KR102270294B1 - Curable resin composition and its use - Google Patents

Abstract

Provided is a curable resin composition that can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (substrate), heat resistance and transparency, has excellent storage stability, and is useful for various uses such as color filters. Moreover, the hardened|cured material formed of such curable resin composition, and the color filter and display apparatus using the hardened|cured material are also provided.
A curable resin composition comprising a (meth)acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator, wherein the (meth)acrylate-based polymer is a tertiary carbon-containing (meth)acrylate-based monomer unit and a monomer unit having a hydroxyl group , and a curable resin composition having a monomer unit having an active methylene group.

Description

Curable resin composition and its use {CURABLE RESIN COMPOSITION AND ITS USE}

The present invention relates to a curable resin composition and its use.

For the curable resin composition that can be cured by heat or active energy rays, for example, various applications to various uses such as optical members and electric/electronic devices have been studied, and curable resins having excellent properties required for each use Compositions are being developed. Although a color filter is mentioned as an example of a specific use, A color filter is a main member which comprises a liquid crystal display device, a solid-state image sensor, etc., and generally a board|substrate and at least three primary colors (red (R), green (G), blue) In addition to the pixel of (B)) and the resin black matrix BM which partitions them, it is comprised from the protective film etc. which coat|cover and protect a pixel and a resin black matrix, and are formed in order to planarize those unevenness|corrugation.

Usually, when performing pixel formation of a color filter using a curable resin composition, with respect to one pixel color, (1) a coating process of apply|coating a curable resin composition to the whole surface of a board|substrate, (2) a coating process formed by After curing the exposed portion by pattern exposure to the resist film through a photomask, an exposure step of insolubilizing the cured portion, (3) removing the unexposed portion with a developer, and further curing the exposed portion by baking (bake) A method is employed in which a developing/baking (bake) treatment process is performed, and the same process as this is repeated for each color. In consideration of such application to color filter applications, it is required that the curable resin composition have various physical properties such as curability, solvent resistance after curing, adhesion to a substrate, heat resistance, and transparency. Then, the method described in patent documents 1-3 is proposed, for example.

Japanese Patent Laid-Open No. 2007-333847 Japanese Patent Laid-Open No. 2012-022048 Japanese Patent Laid-Open No. 2007-034134

As mentioned above, it is calculated|required that curable resin composition has various physical properties, such as curability, solvent resistance after hardening, adhesiveness with a board|substrate (also called a base material), heat resistance, and transparency. And in recent years, miniaturization, thickness reduction, energy saving of optical members, electric/electronic devices, etc. are progressing, and a new problem arises from the point which high-quality performance is requested|required by members, such as a color filter used with it. have. For example, in a color filter use, as the density|concentration of color materials, such as a pigment and dye, increases, there exists a problem that a color material elutes to a washing|cleaning solvent in a manufacturing process. Therefore, it is required to exhibit a very high degree of solvent resistance after curing. However, it is the present situation that the conventional resin composition cannot fully respond to these requests. For example, in the resin compositions described in Patent Documents 1 and 2, since the solvent resistance is not sufficient, the color material dissolves in the cleaning solvent in the manufacturing process, and the color characteristics may decrease, so there is room for improvement in this point and the like. there was Moreover, in the resin composition of patent document 3, although solvent resistance was improved, there existed room for improving general characteristics, such as adhesiveness and developability, by making further improvement.

The present invention has been made in view of the current situation, and can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to a substrate, heat resistance and transparency, and has excellent storage stability, and is suitable for various uses such as color filters. It aims at providing a useful curable resin composition. Another object of the present invention is to provide a cured product formed of such a curable resin composition, and a color filter and display device using the cured product.

As a result of various studies on curable resin compositions useful for various uses such as color filters, the present inventors have found that when a resin composition containing a (meth)acrylate-based polymer, a polymerizable compound and a photopolymerization initiator is prepared, it has curability. paid attention to Then, the (meth)acrylate-based polymer is a structural unit derived from a tertiary carbon-containing (meth)acrylate-based monomer (also referred to as a tertiary carbon-containing (meth)acrylate-based monomer unit) and a monomer having a hydroxyl group. Assuming that it has a structural unit derived from (also referred to as a monomer unit having a hydroxyl group) and a structural unit derived from a monomer having an active methylene group (also referred to as a monomer unit having an active methylene group), the resin composition has dramatically improved solvent resistance after curing. It has been found that a cured product capable of stably expressing various physical properties such as high transparency, adhesion to a substrate, heat resistance and high hardness was found to be provided. Moreover, when the said resin composition was used, the image development time at the time of alkali image development could also be shortened, and it discovered that productivity improved more and reduction of manufacturing cost also became possible. Such a curable resin composition is especially useful for a color filter use, Especially, it is preferable as a resin composition for forming the pixel for color filters. Therefore, the cured product, color filter, and display device formed from such a curable resin composition are found to be very useful in the optical field and the electric/electronic field as being able to sufficiently respond to the demand for higher performance in recent years, and solving the above problems Thinking about what can be successfully solved, we have arrived at the present invention.

Here, the (meth)acrylate-based polymer contained in the curable resin composition of the present invention has a tertiary carbon-containing (meth)acrylate-based monomer unit, but the unit is easily decomposed by heat. For example, as described later, when the tertiary carbon-containing (meth)acrylate-based monomer giving the monomer unit has a structure in which an oxygen atom adjacent to a (meth)acryloyl group is bonded to a tertiary carbon atom, The OC bond between the oxygen atom adjacent to the (meth)acryloyl group and the tertiary carbon atom adjacent thereto is easily cleaved, thereby decomposing into (meth)acrylic acid and a stable compound generated on the tertiary carbon atom side do. Therefore, for example, when curable resin composition of this invention is used for pixel formation of a color filter, tertiary carbon containing (meth)acrylate type by the heating process after image development (it is also called a baking process or a post-baking process) The monomer unit is decomposed to produce (meth)acrylic acid and a stable compound generated on the tertiary carbon atom side. And, due to the occurrence of an ester crosslinked structure between the hydroxyl group in the polymer and the optionally included ester group and the (meth)acrylic acid produced, it is considered that the curability of the resin composition and the solvent resistance after curing are improved remarkably.

That is, the present invention is a curable resin composition comprising a (meth)acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator, wherein the (meth)acrylate-based polymer is a tertiary carbon-containing (meth)acrylate-based monomer unit, a hydroxyl group It is a curable resin composition which has a monomeric unit which has and has a monomeric unit which has an active methylene group.

This invention is also a hardened|cured material formed by hardening|curing the said curable resin composition.

This invention is also a color filter which has the said hardened|cured material on a board|substrate.

The present invention is also a display device configured using the color filter.

The curable resin composition of the present invention has very good developability, and can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to a substrate, heat resistance and transparency, and is excellent in storage stability and color It is useful for various uses, such as a filter. 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 or the electric/electronic field.

Hereinafter, the present invention will be described in detail. The aspect which combined 2 or 3 or more of each preferable aspect of this invention described below is also a preferable aspect of this invention.

In addition, "A-B" which shows a range means "A or more and B or less."

[Curable resin composition]

Although the curable resin composition of this invention contains a (meth)acrylate-type polymer, a polymeric compound, and a photoinitiator, 1 type or 2 or more types can be used for these containing components, respectively. Moreover, you may contain the other component 1 type, or 2 or more types further as needed.

<(meth)acrylate polymer>

The (meth)acrylate-based polymer has a tertiary carbon-containing (meth)acrylate-based monomer unit, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group. Each structural unit may be 1 type or 2 or more types, respectively. Moreover, you may include 1 type(s) or 2 or more types of structural units (it is also called another monomeric unit) derived from another monomer further as needed.

Hereinafter, the structure of the (meth)acrylate-based polymer will be further described.

(i) tertiary carbon-containing (meth)acrylate-based monomer unit

A tertiary carbon-containing (meth)acrylate-based monomer unit is a structural unit derived from a tertiary carbon-containing (meth)acrylate-based monomer, and a polymerizable carbon-carbon double bond (C=C) that the monomer has is two steps It means the structural unit which became a bond (CC). Here, the tertiary carbon-containing (meth)acrylate-based monomer is a compound having a (meth)acryloyl group and one or two or more tertiary carbon atoms in the molecule, respectively. A tertiary carbon atom means the carbon atom whose other carbon atom couple|bonded with the carbon atom is three.

The tertiary carbon-containing (meth)acrylate-based monomer preferably has a structure in which an oxygen atom adjacent to a (meth)acryloyl group is bonded to a tertiary carbon atom. Thereby, since the tertiary carbon-containing (meth)acrylate-based monomer unit is more easily decomposed by the heating step after image development, the curability of the resin composition and the solvent resistance after curing are remarkably improved as described above.

As the tertiary carbon-containing (meth)acrylate-based monomer, a compound having one polymerizable carbon-carbon double bond in one molecule, that is, a (meth)acryloyl group (CH ₂ =C(R)- It is preferable that it is a compound which has one C(=O)-). Especially, the compound represented by the following general formula (1) is more preferable.

CH ₂ =C(R)-C(=O)-OA (1)

In Formula (1), R represents a hydrogen atom or a methyl group. A represents a monovalent organic group including a structure having a tertiary carbon atom on the oxygen atom side.

In the said General formula (1), the organic group represented by A can be represented by -C(R ¹ )(R ² )(R ³ ), for example. In this case, ^{it is preferable that R<1>} , R<^2>, and R<^3> are the same or different and are a C1-C30 hydrocarbon group. This hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Moreover, it may have a cyclic structure, and may have a substituent further. In addition, R ¹ , R ² and R ³ may be linked to each other at a terminal site to form a cyclic structure. However, from the viewpoint of sufficiently exhibiting the effect derived from the tertiary carbon-containing (meth)acrylate-based monomer unit, R ¹ , R ² and R ³ preferably do not have a cyclic structure, and are connected to each other at the terminal site. It is preferable not to form a cyclic structure.

Moreover, in the present invention, as will be described later, a new compound formed by cleavage of an OC bond between an oxygen atom adjacent to a (meth)acryloyl group and a tertiary carbon atom in A adjacent thereto is easily volatilized. In , it is preferable that the carbon number of the organic group represented by A is 12 or less. Among them, the organic group represented by A is preferably a group derived from t-butyl (meth)acrylate and/or a group derived from t-amyl (meth)acrylate. Moreover, the organic group represented by A may have a branched structure.

In the tertiary carbon-containing (meth)acrylate-based monomer, the tertiary carbon atom bonded to an oxygen atom adjacent to the (meth)acryloyl group is at least one of the adjacent carbon atoms bonded to a hydrogen atom. desirable. For example, when the tertiary carbon-containing (meth)acrylate-based monomer is a compound represented by the general formula (1), and A in the formula is a group represented by -C(R ¹ )(R ² )(R ³ ) , R ¹ , R ² and R ^{3 preferably} contain a carbon atom having at least one hydrogen atom, and the carbon atom is bonded to a tertiary carbon atom. In such a form, the OC bond between the oxygen atom adjacent to the (meth)acryloyl group and the tertiary carbon atom adjacent thereto is cut|disconnected by heating, and (meth)acrylic acid is produced|generated, and at the same time, the A double bond (C=C) is formed between a tertiary carbon atom and a carbon atom adjacent thereto, resulting in a more stable formation of a new compound.

It is preferable that the new compound produced|generated as mentioned above volatilizes. In this case, due to volatilization of the new compound from the cured product, the film thickness of the cured product (cured film) is reduced and, for example, when the curable resin composition further contains a color material, the colorant concentration increases after heating. Therefore, while being able to implement|achieve further thinning, it becomes possible to achieve high color purity improvement and high light-shielding rate improvement of a black matrix more. In consideration of this point, ^{it is preferable that R 1} , R ² and R ³ are the same or different and represent a saturated hydrocarbon group having 1 to 15 carbon atoms. More preferably, it is a C1-C10 saturated hydrocarbon group, More preferably, it is a C1-C5 saturated hydrocarbon group, Especially preferably, it is a C1-C3 saturated hydrocarbon group.

In the (meth)acrylate-based polymer, the content rate of the tertiary carbon-containing (meth)acrylate-based monomer unit is 100% by mass of the total amount of the total monomer units (that is, “the mass of the (meth)acrylate-based polymer is 100 It is equivalent to "mass %"), and it is preferable that it is 5 mass % or more. Thereby, the effect of this invention resulting from a tertiary carbon-containing (meth)acrylate-type monomeric unit will be expressed further. More preferably, it is 15 mass % or more, More preferably, it is 20 mass % or more. In addition, the upper limit of the content rate may be appropriately set in consideration of the content rate of other monomer units. For example, when used for a color filter application, from the viewpoint of further improving pattern characteristics and developability, it is preferably 90 mass% or less. Do. More preferably, it is 75 mass % or less, More preferably, it is 60 mass % or less.

(ii) a monomer unit having a hydroxyl group

A monomer unit having a hydroxyl group is a structural unit derived from a monomer having a hydroxyl group (hydroxyl group), and means a structural unit in which a polymerizable carbon-carbon double bond (C=C) in the monomer becomes a single bond (CC). do. By including such a monomeric unit, sclerosis|hardenability of curable resin composition improves and hardened|cured material excellent in solvent resistance and transparency can be provided.

Although the monomer which has the said hydroxyl group is a monomer which has 1 or 2 or more hydroxyl groups in 1 molecule, hydroxyalkyl (meth)acrylate is preferable, for example. Although carbon number which comprises this hydroxyalkyl group is not specifically limited, For example, 1-20 are preferable, More preferably, it is 1-12, More preferably, it is 2-6.

Specifically as the hydroxyalkyl (meth)acrylate, for example, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, (meth) Acrylic acid 2-hydroxybutyl, (meth)acrylic acid 3-hydroxybutyl, (meth)acrylic acid 4-hydroxybutyl, (meth)acrylic acid 2, 3- dihydroxypropyl, etc. are mentioned.

Said (meth)acrylate-type polymer WHEREIN: It is preferable that the content rate of the monomeric unit which has a hydroxyl group is 5-50 mass % with respect to 100 mass % of total amounts of all the monomer units, for example. When it exists in this range, sclerosis|hardenability becomes more sufficient and solvent resistance improves. Moreover, since hydrophilicity becomes a suitable thing, it becomes possible to reduce more fully generation|occurrence|production of the problem at the time of image development (for example, it peels at the time of image development, or the surface becomes rough and whitens). More preferably, it is 10-40 mass %, More preferably, it is 15-35 mass %.

(iii) a monomer unit having an active methylene group

The monomer unit having an active methylene group is a structural unit derived from a monomer having an active methylene group, and means a structural unit in which a polymerizable carbon-carbon double bond (C=C) in the monomer becomes a single bond (C-C). By including such a monomeric unit, the solvent resistance and developability of curable resin composition become favorable.

Although the said monomer which has an active methylene group is a monomer which has 1 or 2 or more active methylene groups in 1 molecule, For example, the compound represented by following formula (2) is preferable. Thereby, it becomes possible to improve the sensitivity of curable resin composition more. Thus, the form in which the monomer which has an active methylene group is represented by following formula (2) is one of the preferable aspects of this invention.

[Formula 1]

In Formula (2), R<^1> represents a C1-C24 hydrocarbon group which may contain a hydrogen atom or a hetero atom. X represents a divalent group represented by any of the following formulas (2-1) to (2-3). R ² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. R ³ represents a divalent group represented by any of the following formulas (2-4) to (2-6). R ⁴ represents a cyano group (-CN), a nitro group (-NO ₂ ), or a group represented by the following formula (2-7) or (2-8). R ⁵ represents a hydrogen atom or a C1-C24 hydrocarbon group which may contain a hetero atom.

[Formula 2]

In said formula, R<^1> and R<^5> are the same or different, and represent a C1-C24 hydrocarbon group which may contain a hydrogen atom or a hetero atom. Among them, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, a hexoxy group, a cyclohexoxy group, or a formula (2-9) to (2-11), and more preferably a hydrogen atom or a methyl group.

[Formula 3]

R ² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. Among them, a single bond, a methylene group, an ethylene group, a propylene group, a butylene group, a propylene group, a hexylene group, a cyclohexylene group, an octylene group, a decylene group or a dodecylene group is preferable, and more preferably, a single bond, a methylene group, or an ethylene group.

Specific examples of the compound represented by the formula (2) include compounds represented by the following formulas (3-1) to (3-16).

[Formula 4]

In the formulas (3-1) to (3-7) and (3-16), R ⁶ is the same or different and represents a hydrogen atom or a methyl group. That is, the compound which induces|guides|derives the structural unit which consists of a methacryl group may be sufficient, and the compound which guide|induced the structural unit which consists of an acryl group may be sufficient. Among the compounds represented by these formulas (3-1) to (3-16), 2-(methacryloyloxy)ethylacetoacetate (that is, as a compound represented by the above formula (3-1), R ⁶ is a methyl group compound) is particularly preferred.

Moreover, you may use together the unsaturated compound which has an active methine group illustrated by Unexamined-Japanese-Patent No. 2007-34134.

Said (meth)acrylate-type polymer WHEREIN: It is preferable that the content rate of the monomeric unit which has an active methylene group is 3-40 mass % with respect to 100 mass % of the total amount of all the monomer units, for example. When it exists in this range, the effect of solvent resistance will be especially expressed, and developability will also become more favorable. In addition, when the content ratio increases excessively, when used in combination with a colorant or a polyfunctional polymerizable monomer, it becomes incompatible with these and tends to whiten when a cured film is made, and heat resistance colorability is not sufficiently exhibited, and the panel There exists a tendency for the brightness|luminance at the time of doing it not to become more sufficient. More preferably, it is 3-30 mass %, More preferably, it is 4-20 mass %.

(iv) a monomer unit having an acid group

It is preferable that the (meth)acrylate-based polymer further has a monomer unit having an acid group. The monomer unit having an acid group is a structural unit derived from a monomer having an acid group, and means a structural unit in which a polymerizable carbon-carbon double bond (C=C) in the monomer becomes a single bond (C-C). For example, an acrylic acid unit means the structural unit derived from acrylic acid at the time of copolymerizing or graft polymerization of acrylic acid.

The monomer having an acid group is a monomer having one or two or more acid groups in one molecule. As an acidic radical, the functional group which neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group, is mentioned, for example. Especially, a carboxyl group or a carboxylic anhydride group is preferable, More preferably, it is a carboxyl group, More preferably, it is a (meth)acrylic acid group.

As the monomer having an acid group, (meth)acrylic acid is particularly preferred. That is, the monomer unit having an acid group is preferably a (meth)acrylic acid unit. As described above, the form in which the (meth)acrylate-based polymer further has a (meth)acrylic acid unit is one of the preferred aspects of the present invention. Moreover, acrylic acid is more preferable than methacrylic acid from the point of solvent resistance.

In this specification, (meth)acrylic acid means acrylic acid and/or methacrylic acid.

Here, it is preferable that the acid value (AV) of the said (meth)acrylate-type polymer is 20-300 mgKOH/g. Thereby, more sufficient alkali solubility is revealed and it becomes possible to obtain the hardened|cured material which was more excellent in developability. In particular, when an acid value exists in this range, solvent resistance will improve more, and an image development speed will become moderate, adhesiveness improves more, or the possibility that surface roughness arises at the time of image development can be suppressed more. Moreover, solvent resistance further improves by setting content of the monomeric unit (preferably (meth)acrylic acid unit) which has an acidic radical so that an acid value may become this range. The acid value is more preferably 60 to 160 mgKOH/g.

The content ratio of the monomer unit having an acid group (preferably a (meth)acrylic acid unit) is preferably set so that the acid value of the (meth)acrylate polymer is within the above-mentioned preferred range. For example, with respect to 100 mass % of the total amount of all monomer units, it is preferable that it is 2 mass % or more, More preferably, it is 5 mass % or more, More preferably, it is 8 mass % or more. Moreover, it is preferable that it is 50 mass % or less, More preferably, it is 35 mass % or less, More preferably, it is 25 mass % or less.

(v) main chain ring structure

The (meth)acrylate-based polymer preferably has a ring structure in the main chain. When a polymer having a ring structure in the main chain is used as the (meth)acrylate-based polymer, heat resistance, surface hardness, and adhesiveness are more excellent, and, for example, changes over time after exposure to high temperatures are more suppressed, and various physical properties are improved. A cured product that can be expressed more stably can be obtained. Further, in recent display devices, tempered glass is sometimes used for the substrate in order to give various members strength that can withstand the impact from the outside, but as the (meth)acrylate-based polymer, a ring structure in the main chain The use of a polymer having , is very preferable because a cured product capable of exhibiting excellent adhesion to tempered glass even after high-temperature exposure is obtained.

When the (meth)acrylate-based polymer has a ring structure in the main chain, the polymer includes, for example, a tertiary carbon-containing (meth)acrylate-based monomer, a hydroxyl group-containing monomer, and an active methylene group-containing monomer; It is preferable that it is a polymer obtained by copolymerizing the monomer component containing the monomer which can form a ring structure in a principal chain. It is more preferable that this monomer component further contains the monomer (preferably (meth)acrylic acid) which has an acidic radical as mentioned above.

Examples of the ring structure include an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring, and a lactone ring.

Examples of the monomer capable of forming a ring structure in the main chain include an N-substituted maleimide-based monomer, a dialkyl-2,2′-(oxydimethylene)diacrylate-based monomer, and α-(unsaturated alkoxyalkyl). ) It is preferable to use an acrylate-based monomer (preferably an alkyl-(α-allyloxymethyl)acrylate-based monomer) or the like. As such, the (meth)acrylate-based polymer is an N-substituted maleimide-based monomer unit, a dialkyl-2,2′-(oxydimethylene)diacrylate-based monomer unit, and an α-(unsaturated alkoxyalkyl)acrylate-based monomer. The aspect containing at least 1 type of monomeric unit selected from the group which consists of a unit is one of the preferable aspect of this invention.

Here, for example, when an N-substituted maleimide-based monomer and/or a dialkyl-2,2′-(oxydimethylene)diacrylate-based monomer and/or an α-(unsaturated alkoxyalkyl)acrylate-based monomer is used, It is possible to provide a cured product with improved heat resistance, hardness, and dispersibility of the color material. In particular, when a dialkyl-2,2'-(oxydimethylene)diacrylate-based monomer and/or an α-(unsaturated alkoxyalkyl)acrylate-based monomer is used, a cured product having better heat-resistant colorability is obtained.

It is preferable to set it as 60 mass % or less in 100 mass % of total amounts of all the monomer units, and, as for the content rate of the monomeric unit which can form ring structure in the said main chain, it is more preferable to set it as 50 mass % or less. In particular, when it contains an N-substituted maleimide-based monomer, a dialkyl-2,2'-(oxydimethylene)diacrylate-based monomer and/or an α-(unsaturated alkoxyalkyl)acrylate-based monomer, the content ratio thereof is From viewpoints of heat resistance, hardness, color material dispersibility, image development speed, transparency, etc., it is preferable to set it as 2-60 mass %, More preferably, it is 2-50 mass %, More preferably, it is 3-40 mass %.

Examples of the N-substituted maleimide-based monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, and Nt-butylmaleimide. , N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, p-methylbenzylmaleimide, p-butylbenzylmaleimide, p-hydroxybenzylmaleimide, o-chlorobenzylmaleimide, o-dichlorobenzyl maleimide, p-dichlorobenzyl maleimide, etc. are mentioned, These 1 type, or 2 or more types can be used. Among them, from the viewpoint of transparency, N-phenylmaleimide or N-benzylmaleimide is preferable, and N-benzylmaleimide is more preferable.

Examples of the dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer include 2,2'-[oxybis(methylene)]bisacrylic acid, dialkyl-2,2'-[oxy]. Bis(methylene)]bis-2-propenoate, dialkyl-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. are mentioned. Among these, it is preferable to use, for example, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate etc. from a viewpoint of transparency, dispersibility, industrial availability, etc.

Examples of the α-(unsaturated alkoxyalkyl) acrylate-based monomer include α-allyloxymethyl acrylic acid, α-allyloxymethyl methyl acrylate, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl acrylate n-propyl , α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α-allyloxymethyl acrylate n-amyl , α-allyloxymethyl acrylic acid s-amyl, α-allyloxymethyl acrylate t-amyl, and α-allyloxymethyl acrylate neopentyl. In addition, an alkyl-(?-methallyloxymethyl)acrylate-based monomer and the like are also preferable. Among them, an alkyl-(α-allyloxymethyl)acrylate-based monomer is preferable.

In addition, α-(unsaturated alkoxyalkyl)acrylic acid (for example, α-allyloxymethylacrylic acid) is not an acrylic acid ester, but is included in the “α-(unsaturated alkoxyalkyl)acrylate-based monomer” described in this specification. do.

The alkyl-(α-allyloxymethyl)acrylate monomer is preferably methyl-(α-allyloxymethyl)acrylate from the viewpoint of transparency, dispersibility, industrial availability, and the like. .

The α-(unsaturated alkoxyalkyl) acrylate-based monomer can be manufactured, for example, by a manufacturing method disclosed in International Publication No. 2010/114077 pamphlet.

(vi) other monomer units

The (meth)acrylate-based polymer is further, for example, in order to adjust developability, solvent solubility, etc., a structural unit ((meth)acrylic acid derived from a (meth)acrylic acid ester-based monomer that does not correspond to the above-mentioned monomers. ester-based monomer unit), a structural unit derived from an aromatic vinyl-based monomer (also called an aromatic vinyl-based monomer unit), and/or a structural unit derived from other copolymerizable monomers (also called other copolymerizable monomer units) may contain 1 type or 2 or more types.

As said (meth)acrylic acid ester type monomer, when the surface hardness of hardened|cured material etc. is considered, for example, the monomer which has an alicyclic skeleton is preferable. Specifically, for example, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, (3,4-epoxy) Cyclohexyl) methyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dimethylol-tricyclodecanedi ( Meth) acrylate, pentacyclopentadecane dimethanol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, norbornane dimethanol di (meth) acrylate, p-mentane-1,8-dioldi (meth)acrylate, p-mentane-2,8-dioldi(meth)acrylate, p-mentane-3,8-dioldi(meth)acrylate, bicyclo[2.2.2]-octane-1- Methyl-4-isopropyl-5,6-dimethylol di(meth)acrylate, etc. are mentioned. Among these, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate and/or tricyclodecanyl (meth) acrylate from the viewpoint of versatility and availability It is preferable to use Moreover, it is also preferable to use alicyclic epoxy compounds, such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, or ethyl glycidyl (meth)acrylate.

The (meth)acrylic acid ester-based monomer is further, for example, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylic acid i-propyl, (meth) acrylate n-butyl, (meth)acrylic acid s-butyl, (meth)acrylic acid n-amyl, (meth)acrylic acid s-amyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid isodecyl, (meth)acrylic acid ) Tridecyl acrylate, (meth) acrylate octyl, (meth) acrylate isooctyl, (meth) acrylate lauryl, (meth) acrylate stearyl, (meth) acrylate benzyl, (meth) acrylate phenyl, (meth) acrylic acid 2- Methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid phenoxyethyl, (meth)acrylic acid tetrahydrofurfuryl, (meth)acrylic acid N,N-dimethylaminoethyl, α-hydroxymethyl methyl acrylate , α-hydroxymethyl ethyl acrylate, α-hydroxymethyl acrylate t-butyl, α-hydroxymethyl acrylate t-amyl, etc., 1,4-dioxaspiro [4,5] dec-2-ylmethacrylic acid Acid, (meth)acryloylmorpholine, tetrahydrofurfurylacrylate, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth) Acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane and 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane. Among them, from the viewpoint of easily balancing heat resistance, dispersibility of color material, and solvent re-solubility, (meth)alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate, and (meth)acrylic acid Aralkyl (meth)acrylate of benzyl is preferred.

As said aromatic vinylic monomer, styrene, vinyltoluene, (alpha)-methylstyrene, methoxystyrene etc. are mentioned, for example. Among these, styrene and/or vinyltoluene are preferable from the viewpoint of the heat-resistant coloring property of the resin and the heat-resistant decomposition property.

Although it does not specifically limit as said other copolymerizable monomer, For example, (meth)acrylamides, such as N,N- dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; macromonomers having a (meth)acryloyl group at one end of a polymer molecular chain, such as polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether vinyl ethers such as methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether; N-vinyl compounds, such as N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinylimidazole, N-vinyl morpholine, and N-vinyl acetamide; Unsaturated isocyanates, such as (meth)acrylic-acid isocyanatoethyl and allyl isocyanate, etc. are mentioned.

The (meth)acrylate-based polymer is preferably a polymer obtained by polymerizing a monomer component including, for example, a tertiary carbon-containing (meth)acrylate-based monomer, a monomer having a hydroxyl group, and a monomer having an active methylene group. . The said monomer component may further contain 1 type(s) or 2 or more types of other monomers as needed. Preferably, as the monomer component, as described above, a monomer having an acid group (especially preferably (meth)acrylic acid) and a monomer capable of forming a ring structure in the main chain are further included. One type or two or more types may be sufficient as each monomer, respectively.

The blending ratio (mass %) of the monomers to be used for the polymerization, that is, the content ratio of each monomer with respect to 100% by mass of the total amount of the total monomer components, is the content of each monomer unit with respect to 100% by mass of the total amount of all monomer units described above. It is preferable to set it in the same range as the ratio. Among them, in particular, the monomer component includes a tertiary carbon-containing (meth)acrylate monomer (a), a monomer (b) having a hydroxyl group, a monomer (c) having an active methylene group, and a monomer having an acid group (especially preferred preferably (meth)acrylic acid) (d), a monomer (e) capable of forming a ring structure in the main chain, and, if necessary, other monomers (f) other than these (for example, preferably other (meth) ) acrylic acid ester-based monomer), and their mass ratio (a/b/c/d/e/f) is 10 to 40/10 to 40/3 to 40/2 to 50/5 to 20/ It is preferable to set it as 0-20 (however, let the sum total of a-f be 100 mass %). More preferably, they are 10-40/10-40/3-40/2-50/5-20/5-20.

Moreover, it is preferable to set polymerization conditions suitably so that the acid value of the (meth)acrylate-type polymer obtained may be set to 20-300 mgKOH/g.

As a method of superposing|polymerizing the said monomer component, a method normally used, such as bulk polymerization, solution polymerization, emulsion polymerization, can be used, What is necessary is just to select suitably according to the objective and a use. Especially, since solution polymerization is industrially advantageous and structural adjustment, such as molecular weight, is also easy, it is preferable. In addition, polymerization methods based on mechanisms such as radical polymerization, anionic polymerization, cationic polymerization and coordination polymerization can be used as the polymerization mechanism of the monomer component, but the polymerization method based on the radical polymerization mechanism is industrially advantageous because desirable.

When superposing|polymerizing the said monomer component by the solution polymerization method, as a solvent used for superposition|polymerization, if it is inactive to a polymerization reaction, it will not specifically limit. For example, it may be appropriately set according to polymerization conditions such as polymerization mechanism, type and amount of monomer to be used, polymerization temperature, polymerization concentration, etc., but when a solvent is used as a diluent or the like when a curable resin composition is later obtained, the It is efficient and preferable to use a solvent containing a solvent for solution polymerization of the monomer component.

Examples of the solvent include monoalcohols; cyclic ethers; glycol monoethers; glycol ethers; Esters of glycol monoether; alkyl esters; ketones; aromatic hydrocarbons; aliphatic hydrocarbons; One type or two or more types, such as amides, are preferable. As a specific example of these solvents, the compound of Paragraph No. 0042 of Unexamined-Japanese-Patent No. 2015-42697, etc. are mentioned. Among these, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl from the solubility of the obtained polymer, the surface smoothness at the time of forming a coating film, little influence on the human body and the environment, and industrial availability, It is more preferable to use ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and/or ethyl lactate.

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

In the polymerization initiation method in the polymerization reaction, energy necessary for polymerization initiation may be supplied to the monomer component from an active energy source such as heat, electromagnetic waves (eg, infrared rays, ultraviolet rays, X-rays, etc.) and electron beams. Moreover, when a polymerization initiator is used together, since the energy required for polymerization initiation can be reduced significantly and reaction control becomes easy, it is preferable.

Moreover, the molecular weight of the polymer obtained by superposing|polymerizing the said monomer component can be controlled by adjustment of the quantity and kind of polymerization initiator, polymerization temperature, the kind and quantity of a chain transfer agent, etc.

When superposing|polymerizing the said monomer component by a radical polymerization mechanism, it is industrially advantageous and preferable to use the polymerization initiator which generate|occur|produces a radical by heat|fever. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy, and may be appropriately selected according to polymerization conditions such as polymerization temperature, solvent, and type of monomer to be polymerized. Moreover, you may use together reducing agents, such as a transition metal salt and amines, with a polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t- Butylperoxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), Peroxides and azo compounds which are usually used as polymerization initiators, such as dimethyl 2,2'-azobis(2-methylpropionate), hydrogen peroxide, and persulfate, etc. are mentioned, These may be used individually, or 2 or more types are mentioned. You may use it together.

The amount of the polymerization initiator used may be appropriately set depending on the type and amount of the monomer to be used, polymerization conditions such as polymerization temperature and polymerization concentration, and the molecular weight of the target polymer, and is not particularly limited. For example, in order to obtain a polymer with a weight average molecular weight of several thousand - tens of thousands, it is preferable to set it as 0.1-20 mass parts with respect to 100 mass parts of said monomer components. More preferably, it is 0.5-15 mass parts.

In the said polymerization, you may use the chain transfer agent normally used further as needed. Preferably, a polymerization initiator and a chain transfer agent are used together. Moreover, when a chain transfer agent is used at the time of polymerization, there exists a tendency which can suppress the increase in molecular weight distribution and gelatinization.

As said chain transfer agent, For example, mercaptocarboxylic acids; mercaptocarboxylic acid esters; alkyl mercaptans; mercapto alcohols; aromatic mercaptans; mercaptoisocyanurates; disulfides; dithiocarbamates; monomer dimers; 1 type, or 2 or more types, such as halogenated alkyls, are preferable. As a specific example of these chain transfer agents, the compound of Paragraph No. 0049 of Unexamined-Japanese-Patent No. 2015-42697, etc. are mentioned. Among these, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans, mercapto alcohols, aromatic mercaps, etc. from the viewpoint of availability, crosslinking prevention ability, and a small degree of polymerization rate fall. It is preferable to use the compound which has mercapto groups, such as tans and mercaptoisocyanurates. More preferably, they are alkyl mercaptans, mercaptocarboxylic acids, and/or mercaptocarboxylic acid esters, More preferably, they are n-dodecyl mercaptan and/or mercaptopropionic acid.

The amount of the chain transfer agent to be used may be appropriately set depending on the type and amount of the monomer to be used, polymerization conditions such as polymerization temperature and polymerization concentration, and the molecular weight of the target polymer, and is not particularly limited. For example, in order to obtain a polymer with a weight average molecular weight of several thousand - tens of thousands, it is preferable to set it as 0.1-20 mass parts with respect to 100 mass parts of said monomer components. More preferably, it is 0.5-15 mass parts.

Regarding the polymerization conditions, the polymerization temperature may be appropriately set depending on the type and amount of the monomer to be used, the type or amount of the polymerization initiator, etc. For example, 50 to 150°C is preferable, and 70 to 120°C is preferable. more preferably. Moreover, although polymerization time can also be set suitably similarly, for example, 1 to 6 hours are preferable, and 2 to 5 hours are more preferable.

Preferably the weight average molecular weights in terms of polystyrene of the said (meth)acrylate-type polymer are 5000-100,000. When the weight average molecular weight is in this range, the coating property tends to be good when the curable resin composition containing the (meth)acrylate-based polymer is applied, and the film is not easily reduced during development, so it is preferable. . More preferably, they are 5000 (= 0.5 million) - 50,000. Thereby, while it becomes possible to exhibit more favorable developability, while solvent resistance improves, the image development speed also becomes higher. More preferably, it is 10,000 - 40,000, Especially preferably, it is 15,000 - 30,000.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the (meth)acrylate polymer is preferably 1.1 to 6.0. When molecular weight distribution exists in this range, since there exists a tendency excellent in developability, it is preferable. More preferably, it is 1.2-4.0.

In this specification, the weight average molecular weight and number average molecular weight of a polymer can be calculated|required according to the measuring method described in the Example mentioned later.

In the curable resin composition, the content ratio of the (meth)acrylate-based polymer may be appropriately set depending on the use or blending of other components, for example, the solid content of the (meth)acrylate-based polymer is the amount of the curable resin composition. It is preferable that it is 5 mass % or more with respect to 100 mass % of solid content total amounts. Moreover, it is preferable that it is 80 mass % or less. By being in such a range, it becomes possible to exhibit the effect of this invention more notably. More preferably, it is 7-70 mass %, More preferably, it is 10-60 mass %.

In addition, "total solid content of curable resin composition" means the total amount of the component (a solvent etc. which volatilize at the time of formation of hardened|cured material) which form hardened|cured material among the components contained in curable resin composition are excluded.

In this invention, as long as it is a range which does not impair the effect of this invention, you may use together the acrylic polymer normally used in this field|area.

<Polymerizable compound>

The said curable resin composition also contains a polymeric 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. Also referred to as a group) is a low molecular weight compound having For example, the monofunctional compound which has one polymerizable unsaturated group in a molecule|numerator, and the polyfunctional compound which has two or more are mentioned.

Examples of the monofunctional polymerizable monomer include N-substituted maleimide-based monomers or (meth)acrylic acid esters among the compounds exemplified as other monomers preferably contained in the monomer component of the (meth)acrylate-based polymer. ; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; Unsaturated monocarboxylic acids in which the chain|strand extension between unsaturated group and carboxyl group is carried out; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; Unsaturated isocyanates etc. are mentioned. Moreover, the monomer etc. which have an active methylene group or an active methine group can also be used.

As said polyfunctional polymerizable monomer, the following compound etc. are mentioned, for example.

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 Bifunctional (meth)acrylate compounds such as (meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, and bisphenol F alkylene oxide di(meth)acrylate ;

Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide addition trimethylol propane tri (meth)acrylate, ethylene oxide addition ditrimethylolpropane tetra(meth)acrylate, ethylene oxide addition pentaerythritol tetra(meth)acrylate, ethylene oxide addition dipentaerythritol hexa(meth)acrylate, propylene oxide addition Trimethylolpropane tri(meth)acrylate, propylene oxide addition ditrimethylolpropane tetra(meth)acrylate, propylene oxide addition pentaerythritol tetra(meth)acrylate, propylene oxide addition dipentaerythritol hexa(meth)acrylate , ε-caprolactone addition trimethylolpropane tri(meth)acrylate, ε-caprolactone addition ditrimethylolpropanetetra(meth)acrylate, ε-caprolactone addition pentaerythritol tetra(meth)acrylate, ε-capro trifunctional or more than trifunctional polyfunctional (meth)acrylate compounds, such as lactone addition dipentaerythritol hexa (meth)acrylate;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkyl Renoxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene polyfunctional vinyl ethers such as oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition ditrimethylolpropane tetravinyl ether, ethylene oxide addition pentaerythritol tetravinyl ether, and ethylene oxide addition dipentaerythritol hexavinyl ether;

(meth)acrylic acid 2-vinyloxyethyl, (meth)acrylic acid 3-vinyloxypropyl, (meth)acrylic acid 1-methyl-2-vinyloxyethyl, (meth)acrylic acid 2-vinyloxypropyl, (meth)acrylic acid 4- Vinyloxybutyl, (meth)acrylic acid 4-vinyloxycyclohexyl, (meth)acrylic acid 5-vinyloxypentyl, (meth)acrylic acid 6-vinyloxyhexyl, (meth)acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth)acrylic acid 4-vinyloxymethylcyclohexylmethyl ) Acrylic acid p-vinyloxymethylphenylmethyl, (meth)acrylic acid 2-(vinyloxyethoxy)ethyl, (meth)acrylic acid 2-(vinyloxyethoxyethoxyethoxy)ethyl, etc. (meth)acrylic acid containing vinyl ether groups esters;

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkyl Lenoxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene polyfunctional allyl ethers such as oxide addition trimethylolpropane triallyl ether, ethylene oxide addition ditrimethylolpropane tetraallyl ether, ethylene oxide addition pentaerythritol tetraallyl ether, and ethylene oxide addition dipentaerythritol hexaallyl ether;

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

Tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide addition tri (acryloyloxyethyl) isocyanurate, alkylene oxide addition tri ( polyfunctional (meth)acryloyl group-containing isocyanurates, such as methacryloyloxyethyl) isocyanurate;

polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate;

Reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as (meth)acrylic acid 2-hydroxyethyl and (meth)acrylic acid 2-hydroxypropyl polyfunctional urethane (meth)acrylates obtained by

polyfunctional aromatic vinyls such as divinylbenzene;

It is preferable to use a polyfunctional polymeric compound from a viewpoint of improving more sclerosis|hardenability of curable resin composition of this invention among the said polymeric compound. When using a polyfunctional polymeric compound as a polymeric compound, Preferably it is 3 or more as the functional number, More preferably, it is 4 or more, More preferably, it is 5 or more. Moreover, from a viewpoint of suppressing cure shrinkage more, as for a functional number, 10 or less are preferable, More preferably, it is 8 or less.

Moreover, although it does not specifically limit as molecular weight of the said polymeric compound, From a viewpoint of handling, for example, 2000 or less are preferable.

When using a polyfunctional polymeric compound as said polymeric compound, a polyfunctional (meth)acrylate compound, polyfunctional urethane (meth)acrylate from viewpoints of reactivity, economical efficiency, availability, etc. among the said polymeric compound. It is preferable to use the compound which has a (meth)acryloyl group, such as a compound and a (meth)acryloyl group containing isocyanurate compound. More preferably, it is a polyfunctional (meth)acrylate compound, whereby the curable resin composition is more excellent in photosensitivity and curability, and a cured product having still higher hardness and high transparency can be obtained. More preferably, a trifunctional or more polyfunctional (meth)acrylate compound is used.

The content ratio of the polymerizable compound may be appropriately set according to the purpose or use in addition to the type of the polymerizable compound and the (meth)acrylate polymer to be used, but from the viewpoint of more excellent developability and plate making properties, curability It is preferable that it is 2 mass % or more with respect to 100 mass % of solid content total amount of a resin composition, and it is preferable that it is 80 mass % or less. More preferably, it is 5 mass % or more as a lower limit, More preferably, it is 8 mass % or more, Especially preferably, it is 10 mass % or more, More preferably, it is 70 mass % or less as an upper limit, More preferably, 50 mass % or less, Especially preferably, it is 30 mass % or less, Most preferably, it is 20 mass % or less.

<Photoinitiator>

The said curable resin composition further contains a photoinitiator.

Preferably as a photoinitiator, it is a radically polymerizable photoinitiator.

A radically polymerizable photoinitiator generates a polymerization initiation radical by irradiation with active energy rays, such as an electromagnetic wave and an electron beam, The thing normally used can be used 1 type, or 2 or more types. Moreover, you may use together 1 type, or 2 or more types, such as a photosensitizer, a radical photopolymerization accelerator, etc. as needed. You may use a photosensitizer and/or a radical photopolymerization accelerator together with a photoinitiator, and it is not necessary to use it. Although the effect of this invention is fully exhibited even if it does not use a photosensitizer and/or a radical photopolymerization accelerator together, when used together, a sensitivity and sclerosis|hardenability improve more.

Specifically as said photoinitiator, the following compound etc. are mentioned, for example.

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-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxyl) -2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) ) Alkylphenone compounds such as phenyl]-1-butanone; benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Thioxanthone type, such as thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone compound;

2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloro halomethylated triazine-based compounds such as romethyl)-s-triazine; 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3 Halomethylated oxadiazole compounds, such as 4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)- 4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'- Biimidazole type compounds, such as tetraphenyl-1,2'- biimidazole; 1,2-Octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbox oxime ester compounds such as bazol-3-yl]-,1-(O-acetyloxime); oxime ether compounds; titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine-based compounds such as 9-phenylacridine;

It is preferable to use an alkylphenone type compound, an oxime ester type compound, and/or an oxime ether type compound among the said photoinitiator. Although an oxime ester type compound and an oxime ether type compound are called "oxime type compound", when an oxime type compound is used, sclerosis|hardenability of curable resin composition improves remarkably, and the solvent resistance of the hardened|cured material obtained improves dramatically. The effect by using such an oxime type compound is an effect peculiar to the case of using together with the (meth)acrylate type polymer which has a monomeric unit which has an active methylene group. Thus, the form in which the said photoinitiator contains an oxime type compound at least is one of the preferable aspects of this invention. Among oxime-type compounds, an oxime ester-type compound is especially preferable.

Content of the said photoinitiator may just set suitably according to the objective, a use, etc., Although it does not specifically limit, It is preferable that it is 0.1 mass part or more with respect to 100 mass parts of solid content of curable resin composition excluding a photoinitiator. Thereby, the hardened|cured material more excellent in adhesiveness can be obtained, and peeling is suppressed more fully also after high temperature exposure. Moreover, when the balance with the influence, economical efficiency, etc. which the decomposition product of a photoinitiator gives is considered, it is preferable that it is 30 mass parts or less. More preferably, it is 0.5 mass part or more as a lower limit, More preferably, it is 1 mass part or more, Especially preferably, it is 2 mass parts or more, As an upper limit, More preferably, it is 25 mass parts or less, More preferably, it is 20 mass parts or less. .

As a photosensitizer and photoradical polymerization accelerator which may be used together with the said photoinitiator, For example, Dye-type compounds, such as a xanthene dye, a coumarin dye, 3-ketocoumarin-type compound, and a pyromethene dye; dialkylaminobenzene-based compounds such as ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate; Mercaptan-type hydrogen donors, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzoimidazole, etc. are mentioned.

The photosensitizer and radical photopolymerization accelerator do not need to be used as described above, but when used, from the viewpoint of balance between curability, effects of decomposition products, and economic feasibility, 100% by mass of the total solid content of the curable resin composition , it is preferably 0.001 to 20 mass%. More preferably, it is 0.01-15 mass %, More preferably, it is 0.05-10 mass %.

<Other ingredients>

-solvent-

It is preferable that the said curable resin composition also contains a solvent. A solvent is preferably used as a diluent etc. That is, specifically, lowering a viscosity and improving handleability; forming a coating film by drying; It is a low-viscosity organic solvent or water which is used suitably for setting it as the dispersion medium of a color material, etc., and can melt|dissolve or disperse|distribute each component in curable resin composition.

As said solvent, 1 type or 2 types of what is normally used can be used, What is necessary is just to select suitably according to the objective and a use, and it does not specifically limit. For example, monoalcohols; glycols; cyclic ethers; glycol monoethers; glycol ethers; Esters of glycol monoether; alkyl esters; ketones; aromatic hydrocarbons; aliphatic hydrocarbons; amides; Water and the like are preferred. As a specific example of these solvents, the compound of Paragraph No. 0042 of Unexamined-Japanese-Patent No. 2015-42697, etc. are mentioned. For example, as esters of glycol monoether, 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 monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl Ether acetate, 3-methoxybutyl acetate, etc. are mentioned.

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

The said curable resin composition further, according to the required characteristic of each use to which it is applied, for example, a coloring material (it is also called a coloring agent); dispersant; heat resistance improver; leveling agent; development aid; inorganic fine particles such as silica fine particles; Coupling agents, such as a silane type, an aluminum type, and a titanium type; Thermosetting resins, such as a filler, an epoxy resin, a phenol resin, and polyvinyl phenol; Hardening aids, such as a polyfunctional thiol compound; plasticizer; polymerization inhibitor; UV absorbers; antioxidants; polish remover ; antifoam; antistatic agent; slip agent; surface modifiers; Urinary (搖) change agent; thixotropic supplements; quinonediazide compound; polyhydric phenol compound; cationic polymerizable compound; 1 type, or 2 or more types, such as an acid generator, may be included further. For example, when using the said curable resin composition for a color filter use, it is preferable to contain a color material. Thus, the aspect in which the said curable resin composition further contains a color material is also one of the preferable aspects of this invention. Moreover, the aspect containing at least 1 sort(s) chosen from the group which consists of a color material, a dispersing agent, a heat-resistance improving agent, a leveling agent, a coupling agent, and a developing auxiliary agent is also preferable. Hereinafter, these components are demonstrated.

-Color material-

As said color material, a pigment and dye are used preferably, for example. These may be used independently and may be used in combination of 2 or more type. Moreover, you may combine a pigment and dye. For example, when forming the red, blue, and green pixels of a color filter, the method of combining color materials, such as blue and purple, green and yellow, and exhibiting a requested|required color characteristic is used preferably. Moreover, also when forming a black matrix, it can form using a black color material.

Among the above pigments and dyes, for example, in terms of durability, pigments (for example, organic pigments or inorganic pigments) are excellent, and since dyes are excellent in terms of improving luminance of panels, for example, the characteristics required What is necessary is just to select or use them together suitably according to it. Moreover, more preferably, it is an organic pigment among a pigment.

Examples of the pigment include azo pigments, phthalocyanine pigments, polycyclic pigments (eg, quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, Organic pigments, such as an anthraquinone type, a quinophthalone type, a metal complex type, a diketopyrrolopyrrole type), and a dye lake type pigment; White and constitutional pigments (eg, titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), rapeseed pigments (eg, yellow lead, cadmium-based, chromevermillion, nickel titanium, chromium titanium, yellow) iron oxide, bengala, zinc chromate, lead, ultramarine blue, blue blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), black pigment (e.g. carbon black, bone black, graphite, iron black, titanium black, etc.), and inorganic pigments such as bright pigments (eg, pearl pigments, aluminum pigments, bronze pigments, etc.) and fluorescent pigments (eg, zinc sulfide, strontium sulfide, strontium aluminate, etc.). Moreover, yellow, red, purple, blue, green, brown, black, white etc. are mentioned as a color of the pigment which can be used.

The pigment may further be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, or wax coating depending on the purpose or use.

As a specific example of the said pigment, For example, Paragraph Nos. 0103 - 0107 of Unexamined-Japanese-Patent No. 2015-42697, Yellow pigments, such as C.I. Pigment Yellow 1 and 138; C. I. Orange pigments, such as Pigment Orange 1; C. I. Purple pigments such as Pigment Violet 1; Red pigments, such as C.I. Pigment Red 1; C. I. Blue pigments such as Pigment Blue 1; Green pigments, such as C.I. Pigment Green 1 and 58; C. I. Brown pigments such as Pigment Brown 5; black pigments such as aniline black, carbon black, lamp black, bone black, black iron, titanium black, and C.I. Pigment Black 1; White pigments, such as C.I. Pigment White 1, etc. are mentioned. However, the color material of the present invention is not limited thereto. Moreover, a pigment may be used independently and may be used in combination of 2 or more types. “C. I.” stands for color index (C. I. Published by The Society of Dyers and Colorists), and numbers refer to color index numbers.

As said dye, the organic dye described in Unexamined-Japanese-Patent No. 2010-9033, Unexamined-Japanese-Patent No. 2010-211198, Unexamined-Japanese-Patent No. 2009-51896, and Unexamined-Japanese-Patent No. 2008-50599, for example is used. Can be used. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable.

The content rate of the color material (that is, the total proportion of the pigment and the dye) can be appropriately set according to the purpose and use, but the preferred range of the content rate of the color material is 3-70 with respect to 100 mass % of the total solid content of the curable resin composition. mass %. More preferably, it is 5-60 mass %, More preferably, it is 10-50 mass %.

-Dispersant-

The dispersing agent has a site for interaction with a color material and a site for interaction with a dispersion medium (for example, a solvent or binder resin), and has a function of stabilizing dispersion of the color material in a dispersion medium, and is generally a resin type dispersant ( For example, polymeric dispersants), surfactants (for example, low molecular weight dispersants), and pigment derivatives are classified. It is preferable that curable resin composition of this invention contains a dispersing agent with a color material. In addition, as a dispersing agent (that is, a resin type dispersing agent, surfactant, and/or a pigment derivative), a dispersing agent normally used can be used. Moreover, as a dispersing agent, 1 type of thing may be used individually, and 2 or more types may be combined and used for it.

As said resin type dispersing agent, For example, polycarboxylic acid ester, such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydrogen group-containing polycarboxylic acid esters, amides or salts thereof formed by reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, (meth) Acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester-based, modified polyacrylate, ethylene oxide/polypropylene oxide adducts and the like.

In addition, as the structure of the resin-type dispersant, the main chain is an anchor chain having an interaction site with the color material, and the graft chain is a compatible chain having interaction with the dispersion medium. A resin in which the sex chain has a block structure is particularly preferably used.

Specific examples of the resin-type dispersant include products described in Paragraph No. 0112 of JP-A-2015-42697 A. However, it is not limited to these.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, and lauryl. Anionic surfactants, such as ammonium sulfate, sodium stearate, and sodium lauryl sulfate; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; Amphoteric surfactants, such as alkyl betaines, such as alkyl dimethyl amino acetate betaine, and alkyl imidazoline, etc. are mentioned.

The dye derivative is a compound having a structure in which a functional group is introduced into a dye, and the functional group includes, for example, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, an amide group, and a phthalimide group. and the like. Examples of the structure of the matrix dye include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, peryl Rene type, diketopyrrolopyrrole type, etc. are mentioned.

The content ratio of the dispersant (i.e., resin-type dispersant, surfactant and/or dye derivative) may be appropriately set according to the purpose or use, but from the viewpoint of the balance of dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency , for example, it is preferable that it is 0.01-60 mass % with respect to 100 mass % of solid content total amount of curable resin composition. More preferably, it is 0.1-50 mass %, More preferably, it is 0.3-40 mass %.

-Heat resistance improver-

The said heat-resistance improving agent is used suitably for the improvement of heat resistance or intensity|strength. As a heat resistance improving agent, the compound etc. which have an N-(alkoxymethyl)melamine compound, two or more epoxy groups, or oxetanyl group are preferable, for example. In particular, when using the said curable resin composition as a resist for photospacers, a transparent resist for protective films, or a resist for interlayer insulating films, use of these is preferable.

-Leveling agent-

The leveling agent is preferably used for improving leveling properties. As a leveling agent, the surfactant of a fluorine type and a silicone type is preferable.

-Coupling agent-

The coupling agent is preferably used to improve adhesion. As a coupling agent, a silane-type coupling agent is preferable, for example, an epoxy-type, methacrylic-type, and amino-type silane coupling agent is mentioned. Especially, an epoxy-type silane coupling agent is preferable.

-Development aid-

The developing aid is preferably used for improving developability. As a developing auxiliary agent, For example, Monocarboxylic acids, such as (meth)acrylic acid, an acetic acid, and propionic acid; polyhydric carboxylic acids such as maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid, and trimellitic acid; Carboxylic anhydrides, such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride, etc. are preferable.

It does not specifically limit as a manufacturing method of the said curable resin composition, For example, it can prepare by mixing and dispersing the above-mentioned containing component using various mixers and dispersers. A mixing/dispersing process is not specifically limited, What is necessary is just to implement by a normal method. Moreover, you may further include the other process normally performed. Moreover, when the said curable resin composition contains a color material, it is preferable to manufacture through the dispersion processing process of a color material.

In the dispersing treatment step of the color material, for example, first, a color material (preferably an organic pigment), a dispersing agent and a solvent are weighed in predetermined amounts, and a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer , a method of dispersing the color material into fine particles using a disperser such as a kneader or a blender to obtain a liquid color material dispersion (also referred to as a mill base). Preferably, after kneading and dispersing with a roll mill, a kneader, a blender or the like, fine dispersion treatment is performed with a media mill such as a bead mill filled with 0.01 to 1 mm beads. A composition containing a (meth)acrylate-based polymer, a polymerizable compound (polymerizable monomer), and a photopolymerization initiator, and a solvent or a leveling agent, if necessary, which are separately stirred and mixed in the obtained mill base (preferably transparent liquid) is added, mixed, and a uniform dispersion solution is obtained to obtain a curable resin composition.

Moreover, it is preferable that the obtained curable resin composition carries out a filtration process with a filter etc. and removes fine dust.

[Cured material]

The curable resin composition of this invention is especially excellent in photosensitivity and sclerosis|hardenability, and provides the hardened|cured material excellent in basic performance, such as developability, solvent resistance, adhesiveness with a board|substrate, heat resistance, and transparency. Such a cured product is also excellent in image formability and surface smoothness, so that, for example, there is no residue of an unexposed part or background contamination after development. The hardened|cured material formed by hardening|curing such said curable resin composition is one of this invention.

It is preferable that the said hardened|cured material (cured film) is the film thickness (thickness) of 0.1-20 micrometers. Thereby, the request|requirement of the member etc. which used the said hardened|cured material, the display apparatus, etc. can fully meet the reduction|reduction of sizing. More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-8 micrometers.

The cured product is preferably used for various optical members and electrical/electronic devices, such as color filters, inks, printing plates, printed wiring boards, semiconductor devices, and photoresists used in liquid crystal display devices and solid-state imaging devices, for example. do. Especially, it is preferable to use for a color filter. Thus, the color filter formed using the said curable resin composition, ie, specifically, the color filter which has the said hardened|cured material on a board|substrate is also one of this invention. Hereinafter, the color filter will be further described.

[Color filter]

The color filter of this invention consists of a form which has the said hardened|cured material on a board|substrate.

The said color filter WHEREIN: Although the hardened|cured material formed by the curable resin composition of this invention is especially preferable as a segment which requires coloring like each pixel, such as a black matrix and each pixel, such as red, green, blue, yellow, for example, a photo It is preferable also as a segment which does not necessarily require coloring, such as a spacer, a protective layer, and the rib for orientation control.

As a board|substrate used for the said color filter, For example, Glass substrates, such as white plate glass, blue plate glass, alkali tempered glass, silica-coated blue plate glass; Sheet, film, or board|substrate which consist of thermoplastic resins, such as polyester, polycarbonate, polyolefin, polysulfone, the ring-opened polymer of a cyclic olefin, and its hydrogenated substance; a sheet, a film, or a substrate made of a thermosetting resin such as an epoxy resin or an unsaturated polyester resin; Metal substrates, such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate; ceramic substrate; A semiconductor substrate having a photoelectric conversion element; The member etc. which are comprised from various materials, such as a glass substrate (for example, color filter for LCD) provided with a color material layer on the surface, are mentioned. Especially, a glass substrate and the sheet|seat, film, or board|substrate which consist of a heat resistant resin from a heat resistant point are preferable. Moreover, it is preferable that the said board|substrate is a transparent board|substrate.

Moreover, you may give corona discharge treatment, ozone treatment, chemical treatment by a silane coupling agent, etc. to the said base material as needed.

[Manufacturing method of color filter]

In order to obtain the said color filter, for example, for one pixel color (that is, for each pixel of one color), on a board|substrate, the process of arrange|positioning the said curable resin composition (it is also called arrangement|positioning process), and on the board|substrate A method comprising a step of irradiating the arranged curable resin composition with light (also referred to as a light irradiation step), a step of developing treatment with a developer (also referred to as a developing step), and a step of heat treatment (also referred to as a heating step). It is preferable to employ|adopt and employ|adopt the manufacturing method which repeats the method similar to this for each color. In addition, the formation order of each color pixel is not specifically limited.

-batch process (preferably application process)-

It is preferable to implement the said arrangement|positioning process by application|coating. As a method of apply|coating the said curable resin composition on a board|substrate, spin coating, slit coating, roll coating, cast coating etc. are mentioned, for example, Any method can be used preferably.

In the said arrangement|positioning process, after apply|coating the said curable resin composition on a board|substrate further, it is preferable to dry a coating film. Drying of the coating film can be performed using, for example, a hot plate, an IR oven, a convection oven, or the like. Drying conditions are suitably selected according to the boiling point of the solvent component contained, the kind of hardening component, film thickness, the performance of a dryer, etc., Usually, it is preferable to carry out for 10 second - 300 second at the temperature of 50-160 degreeC.

-Light irradiation process-

In the light irradiation step, examples of the light source of the actinic light used include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, etc. of a lamp light source, an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, a laser light source such as a semiconductor laser, etc. are used. Moreover, although a proximity system, a mirror projection system, and a stepper system are mentioned as a system of an exposure machine, a proximity system is used preferably.

In addition, in the irradiation process of an active energy ray, depending on a use, it is good also as irradiating an active energy ray through a predetermined|prescribed mask pattern. In this case, the exposed part is hardened, and the hardened part is made insoluble or poorly soluble in the developer.

-Development process-

The said image development process is a process of developing with a developing solution after the above-mentioned light irradiation process, removing an unexposed part, and forming a pattern. Thereby, a patterned cured film can be obtained. Developing treatment is normally 10-50 degreeC image development temperature, and can be implemented by methods, such as immersion image development, spray image development, brush image development, and ultrasonic image development.

Although it will not specifically limit if the developing solution used in the said image development process melt|dissolves the curable resin composition of this invention, Usually, an organic solvent and alkaline aqueous solution are used, and these mixtures may be used. In addition, when using alkaline aqueous solution as a developing solution, it is preferable to wash with water after image development.

As an organic solvent preferable as said developing solution, an ether solvent, an alcohol solvent, etc. are mentioned, for example. 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, isopropanol, benzyl alcohol, etc. are mentioned.

The said alkaline aqueous solution can contain surfactant, an organic solvent, a buffer, dye, a pigment, etc. as needed other than an alkali agent. As an organic solvent in this case, the organic solvent etc. suitable as a developing solution mentioned above are mentioned.

As said alkali agent, For example, Inorganic alkali agents, such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate; and amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide. These may be used or two or more types may be combined.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinates; Amphoteric surfactants, such as alkyl betaines and amino acids, etc. are mentioned, These may be individual and may combine 2 or more types.

-Heating process-

The said heating process is a process (it is also called a post-hardening process) of further hardening an exposure part (hardened part) by baking after the image development process mentioned above. For example, using a light source such as a high-pressure mercury lamp, for example, a step of post-exposure with a light amount of 0.5 to 5 J/cm 2 , or post-heating at a temperature of 60 to 260° C. for 10 seconds to 120 minutes. process etc. are mentioned. By implementing such a post-curing process, it becomes possible to make the hardness and adhesiveness of the patterned cured film stronger. Moreover, by this heating process, a part of the structural unit of the (meth)acrylate-type polymer contained in the said curable resin composition (that is, a part derived from a part of tertiary carbon-containing (meth)acrylate-type monomer) is decomposed|disassembled Therefore, sclerosis|hardenability and solvent resistance can be improved.

It is preferable that the film thickness of the cured film (namely, the cured film obtained by thermosetting the said curable resin composition) obtained by the said heating process is 0.1-20 micrometers. By using the curable resin composition of this invention, the cured film by which the film thickness was fully reduced can be provided. More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-8 micrometers.

Moreover, when the film thickness of the coating film (namely, cured film) obtained by the said heating process makes the film thickness of the coating film before a heating 100 %, it is preferable that it is 90 % or less. More preferably, it is 80 % or less, More preferably, it is 70 % or less.

The heating process WHEREIN: It is preferable that a heating temperature is 150 degreeC or more. Thereby, since the part derived from a part of the said tertiary carbon-containing (meth)acrylate-type monomer decomposes|disassembles more effectively, it becomes possible to implement|achieve more improvement of curability and solvent resistance. More preferably, it is 160 degreeC or more, More preferably, it is 170 degreeC or more, Especially preferably, it is 180 degreeC or more. Moreover, it is preferable to set it as 260 degrees C or less, More preferably, it is 250 degrees C or less.

Although the heating time in the said heating process is not specifically limited, For example, it is preferable to set it as 5 to 60 minutes. Moreover, a heating method is also although it does not specifically limit, For example, it can implement using heating apparatuses, such as a hot plate, a convection oven, and a high frequency heater.

[display device]

The present invention is also a display device constituted by using the color filter described above.

Moreover, the member for display apparatuses and display apparatus which have hardened|cured material formed with the said curable resin composition are also contained in preferable embodiment of this invention. The cured product (cured film) formed of the curable resin composition is stable, has excellent adhesion to a substrate, etc., has high hardness, exhibits high smoothness, and has high transmittance, so it is particularly preferable as a transparent member. It is also useful as a protective film or an insulating film in various display devices.

As said display apparatus, a liquid crystal display device, a solid-state image sensor, a touchscreen type display apparatus etc. are preferable, for example.

Further, when the cured product (cured film) is used as a member for a display device, the member may be a film-like single-layer or multi-layer member composed of the cured film, and another layer may be added to the single-layer or multi-layer member. The combined member may be sufficient, and the member included in the structure of the said cured film may be sufficient.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, unless otherwise indicated, "part" means "part by mass".

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

<Weight Average Molecular Weight>

Using polystyrene as a standard material and tetrahydrofuran as an eluent, the weight average molecular weight was determined by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation). measured.

<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, dissolved by adding about 3 g of acetone, and then dried naturally at room temperature. And after drying at 140 degreeC under vacuum for 1.5 hours using the hot air dryer (the SPEC company make, brand name: PHH-101), it stood to cool in the desiccator and measured the mass. From the mass decrease, the solid content (mass %) of the polymer solution was calculated.

＜Mountain value＞

3 g of the resin solution was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and an automatic titration device (manufactured by Hiranuma Industrial Co., Ltd., trade name: COM-555) using a 0.1 N aqueous KOH solution as a titrant. , the acid value of the polymer solution was measured, and the acid value (AV) per solid content 1g was calculated|required from the acid value of the solution, and the solid content of the solution.

<Absorbance of Curable Resin Composition>

The curable resin composition is spin-coated on a glass substrate having a width of 5 cm, dried at 100 ° C. for 3 minutes, exposed at 100 mJ with a high-pressure mercury lamp, and heat-treated at 230 ° C. for 30 minutes, with a film thickness of 5 µm A thin film was obtained. Then, it was immersed in 20 g of 1-methyl-2-pyrrolidone at 85 degreeC for 10 minutes, and the hue of 1-methyl-2-pyrrolidone eluted from the coating film was measured with spectrophotometer UV3100 (made by Shimadzu Corporation). Then, the absorbance at 450 nm was determined.

Synthesis Example 1

Synthesis of resin solution 1 (BzMI-t-BMA-MMA-HEMA-AAEM-AA copolymer solution 1)

156.3 parts of propylene glycol monomethyl ether acetate was poured into a reaction tank equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a drip tank inlet, After nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as the dropping tank (A), in a beaker, 10 parts of N-benzylmaleimide, 35 parts of t-butyl methacrylate, 17.1 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 2 parts of methacrylic acid - A mixture of 5 parts of acetoacetoxyethyl, 12.9 parts of acrylic acid, and 2 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Oil Corporation) was prepared by stirring and mixing, and added to the dropping tank (B) , 0.6 parts of n-dodecyl mercaptan and 29.4 parts of propylene glycol monomethyl ether acetate were prepared by stirring and mixing. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition|polymerization was performed. After hold|maintaining 90 degreeC for 30 minute(s) after completion|finish of dripping, it heated up to 115 degreeC, and aged for 90 minutes.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 19500, the acid value was 100 mgKOH/g, and resin solid content was 34.7 mass %.

Synthesis Example 2

Synthesis of resin solution 2 (BzMI-t-BMA-MMA-HEMA-AAEM-AA copolymer solution 2)

The injection amount of the monomer was 10 parts of N-benzylmaleimide, 32.1 parts of t-butyl methacrylate, 10 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, and 15 parts of 2-acetoacetoxyethyl methacrylate. As a result of analyzing the polymer solution obtained by performing the same operation as in Synthesis Example 1 except that it was 12.9 parts of parts and 12.9 parts of acrylic acid, the weight average molecular weight was 20000, the acid value was 100 mgKOH/g, and the resin solid content was 34.6 mass%.

Synthesis Example 3

Synthesis of resin solution 3 (BzMI-t-BMA-MMA-HEMA-AAEM-AA copolymer solution 3)

The injection amount of the monomer was 10 parts of N-benzylmaleimide, 35 parts of t-butyl methacrylate, 7.1 parts of methyl methacrylate, 30 parts of 2-hydroxyethyl methacrylate, and 5 parts of 2-acetoacetoxyethyl methacrylate. The same operation as in Synthesis Example 1 was performed except that the amount of acrylic acid was 12.9 parts, and as a result of analyzing the obtained polymer solution, the weight average molecular weight was 20500, the acid value was 100 mgKOH/g, and the resin solid content was 34.7 mass%.

Synthesis Example 4

Synthesis of resin solution 4 (BzMI-t-BMA-MMA-HEMA-AAEM-AA copolymer solution 4)

The amount of monomer to be charged was 10 parts of N-benzylmaleimide, 32.1 parts of t-butyl methacrylate, 30 parts of 2-hydroxyethyl methacrylate, 15 parts of 2-acetoacetoxyethyl methacrylate, and 12.9 parts of acrylic acid. As a result of performing the same operation as Synthesis Example 1 except that, and analyzing the obtained polymer solution, the weight average molecular weight was 21000, the acid value was 100 mgKOH/g, and the resin solid content was 34.6 mass%.

Synthesis Example 5

Synthesis of resin solution 5 (BzMI-t-BMA-MMA-HEMA-AAEM-MAA copolymer solution 5)

The injection amount of the monomer was 10 parts of N-benzylmaleimide, 35 parts of t-butyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 14.6 parts of methyl methacrylate, and 5 parts of 2-acetoacetoxyethyl methacrylate. The same operation as in Synthesis Example 1 was performed except that 15.4 parts of methacrylic acid was used, and as a result of analyzing the obtained polymer solution, the weight average molecular weight was 19300, the acid value was 100 mgKOH/g, and the resin solid content was 34.7 mass%.

Synthesis Example 6

Synthesis of resin solution 6 (MD-t-BMA-MMA-HEMA-AAEM-AA copolymer solution 6)

The same operation as in Synthesis Example 1 was performed except that dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate (MD) was used instead of N-benzylmaleimide, and the resulting polymer solution was As a result of the analysis, the weight average molecular weight was 20000, the acid value was 100 mgKOH/g, and resin solid content was 34.7 mass %.

Synthesis Example 7

Synthesis of resin solution 7 (AMA-t-BMA-MMA-HEMA-AAEM-AA copolymer solution 7)

The same operation as in Synthesis Example 1 was performed except that methyl-(α-allyloxymethyl)acrylate (AMA) was used instead of N-benzylmaleimide, and the resultant polymer solution was analyzed. As a result, the weight average molecular weight was 19000, The acid value was 100 mgKOH/g, and the resin solid content was 34.7 mass %.

Synthesis Example 8

Synthesis of resin solution 8 (BzMI-t-BMA-MMA-HEMA-AA copolymer solution 8)

Synthesis example 1, except that the injection amount of the monomer was 10 parts of N-benzylmaleimide, 35 parts of t-butyl methacrylate, 22.1 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, and 12.9 parts of acrylic acid. As a result of performing the same operation and analyzing the obtained polymer solution, the weight average molecular weight was 19000, the acid value was 100 mgKOH/g, and resin solid content was 34.7 mass %.

Synthesis Example 9

Synthesis of resin solution 9 (BzMI-MMA-HEMA-AAEM-AA copolymer solution 9)

Synthesis except that the amount of monomer to be charged was 10 parts of N-benzylmaleimide, 52.1 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 5 parts of 2-acetoacetoxyethyl methacrylate, and 12.9 parts of acrylic acid. As a result of performing operation similar to Example 1 and analyzing the obtained polymer solution, the weight average molecular weight was 19500, the acid value was 100 mgKOH/g, and resin solid content was 34.7 mass %.

Synthesis Example 10

Synthesis of resin solution 10 (BzMI-t-BMA-MMA-AAEM-AA copolymer solution 10)

Synthesis Example 1 except that the amount of monomer to be charged was 10 parts of N-benzylmaleimide, 35 parts of t-butyl methacrylate, 37.1 parts of methyl methacrylate, 5 parts of 2-acetoacetoxyethyl methacrylate, and 12.9 parts of acrylic acid. When the same operation was performed and the obtained polymer solution was analyzed, the weight average molecular weight was 19000, the acid value was 100 mgKOH/g, and resin solid content was 34.6 mass %.

In Table 1, the detail of resin solutions 1-10 is shown.

The symbols in Table 1 are as follows.

BzMI: N-benzylmaleimide

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

AMA: methyl-(α-allyloxymethyl)acrylate

MMA: methyl methacrylate

t-BMA: t-butyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

AAEM: methacrylic acid 2-acetoacetoxyethyl

AA: acrylic acid

MAA: methacrylic acid

Preparation Example 1

Preparation of Pigment Dispersion 1

12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparon DA-7301 as a dispersing agent, 2.25 parts of CI Pigment Green 58 as a colorant, and 1.5 parts of CI Pigment Yellow 138 were mixed, followed by mixing with a paint shaker for 3 hours The pigment dispersion 1 was obtained by making it disperse|distribute.

Example 1

2.0 parts of resin solution 1, 0.70 parts of dipentaerythritol hexaacrylate as a radically polymerizable compound, 0.35 parts of Irgacure 369 (made by Chiba Specialty Chemicals) as a radically polymerizable photoinitiator, and pigment dispersion 1 8.5 parts and 6.57 parts of propylene glycol monomethyl ether acetate were mixed as a solvent, and the curable resin composition 1 was obtained. This curable resin composition was spin-coated on the glass substrate, the hardened|cured material was manufactured on the said conditions, and the NMP dissolution test was implemented. When the absorbance of NMP was measured, it was ^{4x10 -2.}

Examples 2 to 7, Comparative Examples 1 to 3

Except having set it as the compounding shown in Tables 2 and 3, it carried out similarly to Example 1, and after obtaining curable resin compositions 2-7 and curable resin compositions 9-11, respectively, the absorbance of NMP after an NMP dissolution test was measured, respectively. The results are shown in Tables 2 and 3.

Example 8, Comparative Example 4

Absorbance of NMP after NMP dissolution test after obtaining curable resin composition 8 and curable resin composition 12 in the same manner as in Example 1 except that the radical polymerization initiator was changed to Irgacure OXE01 (manufactured by Chiba Specialty Chemicals) were measured respectively. The results are shown in Tables 2 and 3.

From the results of Tables 2 and 3, the following were confirmed.

The curable resin compositions obtained in Examples 1 to 7 were resin solutions 1 to 7, containing a polymer having a tertiary carbon-containing (meth)acrylate monomer unit, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group. On the other hand, the polymer which the curable resin composition obtained in Comparative Examples 1-3 has does not have any of these monomeric units. In this regard, Examples 1 to 7 and Comparative Examples 1 to 3 are mainly different from each other. Comparing the results of measuring the absorbance by obtaining a cured product under the same conditions under this difference, in the curable resin composition of Comparative Examples 1 to 3, compared with the curable resin composition of Examples 1 to 7, the absorbance of the cured product is remarkably large. , it can be seen that the color material is eluted from the cured product. If the curability and solvent resistance of the curable composition are insufficient, the absorbance of the eluate increases due to the dissolution of the color material. From the results in Table 2, it is understood that the curable resin composition of the comparative example has insufficient curability and solvent resistance compared to the Examples. can Moreover, it is clear that the solvent resistance is further improved, so that there are many AAEM units and/or HEMA units by comparison with Examples 1, 3, 5-7 and Examples 2 and 4.

Example 8 (using resin solution 4 containing AAEM units and using Irgacure OXE01 as a radically polymerizable photoinitiator) and Example 4 (using resin solution 4 containing AAEM units, using Irgacure 369), in Example 8, since the absorbance was remarkably low, it was found that the solvent resistance was greatly improved. On the other hand, Comparative Example 4 (resin solution 8 containing no AAEM unit was used, and Irgacure OXE01 was used as a radically polymerizable photoinitiator) and Comparative Example 1 (resin solution 8 containing no AAEM unit was used) , using Irgacure 369 as a radical polymerizable photoinitiator), it can be seen that in Comparative Example 4, the absorbance was a little low, and the solvent resistance was hardly improved. From these results, it is clear that the solvent resistance of the resin solution containing an AAEM unit is further improved when an oxime type compound (preferably an oxime ester type compound) is used as a radically polymerizable photoinitiator. In short, the effect that solvent resistance is remarkably improved by using an oxime compound (preferably an oxime ester compound) is a unique effect when using a polymer containing a monomer unit having an active methylene group, such as an AAEM unit. could know that

Moreover, in Example 1 (using the resin solution 1 which used acrylic acid as a raw material), the absorbance is lower than Example 5 (using the resin solution 5 which used methacrylic acid as a raw material). From this point, in solvent resistance, the superiority of using an acrylic acid type polymer rather than a methacrylic acid type polymer was confirmed. In addition, although not shown in a table|surface, all of the hardened|cured material obtained in the Example were excellent also in various physical properties, such as developability, adhesiveness with a board|substrate, and heat resistance.

The member for display devices and the display device containing the hardened|cured material formed of the curable resin composition of this invention can be used suitably in the optical field or an electric/electronic field.

Claims (9)

A curable resin composition comprising a (meth)acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator, the curable resin composition comprising:
The (meth)acrylate-based polymer has a tertiary carbon-containing (meth)acrylate-based monomer unit, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group,
The curable resin composition, characterized in that the tertiary carbon-containing (meth)acrylate-based monomer has a structure in which an oxygen atom adjacent to a (meth)acryloyl group is bonded to a tertiary carbon atom. The method of claim 1,
The (meth) acrylate-based polymer further comprises a (meth) acrylic acid unit curable resin composition. The method of claim 1,
The said monomer which has an active methylene group is represented by following formula (2), Curable resin composition characterized by the above-mentioned.

In Formula (2), R<^1> represents a C1-C24 hydrocarbon group which may contain a hydrogen atom or a hetero atom. X represents a divalent group represented by any of the following formulas (2-1) to (2-3). R ² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. R ³ represents a divalent group represented by any of the following formulas (2-4) to (2-6). R ⁴ represents a cyano group (-CN), a nitro group (-NO ₂ ), or a group represented by the following formula (2-7) or (2-8). R ⁵ represents a hydrogen atom or a C1-C24 hydrocarbon group which may contain a hetero atom.

The method of claim 1,
The (meth) acrylate-based polymer is a curable resin composition, characterized in that it has a ring structure in the main chain. The method of claim 1,
Said (meth)acrylate-type polymer WHEREIN: The content rate of a tertiary carbon-containing (meth)acrylate-type monomeric unit is 5-90 mass % with respect to 100 mass % of the total amount of all monomer units, The monomer which has a hydroxyl group The content rate of the unit is 5 to 50 mass% with respect to 100 mass% of the total amount of all monomer units, and the content rate of the monomer unit having an active methylene group is 3 to 40 mass% with respect to 100 mass% of the total amount of all monomer units. % of the curable resin composition. The method of claim 1,
The curable resin composition further comprises a color material. Hardened|cured material formed by hardening|curing the curable resin composition in any one of Claims 1-6, The hardened|cured material characterized by the above-mentioned. It has the hardened|cured material of Claim 7 on a board|substrate, The color filter characterized by the above-mentioned. A display device comprising the color filter according to claim 8 .