JP2014126812A - Curable resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition that has excellent adhesibility, dispersibility, developability, light resistant colorability, etc., and that has sufficient surface hardness as well as that has no aging of appearance such as discoloration, coloration or crack even after exposure to high temperature environment, and can maintain the dispersibility, and also that can produce cured material capable of stably exhibiting sufficient surface hardness and adhesibility, to provide a cured membrane formed from said curable resin composition, and to provide a display device member and display device having the cured membrane.SOLUTION: A curable resin composition comprises silica microparticles, coupling agent and alkali-soluble resin, and further comprises a polyfunctional (meth)acrylate compound having 2 or more functionalities and amino ketone-based polymerization initiator, and the content of the amino ketone-based polymerization initiator is 10 to 35 pts.mass based on 100 pts.mass of solid total amount of the curable resin composition.

Description

The present invention relates to a curable resin composition and its use. More specifically, a curable resin composition useful for various applications such as various optical members, electrical equipment and electronic devices, such as constituent members of various display devices, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. The present invention relates to a cured film, a display device member, and a display device.

Curable resin compositions that can be cured by heat or active energy rays include, for example, components of various display devices such as liquid crystal display devices, solid-state imaging devices, touch panel display devices, inks, printing plates, printed wiring boards, and semiconductor devices. Various applications have been studied for various uses such as various optical members such as photoresists, electric machines and electronic devices, and curable resin compositions having excellent characteristics required for each use have been developed. Among these applications, the touch panel display device can perform an input operation by touching the screen with a finger, a touch pen, or the like, instead of the conventional input operation using a keyboard, a mouse, or the like due to the development of information technology in recent years. Since it is a display device that can be input and the input operation is intuitive and easy to understand, it has been rapidly spread in recent years.

Such touch panel type display devices are roughly classified into two types, that is, a method using electricity and a method not using it in the principle of detecting the touched position. Resistive film systems and electrostatic capacity systems are used as the methods using electricity, and ultrasonic systems and optical systems are used as non-used systems. It has become. In the resistive film method, a film is usually arranged on a glass substrate through a small spacer, and a transparent conductive film such as ITO (Indium Tin Oxide) is formed on each of the glass substrate and the opposite surface of the film. Although it has the structure described above, the demand for the electrostatic capacity method is increasing due to its weakness against aging and shock, and many malfunctions, and development is in progress.

Generally, a capacitive touch panel display device has a structure in which a transparent conductive film such as ITO is formed on a substrate and a protective film or an insulating film for protecting the transparent conductive film is further formed. In general, the insulating film is required to have high adhesion, durability, transparency and surface hardness with the transparent conductive film. In particular, because it is often exposed to high-temperature environments in the manufacturing stage of touch panel display devices, transparency is maintained without changes over time such as discoloration, coloring, and cracks even after exposure to high-temperature environments. It is required to stably exhibit sufficient surface hardness and adhesion.

One of main components such as a liquid crystal display device and a solid-state image sensor is a color filter. In general, the color filter is composed of a protective film provided to cover and protect the pixel and the resin black matrix and to flatten the unevenness in addition to the base material, the pixel and the resin black matrix (BM). . Similar to the protective film for touch panel display devices, these color filter protective films maintain transparency with no change in appearance over time, such as discoloration, coloring, and cracks, even after exposure to high temperature environments. It is desired to be able to stably exhibit sufficient surface hardness and adhesion.

Examples of conventional curable resin compositions for protective films include, for example, an ethylenically unsaturated compound as a thermal crosslinking agent / a compound having an epoxy group in the molecule, a photopolymerization initiator, a specific alkali-soluble resin, and silica sol. The photosensitive thermosetting resin composition for protective films to contain is disclosed (refer patent document 1). Further, a photocurable composition comprising an alkali-soluble resin, silica fine 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 is provided. It is disclosed (see Patent Document 2).

JP 2007-334290 A JP 2011-039165 A

As described above, protective films and insulating films in various display devices are required to exhibit excellent adhesion, transparency and surface hardness even after being exposed to a high temperature environment. In recent years, with the advancement of technologies such as display devices, there has been a strong demand for higher performance for each member used, but with conventional resin compositions for protective films, However, the present situation is that the demand for higher performance cannot be fully met. For example, since the resin composition described in Patent Document 1 has insufficient adhesion, surface hardness, and dispersibility, there is room for improvement in this respect, and excellent physical properties can be exhibited even after high temperature exposure. There was also room for innovation. In the resin composition described in Patent Document 2, there is room for improvement in order to have sufficient adhesion and surface hardness even after high temperature exposure.

The present invention has been made in view of the above situation, and has excellent adhesion, dispersibility, developability, light-coloring resistance, etc., has sufficient surface hardness, and discolors even after being exposed to a high temperature environment. It is intended to provide a curable resin composition capable of providing a cured product that can maintain dispersibility without deterioration in appearance such as coloration, coloring, and cracks, and can stably exhibit sufficient surface hardness and adhesion. Objective. Another object of the present invention is to provide a cured film formed of such a curable resin composition, and a display device member and a display device having the cured film.

The present inventors have made various studies on curable resin compositions useful for protective films, insulating films, etc. in various display devices. As a result, the composition containing silica fine particles, a coupling agent, and an alkali-soluble resin is considered photosensitive. It has been found that a cured product having adhesion and smoothness can be obtained, and such a composition further contains a polyfunctional (meth) acrylate compound having two or more functions. It has been found that the surface hardness is sufficient. Further, if it contains a predetermined amount of an aminoketone-based polymerization initiator, the curability will be even better, so a cured product that is more excellent in light resistance and in which deterioration over time (coloring, etc.) is further suppressed. I found it possible to get. Since the cured product obtained from such a composition is more sufficiently suppressed from deteriorating, the effects of the present invention such as excellent adhesion, transparency, and surface hardness are more stably exhibited. It becomes possible. Such a curable resin composition is particularly suitable as a protective film or a resin composition for forming an insulating film used for a touch panel display device, a color filter, and the like. It has been found that the structural member and the display device can sufficiently meet the demand for higher performance in recent years, and have conceived that the above-mentioned problems can be solved brilliantly, and have reached the present invention.

Note that the content of the aminoketone polymerization initiator in the present invention is much larger than the amount of the polymerization initiator used in a normal curable resin composition. In general, when an aminoketone polymerization initiator is used in the curable resin composition, the content of the aminoketone polymerization initiator is taken into consideration in view of film reduction and transmittance reduction due to volatilization of the aminoketone polymerization initiator in the curing process. It is normal to set a small number. However, the present inventors have set the content of the aminoketone polymerization initiator in a large amount contrary to such common technical common knowledge, so that the curability of the curable resin composition is sufficiently increased. It was newly found that the light coloring resistance and developability are remarkably improved.

That is, the present invention is a curable resin composition comprising silica fine particles, a coupling agent and an alkali-soluble resin, the curable resin composition further comprising a bifunctional or higher polyfunctional (meth) acrylate compound, and The curable resin composition contains an aminoketone polymerization initiator, and the content of the aminoketone polymerization initiator is 10 to 35 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition.
The present invention is also a cured film formed from the curable resin composition.
The present invention is also a member for a display device having the cured film.
The present invention is also a display device having the cured film.
The present invention is described in detail below. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.

The curable resin composition of the present invention includes silica fine particles, a coupling agent, an alkali-soluble resin, a bifunctional or higher polyfunctional (meth) acrylate compound, and an aminoketone polymerization initiator. Can use 1 type (s) or 2 or more types, respectively. Further, if necessary, one or more other components may be further contained.

In the present specification, the “total amount of solids” means the total amount of silica fine particles, a coupling agent, an alkali-soluble resin and a polymerizable monomer. That is, the total solid content of the curable resin composition refers to the case where silica fine particles, a coupling agent, an alkali-soluble resin, a bifunctional or higher polyfunctional acrylate, and another polymerizable monomer are included. It means the total amount of other polymerizable monomers.

<Silica fine particles>
The silica fine particles are not particularly limited as long as they are metal oxides having silicon atoms, but may be composite metal oxides containing other metal atoms in addition to silicon atoms.
The average particle diameter of the silica fine particles is preferably 1 to 500 nm, for example. By being in this range, the dispersibility and dispersion stability of the silica fine particles become sufficient, and it becomes possible to give a cured product that is excellent in dispersibility and further suppressed in change with time. More preferably, it is 1-300 nm, More preferably, it is 1-200 nm, Most preferably, it is 1-100 nm.
The average particle diameter can be measured, for example, using a laser diffraction particle size distribution measuring machine.

The fine silica particles may be in the form of a dried powder or in the form of a dispersion (such as colloidal silica) dispersed in an organic solvent, but the dispersion of the curable resin composition may be used. From the viewpoint of stability, it is preferable to use a dispersion in which the dispersion is dispersed in an organic solvent. That is, the silica fine particles are preferably contained in the curable resin composition as an organic solvent dispersion.

Examples of the organic solvent (dispersion medium) used for forming the dispersion include ketone solvents, ester solvents, ether solvents, alcohol solvents, amide solvents, xylene, toluene, and the like. These 1 type (s) or 2 or more types can be used. Among them, it is preferable to use a ketone solvent, an ester solvent and / or an ether solvent. More preferably, a ketone-based solvent and / or an ester-based solvent is used, whereby dispersibility can be maintained without changes in appearance such as discoloration, coloring, and cracks even after exposure to high temperatures, and sufficient surface hardness and The effect of the present invention that a cured product having adhesiveness can be obtained can be further exhibited. Thus, a form including the silica fine particles as a dispersion formed by dispersing the silica fine particles in a ketone solvent and / or an ester solvent is also a preferred form of the present invention.

Examples of the ketone solvent include methyl ethyl ketone and methyl isobutyl ketone.
As the ester solvent, for example, ethyl acetate, butyl acetate, propylene glycol monomethyl acetate and the like are suitable.
Examples of the ether solvent include acetylated products of m alkylene glycol and n alkyl ether (m and n are the same or different and are one or more multiple prefixes represented by mono, di, tri, tetra, etc.). Etc. are suitable. Examples of malkylene glycol n alkyl ethers include ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and the like, but ethers having a hydroxyl group at the terminal, such as m alkylene glycol n alkyl ether itself (that is, alcohol having an ether bond). Class) has performance as an alcohol solvent due to its terminal hydroxyl group, and therefore corresponds to an alcohol solvent instead of an ether solvent.
Examples of the alcohol solvent include methanol, isopropanol, ethylene glycol, butanol, and the like, and ethers having a hydroxyl group at the terminal (alcohols having an ether bond) such as the m alkylene glycol n alkyl ether described above. .

When a dispersion formed by dispersing in an organic solvent is used as the silica fine particles, the amount of the organic solvent (dispersion medium) is preferably set to an amount that can sufficiently disperse the silica fine particles. That is, the amount of the organic solvent used can be adjusted so that the content of the silica fine particles in the curable resin composition is within the above-described preferable range and the silica fine particles are sufficiently dispersed. preferable. For example, the total amount of the organic solvent as the dispersion medium is preferably 50 parts by mass or more with respect to 100 parts by mass of the silica fine particles. More preferably, it is 70 mass parts or more, More preferably, it is 100 mass parts or more. Moreover, since there exists a possibility that a hardening process cannot be performed simply when there is too much solvent amount more than necessary, it is suitable that it is 600 mass parts or less. More preferably, it is 550 mass parts or less, More preferably, it is 500 mass parts or less.

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

In the curable resin composition, the content of the silica fine particles is preferably 5% by mass or more in a total solid content of 100% by mass of the curable resin composition. Thereby, the surface hardness of the cured product becomes more sufficient. More preferably, it is 10 mass% or more, More preferably, it is 15 mass% or more, Most preferably, it is 20 mass% or more. In addition, from the viewpoint of developability, dispersion stability, and the like, it is preferably 70% by mass or less. More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less, Most preferably, it is 45 mass% or less.
In the present invention, since a polyfunctional (meth) acrylate compound having two or more functions (preferably a polyfunctional (meth) acrylate compound having three or more functions) is included, it is normally expected that curing shrinkage will increase. In such a case, it is conceivable to increase the content of silica fine particles to reduce curing shrinkage. However, in the present invention, the content of the silica fine particles is reduced by configuring the curable resin composition as described above. Even if it is made low as the above-mentioned suitable range, hardening shrinkage is relieved and the cured film which shows high hardness and high smoothness can be obtained. Therefore, it is possible to sufficiently avoid the deterioration in developability that is assumed when a large amount of silica fine particles is contained.

<Coupling agent>
The above-mentioned coupling agent has a property of bonding with an oxidized surface of an inorganic substance by a hydrolysis reaction or a condensation reaction. In the present invention, for example, ITO or the like is deposited by using this property. Adhesion to the substrate etc. is fully exhibited. Specifically, as such a coupling agent, for example, a coupling agent having a reactive group such as a vinyl group, a (meth) acryl group, an epoxy group, an amino group, a mercapto group, or an isocyanate is preferable. Especially, what has a vinyl group, a (meth) acryloyl group, and / or an epoxy group as a reactive group is preferable. Moreover, what contains silicon, a zirconia, titanium, and / or aluminum etc. as a center metal is suitable, for example, what has silicon as a center metal is preferable, More preferably, it is a silane coupling agent. By using a silane coupling agent, the dispersibility, adhesion and surface hardness of the cured product can be made more satisfactory.
In addition, as a coupling agent which has metals other than silicon as a central metal, a zirco aluminate coupling agent, a titanate coupling agent, etc. are mentioned, for example.

As the silane coupling agent, and one or more reactive groups described above, the alkoxysilane group _{^{(-Si (OR 1) 3-}} n (R 2) n; OR 1 is a hydrolysable group And R ¹ is preferably a hydrocarbon group, R ² is a hydrocarbon group, and n is 0, 1 or 2. Among them, it is preferable to use a silane coupling agent having a vinyl group, a (meth) acryloyl group and / or an epoxy group, and thereby disperse without change over time such as discoloration, coloring, cracks, etc. even after high temperature exposure. It is possible to obtain a cured product that can maintain the properties more sufficiently and that has more sufficient surface hardness and adhesion.

Examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane.
Examples of the silane coupling agent having the (meth) acryloyl group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyltri Examples include methoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyltriethoxysilane.
Specific examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Examples thereof include glycidoxypropylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

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

In the curable resin composition, the content of the coupling agent is preferably 3% by mass or more in a total solid content of 100% by mass of the curable resin composition. By including 3 mass% or more, it can have more sufficient adhesiveness and surface hardness even after high temperature exposure. More preferably, it is 4 mass% or more, More preferably, it is 5 mass% or more. Moreover, it is suitable that it is 30 mass% or less from viewpoints, such as the storage stability of curable resin composition. More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.

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

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, it is preferably 20 mgKOH / g or more and less than 300 mgKOH / g. . Thereby, more sufficient alkali solubility is expressed, and it becomes possible to obtain a cured product having better developability. The lower limit of the acid value is more preferably 30 mgKOH / g or more, and still more preferably 40 mgKOH / g or more. Moreover, 250 mgKOH / g or less is more preferable, More preferably, it is 200 mgKOH / g or less.
The acid value of the polymer is measured, for example, with an automatic titration apparatus (trade name “COM-555” manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 N aqueous KOH solution as the titrant. The acid value per solid content can be calculated from the acid value of the solution and the solid content of the solution. The solid content of the polymer solution can be determined as follows.
About 0.3 g of the polymer solution is weighed into an aluminum cup, dissolved by adding about 1 g of acetone, and then naturally dried at room temperature. Then, using a hot air dryer (trade name “PHH-101” manufactured by Espec Corp.), after drying at 140 ° C. for 3 hours, it is allowed to cool in a desiccator and the mass is measured. From the mass reduction amount, the solid content concentration of the polymer solution is calculated.

The alkali-soluble resin preferably has a weight average molecular weight of 2000 to 250,000. When the molecular weight is within this range, better developability can be exhibited. More preferably, it is 3000-100000, More preferably, it is 4000-50000. In addition, when the alkali-soluble tree has a high molecular weight, the one having a higher acid value is more easily developed.
The weight average molecular weight is determined, for example, by a GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corp.) and column TSKgel SuperHZM-M (manufactured by Tosoh Corp.) with polystyrene as a standard substance and tetrahydrofuran as an eluent. Can do.

As the alkali-soluble resin, for example, a polymer obtained by polymerizing a monomer component containing a monomer having an acid group and a polymerizable double bond (also referred to as a base polymer), as described later, The base polymer is preferably a polymer obtained by reacting a compound having a functional group capable of binding to an acid group and a polymerizable double bond (also referred to as a side chain double bond-containing polymer). The latter side chain double bond-containing polymer is more preferable. In addition, each monomer used can use 1 type (s) or 2 or more types, respectively.

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; maleic acid and fumaric acid. Unsaturated polycarboxylic acids such as acid, itaconic acid, citraconic acid and mesaconic acid; unsaturated carboxyl groups such as succinic acid mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryloyloxyethyl) Unsaturated monocarboxylic acids in which the chain is extended; Unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; Phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); etc. Is mentioned. Among these, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. More preferable are unsaturated monocarboxylic acids in terms of reactivity, alkali solubility, etc., and more preferable is (meth) acrylic acid (that is, acrylic acid and methacrylic acid), and among these, methacrylic acid is particularly preferable. It is an acid.

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

The monomer component includes other radical polymerizable monomer (hereinafter also referred to as “other monomer”) in addition to the above-described monomer having an acid group and a polymerizable double bond. It may be. Examples of such other monomers include N-substituted maleimide monomers, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers, and (meth) acrylic acid ester monomers. One type or two or more types of aromatic vinyl monomers are preferably used. In particular, resins containing N-substituted maleimide monomer units and / or dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer units have improved heat resistance, colorant dispersibility, hardness, etc. It is possible to provide a cured film. Thus, the form in which the alkali-soluble resin is a polymer having an N-substituted maleimide monomer unit and / or a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer unit is the present invention. This is one of the preferred forms.
The above-mentioned resin containing a monomer unit is, for example, a resin containing a monomer-derived constituent unit by a monomer polymerization reaction or a crosslinking reaction.

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

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

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

The content ratio of the N-substituted maleimide monomer and / or dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer (total ratio when two kinds are used) is, for example, the base polymer. It is preferable that it is 1 mass% or more with respect to 100 mass% of components, and it is preferable that it is 40 mass% or less. Within this range, it is possible to obtain a cured film having further improved heat resistance, colorant dispersibility, hardness, and the like. In addition, when the content of the main chain ring structure increases, the adhesion tends to be improved, and when the content ratio of the N-substituted maleimide monomer is too large, the development speed cannot be more appropriate. There is. The content ratio of the N-substituted maleimide monomer and / or dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer is more preferably 2 to 40% by mass, still more preferably 3 to 35% by mass. It is.
In addition, when the addition amount of the N-substituted maleimide monomer is further increased, a cured product that is superior in terms of hardness can be obtained. Further, by using a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer, a cured product that is more excellent in terms of heat-resistant colorability can be obtained.

Examples of the (meth) acrylic acid ester monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth ) N-butyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, (meth) acrylic t- Amyl, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, ( Octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid ester Ril, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (Meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid glycidyl, (meth) acrylic acid β -Methyl glycidyl, (meth) acrylic acid β-ethyl glyci , Methyl (meth) acrylate (3,4-epoxycyclohexyl) methyl, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, etc. , 4-Dioxaspiro [4,5] dec-2-ylmethacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3- Dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (Meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, etc. Examples of commercially available products of these compounds include MMDOL30, MEDOL30, MIBDOL30, CHDOL30, MEDOL10, MIBDOL10, MIBDOL10, CHDOL10, Biscote 150, Biscote 160 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), ACMO (Kojinsha) Manufactured) and the like. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate are preferred in terms of excellent heat resistance. More preferably, methyl (meth) acrylate, benzyl (meth) acrylate and / or cyclohexyl (meth) acrylate are used in terms of excellent heat resistance, adhesion and developability.

It is also preferable to use α- (unsaturated alkoxyalkyl) acrylate as the (meth) acrylic acid ester monomer.
Examples of the α- (unsaturated alkoxyalkyl) acrylate include α-allyloxymethyl acrylic acid, α-allyloxymethyl acrylate methyl, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl acrylate n- Propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α-allyloxy N-amyl methyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopenter α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate, α -Allyloxymethyl acrylate s-hexyl, α Allyloxymethyl acrylate n-heptyl, α-allyloxymethyl acrylate n-octyl, α-allyloxymethyl acrylate s-octyl, α-allyloxymethyl acrylate t-octyl, α-allyloxymethyl acrylate 2 -Ethylhexyl, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate, α-allyloxymethyl acrylate Tridecyl allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-allyloxy Chain saturated hydrocarbon group-containing α such as stearyl methyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate -(Allyloxymethyl) acrylate is preferred. Among them, methyl α-allyloxymethyl acrylate (also referred to as “α- (allyloxymethyl) methyl acrylate”) is particularly preferable.

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

The monomer components used to obtain the base polymer are further methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate and α- (unsaturated alkoxyalkyl) acrylate. A form containing at least one (meth) acrylic acid ester monomer selected from the group consisting of is also a preferred form of the present invention.

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

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

As said other monomer, 1 type (s) or 2 or more types, such as the following compound, can also be used, for example, The content rate shall be 20 mass% or less in 100 mass% of said base polymer components. Is preferred.
(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; heavy materials such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone and polycaprolactam Macromonomers having a (meth) acryloyl group at one end of the combined molecular chain; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Class: 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, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and other vinyl ethers; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole N-vinyl compounds such as N-vinylmorpholine and N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate;

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

The polymerization initiating method in the above polymerization reaction may be performed by supplying energy necessary for initiating polymerization from an active energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc. If an agent is used in combination, the energy required for initiation of polymerization can be greatly reduced, and reaction control is facilitated, which is preferable.
The molecular weight of the polymer obtained by polymerizing the monomer components can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.

When the monomer component is polymerized by a solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction, and the polymerization mechanism and the type of monomer used. May be appropriately set according to the polymerization conditions such as the amount, the polymerization temperature, the polymerization concentration, etc., but when a solvent is used as a diluent or the like later when the curable resin composition is used, a solvent containing the solvent is used. It is efficient and preferable to use for solution polymerization of monomer components.

As said solvent, the following compound etc. are mentioned suitably, for example, These 1 type (s) or 2 or more types can be used.
Monoalcohols such as methanol, ethanol, isopropanol, n-butanol, 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 monoethers such as glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol Jie Glycol ethers such as ether 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; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Esters of glycol monoethers such as propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate; 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-methoxypropionate, methyl 3-ethoxypropionate, 3 -Alkyl esters such as ethyl ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; acetone, methyl ethyl ketone, methyl isobutyrate Ketones such as ruketone 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 ;etc.

Among these solvents, propylene glycol monomethyl ether, propylene are used because of the solubility of the resulting polymer, surface smoothness when forming a coating film, little influence on the human body and the environment, and industrial availability. It is more preferable to use glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, or ethyl lactate.

As the usage-amount of the said solvent, it is suitable that it is 50-1000 mass parts with respect to 100 mass parts of said base polymer components. More preferably, it is 100-500 mass parts.

When the monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable 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. Depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc. And may be selected as appropriate. Moreover, you may use together reducing agents, such as transition metal salt and amines, with a polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butylperoxy- 2-ethylhexanoate, azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis ( 2-methylpropionate), hydrogen peroxide, persulfate, etc., which are usually used as polymerization initiators, such as peroxides and azo compounds, may be used alone or in combination of two or more. May be.

The amount of the polymerization initiator used may be appropriately set according to the type and amount of the monomer used, the polymerization conditions such as the polymerization temperature and the polymerization concentration, the molecular weight of the target polymer, etc., and is particularly limited. It is not a thing. For example, in order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the base polymer component. More preferably, it is 0.5-15 mass parts.

In the above polymerization, a chain transfer agent usually used may be used as necessary. Preferably, a polymerization initiator and a chain transfer agent are used in combination. In addition, when a chain transfer agent is used at the time of superposition | polymerization, it exists in the tendency which can suppress the increase in molecular weight distribution or gelatinization.

Examples of the chain transfer agent include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and n-mercaptopropionic acid n- Octyl, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3- Mercaptocarboxylic esters such as mercaptopropionate); alkyl mercapts such as ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane Mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; Aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; Tris [(3- Mercaptopropionyloxy) -ethyl] isocyanurate and other mercaptoisocyanurates; 2-hydroxyethyl disulfide and diethyl sulfides such as tetraethyl thiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; α-methylstyrene dimer and the like Body dimers; alkyl halides such as carbon tetrabromide. These may be used alone or in combination of two or more.

Among these, mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercaptoisocyanurates, in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. It is preferable to use a compound having a mercapto group such as More preferred are alkyl mercaptans, mercaptocarboxylic acids, mercaptocarboxylic acid esters, and still more preferred are n-dodecyl mercaptan and mercaptopropionic acid.

The amount of the chain transfer agent used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer to be used, polymerization conditions such as polymerization temperature and polymerization concentration, and the molecular weight of the target polymer. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the base polymer component. More preferably, it is 0.5-15 mass parts.

Regarding the polymerization conditions, the polymerization temperature may be appropriately set according to the type and amount of the monomer to be used, the type and amount of the polymerization initiator, and is preferably 50 to 150 ° C, for example, 70 to 120 ° C. is more preferable. Also, the polymerization time can be appropriately set similarly, but for example, 1 to 5 hours is preferable, and 2 to 4 hours is more preferable.

The alkali-soluble resin preferably has a double bond in the side chain. Specifically, a polymer (base polymer) obtained by polymerizing the above monomer components and a compound obtained by reacting a compound having a functional group capable of binding to an acid group and a polymerizable double bond. It is preferably a polymer (also referred to as a side chain double bond-containing polymer).

In the compound having a functional group capable of binding to the acid group and a polymerizable double bond, examples of the polymerizable double bond include a (meth) acryloyl group, a vinyl group, an allyl group, a methallyl group, and the like. A compound having one or more of these compounds is suitable. Of these, a (meth) acryloyl group is preferable in terms of reactivity. In addition, examples of the functional group capable of binding to an acid group include a hydroxy group, an epoxy group, an oxetanyl group, an isocyanate group, and the like, and those having one or more of these as the compound are suitable. . Of these, epoxy groups (including glycidyl groups) are preferred from the viewpoint of the speed of the modification treatment reaction, heat resistance, and dispersibility.

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

As a method for obtaining the side chain double bond-containing polymer, for example, when reacting the base polymer component with a compound having a functional group capable of binding to an acid group and a polymerizable double bond, the base polymer A method in which the amount of the acid group (preferably carboxyl group) of the component is larger than the amount of the compound having a functional group capable of binding to the acid group and a polymerizable double bond; the base polymer component and the acid group And a method of reacting a compound having a polybasic acid anhydride group after reacting with a compound having a functional group and a polymerizable double bond.

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

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

The amount of the catalyst used is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the base polymer component and the compound having a functional group capable of binding to an acid group and a polymerizable double bond group. It is preferable that More preferably, it is 0.1-3.0 mass parts.

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

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

The amount of the polymerization inhibitor used is a functional group capable of bonding with the base polymer component and the acid group from the viewpoint of ensuring sufficient polymerization prevention effect and curability when the curable resin composition is used. And it is preferable that it is 0.001-1.0 mass part with respect to 100 mass parts of total amounts with the compound which has a polymerizable double bond. More preferably, it is 0.01-0.5 mass part.

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

The side chain double bond-containing polymer preferably has a double bond equivalent of 200 to 10,000. By setting it as such a range, it is expected that the sufficient storage stability of the polymer and the good plate-making characteristics in the sensitivity and pattern shape of the curable resin composition of the present invention will be compatible at a higher level. it can. More preferably 250 or more, further preferably 300 or more, particularly preferably 350 or more, more preferably 400 or more, still more preferably 440 or more, more preferably 5000 or less, still more preferably 4000 or less, particularly preferably. 3000 or less, more preferably 2000 or less, and most preferably 1900 or less.
The double bond equivalent is the mass (g) of the solid content of the polymer solution per 1 mol of the double bond of the polymer. The mass of the solid content of the polymer solution here means the mass of the base polymer component, the mass of the compound having a functional group capable of binding to an acid group and a polymerizable double bond group, and the mass of a chain transfer agent. Is the total. It can be determined by dividing the mass of the solid content of the polymer solution by the double bond amount of the polymer. The double bond amount of the polymer can be determined from the amount of the charged acid group and the compound having a functional group capable of bonding and a polymerizable double bond.

In the curable resin composition, the content of the alkali-soluble resin is preferably 5% by mass or more and 70% by mass or less with respect to 100% by mass of the total solid content of the curable resin composition. Is preferred. By being in such a range, it becomes possible to show the effect of the present invention more remarkably. More preferably, it is 10-65 mass%, More preferably, it is 10-50 mass%, Most preferably, it is 10-40 mass, More preferably, it is 10-35 mass%, Most preferably, it is 15-35 mass%.

In the present invention, a particularly preferred form is that the alkali-soluble resin can bind to an acid group in a polymer obtained by polymerizing a monomer component containing a monomer having an acid group and a polymerizable double bond. A polymer obtained by reacting a compound having a functional group and a polymerizable double bond, having an acid value of 40 to 200 mg KOH / g, a weight average molecular weight of 4000 to 50000, and a double bond equivalent of 440 to 1900 g / equivalent The content of the alkali-soluble resin is 10 to 40% by mass with respect to 100% by mass of the total solid content of the curable resin composition. By being a curable resin composition of such a form, it becomes possible to give the hardened | cured material which can make outstanding developability and high hardness still compatible.
%.

<Bifunctional or higher polyfunctional (meth) acrylate compound>
The bifunctional or higher polyfunctional (meth) acrylate compound (hereinafter also simply referred to as “polyfunctional (meth) acrylate compound”) is a compound having two or more (meth) acryloyl groups in one molecule. By including such a compound, the curable resin composition has excellent 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 3 or more, more preferably 4 or more, and still more preferably 5 or more. Further, from the viewpoint of further suppressing curing shrinkage, the functional number is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less.
In addition, although a (meth) acryloyl group means a methacryloyl group and / or an acryloyl group, an acryloyl group is preferable from the viewpoint of better reactivity. That is, the polyfunctional (meth) acrylate compound is particularly preferably a polyfunctional acrylate compound having two or more acryloyl groups.

Although it does not specifically limit as molecular weight of the said polyfunctional (meth) acrylate compound, For example, 2000 or less is suitable from a viewpoint of handling.

Although it does not specifically limit as said polyfunctional (meth) acrylate compound more than bifunctional, For example, the following compound etc. are mentioned.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Bifunctional (meth) acrylate compounds such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate;
Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (Meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol Trifunctional or more polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate;
In the present invention, it is particularly preferable to use a trifunctional or higher polyfunctional (meth) acrylate compound. Thus, the form in which the polyfunctional (meth) acrylate compound having two or more functions is a polyfunctional (meth) acrylate compound having three or more functions is also a preferred form of the present invention.

Although content of the said polyfunctional (meth) acrylate compound is not specifically limited, For example, from a viewpoint excellent in developability and platemaking property, it is 5 mass% or more with respect to 100 mass% of solid content total amount of curable resin composition. It is preferable that the amount is 60% by mass or less. More preferably, it is 8-50 mass%, More preferably, it is 15-50 mass%.

<Aminoketone polymerization initiator>
As the aminoketone polymerization initiator, an aminoketone compound usually used as a photopolymerization initiator may be used. For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (IRGACURE 369), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (IRGACURE 379) and the like ( All of them are manufactured by BASF).

As content of the said amino ketone type | system | group polymerization initiator, it is 10-35 mass parts with respect to 100 mass parts of solid content total amount of the curable resin composition of this invention, for example. In this way, by using a much larger amount of aminoketone-based polymerization initiator than the usual use amount, the curability becomes even better, so that it is more excellent in light resistance and more deteriorated over time (coloring, etc.). It becomes possible to obtain a cured product that is further suppressed. In addition, the cured product obtained from the curable resin composition is more sufficiently suppressed from being deteriorated, so that the effects of the present invention such as excellent adhesion, transparency, and surface hardness are further stabilized. Can be demonstrated. Further, considering the balance between the influence of the decomposition product of the polymerization initiator and the economy, it is appropriate that the amount is 35 parts by mass or less. The content is preferably 12 parts by mass or more, more preferably 15 parts by mass or more. Moreover, Preferably it is 30 mass parts or less, More preferably, it is 25 mass parts or less.

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

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

As the solvent, those usually used can be used, and may be appropriately selected according to the purpose and application, and are not particularly limited, and examples thereof include the following compounds. These may be used alone or in combination of two or more.
Monoalcohols such as methanol, ethanol, isopropanol, n-butanol, 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 monoethers such as glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol Jie Glycol ethers such as ether 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; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Esters of glycol monoethers such as propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate; 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-methoxypropionate, methyl 3-ethoxypropionate, 3 -Alkyl esters such as ethyl ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; acetone, methyl ethyl ketone, methyl isobutyrate Ketones such as ruketone 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; etc.

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

-Other polymerizable monomers-
The curable resin composition may further include a polymerizable monomer other than the polyfunctional (meth) acrylate compound (also referred to as other polymerizable monomer). The other polymerizable monomer is preferably a radical polymerizable monomer. The radical polymerizable monomer is an active energy ray such as free radical, electromagnetic wave (infrared ray, ultraviolet ray, X-ray, etc.), electron beam, etc. It is a low molecular weight compound having a radical polymerizable unsaturated group that is polymerized by irradiation of the above.

Examples of the radical polymerizable monomer include a monofunctional radical polymerizable compound having one radical polymerizable unsaturated group in the molecule, and a polyfunctional radical polymerizable compound having two or more radicals Except those corresponding to functional (meth) acrylate compounds), and one or more of these can be used. Among these, from the viewpoint of curability, a polyfunctional radically polymerizable compound is preferable. More preferably, (meth) acryloyl such as polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates, (meth) acryloyl group-containing isocyanurates from the viewpoint of reactivity, economy, availability, etc. It is a polyfunctional monomer having a group.
The molecular weight of the radical polymerizable monomer is not particularly limited, but is preferably 2000 or less, for example, from the viewpoint of handling.

The monofunctional radically polymerizable compound is not particularly limited. For example, the above-mentioned (meth) acrylic acid ester monomers; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated groups and carboxyl groups Monocarboxylic acids with extended chain; aromatic vinyl monomers; N-substituted maleimide monomers; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; And the like.

It does not specifically limit as said polyfunctional radically polymerizable compound, For example, the following compounds other than unsaturated polyhydric carboxylic acids and unsaturated acid anhydrides mentioned above are mentioned.
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 alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrile Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethyl Lumpur propane tetravinyl ether, ethylene oxide adduct of pentaerythritol tetravinyl ether, polyfunctional vinyl ethers such as ethylene oxide adduct of dipentaerythritol hexavinyl ether;
(Meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 1-methyl-2-vinyloxyethyl, (meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4 -Vinyloxybutyl, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, ( Vinyl ether group-containing (meth) acrylic such as p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, and 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate Acid esters;

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, Ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethyl Lumpur propane tetra allyl ether, ethylene oxide adduct of pentaerythritol tetra-allyl ether, polyfunctional allyl ethers such as ethylene oxide adduct of dipentaerythritol hexa-allyl ether;
Allyl group-containing (meth) acrylic acid esters such as (meth) acrylic acid allyl;
Multifunctional (meth) acryloyl groups such as tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri (methacryloyloxyethyl) isocyanurate Containing isocyanurates; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate;
Reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl group-containing (meth) acrylic esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Polyfunctional urethane (meth) acrylates obtained by: polyfunctional aromatic vinyls such as divinylbenzene;

The content of the other polymerizable monomer is 10% with respect to 100% by mass of the total solid content of the curable resin composition in order to sufficiently exhibit the effects derived from the polyfunctional (meth) acrylate compound described above. % Or less is preferable. More preferably 5% by mass or less, still more preferably 1% by mass or less, particularly preferably 0% by mass, that is, it is particularly preferable that substantially no polymerizable monomer other than the polyfunctional (meth) acrylate compound is contained. Is preferred.

-Other photoinitiators-
The curable resin composition may further include a photopolymerization initiator other than the aminoketone polymerization initiator (also referred to as other photopolymerization initiator). The other photopolymerization initiator is preferably a radical polymerizable photopolymerization initiator. A radical polymerizable photopolymerization initiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam, and one or more commonly used ones can be used. . In the present invention, if necessary, a photosensitizer or a radical photopolymerization accelerator may be used alone or in combination of two or more. By using a photosensitizer and / or a radical photopolymerization accelerator together with a photopolymerization initiator, sensitivity and curability are further improved.

Specifically as said other photoinitiator, the following compound etc. are mentioned, for example.
2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2 -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) fur Sulfonyl] -1-alkyl phenone compounds such as butanone;
Benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 2-carboxybenzophenone;
Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone;

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, and other halomethylated triazine compounds ;
2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Halomethylated oxadiazole compounds such as diazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1, Biimidazole compounds such as 2'-biimidazole;
1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 Oxime ester compounds such as -yl]-, 1- (O-acetyloxime);
Titanocene compounds such as bis (η5-2,4-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 compounds such as 9-phenylacridine;

Benzyl ketal compounds such as 2,2-dimethoxy-1,2-diphenylethane-1-one (“IRGACURE651”, manufactured by BASF), phenylglyoxylic acid methyl ester (“DAROCUR MBF”, manufactured by BASF);
1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE184”, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (“DAROCUR1173”, manufactured by BASF), 1- [4 -(2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE2959", manufactured by BASF), 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one ("IRGACURE127", manufactured by BASF), [1-hydroxy-cyclohexyl-phenyl-ketone + benzophenone] (" Hydroketone compounds such as “IRGACURE500” (manufactured by BASF);
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide ("LUCIRIN TPO", manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("IRGACURE819", manufactured by BASF) Phosphine oxide compounds such as
Such as bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (“IRGACURE784”, manufactured by BASF) Titanocene compounds;
Oxime ester compounds such as 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (“IRGACURE OXE01”, manufactured by BASF);

Examples of the photosensitizer and photo radical polymerization accelerator include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid. Examples include dialkylaminobenzene compounds such as 2-ethylhexyl; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole.

The content (total amount) of the photosensitizer and the radical photopolymerization accelerator may be appropriately set according to the purpose and application, and is not particularly limited. However, the balance between curability, influence of degradation products, and economic efficiency. From this viewpoint, the amount is preferably 0.001 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention. More preferably, it is 0.01-15 mass parts, More preferably, it is 0.05-10 mass parts.

-Polymerization inhibitor-
The curable resin composition may also contain one or more polymerization inhibitors from the viewpoint of more appropriately controlling the curing reaction. As the polymerization inhibitor, for example, compounds usually used as ultraviolet absorbers, light stabilizers (HALS), antioxidants (including anti-aging agents) and the like can be used. Specific examples include the following compounds.
Tinuvin 400, Tinuvin 405 (2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, (2-ethylhexyl) glycidic acid ester) Reaction product), Tinuvin 460 (2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3-5-triazine), Tinuvin 477 (Water Hydroxyphenyl triazine (HPT) UV absorbers such as dispersed hydroxyphenyl triazine (HPT) UV absorber), Tinuvin 479 (both manufactured by BASF), Adekastab LA-46 (all manufactured by ADEKA), etc .;
Tinuvin PS (2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole), Tinuvin 99-2, Tinuvin 384-2, Tinuvin 900 (2- (2H-benzotriazol-2-yl)- 4,6-bis (1-methyl-1-phenylethyl) phenol), tinuvin 928 (2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- ( 1,1,3,3-tetramethylbutyl) phenol), tinuvin 1130 (all manufactured by BASF), ADK STAB LA-29, ADK STAB LA-31, ADK STAB LA-32, ADK STAB LA-36 (all manufactured by ADEKA) ) Benzotriazole UV absorbers;

Tinuvin 111FDL, Tinuvin 123, Tinuvin 144 (Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{3,5-Bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] Butyl malonate), tinuvin 292 (mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate) Tinuvin 5100 (all manufactured by BASF), ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77, ADK STAB LA-81, ADK STAB LA-82 , ADK STAB LA-87, ADK STAB LA-402XP, ADK STAB Bed LA-502XP (all manufactured by ADEKA Corporation) or the like of a light stabilizer (HALS);

Antage W-300 (4,4′-butylidene-bis (6-tert-butyl-m-cresol)), Antage W-400 (2,2′-methylene-bis (4-methyl-6-tert-butylphenol) ), Antage W-500 (2,2′-methylene-bis (4-ethyl-6-tert-butylphenol)), Antage Crystal (4,4′-thio-bis (6-tert-butyl-m-cresol) )), Antage BHT (2,6-di-tert-butyl-p-cresol), Antage DAH (2,5-di-tert-amylhydroquinone), Antage DBH (2,5-di-tert-butyl-hydroquinone) ), Antage SP (styrenated phenol), Antage 2LX (phenol derivative), Antage 3LX (Fe Nol derivative), Antage W-200 (all manufactured by Kawaguchi Chemical Industry Co., Ltd.), Adeka Stub AO-20, Adeka Stub AO-30, Adeka Stub AO-40, Adeka Stub AO-50, Adeka Stub AO-60, Adeka Stub AO-80, Adeka Stub AO Phenolic antioxidants such as -330 (both manufactured by ADEKA);
ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8C, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 2112RG, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB TP Phosphite antioxidants such as ADEKA)
Thioether antioxidants such as ADK STAB AO-412S and ADK STAB AO-503 (both manufactured by ADEKA);
Antage 3C (N-isopropyl-N′-phenyl-p-phenylenediamine), Antage 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine), Antage STDP-N (phenothiazine derivative) ), ANTAGE LDA (diphenylamine derivative), ANTAGE OD (diphenylamine derivative), ANTAGE DDA (diphenylamine derivative), ANTAGE RD (polymerized 2,2,4-trimethyl-1,2-dihydroquinoline), ANTAGE AW (6- Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), antage F, antage D, antage DP, antage ODPP (all manufactured by Kawaguchi Chemical Co., Ltd.);

Among the above polymerization inhibitors, it is preferable to use at least a phenolic antioxidant. That is, the curable resin composition preferably further contains a phenolic antioxidant. This makes it possible to obtain a cured product that can exhibit even more excellent transparency, hardness, and developability even after being exposed to a high temperature environment.

The content of the polymerization inhibitor may be appropriately set according to the purpose, use, etc., and is not particularly limited, but is 0.001 part by mass or more with respect to 100 parts by mass of the solid content of the curable resin composition. It is preferable. More preferably, it is 0.01 mass part or more, More preferably, it is 0.1 mass part or more. Moreover, it is preferable that it is 5 mass parts or less, More preferably, it is 3 mass parts or less, More preferably, it is 1 mass part or less.
In the present invention, as described above, it is preferable to use a phenolic antioxidant as the polymerization inhibitor. In this case, the total amount of the polymerization inhibitor (that is, the phenolic antioxidant and other polymerization inhibitors). It is preferable that the phenolic antioxidant is 50% by mass or more with respect to 100% by mass. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. Particularly preferably, 100% by mass, that is, substantially only a phenolic antioxidant is used as a polymerization inhibitor.

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

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

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

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

The content of the fluorine-based additive may be appropriately set according to the purpose, application, and the like, and is not particularly limited. It is preferably 10 parts by mass.

The curable resin composition further includes, for example, a coloring material (also referred to as a colorant); a dispersant; a heat resistance improver; a leveling agent; an aluminum-based material, a titanium-based material, etc., depending on the required characteristics of each application to which the curable resin composition is applied. Other coupling agents; development aids; thermosetting resins such as fillers, epoxy resins, phenolic resins, and polyvinylphenol; curing aids such as polyfunctional thiol compounds; plasticizers; ultraviolet absorbers; antioxidants; Antifoaming agent; Antifoaming agent; Antistatic agent; Slip agent; Surface modifying agent; Thixotropic agent; Thixotropic agent; Quinonediazide compound; Polyhydric phenol compound; Cationic polymerizable compound; Acid generator; Two or more kinds may be further included.

<Method for producing curable resin composition>
The curable resin composition can be prepared by mixing and dispersing the above-described components using various mixers and dispersers. Among them, first, silica fine particles are dispersed in an organic solvent (dispersion medium) to obtain an organic solvent dispersion of silica fine particles, and then the dispersion is combined with a coupling agent, an alkali-soluble resin, a polyfunctional (meth) acrylate compound, and It is preferable to obtain a curable resin composition by mixing with other components contained as necessary. By being a curable resin composition thus obtained, it has excellent adhesion, dispersibility, developability, etc., has sufficient surface hardness, and is also discolored and colored even after being exposed to a high temperature environment. In addition, the effect of the present invention can be more fully exhibited that it is possible to provide a cured product that can maintain dispersibility without change in appearance such as cracks over time, and can stably exhibit sufficient surface hardness and adhesion. . Thus, a step of dispersing silica fine particles in an organic solvent to obtain an organic solvent dispersion of silica fine particles (also referred to as “dispersing step”), and a step of mixing the dispersion with a coupling agent and an alkali-soluble resin ( The manufacturing method of the said curable resin composition containing a "mixing process" is also one of the suitable embodiment of this invention.
The said dispersion | distribution process and mixing process are not specifically limited, What is necessary is just to perform by a normal method. Further, it may further include other steps that are normally performed.

[Curing film]
Next, the cured film formed using the curable resin composition of the present invention will be described.
The curable resin composition of the present invention can form a cured film by irradiation (exposure) with an active energy ray. Specifically, for example, it is preferable to form the cured film by applying the curable resin composition on a substrate and drying it, and irradiating (exposing) an active energy ray to the coated surface. Thus, the cured film formed with the said curable resin composition is also one of this invention.

The substrate on which the curable resin composition is applied is not particularly limited, and for example, transparent glass substrates such as white plate glass, blue plate glass, silica-coated blue plate glass; ring opening of polyester, polycarbonate, polyolefin, polysulfone, and cyclic olefin Sheet, film or substrate made of thermoplastic resin such as polymer or hydrogenated product thereof; sheet, film or substrate made of thermosetting resin such as epoxy resin or unsaturated polyester resin; aluminum plate, copper plate, nickel plate, stainless steel Examples include metal substrates such as plates; ceramic substrates; semiconductor substrates having photoelectric conversion elements; members made of various materials such as glass substrates (color filters for LCD) having a color material layer on the surface; Moreover, you may perform the chemical | medical treatment etc. by a corona discharge process, an ozone process, a silane coupling agent, etc. to the said base material as needed.

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

The coating film after being applied to the substrate can be dried using, for example, a hot plate, an IR oven, a convection oven or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but usually at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds. Is preferred.

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

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

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

In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary. Examples of the organic solvent in this case include organic solvents suitable as the developer described above.
Examples of the alkali agent include inorganic substances such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. Alkali agents: Examples include amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and these may be used alone or in combination of two or more. May be combined.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl esters; alkylbenzene sulfonates, alkylnaphthalene sulfonic acids, and the like. Anionic surfactants such as salts, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids, and the like. These may be used alone or in combination of two or more. Also good.

Further, if necessary, a post-curing step may be performed after the development step. The post-curing step is, for example, a post-exposure step using a light source such as a high-pressure mercury lamp, for example, with a light amount of 0.5 to ⁵ J / cm ² , or a temperature of 60 to 260 ° C. for 10 seconds to 120 minutes. Examples include a post-heating step. By performing such a post-curing step, it becomes possible to further strengthen the hardness and adhesion of the patterned cured film.

[Uses of curable resin composition]
As described above, the curable resin composition of the present invention is excellent in adhesion, dispersibility, developability, etc., has sufficient surface hardness, and is also discolored and colored even after being exposed to a high temperature environment. It provides a cured product (cured film) that can maintain dispersibility without any change in appearance such as cracks over time, and can stably exhibit sufficient surface hardness and adhesion. Therefore, the cured product (cured film) formed from such a curable resin composition includes, for example, constituent members of various display devices such as liquid crystal display devices, solid-state imaging devices, touch panel display devices, inks, printing plates, It is preferably used for various applications such as various optical members such as printed wiring boards, semiconductor elements, and photoresists, electric machines and electronic devices. Especially, it is preferable to use for the color filter used for a liquid crystal display device, a solid-state image sensor, etc., and a touchscreen type display device, and especially using the said curable resin composition, the protective film (for color filters for these various display devices) It is preferable to form a protective film, a protective film for a touch panel display device, or the like, or an insulating film (such as an insulating film for a touch panel display device). As a result, the reliability of display quality and imaging quality of various display devices can be sufficiently increased to the extent that it can sufficiently meet the recent demand for higher performance. Thus, the form in which the said curable resin composition is a curable resin composition for protective film or insulating film formation is one of the suitable forms of this invention. Moreover, the cured film formed with the said curable resin composition, the member for display apparatuses which has this cured film, and the display apparatus which has this cured film are also contained in this invention.

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

Since the curable resin composition of the present invention is configured as described above, it has excellent adhesion, dispersibility, developability, etc., has sufficient surface hardness, and even after being exposed to a high temperature environment, It is possible to provide a cured product that can maintain dispersibility without change in appearance such as discoloration, coloring, and cracks with time and can stably exhibit sufficient surface hardness and adhesion. Therefore, a display device member and a display device having a cured film formed of such a curable resin composition are very useful in the optical field, the electric machine / electronic field, and the like.

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

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

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

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

[Film properties]
<Evaluation of physical properties for ITO substrate>
1. Appearance (smoothness), cross-cut test (cross cut), an ITO substrate in which ITO (Indium Tin Oxide) was deposited on a pencil hardness glass with a thickness of 30 nm was prepared. The resin composition obtained on this ITO substrate was applied by spin coating, heat-treated (80 ° C. for 3 minutes), and then a UV aligner equipped with a 2.0 kW ultra-high pressure mercury lamp (made by TOPCON, trade name “ TME-150RNS ”) was exposed at an exposure amount of 60 mJ / cm ² (in terms of 365 nm illuminance), followed by heat treatment (230 ° C. for 30 minutes).
Using the obtained coating film, initial physical property evaluation (appearance, cross cut test, pencil hardness) and post-evaluation after PCT (Pressure Cooker Test) for 3 hours under 120 ° C water vapor pressure conditions (appearance, cross cut test, Pencil hardness).
(1-1) Appearance The appearance of the coating film was evaluated by visual observation. In the table, “transparent” means colorless and transparent.
Moreover, in the appearance evaluation of the coating film after PCT, it was set as “◯” when it was almost the same as the initial appearance, and “X” when it was deteriorated from the initial appearance.
(1-2) Cross cut test A test was conducted according to JIS-K5400-8.5 (1990), and the evaluation was made according to the following criteria.
A: 10 points according to the JIS standard, and a strong resistance is felt when peeling the cello tape (registered trademark).
○: 10 points according to JIS standards.
X1: 8 points according to JIS standards.
X2: 6 points according to JIS standards.
X3: 4 points according to JIS standards.
X4: 2 points according to JIS standards.
× 5: 0 point according to JIS standard.
(1-3) Pencil hardness test A test was conducted according to JIS-K5600-5-4 (1999), but all loads were applied with 500 g of the old JIS version of JIS-K5400 (1990), resulting in scars. The hardest pencil that did not exist was evaluated as the pencil hardness value according to the following criteria.
A: Pencil hardness is 6H or more.
○: Pencil hardness is 5H.
(Triangle | delta): Pencil hardness is 4H-2H.
X: Pencil hardness is H or less.

2. A glass substrate in which ITO (Indium Tin Oxide) was vapor-deposited with a thickness of 30 nm on a light-resistant color-resistant glass was prepared. The obtained resin composition was applied to this glass substrate by a spin coat method, heat-treated (80 ° C. for 3 minutes), and then a UV aligner equipped with a 2.0 kW ultrahigh pressure mercury lamp (trade name, manufactured by TOPCON) : TME-150RNS) was exposed at an exposure amount of 60 mJ / cm ² (in terms of 365 nm illuminance), followed by heat treatment (230 ° C. for 30 minutes).
Using the coating film thus obtained, an exposure amount of 180 mW / cm ² (300 to 400 nm) with a xenon weather meter (trade name: “FAL-25AX-HC-B” manufactured by Suga Test Instruments Co., Ltd.) is 400. The transmittance at 400 nm after time irradiation was measured using a spectrophotometer (manufactured by Shimadzu Corporation, trade name: UV-3100) and evaluated according to the following criteria.
○: transmittance 80% or more Δ: transmittance 70% or more, less than 80% ×: transmittance 70% or less

<Physical property evaluation for glass substrate>
3. Developability The obtained resin composition was applied to a glass substrate by a spin coating method, heat-treated (80 ° C. for 3 minutes), and then provided with a 50 μm line and space opening at a distance of 100 μm from the coating film. Exposure is performed at an exposure amount of 60 mJ / cm ² (365 nm illuminance conversion) using a UV aligner (trade name “TME-150RNS”, manufactured by TOPCON) equipped with a 2.0 kW ultrahigh pressure mercury lamp through a photomask. A 0.05% aqueous solution of potassium hydroxide is sprayed with a spin developing machine for 40 seconds to dissolve and remove the unexposed area, and the remaining exposed area is washed with pure water for 10 seconds to develop it. Evaluation was performed.
In any of the following, the coating film developed through a photomask was evaluated with a surface roughness meter (manufactured by Ryoka System Co., Ltd., trade name VertScan 2.0) according to the following criteria.
(3-1) Developability (line thickening)
○: Reproduced with an opening width of about ± 5 μm.
Δ: An error occurs with a difference of ± 15 μm from the opening width.
X: An error occurs with a difference of ± 25 μm from the opening width.

(Synthesis of resin solution)
First, the resin solution (A) (Exemplary Compounds A-1 to A-10) was synthesized as an alkali-soluble resin contained in the resin composition.

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

Synthesis Example 3 (Synthesis of A-3)
230 parts of PGMEA and 230 parts of PGME were charged into a separable flask with a cooling tube as a reaction tank, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Parts, perbutyl O6 parts, and dropping system 2 were continuously supplied with 13 parts of n-DM, 33 parts of PGMEA, and 33 parts of PGMEA over 3 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours.
Next, 99 parts of 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 liquid, and a nitrogen and oxygen mixed gas (oxygen concentration: 7%) was bubbled at 110 ° C. By continuing the reaction at 115 ° C. for 4 hours, a resin solution A-3 having a double bond equivalent of 594 g / equivalent was obtained.
Various physical properties of the obtained resin solution A-3 were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

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

Synthesis Example 5 (Synthesis of A-5)
In a separable flask with a cooling tube as a reaction tank, 382 parts of PGMEA and 95 parts of PGME were charged, and the temperature was raised to 90 ° C. in a nitrogen atmosphere, and then 12 parts of BzMI, 74 parts of MAA, 170 parts of CHA, 2 -45 parts of hydroxyethyl acrylate (HEA), 10 parts of PGMEA, 2 parts of PGME, 6 parts of perbutyl O, and 12 parts of n-DM, 54 parts of PGMEA, and 14 parts of PGMEA as the dropping system 2 were continuously supplied over 3 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours.
Next, 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 liquid, and a nitrogen and oxygen mixed gas (oxygen concentration: 7%) was bubbled at 110 ° C. By continuing the reaction at 115 ° C. for 3 hours, a resin solution A-5 having a double bond equivalent of 1941 g / equivalent was obtained.
With respect to the obtained resin solution A-5, various physical properties were measured as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 6 (Synthesis of A-6)
A separable flask with a cooling tube as a reaction vessel was charged with 368 parts of PGMEA and 92 parts of PGME and heated to 90 ° C. in a nitrogen atmosphere. Part, perbutyl O6 part, and dropping system 2 were continuously supplied with 13 parts of n-DM, 54 parts of PGMEA and 13 parts of PGMEA over 3 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours.
Next, 25 parts of GMA, 1.0 part of TEA as a catalyst, and 0.5 part of Antage W-400 as a polymerization inhibitor were added to this reaction liquid, and a nitrogen and oxygen mixed gas (oxygen concentration: 7%) was bubbled at 110 ° C. The reaction was continued for 3 hours at 115 ° C. to obtain a resin solution A-6 having a double bond equivalent of 1946 g / equivalent.
With respect to the obtained resin solution A-6, various physical properties were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

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

Synthesis Example 8 (Synthesis of A-8)
After charging 921 parts of PGMEA into a separable flask with a cooling tube as a reaction tank and raising the temperature to 90 ° C. in a nitrogen atmosphere, dimethyl-2,2 ′-[oxybis (methylene)] bis-2 was added as a dropping system 1. -102 parts of propenoate (MD), 182 parts of methacrylic acid (MAA), 175 parts of benzyl methacrylate (BzMA), 51 parts of methyl methacrylate (MMA), 10.2 parts of perbutyl O (trade name, manufactured by NOF Corporation), dropwise As system 2, 16.8 parts of n-DM and 44 parts of PGMEA were continuously supplied over 150 minutes. Then, after maintaining at 90 ° C. for 60 minutes, the temperature was raised to 110 ° C. and polymerization was continued for 3 hours.
Subsequently, 210 parts of glycidyl methacrylate (GMA), 2.2 parts of triethylamine (TEA) as a catalyst, 0.2 part of Antage W-400 and 119 parts of PGMEA as a polymerization inhibitor were added to this reaction liquid, and a mixed gas of nitrogen and oxygen ( The resin solution A-8 having a double bond equivalent of 490 g / equivalent was obtained by continuing the reaction at 110 ° C. for 2 hours and 115 ° C. for 4 hours while bubbling an oxygen concentration of 7%.
With respect to the obtained resin solution A-8, various physical properties were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 9 (Synthesis of A-9)
In a separable flask with a cooling tube as a reaction tank, 181 parts of PGMEA and 45 parts of PGME were charged and heated to 90 ° C. under a nitrogen atmosphere. Parts, 3 parts of perbutyl O, and 7 parts of n-DM, 58 parts of PGMEA, and 15 parts of PGMEA were continuously supplied as dropping system 2 over 3 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours.
Next, 38 parts of PGMEA, 10 parts of PGME, 28 parts of GMA, 0.6 part of TEA as a catalyst, 0.3 part of Antage W-400 as a polymerization inhibitor were added to this reaction solution, and nitrogen and oxygen mixed gas (oxygen concentration 7%) were added. The resin solution A-9 having a double bond equivalent of 1043 g / equivalent was obtained by continuing the reaction at 110 ° C. for 2 hours and 115 ° C. for 7 hours while bubbling.
With respect to the obtained resin solution A-9, various physical properties were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis Example 10 (Synthesis of A-10)
A separable flask with a cooling tube as a reaction vessel was charged with 100 parts of PGMEA and 25 parts of PGME, heated to 90 ° C. under a nitrogen atmosphere, and then added as a dropping system 1 with 39 parts of BzMI, 26 parts of MAA, 65 parts of CHA, 31 parts of PGMEA, and 31 parts of PGMEA. Parts, 2.6 parts perbutyl O, and 2.3 parts of n-DM, 62 parts of PGMEA, and 16 parts of PGMEA as a dropping system 2 were continuously supplied over 3 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours.
Next, 25 parts of PGMEA, 6 parts of PGME, 22 parts of GMA, 0.5 part of TEA as a catalyst and 0.2 part of Antage W-400 as a polymerization inhibitor were added to this reaction solution, and nitrogen and oxygen mixed gas (oxygen concentration 7%) were added. The resin solution A-10 having a double bond equivalent of 1023 g / equivalent was obtained by continuing the reaction while bubbling at 110 ° C. for 2 hours and 115 ° C. for 7 hours.
With respect to the obtained resin solution A-10, various physical properties were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Table 1 shows details of the resin solutions A-1 to A-10.
In addition, regarding the compounding amount of the monomer constituting the resin in Table 1, the numerical values of BzMI, MD, CHA, BzMA, MAA, MMA and HEA constituting the base polymer are based on the total amount of these being 100% by mass. The blending ratio (mass%) of each was described. The value of GMA added to the base polymer is described as the ratio of GMA added to the carboxylic acid content of the monomer having an acid group and a polymerizable double bond (in this case, MAA). , “GMA blending ratio (MAA blending ratio (mass%) with GMA added) = {GMA mole amount (mol) / MAA mole amount (mol)} × MAA blending ratio (mass%)”. For example, in Synthesis Example 1 (A-1), MAA was 60% by mass in the base polymer (100% by mass), and 696 mmol of GMA was added to 60% by mass (2091 mmol) of MAA. The blending ratio of the GMA was defined as “20”.

Abbreviations in Table 1 are as follows.
BzMI: benzyl maleimide 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 content concentration

(Preparation of resin composition)
Preparation Example 1 (Resin Composition b-1)
In terms of solid content, 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), KBM503 (trade name, 10 parts manufactured by Shin-Etsu Silicone Co., Ltd., 5 parts Irgacure 907 (manufactured by Ciba-Gaigi) as a photopolymerization initiator, 0.5 part Antante W-400 (manufactured by Kawaguchi Chemical Co., Ltd.) as a polymerization inhibitor, and further a diluent solvent (propylene glycol monomethyl) Ether acetate (PGMEA) was added to a solid content concentration of 25%, and the mixture was stirred to obtain a resin composition b-1.
About the obtained resin composition b-1, according to the evaluation method mentioned above, the physical property of the coating film was evaluated. The results are shown in Table 2-1.

Preparation Examples 2-22
Each resin composition was obtained in the same manner as in Preparation Example 1 using the raw materials shown in Table 2-1 or Table 2-2 at the blending ratio shown in Table 2-1 or Table 2-2. About each of the obtained resin composition, the physical property of the coating film was evaluated according to the evaluation method mentioned above. The results are shown in Table 2-1 and Table 2-2.

In Tables 2-1 to 2-2, comprehensive evaluation refers to a comparative evaluation of the coating film in five stages of A to E among all the preparation examples, based on the respective physical property evaluation results. The closer this letter is to A, the better the physical properties of the coating film are. When the letter is closer to E, it means that the coating film has not reached the practical level.

Abbreviations in Tables 2-1 and 2-2 are as follows. Moreover, the compounding quantity of each raw material in Table 2-1 and 2-2 is a solid content.
In Tables 2-1 and 2-2, 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, manufactured by Shin-Nakamura Chemical Co., Ltd.)
PE3A: Pentaerythritol triacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
PE4A: Pentaerythritol tetraacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
DPHA: Dipentaerythritol hexaacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
MEK-ST: Methyl ethyl ketone-dispersed 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: Isopropyl alcohol-dispersed silica sol (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.)

KBM503: 2-methacryloxypropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Silicone)
IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name, manufactured by BASF)
IRGACURE127: 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (trade name, manufactured by BASF)
IRGACURE 819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name, manufactured by BASF)
IRGACURE907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name, manufactured by Ciba Specialty Chemicals)

Tinuvin 900: Benzotriazole UV absorber (trade name, manufactured by BASF)
Tinuvin 400: hydroxyphenyltriazine UV 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-4-piperidyl Mixture with sebacate)
ADK STAB AO-40: Phenolic antioxidant (trade name, manufactured by ADEKA)
Antage W-400: Phenolic antioxidant (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.)
ADK STAB PEP-8: Phosphite antioxidant (trade name, manufactured by ADEKA)
ADK STAB AO-412S: Thioether-based antioxidant (trade name, manufactured by ADEKA)
Antage F: Amine-based antioxidant (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.)
F-554: Fluorine-containing / lipophilic group-containing oligomer (nonionic, trade name “Megafac F-554”, manufactured by DIC Corporation)

From the preparation examples shown in Tables 2-1 and 2-2, it was confirmed that the effect of using a predetermined amount of the aminoketone polymerization initiator in the present invention was excellent. For example, when the aminoketone polymerization initiator is used in an amount of 10 to 35 parts by mass with respect to 100 parts by mass of the total solid content (Preparation Examples 3 to 5), the aminoketone polymerization initiator is used in a smaller amount than the above range. Compared to (Preparation Examples 1 and 2) and other polymerization initiators (Preparation Examples 6 to 8) even in the same amount, a cured product having excellent developability and light-coloring resistance can be obtained. I understand that. Therefore, it can be said that the curable resin composition of the present invention can be suitably applied particularly when developability and light coloring resistance are strongly desired.

Claims (5)

A curable resin composition comprising silica fine particles, a coupling agent and an alkali-soluble resin,
The curable resin composition further includes a bifunctional or higher polyfunctional (meth) acrylate compound and an aminoketone polymerization initiator,
Content of this amino ketone type | system | group polymerization initiator is 10-35 mass parts with respect to 100 mass parts of solid content total amount of this curable resin composition, The curable resin composition characterized by the above-mentioned. The curable resin composition according to claim 1, wherein the bifunctional or higher polyfunctional (meth) acrylate compound is a trifunctional or higher polyfunctional (meth) acrylate compound. A cured film formed from the curable resin composition according to claim 1. A member for a display device, comprising the cured film according to claim 3. A display device comprising the cured film according to claim 3.