KR20190127938A - Polymers and Compositions - Google Patents

Abstract

A polymer useful for dispersing inorganic particles, and a composition comprising an inorganic particle and the polymer are provided. A composition containing an ethylenically unsaturated bond, a structural unit (i-1) derived from a polymerizable carboxylic acid compound having a carboxyl group bonded to the ethylenically unsaturated bond via a linking group, an inorganic particle, and ethylene A polymer having a structurally unsaturated bond and a structural unit (i-1) derived from a polymerizable carboxylic acid compound having a carboxyl group bonded to the ethylenically unsaturated bond via a linking group, wherein the polymerizable carboxylic acid compound is N-substituted maleimide A polymer having a structure and having an acid value of at least 20 mgKOH / g and at most 150 mgKOH / g is provided.

Description

Polymers and Compositions

The present invention relates to a polymer and to a composition comprising the polymer and inorganic particles.

In order to improve the dispersibility of particles, such as a pigment in a composition, it is known to mix | blend a dispersing agent. Japanese Unexamined Patent Application Publication No. 2000-327946 (Patent Document 1) describes the use of a water-soluble polymer having a carboxyl group or a derivative group bonded to a molecular backbone as a dispersant for dispersing an inorganic pigment in water.

Japanese Patent Laid-Open No. 2000-327946

An object of the present invention is to provide a polymer useful for dispersing inorganic particles. Another object of the present invention is to provide a composition containing an inorganic particle and the polymer.

This invention provides the composition and polymer shown below.

[1] polymerization having an ethylenically unsaturated bond and a structural unit (i-1) derived from a polymerizable carboxylic acid compound having a carboxyl group bonded to the ethylenically unsaturated bond via a linking group;

Inorganic Particle,

Containing, composition.

[2] The composition of [1], wherein the polymerizable carboxylic acid compound has an N-substituted maleimide structure.

[3] The composition according to [1] or [2], in which the polymer further has a structural unit (i-2) derived from an carboxyl group-free N-substituted maleimide compound.

[4] The composition of [3], wherein the inorganic particles contain a semiconductor quantum dot.

[5] A polymer having an ethylenically unsaturated bond and a structural unit (i-1) derived from a polymerizable carboxylic acid compound having a carboxyl group bonded to the ethylenically unsaturated bond via a linking group,

The polymerizable carboxylic acid compound has an N-substituted maleimide structure,

The polymer whose acid value is 20 mgKOH / g or more and 150 mgKOH / g or less.

The polymer excellent in the ability to disperse an inorganic particle (inorganic particle dispersion ability), and the composition using the same can be provided.

1 is a schematic view showing an example of a graph obtained using a thermogravimetric analyzer.

<Polymer>

The polymer which concerns on this invention is a polymeric carboxylic acid compound which has an ethylenically unsaturated bond and the carboxyl group couple | bonded with the said ethylenically unsaturated bond through a coupling group (Hereinafter, this polymeric carboxylic acid compound is called "polymerizable carboxylic acid compound (I ) Is also referred to as a structural unit (i-1). The polymer may further include structural units other than the structural unit (i-1) such as the structural unit (i-2) and the structural unit (i-3) described later.

The polymer is excellent in inorganic particle dispersing ability and is useful as a dispersant for dispersing inorganic particles.

The dispersing agent contains the said polymer and may consist only of the said polymer.

In addition, unless otherwise indicated, the compound illustrated as each component contained in the dispersing agent or the composition mentioned later in this specification can be used individually or in combination of multiple types.

[1] structural unit (i-1)

The structural unit (i-1) which a polymer has is a structural unit derived from the polymerizable carboxylic acid compound (I) which has an ethylenically unsaturated bond and the carboxyl group couple | bonded with the said ethylenically unsaturated bond via a coupling group.

Only 1 type may be used for a polymerizable carboxylic acid compound (I), and it may use 2 or more types together. That is, a polymer may have 1 type of structural unit (i-1), and may have 2 or more types of structural unit (i-1).

The linking group contained in the polymerizable carboxylic acid compound (I) is a group that is not a direct bond connecting the ethylenically unsaturated bond and the carboxyl group. By the presence of the linking group, the ethylenically unsaturated bond and the carboxyl group are separated by at least one atom.

Between the carbon atom of the ethylenically unsaturated bond couple | bonded with the one end of a coupling group, and the carbon atom of the carboxyl group couple | bonded with the other end of a coupling group, normally 1 or more and 20 or less, Preferably it is two 16 or more, More preferably, 4 or more and 12 or less atoms are interposed. When the number of intervening atoms is zero, the desired sufficient inorganic particle dispersion capacity is not obtained.

A bivalent hydrocarbon group is mentioned as a coupling group, The bivalent hydrocarbon group is not limited to a linear or branched chain, A cyclic structure may be included and the cyclic structure may be included. One or more -CH ₂ -contained in the divalent hydrocarbon group is -O-, -S-, -S (= 0)-, -C (= 0)-, -NH-, or -NR ^1- [R ¹ is Represents a monovalent or divalent hydrocarbon group (for example, an alkyl group or an alkylene group), and at least one -CH ₂ -contained in the hydrocarbon group is -O-, -S-, -S (= O)-, Or may be substituted by a group containing a hetero atom such as -C (= O)-or -NH-.] May be substituted by a group containing a hetero atom such as.

R ¹ may form together with a part of the N atom, ethylenically unsaturated bond, and linking group to which it is bonded to form a ring.

The linking group is preferably a divalent hydrocarbon group in which one or more -CH ₂ -may be substituted with -O-, -C (= O)-, -NH-, or -NR ^1- .

The carboxyl group which the structural unit (i-1) has is preferably disposed at the molecular terminal from the viewpoint of increasing the inorganic particle dispersion ability.

The polymerizable carboxylic acid compound (I) having an N-substituted maleimide structure is preferable in view of improving the heat resistance (thermal stability) of the polymer while maintaining good inorganic particle dispersion ability.

In the case where the polymerizable carboxylic acid compound (I) has an N-substituted maleimide structure, the ethylenically unsaturated bond is a carbon-carbon double bond contained in the maleimide structural portion (ring structure) of the N-substituted maleimide structure.

When the polymerizable carboxylic acid compound (I) has an N-substituted maleimide structure, the carboxyl group is contained in a substituent bonded to the N atom of the maleimide structure portion. A carboxyl group is arrange | positioned at the terminal of the substituent couple | bonded with the N atom preferably from a viewpoint of improving inorganic particle dispersion | distribution ability.

As a polymeric carboxylic acid compound (I) which has N-substituted maleimide structure, the compound represented by a following formula is mentioned.

(In formula, X is a bivalent coupling group which connects the N atom of a maleimide structure, and the C atom of a carboxyl group.)

As a bivalent coupling group represented by X, a bivalent hydrocarbon group is mentioned, The bivalent hydrocarbon group is not limited to a linear or branched chain, A cyclic structure may be included and the cyclic structure may be included. One or more -CH ₂ -contained in the divalent hydrocarbon group is -O-, -S-, -S (= 0)-, -C (= 0)-, -NH-, or -NR ^2- [R ² is , A monovalent hydrocarbon group (e.g., an alkyl group), and one or more -CH ₂ -contained in the hydrocarbon group are -O-, -S-, -S (= O)-, -C (= O May be substituted by a group containing a hetero atom such as)-or -NH-.] May be substituted by a group containing a hetero atom such as.

The divalent linking group represented by X is preferably a divalent hydrocarbon group in which one or more -CH ₂ -may be substituted with -O- or -C (= O)-, more preferably, one or more. -CH ₂ -is a linear divalent hydrocarbon group which may be substituted by -O- or -C (= O)-, and particularly preferably a linear divalent hydrocarbon group.

The carbon number of the divalent hydrocarbon group represented by X is preferably 1 or more and 18 or less, more preferably 2 or more and 14 or less, even more preferably 3 or more 10 from the viewpoint of increasing the inorganic particle dispersion ability. Less than

From the viewpoint of the heat resistance (thermal stability) of the polymer, a preferable example of the divalent hydrocarbon group represented by X is a divalent hydrocarbon group in which -CH ₂ -is not substituted by a group containing the hetero atom.

[2] structural unit (i-2)

The polymer may further have a structural unit (i-2) derived from the carboxyl group-containing N-substituted maleimide compound. By further having a structural unit (i-2), a polymer can improve the heat resistance of a polymer.

Only 1 type may be used for a carboxyl group-free N-substituted maleimide compound, and it may use 2 or more types together. That is, a polymer may have 1 type of structural unit (i-2), and may have 2 or more types of structural unit (i-2).

The substituent at the N position of the N-substituted maleimide compound is not particularly limited, and may be, for example, a monovalent hydrocarbon group. As monovalent hydrocarbon group, C1-C20, linear, branched, cyclic alkyl group, aromatic hydrocarbon group, or group which combined these is mentioned.

Examples of the linear or branched alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group Etc. can be mentioned.

Examples of the cyclic alkyl group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and cyclodecyl group.

A phenyl group, a naphthyl group, etc. are mentioned as an aromatic hydrocarbon group.

When the substituent at the N position is a group containing a cycloalkyl group or an aromatic hydrocarbon group, there is a tendency that the heat resistance of the polymer is likely to be improved.

[3] structural unit (i-3)

The polymer may further have a structural unit (i-3) which is a structural unit other than a structural unit (i-1) and a structural unit (i-2).

The polymer may have one type of structural unit (i-3), or may have two or more types of structural units (i-3).

As the structural unit (i-3), it is derived from polymerizable carboxylic acid compounds other than a polymeric carboxylic acid compound (I) (Hereinafter, this polymeric carboxylic acid compound is also called "polymerizable carboxylic acid compound (II)."). Structural units derived from carboxyl group-free polymerizable compounds other than structural unit (i-3-1) and N-substituted maleimide compounds (compounds forming structural unit (i-2)) containing no carboxyl group 3-2) is mentioned.

As polymeric carboxylic acid compound other than a polymeric carboxylic acid compound (I), Unsaturated monocarboxylic acids, such as (meth) acrylic acid, crotonic acid, (alpha)-(hydroxymethyl) (meth) acrylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, 3,4,5,6-tetrahydrophthalic acid; And unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride, and 3,4,5,6-tetrahydrophthalic anhydride.

In this specification, "(meth) acryl" represents at least 1 sort (s) chosen from the group which consists of an acryl and methacryl. The same applies to notations such as "(meth) acryloyl" and "(meth) acrylate".

As carboxyl group-free polymerizable compounds other than the carboxyl group-free N-substituted maleimide compound,

Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acryl Rate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate [In the technical field, the common name is called "dicyclopentanyl (meth) acrylate". In addition, it may be called "tricyclodecyl (meth) acrylate."] Tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate [In the technical field, a common name is "dicyclo" Pentenyl (meth) acrylate.], Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, (Meth) acrylic acid esters such as propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybi Cyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2 -Ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept 2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxy Cycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bi Ratios of s (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Cyclo unsaturated compounds;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Can be mentioned.

[4] content of structural unit

It is preferable that the ratio of the structural unit (i-1) in a polymer is adjusted so that the acid value of resin solid content conversion of a polymer may become 20 mgKOH / g or more and 150 mgKOH / g or less, More preferably, 40 mgKOH / g or more and 130 mgKOH / g or less, and more preferably 60 mgKOH / g or more and 110 mgKOH / g or less.

When the ratio of the structural unit (i-1) is in the above range, the inorganic particle dispersion ability tends to be excellent. When the ratio of structural unit (i-1) is excessively high, there exists a possibility that a solution may gelatinize at the time of dispersion.

Like the structural unit (i-1), the ratio of the structural unit (i-2) is preferably adjusted so that the acid value of the resin solid content conversion of the polymer is preferably 20 mgKOH / g or more and 150 mgKOH / g or less, More preferably, it adjusts to 40 mgKOH / g or more and 130 mgKOH / g or less, More preferably, it adjusts to 60 mgKOH / g or more and 110 mgKOH / g or less.

Similarly, the ratio of the structural unit (i-3) is preferably adjusted so that the acid value of the resin solid content conversion of the polymer is preferably 20 mgKOH / g or more and 150 mgKOH / g or less, and more preferably 40 mgKOH / g. It is adjusted to be 130 mgKOH / g or more.

In one preferred embodiment, the polymer is a polymer having an ethylenically unsaturated bond and a structural unit (i-1) derived from a polymerizable carboxylic acid compound having a carboxyl group bonded to the ethylenically unsaturated bond via a linking group, The polymerizable carboxylic acid compound has an N-substituted maleimide structure, and an acid value is 20 mgKOH / g or more and 150 mgKOH / g or less. As for the polymer which concerns on this embodiment, an acid value becomes like this. More preferably, it is 40 mgKOH / g or more and 130 mgKOH / g or less, More preferably, it is 60 mgKOH / g or more and 110 mgKOH / g or less.

[5] heat resistance of polymer

It is preferable that a polymer has heat resistance (the property which is hard to decompose when heat is applied, and whose stability is favorable).

It is preferable that the weight reduction rate at the time of holding | maintenance for 30 minutes at 230 degreeC of a polymer is 2.0% or less, It is more preferable that it is 1.8% or less, It is more preferable that it is 1.2% or less, It is especially preferable that it is 1.0% or less. The lower limit is not particularly limited and is usually 0.0% or more.

It is preferable that a decomposition temperature is 240 degreeC or more, It is more preferable that it is 260 degreeC or more, It is more preferable that it is 280 degreeC or more, It is especially preferable that it is 290 degreeC or more. An upper limit is not specifically limited, Usually, it is 400 degrees C or less.

The decomposition temperature of a polymer can be measured as follows. With reference to FIG. 1, after heating up from 50 degreeC to 150 degreeC at the temperature increase rate of 10 degreeC / min using air thermogravimetry, after 150 degreeC to 400 degreeC at the temperature increase rate of 2 degreeC / min, It heats up to and acquires the graph which makes the horizontal axis the temperature (degreeC) and the vertical axis the mass change. The intersection X between the tangent of the horizontal part on the low temperature side and the tangent of the inflection point on the low temperature side in the obtained graph can be referred to as the decomposition temperature of the polymer.

[6] a method for producing a polymer

A polymer can be manufactured with reference to the method described in the document "Experimental method of polymer synthesis" (issued from the first edition of March 1, 1972, first edition of Okayama Chemical Industry Co., Ltd.) and citations described in this document. Can be.

Specifically, a method of introducing a predetermined amount of a monomer component forming a structural unit, a polymerization initiator, a solvent, and the like into a reaction vessel, and stirring, heating, and warming in a deoxygenated atmosphere. The polymerization initiator, the solvent, and the like are not particularly limited, and any of those commonly used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide and the like). have. What is necessary is just to melt | dissolve each monomer as a solvent.

The weight average molecular weight (Mw) of polystyrene conversion of a polymer is from a viewpoint of raising inorganic particle dispersion | distribution capability, Preferably it is 3000 or more and 100000 or less, More preferably, it is 5000 or more and 50000 or less, More preferably, it is 5000 or more and 30000 or less. . The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of a polymer becomes like this. Preferably it is 1.1 or more and 6 or less, More preferably, it is 1.2 or more and 4 or less.

<Dispersant>

Dispersants include such polymers. The dispersing agent may consist of the said polymer, and may contain the said polymer and other components.

As other components, solvents, such as an organic solvent, an additive etc. are mentioned.

The solvent and the additive may be the same as those of the solvent and additive described in the section of <curable resin composition> described later.

As an additive, antioxidant, a ultraviolet absorber, a leveling agent, an aggregation inhibitor, a sedimentation inhibitor, etc. are mentioned.

<Composition (Inorganic Particle-Containing Composition)>

The composition (inorganic particle containing composition) which concerns on this invention contains an inorganic particle and the said polymer. The composition may contain an inorganic particle and the dispersant.

Since the composition contains the polymer, dispersibility of the inorganic particles may be excellent.

[1] inorganic particles

The shape of the inorganic particles is not particularly limited, and may be spherical or substantially spherical or non-spherical. The inorganic particles may be hollow particles.

The average particle diameter of the inorganic particles is not particularly limited and is, for example, 0.5 nm or more and 50 μm or less.

As an inorganic particle, the particle | grains which consist of an inorganic compound are mentioned. As an inorganic compound, Inorganic oxides, such as a titanium oxide, aluminum oxide, a silicon oxide, magnesium oxide, a zinc oxide, barium titanate; Inorganic nitrides such as silicon nitride, boron nitride and aluminum nitride; Inorganic fluorides such as magnesium fluoride and calcium fluoride, and inorganic salts such as calcium carbonate and barium sulfate; Glass; Inorganic semiconductors such as semiconductor quantum dots, and the like. The inorganic particles may be inorganic pigments.

In a conventional dispersant, it is sometimes difficult to uniformly disperse inorganic semiconductor particles such as semiconductor quantum dots. According to the polymer or dispersant according to the present invention, even inorganic semiconductor particles can be dispersed well.

The inorganic semiconductor particles are preferably light emitting (fluorescent) semiconductor particles. The luminescent semiconductor particles are particles made of semiconductor crystals, preferably nanoparticles made of semiconductor crystals.

Preferable examples of the luminescent semiconductor particles are semiconductor quantum dots. The average particle diameter of a semiconductor quantum dot is 0.5 nm or more and 20 nm or less, for example, Preferably they are 1 nm or more and 15 nm or less (for example, 2 nm or more and 15 nm or less). The average particle diameter of a semiconductor quantum dot can be calculated | required using a transmission electron microscope (TEM).

The semiconductor quantum dots are selected from the group consisting of, for example, a periodic table group 2 element, group 11 element, group 12 element, group 13 element, group 14 element, group 15 element and group 16 element. It can comprise with the semiconductor material containing the 1 type (s) or 2 or more types of elements which become.

Specific examples of the semiconductor material which can constitute the semiconductor quantum dots include compounds of Group 14 elements such as SnS ₂ , SnS, SnSe, SnTe, PbS, PbSe, PbTe, and Group 16 elements; Compounds of Group 13 elements and Group 15 elements such as GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, InGaN, InGaP; Group 13 and Group 16 elements such as Ga ₂ O ₃ , Ga ₂ S ₃ , Ga ₂ Se ₃ , Ga ₂ Te ₃ , In ₂ O ₃ , In ₂ S ₃ , In ₂ Se ₃ , In ₂ Te ₃ Compound with; Compounds of Group 12 elements such as ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe and Group 16 elements; As ₂ O ₃ , As ₂ S ₃ , As ₂ Se ₃ , As ₂ Te ₃ , Sb ₂ O ₃ , Sb ₂ S ₃ , Sb ₂ Se ₃ , Sb ₂ Te ₃ , Bi ₂ O ₃ , Bi ₂ S ₃ , Compounds of Group 15 elements and Group 16 elements such as Bi ₂ Se ₃ and Bi ₂ Te ₃ ; Compounds of Group 16 elements and Group 16 elements such as MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe and BaTe; Group 14 element, such as Si, Ge, group 15 element, or group 16 element is included.

The semiconductor quantum dots may have a single layer structure made of a single semiconductor material, and the surface of the core particles (core layer) made of a single semiconductor material may be a coating layer (shell layer) made of one or two or more kinds of semiconductor materials different from this. The core shell structure coated with may be sufficient. In the latter case, as the semiconductor material constituting the shell layer, one having a larger band gap energy than the semiconductor material constituting the core layer is usually used. The semiconductor quantum dots may have two or more types of shell layers. The shape of the semiconductor quantum dots is not particularly limited, and may be, for example, spherical or substantially spherical, rod-shaped, disk-shaped, or the like.

The semiconductor quantum dots may contain an organic ligand which coordinates on the surface of a semiconductor particle. The organic ligand which coordinates on the surface of a semiconductor quantum dot may be an organic compound which has a polar group which shows coordination ability with respect to a semiconductor quantum dot, for example. The organic ligand may be an organic ligand added for the stabilization of the semiconductor quantum dots or from restrictions on the synthesis of the semiconductor quantum dots containing the organic ligand.

The organic ligand may be one kind of ligand or two or more kinds of ligands. When the organic ligand is an organic compound having a polar group, the organic ligand usually coordinates to the semiconductor quantum dots through the polar group.

The polar group is, for example, it is preferable that a thiol group (-SH), carboxyl group (-COOH) and amino (-NH ₂₎ group of at least one member selected from the group consisting of. The polar group selected from the group can be advantageous in terms of enhancing coordination to the semiconductor quantum dots. The organic ligand may have one or two or more polar groups.

Although the molecular weight of the organic ligand coordinated to a semiconductor quantum dot is not specifically limited, For example, 50 or more and 500 or less may be sufficient.

The organic ligand is, for example, the following formula:

Y-Z

It may be an organic compound represented by. In formula, Y is said polar group, Z is a monovalent hydrocarbon group which may contain hetero atoms (N, O, S, a halogen atom, etc.). The hydrocarbon group may have one, two or more unsaturated bonds such as carbon-carbon double bonds.

The hydrocarbon group may have a linear, branched or cyclic structure. Carbon number of the said hydrocarbon group is 1 or more and 40 or less, for example, 1 or more and 30 or less may be sufficient. -CH ₂ -contained in the hydrocarbon group may be substituted with -O-, -S-, -C (= O)-, -NH- or the like. The hydrocarbon group usually does not contain a hetero atom because of the simplicity of preparation of semiconductor quantum dots.

The group Z may contain a polar group. As for the specific examples of the polar group, the above description relating to the polar group Y is cited. The polar group is preferably disposed at the end of the group Z. The group Z usually does not include a polar group because of the simplicity of preparation of the semiconductor quantum dots.

Examples of the organic ligand having a carboxyl group as the polar group Y include saturated or unsaturated fatty acids in addition to formic acid, acetic acid and propionic acid. Saturated or unsaturated fatty acids include butyric acid, pentanic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, Saturated fatty acids such as henic acid and lignoseric acid; Monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, isocenoic acid, erucic acid, nerbonic acid; Polyunsaturated fatty acids such as linoleic acid, α-linolenic acid, γ-linolenic acid, stearic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosaterateic acid, docosadienic acid, adrenic acid (docosaterateic acid) Can be mentioned.

As an organic ligand which has a thiol group or an amino group as polar group Y, the organic ligand in which the carboxyl group of the organic ligand which has a carboxyl group as polar group Y illustrated above was substituted by the thiol group or an amino group is mentioned.

Moreover, when a semiconductor quantum dot contains an organic ligand, the dispersibility of a semiconductor quantum dot may improve. However, organic ligands are often hydrophobic, such as those having hydrocarbon chains due to synthetic restrictions. In this case, the dispersibility of the semiconductor quantum dots is usually improved when a nonpolar solvent is used. By using the polymer or dispersant according to the present invention, the dispersibility of the semiconductor quantum dots containing the organic ligand to the polar solvent can be improved.

[2] Content of Polymer and Dispersant in Composition (Inorganic Particle-Containing Composition)

In one preferable embodiment of this invention, content of the said polymer in a composition (inorganic particle containing composition) is 1 mass part or more and 100 mass parts or less with respect to 100 mass parts of inorganic particles, for example, It is preferable. Preferably it is 2 mass parts or more and 80 mass parts or less, More preferably, they are 4 mass parts or more and 50 mass parts or less. When a composition contains the said dispersing agent, as for content of the dispersing agent in the said composition, 1 mass part or more and 100 mass parts or less of content of the said polymer in the said composition are 100 mass parts of inorganic particles, for example. It adjusts so that it may become 2 mass parts or more and 80 mass parts or less with respect to 100 mass parts of inorganic particles, Preferably it is adjusted so that it may become 4 mass parts or more and 50 mass parts or less.

Moreover, in another preferable embodiment, content of the said polymer in a composition (inorganic particle containing composition) is 5 mass parts or more and 400 mass parts or less with respect to 100 mass parts of inorganic particles, Preferably, Is 10 mass parts or more and 200 mass parts or less, More preferably, they are 50 mass parts or more and 150 mass parts or less. When a composition contains the said dispersing agent, as for content of the dispersing agent in the said composition, 5 mass parts or more and 400 mass parts or less of content of the said polymer in the said composition are 100 mass parts of inorganic particles, for example. It adjusts so that it may become 10 mass parts or more and 200 mass parts or less with respect to 100 mass parts of inorganic particles, More preferably, it adjusts so that it may become 50 mass parts or more and 150 mass parts or less. As said other preferable embodiment, the case where a composition is a resist composition is mentioned.

The composition may contain other components other than the inorganic particles, the polymer, and the dispersant.

As other components, solvents, such as resin (binder resin) and an organic solvent, an additive etc. are mentioned.

Resin (binder resin), a solvent, and an additive may be the same as that of resin, a solvent, and an additive as described in the term of <curable resin composition> mentioned later.

Examples of the additive include polymer compounds other than resins (binder resins), antioxidants, ultraviolet absorbers, adhesion promoters, leveling agents, anti-agglomerating agents, organic acids, organic amine compounds, thiol compounds, curing agents and the like.

<Resin composition>

A resin composition is one Embodiment of the said composition (inorganic particle containing composition), and contains an inorganic particle, the said polymer or the said dispersing agent, and resin (binder resin).

This resin composition can form a film (coating film) containing an inorganic particle by apply | coating this on a board | substrate, for example, drying as needed, and further hardening as needed. The said membrane can be used for the use according to the function of the inorganic particle contained in it, for example.

One suitable example of the inorganic particles is the semiconductor quantum dot described above. The inorganic particles may be light scattering agents, fillers and the like.

Content of resin (binder resin) is 100 mass% of solid content of a resin composition, Preferably they are 5 mass% or more and 70 mass% or less, More preferably, they are 10 mass% or more and 65 mass% or less, More preferably, 15 It is mass% or more and 60 mass% or less.

Content of an inorganic particle is 0.1 mass part or more and 50 mass parts or less in 100 mass parts of solid content of a resin composition, Preferably they are 1 mass part or more and 45 mass parts or less, More preferably, it is 5 mass parts or more. It is 40 mass parts or less.

"Solid content of resin composition" means the sum total of components other than the solvent contained in a resin composition.

The resin composition may contain other components other than the inorganic particles, the polymer, the dispersant, and the resin.

As other components, solvents, such as an organic solvent, an additive etc. are mentioned.

The solvent and the additive may be the same as the solvent and the additive described in the section of <Curable Resin Composition> described later.

Examples of the additive include polymer compounds other than resins (binder resins), antioxidants, ultraviolet absorbers, adhesion promoters, leveling agents, anti-agglomerating agents, organic acids, organic amine compounds, thiol compounds, curing agents and the like.

<Curable Resin Composition>

Curable resin composition is one Embodiment of the said resin composition, and contains an inorganic particle, the said polymer or the said dispersing agent, resin (binder resin), and a polymeric compound.

One suitable example of the inorganic particles is the semiconductor quantum dot described above.

Content of an inorganic particle is 0.1 mass part or more and 50 mass parts or less in 100 mass parts of solid content of curable resin composition, Preferably they are 1 mass part or more and 45 mass parts or less, More preferably, 5 mass parts It is more than 40 mass parts. For example, in the case where the inorganic particles are semiconductor quantum dots, when the content of the inorganic particles is within the above range, sufficient light emission intensity is obtained in the cured film (wavelength conversion film or the like), and the patternability is excellent. There is this.

"Solid content of curable resin composition" means the sum total of components other than the solvent contained in curable resin composition.

[1] resin

Curable resin composition can contain 1 type (s) or 2 or more types of resin. The resin is not particularly limited as long as it can be a binder resin, but when it is desired to impart developability to the cured product of the curable resin composition, the resin is preferably an alkali-soluble resin. Alkali solubility means the property melt | dissolved in the developing solution which is the aqueous solution of an alkali compound.

As alkali-soluble resin, the following resin [K1]-[K6], etc. are mentioned.

Resin [K1]: At least 1 sort (a) (it is also called "(a)" hereafter) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and a C2-C4 cyclic ether structure and ethylene Copolymer of monomer (b) having a unsaturated unsaturated bond (hereinafter also referred to as "(b)");

Resin [K2]: Monomer (c) copolymerizable with (a) and (b) and (a) (however, it differs from (a) and (b).) [Hereinafter, it is also called "(c)." Copolymer with,

Resin [K3]: a copolymer of (a) and (c),

Resin [K4]: Resin obtained by reacting (b) with a copolymer of (a) and (c),

Resin [K5]: Resin obtained by reacting (a) with a copolymer of (b) and (c),

Resin [K6]: Resin obtained by making (a) react with the copolymer of (b) and (c), and also making a carboxylic anhydride react.

As (a), specifically,

(Meth) acrylic acid, crotonic acid, o-, m-, p-vinyl benzoic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], etc. Unsaturated monocarboxylic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene , 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing carboxyl groups, such as [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated (meth) acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) (meth) acrylic acid, is mentioned.

(b) is an ethylenically unsaturated bond with a C2 or more and 4 or less cyclic ether structure (for example, at least 1 sort (s) chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)). The polymeric compound which has a. (b), Preferably, they are a monomer which has a C2-C4 cyclic ether structure and a (meth) acryloyloxy group.

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [ Hereinafter, it is also called "(b2)." The monomer (b3) which has a tetrahydrofuryl group and ethylenically unsaturated bond (hereinafter also called "(b3)") etc. are mentioned.

As (b1), the monomer (b1-1) which has a structure which epoxidized unsaturated aliphatic hydrocarbon is also called "(b1-1)" hereafter.], The monomer which has a structure which epoxidized unsaturated alicyclic hydrocarbon (b1) -2) (hereinafter also referred to as "(b1-2)").

As (b1-1), glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and o-vinyl benzyl glyco Cylyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α- Methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl ) Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2 , 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, and the like. have.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (for example, ceoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), and 3,4-epoxycyclohexylmethyl (Meth) acrylate (for example, cyclomer A400; Daicel Chemical Co., Ltd. product), 3, 4- epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer M100; diecell chemical industry 3) 4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate etc. are mentioned.

It is preferable that the monomer (b2) which has an oxetanyl group and ethylenically unsaturated bond is a monomer which has an oxetanyl group and a (meth) acryloyloxy group. Preferred examples of (b2) are 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) Acryloyloxyethyl oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

It is preferable that the monomer (b3) which has a tetrahydrofuryl group and ethylenically unsaturated bond is a monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group.

Preferable examples of (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Specific examples of (c),

Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acryl Rate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate [In the technical field, the common name is called "dicyclopentanyl (meth) acrylate". In addition, it may be called "tricyclodecyl (meth) acrylate."] Tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate [In the technical field, a common name is "dicyclo" Pentenyl (meth) acrylate.], Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, (Meth) acrylic acid esters such as propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybi Cyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2 -Ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept 2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxy Cycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bi Ratios of s (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Cyclo unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Can be mentioned.

Especially, from a viewpoint of copolymerization reactivity, the heat resistance of the film | membrane obtained from curable resin composition, or developability at the time of patterning, (c) is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, Benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentenyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [ 2.2.1] hept-2-ene and the like.

In resin [K1], it is preferable that the ratio of the structural unit derived from each exists in the following ranges among all the structural units which comprise resin [K1].

structural unit derived from (a); 2 mol% or more and 50 mol% or less (more preferably 10 mol% or more and 45 mol% or less),

the structural unit derived from (b), especially the structural unit derived from (b1); 50 mol% or more and 98 mol% or less (more preferably 55 mol% or more and 90 mol% or less).

When the ratio of the structural unit of resin [K1] exists in the said range, it exists in the tendency which is excellent in the storage stability of resin, the developability of a film obtained from curable resin composition, and solvent resistance.

Resin [K1] is referred to the method described in the document "Experimental method of polymer synthesis" (Osaka Chemicals Co., Ltd., First Edition, First Edition, March 1, 1972) and the cited reference described in the document. Can be prepared.

Specifically, a method of introducing a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent, and the like into a reaction vessel and stirring, heating, and warming in a deoxygenated atmosphere. The polymerization initiator, the solvent, and the like are not particularly limited, and any of those commonly used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide and the like). . What is necessary is just to melt | dissolve each monomer as a solvent, and the organic solvent etc. which are mentioned later may be used.

In addition, the obtained copolymer may use the solution after reaction as it is, the solution which concentrated or diluted may be used, and the thing taken out as solid (powder) by methods, such as reprecipitation, may be used.

In resin [K2], it is preferable that the ratio of the structural unit derived from each exists in the following ranges among all the structural units which comprise resin [K2].

structural unit derived from (a); 4 mol% or more and 45 mol% or less (more preferably 10 mol% or more and 30 mol% or less),

the structural unit derived from (b), especially the structural unit derived from (b1); 2 mol% or more and 95 mol% or less (more preferably 5 mol% or more and 80 mol% or less),

structural unit derived from (c); 1 mol% or more and 65 mol% or less (more preferably 5 mol% or more and 60 mol% or less).

When the ratio of the structural unit of resin [K2] exists in the said range, there exists a tendency which is excellent in the storage stability of resin, the developability, solvent resistance, heat resistance, and mechanical strength of the film | membrane obtained from curable resin composition.

Resin [K2] can be manufactured similarly to the method described as a manufacturing method of resin [K1]. Specifically, the method of introducing the predetermined amount of (a), (b) (especially (b1)) and (c), a polymerization initiator, and a solvent in a reaction container, and stirring, heating, and keeping warm in a deoxidation atmosphere is mentioned. Can be. The obtained copolymer may use the solution after reaction as it is, the solution concentrated or diluted, and the thing taken out as solid (powder) by methods, such as reprecipitation, may be used.

In resin [K3], it is preferable that the ratio of the structural unit derived from each exists in the following ranges among all the structural units which comprise resin [K3]. structural unit derived from (a); 2 mol% or more and 55 mol% or less (more preferably 10 mol% or more and 50 mol% or less),

structural unit derived from (c); 45 mol% or more and 98 mol% or less (more preferably, 50 mol% or more and 90 mol% or less).

Resin [K3] can be manufactured similarly to the method described as a manufacturing method of resin [K1].

Resin [K4] obtains the copolymer of (a) and (c), and has the cyclic ether structure of 2 or 4 carbon atoms which (b) has, especially the oxirane ring which (b1) has, It can be prepared by addition to the main acid and / or carboxylic anhydride. Specifically, the copolymer of (a) and (c) is manufactured similarly to the method described as a manufacturing method of resin [K1] first. In this case, it is preferable that the ratio of the structural unit derived from each exists in the following ranges among all the structural units which comprise the copolymer of (a) and (c).

structural unit derived from (a); 5 mol% or more and 50 mol% or less (more preferably 10 mol% or more and 45 mol% or less),

structural unit derived from (c); 50 mol% or more and 95 mol% or less (more preferably 55 mol% or more and 90 mol% or less).

Next, to the carboxylic acid and / or carboxylic anhydride derived from (a) in the said copolymer, the oxirane ring which C2 or more and 4 or less cyclic ether structure which (b) has, especially (b1) has React. Specifically, following the preparation of the copolymers of (a) and (c), the atmosphere in the flask is replaced with nitrogen from air, and (b) (particularly (b1)), carboxylic acid or carboxylic anhydride and cyclic ether structure Reaction catalyst (e.g., tris (dimethylaminomethyl) phenol, etc.), polymerization inhibitor (e.g., hydroquinone, etc.) and the like were placed in a flask, and the reaction time was 60 hours or more and 130 degrees C or less for 1 hour or more and 10 hours. Resin [K4] can be obtained by reacting with the following reaction time.

It is preferable that the usage-amount of (b), especially (b1) are 5 mol or more and 80 mol or less with respect to 100 mol of (a), More preferably, they are 10 mol or more and 75 mol or less. By setting it as this range, there exists a tendency for the balance of the storage stability of resin, the developability, solvent resistance, heat resistance, mechanical strength, and the sensitivity of the film | membrane obtained from curable resin composition to become favorable. Since the reactivity of a cyclic ether structure is high and it is hard to remain unreacted (b), as (b) used for resin [K4], (b1) is preferable and (b1-1) is more preferable.

It is preferable that the usage-amount of the said reaction catalyst is 0.001 mass% or more and 5 mass% or less with respect to the total amount of (a), (b) (especially (b1)) and (c). It is preferable that the usage-amount of the said polymerization inhibitor is 0.001 mass% or more and 5 mass% or less with respect to the total amount of (a), (b) and (c).

Reaction conditions, such as an introduction | transduction method, reaction temperature, and time, can be adjusted suitably considering a heat generation amount by a manufacturing facility, superposition | polymerization, etc. In addition, similarly to polymerization conditions, the introduction method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production facility, polymerization, and the like.

Resin [K5] is a 1st step and obtains the copolymer of (b) (especially (b1)) and (c) similarly to the manufacturing method of resin [K1] mentioned above. In the same manner as described above, the obtained copolymer may be used as it is, the concentrated or diluted solution may be used, or one obtained as a solid (powder) may be used by a method such as reprecipitation.

It is preferable that the ratio of the structural unit derived from (b) (especially (b1)) and (c) exists in the following ranges with respect to the total number of moles of all the structural units which comprise said copolymer.

the structural unit derived from (b), especially the structural unit derived from (b1); 5 mol% or more and 95 mol% or less (more preferably, 10 mol% or more and 90 mol% or less),

structural unit derived from (c); 5 mol% or more and 95 mol% or less (more preferably, 10 mol% or more and 90 mol% or less).

In addition, on the cyclic ether structure derived from (b) which the copolymer of (b) (especially (b1)) and (c) has on the conditions similar to the manufacturing method of resin [K4], the carb which (a) has Resin [K5] can be obtained by making a main acid or carboxylic anhydride react. It is preferable that the usage-amount of (a) made to react with said copolymer is 5 mol or more and 80 mol or less with respect to 100 mol of (b) (especially (b1)). Since the reactivity of a cyclic ether structure is high and it is hard to remain unreacted (b), as (b) used for resin [K5], (b1) is preferable and (b1-1) is more preferable.

Resin [K6] is resin which made carboxylic anhydride further react with resin [K5].

A carboxylic anhydride is made to react with the hydroxyl group which arises by reaction of a cyclic ether structure and carboxylic acid or carboxylic anhydride.

As the carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), and the like.

The solution acid value of the resin is preferably 5 mg-KOH / g or more and 180 mg-KOH / g or less, more preferably 10 mg-KOH / g or more and 100 mg-KOH / g or less, still more preferably 12 It is more than mg-KOH / g and 50 mg-KOH / g or less. An acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1 g of resin, and can be calculated | required by titration using the potassium hydroxide aqueous solution, for example.

The weight average molecular weight of polystyrene conversion of resin becomes like this. Preferably it is 3000 or more and 100000 or less, More preferably, it is 5000 or more and 50000 or less, More preferably, it is 5000 or more and 30000 or less. When molecular weight exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high, and the residual film ratio and hardness of the pattern obtained are also high. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin becomes like this. Preferably it is 1.1 or more and 6 or less, More preferably, it is 1.2 or more and 4 or less.

Content of resin is in 100 mass% of solid content of curable resin composition, Preferably it is 5 mass% or more and 70 mass% or less, More preferably, it is 10 mass% or more and 65 mass% or less, More preferably, it is 15 mass% or more It is 60 mass% or less. When content of resin exists in the said range, there exists a tendency for the solubility to the developing solution of an unexposed part to be high.

[2] polymerizable compounds

The polymeric compound contained in curable resin composition will not be specifically limited if it is a compound which can superpose | polymerize by active radical etc. which generate | occur | produce from a polymerization initiator etc. by light irradiation, etc., The compound etc. which have a polymerizable ethylenically unsaturated bond are mentioned.

Curable resin composition can contain 1 type (s) or 2 or more types of polymeric compounds.

It is preferable that the weight average molecular weight (Mw) of a polymeric compound is 3000 or less.

Especially, it is preferable that a polymeric compound is a photopolymerizable compound which has 3 or more of ethylenically unsaturated bonds.

Examples of the photopolymerizable compound having three or more ethylenically unsaturated bonds include trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylic acid. Elate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylic Ethylene, modified tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol Tetra (meth) acrylate, propylene glycol modified diphene Pentaerythritol and the like hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Content of a polymeric compound is 20 mass parts or more and 150 mass parts or less with respect to 100 mass parts of resin (binder resin) in curable resin composition, More preferably, they are 80 mass parts or more and 120 mass parts or less.

[3] polymerization initiator

Curable resin composition may contain a polymerization initiator. The polymerization initiator is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and can initiate polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, acyl phosphine oxide compounds and the like.

Curable resin composition can contain 1 type (s) or 2 or more types of polymerization initiators in consideration of a sensitivity, patterning property, etc ..

Since a polymerization initiator is advantageous in the point which makes the pattern shape which has a sensitivity and a desired line width precisely, it is preferable to contain oxime type compounds, such as an O-acyl oxime compound.

An O-acyl oxime compound is a compound which has a structure represented by following formula (d). Hereinafter, * represents a bonding hand.

As the O-acyl oxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 -One-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6 -(2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl -2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1- [4- (2-hydroxyethyloxy) phenylsulfanylphenyl] propane-1-one-2-imine, N -Acetyloxy-1- [4- (1-methyl-2-methoxyethoxy) -2-methylphenyl] -1- (9-ethyl-6-nitro-9H-carbazol-3-yl) methane-1 Immigration, etc.

Commercial products, such as Irgacure (registered trademark) OXE01, the same OXE02, the same OXE03 (above, made by BASF Corporation), N-1919, NCI-930, and NCI-831 (above, made by ADEKA Corporation), may be used. . These O-acyl oxime compounds are advantageous in that they can improve lithographic performance.

The alkylphenone compound is a compound having a partial structure represented by the following formula (d4) or a partial structure represented by the following formula (d5). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a structure represented by formula (d4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-mor Polynophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1- On etc. can be mentioned. You may use commercially available products, such as Irgacure 369, 907, and 379 (above, BASF Corporation).

Examples of the compound having a structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxy Ethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α -Diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

In terms of sensitivity, as the alkylphenone compound, a compound having a structure represented by formula (d4) is preferable.

As a biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxy Phenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl ) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (For example, see Unexamined-Japanese-Patent No. 48-38403, Unexamined-Japanese-Patent No. 62-174204, etc.). And imidazole compounds in which the phenyl group at the 4,4 ', 5,5'-position is substituted with a carboalkoxy group (see, for example, JP-A-7-10913). .

Especially, as a biimidazole compound, the compound represented by the following formula or its mixture is preferable.

As the triazine compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

2,4,6-trimethyl benzoyl diphenyl phosphine oxide etc. are mentioned as an acyl phosphine oxide compound.

Furthermore, as a polymerization initiator, Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound and the like. It is preferable to use these in combination with the polymerization start adjuvant (especially amines) mentioned later.

As a polymerization initiator, the polymerization initiator containing at least 1 sort (s) chosen from the group which consists of an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound is preferable, and O-acyl oxime compound The polymerization initiator containing these is more preferable.

Content of a polymerization initiator is 0.1 mass part or more and 30 mass parts or less with respect to 100 mass parts of total amounts of resin (binder resin) and a polymeric compound, More preferably, they are 1 mass part or more and 25 mass parts or less, More preferably, they are 1 mass part or more and 20 mass parts or less. When content of a polymerization initiator exists in the said range, since there exists a tendency for high sensitivity and shortening an exposure time, there exists a tendency for productivity of a cured film to improve.

[4] polymerization start aid

Curable resin composition can contain a polymerization start adjuvant. A polymerization start adjuvant is a compound or a sensitizer used in order to accelerate superposition | polymerization of the polymeric compound in which superposition | polymerization was started with a polymerization initiator. When it contains a polymerization start adjuvant, it is used in combination with a polymerization initiator.

Curable resin composition can contain 1 type (s) or 2 or more types of polymerization start adjuvant.

An amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned as a polymerization start adjuvant. Especially, a thioxanthone compound is preferable.

As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl, 4-dimethylamino benzoic acid ethyl, 4-dimethylamino benzoic acid isoamyl, 2-dimethylaminoethyl benzoic acid, 4-dimethylamino benzoic acid 2 -Ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'- Bis (ethylmethylamino) benzophenone etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxy Anthracene, 2-ethyl-9, 10-dibutoxy anthracene, etc. are mentioned.

As the thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxythioke Santon etc. can be mentioned.

As the carboxylic acid compound, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenyl sulfone Panyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthyl thioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, etc. are mentioned.

Content of a polymerization start adjuvant becomes like this. Preferably it is 0.1 mass part or more and 30 mass parts or less, More preferably, it is 1 mass part or more and 20 mass parts or less with respect to 100 mass parts of total amounts of resin (binder resin) and a polymeric compound. When content of a polymerization start adjuvant exists in the said range, productivity of a cured film can be improved further.

[5] solvents

Curable resin composition can contain a solvent. It is preferable that a solvent is an organic solvent.

Curable resin composition can contain 1 type (s) or 2 or more types of solvents.

Examples of the solvent include ester solvents (solvents containing -C (= O) -O-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (-C (= O) -O- and Solvents containing -O-), ketone solvents other than ester solvents (solvents containing -C (= O)-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutane, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, cyclohexyl acetate, 2-methylcyclohexyl acetate, cyclohexyl propionate, cis-3,3,5-acetic acid Trimethylcyclohexyl, 4-tert- butylcyclohexyl acetate, cyclohexyl butyrate, isopropyl cyclohexane carboxylic acid, (gamma) -butyrolactone, etc. are mentioned.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl anisole, Methoxycyclohexane, etc. are mentioned.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate butyl, ethoxy acetate methyl, ethoxy acetate ethyl, 3-methoxy propionate methyl, 3-methoxy propionate ethyl, 3-ethoxy propionate methyl, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl To ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl And the like Le acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentane On, 2-acetylcyclopentanone, cyclohexanone, 2-acetylcyclohexanone, isophorone and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like.

Benzene, toluene, xylene, mesitylene etc. are mentioned as an aromatic hydrocarbon solvent.

Examples of the amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

The solvent is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy propionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol from the viewpoint of applicability and dryness. Monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, cyclohexyl acetate, methoxycyclohexane And at least one member selected from the group consisting of cyclohexanecarboxylic acid isopropyl, cyclopentanone, cyclohexanone, cyclohexanol, benzene, toluene, xylene and mesitylene, and propylene glycol monomethyl ether acetate , Propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, More preferably, at least one selected from the group consisting of ethyl 3-ethoxypropionate, cyclohexyl acetate, methoxycyclohexane, cyclohexanecarboxylic acid isopropyl, cyclopentanone, cyclohexanone and cyclohexanol is more preferable. .

Content of a solvent is in 100 mass% of curable resin composition, Preferably they are 60 mass% or more and 95 mass% or less, More preferably, they are 65 mass% or more and 92 mass% or less.

That is, solid content of curable resin composition becomes like this. Preferably they are 5 mass% or more and 40 mass% or less, More preferably, they are 8 mass% or more and 35 mass% or less.

When content of a solvent exists in the said range, the applicability | paintability of curable resin composition and the flatness at the time of application | coating tend to become favorable, and also when the inorganic particle is a semiconductor quantum dot, there exists a tendency for the light emission characteristic of a cured film to become favorable. .

[6] leveling agents

Curable resin composition can contain a leveling agent.

Curable resin composition can contain 1 type (s) or 2 or more types of leveling agents.

Examples of the leveling agent include silicone-based surfactants (without fluorine atoms), fluorine-based surfactants, silicon-based surfactants having fluorine atoms, and the like. These may have a polymeric group in a side chain.

As silicone type surfactant, surfactant etc. which have a siloxane bond in a molecule | numerator are mentioned. Specifically, Toray silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name: manufactured by Toray Dow Corning, Inc.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.) have.

As a fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned in a molecule | numerator. Specifically, Fluorad (registered trademark) FC430, East FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Park (registered trademark) F142D, East F171, East F172, East F173, East F177, East F183, East F554 , Copper R30, copper RS-718-K (made by DIC Corporation), FTOP (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (made by Mitsubishi Material Electrochemical Co., Ltd.), suffron (Surflon) (trademark) S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Research Institute), etc. are mentioned.

As silicone type surfactant which has a fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned in a molecule | numerator. Specifically, Megapak R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

Content of a leveling agent is 0.001 mass% or more and 0.2 mass% or less in 100 mass% of curable resin compositions, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably, it is 0.005 mass% or more and 0.05 mass% or less. .

[7] antioxidants

Curable resin composition can contain antioxidant. Thereby, heat resistance and light resistance of curable resin composition can be improved.

Curable resin composition can contain 1 type (s) or 2 or more types of antioxidant.

The antioxidant is not particularly limited as long as it is an industrially used antioxidant, and examples thereof include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.

As a phenolic antioxidant, Irganox® 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], BASF Corporation 1076 (Irganox 1076: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, BASF Corporation), 1330 (Irganox 1330: 3, 3 ', 3 ", 5,5', 5" -hexa-t-butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol, BASF )), Copper 3114 (Irganox 3114: 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione, manufactured by BASF Corporation, Copper 3790 (Irganox 3790: 1,3,5-tris ((4-t-butyl-3-hydroxy-2,6-xylyl)) Methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF Corporation), Copper 1035 (Irganox 1035: thiodiethylenebis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Copper 1135 (Irganox 1135: benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 branched alkyl ester, BASF ( ) First), copper 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF Corporation), copper 3125 (Irganox 3125, manufactured by BASF Corporation), copper 565 (Irganox 565 : 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ', 5'-di-t-butylanilino) -1,3,5-triazine, manufactured by BASF Corporation AdecastaB® AO-80 (AdecastaB AO-80: 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, made by ADEKA Co., Ltd., Smizer (registered trademark) BHT, copper GA-80, copper GS (The Sumitomo Chemical Co., Ltd. product), Cyanox (trademark) 1790 (Cyanox 1790, Cytec Co., Ltd.), vitamin E (Aizai Corporation make), etc. are mentioned.

Examples of phosphorus antioxidants include Irgafos® 168 (Irgafos 168: Tris (2,4-di-t-butylphenyl) phosphite, manufactured by BASF Corporation), and Copper 12 (Irgafos 12: Tris [2- [ [2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, manufactured by BASF Corporation), Copper 38 (Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, made by BASF Corporation), adecastab (registered trademark) 329K, copper PEP36, copper PEP-8 (above, made by ADEKA Co., Ltd.), Sandstab P-EPQ (made by Client), Weston (registered trademark) 618, East 619G (above, made by GE), Ultranox 626 (made by GE), sizing GP (6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f ] [1.3.2] dioxaphosphine) (made by Sumitomo Chemical Co., Ltd.), etc. are mentioned.

As the sulfur-based antioxidant, β of polyols such as dialkylthiodipropionate compounds such as thiodipropionic acid dilauryl, dimyristyl or distearyl, and tetrakis [methylene (3-dodecylthio) propionate] methane -Alkyl mercaptopropionic acid ester compound, etc. are mentioned.

[8] other ingredients

If necessary, the curable resin composition may contain one kind or two or more kinds of additives such as polymer compounds other than resins (binder resins), adhesion promoters, ultraviolet absorbers, anti-agglomerating agents, organic acids, organic amine compounds, thiol compounds, and curing agents. have.

Examples of the polymer compound other than the resin (binder resin) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxyoxytrimethoxysilane, 3-glycidoxyoxymethyldimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxy Silane and the like.

As a ultraviolet absorber, Benzotriazole type compounds, such as 2- (2-hydroxy-3- tert- butyl- 5-methylphenyl) -5-chloro benzotriazole; Benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone; Benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; Triazine compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol; Etc. can be mentioned.

Examples of the aggregation inhibitor include sodium polyacrylate.

As a hardening | curing agent, the compound which can react with the carboxyl group in resin, and can crosslink resin, the compound which can superpose | polymerize and harden | cure alone, etc. are mentioned specifically, an epoxy compound, an oxetane compound, etc. are mentioned.

[9] Preparation Method of Curable Resin Composition

Curable resin composition can be prepared by mixing an inorganic particle, a polymer or a dispersing agent, resin, a polymeric compound, and a solvent, and the other components normally used as needed.

The method of mixing an inorganic particle, a polymer or a dispersing agent, and a solvent, preparing the dispersion liquid in which the inorganic particle was disperse | distributed beforehand, and mixing this dispersion liquid and the remaining components to prepare curable resin composition is an example of a preferable preparation method.

In addition, the semiconductor quantum dot which has the organic ligand as the said inorganic particle, for example, prepares or prepares the semiconductor quantum dot which the organic ligand coordinates, and then reduces the coordination amount of the organic ligand with respect to the said semiconductor quantum dot. The ligand reduction process may be performed. The ligand reduction process may be, for example, a process of extracting an organic ligand coordinated to a semiconductor quantum dot with a suitable solvent.

<Film formed from resin composition and curable resin composition>

The film (layer) which consists of a resin composition can be dried as needed, and can be further hardened as needed and can form a film (coating film).

Moreover, after drying the film (layer) which consists of curable resin composition as needed, a cured film can be obtained by making it harden | cure. At this time, the patterned cured film can be obtained by patterning by methods, such as the photolithographic method, the inkjet method, and the printing method.

It is preferable that the patterning method is a photolithography method. The photolithographic method is a method of apply | coating curable resin composition to a board | substrate, drying, forming a curable resin composition layer, exposing the said curable resin composition layer through a photomask, and developing it.

As a board | substrate, glass plates, such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass which silica-coated the surface, resin plates, such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, aluminum on the said board | substrate, Silver, a copper, palladium alloy thin film, etc. can be used.

Formation of the patterned cured film by the photolithographic method can be performed by well-known or the usual apparatus and conditions, For example, it can form as follows. First, curable resin composition is apply | coated on a board | substrate, volatile components, such as a solvent, are removed and dried by heat-drying (prebaking) and / or drying under reduced pressure, and a curable resin composition layer is obtained.

As a coating method, a spin coating method, the slit coating method, the slit and spin coating method, etc. are mentioned.

30 degreeC or more and 120 degrees C or less are preferable, and, as for the temperature in the case of heat-drying, 50 degreeC or more and 110 degrees C or less are more preferable. It is preferable that they are 10 seconds or more and 10 minutes or less, and, as for a heat time, it is more preferable that they are 30 seconds or more and 5 minutes or less.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20 degreeC or more and 25 degrees C or less under the pressure of 50 Pa or more and 150 Pa or less. The film thickness of a curable resin composition layer is not specifically limited, It can select suitably according to the desired film thickness of a cured film.

Next, curable resin composition layer is exposed through the photomask for forming a desired pattern. The pattern on the said photomask is not specifically limited, The pattern according to the intended use is used. As a light source used for exposure, the light source which produces the light of the wavelength of 250 nm or more and 450 nm or less is preferable. For example, the bandpass filter which cuts the light of less than 350 nm using the filter which cuts this wavelength range, or extracts these wavelength ranges the light of 436 nm vicinity, 408 nm vicinity, and 365 nm vicinity is used. May be taken out selectively.

As a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, for exposure, since the parallel light beam can be irradiated uniformly to the whole exposure surface, or the exact alignment of the board | substrate with a photomask and curable resin composition layer can be performed. .

The pattern of the curable resin composition layer is formed on a board | substrate by developing and making the curable resin composition layer after exposure contact a developing solution. By development, the unexposed part of a curable resin composition layer melt | dissolves in a developing solution and is removed.

It is preferable that a developing solution is aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, for example. The density | concentration in the aqueous solution of these alkaline compounds becomes like this. Preferably they are 0.01 mass% or more and 10 mass% or less, More preferably, they are 0.03 mass% or more and 5 mass% or less. The developing solution may further contain surfactant.

As a developing method, a paddle method, a dipping method, a spray method, etc. are mentioned. Further, the substrate may be tilted at any angle during development. It is preferable to wash with water after image development.

It is preferable that the pattern of the obtained curable resin composition layer is post-baked. It is preferable that it is 60 degreeC or more and 250 degrees C or less, and, as for a postbaking temperature, it is more preferable that they are 110 degreeC or more and 240 degrees C or less. It is preferable that they are 1 minute or more and 120 minutes or less, and, as for postbaking time, it is more preferable that they are 10 minutes or more and 60 minutes or less.

The film thickness of the cured film after postbaking is 1 micrometer or more and 10 micrometers or less, for example, Preferably they are 3 micrometers or more and 10 micrometers or less.

The cured film formed from the resin composition and curable resin composition and the patterned cured film formed from a resin composition can be applied to the use according to the function of the inorganic particle contained in it, for example.

For example, in the case where the inorganic particles are semiconductor quantum dots or colored pigments such as inorganic pigments, the coating film, cured film, and patterned cured film may be a wavelength conversion film (wavelength) that emits light having a wavelength different from that of incident light. Can be suitably used as a conversion filter). The wavelength conversion film can be suitably used for display devices such as a liquid crystal display device and an organic EL device.

Since the polymer and the dispersing agent which concern on this invention are excellent in the ability to disperse | distribute to an inorganic particle, the said wavelength conversion film can exhibit the outstanding luminescence characteristic.

In particular, the cured film and the patterned cured film formed from the curable resin composition containing the polymer or the dispersing agent and the semiconductor quantum dot according to the present invention can uniformly disperse the semiconductor quantum dots, thereby preventing fluorescence emission in a desired wavelength region. The color reproducibility shown may be excellent, and the light uniformity may be excellent.

Moreover, when an inorganic particle is a light scattering agent, the said coating film, cured film, and the patterned cured film can be used as a light scattering layer. The said wavelength conversion film may contain the light scattering agent, and the light emission characteristic of a wavelength conversion film can be improved by this.

EXAMPLE

Although an Example is shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited by these examples. In the example,% and part which show content-usage-amount are a mass reference | standard unless there is particular notice.

<Comparative Example 1>

(1) Preparation of Polymer

450 parts of propylene glycol monomethyl ether acetate (PGMEA) was introduce | transduced into the flask provided with the cooling tube and the stirrer, and nitrogen-substituted. 89 parts of methyl methacrylate (made by Tokyo Chemical Co., Ltd.), 11 parts of methacrylic acid, 2,2'- azobis (2, 4- dimethylvaleronitrile) (made by Wakojun Yaku company, stirring at 70 degreeC). ) 6 parts, a mixed solution of 6 parts of pentaerythritol tetrakis (3-mercaptopropionate) [PEMP] (manufactured by SC Organic Chemicals Co., Ltd.) and 450 parts of PGMEA was added dropwise over 30 minutes, and the polymerization reaction was performed at the same temperature for 2 hours. It was done. After slow cooling to room temperature, the reaction solution was added dropwise to ethanol, and the precipitate was collected by filtration and dried with a vacuum dryer at 40 ° C to obtain a white powder of a polymer (dispersant). Hereinafter, this polymer is called polymer H1.

Polymer H1 has the following structural unit.

(2) Preparation of Composition

A core shell semiconductor quantum dot INP530 (manufactured by NN-LABS) having a structure of InP (core) / ZnS (first shell) / ZnS (second shell) was prepared. Oleylamine is coordinated on the surface of this semiconductor quantum dot.

The solvent substitution process was performed with respect to said semiconductor quantum dot QD in the following procedure. First, 2 volume parts of hexane was added and diluted to 1 volume part of the dispersion containing QD mentioned above. Thereafter, 30 parts by volume of ethanol was added to precipitate QD, and centrifugation was performed. The supernatant was removed and 3 parts by volume of hexane was added to redisperse the QD. Such treatment (precipitation by centrifugation → centrifugation → removal of supernatant → re-dispersion by addition of hexane) was performed three times in total. However, at the time of redispersion in the third time, cyclohexyl acetate (CHXA) instead of hexane was added so that the concentration of QD (including oleylamine ligand) was 20% by mass to obtain a QD dispersion.

20 parts of powder of the polymer H1 obtained in the above (1), 40 parts of PGMEA and 40 parts of CHXA were mixed to prepare a polymer solution.

Moreover, 20 parts of antioxidants (phenolic-type antioxidant "Smallizer (trademark) GP" by Sumitomo Chemical Co., Ltd.) and 80 parts of PGMEA were mixed, and the antioxidant solution was prepared.

25.0 parts of the QD dispersion, 14.0 parts of the polymer solution and 1.9 parts of the antioxidant solution were placed in a flask, and heated and stirred at 120 ° C. for 12 hours, followed by cooling to room temperature to obtain a composition.

(3) Measurement of the weight average molecular weight Mw of the polymer

The weight average molecular weight Mw (standard polystyrene conversion value by gel permeation chromatography (GPC)) of the polymer H1 obtained by said (1) was measured. The results are shown in Table 1.

The measurement of the weight average molecular weight Mw was performed on condition of the following using GPC method.

Device; HLC-8120GPC (manufactured by Tosoh Corporation),

column; PLgel mixC + GuardColumn,

Column temperature; 40 ℃,

menstruum; DMF (30 mM LiBr, 10 mM H3P04),

Flow rate; 1.0 mL / min,

Test liquid solids concentration; 0.001-0.01% by weight,

Injection amount; 100 μL,

Detectors; RI-8020 / UV-8020 (254 nm),

Calibration standards; TSK STANDARD POLYSTYRENE

                 F-128, F-40, F-10, F-4, F-1, A-5000 (made by Tosoh Corporation).

(4) Evaluation of the heat resistance of the polymer

The decomposition temperature of the polymer was measured as follows.

30 mg of the powder of the polymer H1 obtained in the above (1) was measured and put into an aluminum pan, using a thermogravimetric analyzer "TGDTA6200" (manufactured by Seiko Instrument) at an elevated temperature of 10 ° C / min under air flow. After heating up from 50 degreeC to 150 degreeC, it heated up from 150 degreeC to 400 degreeC at the temperature increase rate of 2 degree-C / min, and obtained the graph which made the horizontal axis the temperature (degreeC) and the vertical axis the mass change. The intersection X of the tangent of the horizontal part of the low temperature side in the obtained graph, and the tangent of the inflection point of the low temperature side was made into the decomposition temperature of polymer H1. The results are shown in Table 1.

(5) Evaluation of Dispersibility of Composition

The composition obtained in said (2) was visually observed, and the dispersibility of the inorganic particle in a composition was evaluated based on the following evaluation criteria. The results are shown in Table 1.

(Circle): The dispersion state of an inorganic particle is uniform, and a deposit is not recognized visually.

X: The dispersion state of an inorganic particle is nonuniform, and a deposit is confirmed visually.

<Example 1>

(1) Preparation of Polymer

450 parts of propylene glycol monomethyl ether acetate (PGMEA) was introduce | transduced into the flask provided with the cooling tube and the stirrer, and nitrogen-substituted. 71 parts of methyl methacrylate (made by Tokyo Chemical Co., Ltd.), succinic acid 1- [2- (methacryloyloxy) ethyl] (made by Sigma Aldrich Japan) at the same temperature, stirring at 70 degreeC, 2,2 6 parts of '-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), 6 parts of pentaerythritol tetrakis (3-mercaptopropionate) [PEMP] (manufactured by SC Organic Chemical Co., Ltd.), and PGMEA The mixed solution of 450 parts was dripped over 30 minutes, and the polymerization reaction was performed at the same temperature for 2 hours.

The reaction solution was slowly cooled to room temperature, and then added dropwise to ethanol, and the precipitate was collected by filtration and dried with a vacuum dryer at 40 ° C to obtain a white powder of a polymer (dispersant). Hereinafter, this polymer is called polymer A1.

Polymer A1 has the following structural unit.

(2) Preparation of Composition

A composition was obtained in the same manner as in Comparative Example 1 except that Polymer A1 obtained in the above (1) was used instead of Polymer H1.

(3) Measurement of the weight average molecular weight Mw of the polymer, evaluation of the heat resistance of the polymer, and evaluation of the dispersibility of the composition

It carried out similarly to the comparative example 1, and measured and evaluated about the polymer A1 and the composition obtained by said (2). The results are shown in Table 1.

Moreover, the decomposition rate of the polymer A1 was measured.

30 mg of the powder of the polymer A1 obtained in the above (1) was measured and put into an aluminum pan, and heated at 10 ° C / min under an air stream using a thermogravimetric analyzer "TGDTA6200" (manufactured by Seiko Instrument). From the temperature decrease from 50 degreeC to 230 degreeC, and hold | maintained 30 minutes at 230 degreeC, Furthermore, from the mass reduction amount at the time of 30 minutes holding at 230 degreeC, the following formula:

The decomposition rate was calculated based on the decomposition rate (%) = {mass loss amount (mg) / quantity (mg) measured in the aluminum pan} x100. The decomposition rate was 1.91%.

<Example 2>

(1) Preparation of Polymer

450 parts of propylene glycol monomethyl ether acetate (PGMEA) was introduce | transduced into the flask provided with the cooling tube and the stirrer, and nitrogen-substituted. 51 parts of methyl methacrylates (made by Tokyo Chemical Co., Ltd.), 20 parts of N-cyclohexyl maleimide (made by Tokyo Chemical Co., Ltd.), succinic acid 1- [2- (methacryloyloxy), stirring at 70 degreeC. Ethyl] (manufactured by Sigma Aldrich Japan) 29 parts, 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) 6 parts, pentaerythritol tetrakis (3-mercaptopropionate) A mixture solution of 6 parts of PEPE (manufactured by SC Organic Chemical Co., Ltd.) and 450 parts of PGMEA was added dropwise over 30 minutes, and polymerization reaction was performed at the same temperature for 2 hours. The reaction solution was slowly cooled to room temperature, and then added dropwise to ethanol, and the precipitate was collected by filtration and dried with a vacuum dryer at 40 ° C to obtain a white powder of a polymer (dispersant). Hereinafter, this polymer is called polymer A2.

Polymer A2 has the following structural units.

(2) Preparation of Composition

A composition was obtained in the same manner as in Comparative Example 1 except that Polymer A2 obtained in the above (1) was used instead of the Polymer H1.

(3) Measurement of the weight average molecular weight Mw of the polymer, evaluation of the heat resistance of the polymer, and evaluation of the dispersibility of the composition

It carried out similarly to the comparative example 1, and measured and evaluated about the polymer A2 and the composition obtained by said (2). The results are shown in Table 1. Moreover, it was 1.71% when the decomposition rate of the polymer A2 was measured similarly to Example 1.

<Example 3>

(1) Preparation of Polymer

450 parts of propylene glycol monomethyl ether acetate (PGMEA) was introduce | transduced into the flask provided with the cooling tube and the stirrer, and nitrogen-substituted. 74 parts of methyl methacrylate (made by Tokyo Chemical Co., Ltd.), 26 parts of 6-maleimide hexanoic acid (made by Tokyo Chemical Co., Ltd.), 2,2'- azobis (2, 4- dimethyl) at the same temperature, stirring at 70 degreeC. 6 parts of valeronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), 6 parts of pentaerythritol tetrakis (3-mercaptopropionate) [PEMP] (manufactured by SC Organic Chemicals Co., Ltd.) and 450 parts of PGMEA were added dropwise over 30 minutes. The polymerization reaction was carried out at the same temperature for 2 hours. The reaction solution was slowly cooled to room temperature, and then added dropwise to ethanol, and the precipitate was collected by filtration and dried with a vacuum dryer at 40 ° C to obtain a white powder of a polymer (dispersant). Hereinafter, this polymer is called polymer A3.

Polymer A3 has the following structural units.

(2) Preparation of Composition

A composition was obtained in the same manner as in Comparative Example 1 except that Polymer A3 obtained in the above (1) was used instead of the polymer H1.

(3) Measurement of the weight average molecular weight Mw of the polymer, evaluation of the heat resistance of the polymer, and evaluation of the dispersibility of the composition

It carried out similarly to the comparative example 1, and measured and evaluated about the polymer A3 and the composition obtained by said (2). The results are shown in Table 1. Moreover, it was 0.95% when the decomposition rate of the polymer A3 was measured similarly to Example 1.

¹ H-NMR data of polymer A3 is as follows.

¹ H-NMR (CDCl ₃ , 400 MHz, TMS) δ (ppm): δ = 4.05-4.20 (br, NCH ₂ , 2H), 3.75-3.50 (br, CH ₃ , 3H), 3.35-3.30 (br, CH, 1H), 2.7-2.63 (br, 1H), 2.35-2.25 (t, CH ₂ C═O, 2H), 1.2-2.1 (br, CH ₂ and methacryl polymer backbone) ppm

The ratio of each structural unit was calculated from the integral ratio of δ = 3.75-3.50 (derived from methyl methacrylate) and δ = 4.05-4.20 (derived from 6-maleimidehexanoic acid), confirming that the polymer was obtained at an introduction ratio. It was.

<Example 4>

(1) Preparation of Polymer

450 parts of propylene glycol monomethyl ether acetate (PGMEA) was introduce | transduced into the flask provided with the cooling tube and the stirrer, and nitrogen-substituted. 74 parts of N-cyclohexyl maleimide (made by Tokyo Chemical Co., Ltd.), 26 parts of 6-maleimide hexanoic acid (made by Tokyo Chemical Co., Ltd.), 2,2'- azobis (2,4, stirring at 70 degreeC, stirring. 6 parts of dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), 6 parts of pentaerythritol tetrakis (3-mercaptopropionate) [PEMP] (manufactured by SC Organic Chemicals Co., Ltd.), and 450 parts of PGMEA were taken for 30 minutes. It was dripped and the polymerization reaction was performed at the same temperature for 2 hours. The reaction solution was slowly cooled to room temperature, and then added dropwise to ethanol, and the precipitate was collected by filtration and dried with a vacuum dryer at 40 ° C to obtain a white powder of a polymer (dispersant). Hereinafter, this polymer is called polymer A4.

Polymer A4 has the following structural units.

(2) Preparation of Composition

A composition was obtained in the same manner as in Comparative Example 1 except that Polymer A4 obtained in the above (1) was used instead of the Polymer H1.

(3) Measurement of the weight average molecular weight Mw of the polymer, evaluation of the heat resistance of the polymer, and evaluation of the dispersibility of the composition

It carried out similarly to the comparative example 1, and measured and evaluated about the polymer A4 and the composition obtained by said (2). The results are shown in Table 1. Moreover, it was 0.12% when the decomposition rate of the polymer A4 was measured similarly to Example 1.

¹ H-NMR data of polymer A4 is as follows.

¹ H-NMR (CDCl ₃ , 400 MHz, TMS) δ (ppm): δ = 4.10-4.25 (br, NCH ₂ , 2H), 3.70-3.20 (br, NCH, 1H), 2.90-2.70 (br, CH , 2H), 2.40-2.10 (br, CH ₂ C═O, 2H), 2.35-2.25 (t, CH ₂ C═O, 2H), 2.20-1.00 (br, CH ₂ ) ppm

The ratio of each structural unit was calculated from the integral ratio of δ = 4.10-4.25 (derived from 6-maleimide hexanoic acid) and δ = 2.90-2.70 (derived from a common backbone skeleton), and it was confirmed that a polymer was obtained at an introduction ratio. .

<Example 5>

(1) Preparation of Composition

9 parts of titanium oxide particles (TiO ₂ particles, manufactured by CIK NanoTek), 1 part of polymer A1 obtained in Example 1 (1), 90 parts of propylene glycol monomethyl ether acetate (PGMEA) were added to a glass bottle, and The composition was obtained by shaking with time.

(2) Evaluation of Dispersibility of Composition

In the same manner as in Comparative Example 1, dispersibility was evaluated for the composition obtained in the above (1). The results are shown in Table 1.

<Example 6>

(1) Preparation of Composition

7.5 parts of hollow silica particles (hollow SiO ₂ particles, manufactured by Nitetsu Mining Co., Ltd.), 2.5 parts of polymer A1 obtained in (1) of Example 1, and 90 parts of propylene glycol monomethyl ether acetate (PGMEA) were added to the glass bottle, The composition was obtained by shaking with a mill for 8 hours.

(2) Evaluation of Dispersibility of Composition

In the same manner as in Comparative Example 1, dispersibility was evaluated for the composition obtained in the above (1). The results are shown in Table 1.

<Example 7>

(1) Preparation of Composition

To the glass bottle, 9 parts of calcium carbonate particles (CaCO ₃ particles, manufactured by Shiraishi Chemical Co., Ltd.), 1 part of polymer A1 obtained in (1) of Example 1, and 90 parts of propylene glycol monomethyl ether acetate (PGMEA) were added to the glass jar. The composition was obtained by shaking for 8 hours.

(2) Evaluation of Dispersibility of Composition

In the same manner as in Comparative Example 1, dispersibility was evaluated for the composition obtained in the above (1). The results are shown in Table 1.

TABLE 1

Claims (5)

A polymer having an ethylenically unsaturated bond and a structural unit (i-1) derived from a polymerizable carboxylic acid compound having a carboxyl group bonded to the ethylenically unsaturated bond via a linking group,
Including an inorganic particle, composition. The method of claim 1,
The polymerizable carboxylic acid compound has an N-substituted maleimide structure. The method according to claim 1 or 2,
The composition in which the said polymer further has a structural unit (i-2) derived from the N-substituted maleimide compound containing no carboxyl group. The method of claim 3, wherein
The inorganic particle comprises a semiconductor quantum dot. As a polymer which has an ethylenically unsaturated bond and the structural unit (i-1) derived from the polymeric carboxylic acid compound which has a carboxyl group couple | bonded with the said ethylenically unsaturated bond through a coupling group,
The polymerizable carboxylic acid compound has an N-substituted maleimide structure,
The polymer whose acid value is 20 mgKOH / g or more and 150 mgKOH / g or less.

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