonding and a polymerizable double bond.

The curable resin composition may further contain one or more alkali-soluble resins other than the alkali-soluble resin (i) as necessary. Such an alkali-soluble resin is not particularly limited. For example, a resin (polymer) having no ethylenically unsaturated group in the side chain (hereinafter, also referred to as “alkali-soluble resin (ii)”) is preferable. Furthermore, it is preferable to include. Among these, a polymer (resin) obtained by polymerizing a monomer component containing an aromatic vinyl compound and a maleic anhydride derivative and / or a hydrolyzate thereof is more preferable. By including such an alkali-soluble resin (ii), it becomes possible to more fully exhibit the action and effect of the present invention that gives a cured product having extremely excellent electrical characteristics and sufficient adhesion and surface hardness. In addition, the cured product has excellent light resistance.

The alkali-soluble resin (ii) preferably has an acid value (AV) of, for example, 20 mgKOH / g or more and less than 300 mgKOH / g. Thereby, more sufficient alkali solubility is expressed, and it becomes possible to obtain a cured product having better developability. More preferably, it is 30 mgKOH / g or more, More preferably, it is 40 mgKOH / g or more. Moreover, 290 mgKOH / g or less is more preferable.

The alkali-soluble resin (ii) preferably has a weight average molecular weight of 100 or more. Thereby, the hardened | cured material with higher surface hardness can be obtained. More preferably, it is 1000 or more, More preferably, it is 5000 or more. Moreover, it is preferable that it is 250,000 or less from viewpoints, such as a viscosity. More preferably, it is 100,000 or less, More preferably, it is 50,000 or less, Especially preferably, it is 30,000 or less, Most preferably, it is 20,000 or less.

The alkali-soluble resin (ii) is an optional component. When it is included, the content is preferably 90 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (i). As a result, it is possible to more fully demonstrate the effect of the present invention to give a cured product having extremely excellent electrical characteristics and sufficient adhesion and surface hardness, and the cured product is also excellent in light resistance. It will be. More preferably, it is 85 mass parts or less, More preferably, it is 80 mass parts or less. Moreover, it is suitable that it is 10 mass parts or more, More preferably, it is 20 mass parts or more, More preferably, it is 30 mass parts or more.

<Polyfunctional (meth) acrylate compound>
The curable resin composition contains a trifunctional or higher polyfunctional (meth) acrylate compound.
A trifunctional or higher polyfunctional (meth) acrylate compound is a compound having three or more (meth) acryloyl groups in one molecule. By including such a compound, the resin composition is photosensitive. And it becomes excellent in curability, and it becomes possible to obtain a cured film with high hardness.
Here, the (meth) acryloyl group means a methacryloyl group and / or an acryloyl group. In the present invention, an acryloyl group is preferable from the viewpoint of excellent reactivity. That is, the polyfunctional (meth) acrylate compound is particularly preferably a polyfunctional acrylate compound having three or more acryloyl groups.

The functional number of the polyfunctional (meth) acrylate compound is 3 or more. Thereby, photosensitivity and sclerosis | hardenability are improved and the hardness and transparency of hardened | cured material can be improved. The number of functional groups is preferably 4 or more, more preferably 5 or more. Moreover, it is preferable that it is 10 or less from a viewpoint of suppressing 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 a fluorene skeleton, since the hardness of hardened | cured material can be improved more, it is preferable. Therefore, the polyfunctional (meth) acrylate compound may be a polyfunctional (meth) acrylate compound having a fluorene skeleton.

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

Although it does not specifically limit as said polyfunctional (meth) acrylate compound, For example, the following compound etc. are mentioned.
Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (Meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol Hexa (meth) acrylate and the like.

In the curable resin composition, the content ratio of the polyfunctional (meth) acrylate compound is the total amount of the alkali-soluble resin (the alkali-soluble resin (i) and other alkali-soluble resins that may further be included as necessary). The total amount is preferably 120 parts by mass or less with respect to 100 parts by mass. Within this range, a cured product (cured film) that is more excellent in electrical properties can be obtained. More preferably, it is 110 mass parts or less, More preferably, it is 100 mass parts or less, More preferably, it is 90 mass parts or less, Especially preferably, it is 80 mass parts or less, Most preferably, it is 70 mass parts or less. Moreover, it is preferable that it is 20 mass parts or more from a viewpoint of improving developability more. More preferably, it is 30 mass parts or more, More preferably, it is 35 mass parts or more, Most preferably, it is 40 mass parts or more.

<Other polymerizable monomers>
The curable resin composition may further contain a polymerizable monomer (also referred to as other polymerizable monomer) other than the polyfunctional (meth) acrylate compound as necessary. A polymerizable monomer is a polymerizable unsaturated bond (polymerizable unsaturated group) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.) and electron beams. The other polymerizable monomer is preferably a radical polymerizable monomer.

Examples of the radical polymerizable monomer include a monofunctional radical polymerizable compound having one radical polymerizable unsaturated group in the molecule, and a polyfunctional radical polymerizable compound having two or more radicals Except those corresponding to functional (meth) acrylate compounds), and one or more of these can be used.
The molecular weight of the radical polymerizable monomer is not particularly limited, but is preferably 2000 or less, for example, from the viewpoint of handling.

The monofunctional radically polymerizable compound is not particularly limited, and examples thereof include (meth) acrylic acid ester monomers; (meth) acrylamides; unsaturated monocarboxylic acids; and between unsaturated groups and carboxyl groups. Unsaturated monocarboxylic acids whose chain is extended; aromatic vinyl monomers; N-substituted maleimide monomers; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; Is mentioned. Among these, a (meth) acrylic acid ester monomer is preferable, that is, a monofunctional (meth) acrylate compound is preferable.

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

The aliphatic hydrocarbon group preferably has 5 to 24 carbon atoms. As a result, the surface hardness of the cured product becomes more sufficient, and the compatibility with other components is also improved. The number of carbon atoms is preferably 8 or more, more preferably 10 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 (meta ) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate (also called lauryl (meth) acrylate) ), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) It has an aliphatic hydrocarbon group consisting of a linear or branched chain such as acrylate, 2-decyltetradecyl (meth) acrylate, 2-decyltetradecanyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate and the like. Compounds; compounds having an aliphatic hydrocarbon group having a cyclic structure such as isobornyl (meth) acrylate and adamantyl (meth) acrylate; and the like. Among these, compounds having an aliphatic saturated hydrocarbon group having a preferable carbon number described above are more preferable.

Examples of the polyfunctional radically polymerizable compound include those described in JP2013-227485A [0097] to [0098] in addition to the unsaturated polyvalent carboxylic acids and unsaturated acid anhydrides described above. Bifunctional (meth) acrylates; polyfunctional vinyl ether compounds; vinyl ether group-containing (meth) acrylate compounds; polyfunctional allyl ether compounds; allyl group-containing (meth) acrylic acid esters; polyfunctional (meth) acryloyl group-containing isocyanurates Polyfunctional allyl group-containing isocyanurates; polyfunctional urethane (meth) acrylates; polyfunctional aromatic vinyls; and the like.

When the curable resin composition contains a compound having one (meth) acryloyl group and an aliphatic hydrocarbon group having 5 to 24 carbon atoms in one molecule, which is an optional component described above, the content ratio thereof Is preferably 3 to 20% by mass in a total solid content of 100% by mass. Thereby, transparency of hardened | cured material can be improved more and an electrical property improvement can be implement | achieved further. More preferably, it is 4 mass% or more, More preferably, it is 15 mass% or less, More preferably, it is 12 mass% or less.

The content ratio of the polymerizable monomer other than the compound having one (meth) acryloyl group and an aliphatic hydrocarbon group having 5 to 24 carbon atoms in one molecule is, for example, a curable resin composition. The total solid content of 100% by mass is preferably 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 1 mass% or less.

<Photopolymerization initiator>
It is preferable that the curable resin composition also contains a photopolymerization initiator. Thereby, it becomes possible to improve the sensitivity and curability of the resin composition. Thus, the form in which the said curable resin composition further contains a photoinitiator is one of the suitable forms of this invention.

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

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

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

The content of the photopolymerization initiator may be appropriately set according to the purpose, use, etc., and is not particularly limited, but 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. Thereby, the hardened | cured material excellent by adhesiveness can be obtained, and peeling is suppressed more fully even after high temperature exposure. More preferably, it is 5 mass parts or more, More preferably, it is 7 mass parts or more. Further, considering the balance between the influence of the decomposition product of the photopolymerization initiator, economy, etc., it 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 polymerization initiator as the polymerization initiator. In this case, the total amount of the polymerization initiator (that is, the aminoketone polymerization initiator and other polymerization initiators) The aminoketone polymerization initiator is preferably 20% by mass or more with respect to 100% by mass of the total amount). More preferably, it is 30 mass% or more, More preferably, it is 50 mass% or more, Most preferably, it is 55 mass% or more.

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

<Coupling agent>
It is preferable that the curable resin composition also contains a coupling agent. The coupling agent has a property of bonding with an oxidized surface of an inorganic substance by a hydrolysis reaction or a condensation reaction. By using this property, for example, adhesion to a substrate or the like on which ITO or the like is deposited is performed. It becomes possible to fully exhibit the property. Thus, the form in which the curable resin composition further contains a coupling agent is also one of the preferred forms of the present invention.

Specifically, a coupling agent having a reactive group such as a vinyl group, a (meth) acryl group, an epoxy group, an amino group, a mercapto group, or an isocyanate group is preferable. Especially, what has a vinyl group, a (meth) acryloyl group, and / or an epoxy group as a reactive group is preferable. More preferred is a (meth) acryloyl group. Moreover, what contains silicon, a zirconia, titanium, and / or aluminum etc. as a center metal is suitable, for example, what has silicon as a center metal is preferable, More preferably, it is a silane coupling agent. By using a silane coupling agent, the adhesion and surface hardness of the cured product can be made more satisfactory.

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

As the silane coupling agent, and one or more reactive groups described above, the alkoxysilane group _{^{(-Si (OR 3) 3-}} n (R 4) n; OR 3 is a hydrolyzable group R ³ is preferably a hydrocarbon group, R ⁴ is a hydrocarbon group, and n is 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, so that there is no change over time in appearance such as discoloration, coloring, cracks, etc. even after exposure to high temperatures, A cured product having more sufficient surface hardness and adhesion can be obtained.

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

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

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

Examples of the silane coupling agent having an amino group include N-phenyl-3-aminopropyltrimethoxysilane.
Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

Examples of the silane coupling agent having an isocyanate group include 3-isocyanatopropyltriethoxysilane.

In the curable resin composition, the content of the coupling agent is preferably 3% by mass or more in a total solid content of 100% by mass of the curable resin composition. By including 3 mass% or more, it can have more sufficient adhesiveness 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 suitable that it is 30 mass% or less from viewpoints, such as the storage stability of curable resin composition. More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.

<Fluorine-based additive>
The curable resin composition may also contain one or more fluorine-based additives (also referred to as fluorine additives) from the viewpoint of further improving the curability. Note that the fluorine-based additive also has a function as a leveling agent.

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

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

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

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

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

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

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

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

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

The curable resin composition further has, for example, a coloring material (also referred to as a colorant); a dispersant; a heat resistance improver; a leveling agent; a development aid; a filler; Thermosetting resins such as epoxy resins, phenol resins, and polyvinyl phenols; Curing aids such as polyfunctional thiol compounds; Plasticizers; Polymerization inhibitors; Ultraviolet absorbers; Antioxidants; Matting agents; Slip agent; surface modifier; thixotropic agent; thixotropic agent; quinonediazide compound; polyhydric phenol compound; cationic polymerizable compound; acid generator; . For example, when using the said curable resin composition for a color filter use, it is preferable that a coloring material is included.

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

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

[Curing film]
Next, the cured film formed 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 irradiation (exposure) with an active energy ray. Specifically, for example, the curable resin composition is applied onto a substrate (also referred to as a base material) and dried, and the applied surface is irradiated (exposed) with an active energy ray to form a cured film. It is preferable. Thus, the cured film formed of the said curable resin composition is also one of this invention. Moreover, since the said curable resin composition is used suitably as a resist material, the form whose cured film formed with the said curable resin composition is a resist cured film is also one of the suitable forms of this invention. One.

It is preferable that the cured film has a resistance value reduction time of 100 hours or more by an 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 lowering time is more preferably 150 hours or longer, further preferably 200 hours or longer, particularly preferably 250 hours or longer.
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 touch-inputting a display device screen having a capacitive touch panel. Capacitance type touch panel is a position where a capacitance is formed between the finger and the (transparent) electrode of the touch panel when the user's finger touches the touch panel window, and the position touched by the change in capacitance accompanying this. Is detected. Therefore, it is possible to improve the performance of the display device by improving the electrical characteristics of various portions where the cured film is formed.

The substrate (also referred to as a base material) to which the curable resin composition is applied is not particularly limited. For example, a transparent glass substrate such as white plate glass, blue plate glass, silica coated blue plate glass; polyethylene terephthalate (PET), polyester Sheet or film made of thermoplastic resin such as ring-opening polymer of polycarbonate, polyolefin, polysulfone, cyclic olefin or hydrogenated product thereof; Sheet or film made of thermosetting resin such as epoxy resin or unsaturated polyester resin; Aluminum Metal substrates such as plates, copper plates, nickel plates, and stainless steel plates; ceramic substrates; semiconductor substrates having photoelectric conversion elements; members composed of various materials such as glass substrates (color filters for LCD) having a color material layer on the surface; Etc. Especially, the sheet | seat or film which consists of heat resistant resin among a glass substrate and a plastic substrate from a heat resistant point is preferable. The substrate is preferably a transparent substrate.

Further, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, etc., if necessary, and an inorganic material such as a gas barrier layer or a 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 the member for display apparatuses, it is suitable to form electrodes, such as ITO, on the said board | substrate. In addition, the cured film of this invention is excellent also in adhesiveness with not only a board | substrate but electrodes, such as an ITO film | membrane.

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

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

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

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

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

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

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

Among the post-treatment steps described above, the latter heat treatment step is preferred, and the temperature at that time is preferably 60 ° C. or higher. By performing the heat treatment step in this temperature range, the reactive compound is decomposed, and the effects of the present invention can be more fully exhibited. A form in which the cured film is heat-treated at a temperature of 60 ° C. or higher is also a preferred form of the present invention. The heat treatment temperature is more preferably 80 ° C. or higher, and preferably 300 ° C. or lower. Moreover, although heat processing time is not specifically limited, For example, it is preferable that it is 10 seconds-300 minutes.

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

The member for a display device and the display device of the present invention have the cured film, but may further have one or more other constituent members. The cured film formed from the curable resin composition is stable and excellent in adhesion to a substrate and the like, and has high hardness and good electrical characteristics. Therefore, it is very useful as a protective film or an insulating film in various display devices. Although it does not specifically limit as a display apparatus, For example, a liquid crystal display device, a solid-state image sensor, a touchscreen display apparatus etc. are suitable. As the touch panel display device, a capacitance type device is particularly preferable.

The display device member may be a film-like single layer or multilayer member composed of the cured film, or a member in which another layer is combined with the single layer or multilayer member. It may also be a member (for example, a color filter) that includes the cured film in its configuration.

Since the curable resin composition of the present invention has the above-described configuration, it can provide both a good adhesion and electrical characteristics, and can provide a cured product having sufficient surface hardness and transparency. Therefore, a display device member and a display device having a cured film formed of such a curable resin composition are very useful in the optical field, the electric machine / electronic field, and the like.

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

[Physical properties of resin solution (alkali-soluble resin)]
<Weight average molecular weight, number average molecular weight and dispersity>
Weight average molecular weight (Mw) and polystyrene by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corp.) and column TSKgel SuperHZM-M (manufactured by Tosoh Corp.) using polystyrene as a standard substance and eluent as tetrahydrofuran. The number average molecular weight (Mn) was measured. The degree of dispersion (Mw / Mn) was determined from the measured values of Mw and Mn.

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

<Acid value AV>
1.5 g of the resin solution is precisely weighed and dissolved in a mixed solvent of 90 g of acetone / 10 g of water, and 0.1 T KOH aqueous solution is used as a titrant, and an automatic titrator (trade name “COM-555, manufactured by Hiranuma Sangyo Co., Ltd.) is used. )), The acid value of the resin solution was measured, and the acid value per gram of the solid content was determined from the acid value of the solution and the solid content of the solution.

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

(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 standards.
Δ: 4 to 8 points according to JIS standards.
X: 0 to 2 points according to JIS standards.

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

(3) Film color evaluation test About the coating film (1.5-micrometer-thick cured film) obtained above, the color was evaluated visually. Specifically, the following criteria were used for evaluation.
○: The cured film is colorless and transparent.
Δ: The cured film is light white.
X: The cured film is cloudy.

(4) Light resistance test About the coating film obtained above (cured film having a thickness of 1.5 μm), it was set on the machine in the direction where UV hits from the glass surface using a xenon weather meter (X75SC Suga Test Instruments), and 60 W / M ² (300 to 400 nm integrated light amount), BPT63 ° C., 30% irradiated at 30% RH for 30 h, in accordance with JIS-K5400-8.5 (1990), cross section test of (1) above Evaluation was performed in the same manner as the (Adhesion evaluation) standard.

2. Electrical characteristics (ion migration test)
Using alkali-free glass, an APC alloy with L / S = 10 mm / 1 mm was deposited by an ion sputtering apparatus (Auto Fine Coater JFC-1600: manufactured by JEOL) to produce a glass substrate with metal wiring having simple wiring.
Next, using the obtained glass substrate, the resin composition obtained in each preparation example was applied by a spin coat method and subjected to heat treatment (80 ° C. for 3 minutes), and then the end portion of 1 cm was masked and 2.0 kW. Is exposed at an exposure amount of 60 mJ / cm ² (in terms of 365 nm illuminance) using a UV aligner (trade name “TME-150RNS” manufactured by TOPCON) equipped with a super high-pressure mercury lamp, and after alkali development, heat treatment (230 ° C. 30 minutes) to obtain an insulating substrate with metal wiring.
Next, the metal part exposed by alkali development of the obtained insulating substrate with metal wiring is hardened at 150 ° C. for 30 minutes using a silver paste (XA-910, manufactured by Fujikura Kasei Co., Ltd.), thereby wiring with the migration device. Connected.
Using this evaluation sample, a voltage of 5 V was applied for a certain period of time under a constant temperature and humidity condition of 80 ° C. and 95% RH, and the time (h) during which the resistance value decreased was reduced to an ion migration device (MIG-87: manufactured by IMV). ).

(Synthesis of resin solution)
First, the resin solution B (No. B-1 to B-12) was synthesized.

Synthesis Example 1 (Synthesis of B-1)
456 parts of propylene glycol monomethyl ether (PGME) was charged into a separable flask with a cooling tube as a reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Then, 30 parts of benzylmaleimide (BzMI) as a dropping system 1, methacrylic acid (MAA) 180 parts, cyclohexyl acrylate (CHA) 90 parts, PGME 30 parts, perbutyl O (trade name, manufactured by NOF Corporation) 6 parts, dropping system 2 as n-dodecyl mercaptan (n-DM) 9 parts, PGME 71 parts Each was continuously fed over 3 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours.
Next, 99 parts of glycidyl methacrylate (GMA), 1.2 parts of triethylamine (TEA) as a catalyst, and 0.6 parts of Antage W-400 (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added to the reaction solution. Then, while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%), the reaction was continued at 110 ° C. for 2 hours and 115 ° C. for 4 hours to obtain a resin solution B-1 having a double bond equivalent of 588 g / equivalent. .
With respect to the obtained resin solution B-1, various physical properties (weight average molecular weight Mw, solid content concentration NV, acid value AV per solid content, and degree of dispersion) were measured. The results are shown in Table 1.

Synthesis Example 2 (Synthesis of B-2)
A separable flask with a cooling tube as a reaction vessel was charged with 185 parts of propylene glycol monomethyl ether acetate (PGMEA) and 185 parts of PGME, heated to 90 ° C. under a nitrogen atmosphere, and then 25 parts of BzMI and 143 parts of MAA as a dropping system 1. , CHA 83 parts, PGMEA 13 parts, PGME 13 parts, perbutyl O 5 parts, dropping system 2 and 11 parts of n-DM, PGMEA 34 parts and PGM 34 parts were continuously supplied over 3 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours. Next, 124 parts of GMA, 1.1 parts of TEA as a catalyst, and 0.6 parts of Antage W-400 as a polymerization inhibitor were added to this reaction solution, and 110 ° C. while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%). By continuing the reaction for 2 hours at 115 ° C. for 7 hours, a resin solution B-2 having a double bond equivalent of 444 g / equivalent was obtained.
With respect to the obtained resin solution B-2, various physical properties were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

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

Synthesis Example 4 (Synthesis of B-4)
In a separable flask with a cooling tube as a reaction tank, 382 parts of PGMEA and 95 parts of PGME were charged, and the temperature was raised to 90 ° C. in a nitrogen atmosphere, and then 12 parts of BzMI, 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 dropping system 2, 54 parts of PGMEA, and 14 parts of PGMEA were continuously supplied over 3 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours.
Next, 25 parts of GMA, 1.0 part of TEA as a catalyst and 0.5 part of Antage W-400 as a polymerization inhibitor were added to this reaction solution, and 110 ° C. while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%). By continuing the reaction at 115 ° C. for 3 hours for 2 hours, a resin solution B-4 having a double bond equivalent of 1941 g / equivalent was obtained.
With respect to the obtained resin solution B-4, various physical properties were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 5 (Synthesis of B-5)
460 parts of PGME were charged into a separable flask with a cooling tube as a reaction tank and heated to 90 ° C. in a nitrogen atmosphere, and then 30 parts of BzMI, 249 parts of MAA, 21 parts of CHA, 30 parts of PGME, 30 parts of PGME and 6 perbutyl O were added as the dropping system 1. In addition, 13 parts of n-DM and 67 parts of PGME were continuously fed over 3 hours as the dropping system 2 and the dropping system 2, respectively. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours.
Next, 125 parts of PGME, 248 parts of GMA, 1.6 parts of TEA as a catalyst, and 0.8 parts of Antage W-400 as a polymerization inhibitor are added to the reaction solution, and a mixed gas of nitrogen and oxygen (oxygen concentration 7%) is bubbled. The resin solution B-5 having a double bond equivalent of 323 g / equivalent was obtained by continuing the reaction at 110 ° C. for 2 hours and 115 ° C. for 10 hours.
With respect to the obtained resin solution B-5, various physical properties were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 6 (Synthesis of B-6)
After charging 921 parts of PGMEA into a separable flask with a cooling tube as a reaction tank and raising the temperature to 90 ° C. in a nitrogen atmosphere, dimethyl-2,2 ′-[oxybis (methylene)] bis-2 was added as a dropping system 1. -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 Were continuously fed over 150 minutes each. Then, after maintaining at 90 ° C. for 60 minutes, 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 part of Antage W-400 and 119 parts of PGMEA as an inhibitor are added to this reaction liquid, and nitrogen and oxygen mixed gas (oxygen concentration 7%) are bubbled. The resin solution B-6 having a double bond equivalent of 490 g / equivalent was obtained by continuing the reaction at 110 ° C. for 2 hours and 115 ° C. for 4 hours.
With respect to the obtained resin solution B-6, various physical properties were measured as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 7 (Synthesis of B-7)
After charging 921 parts of PGMEA into a separable flask with a cooling tube 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 are added as the dropping system 1. 175 parts of BzMA, 51 parts of MMA, 10.2 parts of perbutyl O, 16.8 parts of n-DM and 44 parts of PGMEA as a dropping system 2 were continuously fed over 150 minutes. Then, after maintaining at 90 ° C. for 60 minutes, 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 part of Antage W-400 and 119 parts of PGMEA as an inhibitor are added to this reaction liquid, and nitrogen and oxygen mixed gas (oxygen concentration 7%) are bubbled. The resin solution B-7 having a double bond equivalent of 490 g / equivalent was obtained by continuing the reaction at 110 ° C. for 2 hours and 115 ° C. for 4 hours.
With respect to the obtained resin solution B-7, various physical properties were measured as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 8 (Synthesis of B-8)
154 parts of PGMEA and 38 parts of PGME were charged into a separable flask with a cooling tube as a reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Then, as a dropping system 1, 51 parts of BzMI, 34 parts of MAA, 85 parts of CHA, 41 parts of PGMEA, 41 parts of PGME10 Part, 3.4 parts of perbutyl O, and 7.3 parts of n-DM, 58 parts of PGMEA, and 15 parts of PGMEA as a dropping system 2 were continuously supplied over 3 hours. Then, after maintaining 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 part of TEA as a catalyst, 0.3 part of Antage W-400 as a polymerization inhibitor were added to this reaction liquid, and nitrogen and oxygen mixed gas (oxygen concentration 7%) was added. While bubbling, the reaction was continued at 110 ° C. for 2 hours and 115 ° C. for 7 hours to obtain a resin solution B-8 having a double bond equivalent of 1045 g / equivalent.
With respect to the obtained resin solution B-8, various physical properties were measured as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Examples 9 to 12 (Synthesis of B-9 to B-12)
It is almost the same as Synthesis Example 1 except that the type of monomer constituting the base polymer and its blending ratio, and the blending ratio of GMA to be added are changed as shown in Table 1 and the solvent is changed to PGMEA only. Resin solutions B-9 to B-12 were obtained by the above procedure.
Various physical properties of the obtained resin solution were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Table 1 shows details of the resin solutions B-1 to B-12.
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 a monomer total amount was 100 mass%. Moreover, the numerical value of GMA added to the base polymer is the GMA added to the carboxylic acid content of the monomer having an acid group and a polymerizable double bond (MAA corresponds in Synthesis Examples 1 to 10). Is expressed as mass% in terms of MAA mass, and “the blending ratio (mass%) of GMA in terms of MAA mass = {molar amount of GMA (mol) / molar amount of MAA (mol)} × MAA blending ratio ( Mass%) ”. For example, in Synthesis Example 1 (B-1), MAA was 60% by mass in the base polymer (100% by mass), and 696 mmol of GMA was added to 60% by mass (2091 mmol) of MAA. The blending ratio of the GMA was defined as “20”.

Abbreviations in Table 1 are as follows.
BzMI: benzylmaleimide CHMI: N-cyclohexylmaleimide MD: dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate AMA: α-allyloxymethyl acrylate CHA: cyclohexyl acrylate CHMA: cyclohexyl methacrylate BzMA: benzyl methacrylate MAA: Methacrylic acid STMA: Stearyl methacrylate MMA: Methyl methacrylate HEA: 2-hydroxyethyl acrylate GMA: Glycidyl methacrylate AV: Acid value Mw: Weight average molecular weight NV of the finally obtained polymer NV: Solid content concentration

[Preparation of resin composition and evaluation test of coating film]
Preparation Example 1 (Resin Composition b-1)
In terms of solid content, 25 parts of resin solution B-9, 35 parts of dipentaerythritol hexaacrylate (DPHA), 10 parts of isobornyl acrylate (IB-XA), 20 parts of SMA17352, 10 parts of KBM503 as a coupling agent 20 parts of IRGACURE907 as a photopolymerization initiator, 0.2 part of F-554 as a fluorine additive, 0.5 part of Antage W-400 as a polymerization inhibitor, and a dilution solvent (PGMEA) at a solid content concentration of 25% It added so that it might become, and the resin composition b-1 was obtained by stirring.
About the obtained resin composition b-1, according to the evaluation method mentioned above, the physical property of the coating film (cured film) was evaluated. The results are shown in Table 2.

Preparation Examples 2-6
Resin compositions b-2 to b-6 were obtained in the same manner as in Preparation Example 1, using the raw materials shown in the table at the mixing ratios shown in Table 2. About each of the obtained resin composition, the physical property of the coating film was evaluated according to the evaluation method mentioned above. The results are shown in Table 2.

Abbreviations in Table 2 are as follows. The amount of each raw material in Table 2 is the solid content. In Table 2, the use of a diluting solvent (PGMEA: propylene glycol monomethyl ether acetate) is omitted.
SMA17352: Styrene / maleic anhydride copolymer (Mw by GPC = 7000, styrene / maleic anhydride molar ratio = 1/1) (trade name, manufactured by Kawa Crude Chemical 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 Chemical Co., Ltd.)
DPHA: Dipentaerythritol hexaacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
A-9300: Ethoxylated isocyanuric acid triacrylate (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
IB-XA: Isobornyl acrylate (trade name “light acrylate IB-XA”, manufactured by Kyoeisha Chemical Co., Ltd. NBAC-ST: butyl acetate dispersed silica sol (trade name, manufactured by Nissan Chemical Industries, Ltd.)
KBM503: 2-methacryloxypropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Silicone)
IRGACURE907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name, manufactured by Ciba Specialty Chemicals)
F-554: Fluorine-containing / lipophilic group-containing oligomer (nonionic, trade name “Megafac F-554”, manufactured by DIC Corporation)
Antage W-400: Phenolic antioxidant (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.)

From Table 2, the following was confirmed.
The resin compositions b-1 to b-3 obtained in Preparation Examples 1 to 3 all have an alkali-soluble resin having a dispersity (Mw / Mn) of 2.0 to 3.5 and a trifunctional or higher polyfunctionality. In contrast to the functional (meth) acrylate compound, the resin compositions b-4 to b-5 obtained in Preparation Examples 4 to 5 use an alkali-soluble resin having a dispersity outside the range. Under such a difference, when the physical property results of the coating films obtained from both were compared, the coating films obtained from the resin compositions b-1 to b-3 were obtained from the resin compositions b-4 to b-5. It was confirmed that the resistance value decrease time, which is an evaluation index of electrical characteristics, was remarkably long compared to the coating film. Moreover, it turned out that the coating film obtained from resin composition b-1 to b-3 exists in a sufficient level also at the point of transparency, adhesiveness, and surface hardness. Therefore, it was confirmed that the curable resin composition having the configuration of the present invention is extremely excellent in electric characteristics and can provide a cured product having sufficient adhesion, surface hardness and transparency. Moreover, according to the comparison between the coating film obtained from the resin compositions b-1 to b-3 and the coating film obtained from the resin composition b-6 of Preparation Example 6, from the viewpoint of electrical characteristics, the resin composition Inorganic matter should not be contained in the product as much as possible (as described above, preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0% by mass with respect to 100% by mass of the total solid content of the resin composition. %) Was found to be suitable. Moreover, in terms of surface hardness, it became good when a small amount of inorganic fine particles were contained, and the adhesion could be maintained.
Although not shown above, when only a monofunctional or bifunctional (meth) acrylate compound is used as the polymerizable monomer, a coating film (cured film) may be used even if other conditions are the same. The surface hardness of was not sufficient as compared with the coating films obtained from the resin compositions b-1 to b-3 and b-6.

Claims (5)

A curable resin composition comprising an alkali-soluble resin having a dispersity (Mw / Mn) of 2.0 to 3.5 and a trifunctional or higher polyfunctional (meth) acrylate compound. The curable resin composition according to claim 1, wherein the alkali-soluble resin having a dispersity of 2.0 to 3.5 is a polymer having a ring structure in the main chain. A cured film formed from the curable resin composition according to claim 1. A member for a display device, comprising the cured film according to claim 3. A display device comprising the cured film according to claim 3.