KR20190034508A - Curable resin composition and its use - Google Patents

Abstract

Provided are a curable resin composition, a cured film, and a member for a display device and the display device having the cured film. The curable resin composition is excellent in adhesion, dispersibility, developability and the like, has sufficient surface hardness, can maintain dispersibility even after exposure under a high temperature environment without change in appearance such as discoloration, cracks and the like, and also is capable of imparting a cured product capable of stably exhibiting sufficient surface hardness and adhesion. The cured film formed by such the curable resin composition. The curable resin composition comprises fine silica particles, a coupling agent, and an alkali-soluble resin.

Description

CURABLE RESIN COMPOSITION AND ITS USE [0002]

The present invention relates to a curable resin composition and a use thereof. More specifically, the present invention relates to a curable resin composition useful for various uses such as various optical members such as constituent members of various display devices, ink, printing plate, printed wiring board, semiconductor element, and photoresist, And a display device.

The curable resin composition that can be cured by heat or an active energy ray can be used as a component of various display devices such as a liquid crystal display device, a solid-state image pickup device, a touch panel type display device, an ink, a printing plate, Various applications of various optical members such as light-emitting diodes, devices, and photoresists, and electric and electronic devices have been examined variously, and a curable resin composition excellent in characteristics required for each application has been developed. Among these applications, a touch panel type display device refers to a display device capable of performing an input operation by contacting a screen with a finger or a touch pen instead of a conventional input operation by a keyboard or a mouse, , The input operation is intuitively easy to understand and easy to use, so that it has become popular recently.

Such a touch panel type display device is roughly classified into two types, that is, a method of using electricity and a method of not using electricity, on the principle of detecting a generally touched position. There are resistance film type and electrostatic capacity type in the method of using electricity, and ultrasonic type and optical type in the case of not using it, and resistance film type is mainstream in that the manufacturing cost is low and the weight is easy . In the resistive film type, a film is usually disposed on a glass substrate via a minute spacer, and a transparent conductive film such as ITO (Indium Tin Oxide) is formed on each of the surfaces of the glass substrate and the film facing each other However, the demand for the capacitance type is increasing due to the fact that it is vulnerable to time-dependent changes and shocks, and that there are a lot of malfunctions, and development is proceeding.

The capacitive touch panel type 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 formed. In the protective film or insulating film, High adhesion, durability, transparency and surface hardness to a conductive film are required. In particular, since the touch panel type display device is often exposed to a high temperature environment at the manufacturing stage, transparency can be maintained because there is no change in appearance over time such as discoloration, coloring, cracking, Further, it is demanded that it can stably exhibit sufficient surface hardness and adhesion.

In addition, there is a color filter in one of major members such as a liquid crystal display device and a solid-state image pickup device. The color filter generally comprises a protective film formed to cover and protect the pixels and the resin black matrix in addition to the substrate, the pixel and the resin black matrix (BM), and to planarize the concavities and convexities thereof. Such a protective film for a color filter as well as a protective film in a touch panel type display device can maintain transparency because there is no change in appearance over time such as discoloration, coloring and cracking even after exposure under a high temperature environment, It is desired to stably exhibit surface hardness and adhesion.

As the conventional curable resin composition for a protective film, for example, a photosensitive thermosetting resin composition for a protective film containing an ethylenically unsaturated compound as a heat crosslinking agent / a compound having an epoxy group in a molecule, a photopolymerization initiator, a specific alkali- (See Patent Document 1). Further, a photocurable composition containing an alkali-soluble resin, fine silica particles, a (meth) acrylate compound having a fluorene skeleton, a (meth) acrylate compound having an alkoxysilane moiety, a photopolymerization initiator, a polyfunctional epoxy compound and an organic solvent (See Patent Document 2).

Japanese Patent Application Laid-Open No. 2007-334290 Japanese Laid-Open Patent Publication No. 2011-039165

As described above, a protective film and an insulating film in various display devices are required to be able to stably exhibit excellent adhesion, transparency, and surface hardness even after exposure to a high temperature environment. In addition, in recent years, along with advances in the technology of display devices and the like, higher performance is strongly demanded for each member to be used. However, the conventional resin composition for a protective film can not sufficiently cope with the demand for high performance, to be. For example, in the resin composition described in Patent Document 1, adhesion, surface hardness, and dispersibility are not sufficient. Therefore, there is room for improvement in this respect, and research for making it possible to exhibit excellent physical properties even after high- There was also room for. In the resin composition described in Patent Document 2, there is room for research to have sufficient adhesion and surface hardness even after high temperature exposure.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-described circumstances, and has an excellent adhesion, dispersibility, developability, It is an object of the present invention to provide a curable resin composition which is capable of maintaining a dispersibility because of no change and capable of imparting a cured product capable of stably exhibiting sufficient surface hardness and adhesion. The present invention also aims to provide a cured film formed from such a curable resin composition, and a display device member and a display device having the cured film.

The inventors of the present invention have conducted various investigations on a curable resin composition useful for a protective film, an insulating film and the like in various display devices. As a result, it has been found that when a composition containing fine silica particles, a coupling agent and an alkali soluble resin is used, Of the cured product. When the curable resin composition contains (1) a polyfunctional (meth) acrylate compound having three or more functional groups and the alkali-soluble resin is an N-substituted maleimide monomer unit and / or a dialkyl- (2) a polymer having a 2 '- (oxydimethylene) diacrylate monomer unit, or (2) a polymer containing a ketone-based solvent and / or an ester- And a ring-shaped zine form, the obtained cured product is excellent in adhesion, dispersibility, photosensitivity, developability and the like, has a sufficient surface hardness, and is excellent in discoloration, coloration and cracking It was found that there is no change in appearance over time and that the dispersibility can be maintained, and the surface hardness and adhesion can be sufficiently obtained.

More specifically, the inventors of the present invention found that the addition of the polymerizable monomer to the composition containing the fine silica particles, the coupling agent and the alkali-soluble resin further improves the photosensitivity and curability of the form of (1) It has been found that there is a difference in hardness properties such as surface hardness and adhesion depending on the type of alkali soluble resin or polymerizable monomer. Thus, when the alkali-soluble resin is a polymer having a specific monomer unit and a polyfunctional (meth) acrylate compound having three or more functional groups is used as the polymerizable monomer, the resulting cured product is excellent in adhesion, dispersibility, Has sufficient surface hardness and has no change in appearance over time such as discoloration, coloring and cracking even after exposure to high temperature, so that the dispersibility can be maintained and sufficient surface hardness and adhesion can be obtained. In particular, the adhesion to a transparent conductive film such as ITO is excellent.

Here, from the viewpoint of suppressing the change with time in appearance of the cured product and improving the adhesion, it is desired to suppress the curing shrinkage. Therefore, the curable resin composition is required to have a crosslinking property such as a trifunctional or more polyfunctional (meth) It is a common practice to avoid the compounding of compounds having high properties. However, the inventors of the present invention have found that by using a curable resin composition having such a constitution that a trifunctional or more polyfunctional (meth) acrylate compound is essential and also contains an alkali-soluble resin having a specific monomer unit, silica fine particles and a coupling agent, (Meth) acrylate compound having a trifunctional or more functional group, the surface hardness of the cured product can be remarkably improved due to the compound, and the high smoothness, high adhesion and high hardness can be achieved I found out.

With respect to the embodiment (2), the present inventors have found that, when an organic solvent is further contained in a composition containing fine silica particles, a coupling agent and an alkali-soluble resin, It has been found that there are differences in the properties of the cured product such as adhesion and the like depending on the kind of the organic solvent used and the kind of the organic solvent used. When the composition contains silica fine particles, an alkali-soluble resin, and a ketone solvent and / or an ester solvent, adhesion of the cured product is improved, and there is still a problem in terms of appearance and physical properties of the cured product after high- When the silane coupling agent is further added to this composition and the silane coupling agent is specified for a compound containing an epoxy group, the resulting cured product has excellent adhesion, dispersibility, photosensitivity, and sufficient surface hardness And that after the exposure at a high temperature, there is no change in appearance over time such as discoloration, coloration, cracking, etc., so that the dispersibility can be maintained and sufficient surface hardness and adhesion can be obtained. In particular, the adhesion to the glass substrate is excellent.

These curable resin compositions are particularly preferable as a protective film or a resin composition for forming an insulating film used in a touch panel type display device, a color filter, etc., and a cured film, a display device member, and a display device formed therefrom The present invention has been accomplished on the basis of being able to find out that it can sufficiently cope with the demand and solve the above problem well.

That is, the present invention relates to a curable resin composition containing fine silica particles, a coupling agent and an alkali-soluble resin, wherein the curable resin composition further contains a trifunctional or more polyfunctional (meth) acrylate compound and the alkali- N-substituted maleimide-based monomer units and / or dialkyl-2,2 '- (oxydimethylene) diacrylate-based monomer units, or additionally a ketone-based solvent and / or an ester- , And the coupling agent is a silane coupling agent containing an epoxy group.

The present invention is also preferably such that the curable resin composition satisfies at least one of the following (a), (b), (c) and (d). Particularly preferred forms are those in which the curable resin composition at least satisfies both of (a) and (b) below, at least one of the following (a) and (c) And (c) are satisfied at least.

(a) the curable resin composition further contains an amino ketone polymerization initiator and a phenol-based antioxidant.

(b) the curable resin composition further contains an amino ketone polymerization initiator and the content of the amino ketone polymerization initiator is 10 to 35 parts by mass based on 100 parts by mass of the total solid content of the curable resin composition.

(c) the curable resin composition further contains a fluorine-based additive, and the content of the fluorine-based additive is 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the solid content of the curable resin composition.

(d) The curable resin composition further contains at least two polymerization initiators selected from the group consisting of an amino ketone polymerization initiator, a hydro ketone polymerization initiator and a benzyl ketal polymerization initiator.

The present invention is also a cured film formed by the curable resin composition.

The present invention is also a member for a display device having the cured film.

The present invention is also a display device having the cured film.

Hereinafter, the present invention will be described in detail. Further, two or three or more combinations of the respective preferred embodiments of the present invention described below are also preferable forms of the present invention.

The curable resin composition of the present invention is a curable resin composition comprising (1) silica fine particles, a coupling agent, an alkali-soluble resin, and a polyfunctional (meth) acrylate compound having three or more functional groups and the alkali- Or a polymer having a dialkyl-2,2 '- (oxydimethylene) diacrylate monomer unit (this type of curable resin composition is also referred to as "curable resin composition (1)"), or (2) (The curable resin composition of this type is referred to as a " curable resin composition (hereinafter referred to as " curable resin composition ") which is a silane coupling agent containing a fine particle, a coupling agent, an alkali-soluble resin, and a ketone solvent and / or an ester solvent and whose coupling agent contains an epoxy group 2) "). ≪ / RTI > It is also possible to satisfy both of (1) and (2).

In the present specification, the "total solid content" means the total amount of the fine silica particles, the coupling agent, the alkali-soluble resin and the polymerizable monomer. For example, the total solid content of the curable resin composition (1) means the total amount of the polymerizable monomer (1) when the fine particles of silica, the coupling agent, the alkali soluble resin, the polyfunctional acrylate having three or more functions, . The total solid content of the curable resin composition (2) means the total amount of the polymerizable monomer in the case of containing the fine silica particles, the coupling agent and the alkali-soluble resin, and further the polymerizable monomer.

[Curable resin composition (1)]

First, the curable resin composition (1) will be described below.

The curable resin composition (1) of the present invention contains fine silica particles, a coupling agent, an alkali-soluble resin, and a polyfunctional (meth) acrylate compound having three or more functional groups. These components may be used alone or in combination of two or more . In addition, if necessary, one or more other components may be further contained.

≪ Silica fine particles &

The silica fine particles are not particularly limited as long as they are metal oxides having a silicon atom, but may be composite metal oxides containing further metal atoms in addition to silicon atoms. The average particle diameter of the fine silica particles is preferably 1 to 500 nm, for example. Within this range, the dispersibility and dispersion stability of the silica fine particles become sufficient, and it becomes possible to impart a cured product having better dispersibility and further suppressing the change over time. More preferably 1 to 300 nm, further preferably 1 to 200 nm, and particularly preferably 1 to 100 nm.

The average particle diameter can be measured using, for example, a laser diffraction particle size distribution meter.

The fine silica particles may be in the form of a dried powder or may be in the form of a dispersion (colloidal silica or the like) dispersed in an organic solvent. However, from the viewpoint of dispersion stability of the curable resin composition, dispersion It is preferable to use a sphere-shaped body. That is, the fine silica particles are preferably contained in the curable resin composition as an organic solvent dispersion.

Examples of the organic solvent (dispersion medium) used in the formation of the dispersion include an alcohol solvent, an amide solvent, xylene, toluene and the like in addition to a ketone solvent, an ester solvent and an ether solvent , And one or more of these may be used. Among them, it is preferable to use a ketone solvent, an ester solvent and / or an ether solvent. It is more preferable to use a ketone solvent and / or an ester solvent so that the dispersibility can be maintained without changing the appearance over time such as discoloration, coloration and cracking even after exposure at a high temperature, It is possible to further exhibit the effect of the present invention that a cured product having adhesion can be obtained. As such, the form in which the fine silica particles are dispersed in a ketone solvent and / or an ester solvent is also one of the preferred forms of the present invention.

Examples of the ketone-based solvent include methyl ethyl ketone, methyl isobutyl ketone, and the like.

As the ester solvent, ethyl acetate, butyl acetate, and the like are preferable.

The ether solvent includes, for example, acetylates of m alkylene glycol n alkyl ethers (m and n are the same or different and are one or more multiples of the prefix represented by mono, di, tri, tetra, etc.) . m alkylene glycol n alkyl ether include, for example, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and the like, and ethers having a terminal hydroxyl group such as alkylene glycol n alkyl ether itself That is, alcohols having an ether bond) have an ability as an alcohol-based solvent due to the terminal hydroxyl group thereof, and thus are not ether-based solvents but alcohol-based solvents.

Examples of the alcohol solvent include alcohols having a terminal hydroxyl group (alcohols having an ether bond), such as methanol, isopropanol, ethylene glycol, butanol and the like, as well as the above alkylene glycol n alkyl ether .

When a dispersion comprising the fine silica particles dispersed in an organic solvent is used, the amount of the organic solvent (dispersion medium) is preferably such that the fine silica particles can be sufficiently dispersed. That is, it is preferable to control the amount of the organic solvent so that the content of the silica fine particles in the curable resin composition falls within the above-mentioned preferable range, and the fine silica particles are sufficiently dispersed. For example, it is preferable that the total amount of the organic solvent as the dispersion medium is 50 parts by mass or more based on 100 parts by mass of the silica fine particles. More preferably 70 parts by mass or more, and even more preferably 100 parts by mass or more. If the amount of the solvent is excessively larger than necessary, there is a possibility that the curing treatment can not be carried out easily, so that it is preferably 600 parts by mass or less. More preferably 550 parts by mass or less, and even more preferably 500 parts by mass or less.

The organic solvent dispersion can be obtained by sufficiently dispersing the silica fine particles in the above-mentioned organic solvent, but a commercially available product may also be used. MEK-ST-ZL, MEK-ST-UP, MEK-AC-2101, MEK-AC-4101, MEK-EC-2104 and MEK-ST-L are commercially available products. -2202, MEK-AC-5101, and the like; Organosilica sol containing methyl isobutyl ketone such as MIBK-ST, MIBK-SD and MIBK-SD-L as a dispersion medium; Organosilica sol containing ethyl acetate as a dispersion medium such as EAC-ST; Organosilica sol containing a butyl acetate such as NBAC-ST as a dispersion medium; Organosilica sol containing methanol as a dispersion medium, such as methanol silica sol and MA-ST-M; Organosilica sol containing isopropanol such as IPA-ST and IPA-ST-L as a dispersion medium; Organosilica sol containing ethylene glycol as a dispersion medium such as EG-ST; Organosilica sol containing xylene / n-butanol such as XBA-ST as a dispersion medium; Organosilica sol containing an alkylene glycol monoalkyl ether such as NPC-ST-30 or PGM-ST as a dispersion medium; Organosilica sol containing dimethylacetamide such as DMAC-ST as a dispersion medium; And organosilica sol containing toluene such as TOL-ST as a dispersion medium (all manufactured by Nissan Chemical Industries, Ltd.).

In the curable resin composition (1), the content of the fine silica particles is preferably 5% by mass or more, based on 100% by mass of the total solid content of the curable resin composition (1). Thereby, the surface hardness of the cured product becomes more sufficient. More preferably not less than 10% by mass, still more preferably not less than 15% by mass, and particularly preferably not less than 20% by mass. Further, from the viewpoints of developability and dispersion stability, it is preferably 70 mass% or less. More preferably 60 mass% or less, further preferably 50 mass% or less, particularly preferably 45 mass% or less.

Further, in the present invention, since the polyfunctional (meth) acrylate compound having three or more functionalities is contained, it is expected that the curing shrinkage is usually large. In such a case, it is conceivable to increase the content of the fine silica particles to reduce the curing shrinkage. In the present invention, the curable resin composition has the above-mentioned constitution, and the content of the fine silica particles is lowered by the above- The cured shrinkage is alleviated, and a cured film having high hardness and high smoothness can be obtained. Therefore, it is possible to sufficiently avoid the deterioration of developability, which is expected in the case of containing a large amount of silica fine particles.

<Coupling agent>

The coupling agent has a property of being bonded to an oxidized surface of an inorganic substance by a hydrolysis reaction or a condensation reaction. In the present invention, by using this property, adhesion to, for example, a substrate on which ITO or the like is deposited is sufficiently exhibited . Specific examples of such coupling agents include coupling agents having reactive groups such as vinyl group, (meth) acryl group, epoxy group, amino group, mercapto group and isocyanato group. Among them, those having a vinyl group, a (meth) acryloyl group and / or an epoxy group are preferable as a reactive group. The center metal preferably contains, for example, silicon, zirconia, titanium and / or aluminum, and among these, it is preferable to have silicon as a center metal, more preferably a silane coupling agent. By using the silane coupling agent, the dispersibility, adhesion and surface hardness of the cured product can be made more sufficient. Examples of the coupling agent having a metal other than silicon as a central metal include a zirconylate coupling agent and a titanate coupling agent.

As the silane coupling agent, an alkoxysilane group (-Si (OR ¹ ) _3-n (R ² ) _n ; OR ¹ represents a hydrolyzable group and at least one of R ¹ R ² is a hydrocarbon group, and n is 0, 1 or 2, is preferable. Among them, it is preferable to use a silane coupling agent having a vinyl group, a (meth) acryloyl group and / or an epoxy group, so that there is no change in appearance over time such as discoloration, And a cured product having more sufficient surface hardness and adhesion can be obtained.

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

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

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

Examples of the silane coupling agent having an amino group include N-phenyl-3-aminopropyltrimethoxysilane and the like.

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

Examples of the silane coupling agent having an isocyanato group include 3-isocyanatepropyltriethoxysilane and the like.

In the curable resin composition (1), 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 (1). By containing not less than 3% by mass, even after high temperature exposure, it is possible to have more sufficient adhesion and surface hardness. More preferably not less than 4% by mass, and further preferably not less than 5% by mass. From the viewpoint of storage stability and the like of the curable resin composition, it is preferably 30 mass% or less. More preferably 25 mass% or less, and further preferably 20 mass% or less.

<Alkali-soluble resin>

The alkali-soluble resin is a polymer having alkali solubility and having an N-substituted maleimide monomer unit and / or a dialkyl-2,2 '- (oxydimethylene) diacrylate monomer unit (hereinafter, Quot;). This makes it possible to impart a cured film excellent in heat resistance, dispersibility of coloring material, hardness and the like as well as the curable resin composition having developability.

The alkali-soluble resin (specific polymer) is also preferably a polymer having an acid group in the molecule. In this case, the acid value (AV) of the specific polymer 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 can be expressed, and a cured product having more excellent developing properties can be obtained. The lower limit of the acid value is more preferably 30 mgKOH / g or more, and still more preferably 40 mgKOH / g or more. It is more preferably 250 mgKOH / g or less, and still more preferably 200 mgKOH / g or less.

The acid value of the polymer is measured by measuring the acid value of the polymer solution with an automatic titration apparatus (trade name: "COM-555", manufactured by Hiranuma Industrial Co., Ltd.) using, for example, a KOH aqueous solution of 0.1 N as a titration solution, And the acid value per solid fraction from the solid content of the solution. The solid content of the polymer solution can be determined as follows.

Approximately 0.3 g of the polymer solution is weighed into an aluminum cup, and about 1 g of acetone is added to dissolve the solution, followed by natural drying at room temperature. After drying at 140 DEG C for 3 hours using a hot-air drier (product name: PHH-101, manufactured by Especa), it is cooled in a desiccator and its mass is measured. The solid content concentration of the polymer solution is calculated from the mass reduction amount.

The specific polymer preferably has a weight average molecular weight of 2000 to 250,000. When the molecular weight is in this range, it is possible to exhibit better developability. More preferably from 3,000 to 100,000, and still more preferably from 4,000 to 50,000. In addition, when the alkali-soluble resin has a high molecular weight, the resin having a higher acid value tends to be developed.

The weight average molecular weight can be measured by GPC (gel permeation chromatography) using HLC-8220 GPC (manufactured by Tosoh Corporation) and column TSKgel SuperHZM-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent ) Method.

The specific polymer has an N-substituted maleimide-based monomer unit and / or a dialkyl-2,2 '- (oxydimethylene) diacrylate-based monomer unit, and it is preferable that the specific polymer further has an acid group as described above. Among them, it is preferable to use a copolymer obtained by polymerizing an N-substituted maleimide-based monomer and / or a dialkyl-2,2 '- (oxydimethylene) diacrylate-based monomer and a monomer component containing an acid group and a monomer having a polymerizable double bond (Hereinafter also referred to as &quot; specific polymer base polymer &quot;) and a polymer obtained by reacting the specific polymer base polymer with a compound having a functional group capable of bonding to the acid group and a polymerizable double bond, Bond-containing polymer). More preferably, it is the latter side chain double bond-containing polymer. Each of the monomers to be used may be used alone or in combination of two or more.

Examples of the N-substituted maleimide monomer in the monomer component include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butyl maleimide, N-dodecyl maleimide, N-benzyl maleimide and N-naphthyl maleimide. One or more of these may be used. Of these, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable in view of low coloration and excellent coloring material dispersibility.

Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimides such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; substituted phenol-substituted benzylmaleimides such as p-hydroxybenzylmaleimide; halogen-substituted benzylmaleimides such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide.

As the dialkyl-2,2 '- (oxydimethylene) diacrylate monomer, from the viewpoints of low coloration, dispersibility, easiness in industrial availability, etc., for example, dimethyl- - [oxybis (methylene)] bis-2-propenoate, and the like.

The content ratio of the N-substituted maleimide-based monomer and / or dialkyl-2,2 '- (oxydimethylene) diacrylate-based monomer (in the case of using two kinds thereof) is, Is preferably 1% by mass or more, more preferably 30% by mass or less, based on 100% by mass of the specific polymer base polymer. Within this range, it becomes possible to obtain a cured film having improved heat resistance, dispersibility of coloring material, hardness, and the like. Also, if the content ratio of the N-substituted maleimide-based monomer is excessively large, the developing speed may not be more appropriate. More preferably from 2 to 25% by mass, and still more preferably from 3 to 20% by mass.

Further, if the addition amount of the N-substituted maleimide-based monomer is further increased, a cured product superior in hardness can be obtained. Further, by using a dialkyl-2,2 '- (oxydimethylene) diacrylate monomer, a cured product superior in heat resistance coloring property can be obtained.

In the acid group and the monomer having a polymerizable double bond, examples of the acid group include functional groups that are subjected to a neutralization reaction with an alkaline number such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group and a sulfonic acid group, They may have only one kind or two kinds or more of them. Among them, a carboxyl group and a carboxylic acid anhydride group are preferable, and a carboxyl group is more preferable.

Specific examples of the monomer having an acid group and a polymerizable double bond include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; Unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; Unsaturated monocarboxylic acids in which an unsaturated group such as succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryloyloxyethyl) and a carboxyl group is extended in chain; Unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; And a phosphoric acid group-containing unsaturated compound such as Light Ester P-1M (manufactured by Kyowa Chemical Co., Ltd.). Among them, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. More preferably, it is preferable to use unsaturated monocarboxylic acids from the viewpoints of reactivity and alkali solubility, more preferably (meth) acrylic acid (i.e., acrylic acid and methacrylic acid) Is methacrylic acid.

The content of the acid group and the monomer having a polymerizable double bond is preferably 5% by mass or more with respect to, for example, 100% by mass of the specific polymer base polymer. As a result, the curing resin composition becomes more soluble in alkali and more useful for applications requiring developability, for example. Further, it is preferably 85% by mass or less from the viewpoint of maintaining excellent appearance and adhesion of the cured product even after high-temperature exposure. More preferably from 10 to 80% by mass, and still more preferably from 15 to 75% by mass.

The monomer component may further contain another monomer. As other monomers, for example, one or two or more of (meth) acrylate-based monomers and aromatic vinyl-based monomers are preferably used.

Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i- (Meth) acrylate, t-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylate, (Meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isobutyl (meth) acrylate, isobutyl (Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, 2-ethoxyethyl acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (Meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethylacrylate, 4-dioxaspiro [4,5] dec-2-yl methacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl- (Meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxy Methyl-2-cyclohexyl-1,3-dioxolane, and 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane. MIBDOL 10, MIBDOL 10, CHDOL 10, Viscot 150, Viscot 160 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (commercially available from Osaka Organic Chemical Industry Co., Ltd.) , ACMO (manufactured by Kojin), and the like. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate and benzyl (meth) acrylate are preferable from the viewpoint of excellent heat resistance. More preferably, methyl (meth) acrylate, benzyl (meth) acrylate and / or cyclohexyl (meth) acrylate are used because they are excellent in heat resistance, adhesion and developability.

As the (meth) acrylate-based monomer, it is also preferable to use? - (unsaturated alkoxyalkyl) acrylate.

Examples of the α- (unsaturated alkoxyalkyl) acrylate include α-allyloxymethylacrylic acid, α-allyloxymethylacrylic acid methyl, α-allyloxymethyl acrylate, α-allyloxymethylacrylic acid n- Allyloxymethyl acrylate, n-butyl allyloxymethyl acrylate, n-butyl allyloxymethyl acrylate, s-butyl allyloxymethyl acrylate, t-butyl allyloxymethylacrylate, n-amyl allyloxymethyl acrylate, Amyl, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethylacrylate, n-hexyl α-allyloxymethylacrylate, s-hexyl α-allyloxymethylacrylate, α- N-heptyl allyloxymethylacrylate, n-octyl alpha -allyloxymethyl acrylate, s-octyl alpha -allyloxymethylacrylate, t-octyl alpha -allyloxymethylacrylate, 2-ethylhexyl alpha -allyloxymethylacrylate, - caprylyl allyloxymethylacrylate, nonyl allyloxymethyl acrylate,? -Allyloxy Allyloxymethylacrylic acid decyl, α-allyloxymethylacrylic acid undecyl, α-allyloxymethylacrylic acid lauryl, α-allyloxymethylacrylic acid tridecyl, α-allyloxymethylacrylic acid myristyl, α-allyloxymethylacrylic acid pentadecyl, α Allyloxymethylacrylic acid octyl,? -Allyloxymethylacrylic acid esters,? -Allyloxymethylacrylic acid esters,? -Allyloxymethylacrylic acid esters, (Allyloxymethyl) acrylate having a chain-like saturated hydrocarbon group such as seryl, α-allyloxymethylacrylic acid mellisil and the like are preferable. Among them, methyl α-allyloxymethyl acrylate (also referred to as "α- (allyloxymethyl) methyl acrylate") is particularly preferable.

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

Further, it is preferable that the monomer component used for obtaining the specific polymer base polymer is a copolymer of a monomer constituted by a group consisting of methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate and α- (unsaturated alkoxyalkyl) The form containing at least one (meth) acrylate monomer selected is also one of the preferred forms of the present invention.

Examples of the aromatic vinyl-based monomer include styrene, vinyltoluene,? -Methylstyrene, methoxystyrene, and the like. Among them, styrene and vinyltoluene are preferable from the viewpoints of heat resistance and decomposition resistance of the resin.

The content ratio of the (meth) acrylic ester monomer and / or the aromatic vinyl monomer (when the two kinds are used, the total content thereof) is, for example, 1 to 80 % By mass. Within this range, a cured product having superior heat resistant coloring property, coloring material dispersibility, and alkali solubility can be obtained. More preferably from 5 to 75% by mass, and still more preferably from 10 to 70% by mass.

As the other monomer, for example, one or more of the following compounds may be used, and the content thereof is preferably 20 mass% or less in 100 mass% of the specific polymer base polymer .

(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; Macromonomers having a (meth) acryloyl group at one terminal of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone and polycaprolactam; Conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, , Methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine and N-vinylacetamide; Unsaturated isocyanates such as isocyanatoethyl (meth) acrylate, allyl isocyanate, and the like.

As a method of polymerizing the monomer component, a conventionally used method such as bulk polymerization, solution polymerization, emulsion polymerization and the like can be used, and it may be appropriately selected according to the purpose and use. Among them, solution polymerization is industrially advantageous and structural adjustment such as molecular weight is easy, which is preferable. The polymerization mechanism for the monomer component may be a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cation polymerization, or coordination polymerization, but the polymerization method based on a radical polymerization mechanism is industrially advantageous desirable.

The polymerization initiating method in the polymerization reaction can be carried out by supplying energy required for initiation of polymerization from an active energy source such as heat or electromagnetic wave (infrared ray, ultraviolet ray, X-ray, etc.) or electron beam to the monomer component, The energy required for initiating the polymerization can be greatly lowered and the reaction control becomes easy, which is preferable. The molecular weight of the polymer obtained by polymerizing the monomer components can be controlled by controlling the amount and type of the polymerization initiator, the polymerization temperature, the kind and amount of the chain transfer agent, and the like.

When the monomer component is polymerized by the solution polymerization method, the solvent used in the polymerization is not particularly limited as long as it is inert to the polymerization reaction. The polymerization mechanism, the kind and amount of the monomer to be used, the polymerization temperature, . When a solvent is used as a diluent or the like in a later-described curable resin composition, it is preferable to use a solvent containing the solvent for solution polymerization of the monomer component.

As the solvent, for example, the following compounds are preferably used, and one or more of them may be used.

Monohydric alcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; Glycols such as ethylene glycol and propylene glycol; Cyclic ethers such as tetrahydrofuran and dioxane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol monoethers such as propylene glycol monobutyl ether and 3-methoxybutanol; A glycol such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether and the like Ethers; Ethylene glycol monomethyl ether acetate, 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 A glycol monoacetate such as acetone, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, Esters of ethers; Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3- Methyl esters such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate and ethyl acetoacetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Aliphatic hydrocarbons such as hexane, cyclohexane, and octane; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate are preferable because of solubility of the obtained polymer, surface smoothness upon formation of a coating film, Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and ethyl lactate are more preferably used.

The amount of the solvent to be used is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the specific polymer base polymer. More preferably, it is 100 to 500 parts by mass.

When the monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy, and may be appropriately selected depending on the polymerization conditions such as the polymerization temperature, the solvent, and the kind of the monomer to be polymerized. In addition, a reducing agent such as a transition metal salt or an amine may be used together with the polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t Azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and the like. , Peroxides and azo compounds which are conventionally used as polymerization initiators such as dimethyl 2,2'-azobis (2-methylpropionate), hydrogen peroxide and persulfate, etc. These may be used alone or in combination of two kinds Or more may be used in combination.

The amount of the polymerization initiator to be used may be suitably set according to the kind and amount of the monomer to be used, the polymerization conditions such as the polymerization temperature and the polymerization concentration, the molecular weight of the target polymer, and the like, and is not particularly limited. For example, in order to obtain a polymer having a weight average molecular weight of several thousands to several tens of thousands, it is preferable that the amount is 0.1 to 20 parts by mass relative to 100 parts by mass of the specific polymer base polymer. More preferably 0.5 to 15 parts by mass.

In the polymerization, a chain transfer agent conventionally used may also be used if necessary. Preferably, the polymerization initiator and the chain transfer agent are used in combination. Further, when a chain transfer agent is used at the time of polymerization, there is a tendency that increase in the molecular weight distribution and gelation can be suppressed.

Examples of the chain transfer agent include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; Methyl mercaptopropionate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, Mercaptocarboxylic acid esters such as propane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) Ryu; Alkyl mercaptans such as ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, and 1,2-dimercaptoethane; Mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; Aromatic mercaptans such as benzene thiol, m-toluene thiol, p-toluene thiol, and 2-naphthalene thiol; Mercaptoisocyanurates such as tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate; Disulfides such as 2-hydroxyethyl disulfide and tetraethyl thiuram disulfide; Dithiocarbamates such as benzyldiethyldithiocarbamate; monomer dimers such as? -methylstyrene dimer; And halogenated alkyls such as carbon tetrabromide and the like. These may be used alone or in combination of two or more.

Among these, from the viewpoints of availability, crosslinking inhibition ability, and degree of decrease in the polymerization rate, it is preferable to use at least one selected from the group consisting of mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkylmercaptans, mercaptoalcohols, It is preferable to use a compound having a mercapto group such as a mercury group, a mercury group, a mercury group or a mercaptoisocyanurate. More preferred are alkyl mercaptans, mercaptocarboxylic acids and mercaptocarboxylic acid esters, more preferably n-dodecyl mercaptan and mercaptopropionic acid.

The amount of the chain transfer agent to be used is not particularly limited and may be suitably set according to the kind and amount of the monomer to be used, the polymerization conditions such as the polymerization temperature and the polymerization concentration, the molecular weight of the target polymer, It is preferable that the content of the polymer is 0.1 to 20 parts by mass based on 100 parts by mass of the specific polymer base polymer. More preferably 0.5 to 15 parts by mass.

With respect to the conditions for the polymerization, the polymerization temperature may be suitably set according to the kind and amount of the monomers to be used, the kind and amount of the polymerization initiator, and the like, for example, preferably from 50 to 150 ° C, desirable. The polymerization time can also be suitably set, for example, preferably from 1 to 5 hours, more preferably from 2 to 4 hours.

The specific polymer preferably also has a double bond in the side chain. Specifically, a polymer (also referred to as a side chain double bond-containing polymer) obtained by reacting a polymer (specific polymer base polymer) obtained by polymerizing the monomer component with a compound having a functional group capable of bonding to the acid group and a polymerizable double bond, .

Examples of the polymerizable double bond in the compound having a functional group capable of bonding with the acid group and a polymerizable double bond include a (meth) acryloyl group, a vinyl group, an allyl group and a methallyl group, As the compound, it is preferable to have one or more of these compounds. Among them, in terms of reactivity, a (meth) acryloyl group is preferable. Examples of the functional group capable of bonding to the acid group include a hydroxyl group, an epoxy group, an oxetanyl group, and an isocyanate group, and it is preferable that the compound has one or more of these compounds . Among them, an epoxy group (including a glycidyl group) is preferable in terms of the rate of denaturation reaction, heat resistance, and dispersibility.

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

As a method for obtaining the above-mentioned side chain double bond-containing polymer, for example, when a specific polymer base polymer is reacted with a compound having a functional group capable of bonding to the acid group and a polymerizable double bond, An amount of an acid group (preferably a carboxyl group) is made excess in excess of the amount of a compound having a functional group and a polymerizable double bond capable of bonding to the acid group; A method of reacting the above specific polymer base polymer with a compound having a functional group capable of binding an acid group and a polymerizable double bond and then further reacting a compound having a polybasic acid anhydride group.

The step of reacting the specific polymer base polymer (preferably a polymer having a carboxyl group) with a compound having a functional group capable of bonding to the acid group and a compound having a polymerizable double bond is preferably carried out in order to ensure a favorable reaction rate and to prevent gelation , And 50 to 160 캜. More preferably 70 to 140 占 폚, and still more preferably 90 to 130 占 폚. In addition, in order to improve the reaction rate, an esterification or transesterification basic catalyst or an acid catalyst commonly used as a catalyst may be used. Among them, since a side reaction is reduced, it is preferable to use a basic catalyst.

Examples of the basic catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tri-n-octylamine and tetramethylethylenediamine; Quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide and n-dodecyltrimethylammonium chloride; Urea compounds such as tetramethylurea; Alkyl guanidines such as tetramethyl guanidine; Amide compounds such as dimethylformamide and dimethylacetamide; Tertiary phosphines such as triphenylphosphine and tributylphosphine; And quaternary phosphonium salts such as tetraphenylphosphonium bromide and benzyltriphenylphosphonium bromide. One or more of these may be used. Among them, dimethylbenzylamine, triethylamine, tetramethylurea and triphenylphosphine are preferable in view of reactivity, handleability and halogen-free.

The amount of the catalyst to be used is preferably 0.01 to 5.0 parts by mass per 100 parts by mass of the total amount of the specific polymer base polymer and the compound having a functional group capable of bonding to the acid group and a polymerizable double bond group. More preferably 0.1 to 3.0 parts by mass.

The step of reacting the specific polymer base polymer with a compound having a functional group capable of bonding to the acid group and a compound having a polymerizable double bond may also be carried out by adding a polymerization inhibitor in order to prevent gelation, . As the molecular oxygen-containing gas, air or oxygen gas diluted with an inert gas such as nitrogen is usually used and injected into the reaction vessel.

As the polymerization inhibitor, conventionally used polymerization inhibitors for radical polymerizable monomers can be used. For example, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, methoquinone, 6- di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis -6-t-butylphenol), organic acid copper salts and phenothiazine. One or more of these can be used. Among them, phenol-based inhibitors are preferable from the viewpoint of low coloration and polymerization inhibition ability, and from the viewpoint of availability and economy, 2,2'-methylenebis (4-methyl-6-t- butylphenol), methoquinone , 6-t-butyl-2,4-xylenol and 2,6-di-t-butylphenol are more preferable.

The amount of the polymerization inhibitor to be used is not particularly limited as long as it has sufficient polymerization inhibiting effect and curability when it is used as a curable resin composition and the specific polymer base polymer is a polymer having a functional group capable of bonding with an acid group and a polymerizable double bond Is preferably 0.001 to 1.0 part by mass based on 100 parts by mass of the total amount of the compound. More preferably 0.01 to 0.5 parts by mass.

Examples of the compound having a polybasic acid anhydride group include, for example, succinic anhydride, dodecenylsuccinic acid, pentadecenylsuccinic acid, octadecenylsuccinic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride , Maleic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, anhydroglutaric acid, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. One or more of these may be used.

The side chain double bond-containing polymer preferably has a double bond equivalent of 200 to 10,000. It is expected that satisfactory storage stability of the polymer and satisfactory plate making (plate-making) characteristics in the sensitivity, pattern shape, etc. of the curable resin composition of the present invention can be achieved at a higher level by setting to such a range. More preferably 250 or more, further preferably 300 or more, particularly preferably 350 or more, most preferably 400 or more, still more preferably 5000 or less, still more preferably 4000 or less, particularly preferably 3000 Or less.

The double bond equivalent is the mass of the solid content of the polymer solution per 1 mol of the double bond of the polymer. Here, the mass of the solid content of the polymer solution means the mass of the specific polymer base polymer, the mass of the compound having a functional group capable of bonding to the acid group and the polymerizable double bond group, and the mass of the chain transfer agent. 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 added acid group and the amount of the compound having a functional group capable of bonding and a polymerizable double bond.

The content of the alkali-soluble resin in the curable resin composition (1) is preferably 5% by mass or more, more preferably 70% by mass or less, based on 100% by mass of the total solid content of the curable resin composition (1) . Within this range, the effects of the present invention can be more remarkably exhibited. More preferably 10 to 65% by mass, still more preferably 15 to 60% by mass, and particularly preferably 15 to 50% by mass.

<Polyfunctional (meth) acrylate compound having three or more functional groups>

The trifunctional or higher polyfunctional (meth) acrylate compound (hereinafter, simply referred to as "polyfunctional (meth) acrylate compound") is a compound having three or more (meth) acryloyl groups in one molecule. By containing such a compound, the curable resin composition becomes excellent in photosensitivity and curability, and a cured film having extremely high hardness can be obtained. The number of functional groups of the polyfunctional (meth) acrylate compound is preferably 4 or more, and more preferably 5 or more. From the viewpoint of further suppressing the curing shrinkage, the number of functional groups is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less.

Further, the (meth) acryloyl group means a methacryloyl group and / or an acryloyl group, and an acryloyl group is preferable in view of better reactivity. That is, the polyfunctional (meth) acrylate compound is particularly preferably a polyfunctional acrylate compound having three or more acryloyl groups.

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

Examples of the trifunctional or higher polyfunctional (meth) acrylate compound include, but are not limited to, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (Meth) acrylate, ethylene oxide added trimethylol propane tri (meth) acrylate, ethylene oxide added ditrimethylol propane tetra (meth) acrylate, ethylene oxide addition pentaerythritol tetra (Meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, (Meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra Acrylate,? -Caprolactone-added trimethylolpropane tri (meth) acrylate,? -Caprolactone added ditrimethylolpropane tetra (meth) acrylate,? -Caprolactone-added pentaerythritol tetra ε-caprolactone added dipentaerythritol hexa (meth) acrylate, and the like.

The content of the polyfunctional (meth) acrylate compound is not particularly limited. For example, the content of the polyfunctional (meth) acrylate compound is preferably 5% by mass or less based on 100% by mass of the total solid content of the curable resin composition (1) By mass or more, more preferably 60% by mass or less. More preferably from 8 to 50% by mass, and still more preferably from 10 to 40% by mass.

<Other Ingredients>

- Photopolymerization initiator -

It is preferable that the curable resin composition further contains a photopolymerization initiator. The photopolymerization initiator is preferably a radical polymerizable photopolymerization initiator. The radical polymerizable photopolymerization initiator is one which generates polymerization initiating radicals by irradiation of active energy rays such as electromagnetic waves and electron beams, and one or two or more commonly used ones can be used. If necessary, one or more photo sensitizers or photo radical polymerization accelerators may be used in combination. By using a photosensitizer and / or a photo radical polymerization accelerator together with the photo polymerization initiator, sensitivity and curability are further improved.

Specific examples of the photopolymerization initiator include the following compounds.

Hydroxy-2-methyl-1-phenylpropan-1-one, 1, 2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, Hydroxy-1- {4- [4- (2-hydroxy-2-hydroxy- Benzyl] -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) (Dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) Phenyl] -1-butanone;

Benzophenone compounds such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 2-carboxybenzophenone;

Benzoin-based compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;

A thioxanthone system such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone and 2,4- Compound;

(Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s- Bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis Halomethylated triazine compounds such as trichloromethyl) -s-triazine;

(2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ A halomethylated oxadiazole-based compound such as 4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;

Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) Imidazole-based compounds such as tetraphenyl-1,2'-biimidazole;

Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbaldehyde, 1- Oxazol-3-yl] -, 1- (O-acetyloxime);

Titanocene compounds such as bis (? 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium;

benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid;

Acridine-based compounds such as 9-phenylacridine;

Benzyl ketone such as 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651, BASF), phenylglyoxylic acid methyl ester (DAROCUR MBF, Debulking compound;

Methyl-1-phenyl-propan-1-one (&quot; DAROCUR 1173 &quot;, product of BASF), 1 -hydroxy-cyclohexyl- Hydroxy-2-methyl-1-propan-1-one ("IRGACURE 2959", BASF), 2-hydroxy- 1-one ("IRGACURE 127", manufactured by BASF), [1-methyl-2- -Hydroxy-cyclohexyl-phenyl-ketone + benzophenone] ("IRGACURE 500", manufactured by BASF);

(2,4,6-trimethylbenzoyl) -phenylphosphine oxide (&quot; IRGACURE 819 &quot;, manufactured by BASF), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide Phosphine oxide-based compounds;

(IRGACURE 907, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-methoxyphenyl) -Morpholinophenyl) -butanone-1 ("IRGACURE 369" from BASF), 2-dimethylamino-2- (4-methyl- ) -Butan-1-one ("IRGACURE 379", manufactured by BASF);

Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium ("IRGACURE 784" A titanocene-based compound such as &lt; RTI ID = 0.0 &gt;

Oxime ester compounds such as 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] ("IRGACURE OXE01", BASF)

Among the above photopolymerization initiators, it is particularly preferable to use at least an amino ketone compound (also referred to as an amino ketone polymerization initiator). That is, it is preferable that the curable resin composition (1) further contains an amino ketone polymerization initiator. As a result, the hardness and developability are more excellent. It is also preferable to use a hydroketone-based compound (also referred to as a hydroketone-based polymerization initiator) or a benzylketal-based compound (also referred to as a benzylketal-based polymerization initiator).

Examples of the photosensitizer or photoradical polymerization accelerator that may be used in combination with the photopolymerization initiator include a pigment compound such as a xanthine dye, a coumarin dye, a 3-ketocmarine compound, a pyromethene dye, or the like; Dialkylaminobenzene-based compounds such as ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate; Mercapto-based hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole.

The content of the photopolymerization initiator may be suitably set according to the purpose, use, and the like, and is not particularly limited, but is preferably 2 parts by mass or more based on 100 parts by mass of the total solid content of the curable resin composition (1). As a result, a cured product having more excellent adhesion can be obtained, and the peeling can be sufficiently suppressed even after the high temperature exposure. In view of the balance between the effect of the decomposition product of the photopolymerization initiator and the economic efficiency, it is preferably 35 parts by mass or less. More preferably 30 parts by mass or less, and still more preferably 25 parts by mass or less.

The content (total amount) of the photosensitizer and the photo-radical polymerization accelerator is not particularly limited and may be suitably set according to the purpose and use, but from the viewpoint of the balance between the curing property, Is preferably 0.001 to 20 parts by mass based on 100 parts by mass of the total solid content of the curable resin composition (1). More preferably from 0.01 to 15 parts by mass, and still more preferably from 0.05 to 10 parts by mass.

-solvent-

The curable resin composition (1) preferably further contains a solvent. The solvent is preferably used as a diluent or the like. Specifically, specifically, viscosity is lowered to improve handling properties; A coating film is formed by drying; Be a dispersion medium of a coloring material; , And is an organic solvent or water having a low viscosity capable of dissolving or dispersing each component contained in the curable resin composition.

As the above-mentioned solvent, those which are conventionally used can be used, and they are appropriately selected depending on the purpose and use, and are not particularly limited, and examples thereof include the following compounds. These may be used alone or in combination of two or more.

Monohydric alcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; Glycols such as ethylene glycol and propylene glycol; Cyclic ethers such as tetrahydrofuran and dioxane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol monoethers such as propylene glycol monobutyl ether and 3-methoxybutanol; A glycol such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether and the like Ethers; Ethylene glycol monomethyl ether acetate, 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 A glycol monoacetate such as acetone, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, Esters of ethers; Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3- Methyl esters such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate and ethyl acetoacetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Aliphatic hydrocarbons such as hexane, cyclohexane, and octane; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Water and so on.

The amount of the solvent to be used is not particularly limited, but is preferably 10 to 90% by mass based on 100% by mass of the total amount of the curable resin composition of the present invention. More preferably from 20 to 80% by mass.

Other polymeric monomers -

The curable resin composition (1) may further contain a polymerizable monomer other than the polyfunctional (meth) acrylate compound (also referred to as another polymerizable monomer). As the other polymerizable monomer, the radical polymerizable monomer is preferably a radical polymerizable monomer. The radical polymerizable monomer means a radical polymerizable unsaturated group which is polymerized by irradiating active energy rays such as free radicals, electromagnetic waves (infrared rays, ultraviolet rays, X rays) .

As the radically polymerizable monomer, a monofunctional radically polymerizable compound having one radically polymerizable unsaturated group in the molecule and a multifunctional radically polymerizable compound having two or more radically polymerizable compounds (provided that the above multifunctional (meth) acrylate compound ), And one or more of these can be used. Among them, a multifunctional radically polymerizable compound is preferable from the viewpoint of curability. (Meth) acrylates, (meth) acryloyl group-containing isocyanurates and the like are preferably used in view of reactivity, economy, availability and the like Meth) acryloyl group.

The molecular weight of the radically polymerizable monomer is not particularly limited, but from the viewpoint of handling, it is preferably 2000 or less, for example.

The monofunctional radically polymerizable compound is not particularly limited and includes, for example, the above-mentioned (meth) acrylic ester monomers; (Meth) acrylamides; Unsaturated monocarboxylic acids; Unsaturated monocarboxylic acids having a chain extending between an unsaturated group and a carboxyl group; Aromatic vinyl monomers; N-substituted maleimide-based monomer; Conjugated dienes; Vinyl esters; Vinyl ethers; N-vinyl compounds; Unsaturated isocyanates and the like.

The multifunctional radically polymerizable compound is not particularly limited. For example, in addition to the above-described unsaturated polycarboxylic acids and unsaturated acid anhydrides, the following compounds may be mentioned.

Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (Meth) acrylates such as (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate and bisphenol F alkylene oxide di ;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkyl Trimethylolpropane trivinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol penta vinyl ether, dipentaerythritol hexa vinyl ether, ethylene Polyfunctional vinyl ethers such as trimethylolpropane trivinyl ether with oxide addition, ditrimethylolpropane tetravinylether with ethylene oxide addition, pentaerythritol tetravinylether with ethylene oxide and dipentaerythritol hexa vinyl ether with ethylene oxide addition;

(Meth) acrylate, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl- Vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl Containing vinyl ether groups such as p-vinyloxymethylphenylmethyl acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate and 2- (vinyloxyethoxyethoxyethoxy) ethyl Esters;

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexane diol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkyl Trimethylolpropane triallyl ether, glycerine triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaerythritol ether, dipentaerythritol hexaallyl ether, ethylene Polyfunctional allyl ethers such as an addition-numbered trimethylolpropane triallyl ether, an ethylene oxide-added ditrimethylolpropane tetraallyl ether, an ethylene oxide-added pentaerythritol tetraallyl ether, and an ethylene oxide-added dipentaerythritol hexaallyl ether;

(Meth) acrylate; allyl group-containing (meth) acrylate esters such as allyl (meth) acrylate;

(Methacryloyloxyethyl) isocyanurate, alkylene oxide adduct tri (acryloyloxyethyl) isocyanurate, alkylene oxide adduct trie (acryloyloxyethyl) isocyanurate, Polyfunctional (meth) acryloyl group-containing isocyanurates such as methacryloyloxyethyl) isocyanurate; Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate;

(Meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, such as tolylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate, Polyfunctional urethane (meth) acrylates; And polyfunctional aromatic vinyls such as divinylbenzene.

The content of the other polymerizable monomer is preferably 10% by mass or less based on 100% by mass of the total solid content of the curable resin composition (1) in order to sufficiently exhibit the effect derived from the above-mentioned polyfunctional (meth) . , More preferably not more than 5% by mass, further preferably not more than 1% by mass, particularly preferably 0% by mass, that is, substantially no polymerizable monomer other than the polyfunctional (meth) desirable.

- Polymerization inhibitor -

The curable resin composition (1) may also contain one or more polymerization inhibitor from the viewpoint of more appropriately controlling the curing reaction. As the polymerization inhibitor, for example, a compound usually used as an ultraviolet absorber, a light stabilizer (HALS), an antioxidant (including an antioxidant) and the like can be used. Specific examples thereof include the following compounds.

(2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl ) Glycidic acid ester), Tinuvin 460 (2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -Hydroxyphenyltriazine (HPT) based ultraviolet absorber), Tinuvin 479 (all manufactured by BASF), and Adekastab LA-46 (all manufactured by ADEKA) A hydroxyphenyltriazine (HPT) -based ultraviolet absorber;

Tinuvin PS (2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole), Tinuvin 99-2, Tinuvin 384-2, Tinuvin 900 (1-methyl-1-phenylethyl) phenol), Tinuvin 928 (2- (2H-benzotriazol- Phenol), tinuvin 1130 (all manufactured by BASF), adecastab LA-29, adecastab LA-31, adecas Benzotriazole-based ultraviolet absorbers such as Tabla LA-32 and Adecastab LA-36 (all manufactured by ADEKA);

Tinuvin 111FDL, Tinuvin 123, Tinuvin 144 (bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1,1- (Hydroxyphenyl) methyl] butyl malonate), Tinuvin 292 (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6 (Mixture of pentamethyl-4-piperidyl sebacate), Tinuvin 5100 (all from BASF), Adekastab LA-52, Adekastab LA-57, Adekastab LA-63P, Adekastab LA Adekastab LA-82, Adekastab LA-72, Adekastab LA-72, Adekastab LA-72, Adekastab LA-77, Adekastab LA- A light stabilizer (HALS) such as 502XP (all manufactured by ADEKA);

Anthage W-300 (4,4'-butylidene-bis (6-tert-butyl-m-cresol) (4-ethyl-6-tert-butylphenol), Antage W-500 (2,2'-methylene- tert-butyl-m-cresol), Anthese BHT (2,6-di-tert-butyl-p-cresol), Anthese DAH (2,5-di-tert-amylhydroquinone) (Phenol derivatives), ANTIAGE 3LX (phenol derivatives), ANTIAGE W-200 (all manufactured by Kawaguchi Chemical Co., Ltd.), 2,5-di-tert- butyl- Adecastab AO-20, Adecastab AO-30, Adecastab AO-40, Adecastab AO-50, Adecastab AO-60, Adecastab AO-80, Adecastab AO- -330 (all manufactured by ADEKA);

Adecastab PEP-8C, adecastab PEP-36, adecastab HP-10, adecastab 2112, adecastab 2112RG, adecastab 1178, Phosphite-based antioxidants such as Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, and Adekastab TPP (both manufactured by ADEKA);

Thioether-based antioxidants such as adecastab AO-412S and adecastab AO-503 (all manufactured by ADEKA);

(N-isopropyl-N'-phenyl-p-phenylenediamine), Antage 6C (N- (1,3-dimethylbutyl) (Diphenylamine derivative), ANTIAGE LDA (Diphenylamine derivative), ANTIDE OD (Diphenylamine derivative), ANTIAGE DDA (Diphenylamine derivative) 1,2-dihydroquinoline), Anthage AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), Anthage F, Anthage D, Anthage DP , Antideoxy ODPP (all manufactured by Kawaguchi Chemical Industry Co., Ltd.), and the like.

Among the above-mentioned polymerization inhibitors, it is preferable to use at least phenol-based antioxidants. That is, it is also preferable that the curable resin composition (1) further contains a phenol-based antioxidant. This makes it possible to obtain a cured product which can stably exhibit even more excellent transparency, hardness and developability even after being exposed in a high temperature environment.

The content of the polymerization inhibitor may be suitably set according to the purpose, use, and the like, and is not particularly limited, but is preferably 0.001 part by mass or more based on 100 parts by mass of the total solid content of the curable resin composition (1). More preferably 0.01 part by mass or more, and further preferably 0.1 part by mass or more. It is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 1 part by mass or less.

- fluorine additive -

The curable resin composition (1) may also contain one or two or more fluorine-based additives (also referred to as a fluorine additive) from the viewpoint of further improving the curability. As the fluorine-based additive, a compound having a fluorine atom in its structure, for example, a compound usually used as a fluorine-based surfactant or a fluorine-based surface modifier can be used.

The fluorine-based additive has a high solubility in various organic solvents (for example, an ether solvent, an ester solvent, a ketone solvent, an alcohol solvent, etc.) from the viewpoint that it is preferable not to separate the components from the curable resin composition And is more preferably used. Specifically, for example, it is preferable that the HLB value (hydrophilic lipophilic balance) is in the range of 0 to 16. The HLB value is more preferably 1 to 13.

In addition, the HLB value is obtained by, for example, the Griffin method or Davis method.

The fluorine-based additive preferably further contains 0.01 to 80% by mass of fluorine in a total amount of 100% by mass of the fluorine-based additive.

The fluorine content can be quantified by, for example, ion chromatography.

As the fluorine-based additive, nonionic or anionic ones may be present, but nonionic ones are preferred from the viewpoint of dispersibility with resins and the like.

Specific examples of the fluorine-based additive include perfluorobutanesulfonate (Megafac F-114), perfluoroalkyl group-containing carboxylate (Megafac F-410), perfluoroalkylethylene oxide adducts (Megafac EXP-TF-2149), perfluoroalkyl group-containing phosphoric ester (Megafac EXP-TF-2148), perfluoroalkyl group-containing phosphate ester amine neutralizer F-551, F-551, F-561, F-551, F-551, F- F-557, F-557, F-559, F-562, R-40 and F-557, oligomers having a fluorine group, a hydrophilic group and a lipophilic group, EXP-TF-1760), fluorine group, hydrophilic group, lipophilic group, UV reactive group-containing oligomer (Megapak® RS-72-K, RS-75, RS-76- (All manufactured by DIC). Among them, a compound containing a lipophilic group (an oligomer having a fluorine group or a lipophilic group, an oligomer having a fluorine group, a hydrophilic group or a lipophilic group, a fluorine group, a hydrophilic group, a lipophilic group or a UV reactive group-containing oligomer) is preferable.

The content of the fluorine-based additive may be suitably set according to purposes, applications, etc., and is not particularly limited, but is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total solid content of the curable resin composition (1) of the present invention. More preferably not less than 0.2 parts by mass, more preferably not less than 0.5 parts by mass, particularly preferably not less than 0.8 parts by mass, most preferably not less than 1 part by mass, more preferably not more than 5 parts by mass, further preferably not more than 5 parts by mass 4 parts by mass or less, and particularly preferably 3 parts by mass or less.

The curable resin composition (1) may further contain, for example, a coloring material (also referred to as a coloring agent); Dispersing agent; Heat resistance improver; Leveling agents; Other coupling agents such as aluminum-based and titanium-based coupling agents; A development aid; Thermosetting resins such as filler, epoxy resin, phenol resin, and polyvinyl phenol; Curing auxiliary agents such as polyfunctional thiol compounds; Plasticizers; Ultraviolet absorber; Antioxidants; Polish remover; Defoamer; An antistatic agent; Slip agent; Surface modifiers; A yoghurt change agent; Urethral adjuvant; Quinone diazide compounds; Polyhydric phenol compounds; Cationic polymerizable compounds; Acid generators, and the like may be further contained.

&Lt; Process for producing curable resin composition (1)

The curable resin composition (1) can be prepared by mixing and dispersing the above-mentioned contained components using various mixers or dispersers. Among them, first, silica fine particles are first dispersed in an organic solvent (dispersion medium) to obtain an organic solvent dispersion of fine silica particles, and then the dispersion is dispersed with a coupling agent, an alkali soluble resin, a polyfunctional (meth) It is preferable to obtain a curable resin composition by mixing with other components contained. The curable resin composition thus obtained is excellent in adhesion, dispersibility, developability and the like, has a sufficient surface hardness, and can exhibit changes in appearance over time such as discoloration, coloration and cracking even after exposure in a high temperature environment The effect of the present invention that the dispersibility can be maintained and the cured product capable of stably exhibiting sufficient surface hardness and adhesion can be imparted. As described above, the step of dispersing the silica fine particles in an organic solvent to obtain an organic solvent dispersion of fine silica particles (also referred to as a &quot; dispersing step &quot;), a step of mixing the dispersion with a coupling agent and an alkali- Hereinafter also referred to as &quot; curable resin composition &quot;) is also one of the preferred embodiments of the present invention.

The dispersion step and the mixing step are not particularly limited and may be carried out by a conventional method. In addition, it is also possible to additionally include another process which is usually carried out.

[Curable resin composition (2)]

Next, the curable resin composition (2) will be described.

The curable resin composition (2) of the present invention contains at least one solvent selected from the group consisting of silica fine particles and a silane coupling agent containing an epoxy group, an alkali soluble resin, a ketone solvent and an ester solvent, One or more kinds of the components may be used. In addition, if necessary, one or more other components may be further contained.

&Lt; Silica fine particles, ketone type solvent and ester type solvent >

Preferable forms of the silica fine particles, the ketone type solvent and the ester type solvent which can be contained in the curable resin composition (2) are the same as each of the respective components that can be contained in the above-mentioned curable resin composition (1).

In the curable resin composition (2), the content of the fine silica particles is preferably 10% by mass or more of 100% by mass of the total solid content of the curable resin composition (2). Thereby, the surface hardness of the cured product becomes more sufficient. More preferably not less than 15% by mass, and further preferably not less than 20% by mass. In view of the dispersibility and storage stability of the curable resin composition, it is preferably 80% by mass or less. More preferably 75 mass% or less, and further preferably 70 mass% or less.

In the curable resin composition (2), it is preferable to use at least a ketone-type solvent among the ketone type solvent and the ester type solvent. More preferably, a ketone solvent is used as a dispersion medium of the fine silica particles. That is, it is particularly preferable that the curable resin composition (2) contains a dispersion of silica fine particles dispersed in a ketone solvent. As a result, it is possible to more fully exhibit the effect that the dispersibility can be maintained and the cured product having sufficient surface hardness and adhesion can be obtained without any change in appearance over time such as discoloration, coloration and cracking even after exposure at a high temperature .

In the curable resin composition (2), the content of the ketone-based solvent and / or ester-based solvent is preferably such that the fine particles of silica are sufficiently dispersed. That is, for example, when a dispersion comprising silica fine particles dispersed in a ketone type solvent and / or an ester type solvent is used, the content ratio of the silica fine particles in the curable resin composition (2) falls within the above-mentioned preferable range , And the amount of the ketone-based solvent and / or the ester-based solvent is adjusted so that the fine silica particles are sufficiently dispersed. For example, it is preferable that the total amount of the ketone solvent and / or the ester solvent is 50 parts by mass or more based on 100 parts by mass of the fine silica particles. More preferably 70 parts by mass or more, and even more preferably 100 parts by mass or more. If the amount of the solvent is excessively larger than necessary, there is a possibility that the curing treatment can not be carried out easily, so that it is preferably 600 parts by mass or less. More preferably 550 parts by mass or less, and even more preferably 500 parts by mass or less.

<Epoxy group-containing silane coupling agent>

The curable resin composition (2) contains a silane coupling agent having an epoxy group (also referred to as an epoxy group-containing silane coupling agent). Specifically, it is preferable that an epoxy group (including glycidyl group) and an alkoxysilane group (-Si (OR ¹ ) _3-n (R ² ) _n ; OR ¹ represents a hydrolyzable group and R ¹ is a hydrocarbon group R ² represents a hydrocarbon group, and n is 0, 1 or 2. By using the epoxy group-containing silane coupling agent in the curable resin composition (2), it is possible to further suppress the change in appearance over time such as discoloration, coloration and cracking even after exposure at a high temperature, It becomes possible to obtain a cured product having hardness and adhesion.

In the curable resin composition (2), the content of the epoxy group-containing silane coupling agent is preferably 5% by mass or more based on 100% by mass of the total solid content of the curable resin composition (2). By containing not less than 5% by mass, even after high temperature exposure, it is possible to have more sufficient adhesion and surface hardness. More preferably not less than 6% by mass, and still more preferably not less than 7% by mass. From the viewpoint of storage stability and the like of the curable resin composition, it is preferably 30 mass% or less. More preferably 25 mass% or less, and further preferably 20 mass% or less.

In the curable resin composition (2), another coupling agent (for example, a silane coupling agent having an amino group, a vinyl group, a (meth) acryl group, a mercapto group, or the like as a reactive group, etc.) may be used in combination. In this case, the amount of other coupling agent is preferably 100 parts by mass or less based on 100 parts by mass of the epoxy group-containing silane coupling agent.

<Alkali-soluble resin>

In the curable resin composition (2), the alkali-soluble resin may be a resin exhibiting alkali solubility, but it is preferably a polymer having an acid group in the molecule (also referred to as "acid group-containing polymer"). As a result, the curable resin composition (2) becomes developable. Examples of the acid group include a functional group capable of neutralizing with an alkaline water such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, a sulfonic acid group, etc., and may have only one kind or two or more kinds thereof do. Among them, a carboxyl group and a carboxylic acid anhydride group are preferable, and a carboxyl group is more preferable.

When the alkali-soluble resin is a polymer having an acid group, the acid value (AV) of the alkali-soluble resin is not particularly limited. For example, the acid value (AV) of the specific polymer contained in the curable resin composition (1) Is preferably in the same range as the above range.

The weight average molecular weight of the alkali-soluble resin is preferably in the same range as the weight average molecular weight of the specific polymer contained in the curable resin composition (1).

Examples of the alkali-soluble resin include 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, and a polymer (also referred to as a base polymer) Is preferably a polymer (also referred to as a side chain double bond-containing polymer) obtained by reacting a compound having a functional group and a polymerizable double bond. More preferably, it is the latter side chain double bond-containing polymer. Each of the monomers to be used may be used alone or in combination of two or more.

Specific examples and preferred forms of the monomer having an acid group and a polymerizable double bond and a content of the monomer relative to a total amount of 100 mass% of the base polymer component are the same as those described above for the curable resin composition (1) .

The monomer component may contain other radically polymerizable monomers (hereinafter also referred to as &quot; other monomers &quot;) in addition to the above-mentioned monomers having an acid group and a polymerizable double bond. Examples of such other monomers include N-substituted maleimide-based monomers, dialkyl-2,2 '- (oxydimethylene) diacrylate-based monomers, (meth) acrylate-based monomers, aromatic vinyl- Are preferably used. In particular, a resin containing an N-substituted maleimide monomer unit and / or a dialkyl-2,2 '- (oxydimethylene) diacrylate monomer unit imparts a cured film having improved heat resistance, colorant dispersibility, .

The resin containing the above-mentioned monomer unit is a resin containing a monomer-derived constituent unit by, for example, a polymerization reaction or a crosslinking reaction of a monomer.

Specific examples and preferable forms of the N-substituted maleimide-based monomer and dialkyl-2,2 '- (oxydimethylene) diacrylate-based monomer, and N-substituted maleimide-based monomers relative to a total amount of the base polymer component of 100% (The proportion of the total of the two kinds, if used) of the dialkyl-2,2'- (oxydimethylene) diacrylate monomer and / or the dialkyl-2,2 ' Respectively.

The specific examples and preferable forms of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer and the preferable content of the (meth) acrylic ester monomer and / or the aromatic vinyl monomer with respect to the total amount of the base polymer component of 100 mass% (The ratio of the total when two kinds are used) are the same as those described above in the description of the curable resin composition (1).

The other monomer may also be one or more of the compounds exemplified as other monomers with respect to the curable resin composition (1). The content of the other monomer may be 20 mass% or more, Or less.

(Polymerization method, polymerization conditions, solvent, additive, etc.) of the polymerization reaction of the monomer component are the same as those described above in the description of the curable resin composition (1).

The alkali-soluble resin preferably has a double bond in the side chain. Specifically, the polymer is preferably a polymer (side chain double bond-containing polymer) obtained by reacting a polymer (base polymer) obtained by polymerizing the monomer component with a compound having a functional group capable of bonding to the acid group and a polymerizable double bond . Specific examples and preferable forms of the compound having a functional group and a polymerizable double bond capable of bonding to an acid group are the same as those described above.

The preferable range of the double bond equivalent of the side chain double bond-containing polymer or the side chain double bond-containing polymer is the same as each of the above-described descriptions in the description of the curable resin composition (1).

The content of the alkali-soluble resin in the curable resin composition (2) is preferably 5% by mass or more, more preferably 70% by mass or less, based on 100% by mass of the total solid content of the curable resin composition (2) . Within this range, the effects of the present invention can be more remarkably exhibited. More preferably from 10 to 65% by mass, and still more preferably from 15 to 60% by mass.

<Other Ingredients>

- polymerizable monomers -

The curable resin composition (2) preferably further contains a polymerizable monomer. As the polymerizable monomer, it is preferably a radical polymerizable monomer. By containing such a compound, the curable resin composition (2) is more excellent in photosensitivity and curability.

The molecular weight of the radically polymerizable monomer is not particularly limited, but from the viewpoint of handling, it is preferably 2000 or less, for example.

Examples of the radically polymerizable monomer include a trifunctional or more polyfunctional (meth) acrylate compound that the curable resin composition (1) may contain, and a compound described as another polymerizable monomer. Among them, a multifunctional radically polymerizable compound having two or more radically polymerizable unsaturated groups in the molecule is preferable from the viewpoint of curability. (Meth) acrylates, (meth) acryloyl group-containing isocyanurates and the like are preferably used in view of reactivity, economy, availability and the like Meth) acryloyl group. More preferably, it is a trifunctional or more polyfunctional (meth) acrylate compound.

The content of the polymerizable monomer may be appropriately set according to the kind of the monomer or the alkali-soluble resin to be used. However, it is preferable that the content of the polymerizable monomer is about 100% by mass or less based on 100% by mass of the total solid content of the curable resin composition (2) , And preferably from 5 to 60 mass%. More preferably from 8 to 55% by mass, and still more preferably from 10 to 50% by mass.

- Photopolymerization initiator -

The curable resin composition (2) preferably further contains a photopolymerization initiator. The preferred forms and content of the photopolymerization initiator are the same as those described above in the description of the curable resin composition (1). In the same manner as the curable resin composition (1), a photosensitizer or photo radical polymerization accelerator may be used in combination, and the content thereof is also the same as that described above.

-solvent-

The curable resin composition (2) preferably further contains a solvent. The preferable form of the solvent and the preferable range of the amount to be used are the same as those described above in the description of the curable resin composition (1).

- Polymerization inhibitor -

The curable resin composition (2) may further contain one or more polymerization inhibitor. Preferable forms of the polymerization inhibitor and preferable ranges of the amounts to be used are the same as those described above in the description of the curable resin composition (1).

- fluorine additive -

The curable resin composition (2) may further contain one or more kinds of fluorine-based additives. Preferable forms of the fluorine-based additive and preferred ranges of the amounts to be used are the same as those described above in the description of the curable resin composition (1).

The curable resin composition (2) may contain one or more kinds of other additives or the like depending on the required properties of each application to which the curable resin composition (2) is applied. Other additives include, for example, those described above in the description of the curable resin composition (1).

&Lt; Process for producing curable resin composition (2)

The curable resin composition (2) can be prepared by mixing and dispersing the above-mentioned contained components using various mixers or dispersers. Among them, first, silica fine particles are first dispersed in a ketone type solvent and / or an ester type solvent to obtain an organic solvent dispersion of fine silica particles, and then the dispersion is mixed with a silane coupling agent, an alkali soluble resin and other components To obtain a curable resin composition. By the curable resin composition thus obtained, the effects of the present invention are more fully exhibited. As described above, the step of dispersing the silica fine particles in a ketone type solvent and / or an ester type solvent to obtain an organic solvent dispersion of fine silica particles (also referred to as a &quot; dispersing step &quot;) and a step of dispersing the dispersion in a silane coupling agent and an alkali- The method of producing the curable resin composition containing the mixing step (also referred to as &quot; mixing step &quot;) is also one of the present invention.

The dispersion step and the mixing step are not particularly limited and may be carried out by a conventional method. In addition, other conventional processes may be further included

[Curable resin composition in the form of (a) to (d)] [

The curable resin composition (the curable resin composition (1) or (2)) of the present invention may also be in a form satisfying at least one of the above-mentioned (a) to (d). The form in which the curable resin composition satisfies the above (a), (b), (c) or (d) is a preferred form of the present invention. Further, a form that satisfies at least two of (a) to (d) is also a preferred form of the present invention. Among them, it is more preferable that the curable resin composition (1) satisfies at least one of (a) to (d). A particularly preferred form of the present invention is a form in which the curable resin composition at least satisfies both of (a) and (b), at least both of (a) and (c) ), And (b) and (c). By these forms, the effects of the present invention (in particular, developability and light resistance) can be more remarkably expressed.

<Form of (a)>

The curable resin composition of the above (a) contains an amino ketone polymerization initiator and a phenol-based antioxidant. The curing reaction can be more appropriately controlled by the combined use thereof, so that a cured product capable of stably exhibiting excellent transparency, hardness, adhesion, and developability even after exposure under a high-temperature exposure can be obtained.

Specific examples of the aminoketone-based polymerization initiator and the phenol-based antioxidant are as described above.

In the embodiment (a), the content of the aminoketone-based polymerization initiator is preferably 2 parts by mass or more based on, for example, 100 parts by mass of the total solid content of the curable resin composition of the present invention. As a result, the hardness and developability of the cured product can be further enhanced. More preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more. In view of the balance between the effect of decomposition products of the polymerization initiator and the economical efficiency, it is preferable that the amount is 35 parts by mass or less. More preferably 30 parts by mass or less, and still more preferably 25 parts by mass or less.

Further, other polymerization initiators may be used in combination with the aminoketone-based polymerization initiator. In this case, it is preferable that the amino ketone polymerization initiator is 20 mass% or more based on 100 mass% of the total amount of the polymerization initiator (that is, the total amount of the amino ketone polymerization initiator and the other polymerization initiator). More preferably 30% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more.

In the embodiment (a), the content of the phenol-based antioxidant is preferably 0.001 part by mass or more based on, for example, 100 parts by mass of the total solid content of the curable resin composition of the present invention. Within this range, it becomes possible to more appropriately control the curing reaction. More preferably 0.01 part by mass or more, and further preferably 0.1 part by mass or more. It is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 1 part by mass or less.

Further, other polymerization inhibitors may be used in combination with the phenol-based antioxidant. In this case, it is preferable that the phenolic antioxidant is 50% by mass or more based on 100% by mass of the total amount of the polymerization inhibitor (i.e., the total amount of the phenol-based antioxidant and the other polymerization inhibitor). It is more preferably 70 mass% or more, and further preferably 90 mass% or more. Particularly preferably 100% by mass, that is, substantially only the phenol-based antioxidant is used as the polymerization inhibitor.

<Form of (b)>

Regarding the form of (b), specific examples of the aminoketone-based polymerization initiator are as described above. In the embodiment (b), the content of the aminoketone-based polymerization initiator is 10 to 35 parts by mass based on 100 parts by mass of the total solid content of the curable resin composition of the present invention. By using such a large amount of an aminoketone-based polymerization initiator, the curability becomes better, and a cured product having excellent light resistance and further suppressing deterioration over time (coloring, etc.) can be obtained. Further, the cured product obtained by the curable resin composition of the above-mentioned (b) form is more sufficiently inhibited from being deteriorated, so that the effect of the present invention such as excellent adhesion, transparency and surface hardness can be more stably exhibited . In view of the balance between the effect of the decomposition product of the polymerization initiator and the economical efficiency, it is suitably 35 parts by mass or less. The content is more preferably 12 parts by mass or more, and still more preferably 15 parts by mass or more. It is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less.

Further, other polymerization initiators may be used in combination with the aminoketone-based polymerization initiator. In this case, it is preferable that the amino ketone polymerization initiator is 20 mass% or more based on 100 mass% of the total amount of the polymerization initiator (that is, the total amount of the amino ketone polymerization initiator and the other polymerization initiator). More preferably 30% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more.

In the embodiment (b), it is further preferable to further contain a phenol-based antioxidant. This makes it possible to obtain a cured product having a sufficiently high transparency, hardness and adhesiveness, and more excellent developing property because the curing reaction is appropriately controlled.

The preferable range of the content of the phenol-based antioxidant is the same as that of the above-mentioned (a).

<Form of (c)>

Regarding the mode (c), specific examples of the fluorine-based additive are as described above.

In the embodiment (c), the content of the fluorine-based additive is 0.1 to 10 parts by mass based on 100 parts by mass of the total solid content of the curable resin composition of the present invention. By containing such an amount of the fluorine-based additive, it becomes possible to obtain a cured product in which the light resistance and developability are more excellent and the deterioration (coloring and hardness reduction, etc.) is further suppressed over time. The content is more preferably 0.2 parts by mass or more, still more preferably 0.5 parts by mass or more, particularly preferably 0.8 parts by mass or more, further preferably 1 part by mass or more, and still more preferably 5 parts by mass or less More preferably 4 parts by mass or less, particularly preferably 3 parts by mass or less.

In the embodiment (c), it is further preferable to further contain a phenol-based antioxidant. As a result, the curing reaction is appropriately controlled, so that a cured product having a sufficiently high transparency, hardness and adhesiveness and being more developable can be obtained.

The preferable range of the content of the phenol-based antioxidant is the same as that of the above-mentioned (a).

< Form of (d) >

The curable resin composition of (d) contains at least two polymerization initiators selected from the group consisting of an amino ketone polymerization initiator, a hydro ketone polymerization initiator and a benzyl ketal polymerization initiator. Thus, both the surface hardening property and the inner hardening property are sufficiently improved. Therefore, even if the hardening reaction proceeds by, for example, high temperature exposure, the initial hardening has already proceeded sufficiently, It is alleviated that the curing reaction proceeds excessively. Therefore, even after exposure under a high-temperature exposure, the influence on the adhesion of the cured product to ITO or the like is more sufficiently suppressed. Therefore, even when the obtained cured product is exposed in a high-temperature environment, there is no change in appearance over time such as discoloration, coloration and cracking, so that transparency can be maintained and sufficient surface hardness, developability and adhesiveness to the substrate can be exhibited It is possible to further exert the action and effect of the present invention.

In the embodiment (d), it is particularly preferable to use at least an amino ketone polymerization initiator. That is, the curable resin composition preferably contains at least one selected from the group consisting of an amino ketone polymerization initiator, a hydro ketone polymerization initiator, and a benzyl ketal polymerization initiator. It is possible to sufficiently enhance the internal curability of the curable resin composition by the aminoketone-based polymerization initiator and to further increase the surface curability by the hydroketone-based polymerization initiator and / or the benzyl ketal-based polymerization initiator. , The curability as a whole is further improved.

Specific examples of the aminoketone-based polymerization initiator, the hydroketone-based polymerization initiator and the benzylketal-based polymerization initiator are as described above.

In the mode (d), the content of the at least two polymerization initiators selected from the group consisting of an amino ketone polymerization initiator, a hydro ketone polymerization initiator and a benzyl ketal polymerization initiator is preferably such that the total amount of the curing resin It is preferably 2 parts by mass or more based on 100 parts by mass of the total solid content of the composition. As a result, the hardness of the cured product can be further increased. More preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more. In view of the balance between the effect of decomposition products of the polymerization initiator and the economic efficiency, the total amount of the polymerization initiator is preferably 35 parts by mass or less. More preferably 30 parts by mass or less, and still more preferably 25 parts by mass or less.

In the embodiment (d), as described above, it is preferable to contain an amino ketone polymerization initiator, a hydro ketone polymerization initiator and / or a benzyl ketal polymerization initiator. In this case, the mass ratio of the polymerization initiator (the total amount of the amino ketone polymerization initiator / the hydro ketone polymerization initiator and the benzyl ketal polymerization initiator) is preferably 20 to 90/10 to 80 (mass%). More preferably 30 to 80/20 to 70, still more preferably 50 to 80/20 to 50, particularly preferably 55 to 80/20 to 45.

In the form of (d) above, it is further preferable to further contain a phenol-based antioxidant. As a result, the curing reaction is appropriately controlled, so that a cured product having a sufficiently high transparency, hardness and adhesiveness and being more developable can be obtained.

The preferable range of the content of the phenol-based antioxidant is the same as that of the above-mentioned (a).

[Coating film]

Next, the cured film formed by using the curable resin composition (curable resin composition (1) and / or (2)) of the present invention will be described.

The curable resin composition (curable resin composition (1) and / or (2)) of the present invention can form a cured film by irradiating (exposing) an active energy ray. Specifically, for example, it is preferable to form the cured film by applying the curable resin composition on a substrate, drying it, and irradiating (exposing) the surface with the active energy ray. Thus, the cured film formed by the curable resin composition is also one of the present invention.

The base material to which the curable resin composition is applied is not particularly limited, and examples thereof include transparent glass substrates such as white plate glass, cheongyeong glass, and silica-coated cheongpan glass; A sheet, film or substrate made of a thermoplastic resin such as a ring-opening polymer of polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin or hydrogenated product thereof; A sheet, a film or a substrate made of a thermosetting resin such as an epoxy resin or an unsaturated polyester resin; A metal substrate such as an aluminum plate, a copper plate, a nickel plate, or a stainless steel plate; A ceramic substrate; A semiconductor substrate having a photoelectric conversion element; And a glass substrate (color filter for LCD) having a color material layer on its surface. The base material may be subjected to a corona discharge treatment, an ozone treatment, a chemical treatment with a silane coupling agent or the like, if necessary.

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

The coating film after the application to the substrate can be dried, for example, by using a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected depending on the boiling point of the solvent components contained therein, the kind of the curing component, the film thickness, the performance of the drier, and the like, and it is generally preferably carried out at a temperature of 50 to 160 ° C for 10 seconds to 300 seconds.

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 ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, A laser light source such as a laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, or a semiconductor laser is used. The exposure system may be a proxy mode, a mirror projection system, or a stepper system, but a proximity system is preferably used.

In the step of irradiating the active energy beam, an 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 becomes insoluble or hardly soluble in the developer.

If necessary, a step (hereinafter also referred to as &quot; developing step &quot;) of forming a pattern by removing the unexposed portion by developing with a developing solution after the step of irradiating the active energy beam may be performed. As a result, a patterned cured film can be obtained.

The developing treatment in the developing step is usually carried out by a method such as immersion, spraying, brushing, or ultrasonic development at a developing temperature of 10 to 50 캜. When an alkaline aqueous solution is used as the developing solution, it is preferable to rinse with water after development.

The developing solution 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, or a mixture thereof may be used.

As the organic solvent preferable as the developer, for example, an ether solvent or an alcohol solvent can be mentioned. Specific examples of the solvent include dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkylphenyl ethers, aralkyl Phenyl ethers, diaromatic ethers, 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 preferable as the above-mentioned developer.

Examples of the alkali agent include inorganic alkaline agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, sodium secondary phosphate, sodium carbonate, potassium carbonate and sodium hydrogen carbonate; And amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide, Or two or more of them may be combined.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters; Anionic surfactants such as alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfuric acid salts, alkylsulfonic acid salts and sulfosuccinic acid ester salts; Amphoteric surfactants such as alkyl betaines and amino acids, and the like, and they may be used singly or in combination of two or more kinds.

If necessary, a post-curing step may be performed after completion of the developing step. The post-curing step is a step of, for example, post-exposure using a light source such as a high-pressure mercury lamp at a light amount of 0.5 to 5 J / cm 2, for example, Followed by post-heating for a minute. By performing such a post-curing step, it becomes possible to make the hardness and adhesion of the patterned cured film stronger.

[Uses and the like of the curable resin composition (1) and / or (2)] [

As described above, the curable resin composition (curable resin composition (1) and / or (2)) of the present invention is excellent in adhesion, dispersibility, developability and the like, has sufficient surface hardness, (Cured film) capable of maintaining dispersibility and stably exhibiting sufficient surface hardness and adhesiveness without change in appearance such as discoloration, coloration and cracking even after being exposed under the above-mentioned conditions . Therefore, the cured product (cured film) formed from such a curable resin composition can be used as a component of various display devices such as a liquid crystal display device, a solid-state image pickup device, a touch panel type display device, an ink, , Semiconductor devices, photoresists, various optical members, electric and electronic devices, and the like. In particular, it is preferable to use the curable resin composition for a color filter or a touch panel type display device used for a liquid crystal display device, a solid-state image pickup device, or the like. Particularly, A protective film for a touch panel type display device, or the like), an insulating film (an insulating film for a touch panel type display device, etc.). This makes it possible to sufficiently enhance the display quality of various display devices and the reliability of the image quality so as to sufficiently cope with recent demands for high performance. The form in which the curable resin composition is a protective film or a curable resin composition for forming an insulating film is one of the preferred embodiments of the present invention. The present invention also includes a cured film formed from the curable resin composition, a member for a display device having the cured film, and a display device having the cured film.

The member for a display device and the display device of the present invention have a cured film formed by the curable resin composition (the curable resin composition (1) or (2)). The cured film formed from the curable resin composition stably exhibits excellent adhesion to a substrate and the like, has a high hardness, exhibits high smoothness, and has a high transmittance. Therefore, it is particularly preferable as a transparent member, and is very useful as a protective film or an insulating film in various display devices. The display device is not particularly limited, and for example, a liquid crystal display device, a solid-state image pickup device, a touch panel type display device and the like are preferable. The touch panel type display device is preferably a capacitive type display device.

Further, the display device member may be a film-like single layer or multi-layer member constituted of the cured film, or may be a member combined with another layer in addition to the single layer or multi-layer member, (For example, a color filter or the like).

Since the curable resin composition of the present invention has the above-described constitution, it is excellent in adhesion, dispersibility, developability and the like, has sufficient surface hardness, and has excellent appearance such as discoloration, coloration and cracking The cured product can maintain dispersibility and can stably exhibit sufficient surface hardness and adhesion. Therefore, a display device member and a display device having a cured film formed from such a curable resin composition are very useful in the optical field, the electric field, and the electronic field.

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 stated, &quot; part &quot; means &quot; part by mass &quot; and &quot;% &quot; means &quot;% by mass &quot;, respectively.

In the following synthesis examples and adjustment examples, various physical properties and the like were measured as follows.

[Physical properties of resin solution (alkali-soluble resin)] [

&Lt; Weight average molecular weight &

The weight average molecular weight was measured by GPC (gel permeation chromatography) using polystyrene as a standard substance and tetrahydrofuran as an eluent with HLC-8220GPC (manufactured by Tosoh Corporation) and column TSKgel SuperHZM-M (manufactured by Tosoh Corporation) .

&Lt; Solid content concentration >

Approximately 0.3 g of the polymer solution was weighed into an aluminum cup, and about 1 g of acetone was added to dissolve the solution, followed by natural drying at room temperature. After drying at 140 DEG C for 3 hours using a hot-air dryer (trade name "PHH-101" manufactured by Especa), the mass was measured by cooling in a desiccator. The solid concentration (NV, mass%) of the polymer solution was calculated from the mass reduction amount.

<Acid value>

1.5 g of the resin solution was precisely weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water and 0.1 g of a KOH aqueous solution was used as a titration solution in an automatic titration apparatus (trade name: "COM-555" , 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]

&Lt; Evaluation of physical properties on glass substrate &

1. Appearance (smoothness), cross-cut test (cross-cut), pencil hardness

The resulting resin composition was applied to a glass substrate by a spin coat method, and subjected to heat treatment (at 80 DEG C for 3 minutes), followed by UV aligner (TME-150RNS manufactured by TOPCON Co., Ltd.) Exposure was carried out at an exposure dose of 60 mJ / cm 2 (365 nm in terms of roughness), and heat treatment (at 230 캜 for 30 minutes) was carried out.

(External appearance, cross-cut test, pencil hardness) after 3 hours of PCT (Pressure Cooker Test) at 120 占 폚 water vapor pressure was performed using the obtained coating film .

(1-1) Appearance

The appearance of the coated film was visually evaluated. In the table, "transparent" means that it is colorless transparent.

In the appearance evaluation of the coated film after the PCT, it was evaluated as &quot;? &Quot; when it was almost the same as the initial appearance, and when it was deteriorated from the initial appearance, it was evaluated as &quot;

(1-2) Crosscut test

The test was conducted in accordance with JIS-K 5400-8.5 (1990), and evaluated by the following criteria.

?: It is 10 points in the JIS standard, and a strong resistance is felt when the cell tape (R) is peeled off.

○: 10 points in JIS standard

× 1: 8 points in JIS standard

× 2: 6 points in JIS standard

× 3: 4 points in JIS standard

× 4: Two points in JIS standard

× 5: 0 point in JIS standard

(1-3) Pencil hardness test (employed in preparation examples in Tables 2 to 4 and Tables 6-1 to 9-2)

The tests were carried out in accordance with JIS-K 5600-5-4 (1999), all of which were carried out at 500 g of JIS-K 5400 (1990) of the old JIS version and the hardest pencils The pencil hardness was evaluated as follows.

?: Pencil hardness of 6H or more

○: Pencil hardness is 5H

?: Pencil hardness of 4H to 2H

X: Pencil hardness is H or less

 (1-4) Pencil hardness test (employed in preparation example in Table 5)

The tests were carried out in accordance with JIS-K 5600-5-4 (1999). All the loadings were carried out at 1 kg of JIS-K 5400 (1990) of the old JIS version, and the hardest pencils And evaluated as the value of pencil hardness.

2. Developability

Similarly, after the obtained resin composition was applied to a glass substrate by a spin coat method and subjected to a heat treatment (80 占 폚 for 3 minutes), a photomask having a line-and-space opening of 50 占 퐉 at a distance of 100 占 퐉 from the coating film (Trade name "TME-150RNS", manufactured by TOPCON) equipped with a 2.0 kW ultra-high pressure mercury lamp, exposure was performed at an exposure amount of 60 mJ / cm 2 (365 nm in terms of roughness) The aqueous solution of potassium hydroxide was dispersed for 40 seconds with a spin developing machine to dissolve and remove the unexposed portions, and the remaining exposed portions were washed with pure water for 10 seconds to develop, thereby evaluating developability.

The developed coating film was evaluated by the surface roughness meter (trade name: VertScan2.0, manufactured by Ryoka Co., Ltd.) through the following photomask under the following criteria.

(2-1) Developability (residue)

○: Unexposed portion, the exposed portion is flowing cleanly without residue.

X: Residues can be confirmed in unexposed areas.

(2-2) Developability (line thickening)

?: The opening width was reproduced in the order of 占 5 占 퐉.

DELTA: An error was caused by a difference of +/- 15 mu m from the opening width.

X: Error is caused by a difference of +/- 25 mu m from the opening width.

(2-3) Developability (edge)

A: The pattern edge is close to a square.

B: The pattern edge is rounded.

Also, the evaluation of line thickening and edge is strictly evaluated as to the developability rather than the evaluation of the residue. Therefore, the better the line thickening and edge evaluation, the better the developability.

&Lt; Evaluation of physical properties on ITO substrate >

1. Appearance (smoothness), cross-cut test (cross-cut), pencil hardness

An ITO substrate on which ITO (Indium Tin Oxide) was deposited with a thickness of 30 nm was prepared. (Appearance, cross-cut test, pencil hardness) at 120 ° C under a steam pressure condition for 3 hours, in the same manner as in the evaluation of the physical properties of the glass substrate described above except that the ITO substrate was used instead of the glass substrate (Appearance, crosscut test, pencil hardness) after the PCT.

2. Light coloring property

A glass substrate on which ITO (Indium Tin Oxide) was deposited with a thickness of 30 nm was prepared. The resin composition thus obtained was coated on the glass substrate by a spin coat method and subjected to heat treatment (80 DEG C for 3 minutes), followed by UV aligner (trade name: TME-150RNS, manufactured by TOPCON Co., Ltd.) Exposure was carried out at an exposure dose of 60 mJ / cm 2 (365 nm in terms of roughness), and heat treatment (at 230 캜 for 30 minutes) was carried out.

The coated film thus obtained was irradiated with 400 mh of an exposure dose of 180 mW / cm 2 (300 to 400 nm) for 400 hours with a xenon weather meter (product name: "FAL-25AX-HC-B" Was measured using a spectrophotometer (trade name: UV-3100, manufactured by Shimadzu Corporation), and evaluated according to the following criteria.

○: transmittance of 80% or more

?: Transmittance of not less than 70% and less than 80%

X: transmittance less than 70%

[Synthesis of Resin Solution]

First, the resin solution (A) (Exemplary Compounds A-1 to A-9) was synthesized as the alkali-soluble resin contained in the resin composition.

Synthesis Example 1 (Synthesis of A-1)

456 parts of propylene glycol monomethyl ether (PGME) was poured into a separable flask equipped with a cooling tube as a reaction tank, and the mixture was heated to 90 DEG C in a nitrogen atmosphere. Then, 30 parts of benzylmaleimide (BzMI) (N-dodecyl mercaptan (n-DM)) 9 as the lower phase 2, 180 parts of cyclohexyl acrylate (CHA), 30 parts of PGME, 6 parts of perbutyl O (trade name, And 71 parts of PGME were continuously supplied over 3 hours, respectively. Thereafter, the temperature was maintained at 90 캜 for 30 minutes, the temperature was raised to 115 캜, and polymerization was continued for 1.5 hours.

Subsequently, 99 parts of glycidyl methacrylate (GMA), 1.2 parts of triethylamine (TEA) as a catalyst, and 0.6 part of ANTIAGE W-400 (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.) And the reaction was continued at 110 DEG C for 2 hours and at 115 DEG C for 4 hours while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%) to obtain a resin solution A-1 having a double bond equivalent of 588 g / equivalent.

Various physical properties (weight average molecular weight, solid content concentration and acid value per solid content) of the obtained resin solution A-1 were measured. The results are shown in Table 1.

Synthesis Example 2 (Synthesis of A-2)

185 parts of propylene glycol monomethyl ether acetate (PGMEA) and 185 parts of PGME were placed in a separable flask equipped with a cooling tube as a reaction tank, and after raising the temperature to 90 DEG C under a nitrogen atmosphere, 25 parts of BzMI and 143 parts of MAA , 83 parts of CHA, 13 parts of PGMEA, 13 parts of PGME, 5 parts of perbutyl O, 11 parts of n-DM as a lower aliphatic phase 2, 34 parts of PGMEA and 34 parts of PGME were continuously supplied over 3 hours. Thereafter, the temperature was maintained at 90 캜 for 30 minutes, the temperature was raised to 115 캜, and polymerization was continued for 1.5 hours.

Subsequently, 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 the mixture was stirred for 2 hours at 110 占 폚 while bubbling nitrogen and oxygen mixed gas (oxygen concentration: 7% , And the reaction was continued at 115 DEG C for 7 hours to obtain a resin solution A-2 having a double bond equivalent of 444 g / equivalent.

Various physical properties were measured for Resin Solution A-2 obtained in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 3 (Synthesis of A-3)

230 parts of PGMEA and 230 parts of PGME were charged into a separable flask equipped with a cooling tube as a reaction tank and heated to 90 DEG C under a nitrogen atmosphere. Then, 30 parts of BzMI, 114 parts of MAA, 156 parts of CHA, 15 parts of PGMEA , 15 parts of PGME, 6 parts of perbutyl O, 13 parts of n-DM as a low boiling point 2, 33 parts of PGMEA and 33 parts of PGME were continuously supplied over 3 hours, respectively. Thereafter, the temperature was maintained at 90 캜 for 30 minutes, the temperature was raised to 115 캜, and polymerization was continued for 1.5 hours.

Subsequently, 99 parts of GMA, 1.2 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 the mixture was stirred at 110 占 폚 for 2 hours with bubbling nitrogen and oxygen mixed gas (oxygen concentration 7% , And the reaction was continued at 115 DEG C for 4 hours to obtain a resin solution A-3 having a double bond equivalent of 594 g / equivalent.

Various properties were measured for the resin solution A-3 obtained in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 4 (Synthesis of A-4)

90 parts of PGMEA and 90 parts of PGME were placed in a separable flask equipped with a cooling tube as a reaction tank and heated to 90 DEG C under a nitrogen atmosphere. Then, 60 parts of MAA, 76 parts of CHA, 2.7 parts of perbutyl O, 5.7 parts of n-DM as a lower phase 2, 37 parts of PGMEA and 37 parts of PGME were continuously supplied over 3 hours, respectively. Thereafter, the temperature was maintained at 90 캜 for 30 minutes, the temperature was raised to 115 캜, and polymerization was continued for 1.5 hours.

Subsequently, 45 parts of GMA, 0.5 parts of TEA as a catalyst, and 0.3 part of Antage W-400 as a polymerization inhibitor were added to this reaction solution and the mixture was stirred at 110 占 폚 for 2 hours while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7% , And the reaction was continued at 115 DEG C for 4 hours to obtain a resin solution A-4 having a double bond equivalent of 593 g / equivalent.

Various physical properties were measured for the resin solution A-4 obtained in the same manner as in Synthesis Example 1. [ The results are shown in Table 1.

Synthesis Example 5 (Synthesis of A-5)

382 parts of PGMEA and 95 parts of PGME were charged into a separable flask equipped with a cooling tube as a reaction tank and the temperature of the resin composition was raised to 90 DEG C under a nitrogen atmosphere. Then, 12 parts of BzMI, 74 parts of MAA, 170 parts of CHA, , 45 parts of hydroxyethyl acrylate (HEA), 10 parts of PGMEA, 2 parts of PGME, 6 parts of perbutyl O, 12 parts of n-DM as a lower alower 2, 54 parts of PGMEA and 14 parts of PGME were continuously Respectively. Thereafter, the temperature was maintained at 90 캜 for 30 minutes, the temperature was raised to 115 캜, and polymerization was continued for 1.5 hours.

Subsequently, 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 the mixture was heated at 110 DEG C for 2 hours while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7% , And the reaction was continued at 115 DEG C for 3 hours to obtain a resin solution A-5 having a double bond equivalent of 1941 g / equivalent.

Various physical properties were measured for the obtained resin solution A-5 in the same manner as in Synthesis Example 1. [ The results are shown in Table 1.

Synthesis Example 6 (Synthesis of A-6)

368 parts of PGMEA and 92 parts of PGME were charged into a separable flask equipped with a cooling tube as a reaction tank and heated to 90 DEG C under a nitrogen atmosphere. Then, 30 parts of BzMI, 75 parts of MAA, 195 parts of CHA and 24 parts of PGMEA , 6 parts of PGME, 6 parts of perbutyl O, 13 parts of n-DM as a low-boiling point 2, 54 parts of PGMEA and 13 parts of PGME were continuously supplied over 3 hours, respectively. Thereafter, the temperature was maintained at 90 캜 for 30 minutes, the temperature was raised to 115 캜, and polymerization was continued for 1.5 hours.

Subsequently, 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 the mixture was heated at 110 DEG C for 2 hours while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7% , And the reaction was continued at 115 DEG C for 3 hours to obtain a resin solution A-6 having a double bond equivalent of 1946 g / equivalent.

Various properties were measured for the resin solution A-6 obtained in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 7 (Synthesis of A-7)

460 parts of PGME was charged into a separable flask equipped with a cooling tube as a reaction tank, and after raising the temperature to 90 DEG C under a nitrogen atmosphere, 30 parts of BzMI, 249 parts of MAA, 21 parts of CHA, 30 parts of PGME, , 13 parts of n-DM as a lower stream 2, and 67 parts of PGME were continuously supplied over 3 hours, respectively. Thereafter, the temperature was maintained at 90 캜 for 30 minutes, the temperature was raised to 115 캜, and polymerization was continued for 1.5 hours.

Subsequently, 125 parts of PGME, 248 parts of GMA, 1.6 parts of TEA as a catalyst and 0.8 part of Antage W-400 as a polymerization inhibitor were added to this reaction solution, and while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%) The reaction was continued at 110 캜 for 2 hours and at 115 캜 for 10 hours to obtain a resin solution A-7 having a double bond equivalent of 323 g / equivalent.

Various physical properties were measured for Resin Solution A-7 obtained in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 8 (Synthesis of A-8)

As a reaction vessel, 921 parts of PGMEA was poured into a separable flask equipped with a cooling tube, and the mixture was heated to 90 DEG C under a nitrogen atmosphere. Dimethyl-2,2 '- [oxybis (methylene)] bis- (MMA), 10 parts of perbutyl O (trade name, manufactured by Nippon Oil and Fats Co., Ltd.), 102 parts of phenol (MD), 182 parts of methacrylic acid (MAA), 175 parts of benzylmethacrylate , 16.8 parts of n-DM as a lower stream 2, and 44 parts of PGMEA were fed continuously over 150 minutes. Thereafter, the temperature was maintained at 90 캜 for 60 minutes, the temperature was raised to 110 캜, and the polymerization was continued for 3 hours.

 Subsequently, 210 parts of glycidyl methacrylate (GMA), 2.2 parts of triethylamine (TEA) as a catalyst, 0.2 parts of ANTIAGE W-400 as a polymerization inhibitor, and 119 parts of PGMEA were added to this reaction solution, The reaction was continued at 110 DEG C for 2 hours and at 115 DEG C for 4 hours while bubbling the mixed gas (oxygen concentration: 7%) to obtain a resin solution A-8 having a double bond equivalent of 490 g / equivalent.

Various properties were measured for the obtained resin solution A-8 in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 9 (Synthesis of A-9)

181 parts of PGMEA and 45 parts of PGME were placed in a separable flask equipped with a cooling tube as a reaction tank and heated to 90 DEG C under a nitrogen atmosphere. 17 parts of BzMI, 34 parts of MAA, 119 parts of CHA and 14 parts of PGMEA 3 parts of PGME, 3 parts of perbutyl O, 7 parts of n-DM as a low boiling point 2, 58 parts of PGMEA and 15 parts of PGME were continuously supplied over 3 hours, respectively. Thereafter, the temperature was maintained at 90 캜 for 30 minutes, the temperature was raised to 115 캜, and polymerization was continued for 1.5 hours.

Subsequently, 38 parts of PGMEA, 10 parts of PGME, 28 parts of GMA, 0.6 parts of TEA as a catalyst, and 0.3 part of Antage W-400 as a polymerization inhibitor were added to this reaction liquid and nitrogen gas, oxygen mixed gas (oxygen concentration 7% The reaction was continued at 110 캜 for 2 hours and at 115 캜 for 7 hours to obtain a resin solution A-9 having a double bond equivalent of 1043 g / equivalent.

Various physical properties were measured for the resulting resin solution A-9 in the same manner as in Synthesis Example 1. [ The results are shown in Table 1.

Table 1 shows the details of Resin Solutions A-1 to A-9.

The numerical values of BzMI, MD, CHA, BzMA, MAA, MMA, and HEA constituting the base polymer with respect to the amount of the monomer constituting the resin in Table 1 are as follows: Ratio (% by mass) is described. The GMA value added to the base polymer is described as the GMA ratio added to the carboxylic acid fraction of the monomer having the acid group and the polymerizable double bond (in this case, MAA), and the &quot; GMA blend ratio (Mass%)) = (molar amount of GMA / molar amount of MAA (mol)) × MAA compounding ratio (mass%). For example, in Synthesis Example 1 (A-1), MAA is 60 mass% in the base polymer (100 mass%), and 696 mmol of GMA is added to the 60 mass% (2091 mmol) MAA , And the compounding ratio of the GMA was defined as &quot; 20 &quot;.

[Table 1]

The abbreviations in Table 1 are as follows.

BzMI: Benzylmaleimide

MD: dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate

CHA: cyclohexyl acrylate

BzMA: Benzyl methacrylate

MAA: methacrylic acid

MMA: methyl methacrylate

HEA: 2-hydroxyethyl acrylate

GMA: glycidyl methacrylate (glycidyl methacrylate)

AV: acid value

Mw: molecular weight of the finally obtained polymer

NV: Solid concentration

[Adjustment of Resin Composition]

Preparation Example 1-1 (Resin composition 1-1)

25 parts of resin solution A-2 in terms of solid content, 20 parts of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (A-BPEF, Shin Nakamura Chemical Co., 45 parts of ethyl ketone dispersed silica sol (MEK-ST, manufactured by Nissan Chemical Industries, Ltd.), 10 parts of 2-methacryloxypropyltrimethoxysilane (KBM 503, manufactured by Shinetsu Silicone Co., Ltd.), IRGACURE 907 (Manufactured by Guy Kno, Inc.), and a diluting solvent (propylene glycol monomethyl ether acetate; PGMEA) were added so as to have a solid content concentration of 25% and stirred to obtain Resin Composition 1-1.

The obtained Resin Composition 1-1 was evaluated for physical properties of the coating film in accordance with the evaluation method described above. The results are shown in Table 2.

Preparation Examples 1-2 to 1-20 (Resin compositions 1-2 to 1-20)

Each resin composition was obtained in the same manner as in Preparation Example 1-1 at the blending ratios shown in Tables 2 to 4. With respect to each of the obtained resin compositions, the physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Tables 2 to 4.

[Table 2]

[Table 3]

[Table 4]

In Tables 2 to 5 and Tables 6-1 to 9-2, the comprehensive evaluation means that, based on the results of evaluation of physical properties, the coating film is relatively changed from 6 to 6 of "0, 1, 2, 3, 4, 5" . The larger the number (that is, closer to 5) means that the coating film has excellent physical properties, and when the number is smaller (that is, 0), it means that the coating film has not reached the practical level.

The abbreviations in Tables 2 to 5 and Tables 6-1 to 9-2 are as follows. The blending amounts of the raw materials in Tables 2 to 5 and Tables 6-1 to 9-2 are solid contents.

In Tables 2 to 5 and Tables 6-1 to 9-2, the use of a diluting solvent (PGMEA: propylene glycol monomethyl ether acetate) is omitted.

A-BPEF: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (trade name, Shin Nakamura Chemical Co.,

PE3A: pentaerythritol triacrylate (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.)

PE4A: pentaerythritol tetraacrylate (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.)

DPHA: dipentaerythritol hexaacrylate (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.)

Viscot # 802: A mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

MEK-ST: methyl ethyl ketone dispersed silica sol (trade name, manufactured by Nissan Chemical Industries, Ltd.)

MEK-ST-L: methyl ethyl ketone dispersion silica sol (trade name, manufactured by Nissan Chemical Industries, Ltd.)

EAC-ST: Ethyl acetate dispersed silica sol (trade name, manufactured by Nissan Chemical Industries, Ltd.)

NBAC-ST: butyl acetate-dispersed silica sol (trade name, manufactured by Nissan Chemical Industries, Ltd.)

IPA-ST: Silica sol dispersed in isopropyl alcohol (trade name, manufactured by Nissan Chemical Industries, Ltd.)

PGM-ST: Propylene glycol monomethyl ether dispersed silica sol (trade name, manufactured by Nissan Chemical Industries, Ltd.)

PMA-ST: Propylene glycol monomethyl acetate dispersed silica sol (trade name, manufactured by Nissan Chemical Industries, Ltd.)

KBM 403: 3-glycidoxypropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.)

KBM 503: 2-methacryloxypropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.)

KBM 1003: vinyltrimethoxysilane (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.)

IRGAGURE 651: 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name, manufactured by BASF)

IRGAGURE 127: Synthesis of 2-hydroxy-1- {4- [4- (2-hydroxy-2- methyl- propionyl) -benzyl] -phenyl} -2-methyl-propan- Produce)

IRGAGURE 819: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name, manufactured by BASF)

IRGAGURE 784: bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro- Produce)

IRGAGURE OXE01: 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] (trade name,

IRGAGURE 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (trade name, manufactured by Chiba Specialty Chemicals)

Tinuvin 900: Ultraviolet absorber based on benzotriazole (trade name, manufactured by BASF)

Tinuvin 400: hydroxyphenyltriazine type ultraviolet absorber (trade name, manufactured by BASF)

Tinuvin 292: Light stabilizer (trade name, manufactured by BASF, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl Piperidyl sebacate &lt; / RTI &gt;

Adekastab AO-40: phenolic antioxidant (trade name, manufactured by ADEKA)

ANTIAGE W-400: phenolic antioxidant (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.)

Adekastab PEP-8: Phosphite antioxidant (trade name, manufactured by ADEKA)

Adecastab AO-412S: Thioether-based antioxidant (trade name, manufactured by ADEKA)

ANTIAGE F: Amine antioxidant (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.)

F-552: oligomer containing fluorine group and lipophilic group (nonionic, trade name: Megafac F-552, manufactured by DIC)

F-554: oligomer containing fluorine group and lipophilic group (nonionic, trade name: Megapac F-554, manufactured by DIC Corporation)

F-556: oligomer containing fluorine group, hydrophilic group and lipophilic group (nonionic, trade name: Megapac F-556, manufactured by DIC)

F-557: oligomer containing fluorine group, hydrophilic group and lipophilic group (nonionic, trade name: Megafac F-557, manufactured by DIC)

Preparation Example 2-17 (Resin composition 2-17)

25 parts of resin solution A-2, 20 parts of dipentaerythritol hexaacrylate (DPHA), 45 parts of MEK-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.), and KBM 403 (trade name, (Propylene glycol monomethyl ether acetate; PGMEA) was added so as to have a solid concentration of 30%, and the mixture was stirred to obtain a resin Composition 2-17 was obtained.

With respect to the obtained Resin Composition 2-17, the physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Table 5.

Preparation Examples 2-19, 2-25, 2-31, 2-12, 2-13, 2-3

At the compounding ratios shown in Table 5, the respective resin compositions were obtained in the same manner as in Preparation Example 2-17. With respect to each of the obtained resin compositions, the physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Table 5.

[Table 5]

Preparation Example a-1 (Resin composition a-1)

25 parts of resin solution A-9, 20 parts of dipentaerythritol hexaacrylate (DPHA), 45 parts of NBAC-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.), and KBM 503 (trade name, (Propylene glycol monomethyl ether acetate; PGMEA) was added so as to have a solid content concentration of 25%, and the mixture was stirred to obtain a resin Composition a-1 was obtained.

With respect to the obtained resin composition a-1, the physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Table 6-1.

Preparation examples a-2 to a-15, a-17 and a-23

Using the raw materials shown in Table 6-1 or Table 6-2 at the compounding ratios shown in Table 6-1 or Table 6-2, the respective resin compositions were obtained in the same manner as in Preparation Example a-1. With respect to each of the obtained resin compositions, the physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Tables 6-1 and 6-2.

[Table 6-1]

[Table 6-2]

Preparation Example b-1 (Resin composition b-1)

25 parts of resin solution A-9, 20 parts of dipentaerythritol hexaacrylate (DPHA), 45 parts of NBAC-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.), and KBM 503 (trade name, 5 parts of Irgacure 907 (manufactured by Ciba Geigy) as a photopolymerization initiator, 0.5 part of Antage W-400 (manufactured by Kawaguchi Chemical Industrial Co., Ltd.) as a polymerization inhibitor, and 10 parts of a diluting solvent (propylene glycol mono Methyl ether acetate; PGMEA) was added thereto so as to have a solid content concentration of 25% and stirred to obtain a resin composition b-1.

With respect to the obtained resin composition b-1, the physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Table 7-1.

Preparation examples b-2 to b-8, b-11, b-16

Using the raw materials shown in Table 7-1 or Table 7-2 at the compounding ratios shown in Table 7-1 or Table 7-2, the respective resin compositions were obtained in the same manner as in Preparation Example b-1. With respect to each of the obtained resin compositions, the physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Tables 7-1 and 7-2.

[Table 7-1]

[Table 7-2]

Preparation Example c-1 (Resin composition c-1)

25 parts of resin solution A-9, 20 parts of dipentaerythritol hexaacrylate (DPHA), 45 parts of NBAC-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.), and KBM 503 (trade name, 10 parts as a photopolymerization initiator, 9 parts of Irgacure 907 (manufactured by Ciba Geigy), 0.5 part of Anthage W-400 (manufactured by Kawaguchi Chemical Industrial Co., Ltd.) as a polymerization inhibitor and F-552 (Propylene glycol monomethyl ether acetate; PGMEA) was added so as to have a solid content concentration of 25%, and the mixture was stirred to obtain a resin composition c-1.

With respect to the obtained resin composition c-1, the physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Table 8-1.

Preparation examples c-2 to c-7, c-18

Using the raw materials shown in Table 8-1 or Table 8-2 at the blending ratios shown in Table 8-1 or Table 8-2, the respective resin compositions were obtained in the same manner as in Preparation Example c-1. With respect to each of the obtained resin compositions, the physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Tables 8-1 and 8-2.

[Table 8-1]

[Table 8-2]

Preparation Example d-1 (Resin composition d-1)

25 parts of resin solution A-9, 20 parts of dipentaerythritol hexaacrylate (DPHA), 45 parts of NBAC-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.), and KBM 503 (trade name, 9 parts of Irgacure 907 (manufactured by Ciba Geigy) as a photopolymerization initiator, 0.5 part of Antage W-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor, and 10 parts of a diluting solvent (propylene glycol mono Methyl ether acetate; PGMEA) was added thereto so as to have a solid content concentration of 25% and stirred to obtain a resin composition d-1.

With respect to the obtained resin composition d-1, physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Table 9-1.

Preparation examples d-2 to d-10, d-13, d-18

Using the raw materials shown in Table 9-1 or Table 9-2 at the compounding ratios shown in Table 9-1 or Table 9-2, the respective resin compositions were obtained in the same manner as in Preparation Example d-1. With respect to each of the obtained resin compositions, the physical properties of the coating film were evaluated according to the above-described evaluation method. The results are shown in Tables 9-1 and 9-2.

[Table 9-1]

[Table 9-2]

Claims (7)

A curable resin composition comprising fine silica particles, a coupling agent and an alkali-soluble resin,
The curable resin composition according to any one of claims 1 to 3, wherein the curable resin composition further comprises a trifunctional or more polyfunctional (meth) acrylate compound and at least one of a ketone solvent, an ester solvent, a ketone solvent and an ester solvent, An antioxidant,
And the alkali-soluble resin is an N-substituted maleimide-based monomer unit, a dialkyl-2,2 '- (oxydimethylene) diacrylate-based monomer unit or an N-substituted maleimide- 2 '- (oxydimethylene) diacrylate monomer units, and further has an acid group. The method according to claim 1,
The curable resin composition may further contain a fluorine-based additive,
The content of the fluorine-based additive is 0.1 to 10 parts by mass based on 100 parts by mass of the total solid content of the curable resin composition. The method according to claim 1,
Wherein the curable resin composition further contains at least one polymerization initiator selected from the group consisting of a hydro ketone polymerization initiator and a benzyl ketal polymerization initiator. The method according to claim 1,
Wherein the content of the aminoketone-based polymerization initiator is 10 to 35 parts by mass based on 100 parts by mass of the total solid content of the curable resin composition. A cured film formed by the curable resin composition according to any one of claims 1 to 4. A member for a display device having the cured film according to claim 5. A display device having the cured film according to claim 5.