JP6771063B2 - Curable resin composition and its use - Google Patents

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 member for a display device, and a display device.

Various applications of the curable resin composition that can be cured by heat or active energy rays to components of various display devices such as liquid crystal display devices, solid-state image sensors, and touch panel display devices have been studied. There is. For example, a capacitance type touch panel display device generally has a structure in which a transparent conductive film such as ITO is formed on a substrate, and a protective film or an insulating film for protecting the transparent conductive film is further formed. , Constituent members such as a protective film and an insulating film are usually required to have high adhesion to a transparent conductive film, durability, and surface hardness. Recently, as display devices have become higher in definition, improvements in electrical characteristics have been required. Regarding the conventional curable resin composition, for example, Patent Document 1 describes a photosensitive resin composition containing a binder polymer having a dispersity of 2.5 to 6.0 and a photopolymerizable compound having a specific structure. Is disclosed. Further, Patent Document 2 discloses a method for producing a polymer for a photoresist having a narrow molecular weight distribution.

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

Japanese Patent No. 4900154 JP-A-2009-249425 Japanese Unexamined Patent Publication No. 2013-125977

As described above, a cured product of a curable resin composition typified by a protective film, an insulating film, or the like in various display devices is required to have excellent adhesion and surface hardness, and to have good electrical characteristics. Has been done. In recent years, with the increase in definition of display devices and the like, there is a strong demand for higher performance for each member used, but with conventional resin compositions, this performance has been improved. The current situation is that we cannot fully meet the demands of. For example, the composition described in Patent Document 1 has room for ingenuity in terms of surface hardness of the cured product. Further, Patent Document 2 describes a method for producing a polymer having a narrow molecular weight distribution (Mw / Mn) of 1.1 to 2.1, but usually, in order to obtain a polymer having a very narrow molecular weight distribution. There is room for improvement in terms of manufacturing method, such as using a special device during synthesis and increasing the dropping speed. Patent Document 2 also 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, but this polymer alone has a surface surface. It is not possible to obtain a cured product having excellent hardness and electrical characteristics.

The present invention has been made in view of the above situation, and provides a curable resin composition capable of providing a cured product having both good adhesion and electrical properties and having 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 capable of achieving high definition by having the cured film.

The present inventors have studied various curable resin compositions, and found that a composition containing an alkali-soluble resin and a polyfunctional (meth) acrylate compound having two or more functionalities is excellent in photosensitivity and curability. I paid attention to that. When a resin having a dispersity (Mw / Mn) within a predetermined range is essentially used as the alkali-soluble resin, and a compound having a functional number of trifunctional or higher is essentially used as the polyfunctional (meth) acrylate compound, it is appropriate. It has been found that a cured film having a high density can be obtained. This cured film can achieve both good adhesion and electrical properties, and also has sufficient surface hardness and transparency. Further, such a curable resin composition is particularly suitable as a resin composition for forming a protective film or an insulating film used for a touch panel display device, a color filter, or the like, and a cured film or display device to be formed from the coating device. We have found that the materials and display devices have excellent electrical characteristics that can sufficiently meet the demand for high definition in recent years, and have come up with the idea that the above problems can be solved brilliantly, and have reached the present invention. 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 polyfunctional (meth) acrylate compound having trifunctionality or higher.
The present invention is also a cured film formed from the curable resin composition.
The present invention is also a display device member having the cured film.
The present invention is also a display device having the cured film.
The present invention will be described in detail below. It should be noted that a form in which two or three or more of the individual preferred forms of the present invention described below are combined is also a preferred form of the present invention.

[Curable resin composition]
The curable resin composition of the present invention (also simply referred to as a resin composition) is an alkali-soluble resin having a dispersity (Mw / Mn) of 2.0 to 3.5 and a trifunctional or higher functional (meth) acrylate. Although it contains a compound, each contained component may be used alone or in combination of two or more. Further, if necessary, one or more other components may be contained.
In the following, 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 forming a cured product (components excluding solvents and the like that volatilize during the formation of the cured product). Specifically, it means the total mass of the alkali-soluble resin, the polyfunctional (meth) acrylate compound, and the components if further containing other polymerizable monomers, coupling agents and / or inorganic fine particles. ..

<Alkali-soluble resin>
The curable resin composition of the present invention contains 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 resin which may be further contained if necessary) is 100% by mass of the total solid content of the curable resin composition. On the other hand, it is preferably 5% by mass or more, and more preferably 70% by mass or less. Within such a range, the effect of the present invention can be exerted more remarkably. It is more preferably 10 to 65% by mass, further preferably 15 to 60% by mass, and particularly preferably 15 to 50% by mass.

The alkali-soluble resin (i) is a resin (polymer) showing alkali solubility. Of 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 functional groups that neutralize 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 have only one of these. It may have two or more kinds. Of these, a carboxyl group and a carboxylic acid 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 degree of dispersion is out of this range, the electrical characteristics will not be good, and the effects of the present invention cannot be exhibited. Further, if this upper limit value is exceeded, the storage stability of the resin composition may not be 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 a molecular weight distribution, and means a value obtained by "weight average molecular weight (Mw) / number average molecular weight (Mn)". The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by the methods described in Examples described later.

The alkali-soluble resin (i) also preferably has a weight average molecular weight of 7,000 or more, more preferably 10,000 or more. Although the reason is not clear, if a compound having a weight average molecular weight of 10,000 or more is used, the polyfunctional (meth) acrylate compound is sufficiently suppressed from remaining on the pattern edge during development, so that the pattern edge is at a right angle ( It approaches (square), that is, the developability is significantly 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 exhibited more stably even after being exposed to a high temperature environment. it can. It is more preferably 11000 or more, particularly preferably 11500 or more, and most preferably 12000 or more. Further, from the viewpoint of viscosity and the like, it is preferably 250,000 or less. It is more preferably 100,000 or less, further preferably 50,000 or less, particularly preferably 30,000 or less, and most preferably 20,000 or less.
When the alkali-soluble resin has a high molecular weight, the higher the acid value, the easier it is to develop.

The acid value (AV) of the alkali-soluble resin (i) is not particularly limited, but is preferably 20 mgKOH / g or more and less than 300 mgKOH / g, for example. As a result, more sufficient alkali solubility is expressed, and it becomes possible to obtain a cured product having better developability. Further, when the acid value is less than 300 mgKOH / g, the dispersity of the alkali-soluble resin (i) can be further controlled. It is more preferably 30 mgKOH / g or more, still more preferably 40 mgKOH / g or more. Further, 250 mgKOH / g or less is more preferable, 230 mgKOH / g or less is more preferable, and 210 mgKOH / g or less is particularly preferable. In particular, when it is 210 mgKOH / g or less, the electrical characteristics of the cured product become better. Even more preferably, it is 200 mgKOH / g or less, and most preferably 150 mgKOH / g or less.
In the present specification, the acid value of the polymer is determined from the acid value of the solution and the solid content of the solution after measuring the acid value of the polymer solution by the method described in Examples described later. 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 also referred to as a polymer having an ethylenically unsaturated group (that is, a double bond) in the side chain (this is also referred to as a "side chain double bond-containing polymer"). ) Is preferable. More preferably, a polymer (also referred to as a base polymer) obtained by polymerizing a monomer component containing a monomer having an acid group and a polymerizable double bond has a functional group capable of binding to an acid group and polymerizable property. It is a polymer obtained by reacting a compound having a double bond. As each monomer used here, one kind or two or more kinds can be used respectively.

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 for example, changes with time after high temperature exposure are further suppressed to improve various physical properties. A cured product that can be expressed more stably can be obtained. 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 one of the preferred forms of the present invention. Therefore, the monomer component forming the base polymer includes one or two monomers capable of introducing a ring structure into the main chain skeleton of the polymer, together with the monomer having an acid group and a polymerizable double bond. It is preferable to include more than a seed. 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 weight having a ring structure in the main chain by cyclization polymerization. Examples thereof include monomers forming 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, silicic acid and vinyl benzoic acid; maleic acid, fumaric acid and itaconic acid. Unsaturated polycarboxylic acids such as acids, citraconic acid, and mesaconic acid; chains between unsaturated groups such as monosuccinate (2-acryloyloxyethyl) and monosuccinate (2-methacryloyloxyethyl) and carboxyl groups. Extended unsaturated monocarboxylic acids; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; unsaturated compounds containing phosphoric acid groups such as light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.); and the like. .. Among these, it is preferable to use carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) from the viewpoint of versatility, availability, and the like. More preferably, unsaturated monocarboxylic acids are used in terms of reactivity, alkali solubility, etc., and more preferably (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid), of which particularly preferred. Is methacrylic acid.

The content ratio of the monomer having an acid group and a polymerizable double bond may be, 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. As a result, the solubility in alkali becomes more sufficient, and for example, the curable resin composition becomes more useful for applications requiring developability. Further, it is preferably 85% by mass or less in that the excellent appearance, adhesion and the like of the cured product can be further maintained even after high temperature exposure. It is more preferably 10 to 80% by mass, still more preferably 15 to 75% by mass.

The above-mentioned monomer component includes one or more kinds of other radically polymerizable monomers (also referred to as other monomers) in addition to the above-mentioned monomers having an acid group and a polymerizable double bond. It may include.

Examples of the other monomer include, as described above, a monomer having a double bond-containing ring structure in the molecule as a monomer capable of introducing a ring structure into the main chain skeleton of the polymer. One or more of the monomers that undergo cyclization polymerization to form a polymer having a ring structure in the main chain are preferable. Examples of such a monomer include an N-substituted maleimide-based monomer, a dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer, and an α- (unsaturated alkoxyalkyl) acrylate group. It is preferable to use at least one selected from the above. As described above, the alkali-soluble resin (i) is an N-substituted maleimide-based monomer unit, a dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer unit, and / or α- (unsaturated). The form of the polymer having an alkoxyalkyl) acrylate-based monomer unit is one of the preferred forms of the present invention.

In particular, resins containing N-substituted maleimide-based monomer units and / or dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer units have heat resistance and dispersibility (for example, colorant dispersibility). ), It becomes possible to provide a cured film having improved hardness and the like.
The resin (polymer) containing the above-mentioned monomer unit means, for example, a resin containing a structural unit derived from the monomer by a polymerization reaction or a cross-linking reaction of the monomer.

In the above monomer component, examples of the N-substituted maleimide-based monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, and N-t-butylmaleimide. , N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide and the like, and one or more of these can be used. Of these, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable, because they are less colored and have excellent dispersibility.

Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide. , O-Dichlorobenzylmaleimide, halogen-substituted benzylmaleimide such as p-dichlorobenzylmaleimide, and the like.

The dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer is, for example, dimethyl-2,2'-[from the viewpoint of low coloring, dispersibility, and easy industrial availability. Oxybis (methylene)] It is preferable to use bis-2-propenoate or the like.

Examples of the α- (unsaturated alkoxyalkyl) acrylate include α-allyloxymethylacrylate, α-allyloxymethylacrylate methyl, α-allyloxymethylacrylate ethyl, and α-allyloxymethylacrylate n-. Propyl, i-propyl α-allyloxymethylacrylate, n-butyl α-allyloxymethylacrylate, s-butyl α-allyloxymethylacrylate, t-butyl α-allyloxymethylacrylate, α-allyloxy N-amyl methylacrylate, s-amyl α-allyloxymethylacrylate, t-amyl α-allyloxymethylacrylate, neopentyl α-allyloxymethylacrylate, n-hexyl α-allyloxymethylacrylate, α -Allyloxymethylacrylate s-hexyl, α-allyloxymethylacrylate n-heptyl, α-allyloxymethylacrylate n-octyl, α-allyloxymethylacrylate s-octyl, α-allyloxymethylacrylate t-octyl, 2-ethylhexyl α-allyloxymethylacrylate, capril α-allyloxymethylacrylate, nonyl α-allyloxymethylacrylate, decyl α-allyloxymethylacrylate, undecyl α-allyloxymethylacrylate , Alpha-allyloxymethylacrylate lauryl, α-allyloxymethylacrylate tridecyl, α-allyloxymethylacrylate myristyl, α-allyloxymethylacrylate pentadecyl, α-allyloxymethylacrylate cetyl, α-allyloxy Heptadecyl methylacrylate, stearyl α-allyloxymethylacrylate, nonadecil α-allyloxymethylacrylate, eikosyl α-allyloxymethylacrylate, ceryl α-allyloxymethylacrylate, melicyl α-allyloxymethylacrylate, etc. The chain-saturated hydrocarbon group-containing α- (allyloxymethyl) acrylate is preferable. In addition, alkyl- (α-metharyloxymethyl) acrylate-based monomers and the like are also preferable. Of these, methyl α-allyloxymethylacrylate (also referred to as α- (allyloxymethyl) methyl acrylate) is particularly suitable.

The α- (unsaturated alkoxyalkyl) acrylate can be produced, for example, by the 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 (the total ratio when two or more kinds are used) is, for example, 1 to 40% by mass with respect to 100% by mass of the base polymer component. It is preferably%. Within this range, it becomes possible to obtain a cured film having further improved heat resistance, dispersibility, surface hardness and the like. Among them, in particular, the content ratio of N-substituted maleimide-based monomer, dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer, and / or α- (unsaturated alkoxyalkyl) acrylate (two or more kinds). When used, the total ratio thereof) is preferably 1 to 40% by mass with respect to 100% by mass of the base polymer component (monomer component forming the base polymer). As the content of the main chain ring structure derived from these monomer components increases, the adhesion tends to improve. Further, when the amount of the N-substituted maleimide-based monomer added is further increased, a cured product having better hardness is obtained, and a dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer is used. As a result, a cured product having better heat resistance and coloring property can be obtained. If the content ratio of the N-substituted maleimide-based monomer is too large, the development speed may not be more appropriate.
The content ratio of the N-substituted maleimide-based monomer, dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer, and / or α- (unsaturated alkoxyalkyl) acrylate is more preferably 2-. It is 40% by mass, more preferably 3 to 35% by mass.

As the other monomer, one or more of other (meth) acrylic acid ester-based monomers and aromatic vinyl-based monomers which do not correspond to the above-mentioned monomers are used. be able to.

The other (meth) acrylic acid ester-based monomers are (meth) other than dialkyl-2,2'-(oxydimethylene) diacrylate-based monomers and α- (unsaturated alkoxyalkyl) acrylates. ) Means an acrylic acid ester-based 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 Hexil, 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, (meth) acrylic Tricyclodecanylate acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylic 3-Hydroxybutyl acid, 4-Hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydro (meth) acrylate Flufuryl, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) acrylic acid In addition to N, N-dimethylaminoethyl, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, etc., 1,4-dioxaspiro [4,5] deca-2-ylmethacrylic acid, (meth) acryloyl Morpholine, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3 -Dioxolan, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, alkoxylated phenyl Butyl T) Examples include acrylate.

Among the above (meth) acrylic acid ester-based monomers, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) are excellent in heat resistance. It is also preferable to use benzyl acrylate and alkoxylated phenylphenol (meth) acrylate. More preferably, methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and / or an alkoxylated phenylphenol (meth) acrylate are excellent in heat resistance, adhesion, and developability. Is to be used.

Examples of the aromatic vinyl-based monomer include styrene, vinyltoluene, α-methylstyrene, methoxystyrene and the like. Of these, styrene and vinyltoluene are preferable in terms of heat-resistant coloring and heat-degradability of the resin.

The content ratio of the (meth) acrylic acid ester-based monomer and / or the aromatic vinyl-based monomer (the total ratio when two or more kinds are used) is, for example, relative to 100% by mass of the base polymer component. It is preferably 1 to 80% by mass. Within this range, a cured product having better heat resistance and alkali solubility can be obtained. It is more preferably 5 to 75% by mass, still more preferably 10 to 70% by mass.

As the other monomer, for example, (meth) acrylamides exemplified in JP2013-227485A; a macromonomer having a (meth) acryloyl group at one end of a polymer molecular chain. One or more kinds such as conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; etc. can also be used. The content ratio is preferably 20% by mass or less based on 100% by mass of the base polymer component.

Here, from the viewpoint of further improving the electrical properties of the cured product, it is preferable that the alkali-soluble resin (i) does not have a hydrophilic group such as a hydroxyl group. Therefore, the monomer component copolymerized to obtain the alkali-soluble resin (i) does not contain a monomer having a hydrophilic group (for example, a (meth) acrylic acid ester having a hydroxyl group) as much as possible. Is preferable. Specifically, the content ratio of the monomer having a hydrophilic group is preferably 20% by mass or less based on 100% by mass of the base polymer component. It is more preferably 10% by mass or less, still more preferably 5% by mass or less.

As a method for polymerizing the above-mentioned monomer components, commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used, and may be appropriately selected depending on the purpose and application. Above all, solution polymerization is preferable because it is industrially advantageous and structural adjustment such as molecular weight is easy. Further, as the polymerization mechanism of the above-mentioned monomer component, a polymerization method based on a mechanism such as radical polymerization, anion polymerization, cationic polymerization, or coordination polymerization can be used, but the polymerization method based on the radical polymerization mechanism is industrial. It is also preferable because it is advantageous for.

Preferred forms of the polymerization reaction are as described in JP2013-227485A. [0053] to [0065]. The polymerization time is preferably 1 to 8 hours, more preferably 1 to 5 hours, still more 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 binding to an acid group and a polymerizable double bond include a (meth) acryloyl group, a vinyl group, an allyl group, and a metalyl group. , As the compound, those having one or more of these are preferable. Of these, the (meth) acryloyl group is preferable in terms of reactivity. Examples of the functional group that can be bonded to the acid group include a hydroxy group, an epoxy group, an oxetanyl group, an isocyanate group, and the like, and as the compound, one having one or more of these is preferable. .. Of these, epoxy groups (including glycidyl groups) are preferable from the viewpoints of speed of transformation 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, and β-ethylglycidyl (meth) acrylate. Examples thereof include vinylbenzyl 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. Above all, 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 the polymerizable double bond is, for example, 1 to 1 to 100 parts by mass of the base polymer component (total amount of monomer components constituting the base polymer). It is preferably 50 parts by mass. More preferably, it is 5 to 45 parts by mass.

The amount (blending ratio) of the compound having a functional group capable of binding to the acid group and the polymerizable double bond is also the amount of the compound having the acid group and the polymerizable double bond constituting the base polymer (this is referred to as "this". Compounding ratio (% by mass) of a compound having a functional group capable of binding to an acid group and a polymerizable double bond (referred to as "compound y") added to the carboxylic acid of "monomer x"). That is, it is determined by "{molar amount of compound y (mol) / molar amount of monomer x (mol)} x {blending ratio of monomer x (mass%)}" so that it is 50% by mass or less. It is preferable to set to. As a result, a cured product having better electrical characteristics can be obtained. More preferably, it is less than 50% by mass, which makes it possible to obtain a cured product having better electrical properties and light resistance. It is more preferably 45% by mass or less, particularly preferably 40% by mass or less, and most preferably 35% by mass or less. Further, it is preferably 5% by mass or more. More preferably, it is 7% by mass or more.
For example, GMA (glycidyl methacrylate) is used as a compound (compound y) having a functional group capable of binding to an acid group and a polymerizable double bond, and a monomer having an acid group and a polymerizable double bond (single). When MAA (methacrylic acid) was used as the metric x), the above-mentioned "blending ratio (mass%) of a compound having a functional group capable of binding to an acid group and a polymerizable double bond" was added. It means mass% of GMA converted to MAA mass, and is obtained by "{mol amount of GMA (mol) / molar amount of MAA (mol)} x MAA compounding ratio (mass%)". It is preferable that this value is within the above-mentioned preferable range.

The alkali-soluble resin (i) is, for example, an acid group (preferably) of the base polymer component when the base polymer component is reacted with a compound having a functional group capable of binding to an acid group and a polymerizable double bond. Is a method of making the amount of (carboxyl group) more than the amount of the functional group capable of binding to the acid group and the compound having a polymerizable double bond; the above base polymer component and the functional group capable of binding to the acid group and polymerization. It is preferable to produce by using a method such as a method of reacting with a compound having a sex double bond and then further reacting with a compound having a polybasic acid anhydride group.

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 gels. In order to prevent the formation, it is preferable to carry out in the temperature range of 50 to 160 ° C. It is more preferably 70 to 140 ° C, still more preferably 90 to 130 ° C. Further, in order to improve the reaction rate, a commonly used basic catalyst for esterification or transesterification or an acidic catalyst can be used as the catalyst. Above all, 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. Tertiary 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 Tertiary phosphonium salts such as bromide and benzyltriphenylphosphonium bromide; and the like; one or more of these can be used. Of these, dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferable in terms of reactivity, handleability, halogen-free, and the like.

The amount of the catalyst used is 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount 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. Is preferable. More preferably, it is 0.1 to 3 parts by mass.

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 is also carried out by adding a polymerization inhibitor to prevent gelation of the molecular oxygen-containing gas. It is preferably performed 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, methquinone, 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. Examples thereof include phenol-based banning agents, organic acid copper salts, phenothiazine, and the like, and one or more of these can be used. Among them, phenolic bans are preferable in terms of low coloring and polymerization inhibitory ability, and from the viewpoint of availability and economy, 2,2'-methylenebis (4-methyl-6-t-butylphenol), methoxinone, 6-t- Butyl-2,4-xylenol and 2,6-di-t-butylphenol are more preferred.

The amount of the polymerization inhibitor used is a functional group capable of binding to the base polymer component and an acid group from the viewpoint of ensuring a sufficient polymerization inhibitory effect and curability when the curable resin composition is obtained. It is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the total amount of the compound having the polymerizable double bond. More preferably, it is 0.01 to 0.5 parts by mass.

Examples of the compound having a polybasic acid anhydride group include succinic anhydride, dodecenyl succinic anhydride, pentadecenyl succinic anhydride, octadecenyl succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, trimellitic anhydride Examples thereof include pyromellitic anhydride, 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. This makes it possible to more fully exert the effects of the present invention. Above all, from the viewpoint of improving electrical characteristics, it is more preferably 400 to 5000. The lower limit value is more preferably 450 or more, particularly preferably 500 or more, and the upper limit value is more preferably 4000 or less, still more preferably 3000 or less, particularly preferably 2000 or less, and most preferably 1500 or less. As described above, the form in which the double bond equivalent of the alkali-soluble resin (i) is 500 to 1500 is also one of the preferred forms of the present invention.

The double bond equivalent is the mass (g) of the solid content of the polymer solution per 1 mol of the double bond of the polymer. The mass of the solid content of the polymer solution referred to here is the mass of the base polymer component, the mass of a 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 sum of. It can be obtained by dividing the mass of the solid content of the polymer solution by the amount of double bonds of the polymer. The amount of the double bond of the polymer can be determined from the amount of the charged acid group and the compound having a functional group that can be bonded 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), if necessary. Such an alkali-soluble resin is not particularly limited, but 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, and the resin is used. Further inclusion is preferred. Above all, 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 is possible to more sufficiently exert the action and effect of the present invention of providing a cured product having extremely excellent electrical properties, sufficient adhesion and surface hardness. In addition, the cured product also 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. As a result, more sufficient alkali solubility is expressed, and it becomes possible to obtain a cured product having better developability. It is more preferably 30 mgKOH / g or more, still more preferably 40 mgKOH / g or more. Further, 290 mgKOH / g or less is more preferable.

The alkali-soluble resin (ii) also preferably has a weight average molecular weight of 100 or more. As a result, a cured product having a higher surface hardness can be obtained. It is more preferably 1000 or more, still more preferably 5000 or more. Further, from the viewpoint of viscosity and the like, it is preferably 250,000 or less. It is more preferably 100,000 or less, further preferably 50,000 or less, particularly preferably 30,000 or less, and most preferably 20,000 or less.

The alkali-soluble resin (ii) is an optional component, but when it is contained, the content thereof is preferably 90 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (i). This makes it possible to more fully exert the action and effect of the present invention of providing a cured product having extremely excellent electrical characteristics, sufficient adhesion and surface hardness, and the cured product is also more excellent in light resistance. It will be. It is more preferably 85 parts by mass or less, still more preferably 80 parts by mass or less. Further, it is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more.

<Polyfunctional (meth) acrylate compound>
The curable resin composition contains a trifunctional or higher functional polyfunctional (meth) acrylate compound.
The trifunctional or higher functional (meth) acrylate compound is a compound having three or more (meth) acryloyl groups in one molecule, and the resin composition is photosensitive by containing such a compound. And it becomes excellent in curability, and it becomes possible to obtain a cured film having high hardness.
Here, the (meth) acryloyl group means a methacryloyl group and / or an acryloyl group, but in the present invention, an acryloyl group is preferable from the viewpoint of being more excellent in reactivity. That is, the 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. As a result, the photosensitivity and curability are enhanced, and the hardness and transparency of the cured product can be improved. The functional number is preferably 4 or more, and more preferably 5 or more. Further, from the viewpoint of further suppressing curing shrinkage, it is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less.
Even a polyfunctional (meth) acrylate compound having a small number of functions is preferable as long as it has a fluorene skeleton because the hardness of the cured product can be further improved. Therefore, the polyfunctional (meth) acrylate compound may be a polyfunctional (meth) acrylate compound having a fluorene skeleton.

The molecular weight of the polyfunctional (meth) acrylate compound is not particularly limited, but from the viewpoint of handling, for example, 2000 or less is preferable. More preferably, it is 1000 or less. Further, 100 or more is preferable.

The polyfunctional (meth) acrylate compound is not particularly limited, and examples thereof include the following compounds.
Trimethylolpropane tri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (Meta) acrylate, propylene oxide-added dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added dimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (Meta) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate, etc.

In the above curable resin composition, the content ratio of the polyfunctional (meth) acrylate compound is the total amount of the alkali-soluble resin (alkali-soluble resin (i) and other alkali-soluble resin which may be further contained if 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) having better electrical characteristics can be obtained. It is more preferably 110 parts by mass or less, further preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, particularly preferably 80 parts by mass or less, and most preferably 70 parts by mass or less. Further, from the viewpoint of further improving the developability, it is preferably 20 parts by mass or more. It is more preferably 30 parts by mass or more, further preferably 35 parts by mass or more, and particularly preferably 40 parts by mass or more.

<Other polymerizable monomers>
The curable resin composition may further contain a polymerizable monomer (also referred to as another polymerizable monomer) other than the polyfunctional (meth) acrylate compound, if necessary. The 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. It is also referred to as a compound having (also referred to as), and is preferably a radically polymerizable monomer as another polymerizable monomer.

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

The monofunctional radically polymerizable compound is not particularly limited, and is, for example, (meth) acrylic acid ester-based monomer; (meth) acrylamides; unsaturated monocarboxylic acids; between unsaturated groups and carboxyl groups. Unsaturated monocarboxylic acids with extended chains; aromatic vinyl-based monomers; N-substituted maleimide-based monomers; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates, etc. Can be mentioned. Among these, a (meth) acrylic acid ester-based monomer is preferable, that is, a monofunctional (meth) acrylate compound is preferable.

Examples of the monofunctional (meth) acrylate compound include a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon group and a monofunctional (meth) acrylate compound having an aromatic ring (aromatic hydrocarbon group). Among them, the former is preferable, and a compound having one (meth) acryloyl group in one molecule and an aliphatic hydrocarbon group having 5 to 24 carbon atoms 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, an alkenyl group). Among them, an aliphatic saturated hydrocarbon group is preferable because the action and effect of the present invention can be more sufficiently exhibited. Specifically, it is preferably a group (n = 5 to 24) represented by C _n H _{2n + 1} .

The number of carbon atoms of the aliphatic hydrocarbon group is preferably 5 to 24. As a result, the surface hardness of the cured product becomes more sufficient, and the compatibility with other contained components becomes more excellent. The number of carbon atoms is preferably 8 or more, and more preferably 10 or more. Further, it is preferably 22 or less, more preferably 20 or less.

The monofunctional (meth) acrylate compound having the above aliphatic hydrocarbon group is preferably, for example, n-amyl (meth) acrylate, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n-hexyl (meth). ) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate (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) acrylate, 2-decyltetradecyl ( Compounds having an aliphatic hydrocarbon group consisting of a straight chain or a branched chain such as meta) acrylate, 2-decyltetradecanyl (meth) acrylate, eikosyl (meth) acrylate, and behenyl (meth) acrylate; isobornyl (meth) acrylate, Examples thereof include compounds having a cyclic aliphatic hydrocarbon group such as adamantyl (meth) acrylate; and the like. Among them, the above-mentioned compound having an aliphatic saturated hydrocarbon group having a preferable carbon number is more preferable.

Examples of the polyfunctional radically polymerizable compound are exemplified in the above-mentioned unsaturated polyvalent carboxylic acids and unsaturated acid anhydrides, as well as Japanese Patent Application Laid-Open No. 2013-227485 [0907] to [0998]. , 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 isocyanurate Classes; 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 based on 100% by mass of the total solid content. As a result, the transparency of the cured product can be further improved, and the electrical characteristics can be further improved. It is more preferably 4% by mass or more, still more preferably 15% by mass or less, still more preferably 12% by 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. It is preferable that the total solid content is 10% by mass or less based on 100% by mass. It is more preferably 5% by mass or less, still more preferably 1% by mass or less.

<Photopolymerization initiator>
It is preferable that the curable resin composition also contains a photopolymerization initiator. This makes it possible to further improve the sensitivity and curability of the resin composition. Such a form in which the curable resin composition further contains a photopolymerization initiator is one of the preferred forms of the present invention.

The photopolymerization initiator is preferably a radically polymerizable photopolymerization initiator. The radically polymerizable photoinitiator is one that generates a polymerization initiator 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. .. Further, if necessary, one or more photosensitizers, photoradical polymerization accelerators, and the like may be used in combination. Sensitivity and curability are further improved by using a photosensitizer and / or a photoradical polymerization accelerator in combination with the photopolymerization initiator.

Specifically, as the photopolymerization initiator, for example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-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-morpho) Aminoketone compounds such as phosphorus-4-yl-phenyl) -butane-1-one ("IRGACURE379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE651", "IRGACURE651", Benzyl ketal compounds such as BASF), phenylglycolic acid methyl ester (“DAROCUR MBF”, BASF); 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE184”, BASF), 2- Hydroxy-2-methyl-1-phenyl-propane-1-one ("DAROCUR1173", manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1- Propane-1-one ("IRGACURE2959", manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane Hydroketone compounds such as -1-one (“IRGACURE 127”, manufactured by BASF), [1-hydroxy-cyclohexyl-phenyl-ketone + benzophenone] (“IRGACURE500”, manufactured by BASF), etc. Alkylphenone-based compounds; benzophenone-based compounds; benzoin-based compounds; thioxanthone-based compounds; halomethylated triazine-based compounds; halomethylated oxadiazole-based compounds; biimidazole-based compounds exemplified in JP-A-227485. Compounds; oxime ester compounds; titanosen compounds; benzoic acid ester compounds; aclydin compounds and the like; phosphenyl oxide compounds; oxime ester compounds; and the like.

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

The content of the photopolymerization initiator may be appropriately set according to the purpose, application, etc., and is not particularly limited, but is 2 parts by mass or more with respect to 100 parts by mass of the total solid content of the curable resin composition. Is preferable. As a result, a cured product having better adhesion can be obtained, and peeling is more sufficiently suppressed even after high temperature exposure. It is more preferably 5 parts by mass or more, still more preferably 7 parts by mass or more. Further, in consideration of the influence of the decomposition product of the photopolymerization initiator and the balance with economic efficiency, the amount is preferably 35 parts by mass or less. More preferably, it is 25 parts by mass or less.

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

Examples of the photosensitizer and the 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. ; Mercaptan-based hydrogen donor; etc. The content (total amount) of the photosensitizer and / or the photoradical polymerization accelerator may be appropriately set according to the purpose and application, and is not particularly limited, but the curability, the influence of decomposition products, and the economy. From the viewpoint of property balance, 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. It is more preferably 0.01 to 15 parts by mass, and further preferably 0.05 to 10 parts by mass.

<Coupling agent>
It is preferable that the curable resin composition also contains a coupling agent. The coupling agent has a property of binding to the oxidized surface of an inorganic substance by subjecting it to a hydrolysis reaction or a condensation reaction. Utilizing this property, for example, adhesion to a substrate on which ITO or the like is deposited is adhered. It becomes possible to exert the sex more fully. As described above, 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, as the coupling agent, for example, a coupling agent having a reactive group such as a vinyl group, a (meth) acrylic group, an epoxy group, an amino group, a mercapto group and an isocyanate group is suitable. Of these, those having a vinyl group, a (meth) acryloyl group and / or an epoxy group as the reactive group are preferable. More preferably, it is a (meth) acryloyl group. Further, as the central metal, for example, those containing silicon, zirconia, titanium and / or aluminum and the like are preferable, and among them, those containing silicon as the central metal are preferable, and a silane coupling agent is more preferable. By using a silane coupling agent, the adhesion and surface hardness of the cured product can be made more sufficient.

Among the above 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 will be further improved.
Examples of the coupling agent having a metal other than silicon as the central metal include a zircoaluminate-based coupling agent and a titanate-based coupling agent.

The silane coupling agent includes one or more of the above-mentioned reactive groups and an alkoxysilane group (-Si (OR ³ ) _3-n (R ⁴ ) _n ; OR ³ is a hydrolyzable group. Representing, R ³ is preferably a hydrocarbon group. R ⁴ represents a hydrocarbon group. N is preferably 0, 1 or 2). Above all, it is preferable to use a silane coupling agent having a vinyl group, a (meth) acryloyl group and / or an epoxy group, whereby the appearance does not change with time such as discoloration, coloring and cracks even after high temperature exposure. It becomes possible to obtain a cured product having more sufficient surface hardness and adhesion.

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

Examples of the silane coupling agent having the (meth) acryloyl group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxipropylmethyldimethoxysilane, and 3- (meth) acryloxipropyltri. Examples thereof include methoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxipropyltriethoxysilane.

Specific examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 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-isocyanatepropyltriethoxysilane and the like.

In the curable resin composition, the content of the coupling agent is preferably 3% by mass or more based on 100% by mass of the total solid content of the curable resin composition. By containing 3% by mass or more, it is possible to have more sufficient adhesion and surface hardness even after high temperature exposure. It is more preferably 4% by mass or more, still more preferably 5% by mass or more. Further, from the viewpoint of storage stability and the like of the curable resin composition, it is preferably 30% by mass or less. It is more preferably 25% by mass or less, still more preferably 20% by mass or less.

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

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

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

Further, the fluorine-based additive preferably contains 0.01 to 80% by mass of fluorine in 100% by mass of the total amount of the fluorine-based additive. The fluorine content can be quantified by, for example, an ion chromatograph method.

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

Specific examples of the above-mentioned fluorine-based additive include perfluorobutane sulfonate (Megafuck F-114), perfluoroalkyl group-containing carboxylate (Megafuck F-410), and perfluoroalkylethylene oxide adduct (Megafuck F-410). Megafuck F-444, EXP / TF-2066), perfluoroalkyl group-containing phosphate ester (Megafuck EXP / TF-2148), perfluoroalkyl group-containing phosphate ester-type amine neutralized product (Megafuck EXP / TF) -2149), Fluorophosphate / hydrophilic group-containing oligomers (Megafuck F-430, EXP / TF-1540), Fluorine-containing / oleophosphate-containing oligomers (Megafuck F-552, F-554, F-558) , F-561, R-41), Fluorophosphate-containing / hydrophilic / lipophilic group-containing oligomers (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 / lipophilic group / UV-reactive group-containing oligomer (Megafuck RS-72-K, RS-75, RS-76- E, RS-76-NS, RS-77) and the like (all manufactured by DIC). Among them, compounds containing lipophilic groups (fluorine-containing group / lipophilic group-containing oligomer, fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, fluorine-containing group / hydrophilic group / lipophilic group / UV-reactive group-containing group Oligomers) are preferred.

The content of the fluorine-based additive may be appropriately set according to the purpose, application, etc., and is not particularly limited, but 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. Is preferable. It is more preferably 0.05 parts by mass or more, still more preferably 5 parts by mass or less, further preferably 4 parts by mass or less, and particularly preferably 3 parts by mass or less.

<Solvent>
The curable resin composition also preferably contains a solvent. The solvent is preferably used as a diluent or the like. That is, specifically, it is suitably used for lowering the viscosity and improving the handleability; forming a coating film by drying; as a dispersion medium for a coloring material; etc., and in a curable resin composition. It is a low-viscosity organic solvent capable of dissolving or dispersing each of the components contained in.

As the solvent, one or more of the usual solvents can be used, and the solvent 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, In addition to glycol monoether esters 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, JP2013-227485. Monoalcohols; glycols; cyclic ethers; glycol monoethers; glycol ethers; alkyl esters; ketones; aromatic hydrocarbons; aliphatic hydrocarbons; amides exemplified in the publication. ; Etc. can be mentioned.

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

The curable resin composition further comprises, for example, a coloring material (also referred to as a colorant); a dispersant; a heat improver; a leveling agent; a developing aid; a filler; depending on the required properties of each application to which it is applied. Thermosetting resins such as epoxy resins, phenol resins, polyvinylphenols; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors; UV absorbers; antioxidants; matting agents; antifoaming agents; antistatic Agents; slip agents; surface modifiers; rocking agents; rocking aids; quinonediazide compounds; polyvalent phenolic compounds; cationically polymerizable compounds; acid generators; etc., which may contain one or more. .. For example, when the curable resin composition is used for a color filter application, it preferably contains a coloring material.

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

<Manufacturing method of curable resin composition>
The method for producing the curable resin composition of the present invention is not particularly limited, and for example, it can be prepared by mixing and dispersing the above-mentioned contained components using various mixers and dispersers. The dispersion step and the mixing step are not particularly limited, and may be carried out by a usual method. In addition, it may further include other steps that are usually performed. When the curable resin composition contains a coloring material, it is preferably produced through a process of dispersing the coloring material.

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

It is preferable that the cured film has a resistance value reduction time of 100 hours or more in the ion migration test. By using such a cured film, the electrical characteristics of the display device member and the like are further improved. The resistance value reduction time is more preferably 150 hours or more, further preferably 200 hours or more, and particularly preferably 250 hours or more.
The ion migration test can be carried out by the method described in Examples described later.

Here, in the display device member having a cured film having good electrical characteristics, for example, high definition can be achieved when touch-inputting a display device screen having a capacitance type touch panel. A capacitive 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 window of the touch panel, and the touched position is caused by the change in capacitance accompanying this. Is to be detected. Therefore, it is possible to improve the performance of the display device by improving the electrical characteristics of various parts on which 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, and is, for example, a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass; polyethylene terephthalate (PET), polyester. , Polycarbonate, Polyethylene, Polysulfone, Cyclic olefin ring-opening polymer and hydrogenated products thereof, etc. Sheet or film; Sheet or film made of thermosetting resin such as epoxy resin, unsaturated polyester resin; Aluminum; Metal substrates such as plates, copper plates, nickel plates, and stainless plates; ceramic substrates; semiconductor substrates with photoelectric conversion elements; members made of various materials such as glass substrates (color filters for LCDs) having a color material layer on the surface; And so on. Among them, from the viewpoint of heat resistance, a glass substrate and a sheet or film made of a heat-resistant resin among plastic substrates are preferable. Further, 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 or the like, if necessary, and inorganics such as a gas barrier layer and a protective film may be applied to both sides or one side of the substrate. A coating film of a component or an organic component may be formed. Further, when the cured film is used as a member for a display device, it is preferable to form an electrode such as ITO on the substrate. The cured film of the present invention is excellent not only in adhesion to a substrate but also to electrodes such as an ITO film.

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

The coating film after being applied to the substrate can be dried by 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. Is preferable.

Examples of the light source of the active energy ray include a lamp light source such as 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 carbon arc, and a fluorescent lamp, and an argon ion laser. , YAG laser, excima laser, nitrogen laser, helium cadmium laser, laser light source such as semiconductor laser, etc. are used. Further, examples of the exposure machine method include a proximity method, a mirror projection method, and a stepper method, and the proximity method is preferably used.
In the step of irradiating the active energy ray, the active energy ray 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 developing solution.

Further, if necessary, after the step of irradiating the active energy light beam, a step of developing with a developing solution to remove an unexposed portion and forming a pattern (also referred to as a developing step) may be performed. This makes it possible to obtain a patterned cured film.
The development process in the above development step can usually be performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, and ultrasonic development. When an alkaline aqueous solution is used as the developing solution, it is preferable to wash with water after the development.

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

In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffer, a dye, a pigment and the like, if necessary. Examples of the organic solvent in this case include an organic solvent suitable as the above-mentioned developer. As the alkaline agent, for example, one or more kinds of inorganic alkaline agents; amines; etc. exemplified in JP2013-227485A [0164] can be used, and as the surfactant, one or more kinds can be used. For example, one or more of nonionic surfactants; anionic surfactants; amphoteric surfactants and the like exemplified in JP2013-227485A [0165] can be used.

Further, if necessary, a post-curing step (also referred to as a post-baking or post-treatment step) may be performed. Examples of the post-curing step include a step of exposing with a light amount of 0.5 to ⁵ J / cm ² using a light source such as a high-pressure mercury lamp, and a step of post-heating (also referred to as a heat treatment step). .. By performing such a post-treatment, the hardness and adhesion of the patterned cured film can be further strengthened.

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

[Use of curable resin composition, etc.]
The curable resin composition of the present invention provides a cured product (cured film) having extremely excellent electrical properties, sufficient adhesion and surface hardness, and high transparency. Therefore, the cured product (cured film) formed from such a curable resin composition can be, for example, components of various display devices such as a liquid crystal display device, a solid-state image sensor, and a touch panel display device, as well as ink and printing. It is preferably used in various applications such as plates, printed wiring boards, semiconductor elements, photoresists, various optical members, and electric / electronic devices. Above all, it is preferable to use it for a color filter used for a liquid crystal display device, a solid-state image pickup device, or a touch panel type display device. In particular, a protective film (color) in these various display devices using the curable resin composition. It is preferable to form a protective film for a filter, a protective film for a touch panel display device, etc.) or an insulating film (an insulating film for a touch panel display device, etc.). As a result, the reliability of the display quality and the image quality of various display devices can be sufficiently improved to the extent that the demand for higher performance in recent years can be sufficiently met. As described above, the curable resin composition is a protective film or a curable resin composition for forming an insulating film, the cured film is a protective film or an insulating film, and the cured film is a cured film for a touch panel. Is also included in the preferred forms of the present invention. Further, a cured film formed by the curable resin composition, a display device member having the cured film, and a display device having the cured film are included in the present invention.

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

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

Since the curable resin composition of the present invention has the above-mentioned structure, it is possible to provide a cured product having both good adhesion and electrical properties, and having sufficient surface hardness and transparency. Therefore, a member for a display device and a display device having a cured film formed of such a curable resin composition are very useful in the fields of optics and electric / electronic fields.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".
In the following synthetic examples and preparation examples, various physical properties 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 weight average molecular weight (Mw) by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh) and column TSKgel SuperHZM-M (manufactured by Tosoh) using polystyrene as a standard substance and tetrahydrofuran as an eluent. 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 concentration NV>
About 0.3 g of the polymer solution was weighed in an aluminum cup, and about 1 g of acetone was added to dissolve the polymer solution, which was then naturally dried at room temperature. Then, using a hot air dryer (manufactured by ESPEC, trade name "PHH-101"), the product was dried at 140 ° C. for 3 hours, then allowed to cool in a desiccator, and the mass was measured. The solid content concentration (NV, mass%) of the polymer solution was calculated from the amount of mass reduction.

<Acid value AV>
1.5 g of the resin solution is precisely weighed, dissolved in a mixed solvent of 90 g of acetone / 10 g of water, and an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., trade name "COM-555") using a 0.1N KOH aqueous solution as a titrator. The acid value of the resin solution was measured, and the acid value per 1 g of the solid content was determined from the acid value of the solution and the solid content of the solution.

[Physical properties of coating film (cured film)]
1. Physical properties for ITO substrate An ITO substrate on which ITO (Indium Tin Oxide) was vapor-deposited at a thickness of 30 nm was prepared. The resin composition obtained on this ITO substrate is applied by a spin coating method, heat-treated (80 ° C. for 3 minutes), and then a UV aligner (manufactured by TOPCON, trade name) equipped with a 2.0 kW ultra-high pressure mercury lamp. TME-150RNS ”) was used to perform exposure at an exposure amount of 60 mJ / cm ² (365 nm illuminance conversion), and heat treatment (230 ° C. for 30 minutes) was performed. Using the obtained coating film, initial physical property evaluation (grind test, pencil hardness test, film color evaluation test) and light resistance evaluation were performed as follows.

(1) Go board test (adhesion evaluation)
The test was conducted according to JIS-K5400-8.5 (1990) and evaluated according to the following criteria.
◯: 10 points according to JIS standard.
Δ: 4 to 8 points according to JIS standards.
×: 0 to 2 points according to JIS standard.

(2) Pencil hardness test (hardness evaluation)
The test was conducted according to JIS-K5600-5-4 (1999), but all the loads were 500 g of the old JIS version of JIS-K5400 (1990), and the hardest pencil that did not cause scars was hardened. It was taken as the value of (surface hardness).
The hardness decreases in the order of 3H>2H>H>F>HB>B>2B>3B> 4B.

(3) Film Color Evaluation Test The color of the coating film (cured film having a thickness of 1.5 μm) obtained above was visually evaluated. Specifically, the evaluation was made according to the following criteria.
◯: The cured film is colorless and transparent.
Δ: The cured film is pale white.
X: The cured film is cloudy.

(4) Light resistance test The coating film (cured film with a thickness of 1.5 μm) obtained above was set in a machine using a xenon weather meter (manufactured by X75SC Suga Test Instruments Co., Ltd.) in the direction in which UV hits from the glass surface, and 60 W A test was performed in accordance with JIS-K5400-8.5 (1990) after irradiating with / m ² (300 to 400 nm integrated light intensity), BPT 63 ° C., and 50% RH for 30 hours, and the grid test of (1) above was performed. The evaluation was performed in the same manner as the criteria of (adhesion evaluation).

2. Electrical characteristics (ion migration test)
Using non-alkali glass, an APC alloy having L / S = 10 mm / 1 mm was vapor-deposited by an ion sputtering device (Autofine 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 coating method and heat-treated (80 ° C. for 3 minutes), and then the end portion 1 cm was masked and 2.0 kW. Exposure was performed at an exposure rate of 60 mJ / cm ² (365 nm illuminance conversion) with a UV aligner (manufactured by TOPCON, trade name "TME-150RNS") equipped with an ultra-high pressure mercury lamp, and after alkaline development, heat treatment (230 ° C.) After 30 minutes), an insulated substrate with metal wiring was obtained.
Next, the metal portion of the obtained insulating substrate with metal wiring, which was subjected to alkali development and exposed, was cured with silver paste (XA-910 manufactured by Fujikura Kasei) at 150 ° C. for 30 minutes to wire to the migration device. Was 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) at which the resistance value decreased was set by an ion migration device (MIG-87: manufactured by IMV). ) Was used for measurement.

[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 tank, the temperature was raised to 90 ° C. in a nitrogen atmosphere, and then 30 parts of benzyl maleimide (BzMI) and methacrylic acid were used as the dropping system 1. (MAA) 180 parts, cyclohexyl acrylate (CHA) 90 parts, PGME 30 parts, perbutyl O (trade name, manufactured by Nippon Yushi Co., Ltd.) 6 parts, n-dodecyl mercaptan (n-DM) 9 parts, PGME 71 parts as dropping system 2. Each was continuously supplied over 3 hours. After that, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and the 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 this 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. ..
Various physical properties (weight average molecular weight Mw, solid content concentration NV, acid value AV per solid content, and dispersity) were measured for the obtained resin solution B-1. The results are shown in Table 1.

Synthesis Example 2 (Synthesis of B-2)
185 parts of propylene glycol monomethyl ether acetate (PGMEA) and 185 parts of PGME are charged in a separable flask with a cooling tube as a reaction tank, the temperature is raised to 90 ° C. in a nitrogen atmosphere, and then 25 parts of BzMI and 143 parts of MAA are used as the dropping system 1. , CHA 83 parts, PGMEA 13 parts, PGME 13 parts, perbutyl O 5 parts, n-DM 11 parts, PGMEA 34 parts, PGME 34 parts as a dropping system 2 were continuously supplied over 3 hours. After that, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and the 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. was added while bubbling nitrogen and an oxygen mixed gas (oxygen concentration 7%). By continuing the reaction at 115 ° C. for 7 hours for 2 hours, a resin solution B-2 having a double bond equivalent of 444 g / equivalent was obtained.
Various physical properties of the obtained resin solution B-2 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)
90 parts of PGMEA and 90 parts of PGME are placed in a separable flask with a cooling tube as a reaction tank, the temperature is raised to 90 ° C. under a nitrogen atmosphere, and then as a dropping system 1, 60 parts of MAA, 76 parts of CHA and 2.7 parts of perbutyl O are added. As the dropping system 2, 5.7 parts of n-DM, 37 parts of PGMEA, and 37 parts of PGME were continuously supplied over 3 hours. After that, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and the 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 while bubbling nitrogen and an oxygen mixed gas (oxygen concentration 7%), 110 ° C. By continuing the reaction at 115 ° C. for 4 hours for 2 hours, a double bond equivalent of 593 g / equivalent of resin solution B-3 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)
382 parts of PGMEA and 95 parts of PGME are charged in a separable flask with a cooling tube as a reaction tank, the temperature of the resin composition is raised to 90 ° C. under a nitrogen atmosphere, and then 12 parts of BzMI, 74 parts of MAA, 170 parts of CHA, 2 parts of BzMI as a dropping system 1 -Hydroxyethyl acrylate (HEA) 45 parts, PGMEA 10 parts, PGME 2 parts, Perbutyl O 6 parts, n-DM as a dropping system 2 12 parts, PGMEA 54 parts, PGME 14 parts, respectively, were continuously supplied over 3 hours. After that, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and the 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. was added while bubbling nitrogen and an oxygen mixed gas (oxygen concentration 7%). By continuing the reaction at 115 ° C. for 3 hours for 2 hours, a double bond equivalent of 1941 g / equivalent of resin solution B-4 was obtained.
Various physical properties of the obtained resin solution B-4 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 was placed in a separable flask with a cooling tube as a reaction tank, the temperature was raised to 90 ° C. in a nitrogen atmosphere, and then 6 parts of BzMI, 249 parts of MAA, 21 parts of CHA, 30 parts of PGME, and perbutyl O were added as a dropping system 1. 13 parts of n-DM and 67 parts of PGME were continuously supplied over 3 hours as the parts and the dropping system 2. After that, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and the polymerization was continued for 1.5 hours.
Next, 125 parts of PGME and 248 parts of GMA, 1.6 parts of TEA as a catalyst, and 0.8 parts of Antage W-400 as a polymerization inhibitor were added to this reaction solution, and while bubbling nitrogen and an oxygen mixed gas (oxygen concentration 7%). By continuing the reaction at 110 ° C. for 2 hours and 115 ° C. for 10 hours, a resin solution B-5 having a double bond equivalent of 323 g / equivalent was obtained.
Various physical properties of the obtained resin solution B-5 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)
921 parts of PGMEA was placed in a separable flask equipped with a cooling tube as a reaction tank, the temperature was raised to 90 ° C. in a nitrogen atmosphere, and then dimethyl-2,2'-[oxybis (methylene)] bis-2 was used as the dropping system 1. -Propenoate (MD) 102 parts, MAA 182 parts, benzyl methacrylate (BzMA) 175 parts, methyl methacrylate (MMA) 51 parts, perbutyl O 10.2 parts, n-DM 16.8 parts as dropping system 2, PGMEA 44 parts Was continuously supplied over 150 minutes each. After that, the temperature was maintained at 90 ° C. for 60 minutes, the temperature was raised to 110 ° C., and the polymerization was continued for 3 hours.
Next, 210 parts of GMA, 2.2 parts of TEA as a catalyst, 0.2 parts of Antage W-400 as a polymerization inhibitor, and 119 parts of PGMEA were added to this reaction solution, and while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%). By continuing the reaction at 110 ° C. for 2 hours and 115 ° C. for 4 hours, a resin solution B-6 having a double bond equivalent of 490 g / equivalent was obtained.
Various physical properties of the obtained resin solution B-6 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 7 (Synthesis of B-7)
921 parts of PGMEA was placed in a separable flask equipped with a cooling tube as a reaction tank, the temperature was raised to 90 ° C. in a nitrogen atmosphere, and then 102 parts of methyl α-allyloxymethylacrylate (AMA) and 182 parts of MAA were used as the dropping system 1. , BzMA 175 parts, MMA 51 parts, perbutyl O 10.2 parts, n-DM 16.8 parts as a dropping system 2, and PGMEA 44 parts were continuously supplied over 150 minutes. After that, the temperature was maintained at 90 ° C. for 60 minutes, the temperature was raised to 110 ° C., and the polymerization was continued for 3 hours.
Next, 210 parts of GMA, 2.2 parts of TEA as a catalyst, 0.2 parts of Antage W-400 as a polymerization inhibitor, and 119 parts of PGMEA were added to this reaction solution, and while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%). By continuing the reaction at 110 ° C. for 2 hours and 115 ° C. for 4 hours, a resin solution B-7 having a double bond equivalent of 490 g / equivalent was obtained.
Various physical properties of the obtained resin solution B-7 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 8 (Synthesis of B-8)
In a separable flask with a cooling tube as a reaction tank, 154 parts of PGMEA and 38 parts of PGME are charged, the temperature is raised to 90 ° C. under a nitrogen atmosphere, and then the dropping system 1 is BzMI 51 parts, MAA 34 parts, CHA 85 parts, PGMEA 41 parts, PGME 10 3.4 parts of perbutyl O, 7.3 parts of n-DM as the dropping system 2, 58 parts of PGMEA, and 15 parts of PGME were continuously supplied over 3 hours. After that, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and the polymerization was continued for 1.5 hours.
Next, 38 parts of PGMEA, 10 parts of PGME, 28 parts of GMA, 0.6 parts of TEA as a catalyst, and 0.3 parts of Antage W-400 as a polymerization inhibitor were added to this reaction solution, and a mixed gas of nitrogen and oxygen (oxygen concentration 7%) was added. By continuing the reaction at 110 ° C. for 2 hours and 115 ° C. for 7 hours while bubbling, a double bond equivalent of 1045 g / equivalent of resin solution B-8 was obtained.
Various physical properties of the obtained resin solution B-8 were measured in the same manner 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 types of monomers constituting the base polymer, their blending ratios, and the blending ratios 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 procedure of.
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 the details of the resin solutions B-1 to B-12.
In addition, as the numerical value of each monomer constituting a base polymer in Table 1, the compounding ratio (mass%) of each monomer is described when the total amount of monomers is 100% by mass. 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 to Synthetic Examples 1 to 10). Is described as mass% converted to MAA mass, and "GMA compounding ratio (mass%) in terms of MAA mass = {GMA molar amount (mol) / MAA molar amount (mol)} x MAA compounding ratio ( It is calculated by "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 this 60% by mass (2091 mmol) of MAA. The blending ratio of the GMA was defined as "20".

The abbreviations in Table 1 are as follows.
BzMI: Benzylmaleimide CHMI: N-cyclohexylmaleimide MD: dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate AMA: α-allyloxymethylacrylate CHA: cyclohexyl acrylate CHMA: cyclohexyl methacrylate BzMA: benzyl methacrylate MAA: STMA Methacrylic Acid: Stearyl Methacrylate MMA: Methyl Methacrylate HEA: 2-Hydroxyethyl Acrylate GMA: Glycydyl Methacrylate AV: Acidity Mw: Weight Average Molecular Weight NV: Solid Content Concentration of Finally Obtained Polymer

[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, and 10 parts of KBM503 as a coupling agent. , 20 parts of IRGACURE907 as a photopolymerization initiator, 0.2 parts of F-554 as a fluorine additive, 0.5 part of Antage W-400 as a polymerization inhibitor, and a solid content concentration of 25% of a dilution solvent (PGMEA). The resin composition b-1 was obtained by adding and stirring the mixture.
The physical properties of the coating film (cured film) of the obtained resin composition b-1 were evaluated according to the evaluation method described above. The results are shown in Table 2.

Preparation Examples 2-6
Using the raw materials shown in the table at the blending ratios shown in Table 2, each resin composition b-2 to b-6 was obtained by the same operation as in Preparation Example 1. The physical properties of the coating film were evaluated for each of the obtained resin compositions according to the evaluation method described above. The results are shown in Table 2.

The abbreviations in Table 2 are as follows. The blending amount of each raw material in Table 2 is the amount of solid content. In Table 2, it is omitted that the diluting solvent (PGMEA: propylene glycol monomethyl ether acetate) was used.
SMA17352: Styrene / maleic anhydride copolymer (Mw = 7000 by GPC, molar ratio of styrene / maleic anhydride = 1/1) (trade name, manufactured by Kawahara Yuka Co., Ltd.)
SMA2625: Styrene / maleic anhydride copolymer (Mw = 9000 by GPC, molar ratio of styrene / maleic anhydride = 2/1) (trade name, manufactured by Kawahara Yuka Co., Ltd.)
DPHA: Dipentaerythritol hexaacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
A-9300: Triacrylate ethoxylated isocyanuric acid (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
IB-XA: Isobornyl acrylate (trade name "Light acrylate IB-XA", manufactured by Kyoeisha Chemical Industries, Ltd. NBAC-ST: Butyl acetate dispersed silica sol (trade name, manufactured by Nissan Chemical Industries, Ltd.))
KBM503: 2-methacryloxypropyltrimethoxysilane (trade name, manufactured by Shinetsu Silicone Co., Ltd.)
IRGACURE907: 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropan-1-one (trade name, manufactured by Ciba Specialty Chemicals)
F-554: Fluorine-containing group / lipophilic group-containing oligomer (nonionic, trade name "Megafuck 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 are all an alkali-soluble resin having a dispersity (Mw / Mn) of 2.0 to 3.5 and a polyfunctional or more trifunctional resin. While the resin compositions b-4 to b-5 obtained in Preparation Examples 4 to 5 contain a functional (meth) acrylate compound, the resin compositions b-4 to b-5 using an alkali-soluble resin having a dispersity outside the above range are used. 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 reduction time, which is an evaluation index of electrical characteristics, was significantly longer than that of the coating film. Further, it was found that the coating films obtained from the resin compositions b-1 to b-3 were at sufficient levels in terms of transparency, adhesion, and surface hardness. Therefore, it was confirmed that the curable resin composition having the constitution of the present invention can provide a cured product having extremely excellent electrical properties and sufficient adhesion, surface hardness and transparency. Further, according to a 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 Ingredients should not contain inorganic fine particles 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, based on 100% by mass of the total solid content of the resin composition. %) Was found to be suitable. Further, in terms of surface hardness, it was improved by containing a small amount of inorganic fine particles, 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, the coating film (cured film) is used even under the same other conditions. The surface hardness of No. 1 was not sufficient as compared with the coating films obtained from the resin compositions b-1 to b-3 and b-6.

Claims (3)

A cured film formed of a curable resin composition.
The curable resin composition contains an alkali-soluble resin having a dispersity (Mw / Mn) of 2.0 to 3.5 and a polyfunctional (meth) acrylate compound having trifunctionality or higher.
The alkali-soluble resin is a polymer having a ring structure in the main chain, and is an N-substituted maleimide-based monomer unit, a dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer unit, and α. It has at least one monomer unit selected from the group consisting of- (unsaturated alkoxyalkyl) acrylate-based monomer units and cyclohexyl (meth) acrylate units, and has a double bond equivalent of 400 to 1500. And
The content ratio of the inorganic fine particles is 3% by mass or less in 100% by mass of the total solid content of the curable resin composition.
The cured film is characterized in that the resistance value reduction time by an ion migration test performed by applying a voltage of 5 V under a constant temperature and humidity condition of 80 ° C. and 95% RH is 100 hours or more. A member for a display device, which has the cured film according to claim 1. A display device having the cured film according to claim 1.