JP6976069B2 - Curable resin composition and its use - Google Patents

Description

The present invention relates to a curable resin composition and its use. More specifically, it is useful for various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, etc. used for liquid crystal display devices and solid-state image sensors, and various applications such as electric and electronic devices. The present invention relates to a curable resin composition, a cured product thereof, a color filter using the cured product, and a display device.

Various curable resin compositions that can be cured by heat or active energy rays include, for example, color filters, inks, printing plates, printed wiring boards, semiconductor devices, photoresists and the like used in liquid crystal display devices and solid-state imaging devices. The application of the above to various applications such as optical members and electric / electronic devices has been studied in various ways, and a curable resin composition having excellent properties required for each application has been developed. Among these applications, the color filter is a main member constituting a liquid crystal display device, a solid-state image sensor, etc., and is generally a substrate, at least three primary colors (red (R), green (G), blue (B)). In addition to the pixels and the resin black matrix (BM) that separates them, it is composed of a protective film or the like provided to cover and protect the pixels and the resin black matrix and to flatten their unevenness. ..

Normally, when the pixels of a color filter are formed using a curable resin composition, each pixel is formed by (1) a coating step of applying the curable resin composition to the entire surface of the substrate and (2) a coating step. The resist film is exposed to a pattern through a photomask to cure the exposed portion, and then the cured portion is insolubilized. (3) The unexposed portion is removed with a developing solution and then fired (baked). A method is adopted in which a developing / firing (baking) processing step of further curing the exposed portion is performed, and the same step is repeated for each color. Considering application to such color filter applications, the curable resin composition has various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (base material), heat resistance, and transparency. Is required to have. Further, in recent years, optical members, electric / electronic devices, and the like are becoming smaller, thinner, and energy-saving, and along with this, members such as color filters used are required to have high-quality performance.

Regarding the conventional curable resin composition, examples of the composition suitable for color filter applications include N-benzylmaleimide monomer unit, tertiary carbon-containing (meth) acrylate monomer unit, and hydroxyl group-containing monomer. A photosensitive resin composition containing a polymerizable compound, a photopolymerization initiator, and a solvent as having a unit of acrylic acid is disclosed (see Patent Document 1).

JP-A-2015-157909

As described above, the curable resin composition is required to have various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (also referred to as a substrate), heat resistance and transparency. ing. In recent years, with the progress of technology such as display devices, there is a strong demand for higher performance for each member used. For example, in color filter applications, heat treatment in the manufacturing process is required. As the brightness decreases due to the thermal coloring of the coating film and the concentration of the coloring material such as pigments and dyes increases, there is a problem that the coloring material elutes into the cleaning solvent in the manufacturing process. Therefore, very high solvent resistance is required after curing. However, the current situation is that conventional resin compositions cannot sufficiently meet these demands. For example, the resin composition described in Patent Document 1 is satisfactory in terms of solvent resistance, but there is room for improvement such as deterioration of heat-resistant coloring property, particularly heat-resistant coloring property at high temperature.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a curable resin composition which can stably exhibit heat resistance and transparency (heat resistance coloring property) and is useful for color filter applications. do. It is also an object of the present invention to provide a cured product formed of such a curable resin composition, and a color filter and a display device using the cured product.

The present inventor has made various studies on curable resin compositions useful for various uses such as color filters, and found that a resin composition containing a (meth) acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator is cured. We paid attention to the fact that it has sex. Then, the (meth) acrylate-based polymer is a structural unit derived from N-cyclohexylmaleimide , and a tertiary carbon-containing (meth) acrylate-based polymer having a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. By having a constituent unit derived from a monomer, a (meth) acrylic acid unit, and a monomer unit having a hydroxyl group in a specific ratio , high transparency and heat resistance (heat-resistant coloring property) can be stably achieved. We have found that a cured product that can be expressed can be obtained . Such a curable resin composition is particularly useful for color filter applications, and is particularly suitable as a resin composition for forming pixels for a color filter. Therefore, a cured product, a color filter, and a display device formed from such a curable resin composition are extremely useful in the optical field and the electric / electronic field as being able to sufficiently meet the demand for higher performance in recent years. We came up with the idea that the above problems could be solved brilliantly, and arrived at the present invention.

Here, the (meth) acrylate-based polymer contained in the curable resin composition of the present invention has a structural unit derived from a tertiary carbon-containing (meth) acrylate-based monomer, and the structural unit is decomposed by heat. Easy to do. Specifically, the OC bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent thereto is easily cleaved, whereby the (meth) acrylic acid and the third carbon atom are easily cleaved. It is decomposed into stable compounds generated on the secondary carbon atom side. Therefore, for example, when the curable resin composition of the present invention is used for forming pixels of a color filter, the above-mentioned tertiary carbon content (meth) is carried out by a heating step (also referred to as a baking step or a post-baking step) after development. ) The structural unit derived from the acrylate-based monomer is decomposed to produce (meth) acrylic acid and a stable compound generated on the tertiary carbon atom side. Then, due to the formation of an ester crosslinked structure between the hydroxyl groups and ester groups in the polymer and the generated (meth) acrylic acid, the curability of the resin composition and the solvent resistance after curing are dramatically improved. It is thought that it will be improved.

Further, the N-substituted maleimide monomer is characterized by excellent pigment dispersibility, heat deformation, and thermal decomposition property, but N-benzylmaleimide and the like used in Patent Document 1 have an aromatic hydrocarbon structure. There was a drawback that the heat-resistant coloring property at high temperature was inferior. In particular, post-baking and thermal coloring in the subsequent heat treatment process cause a decrease in brightness and yellowing. With the improvement of the quality of liquid crystal panels, these have become a problem especially when they are used for pixels, overcoats, interlayer insulating films and the like of color filters. By changing the substituent of maleimide to an alkyl group or a cycloalkyl group instead of a substituent containing an aromatic hydrocarbon structure such as a benzyl group or a phenyl group, the present inventors particularly in a high temperature region such as 250 ° C. The present invention has been completed by finding that the thermal coloring of the group is significantly suppressed.

That is, the present invention is the following <1> to <7>.
<1> A curable resin composition containing a (meth) acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator.
The (meth) acrylate-based polymer contains 2 to 30% by mass of N-alkylmaleimide monomer and / or N-cycloalkylmaleimide monomer unit, and 20 to 30% by mass of tertiary carbon-containing (meth) acrylate-based monomer unit. A curable resin composition comprising 60% by mass, a monomer unit having a hydroxyl group of 10 to 40% by mass, and a (meth) acrylic acid unit of 5 to 25% by mass.
<2> The tertiary carbon-containing (meth) acrylate-based monomer unit is characterized in that it has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. The curable resin composition according to the above.
<3> The curing according to <1> or <2>, wherein the (meth) acrylate-based polymer has a content of 5% by mass or less of a monomer unit containing an aromatic hydrocarbon structure. Sex resin composition.
<4> The curable resin composition according to any one of <1> to <3>, wherein the N-cycloalkylmaleimide monomer unit is a structural unit derived from N-cyclohexylmaleimide.
<5> A cured product obtained by curing the curable resin composition according to any one of <1> to <4>.
<6> A color filter characterized by having the cured product according to <5> on a substrate.
<7> A display device characterized by being configured by using the color filter according to the above <6>.

The curable resin composition of the present invention, because it is constructed as described above, heat resistance and transparency (thermal coloration resistance) can stably exhibit, is useful in color filter applications. Therefore, a color filter and a display device having a cured product (cured film) formed of such a curable resin composition are very useful in the optical field and the electric / electronic field.

The present invention will be described in detail below. It should be noted that a form in which two or three or more of the individual preferred forms of the present invention described below are combined is also a preferred form of the present invention.
[Curable resin composition]
The curable resin composition of the present invention contains a (meth) acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator, and one or more of these components can be used, respectively. Further, if necessary, one or more other components may be further contained.
<(Meta) acrylate-based polymer>
In the above curable resin composition, the (meth) acrylate-based polymer contains 2 to 30% by mass of N-alkylmaleimide and / or N-cycloalkylmaleimide monomer unit with respect to 100% by mass of all constituent units. Is preferable. Having N-alkylmaleimide and / or N-cycloalkylmaleimide monomer unit, which are constituent units derived from N-substituted maleimide monomer, has excellent heat-resistant coloring property, heat-resistant deformability, alkali developability, and pigment dispersion. It can exhibit properties and solvent resistance. Specific examples of the alkyl group of the N-alkylmaleimide monomer include a C = 1 to 20 chain such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 2-ethylhexyl group, and a lauryl group. A state alkyl group is preferred. Further, as the N-cycloalkyl group, a cycloalkyl group such as a cyclohexyl group, a cyclopentyl group, a dicyclopentenyl group, a dicyclopentenyl group, or a tricyclodecanyl group is preferable. Among these, N-cyclohexylmaleimide, which is easily industrially available, has relatively high safety such as skin irritation, and is excellent in handleability, is most preferable.
The copolymerization ratio of the N-alkylmaleimide and / or the N-cycloalkylmaleimide monomer is preferably in the range of 2 to 30% by mass with respect to 100% by mass of the total amount of the monomer components. If it is less than 2% by mass, heat resistance, solvent resistance, and pigment dispersibility may decrease. On the other hand, if it exceeds 30% by mass, the alkali developability may be lowered or the heat-resistant coloring property may be lowered. It is more preferably 5 to 30% by mass, still more preferably 5 to 20% by mass.

In particular, in order to exert the above effect remarkably, 90 parts by mass of N-cyclohexylmaleimide is added to 100 parts by mass of the N-substituted maleimide monomer (N-alkylmaleimide and / or N-cycloalkylmaleimide monomer). As mentioned above, it is preferable to use 95 parts by mass or more, and most preferably 100 parts by mass.
The (meth) acrylate-based polymer also contains a structural unit derived from a tertiary carbon-containing (meth) acrylate-based monomer in the range of 20 to 60% by mass with respect to 100% by mass of the total amount of the monomer components. It is necessary to. The structural unit derived from the tertiary carbon-containing (meth) acrylate-based monomer is a structure in which the polymerizable carbon-carbon double bond (C = C) in the monomer becomes a single bond (CC). Although it means a unit, it is preferable that the monomer has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. That is, it is preferable that the tertiary carbon-containing (meth) acrylate-based monomer has a structure in which an oxygen atom adjacent to the (meth) acryloyl group is bonded to a tertiary carbon atom. The tertiary carbon atom means a carbon atom having three other carbon atoms bonded to the carbon atom.

The tertiary carbon-containing (meth) acrylate-based monomer is a compound having one polymerizable carbon-carbon double bond in the molecule, that is, a (meth) acryloyl group (CH ₂ = C (R)) in the molecule. It is preferable that the compound has one −C (= O) −), and for example, the following general formula (1):
CH ₂ = C (R) -C (= O) -OA (1)
(R represents a hydrogen atom or a methyl group. A represents a monovalent organic group containing a structure having a tertiary carbon atom on the oxygen atom side.) Is preferably a compound represented by.

In the above general formula (1), the organic group represented by A can be represented by, for example, −C (R ¹ ) (R ² ) (R ³ ). In this case, R ¹ , R ² and R ³ are preferably the same or different hydrocarbon groups having 1 to 30 carbon atoms, and the hydrocarbon group may be a saturated hydrocarbon group. However, it may be an unsaturated hydrocarbon group. Further, it may have a cyclic structure or may further have a substituent. Further, R ¹ , R ² and R ³ may be connected to each other at the terminal sites to form an annular structure.
In the present invention, as will be described later, a new product generated by cleaving the OC bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom in A adjacent thereto. The organic group represented by A preferably has 12 or less carbon atoms in that the compound easily volatilizes. Above all, it is preferable that the organic group represented by A is a group derived from t-butyl (meth) acrylate and / or t-amyl (meth) acrylate. Further, the organic group represented by A may have a branched structure.

Here, in the tertiary carbon-containing (meth) acrylate-based monomer, at least one of the adjacent carbon atoms of the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth) acryloyl group is bonded to the hydrogen atom. It is preferable to do so. For example, the tertiary carbon-containing (meth) acrylate-based monomer is a compound represented by the above general formula (1), and A is represented by −C (R ¹ ) (R ² ) (R ³ ). In the case of a group, it is preferable that ^{at least one of R 1} , R ² and R ³ contains a carbon atom having one or more hydrogen atoms, and the carbon atom is bonded to a tertiary carbon atom. In such a form, heating cleaves the OC bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent to it, and at the same time produces (meth) acrylic acid. , A double bond (C = C) is formed between the tertiary carbon atom and the carbon atom adjacent thereto, and a new compound is produced more stably.

It is preferable that the new compound produced as described above is volatile. In this case, the film thickness of the cured product (cured film) is reduced due to the volatilization of the new compound from the cured product, and at the same time, for example, the curable resin composition further contains a coloring material. In some cases, the colorant concentration increases after heating. Therefore, it is possible to realize a further thin film, and it is possible to further improve the color purification and the high shading rate of the black matrix. Considering this point, ^{it is preferable that R 1} , R ² and R ³ are the same or different saturated hydrocarbon groups having 1 to 15 carbon atoms. A saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable, a saturated hydrocarbon group having 1 to 5 carbon atoms is more preferable, and a saturated hydrocarbon group having 1 to 3 carbon atoms is particularly preferable.

The content ratio of the above-mentioned tertiary carbon-containing (meth) acrylate-based monomer unit is preferably 20 to 60% by mass with respect to 100% by mass of the total amount of the monomer components. As a result, the effect of the present invention due to the structural unit derived from the tertiary carbon-containing (meth) acrylate-based monomer is further exhibited. It is more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass. When the content ratio of the tertiary carbon-containing (meth) acrylate monomer unit is less than the above range, the solvent resistance is lowered. On the other hand, if it exceeds the above range, the solvent resistance may be lowered or the alkali developability may be lowered.

The (meth) acrylate-based polymer preferably contains (meth) acrylic acid units in an amount of 5 to 25% by mass based on 100% by mass of the total amount of the monomer components. The acid value (AV) of the polymer is preferably 40 to 200 mgKOH / g. More preferably, it is 60 to 180 mgKOH / g. As a result, more sufficient alkali solubility is developed, and it becomes possible to obtain a cured product having better developability. If the content ratio of the (meth) acrylic acid is less than the above range, the solvent resistance and the alkali developability may be deteriorated. On the other hand, if it exceeds the above range, the alkali solubility becomes too high, and the adhesion to the substrate and the heat resistance may become too high. In addition, the solubility in an organic solvent may decrease or the viscosity may increase significantly. In the present invention, the monomer unit such as (meth) acrylic acid means a structural unit derived from the monomer, and for example, the acrylic acid unit is acrylic acid obtained by copolymerizing or graft-polymerizing acrylic acid. It means the structural unit of origin. In addition, the above (meth) acrylic acid can be used as unsaturated monocarboxylic acids such as crotonic acid, silicic acid and vinyl benzoic acid, and unsaturated polyvalent carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid. The same effect can be achieved by replacing all or part of it.

The (meth) acrylate-based polymer also preferably contains 5 to 40 mass of monomer units having a hydroxyl group (hydroxyl group) in the molecule, with the total amount of all the monomers being 100%. As a result, the curability of the curable resin composition is further improved, and a cured product having further excellent solvent resistance and transparency can be provided. Examples of the monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate. Hydroxyalkyl (meth) acrylates such as butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2,3-dihydroxypropyl (meth) acrylate are preferred.
The content ratio of the monomer unit having a hydroxyl group is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, still more preferably 15 with respect to 100% by mass of the total amount of the monomer components. ~ 30% by mass. If the content ratio of the monomer unit having a hydroxyl group is less than the above range, the curability may be insufficient and the solvent resistance may be lowered. On the other hand, if it exceeds the above range, the hydrophilicity becomes too strong, and there is a risk that it may be peeled off during development or the surface may be roughened and whitened.

The (meth) acrylate-based polymer may contain, for example, an N-alkylmaleimide and / or an N-cycloalkylmaleimide monomer, a tertiary carbon-containing (meth) acrylate-based monomer, an acrylic acid monomer, and a hydroxyl group. It can be obtained by polymerizing a monomer component containing a monomer component having.
As each monomer used, one kind or two or more kinds can be used respectively.

The polymer of the present invention may also have a (meth) acrylic acid ester-based monomer and other copolymerizable monomer units in order to adjust developability, solvent solubility and the like.
As the (meth) acrylic acid ester-based monomer, for example, a monomer having an alicyclic skeleton is preferable in consideration of the surface hardness of the cured product and the like. Specifically, for example, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, dicyclo Penthenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, pentacyclopentadecanedimethanol rudi (meth) acrylate, cyclohexanedimethanol Di (meth) acrylate, norbornan dimethanol di (meth) acrylate, p-menthan-1,8-diol di (meth) acrylate, p-mentan-2,8-diol di (meth) acrylate, p-menthan-3,8- Examples thereof include diol di (meth) acrylate, bicyclo [2.2.2] -octane-1-methyl-4-isopropyl-5,6-dimethylol di (meth) acrylate and the like. Among these, from the viewpoint of versatility, availability, etc., it is preferable to use cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate. It is also preferable to use an alicyclic epoxy compound such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and ethyl glycidyl (meth) acrylate.

The (meth) acrylic acid ester-based monomer also includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth). ) N-butyl acrylate, s-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2--amyl (meth) acrylate Ethylhexyl, (meth) isodecyl acrylate, (meth) tridecyl acrylate, (meth) octyl acrylate, (meth) isooctyl acrylate, (meth) lauryl acrylate, (meth) stearyl acrylate, benzyl (meth) acrylate , (Meta) phenyl acrylate, (meth) 2-methoxyethyl acrylate, (meth) 2-ethoxyethyl acrylate, (meth) phenoxyethyl acrylate, (meth) tetrahydrofurfuryl acrylate, (meth) acrylate N, N-dimethylaminoethyl, methyl α-hydroxymethylacrylic acid, ethyl α-hydroxymethylacrylic acid, t-butyl α-hydroxymethylacrylic acid, t-amyl α-hydroxymethylacrylic acid, etc., as well as 1,4 -Dioxaspiro [4,5] deca-2-ylmethacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfurylacrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolan, 4- (meth) Acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) Acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolan, 4- (meth) ) Acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane and the like can also be mentioned. Among them, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are easy to balance heat resistance, colorant dispersibility, and solvent resolubility. Is preferable.

The above-mentioned other copolymerizable monomer may also be, for example, one or more of the following compounds.
(Meta) acrylamides such as N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide; weights of polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam, etc. Macromonomers having a (meth) acryloyl group at one end of the coalesced molecular chain; conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc. Kind: 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- Vinyl ethers such as hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine and N-vinylacetamide; (meth) Unsaturated isocyanates such as isocyanatoethyl acrylate and allyl isocyanate; N-aromatically substituted maleimides such as N-phenylmaleimide and N-benzylmaleimide; aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; 2,2'-[oxybis (methylene)] bisacrylic acid, dialkyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dialkyl-2,2'-[oxybis (methylene)] bis-2 -Dialkyl-2,2'-(oxydimethylene) diacrylate-based monomers such as propenoate; α-allyloxymethylacrylate, α-methylallyloxymethylacrylate, α-ethyloxymethylacrylate, α-allyloxymethylacrylate n-propyl, α-allyloxymethylacrylate i-propyl, α-allyloxymethylacrylate n-butyl, α-allyloxymethylacrylate s-butyl, α-allyloxymethylacrylic acid Acid t-butyl, α-allyl oxymethyl acrylate n-amyl, α-allyl oxymethyl acrylate s-amyl, α-allyl oxymethyl Examples thereof include α- (unsaturated alkoxyalkyl) acrylate-based monomers such as t-amyl acrylate and neopentyl α-allyloxymethyl acrylate.

Among the above-mentioned copolymerizable monomers, it was found that the monomer having an aromatic hydrocarbon group reduces the heat-resistant coloring property and causes strong coloring by heating at a high temperature. Therefore, the content of the monomer having an aromatic hydrocarbon group is preferably less than 5% by mass, preferably less than 3%, and practically not contained in the total amount of 100% by mass of all the monomers. ..

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

As the compounding ratio (% by mass) at the time of polymerization, N-alkylmaleimide and / or N-cycloalkylmaleimide monomer, tertiary carbon-containing (meth) acrylate-based monomer, monomer having a hydroxyl group, (meth). When polymerizing a monomer component containing acrylic acid and other (meth) acrylic acid ester-based monomers, N-alkylmaleimide and / or N-cycloalkylmaleimide monomer (2-30% by mass), Tertiary carbon-containing (meth) acrylate-based monomers (20-60% by mass), monomers having hydroxyl groups (10-40% by mass), and (meth) acrylic acid (5-25% by mass), (meth). ) The blending ratio of the acrylic acid ester-based monomer (1 to 50% by mass) is preferable.

The polymerization initiation method in the above polymerization reaction may be such that the energy required for the polymerization initiation is supplied to the monomer component from an active energy source such as heat, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.), electron beam, etc., and further polymerization is performed. When an initiator is used in combination, the energy required for the initiation of polymerization can be significantly reduced, and the reaction can be easily controlled, which is preferable.
Further, the molecular weight of the polymer obtained by polymerizing the above-mentioned 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 above-mentioned monomer component is polymerized by the solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction. For example, it may be appropriately set according to the polymerization mechanism, the type and amount of the monomer used, the polymerization temperature, the polymerization concentration, and the like, but when it is later prepared into a curable resin composition, it is used as a solvent as a diluent or the like. When using, it is efficient and preferable to use a solvent containing the solvent for solution polymerization of the monomer component.

As the solvent, for example, the following compounds and the like are preferably mentioned, and one or more of these 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 and 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 monopropyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; Glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether Esters of glycol monoethers such as 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, ethyl 3-ethoxypropionate, methyl acetoacetate, acet Alkyl esters such as ethyl acetate; a Ketones such as seton, methylethylketone, methylisobutylketone, cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane, octane; dimethylformamide, dimethylacetamide, N- Amids such as methylpyrrolidone; etc.

Among these solvents, propylene glycol monomethyl ether and propylene are available because of the solubility of the obtained polymer, the surface smoothness when forming a coating film, the small impact on the human body and the environment, and the ease of industrial availability. It is more preferable to use glycol monopropyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and ethyl lactate.

The amount of the solvent used is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the monomer component. More preferably, it is 100 to 500 parts by mass.

When the above-mentioned 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. The polymerization initiator is not particularly limited as long as it generates radicals by supplying heat energy, and depends on the polymerization conditions such as the polymerization temperature, the solvent, and the type of the monomer to be polymerized. Then, it may be selected as appropriate. Further, a reducing agent such as a transition metal salt or an amine may be used in combination with the polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, and t-butyl peroxy-. 2-Ethylhexanoate, t-amylperoxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-) Examples thereof include peroxides and azo compounds usually used as polymerization initiators such as dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), hydrogen peroxide, and persulfate. May be used alone or in combination of two or more.

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, and the like, and is particularly limited. It's not a thing. For example, in order to obtain a polymer having a weight average molecular weight of several thousand to tens of thousands, it is preferable that the weight average is 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer component. More preferably, it is 0.5 to 15 parts by mass.

In the above polymerization, a commonly used chain transfer agent may also be used, if necessary. It is preferable to use a polymerization initiator and a chain transfer agent in combination. If a chain transfer agent is used during polymerization, it tends to be possible to suppress an increase in molecular weight distribution and gelation.

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-mercaptopropionic acid, and n-mercaptopropionic acid. Octyl, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakiss (3- Mercaptocarboxylic acid esters such as mercaptopropionate); alkyl mercaptans such as ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane; 2-mercaptoethanol, 4-mercapto-1- Mercapto alcohols such as butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol, 2-naphthalenethiol; tris [(3-mercaptopropioniloxy) -ethyl] mercaptoisosia such as isocyanurate. Nulates; Disulfides such as 2-hydroxyethyl disulfide and tetraethylthium disulfide; Dithiocarbamates such as benzyldiethyldithiocarbamate; Monomer dimers such as α-methylstyrene dimer; Alkyl halides such as carbon tetrabromide And so on. These may be used alone or in combination of two or more.

Among these, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercaptoisocyanulates, etc., in terms of availability, cross-linking prevention ability, degree of decrease in polymerization rate, etc. It is preferable to use a compound having a mercapto group such as. More preferably, alkyl mercaptans, mercaptocarboxylic acids and mercaptocarboxylic acid esters are more preferable, and even more preferable are n-dodecyl mercaptan and mercaptopropionic acid.

The amount of the chain transfer agent 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, and the like, and is not particularly limited. For example, in order to obtain a polymer having a weight average molecular weight of several thousand to tens of thousands, it is preferable that the amount is 0.1 to 20 parts by mass with respect to 100 parts by mass of the above-mentioned monomer component. More preferably, it is 0.5 to 15% by mass.

Regarding the above-mentioned polymerization conditions, the polymerization temperature may be appropriately set according to the type and amount of the monomer used, the type and amount of the polymerization initiator, and the like, but for example, 50 to 150 ° C. is preferable, and 70 to 70 to 120 ° C. is more preferable. Further, the polymerization time can be appropriately set in the same manner, but for example, 1 to 6 hours is preferable, and 2 to 5 hours is more preferable.

The (meth) acrylate-based polymer preferably has a weight average molecular weight of 3,000 to 50,000. Within such a range, it becomes possible to exhibit better developability. It is more preferably 8000 to 40,000, and even more preferably 10,000 to 30,000. If the weight average molecular weight is below the above range, the solvent resistance may decrease. Further, if it exceeds the above range, the development speed may be slowed down.
The weight average molecular weight of the polymer can be determined, for example, as in Examples described later.

In the above curable resin composition, the content ratio of the (meth) acrylate-based polymer may be appropriately set according to the intended use, the composition of other components, etc., and for example, the total solid content of them is curable. The total solid content of the resin composition is preferably 5% by mass or more with respect to 100% by mass. Further, it is preferably 80% by mass or less. Within such a range, the effect of the present invention can be more prominently exhibited. It is more preferably 7 to 70% by mass, still more preferably 10 to 60% by mass.
The "total amount of solid content" means the total amount of the components forming the cured product (excluding the solvent that volatilizes when the cured product is formed).
<Polymerizable compound>
The curable resin composition also contains a polymerizable compound. The polymerizable compound is also referred to as a polymerizable monomer, and is a polymerizable unsaturated bond (polymerizable unsaturated bond) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.) and electron beams. It is a low molecular weight compound having a polymerizable unsaturated group). For example, a monofunctional compound having one polymerizable unsaturated group in the molecule and a polyfunctional compound having two or more polymerizable unsaturated groups can be mentioned.
Examples of the monofunctional polymerizable monomer include N-substituted maleimides and (meth) among the compounds exemplified as other monomers preferably contained in the monomer component of the (meth) acrylate-based polymer. ) Acrylic acid esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polyvalent carboxylic acids; unsaturated monocarboxylic acids with a chain extension between unsaturated groups; unsaturated acid anhydrides Classes; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; etc.

Examples of the polyfunctional polymerizable monomer include the following compounds.
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, and bisphenol Falkylene oxide di (meth) acrylate;
Trimethylol Propanetri (meth) Acrylate, Ditrimethylol Propanetetra (Meta) Acrylate, Glycerintri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylrol propanthry (meth) acrylate, ethylene oxide-added ditrimethylolpropanetetra (meth) acrylate, ethylene oxide Addition of pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylol propanetri (meth) acrylate, propylene oxide-added ditrimethylolpropanetetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (Meta) acrylate, propylene oxide-added dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropanetri (meth) acrylate, ε-caprolactone-added ditrimethylolpropanetetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra Trifunctional or higher functional (meth) acrylate compounds such as (meth) acrylate and dipentaerythritol hexa (meth) acrylate with ε-caprolactone;
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, trimetylol propanetrivinyl ether, ditri Methylol propane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylol propanetrivinyl ether, ethylene oxide-added ditrimethylol propanetetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide. Polyfunctional vinyl ethers such as added dipentaerythritol hexavinyl ether;
2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylic acid, 1-methyl-2-vinyloxyethyl (meth) acrylic acid, 2-vinyloxypropyl (meth) acrylic acid, 4 (meth) acrylic acid -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) acrylic acid, 2- (vinyloxyethoxy) ethyl (meth) acrylic acid, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylic acid Acrylic acids;
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 Falkylene oxide diallyl ether, trimethyl propanetriallyl ether, Ditrimethylol propanetetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylol propanetriallyl ether, ethylene oxide-added ditrimethylol propanetetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether;
Allyl group-containing (meth) acrylic acid esters such as allyl (meth) acrylic acid;
Polyfunctional (meth) acryloyl groups such as tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, and alkylene oxide-added tri (methacryloyloxyethyl) isocyanurate. Containing isocyanurates;
Polyfunctional allyl group-containing isocyanates such as triallyl isocyanurate;
By reaction between polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Obtained polyfunctional urethane (meth) acrylates;
Polyfunctional aromatic vinyls such as divinylbenzene; etc.

Among the above-mentioned polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further enhancing the curability of the curable resin composition of the present invention. When a polyfunctional polymerizable compound is used as the polymerizable compound, the functional number is preferably 3 or more, more preferably 4 or more, and further 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.
The molecular weight of the polymerizable compound is not particularly limited, but from the viewpoint of handling, for example, 2000 or less is preferable.

When a polyfunctional polymerizable compound is used as the polymerizable compound, among the polymerizable compounds, a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate are used from the viewpoints of reactivity, economy, availability and the like. It is preferable to use a compound having a (meth) acryloyl group, such as a compound or a (meth) acryloyl group-containing isocyanurate compound. More preferably, it is a polyfunctional (meth) acrylate compound, which makes the curable resin composition more excellent in photosensitivity and curability, and makes it possible to obtain a cured product having higher hardness and higher transparency. .. More preferably, a polyfunctional (meth) acrylate compound having three or more functionalities is used.

The content ratio of the polymerizable compound may be appropriately set according to the type of the polymerizable compound to be used, the type of the (meth) acrylate-based polymer, the purpose, the application, etc., but is excellent in developability and plate-making property. Therefore, it is preferably 2% by mass or more, and more preferably 80% by mass or less, based on 100% by mass of the total solid content of the curable resin composition. The lower limit is more preferably 5% by mass or more, further preferably 8% by mass or more, particularly preferably 10% by mass or more, and the upper limit is more preferably 70% by mass or less, still more preferably 50% by mass or less, particularly preferably. Is 30% by mass or less, most preferably 20% by mass or less.
<Photopolymerization initiator>
The curable resin composition further contains a photopolymerization initiator. The photopolymerization initiator is preferably a radically polymerizable photopolymerization initiator. The radically polymerizable photoinitiator 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. .. Further, if necessary, one kind or two or more kinds of a photosensitizer, a photoradical polymerization accelerator and the like may be used in combination. A photosensitizer and / or a photoradical polymerization accelerator may or may not be used together with the photopolymerization initiator. The effect of the present invention is sufficiently exhibited without the combined use of a photosensitizer and / or a photoradical polymerization accelerator, but when used in combination, the sensitivity and curability are further improved.

Specific examples of the photopolymerization initiator include the following compounds.
2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4- (2) -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-Methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Alkylphenone compounds such as butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; benzophenone, 4, Phenylphenone compounds such as 4'-bis (dimethylamino) benzophenone, 2-carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2- Thioxanthone compounds such as 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) Halomethylated triazine compounds such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine 2-Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-benzofuryl) vinyl] -1,3,4- Halomethylated oxadiazole compounds such as oxadiazole, 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, Biimidazole compounds such as 2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Il] -, Oxym ester compounds such as 1- (O-acetyloxime); bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) -1-Il) -phenyl) Titanosen-based compounds such as titanium; benzoic acid ester-based compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridin-based compounds such as 9-phenylaclydin.

Examples of the photosensitizer and the photoradical polymerization accelerator that may be used in combination with the above photopolymerization initiator include dye-based compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin dyes, and pyrromethene dyes; 4-dimethylamino. Examples thereof include dialkylaminobenzene compounds such as ethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; and mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole.

The content of the photopolymerization initiator may be appropriately set according to the purpose, application, etc., and is not particularly limited, but is 0 with respect to 100 parts by mass of the total solid content of the curable resin composition excluding the photopolymerization initiator. It is preferable that the amount is 1 part by mass or more. As a result, a cured product having better adhesion can be obtained, and peeling is more sufficiently suppressed even after high temperature exposure. Further, in consideration of the influence of the decomposition product of the photopolymerization initiator and the balance with economic efficiency, the amount is preferably 30 parts by mass or less. The lower limit is more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, particularly preferably 2 parts by mass or more, and the upper limit value is more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less. be.

The photosensitizer and the photoradical polymerization accelerator may not be used as described above, but when they are used, they are curable resins from the viewpoint of the balance between curability, the influence of decomposition products and economic efficiency. It is preferably 0.001 to 20% by mass with respect to 100% by mass of the total solid content of the composition. It is more preferably 0.01 to 15% by mass, still more preferably 0.05 to 10% by mass.
<Other ingredients>
− Solvent −
It is preferable that the curable resin composition also contains a solvent. The solvent is preferably used as a diluent or the like. That is, specifically, it is suitably used for lowering the viscosity and improving the handleability; forming a coating film by drying; as a dispersion medium for a coloring material; and the like, and is used in a curable resin composition. A low-viscosity organic solvent or water capable of dissolving or dispersing each of the components contained in the above.

As the solvent, a solvent that is normally used can be used and may be appropriately selected depending on the purpose and application, and is 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 and 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 Glycol ethers such as diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Esters of glycol monoethers such as 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, acetate Isopropyl, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Alkyl esters such as ethyl propionate, methyl acetoacetate, ethyl acetoacetate; ketones such as acetone, methyl ethyl ketone, methylisobutylketone, cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene; hexane, cyclohexane, Aliphatic hydrocarbons such as octane; amides such as dimethylformamide, dimethylacetamide, 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 contained in an amount of 10 to 90% by mass in the total amount of 100% by mass of the curable resin composition of the present invention. It is preferable to do so. More preferably, it is 20 to 80% by mass.

The curable resin composition further comprises, for example, a coloring material (also referred to as a colorant); a dispersant; a heat resistance improver; a leveling agent; a developing aid; silica fine particles, depending on the required properties of each application to which the curable resin composition is applied. Inorganic fine particles such as; Coupling agents such as silane-based, aluminum-based, titanium-based; Thermosetting resins such as fillers, epoxy resins, phenol resins, polyvinylphenols; Curing aids such as polyfunctional thiol compounds; Plastics; Polymerization Banners; UV absorbers; Antioxidants; Matters; Antifoaming agents; Antistatic agents; Slip agents; Surface modifiers; Shaking change agents; Shaking aids; Kinondiazide compounds; Polyhydric phenol compounds; Cationic polymerization One or more of sex compounds; acid generators; etc. may be further contained. For example, when the curable resin composition is used for a color filter application, it is preferable to include a coloring material. As described above, the form in which the curable resin composition further contains a coloring material is also one of the preferred forms of the present invention. Further, a form containing at least one selected from the group consisting of a coloring material, a dispersant, a heat resistance improving agent, a leveling agent, a coupling agent and a developing aid is also suitable. Hereinafter, these contained components will be described.
-Color material-
As the coloring material, for example, pigments and dyes are preferably used. These may be used alone or in combination of two or more. Moreover, you may combine a pigment and a dye. For example, when forming red, blue, and green pixels of a color filter, a method of exhibiting desired color characteristics by combining color materials such as blue and purple and green and yellow is preferably used. Further, when forming a black matrix, it can also be formed by using a black coloring material.
Among the above pigments and dyes, for example, the pigment (for example, an organic pigment or an inorganic pigment) is excellent in terms of durability, and the dye is excellent in terms of improving the brightness of, for example, a panel, etc. These may be selected or used together. Among the pigments, organic pigments are more preferable.

Examples of the pigment include azo pigments, phthalocyanine pigments, and polycyclic pigments (for example, quinacridone-based, perylene-based, perinone-based, isoindolinone-based, isoindolin-based, dioxazine-based, thioindigo-based, anthraquinone-based, and quinophthalone-based pigments. , Metal complex type, diketopyrrolopyrrole type, etc.), organic pigments such as dye lake type pigments; white / extender pigments (eg, titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), Yes Color pigments (eg yellow lead, cadmium, chrome vermillion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, lead tan, ultramarine, dark blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.) , Black pigments (eg carbon black, bone black, graphite, iron black, titanium black, etc.), bright material pigments (eg pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (eg zinc sulfide, strontium sulfide, strontium aluminate, etc.) Etc.) and other inorganic pigments. Examples of the pigment colors that can be used include yellow, red, purple, blue, green, brown, black, and white.

The pigment may also be surface-treated such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, and wax coating, depending on the purpose and application.

Specific examples of the above pigments are shown below by color index (CI; published by The Society of Dyers and Colorists) number, but the coloring material of the present invention is not limited to these. Further, these may be used alone or in combination of two or more. The following "CI" means a color index, and the number means a color index number.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 49, 53, 55, 60, 61, 61: 1, 62, 62: 1, 63, 65, 71, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 123, 124, 126, 127, 127: 1, 128, 129, 130, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170.172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 209, 209: 1, 212, 213, 214, 215, 219 and the like can be mentioned.

Examples of the orange pigment include C.I. I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 31, 34, 36, 38, 39, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, 81 and the like can be mentioned.
Examples of the purple pigment include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 13, 14, 15, 16, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 39, 42, 44, 47, 49, 50 and the like can be mentioned.

Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 37, 38, 40, 41, 42, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 49: 1, 49: 2, 50: 1, 52, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 54, 57, 57: 1, 57: 2, 58, 58: 2, 58: 4, 60, 60: 1, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 89, 90: 1, 95, 97, 101, 101: 1, 102, 104, 105, 106, 108, 108: 1, 109, 112, 113, 114, 122, 123, 136, 144, 146, 147, 149, 150, 151, 164, 166, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 215, 216, 220, 221, 224, 226, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 248, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 279 and the like.

Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17, 17: 1, 19, 24, 24: 1, 25, 26, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80 and the like can be mentioned.
Examples of the green pigment include C.I. I. Pigment Greens 1, 2, 4, 7, 8, 10, 13, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like.

Examples of the brown pigment include C.I. I. Pigment Brown 5, 6, 23, 24, 25, 32, 41, 42 and the like.
Examples of the black pigment include aniline black, carbon black, lamp black, bone black, black iron, titanium black, and C.I. I. Pigment Black 1, 6, 7, 9, 10, 11, 12, 13, 20, 31, 32, 34 and the like. Examples of the white pigment include C.I. I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28 and the like.

As the dye, for example, the organic dyes described in JP-A-2010-9033, JP-A-2010-21198, JP-A-2009-51896, and JP-A-2008-50599 can be used. can. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable.

The content ratio of the color material (that is, the total ratio of the pigment and the dye) can be appropriately set according to the purpose and application, but the preferable range of the content ratio of the color material is the solid of the curable resin composition. It is 3 to 70% by mass with respect to 100% by mass of the total amount. It is more preferably 5 to 60% by mass, still more preferably 10 to 50% by mass.
-Dispersant-
The dispersant has a site of interaction with a coloring material and a site of interaction with a dispersion medium (for example, a solvent or a binder resin), and has a function of stabilizing dispersion of the color material in the dispersion medium. Yes, it is generally classified into a resin type dispersant (for example, a polymer dispersant), a surfactant (for example, a low molecular weight dispersant), and a dye derivative. The curable resin composition of the present invention preferably contains a dispersant together with a coloring material. As the dispersant (that is, a resin-type dispersant, a surfactant and / or a dye derivative), a commonly used dispersant can be used. Further, as the dispersant, one kind may be used alone, or two or more kinds may be used in combination.

Examples of the resin type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , Long-chain polyaminoamidophosphates, hydrogen group-containing polycarboxylic acid esters, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups, (meth) acrylic acid-styrene. Copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, polyvinylpyrrolidones, polyesters, modified polyacrylates, ethylene oxide / polypropylene oxide adducts, etc. Can be mentioned.
The structure of the resin-type dispersant is a resin having a graft structure in which the main chain is an anchor chain having an interaction site with a coloring material and the graft chain is a compatible chain having an interaction with a dispersion medium. Alternatively, a resin in which the anchor chain and the compatible chain have a block structure is particularly preferably used.

Examples of the trade names of the resin-type dispersants include the following. However, it is not limited to these.
EFKA-46, 47,48,745, 1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4540, 4550, 6750, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN470, 472, 480, 482, K-SPERSE131, 152570, 5207 (all manufactured by EFKA ADDITIVES); Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti- Terra-205, Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, 160, 161, 162, 163, 164, 166, 182, P-104, P-104S, P105, 220S, 203, 204, 205, 2000, 2001, 9075, 9076, 9077 (all manufactured by Big Chemie); SOLSERSE3000, 5000, 9000, 12000, 13240, 13940, 17000, 20000, 22000, 24000 , 24000GR, 26000, 28000 (above, manufactured by Japan Lubrizol); Disperlon 7301, 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 152MS (above, manufactured by Kusumoto Kasei); , 822, 880, PN-411, PA-111 (all manufactured by Ajinomoto Fine Techno Co., Ltd.); KP series (manufactured by Shin-Etsu Chemical Co., Ltd.); Polyflow series (manufactured by Kyoeisha Chemical Co., Ltd.); Megafuck series (DIC (DIC) ); Disper aid series (manufactured by San Nopco); etc.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, sodium alkylnaphthalline sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, and ammonium lauryl sulfate. Anionic surfactants such as sodium stearate and sodium lauryl sulfate; nonions such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate. Sexual surfactants; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazolin; and the like.

The dye derivative is a compound having a structure in which a functional group is introduced into the dye, and examples of the functional group include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, and an amide group. , A phthalimide group and the like. The structure of the parent dye is, for example, azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrone, perylene, diketopyrrolopyrrole. The system etc. can be mentioned.

The content ratio of the above dispersant (that is, resin-type dispersant, surfactant and / or dye derivative) may be appropriately set according to the purpose and application, but has dispersion stability and durability (heat resistance and light resistance). , Weather resistance, etc.) and transparency, for example, 0.01 to 60% by mass is preferable with respect to 100% by mass of the total solid content of the curable resin composition. It is more preferably 0.1 to 50% by mass, still more preferably 0.3 to 40% by mass.
-Heat resistance improver-
The heat resistance improver is preferably used for improving heat resistance and strength. As the heat resistance improving agent, for example, an N- (alkoxymethyl) melamine compound, a compound having two or more epoxy groups or an oxetanyl group, and the like are suitable. In particular, when the curable resin composition is used as a resist for a photo spacer, a transparent resist for a protective film, or a resist for an interlayer insulating film, their use is preferable.

In addition, the curable resin composition of the present invention preferably contains an antioxidant in order to prevent heat-resistant coloring of the cured product. The N-substituted maleimide monomer unit is thermally stable and has little decomposition or coloring, but at a high temperature of 230 ° C to 250 ° C, N atoms are oxidized and some coloring occurs. With the recent improvement in the quality of liquid crystal panels, further reduction of thermal coloring is required. Therefore, as a result of diligent studies, the present inventors have found that the addition of an antioxidant can significantly reduce thermal coloring at high temperatures.

As the antioxidant used in the present invention, a hindered phenol-based antioxidant and a phosphite ester-based antioxidant are preferable. Examples of the hindered phenolic antioxidant include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-octadecyl-β- (4'-hydroxy-3', 5'-di-t-butylphenyl) propionate, 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylfienyl) propionyloxy] ethyl ] 2,4,8,10-tetraoxaspiro [5,5] -undecane, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di- t-pentylphenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,6-di-t-butyl-4-methyl Phenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethyl Phenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-) Methylcyclohexyl) -4,6-dimethylphenol, 2,6-diokudadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2, 6-Di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundecyl-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadecyl-) Alkylated monophenols such as 1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridecyl-1'-yl) phenol and mixtures thereof;
2,4-Dioctylthiomethyl-6-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4 -Alkylthiomethylphenols such as nonylphenols and mixtures thereof;
2,2'-Methylenebis (4-methyl-6-t-butylphenol), 2,2'-Methylenebis (4-ethyl-6-t-butylphenol), 2,2'-Methylenebis [4-Methyl-6-(4-Methyl-6- ( α-Methylcyclohexyl) phenol]], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-methylenebis (4) , 6-di-t-butylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4-isobutyl-6-t-butylphenol), 2, 2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (6) -T-butyl-2-methylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,1 -Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-t-butyl-5-methyl-2) -Hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-t-butyl-4-hydroxy) -2-Methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis-3'-t-butyl-4'-hydroxyphenyl] butyrate], bis (3-t-butyl-4) -Hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-t-butyl-2'-hydroxy-5'-methylbenzyl) -6-t-butyl-4-methylphenyl] terephthalate, 1 , 1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-t) -Butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra (5-t-butyl-4-hydroxy-2-methylphenyl) pentane and theirs. Alkyridene bisphenol such as a mixture and its derivatives;
And so on. Phosphite ester antioxidants include triphenylphosphite, tris (nonylphenyl) phosphite, triethylphosphite, tridecylphosphite, tris (tridecyl) phosphite, diphenylmono (2-ethylhexyl) phosphite, Diphenylmonodecylphosphite, diphenylmono (tridecyl) phosphite, tristearyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite and the like are preferable.
Of these, hindered phenolic antioxidants, which have high antioxidant capacity and are easily industrially available, are preferable. In particular, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] has a high antioxidant effect, is easily industrially available, and has high compatibility with cured products. preferable.
The preferable blending amount of the antioxidant is 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, based on the (meth) acrylate-based polymer (solid content: 100% by mass). Most preferably, it is 0.1 to 1% by mass. If the blending amount of the antioxidant is less than the above range, the anticoloring effect may be reduced, and if it exceeds the above range, the curing of the photosensitive resin composition may be hindered or the antioxidant itself may be heated. Decompositions of antioxidants remain during coloring or heating, and for example, when a curable composition for manufacturing a color filter for a liquid crystal panel is used, the decomposition products may seep into the liquid crystal and the reliability may decrease.
-Leveling agent-
The leveling agent is preferably used for improving the leveling property. As the leveling agent, a fluorine-based or silicon-based surfactant is preferable.
-Coupling agent-
The coupling agent is preferably used for improving adhesion. As the coupling agent, a silane-based coupling agent is preferable, and examples thereof include epoxy-based, methacrylic-based, and amino-based silane coupling agents. Of these, epoxy-based silane coupling agents are preferable.
-Developing aid-
The developing aid is preferably used for improving developability. Examples of the developing aid include monocarboxylic acids such as (meth) acrylic acid, acetic acid and propionic acid; polyvalent carboxylic acids such as maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid and trimellitic acid; maleic anhydride. , Carboxylic acid anhydrides such as succinic anhydride, tetrahydrophthalic acid anhydride, trimellitic acid anhydride; and the like are suitable.

The method for producing the curable resin composition is not particularly limited, and for example, it can be prepared by mixing and dispersing the above-mentioned contained components using various mixers and dispersers. The mixing / dispersing step is not particularly limited and may be carried out by a usual method. Moreover, it may further include other steps which are usually performed. When the curable resin composition contains a coloring material, it is preferable to manufacture the curable resin composition through a coloring material dispersion treatment step. As the coloring material dispersion treatment step, for example, first, a coloring material (preferably). Weigh each predetermined amount of organic pigment), dispersant and solvent, and use a disperser such as a paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender, etc. to disperse the color material into fine particles to disperse the liquid color material. A method of using a liquid (also called a mill base) can be mentioned. Preferably, the kneading and dispersing treatment is performed with a roll mill, a kneader, a blender or the like, and then the fine dispersion treatment is carried out with a media mill such as a bead mill filled with beads of 0.01 to 1 mm. A composition containing a (meth) acrylate-based polymer, a polymerizable monomer, a photopolymerization initiator, and a solvent, a leveling agent, etc., if necessary, which have been separately stirred and mixed in the obtained mill base. (Preferably a transparent liquid) is added and mixed to obtain a uniform dispersion solution, and a curable resin composition can be obtained.
The obtained curable resin composition is preferably filtered with a filter or the like to remove fine dust.
[Cursed product]
As described above, the curable resin composition of the present invention provides a cured product having excellent basic performance of heat resistance and transparency (heat-resistant coloring property). Such a cured product also has , for example, no residue in an unexposed portion, ground stains, or the like after development. A cured product obtained by curing such a curable resin composition is also one of the present inventions.

The cured product (cured film) preferably has a film thickness (thickness) of 0.1 to 20 μm. This makes it possible to sufficiently meet the demand for lowering the height of members and the like using the cured product and display devices. It is more preferably 0.5 to 10 μm, still more preferably 0.5 to 8 μm.

The cured product is used for various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, etc. used for liquid crystal display devices, solid-state image pickup devices, etc., and for electric / electronic equipment, etc. It is preferably used in. Above all, it is preferable to use it for a color filter. As described above, a color filter using the curable resin composition, that is, specifically, a color filter having the cured product on a substrate is also one of the present inventions. Hereinafter, the color filter will be further described.
<Color filter>
The color filter of the present invention has a form in which the cured product is contained on a substrate.
In the above color filter, the cured product formed by the curable resin composition of the present invention is particularly suitable as a black matrix or a segment requiring coloring such as each pixel of red, green, blue, yellow, etc. However, it is also suitable as a segment that does not necessarily require coloring, such as a photo spacer, a protective layer, and an orientation control rib.

Examples of the substrate used for the color filter include glass substrates such as white plate glass, blue plate glass, alkali-reinforced glass, and silica-coated blue plate glass; a ring-opened polymer of polyester, polycarbonate, polyolefin, polysulfone, and cyclic olefin, and hydrogen thereof. Sheets, films or substrates made of thermoplastic resins such as additives; Sheets, films or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; Metal substrates such as aluminum plates, copper plates, nickel plates and stainless steel plates Examples thereof include a ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a member made of various materials such as a glass substrate having a color material layer on the surface (for example, a color filter for LCD); and the like. Above all, from the viewpoint of heat resistance, a glass substrate, a sheet, a film or a substrate made of a heat resistant resin is preferable. Further, it is preferable that the substrate is a transparent substrate.
Further, the base material may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent or the like, if necessary.
<Manufacturing method of color filter>
To obtain the color filter, for example, a step of arranging the curable resin composition on a substrate (also referred to as an arranging step) for each pixel color (that is, for each pixel of one color) and an arrangement on the substrate. It includes a step of irradiating the cured resin composition with light (also referred to as a light irradiation step), a step of developing with a developing solution (also referred to as a developing step), and a step of heat treating (also referred to as a heating step). It is preferable to adopt a method and adopt a manufacturing method in which the same method is repeated for each color. The order of forming the pixels of each color is not particularly limited.
-Arrangement process (preferably coating process)-
It is preferable that the arrangement step is performed by coating. Examples of the method of applying the curable resin composition on the substrate include spin coating, slit coating, roll coating, cast coating and the like, and any of these methods can be preferably used.
In the arrangement step, it is also preferable to apply the curable resin composition onto the substrate and then dry the coating film. The coating film can be dried by using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but usually, the drying is performed at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds. Suitable.
-Light irradiation process-
Examples of the light source of the active light used in the above light irradiation step 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 carbon arc, and a fluorescent lamp. Laser light sources such as lamp light sources, argon ion lasers, YAG lasers, excima lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers are used. Further, examples of the exposure machine method include a proximity method, a mirror projection method, and a stepper method, and the proximity method is preferably used.
In the process of irradiating the active energy ray, the active energy ray may be irradiated through a predetermined mask pattern depending on the application. In this case, the exposed portion is cured, and the cured portion is insoluble or sparingly soluble in the developing solution.
-Development process-
The developing step is a step of forming a pattern by removing an unexposed portion by developing with a developing solution after the above-mentioned light irradiation step. This makes it possible to obtain a patterned cured film. The development process can usually be performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, and ultrasonic development.

The developer used in the development step is not particularly limited as long as it dissolves the curable resin composition of the present invention, but an organic solvent or an alkaline aqueous solution is usually used, and a mixture thereof may be used. .. When an alkaline aqueous solution is used as the developing solution, it is preferable to wash it with water after developing.

Examples of the organic solvent suitable for the developer include ether-based solvents and alcohol-based solvents. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkylphenyl ethers, aralkylphenyl ethers, diaromatic ethers. Kind, isopropanol, benzyl alcohol and the like.

In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffer, a dye, a pigment and the like, if necessary. Examples of the organic solvent in this case include an organic solvent suitable for the above-mentioned developer.
Examples of the alkaline agent include inorganic substances such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, sodium secondary phosphate, sodium carbonate, potassium carbonate, and sodium hydrogencarbonate. Alkaline agents; trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and other amines can be mentioned, and these can be used alone in two or more kinds. May be combined.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitanoic acid alkyl esters and monoglyceride alkyl esters; alkylbenzene sulfonates and alkylnaphthalene sulfonic acids. Anionic surfactants such as salts, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids, etc., which may be used alone or in combination of two or more. It is also good.
-Heating process-
The heating step is a step (also referred to as a post-curing step) in which the exposed portion (cured portion) is further cured by firing after the above-mentioned developing step. For example, a step of post-exposure using a light source such as a high-pressure mercury lamp with a light ^{amount of 0.5 to 5} J / cm 2 or a step of post-heating at a temperature of 150 to 280 ° C. for 10 seconds to 120 minutes is performed. Can be mentioned. By performing such a post-curing step, it becomes possible to further strengthen the hardness and adhesion of the patterned cured film. Further, by this heating step, it is derived from a part of the structural unit of the (meth) acrylate-based polymer contained in the curable resin composition (that is, a part of the tertiary carbon-containing (meth) acrylate-based monomer). Since the portion) is decomposed, curability and solvent resistance can be improved.

The thickness of the cured film obtained by the heating step (that is, the cured film obtained by thermally curing the curable resin composition) is preferably 0.1 to 20 μm. By using the curable resin composition of the present invention, it is possible to provide a cured film having a sufficiently reduced film thickness. It is more preferably 0.5 to 10 μm, still more preferably 0.5 to 8 μm.
The film thickness of the coating film (that is, the cured film) obtained by the heating step is preferably 90% or less, assuming that the film thickness of the coating film before heating is 100%. It is more preferably 80% or less, still more preferably 70% or less.

In the heating step, the heating temperature is preferably 150 ° C. or higher. As a result, the portion derived from a part of the tertiary carbon-containing (meth) acrylate-based monomer is more effectively decomposed, so that it becomes possible to further improve the curability and the solvent resistance. .. Further, the curable composition of the present invention is characterized by having very little heat-resistant coloring, especially at high temperatures. Therefore, heat treatment at a higher temperature is possible, and the curability and solvent resistance are excellent. It is more preferably 180 ° C. or higher, further preferably 220 ° C. or higher, and particularly preferably 235 ° C. or higher. The temperature is preferably 280 ° C or lower, more preferably 260 ° C or lower. If the heating temperature exceeds the above range, thermal decomposition may occur, which may cause contamination by decomposition products and increase in thermal coloring, which is not preferable.

The heating time in the heating step is not particularly limited, but is preferably 5 to 60 minutes, for example. Further, the heating method is not particularly limited, but for example, it can be performed by using a heating device such as a hot plate, a convection oven, or a high frequency heater.
[Display device]
The present invention is also a display device configured by using the above color filter.
In addition, a display device member and a display device having a cured product formed of the curable resin composition are also included in a preferred embodiment of the present invention. The cured product (cured film) formed by the curable resin composition is stable, has excellent adhesion to a substrate or the like, has high hardness, exhibits high smoothness, and has a high transmittance. Therefore, it is particularly suitable as a transparent member, and is also useful as a protective film or an insulating film in various display devices.

As the display device, for example, a liquid crystal display device, a solid-state image sensor, a touch panel type display device, or the like is suitable.
When the cured product (cured film) is used as a display device member, the member may be a film-shaped single-layer or multilayer member composed of the cured film, or the single-layer or multilayer member. It may be a member in which another layer is further combined with the member of the above, or it may be a member including the cured film in the composition.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means "part by mass".
In the following synthetic examples and the like, various physical properties and the like were measured as follows.
<Weight average molecular weight>
The weight average molecular weight was measured by the GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent.
<Solid content>
About 1 g of a polymer solution (also referred to as a resin solution or a polymer solution) was weighed in an aluminum cup, about 3 g of acetone was added to dissolve the solution, and then the mixture was naturally dried at room temperature. Then, using a hot air dryer (manufactured by ESPEC, trade name: PHH-101), the product was dried at 140 ° C. under vacuum for 1.5 hours, then allowed to cool in a desiccator, and the mass was measured. The solid content (mass%) of the polymer solution was calculated from the amount of mass reduction.
<Acid value>
3 g of the resin solution is precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555) using a 0.1-specified KOH aqueous solution as a titration solution. ), The acid value of the polymer solution was measured, and the acid value (AV) per 1 g of the solid content was determined from the acid value of the solution and the solid content of the solution.
<Heat-resistant coloring of curable resin composition>
The curable resin composition is applied to a non-alkali glass plate using a spin coater so that the total thickness after drying is 3 μm, dried on a hot plate at 100 degrees for 3 minutes, and then an ultra-high pressure mercury lamp is applied. The ultraviolet rays were irradiated so that the irradiation amount was 100 mJ / cm ^2. After irradiation, the test piece was further dried on a hot plate at 230 ° C. for 30 minutes to prepare a test piece. The obtained test piece is heated on a hot plate at 250 ° C. for 3 hours, cooled to room temperature, and then b ^* value after the heat resistance test using a spectrocolorimeter (“EE-6000” manufactured by Nippon Denshoku Kogyo Co., Ltd.). Was measured.
Synthesis example 1
A reaction tank equipped with a synthetic thermometer, a stirrer, a gas introduction tube, a cooling tube and a dropping tank introduction port for the resin solution 1 (CHMI-t-BMA-MMA-HEMA-AA copolymer solution 1), propylene glycol monomethyl ether. 190 parts of acetate was charged, substituted with nitrogen, and then heated to 90 ° C. On the other hand, as a dropping tank (A), 10 parts of N-cyclohexylmaleimide, 35 parts of t-butyl methacrylate, 20 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 15 parts of acrylic acid and t-amylper were placed in a beaker. Prepare a mixture of 2.2 parts of oxy-2-ethylhexanoate (“Luperox 575” manufactured by Alchema Yoshitomi Co., Ltd.) with stirring, and put 1.0 part of n-dodecyl mercaptan and propylene glycol monomethyl in the dropping tank (B). A mixture of 10 parts of ether acetate was prepared. After the temperature of the reaction vessel reached 90 ° C., the dropping was started from the dropping tank over 3 hours while maintaining the same temperature, and the polymerization was carried out. After the dropping was completed, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and the mixture was aged for 90 minutes.
When the obtained polymer solution was analyzed, the weight average molecular weight was 18,000, the acid value was 120 mgKOH / g, and the resin solid content was 34.3% by mass.

Synthesis example 2
The amount of synthetic monomer charged in the resin solution 2 (CHMI-t-BMA-MMA-HEMA-AA copolymer solution 2) was 20 parts of N-cyclohexylmaleimide, 35 parts of t-butyl methacrylate, and 10 parts of methyl methacrylate. The same operation as in Synthesis Example 1 was carried out except that the parts were 20 parts of 2-hydroxyethyl methacrylate and 15 parts of acrylic acid, and the amount of n-dodecyl mercaptan charged was 0.6 part, and the obtained polymer solution was analyzed. As a result, the weight average molecular weight was 18,000, the acid value was 120 mgKOH / g, and the resin solid content was 33.8% by mass.

Synthesis example 3
The amount of synthetic monomer charged in the resin solution 3 (CHMI-t-BMA-MMA-HEMA-MAA copolymer solution 3) was 10 parts of N-cyclohexylmaleimide, 35 parts of t-butyl methacrylate, 16 parts of methyl methacrylate. The same operation as in Synthesis Example 1 was carried out except that the parts were 20 parts of 2-hydroxyethyl methacrylate and 19 parts of methacrylic acid, and the amount of n-dodecyl mercaptan charged was 0.8 part, and the obtained polymer solution was analyzed. As a result, the weight average molecular weight was 20000, the acid value was 120 mgKOH / g, and the resin solid content was 33.0% by mass.

Synthesis example 4
Synthesis of resin solution 4 (BzMI-t-BMA-MMA-HEMA-AA copolymer solution 4) The same operation as in Synthesis Example 1 was performed except that N-benzylmaleimide was used instead of N-cyclohexylmaleimide. When the obtained polymer solution was analyzed, the weight average molecular weight was 18,000, the acid value was 120 mgKOH / g, and the resin solid content was 33.6% by mass.
Synthesis example 5
Resin solution 5 (CHMI-t-BMA-MMA-HEMA-AA copolymer solution 5)
The same operation as in Synthesis Example 1 was carried out except that the amount of the monomer charged was 35 parts of N-cyclohexylmaleimide, 30 parts of t-butyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate and 15 parts of acrylic acid. When the obtained polymer solution was analyzed, the weight average molecular weight was 22000, the acid value was 120 mgKOH / g, and the resin solid content was 33.9% by mass.

Example 1
100 parts of resin solution 1, 20 parts of dipentaerythritol hexaacrylate as radically polymerizable compound, 2 parts of Irgacure 907 (manufactured by BASF) as a radically polymerizable photopolymerization initiator, and Irganox 1010 (BASF) as an antioxidant. (Manufactured) was mixed with 0.2 parts and 55 parts of propylene glycol monomethyl ether acetate to obtain a curable resin composition 1. The obtained curable resin composition 1 was evaluated for heat-resistant coloring by the above method. ^{The b *} value after the heat resistance test was measured and found to be 1.0.

Example 2
The curable resin composition 2 was measured in the same manner as in Example 1 except that the resin solution 2 was used, and it was 2.5.

Example 3
The curable resin composition 3 was measured in the same manner as in Example 1 except that the resin solution 3 was used, and it was 1.2.

Comparative Example 1
The curable resin composition 3 was measured in the same manner as in Example 1 except that the resin solution 4 was used, and the result was 3.3. In Comparative Example 1, it was found that the heat-resistant coloring property at 250 ° C. was inferior to that of Examples 1 to 3.

Comparative Example 2
The curable resin composition 3 was measured in the same manner as in Example 1 except that the resin solution 5 was used, and the result was 2.8. In Comparative Example 2, it was found that the heat-resistant coloring property at 250 ° C. was inferior to that of Examples 1 to 3.

As described above, it is clear that the curable resin composition of the present invention has very little heat-resistant coloring property in the heat treatment at a high temperature of 250 ° C.

The display device member and the display device containing the cured product formed by the curable resin composition of the present invention can be suitably used in the optical field and the electric / electronic field.

Claims (9)

A curable resin composition containing a (meth) acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator.
The (meth) acrylate-based polymer contains 2 to 30% by mass of a structural unit derived from N-cyclohexylmaleimide , and a tertiary carbon having a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. (Meta) acrylate-based monomer unit 20-60% by mass, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid A monomer unit having a hydroxyl group selected from 2-hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2,3-dihydroxypropyl (meth) acrylate. %, And a curable resin composition for a color filter , characterized by having 5 to 25% by mass of (meth) acrylic acid units. The curable resin composition for a color filter according to claim 1 , wherein the (meth) acrylate-based polymer has a content of 5% by mass or less of a monomer unit containing an aromatic hydrocarbon structure. .. The curable resin composition for a color filter according to claim 1 or 2, wherein the (meth) acrylate-based polymer has a weight average molecular weight of 3,000 to 20,000. The curable resin composition for a color filter is characterized by containing 0.1 to 1% by mass of an antioxidant with respect to the (meth) acrylate-based polymer (solid content: 100% by mass). Item 6. The curable resin composition for a color filter according to any one of Items 1 to 3. A method for producing a curable resin composition in which a (meth) acrylate-based polymer, a polymerizable compound and a photopolymerization initiator are mixed, wherein the (meth) acrylate-based polymer is N-cyclohexylmaleimide 2 to 30% by mass. , 20-60% by mass of tertiary carbon-containing (meth) acrylate-based monomer having a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom, 2-hydroxyethyl (meth) acrylate. , (Meta) 2-hydroxypropyl acrylate, (meth) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , A polymer obtained by mixing and synthesizing 10 to 40% by mass of a polymer having a hydroxyl group selected from 2,3-dihydroxypropyl (meth) acrylic acid and 5 to 25% by mass of (meth) acrylic acid. A method for producing a curable resin composition for a color filter. The curable resin composition for a color filter according to claim 5, wherein the antioxidant is blended in an amount of 0.1 to 1% by mass with respect to the (meth) acrylate-based polymer (solid content: 100% by mass). How to make things. A cured product obtained by curing the curable resin composition for a color filter according to any one of claims 1 to 4. A color filter comprising the cured product according to claim 7 on a substrate. A display device characterized by being configured by using the color filter according to claim 8.