TW201434936A - Dispersing agent for inorganic particles, composition containing the dispersing agent, curable composition, cured product and film - Google Patents

Abstract

The present invention provides a dispersing agent for inorganic particles, which is composed of a block copolymer containing a polymer block (a) and a polymer block (b), wherein the polymer block (a) contains a compound selected from the group consisting of tertiary amines At least one repeating unit of the repeating unit of the group and the repeating unit having the quaternary ammonium salt structure, the polymer block (b) containing a repeating unit selected from the group consisting of having a crosslinkable functional group and having a trapping radical At least one repeating unit of the repeating unit composition of the functional structure is formed by oxidation of light.

Description

Dispersing agent for inorganic particles, composition containing the dispersing agent, curable composition, cured product and film

The present invention relates to a dispersing agent for inorganic particles which can uniformly disperse inorganic particles in a solvent or a resin, or a composition containing the dispersing agent and inorganic particles. Furthermore, the present invention relates to a curable composition containing the dispersant for inorganic particles and a curable component, a cured product obtained by curing the curable composition, and a film obtained by curing the curable composition.

The priority is claimed based on Japanese Patent Application No. 2013-004098 filed on January 11, 2013 in Japan, and Japanese Patent Application No. 2013-006985 filed on January 18, 2013 in Japan. herein.

The properties of various materials can be changed by uniformly dispersing the inorganic particles in the medium. For example, zirconia may be dispersed in a transparent resin to thereby change the refractive index of the transparent resin. The inorganic particles are easily aggregated, and generally have low dispersibility in a medium such as a solvent or a resin. Therefore, in order to disperse inorganic particles in a solvent, a resin, etc., a dispersing agent is used.

As such a dispersing agent, there are ionic or nonionic surfactant-based dispersing agents, or polymer-based dispersing agents such as polyvinyl alcohols, polyacrylic acid, and acrylic copolymers, or eighteen A guanamine-based dispersing agent such as guanamine or ethylbisguanamine. Patent Document 1 proposes a polymer-based dispersant comprising a block polymer having atomic mobile polymerization (ATRP) polymerization initiator fragments and having two types of blocks having different polarities.

[Patent Document 1] Japanese Patent Publication No. 2002-534542

Since the dispersing agent generally has a small molecular weight, if a dispersing agent is used in a large amount in order to disperse the inorganic particles, the hardness of a material composed of a polymer compound, for example, a resin or the like may be lowered.

Further, the resin material containing the inorganic particles dispersed in the resin is required to have weather resistance, and in particular, it is not easily yellowed by light such as UV. In addition to the dispersing agent for dispersing the inorganic particles, a hindered amine-based light stabilizer or the like is added, whereby uniform dispersion of the inorganic particles and improvement of light resistance can be achieved. However, when a large amount of a dispersing agent and a light stabilizer are added, there is a tendency that the mechanical strength of the resin material is lowered, and even if high light resistance is required, such a large amount cannot be added to the resin.

An object of the present invention is to provide a composition which can uniformly disperse inorganic particles in a solvent or a resin, and can improve the composition of the composition containing the dispersed inorganic particles or the cured product thereof (the composition containing the dispersed inorganic particles can be improved) The dispersing agent for inorganic particles and the composition containing the dispersing agent and the inorganic particles are not required to reduce the light resistance of the material, such as the hardness of the resin cured product containing the dispersed inorganic particles. Further, an object of the present invention is to provide a curable composition containing a dispersant for an inorganic particle and a curable component, a cured product obtained by curing the curable composition, and a film obtained by curing the curable composition. .

The inventors of the present invention conducted intensive studies to solve the above problems, and the results were Now, the block copolymer containing the polymer block (a) and the polymer block (b) has excellent characteristics as a dispersing agent for inorganic particles, wherein the polymer block (a) contains a compound selected from the group consisting of tertiary amines At least one repeating unit of the repeating unit of the group and the repeating unit having the quaternary ammonium salt structure, the polymer block (b) containing a repeating unit selected from the group consisting of having a crosslinkable functional group and having a trapping radical The present invention is completed by at least one repeating unit of the repeating unit composition of the structure of the function, and the radical is generated by oxidation of light.

That is, the present invention includes the following aspects.

[1] A dispersing agent for inorganic particles, comprising a block copolymer comprising a polymer block (a) and a polymer block (b), wherein the polymer block (a) contains a compound selected from the group consisting of tertiary amines At least one repeating unit of the repeating unit of the group and the repeating unit having the quaternary ammonium salt structure, the polymer block (b) containing a repeating unit selected from the group consisting of having a crosslinkable functional group and having a trapping radical At least one repeating unit of the repeating unit composition of the functional structure is formed by oxidation of light.

[2] The dispersing agent for inorganic particles according to [1], wherein the repeating unit having a crosslinkable functional group is a repeating unit represented by the formula (I).

(In the formula (I), R ¹ represents a hydrogen atom or a C1 to C3 alkyl group, and R ² and R ³ each independently represent a hydrogen atom or a C1 to C6 alkyl group, and Q represents an oxygen group which may have an alkyl group as a substituent. a saturated heterocyclic group, or a C2~C20 alkenyl group, n1 represents a repeating number of CR ² R ³ and is an integer of 0 to 6)

[3] The dispersing agent for inorganic particles according to [1], wherein the repeating unit having a structure having a function of capturing a radical is a repeating unit represented by the formula (I'), wherein the radical is oxidized by light. produce.

(In the formula (I'), R ⁰ represents a hydrogen atom or a C1 to C3 alkyl group, and P ¹ , P ² , P ³ and P ⁴ each independently represent a C1 to C6 alkyl group, P ¹ , P ² , P ³ And the alkyl groups of C1 to C6 of P ⁴ may be bonded to each other to form a ring, X represents a divalent linking group, Y represents a hydrogen atom, an oxyl group or an alkyl group of C1 to C6, and n2 represents 0 or 1 , r represents C1~C3 alkyl, m represents 0 or 1)

[4] The dispersing agent for inorganic particles according to [1], which is composed of a block copolymer containing a polymer block (a) and a polymer block (b), wherein the polymer block (a) contains four a repeating unit of the ammonium salt structure, the polymer block (b) contains a 2,2,6,6-tetraalkylpiperidine structure, a 2,2,5,5-tetraalkylpyrrole structure, 1,2 , a repeating unit of a 2,6,6-pentaalkylpiperidine structure or a 1,2,2,5,5-pentapyrrolidinium structure.

[5] The dispersing agent for inorganic particles according to any one of [1] to [4], which has a quaternary ammonium salt structure The repeating unit is a repeating unit represented by the formula (II).

(In the formula (II), R ⁴ represents a hydrogen atom or a C1 to C3 alkyl group, and R ⁵ , R ⁶ and R ⁷ each independently represent a C1 to C6 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group, and X represents C1~C10 alkyl or C1~C10 alkyl-O-C1~C10 alkyl, Z ^- represents relative anion (counteranion)

[6] The dispersing agent for inorganic particles according to any one of [1] to [5] wherein the polymer block (b) further contains a repeating unit represented by the formula (III).

(In the formula (III), R ⁸ represents a hydrogen atom or a C1 to C3 alkyl group, and R ⁹ represents a C1 to C20 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group)

[7] A composition comprising the inorganic particles, the dispersing agent for inorganic particles according to any one of [1] to [6], and a dispersion medium.

[8] A curable composition comprising the inorganic particles, the dispersing agent for inorganic particles according to any one of [1] to [6], and a curable component.

[9] A cured product obtained by hardening a curable composition of [8].

[10] A film obtained by curing the curable composition of [8].

The dispersing agent for inorganic particles of the present invention has excellent dispersibility. Furthermore, the cured product obtained by curing the curable composition of the present invention exhibits good hardness, or the composition obtained by dispersing the inorganic particles of the present invention in a dispersion medium such as a resin is excellent in light resistance.

The dispersing agent for inorganic particles of the present invention is composed of a block copolymer containing a polymer block (a) and a polymer block (b).

The polymer block (a) is one containing at least one repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt structure.

The repeating unit having a quaternary ammonium salt structure is not particularly limited as long as it has a quaternary ammonium salt structure in a repeating unit. As a preferred repeating unit having a quaternary ammonium salt structure, a repeating unit represented by the formula (II) can be cited.

In the formula (II), R ⁴ represents a hydrogen atom or a C1 to C3 alkyl group, and R ⁵ , R ⁶ and R ⁷ each independently represent a C1 to C6 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group, and X represents C1. ~ C10 alkylene or C1 ~ C10 alkylene group -O-C1 ~ C10 alkylene group, Z ^- represents a counter anion. Further, C1, C3, C6, C10 and the like represent the number of carbon atoms constituting the group.

In the present invention, the alkyl group may be a straight chain or a branched chain. Examples of the C1-C3 alkyl group include a methyl group, an ethyl group, a n-propyl group, and an isopropyl group. Examples of the C1 to C6 alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, an isobutyl group, a tertiary butyl group, a n-pentyl group, and a n-hexyl group.

Examples of the C1 to C10 alkylene group include a methylene group, an ethylidene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a butane- 2,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, hexane-1,6-diyl , octane-1,8-diyl, decane-1,10-diyl and the like.

Examples of the C6-C10 aryl C1-C6 alkyl group include a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 1-phenyl-n-hexyl group, a naphthalen-1-ylmethyl group, and a 2-naphthalene- 2-ylethyl, 1-naphthalen-2-yl-n-propyl, indol-1-ylmethyl and the like.

Examples of Z ^- include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , CH ₃ COO ^- , PF ₆ ^- and the like.

The ratio of the polymer block (a) to at least one repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt structure is preferably from 10 to 100% by mass. If the polymer block (a) contains a ratio of at least one repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt structure, there is a dispersing agent for inorganic particles. The tendency of the dispersion performance to decrease.

The polymer block (a) may also contain repeating units having no tertiary amino group or quaternary ammonium salt structure. As the repeating unit, for example, it is exemplified by (meth)acrylic acid The repeating unit of the monomer, the repeating unit derived from the aromatic vinyl monomer, the repeating unit derived from the conjugated diene monomer, and the like.

The polymer block (a) may be at least one repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt structure, and having no tertiary or tertiary ammonium. The repeating units of the salt structure are randomly connected, and may be alternately connected.

The polymer block (a) can be, for example, a monomer having a tertiary amino group and/or a monomer having a quaternary ammonium salt structure, and optionally a tertiary amino group or a quaternary ammonium salt structure. It is obtained by bulk polymerization, or can be obtained by polymerizing a monomer having a tertiary amino group with another monomer copolymerizable with it, and then quaternizing all or a part of the tertiary amine group.

As the monomer having a quaternary ammonium salt structure, for example, a monomer represented by the formula (IIm1) can be cited. The symbol in the formula (IIm1) has the same meaning as the symbol in the formula (II). Specific examples of the monomer having a quaternary ammonium salt structure include (meth)acryloxyethyltrimethylammonium fluoride and (meth)acryloxyethyltrimethylammonium chloride. , (meth) propylene oxiranyl ethyl trimethyl ammonium bromide, (meth) propylene oxiranyl ethyl trimethyl ammonium iodide, (methyl) propylene methoxy propyl trimethyl fluorination Ammonium, (meth) propylene methoxy propyl trimethyl ammonium chloride, (meth) propylene methoxy propyl trimethyl ammonium bromide, (methyl) propylene methoxy propyl trimethyl iodine Ammonium, (a Base) propylene methoxy butyl trimethyl ammonium fluoride, (meth) propylene methoxy butyl trimethyl ammonium chloride, (meth) propylene methoxy butyl trimethyl ammonium bromide, ( Methyl) propylene methoxy butyl trimethyl ammonium iodide or the like. These may be used alone or in combination of two or more.

As the monomer having a tertiary amino group, for example, a monomer represented by the formula (IIm2) can be cited. The symbol in the formula (IIm2) has the same meaning as the symbol in the formula (II). Specific examples of the monomer having a tertiary amino group include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and dimethylaminobutyl (meth)acrylate. Ester, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, dimethylaminoethoxy (meth)acrylate Ethyl ester, dimethylaminoethoxypropyl (meth)acrylate, diethylaminobutoxybutyl (meth)acrylate, and the like. These may be used alone or in combination of two or more.

As another monomer which can be used to obtain the polymer block (a), (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, (methyl) ) hexyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, etc. (methyl Acrylate; styrene; o-methyl styrene, p-methyl styrene, p-terphenyl styrene, α-methyl styrene, three-stage Styrene, butylene styrene, p-(1-ethoxyethoxy)styrene, 2,4-dimethylstyrene, vinyl aniline, vinyl benzoic acid, etc. a derivative; a vinyl heteroaryl group such as 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylthiophene, 4-vinylthiophene; vinylnaphthalene; , vinyl hydrazine, etc.; 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-tributyl-1,3-butadiene, 2-benzene -1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl -1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-octadiene, 4,5-diethyl-1,3-octadiene, 3-butyl -1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1,3-tricyclodecadiene, laurelene a conjugated diene such as chloroprene or the like. These may be used alone or in combination of two or more.

The polymer block (b) of the present invention is one containing at least one repeating unit selected from the group consisting of a repeating unit having a crosslinkable functional group and a repeating unit having a structure having a function of capturing a radical, and the above freedom The base system is produced by oxidation of light.

The polymer block (b) contains a repeating unit having a crosslinkable functional group as a first aspect, and the polymer block (b) contains a repeating unit having a structure having a function of capturing a radical, and The case where the radical is generated by oxidation of light is referred to as a second aspect and will be described below.

(first aspect)

In the first aspect of the invention, the polymer block (b) is a repeating unit containing a crosslinkable functional group. The crosslinkable functional group is preferably non-polar or low polarity. Examples of the non-polar or low-polarity crosslinkable functional group include a group having a carbon-carbon double bond such as a vinyl group or a 2-propen-2-yl group, an oxirane group or an oxetanyl group. An oxygen-containing saturated heterocyclic group or the like. Non-polar or low polarity The crosslinkable functional group can be appropriately set according to the functional group contained in the curable component contained in the curable composition of the present invention. The repeating unit having a preferred non-polar or low-polar crosslinkable functional group in the dispersing agent for inorganic particles of the present invention may be a repeating unit represented by the formula (I).

In the formula (I), R ¹ represents a hydrogen atom or a C1 to C3 alkyl group, and R ² and R ³ each independently represent a hydrogen atom or a C1 to C6 alkyl group, and Q represents an oxygen-containing saturated group which may have an alkyl group as a substituent. A heterocyclic group or a C2 to C20 alkenyl group, and n1 represents a repeating number of CR ² R ³ and is an integer of any of 0 to 6.

The C1-C3 alkyl group or the C1-C6 alkyl group is as described in the description of the formula (II).

The oxygen-saturated heterocyclic group in Q is a saturated heterocyclic group containing at least one oxygen atom as an atom constituting the ring. Further, in addition to the oxygen atom, other hetero atoms such as a nitrogen atom or a sulfur atom may be contained as atoms constituting the ring. The number of atoms of the constituent ring of the oxygen-saturated heterocyclic group is preferably from 3 to 8, more preferably from 3 to 6.

Specific examples of the oxygen-containing saturated heterocyclic group include an oxiranyl group, an oxocyclobutyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group. Olinyl, thio Orolinic group and the like. Among these, an oxiranyl group, an oxocyclobutyl group, a tetrahydrofuranyl group, or a tetrahydropyranyl group is preferable.

The atom constituting the ring of the oxygen-saturated heterocyclic group in Q may also be substituted with a C1 to C6 alkyl group. The C1-C6 alkyl group is as described in the description of formula (II).

Examples of the C2 to C20 alkenyl group in Q include a vinyl group and a 1-propenyl group. 2-propen-1-yl, 2-propen-2-yl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2 - propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, heptenyl, octenyl, nonenyl, pentadecyl, eicosene Base, behenyl, and the like. Among these, a C2 to C6 alkenyl group is preferred, and a vinyl group is more preferred.

In the first aspect of the invention, the ratio of the repeating unit represented by the formula (I) contained in the polymer block (b) is preferably from 20 to 100% by mass. When the ratio of the repeating unit represented by the formula (I) contained in the polymer block (b) is low, the hardness of the cured product obtained by curing the curable composition tends to decrease.

In the first aspect of the invention, the polymer block (b) preferably further contains a repeating unit represented by the formula (III).

In the formula (III), R ⁸ represents a hydrogen atom or a C1 to C3 alkyl group, and R ⁹ represents a C1 to C20 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group.

The C1-C3 alkyl group and the C6-C10 aryl C1-C6 alkyl group are as described in the description of the formula (II).

Examples of the C1-C20 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, isopentyl, Neopentyl, tertiary amyl, Base, heptyl, octyl, decyl, decyl, eleven, twelfth, twenty base, and the like. Among these, a C1 to C6 alkyl group is preferred.

In the first aspect of the invention, the ratio of the repeating unit represented by the formula (III) contained in the polymer block (b) is preferably 80% by mass or less. When the ratio of the repeating unit represented by the formula (III) contained in the polymer block (b) is in the above range, the hardness of the cured product obtained by curing the curable composition tends to increase.

In the first aspect of the present invention, the polymer block (b) may contain a repeating unit having no quaternary ammonium salt structure in addition to the repeating unit represented by the formula (I) and the formula (III). Examples of the repeating unit include a repeating unit derived from an aromatic vinyl monomer, a repeating unit derived from a conjugated diene monomer, and the like.

In the first aspect of the present invention, the polymer block (b) may be a repeating unit represented by the formula (I), a repeating unit represented by the formula (III), and optionally represented by the formula (I) and formula (III). The repeating units other than the repeating unit and having no quaternary ammonium salt structure are randomly connected, and may be alternately joined.

In the first aspect of the invention, the polymer block (b) can be obtained, for example, by polymerizing a monomer having a non-polar or low-polarity crosslinkable functional group with other monomers copolymerizable with it as needed.

Examples of the monomer having a non-polar or low-polarity crosslinkable functional group include glycidyl (meth)acrylate, oxycyclobutane-2-ylmethyl (meth)acrylate, and (methyl). Oxycyclobutane-3-ylmethyl acrylate, (2-methyloxocyclobutan-2-yl)methyl (meth)acrylate, (meth)acrylic acid (3-methyloxetane-3 -yl)methyl ester, (2-ethyloxycyclobutane-2-yl)methyl (meth)acrylate, (meth)acrylic acid (3-ethyloxycyclobutane-3) -yl)methyl ester, (3-propyloxycyclobutane-3-yl)methyl (meth)acrylate, 2-(oxocyclobutan-2-yl)ethyl (meth)acrylate, (A) 2-(oxycyclobutane-3-yl)ethyl acrylate, (tetrahydrofuran-2-yl)methyl (meth) acrylate, (tetrahydrofuran-3-yl)methyl (meth) acrylate, (A) (meth)acrylic acid (2-methyltetrahydrofuran-2-yl)methyl ester, (meth)acrylic acid (3-methyltetrahydrofuran-3-yl)methyl ester, (meth)acrylic acid (5-methyltetrahydrofuran-2- Methyl), (4-methyltetrahydrofuran-2-yl)methyl (meth)acrylate, (3-methyltetrahydrofuran-2-yl)methyl (meth)acrylate, (meth)acrylic acid (2) -Methyltetrahydrofuran-3-yl)methyl ester, (5-methyltetrahydrofuran-3-yl)methyl (meth)acrylate, (4-methyltetrahydrofuran-3-yl)methyl (meth)acrylate, 2-(tetrahydrofuran-3-yl)ethyl (meth)acrylate, ethylene oxide-2-ylmethyl (meth)acrylate, (meth)acrylic acid (3-methyloxirane-2- Methyl), (meth)acrylic acid (2-methyloxiran-2-yl)methyl ester, etc., or allyl (meth)acrylate, 2-methyl-2-(meth)acrylate Propylene ester, (E)-butene-2-(meth)acrylate, ( (meth)acrylic acid (Z)-butene-2-ester, 3-butenyl (meth)acrylate, 3-methyl-3-butenyl (meth)acrylate, (meth)acrylic acid (E) -penten-3-yl ester, (Z)-penten-3-yl (meth)acrylate, 3-methyl-2-butenyl (meth)acrylate, and the like. Among these, allyl (meth)acrylate is preferred.

In the first aspect of the present invention, as other monomers which can be used to obtain the polymer block (b), methyl (meth)acrylate, ethyl (meth)acrylate, or (meth)acrylic acid can be cited. Butyl ester, n-butyl (meth)acrylate, benzyl (meth)acrylate, and the like. Further, as another monomer which can be used to obtain the polymer block (b), the same as those exemplified as the other monomer polymer which can be used to obtain the polymer block (a) can be cited.

(second aspect)

In the second aspect of the present invention, the polymer block (b) is a repeating unit containing a structure having a function of trapping a radical generated by oxidation using light. The structure which has a function of capturing the radical which generate|occur|produces by the oxidation of the light is a structure which can be seen by a hindered amine light stabilizer, and, for example, the structure which the nitrogen atom is bonded with the large- Specific examples thereof include a 2,2,6,6-tetraalkylpiperidine structure, a 2,2,5,5-tetraalkylpyrrole structure, and a 1,2,2,6,6-pentaalkyl group. Piperidine structure, 1,2,2,5,5-pentapyrrolidinium structure, and the like.

As a 2,2,6,6-tetraalkylpiperidine structure, a 2,2,5,5-tetraalkylpyrrole structure, a 1,2,2,6,6-pentacyclopiperidine structure, 1 a repeating unit such as a 2,2,5,5-pentapyrrolidinium structure, preferably a repeating unit represented by the formula (I').

In the formula (I'), R ⁰ represents a hydrogen atom or a C1 to C3 alkyl group, and P ¹ , P ² , P ³ and P ⁴ each independently represent a C1 to C6 alkyl group, P ¹ , P ² , P ³ and The alkyl groups of C1 to C6 of P ⁴ may also be bonded to each other to form a ring, X represents a divalent linking group, Y represents a hydrogen atom, an oxy group or an alkyl group of C1 to C6, n2 represents 0 or 1, and r represents C1~. C3 alkyl, m represents 0 or 1.

The C1-C3 alkyl group or the C1-C6 alkyl group is as described in the description of the formula (II).

The divalent linking group in X is not particularly limited, and is preferably a single bond, a C1 to C6 alkylene group or a C2 to C6 alkyleneoxy group, more preferably a single bond or a C1 to C6 alkylene oxide. More preferably, it is a single bond.

Examples of the alkylene group of C1 to C6 include a methylene group, an exoethyl group, a propyl group, a methyl group ethyl group, a butyl group, a 1,2-dimethylmethyl group, a pentyl group, and 1 - methyl butyl, 2-methyl butyl and the like.

Examples of the alkoxy group of C2 to C6 include an exoethoxy group, a 1,2-propenyloxy group, a 1,3-propenyloxy group, a 1,2-butoxy group, and a 1,4-extension. Butoxy and 1,6-extended hexyloxy and the like.

In the second aspect of the present invention, the ratio of the repeating unit represented by the formula (I') contained in the polymer block (b) is preferably from 20 to 100% by weight. When the ratio of the repeating unit represented by the formula (I') contained in the polymer block (b) is low, the light resistance of the composition tends to be lowered.

In the second aspect of the present invention, the polymer block (b) preferably further contains a repeating unit represented by the formula (III).

In the formula (III), R ⁸ represents a hydrogen atom or a C1 to C3 alkyl group, and R ⁹ represents a C1 to C20 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group.

C1~C3 alkyl and C6~C10 aryl C1~C6 alkyl are as described in formula (II) Narrator.

Examples of the C1-C20 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, isopentyl, Neopentyl, tertiary amyl, hexyl, heptyl, octyl, decyl, decyl, eleven, twelve, twenty, and the like. Among these, a C1 to C6 alkyl group is preferred.

In the second aspect of the present invention, the ratio of the repeating unit represented by the formula (III) contained in the polymer block (b) is preferably 80% by mass or less. When the ratio of the repeating unit represented by the formula (III) contained in the polymer block (b) is in the above range, the dispersibility of the inorganic particles tends to be improved.

In a second aspect of the invention, the polymer block (b) may in turn contain repeating units having crosslinkable functional groups. The crosslinkable functional group is preferably non-polar or low polarity. Examples of the non-polar or low-polarity crosslinkable functional group include oxygen-containing saturated groups such as a vinyl group or a 2-propen-2-yl group having a carbon-carbon double bond, an oxiranyl group or an oxocyclobutyl group. Heterocyclic group and the like. The non-polar or low-polarity crosslinkable functional group can be appropriately set according to the functional group contained in the curable component contained in the curable composition of the present invention. The repeating unit having a preferred crosslinkable functional group in the dispersing agent for inorganic particles of the present invention may be a repeating unit represented by the formula (IV).

In the formula (IV), R ¹⁰ represents a hydrogen atom or a C1 to C3 alkyl group, and R ¹¹ and R ¹² each independently represent a hydrogen atom or a C1 to C6 alkyl group, and Q represents an oxygen-containing saturated group which may have an alkyl group as a substituent. Heterocyclyl or C2~C20 alkenyl, m represents the repeat number of CR ¹¹ R ¹² and is any integer from 0 to 6.

The C1-C3 alkyl group or the C1-C6 alkyl group is as described in the description of the formula (II).

The oxygen-saturated heterocyclic group in Q is a saturated heterocyclic group containing at least one oxygen atom as an atom constituting the ring. Further, in addition to the oxygen atom, other hetero atoms such as a nitrogen atom or a sulfur atom may be contained as atoms constituting the ring. The number of atoms of the constituent ring of the oxygen-saturated heterocyclic group is preferably from 3 to 8, more preferably from 3 to 6.

Specific examples of the oxygen-containing saturated heterocyclic group include an oxiranyl group, an oxocyclobutyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group. Olinyl, thio Orolinic group and the like. Among these, an oxiranyl group, an oxocyclobutyl group, a tetrahydrofuranyl group, or a tetrahydropyranyl group is preferable.

The atom constituting the ring of the oxygen-saturated heterocyclic group in Q may also be substituted with a C1 to C6 alkyl group. The C1-C6 alkyl group is as described in the description of formula (II).

Examples of the C2 to C20 alkenyl group in Q include a vinyl group, a 1-propenyl group, a 2-propen-1-yl group, a 2-propen-2-yl group, a 1-butenyl group, a 2-butenyl group, and 3 -butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl-2-butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl , heptenyl, octenyl, nonenyl, pentadecenyl, behenyl, behenyl, and the like. Among these, a C2 to C6 alkenyl group is preferred, and a vinyl group is more preferred.

In the second aspect of the present invention, the ratio of the repeating unit represented by the formula (IV) contained in the polymer block (b) is preferably 80% by mass or less. When the ratio of the repeating unit represented by the formula (IV) contained in the polymer block (b) is increased, there is a cured product obtained by hardening the curable composition. The tendency for the hardness to become higher.

In the second aspect of the present invention, the polymer block (b) may further contain no tertiary amino group in addition to the repeating unit represented by the formula (I'), the formula (III) and the formula (IV). Or a repeating unit of a quaternary ammonium salt structure. Examples of the repeating unit include a repeating unit derived from an aromatic vinyl monomer, a repeating unit derived from a conjugated diene monomer, and the like.

In the second aspect of the present invention, the polymer block (b) may be randomly connected to the above repeating units, or may be alternately joined.

In the second aspect of the present invention, the polymer block (b) can be polymerized, for example, by a monomer having a function of capturing a radical generated by oxidation using light, and other monomers copolymerizable with it as needed. obtain.

The following compounds are exemplified as the monomer having a function of capturing radicals generated by oxidation of light.

Examples of the monomer having a non-polar or low-polarity crosslinkable functional group include glycidyl (meth)acrylate, oxycyclobutane-2-ylmethyl (meth)acrylate, and (methyl). Oxycyclobutane-3-ylmethyl acrylate, (2-methyloxocyclobutan-2-yl)methyl (meth)acrylate, (meth)acrylic acid (3-methyloxetane-3 -yl)methyl ester, (2-ethyloxycyclobutane-2-yl)methyl (meth)acrylate, (3-ethyloxycyclobutane-3-yl)methyl (meth)acrylate, (3-propyloxycyclobutane-3-yl)methyl (meth)acrylate, (methyl) 2-(oxocyclobutane-2-yl)ethyl acrylate, 2-(oxocyclobutane-3-yl)ethyl (meth)acrylate, (tetrahydrofuran-2-yl)methyl (meth)acrylate , (meth)acrylic acid (tetrahydrofuran-3-yl)methyl ester, (meth)acrylic acid (2-methyltetrahydrofuran-2-yl)methyl ester, (meth)acrylic acid (3-methyltetrahydrofuran-3-yl) Methyl ester, (5-methyltetrahydrofuran-2-yl)methyl (meth)acrylate, (4-methyltetrahydrofuran-2-yl)methyl (meth)acrylate, (meth)acrylic acid (3- Methyltetrahydrofuran-2-yl)methyl ester, (2-methyltetrahydrofuran-3-yl)methyl (meth)acrylate, (5-methyltetrahydrofuran-3-yl)methyl (meth)acrylate, ( (4-methyltetrahydrofuran-3-yl)methyl (meth)acrylate, 2-(tetrahydrofuran-3-yl)ethyl (meth)acrylate, ethylene oxide-2-ylmethyl (meth)acrylate , (3-methyloxiran-2-yl)methyl (meth)acrylate, (2-methyloxiran-2-yl)methyl (meth)acrylate, or the like (methyl) Alkenyl acrylate, 2-methyl-2-propenyl (meth)acrylate, (E)-buten-2-yl (meth)acrylate, (Z)-butene (meth)acrylate 2-based ester, 3-butenyl (meth)acrylate, (A 3-methyl-3-butenyl acrylate, (E)-penten-3-yl (meth) acrylate, (Z)-penten-3-yl (meth) acrylate, (methyl) ) 3-methyl-2-butenyl acrylate or the like. Among these, allyl (meth)acrylate is preferred.

In the second aspect of the present invention, as the monomer which can be used to obtain the polymer block (b), methyl (meth) acrylate, ethyl (meth) acrylate or (meth) acrylate can be cited. Butyl ester, n-butyl (meth)acrylate, benzyl (meth)acrylate, and the like. Further, as other monomers which can be used to obtain the polymer block (b), the same as those exemplified as other monomers which can be used to obtain the polymer block (a) can be cited.

The mass ratio of the polymer block (a) to the polymer block (b) of the present invention is not The limit is particularly preferably 20/80 to 80/20, more preferably 40/60 to 60/40. Further, since the polymer block (a) is more polar than the polymer block (b), it has a relatively high affinity with a polar solvent or a functional group having polarity. On the other hand, the polymer block (b) has a relatively high affinity with a non-polar solvent or a non-polar functional group. Generally, the surface of the inorganic particles has a functional group such as a hydroxyl group. The mass ratio of the polymer block (a) to the polymer block (b) is set according to the polarity intensity of the surface of the inorganic particles and the polarity of the dispersion medium, so that the inorganic particles of the inorganic particles of the present invention can be adjusted to be dissolved by the inorganic particles of the dispersant. And the ability to disperse.

The block copolymer constituting the dispersing agent for inorganic particles of the present invention may contain the polymer block (c) in addition to the polymer block (a) and the polymer block (b).

The polymer block (c) is a polymer block containing a repeating unit having no crosslinkable functional group and a quaternary ammonium salt structure. Specifically, a polymer block containing a repeating unit derived from a (meth)acrylic monomer, an aromatic vinyl monomer, or a conjugated diene monomer can be mentioned. The (meth)acrylic monomer, the aromatic vinyl monomer, the conjugated diene monomer, and the like are exemplified as those described above.

Further, the block copolymer of the present invention preferably has a number average molecular weight of 1,000 to 200,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 30,000. Further, the molecular weight distribution of the block copolymer of the present invention is preferably from 1.0 to 2.5, more preferably from 1.0 to 2.0, based on the ratio of the weight average molecular weight to the number average molecular weight.

Further, the weight average molecular weight and the number average molecular weight are data measured by gel permeation chromatography (GPC) using N,N-dimethylformamide as a solvent, and the molecular weight of the standard polymethyl methacrylate is utilized. The value of the conversion.

Block copolymers are not particularly limited by their method of manufacture. Block copolymers such as It is obtained by the following method: 1) obtaining a polymer block (a) by using a monomer obtained to obtain a polymer block (a), followed by adding a monomer for obtaining a polymer block (b) , the molecular chain of the polymer block (b) is grown from the end of the polymer block (a); 2) the polymer block (b) is obtained by polymerizing the monomer to obtain the polymer block (b), Next, adding a monomer for obtaining the polymer block (a), causing the molecular chain of the polymer block (a) to grow from the end of the polymer block (b); or 3) using to obtain a polymer block The monomer of (a) is polymerized to obtain a polymer block (a), and further, a polymer block (b) is obtained by using a monomer obtained to obtain a polymer block (b), and the obtained polymer block is obtained. (a) Coupling with the polymer block (b).

The block copolymer preferably contains a method of sequentially growing a molecular chain as in the above 1) or 2). Such sequential polymerization is preferably carried out by a living polymerization method. Examples of the living polymerization method include a living radical polymerization method and a living anionic polymerization method. Among these, the living anionic polymerization method is preferable in terms of strictly controlling the composition or molecular weight.

In a sequential polymerization, the polymerization of the monomer used to obtain the original polymer block, the switching to the polymerization of the monomer used to obtain the next polymer block can be used to obtain the original polymer block. The time at which the body completely disappears may be performed, or may be performed at a point in time when the body is slightly left. Depending on the residual amount of monomer used to obtain the original polymer block, there will be a case where a taper portion is formed between the two polymer blocks. The progress of the polymerization can be confirmed by detecting the residual amount of the monomer by gas chromatography or liquid chromatography. Further, after the addition of the monomer for obtaining the first polymer block, the mixture may be stirred for 1 minute to 1 hour depending on the type of the monomer or the solvent, after which the addition is started to obtain the second polymerization. The monomer of the block.

The anionic polymerization initiator used in the living anionic polymerization for obtaining the block copolymer of the present invention is not particularly limited. For example, an alkali metal, an organic alkali metal compound or the like can be used.

Examples of the alkali metal include lithium, sodium, potassium, rubidium, and the like. The organic alkali metal compound may, for example, be an alkylate, an allyl compound, an aryl compound or a lithium decylamine compound. Specific examples thereof include ethyl lithium, n-butyl lithium, secondary butyl lithium, tertiary butyl lithium, ethyl sodium, biphenyl lithium, naphthyl lithium, triphenyl lithium, and naphthyl sodium. Naphthyl potassium, methyl 2-lithium isobutyrate, ethyl 2-lithium isobutyrate, isopropyl 2-lithium isobutyrate, sodium α-methylstyrene dianion, 1,1-diphenylhexyl Lithium, 1,1-diphenyl-3-methylpentyllithium, 1,4-dilithium-2-butene, 1,6-dilithium hexane, polystyrene lithium, cumyl potassium, Propyl phenyl hydrazine, lithium dimethyl decylamine, lithium diethyl guanamine, lithium dibutyl amide, lithium dipropyl amide, lithium diisopropyl guanamine, lithium diheptyl amide, two Lithium hexyl amide, lithium dioctyl decylamine, and the like. These anionic polymerization initiators may be used alone or in combination of two or more.

The anionic polymerization initiator is used in an amount of from 1 mol to the total of the monomers used, and is usually from 0.0001 to 0.2 mol, preferably from 0.0005 to 0.1 mol. By using an anionic polymerization initiator of this range, the target polymer can be preferably produced in a yield. The polymerization temperature is not particularly limited as long as it is a temperature range in which the monomer is consumed and the polymerization is terminated without causing a side reaction such as a shift reaction or a reaction, and is preferably in the range of -100 ° C or higher and the solvent boiling point or lower. Further, the concentration of the monomer relative to the polymerization solvent is not particularly limited, but is preferably from 1 to 40% by mass, more preferably from 2 to 15% by mass.

It is generally more difficult to polymerize a monomer having a quaternary ammonium salt structure by living anionic polymerization. Therefore, when a block copolymer is produced by living anionic polymerization, The monomer having a tertiary amino group is polymerized, and then the tertiary amine group is quaternized by a known method. The quaternization can be carried out using a well-known substance as an alkylating agent for a tertiary amine. Specific examples thereof include benzyl chloride, benzyl bromide, and benzyl iodide; halogenated alkane such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate; Alkyl sulfate and the like.

The solvent which can be used for the living anionic polymerization is not particularly limited as long as it is a solvent which does not participate in the polymerization reaction and is compatible with the polymer. Specifically, it can be exemplified by diethyl ether, tetrahydrofuran, and Alkane, three a polar solvent such as an ether such as an alkane; a polar solvent such as a tertiary amine such as tetramethylethylenediamine or hexamethylphosphonium triamine; or a nonpolar solvent such as an aliphatic, aromatic or alicyclic hydrocarbon compound such as hexane or toluene or Low polar solvent. These solvents may be used alone or in combination of two or more. In the production method of the present invention, even when a nonpolar solvent or a low polar solvent is used in combination with a polar solvent, the polymerization can be controlled with high precision. For example, a nonpolar solvent or a low polar solvent can be used with respect to all solvents. It is preferably 5% by volume or more, more preferably 20% by volume or more, and still more preferably 50% by volume or more.

In the present invention, an organic metal such as dialkylzinc such as diethylzinc or dialkylmagnesium such as dibutylmagnesium or triethylaluminum may be used as a polymerization stabilizer or a monomer or a solvent.

In the living anionic polymerization, an additive such as an alkali metal salt or an alkaline earth metal salt may be added at the start of polymerization or during the polymerization as needed. Specific examples of such an additive include inorganic acid salts or halides such as sulfates, nitrates, and borates of sodium, potassium, barium, and magnesium, and more specifically, lithium or barium chloride or bromine. Compound, iodide, or lithium borate, magnesium nitrate, sodium chloride, potassium chloride, and the like. Among these, lithium halides such as lithium chloride, lithium bromide, lithium iodide, lithium fluoride, and particularly preferably lithium chloride are preferred.

The block copolymer obtained in the above manner can be directly or dissolved in a solvent. It is used as a dispersing agent for inorganic particles. The dispersing agent for inorganic particles of the present invention is suitable for uniformly dispersing inorganic particles in a dispersion medium.

The composition of the present invention contains inorganic particles, a dispersing agent for inorganic particles of the present invention, and a dispersion medium. In the composition of the present invention, it is preferred that the inorganic particles are uniformly dispersed in the dispersion medium.

The inorganic particles used in the composition of the present invention are not particularly limited. The primary particle diameter of the inorganic particles is not particularly limited, but is preferably 1000 nm or less, more preferably 500 nm or less, still more preferably 200 nm or less, and most preferably 100 nm or less.

Examples of the material constituting the inorganic particles include cerium oxide, diatomaceous earth, alumina, zinc oxide, titania, zirconia, calcium oxide, magnesium oxide, iron oxide, and oxidation. Metal oxides such as copper, tin oxide, chromium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, ferrite, etc.; , metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and basic magnesium carbonate; metal carbonates such as heavy calcium carbonate, light calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite; calcium sulfate, Metal sulphate such as barium sulfate or gypsum fiber; calcium citrate (apatite, hard strontite), kaolin, clay, talc, mica, montmorillonite, bentonite, activated clay, sepiolite, filamentous aluminite Metal sericates such as sericite, glass fiber, glass beads, glass flake; metal nitrides such as aluminum nitride, boron nitride, tantalum nitride; potassium titanate, calcium titanate, magnesium titanate, Metal titanium such as barium titanate, lead zirconate titanate or aluminum borate a metal borate such as zinc borate or aluminum borate; a metal phosphate such as tricalcium phosphate; a metal sulfide such as molybdenum sulfide; a metal carbide such as niobium carbide; a carbon such as carbon black, graphite or carbon fiber; a metal such as gold or silver. monomer. The particles composed of these materials may be used alone or in combination of two or more. Among these, preferably gold It is an oxide, more preferably zirconia.

The amount of the inorganic particles contained in the composition of the present invention is preferably from 1 to 80% by mass, more preferably from 5 to 50% by mass. In addition, the amount of the dispersing agent for inorganic particles of the present invention used in the composition of the present invention is preferably from 1 to 200 parts by mass, more preferably from 5 to 100 parts by mass, even more preferably from 100 parts by mass to the inorganic particles. 10 to 50 parts by mass.

In the composition of the present invention, as a dispersion medium, a liquid or a solid can be used.

Examples of the liquid dispersion medium include water; aliphatic hydrocarbons such as hexane, decane, dodecane, and tetradecane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene and xylene; and acetone and methyl groups. Ketones such as ethyl ketone and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate; methanol, ethanol, n-propanol, isopropanol, Alcohols such as n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin; tetrahydrofuran, two Ethers such as alkane, ethylene glycol monomethyl ether (methyl stilbene), ethylene glycol monoethyl ether (ethyl celecoxib), ethylene glycol monobutyl ether (butyl succinyl), and the like. Among these, from the viewpoint of the high dispersibility of the inorganic particles, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, esters, and alcohols are preferable, and ketones are more preferable. These liquid dispersion media may be used alone or in combination of two or more.

The amount of the liquid dispersion medium used in the composition of the present invention can be appropriately set in view of the viscosity of the composition and the like. The amount of the liquid dispersion medium which can be contained in the composition of the present invention is preferably from 10 to 50% by mass.

Examples of the solid dispersion medium include a thermoplastic resin, a thermosetting resin, and a photocurable resin. Further, in the present invention, the photocurable resin and the thermosetting resin may be referred to as a curable component. In the present invention, it is preferred to use a curable component as a solid dispersion medium. A hardening composition.

Examples of the thermoplastic resin include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, fluororesin, ABS resin, AS resin, acrylic resin, and polyfluorene. Amine, polyacetal, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polyfluorene, polyether oxime , amorphous polyarylate, liquid crystal polymer, polyether ether ketone, thermoplastic polyimide, polyamidimide and the like. The thermoplastic resin can be melted or dissolved in a solvent by heating, and kneaded or mixed with the inorganic particles and the inorganic particles with a dispersing agent.

The thermosetting resin is a one that changes from a liquid to a solid by application of heat. Examples of the thermosetting resin include a phenol resin, an epoxy resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, a polyurethane, a thermosetting polyimine, and the like. Further, examples of the thermosetting resin include those containing at least a monomer, an optional oligomer, and a thermal polymerization initiator.

Further, the photocurable resin is changed from a liquid to a solid by irradiation with light (such as ultraviolet rays). Examples of the photocurable resin include those containing at least a monomer, an optional oligomer, and a photopolymerization initiator.

Examples of the monomer or oligomer used in the photocurable resin or the thermosetting resin include monofunctional (meth)acrylate monomers, monoethylenically unsaturated compounds such as styrene and acrylonitrile; and diethylene glycol. Di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(methyl) Acrylate, triethyl (di)ethyl acrylate, PEG #200 di(meth) acrylate, PEG #400 di(meth) acrylate, PEG #600 di(meth) acrylate, di (a) Base) neopentyl acrylate, Dimethylol tricyclodecane di(meth)acrylate, dipentaerythritol hexa(meth) acrylate, neopentyl alcohol tri(meth) acrylate, neopentyl alcohol tetra(methyl) a polyfunctional (meth) acrylate monomer such as acrylate, trimethylolpropane triacrylate or trimethylolpropane tetraacrylate; (meth) acrylate; epoxy (meth) acrylate, etc. .

Among these, dipentaerythritol hexa(meth) acrylate, neopentyl alcohol tri(meth) acrylate, neopentyltetrakis (meth) acrylate, trimethylolpropane are preferred. A polyfunctional (meth) acrylate monomer such as triacrylate or trimethylolpropane tetraacrylate. In addition, these may be used alone or in combination of two or more.

As a polymerization initiator, there is a person who starts a polymerization reaction by light irradiation (photopolymerization initiator) and a polymerization initiator (thermal polymerization initiator) by heating. Specific examples of the polymerization initiator include organic peroxides, imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azides, titanocenes, and aluminates. Compound, N-alkoxypyridinium salt, 9-oxosulfur Derivatives, etc.

Examples of the organic peroxide include a tertiary butyl hydroperoxide, hydroperoxide, menthane, cumene hydroperoxide, and diisopropylbenzene hydroperoxide; a tertiary butyl group; Peroxy esters such as oxidized laurate, tertiary butyl peroxybenzoate, and tertiary butyl peroxy phthalate; 1,5-di-tert-butylperoxy-3,3, Peroxy ketals such as 5-trimethylcyclohexane; ketone peroxides such as ethyl acetoxyacetate; and bismuth peroxides such as benzamidine peroxide.

Further, examples thereof include benzoin, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxyphenylacetophenone, 2-ethylhydrazine, 1,3-Di(tertiary butyldioxycarbonyl)benzophenone, 4,4'-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-iso Oxazolone, 2-mercaptobenzimidazole, bis(2,4,5-triphenyl)imidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name Irgacure 651) , manufactured by Ciba Specialty Chemicals Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4- Polinylphenyl)-butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), bis(η 5-2,4-dicyclopentadien-1-yl)-bis (2) , 6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium) (trade name Irgacure 784, manufactured by Ciba Specialty Chemicals Co., Ltd.), dicumyl peroxide, and perbenzoic acid T-butyl perbenzoate, tertiary butyl peroxyhexyne-3 and the like. These polymerization initiators may be used alone or in combination of two or more.

In the curable composition of the first aspect of the invention, the content of the inorganic particles is preferably from 1 to 100 parts by mass based on 100 parts by mass of the polyfunctional monomer, and the content of the polymerization initiator is relative to the polyfunctional monomer. The content of the dispersant for inorganic particles according to the first aspect of the present invention is preferably from 1 to 200 parts by mass per 100 parts by mass of the inorganic particles, in terms of 100 parts by mass, preferably 0.5 to 10 parts by mass. When the curable composition containing each component in such a ratio is hardened, a cured product having a high hardness can be obtained.

In the curable composition of the second aspect of the present invention, the content of the inorganic particles is preferably from 1 to 100 parts by mass based on 100 parts by mass of the polyfunctional monomer, and the content of the polymerization initiator is relative to the polyfunctional monomer. The content of the dispersing agent for inorganic particles of the second aspect of the present invention is preferably from 1 to 200 parts by mass per 100 parts by mass of the inorganic particles, in terms of 100 parts by mass, preferably 0.5 to 10 parts by mass. When the curable composition containing each component in such a ratio is cured, a cured product excellent in light resistance can be obtained.

The composition or curable composition of the present invention can be appropriately mixed by mixing the components And prepared. In the preparation of the curable composition, the inorganic particles of the present invention may be mixed with a dispersant, inorganic particles and a liquid dispersion medium to prepare a liquid composition of the present invention, which is mixed with a curable component.

The curable composition of the present invention can be formed into a desired shape such as a film according to the use, and then subjected to light irradiation and/or heating to obtain a cured product.

Heating is not particularly limited by the method, and it can be carried out by a known means such as a heater.

In the light irradiation, for example, energy rays such as ultraviolet rays, visible rays, X-rays, and electron beams can be used. Among these, ultraviolet rays are preferably used.

The irradiation of visible light can be performed, for example, using an incandescent bulb, a fluorescent lamp, or the like. The irradiation of ultraviolet rays can be carried out, for example, using a metal halide lamp, a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer lamp, a metal halide lamp or the like. The wavelength range of the ultraviolet ray to be irradiated is not particularly limited, but is preferably 150 nm to 400 nm, more preferably 200 nm to 380 nm. The environment under light irradiation may also be an atmospheric environment, preferably an inert gas atmosphere such as nitrogen or carbon dioxide or a low oxygen concentration environment. The temperature at the time of light irradiation is not particularly limited, but is preferably 10 to 200 °C.

The progress of the hardening can be observed using a Fourier transform infrared spectroscopy apparatus or a photochemical reaction calorimeter. By this observation, suitable curing conditions (light irradiation time, light intensity, etc., heating temperature, heating time, etc.) of the curable composition can be set.

In the case of using the dispersing agent for inorganic particles according to the first aspect of the present invention, the curable composition of the present invention is a cross-linking functional group in the curable component with the dispersing agent for inorganic particles of the present invention at the time of curing. The functional group is reacted, and the inorganic particles are combined with a dispersing agent and a solid dispersion medium which is a high molecular weight resin component. Therefore, a cured product in which the dispersing agent for inorganic particles does not bleed out and has a higher hardness than the conventional curable composition can be obtained. Hardening composition When it is formed into a film and hardened, a film of high hardness can be obtained.

Moreover, when the dispersing agent for inorganic particles of the second aspect of the present invention is used, the curable composition of the present invention can obtain a cured product excellent in light resistance. In particular, when the curable composition is formed into a film and cured, a film excellent in light resistance can be obtained.

[Examples]

The invention is illustrated in more detail by showing examples. However, the technical scope of the present invention is not limited to the embodiments.

Comparative example 1

239.6 g of tetrahydrofuran and 0.3 g of lithium chloride were added to a 500 mL flask, and the mixture was cooled to -60 °C. A hexane solution (concentration: 15.4% by mass) containing 5.3 g of n-butyllithium was added thereto, and then 1.4 g of diisopropylamine was added thereto, followed by stirring for 10 minutes. To the mixture was added dropwise 18.1 g of N,N-dimethylaminoethyl methacrylate (hereinafter abbreviated as DMAEMA) over 5 minutes. After the completion of the dropwise addition, the mixture was stirred until DMAEMA could not be detected by gas chromatography. Thereafter, 42.2 g of methyl methacrylate (hereinafter abbreviated as MMA) was added dropwise over 30 minutes. After the completion of the dropwise addition, the mixture was stirred until the MMA could not be detected by gas chromatography. Then, 2.0 g of methanol was added to make the activity disappear. A block copolymer having a polymer block of DMAEMA and MMA, a block copolymer having a number average molecular weight (Mn) of 5480 and a molecular weight distribution (Mw/Mn) of 1.15 was obtained. Further, the number average molecular weight and the weight average molecular weight are values converted from the molecular weight of the standard polymethyl methacrylate measured by gel permeation chromatography using N,N-dimethylformamide as a solvent. .

80 mL of ethyl acetate was added to the liquid containing the block copolymer. Next, it was washed three times with water. Then, the obtained polymer was dissolved in propylene glycol 1-monomethyl ether 2-acetate (PGMEA). Add 0.8 mole of benzyl chloride to DMAEMA 1 Moore (hereinafter, abbreviated as BzCl). A mixed liquid composed of 70% by mass of PGMEA and 30% by mass of 1-methoxy-2-propanol (hereinafter abbreviated as PGME) was added so that the solid content concentration was 35%. Then, it was aged at 80 ° C for 5 hours to obtain a dispersant A for inorganic particles.

Example 1

114.4 g of tetrahydrofuran and 0.1 g of lithium chloride were added to a 200 mL flask, and the mixture was cooled to -60 °C. A hexane solution (concentration: 15.4% by mass) containing 2.1 g of n-butyllithium was added thereto, and then 0.5 g of diisopropylamine was added thereto, followed by stirring for 10 minutes. It took 5 minutes to add DMAEMA 7.4g. After the completion of the dropwise addition, the mixture was stirred until DMAEMA could not be detected by gas chromatography. Thereafter, a mixture of 7.2 g of MMA and 9.6 g of allyl acrylate (hereinafter abbreviated as AMA) was added dropwise over 15 minutes. After the completion of the dropwise addition, the mixture was stirred until gas chromatography was not able to detect MMA and AMA. Then, 0.8 g of methanol was added to make the activity disappear. A block copolymer having a polymer block of DMAEMA and a copolymer block of MMA/AMA, a number average molecular weight (Mn) of 6000, and a molecular weight distribution (Mw/Mn) of 1.14 was obtained.

80 mL of ethyl acetate was added to the liquid containing the block copolymer. Next, it was washed three times with water. Then, the obtained polymer was dissolved in PGMEA. 0.8 mole of BzCl was added relative to DMAEMA 1 molar. A mixed liquid composed of 70% by mass of PGMEA and 30% by mass of PGME was added so that the solid content concentration was 35%. Then, it was aged at 80 ° C for 5 hours to obtain a dispersant B for inorganic particles.

Example 2

To a 200 mL flask, 101.6 g of tetrahydrofuran and 0.1 g of lithium chloride were added, and the mixture was cooled to -60 °C. A hexane solution (concentration: 15.4% by mass) containing 2.1 g of n-butyllithium was added thereto, and then 0.6 g of diisopropylamine was added thereto, followed by stirring for 10 minutes. It took 5 minutes to add DMAEMA 7.3 g to it. After the drop is over, Stir until the DMAEMA cannot be detected by gas chromatography. Next, 9.6 g of allylic acrylate (hereinafter abbreviated as AMA) and 2,2,6,6-tetramethyl-4-piperidyl methacrylate (hereinafter, abbreviated as TMPMA) were added dropwise over 15 minutes. ) 7.2 g of the mixture. After the completion of the dropwise addition, the mixture was stirred until gas chromatography could not detect AMA and TMPMA. Then, 0.8 g of methanol was added to make the activity disappear. A block copolymer having a polymer block of DMAEMA and an AMA/TMPMA copolymer block having a number average molecular weight (Mn) of 5780 and a molecular weight distribution (Mw/Mn) of 1.16 was obtained.

80 mL of ethyl acetate was added to the liquid containing the block copolymer. Next, it was washed three times with water. Then, the obtained polymer was dissolved in PGMEA. 0.8 mole of BzCl was added relative to DMAEMA 1 molar. A mixed liquid composed of 70% by mass of PGMEA and 30% by mass of PGME was added so that the solid content concentration was 35%. Then, it was aged at 80 ° C for 5 hours to obtain a dispersant C for inorganic particles.

Comparative example 2

45.0 parts by mass of zirconia particles (manufactured by Nippon Denshi Co., Ltd., PCS60; primary particle diameter: 15 nm, specific surface area ^: 65 m ^{2 /} g), 14.3 parts by mass of dispersant A for inorganic particles, and 65.7 parts by mass of methyl ethyl ketone were mixed. 50 g of this mixture was placed in a dispersing machine (manufactured by AIMEX, 1500 rpm, 150 g of zirconium oxide particles having a particle diameter of 0.1 mm), and dispersed for 3 hours to obtain a dispersion A. The median diameter of the inorganic particles in the dispersion A was 67 nm.

Example 3

Dispersion B was prepared in the same manner as in Comparative Example 2 except that the dispersant A for inorganic particles was changed to dispersant B for inorganic particles. The median diameter of the inorganic particles in the dispersion B was 45 nm.

Example 4

The dispersion C was prepared in the same manner as in Comparative Example 2 except that the dispersant A for the inorganic particles was changed to the dispersant C for inorganic particles. The median diameter of the inorganic particles in the dispersion C was 44 nm.

According to the above results, it is understood that the dispersing agents A and C of the inorganic particles of the present invention have a higher ability to agglomerate and disperse the inorganic particles than the dispersing agent A for inorganic particles.

Comparative example 3

125 parts by mass of the dispersion A, 50 parts by mass of dipentaerythritol hexaacrylate, and a photopolymerization initiator (2-methyl-1-(4-methylphenylthio)-2- 2 parts by mass of morphyl propane-1-one, Irgacure 907), and 325 parts by mass of methyl ethyl ketone were mixed to obtain a curable composition.

The obtained curable composition was applied onto a polyethylene terephthalate film to a thickness of 2 μm using a #12 bar coater, dried at 80 ° C for 3 minutes, and irradiated with a high pressure mercury lamp at 400 mJ/cm ^{2 .} Light, thereby obtaining a cured film A. The Martens hardness of the cured film A was 251.2 N/mm. Further, the Martens hardness was measured using a Picentor.

Example 5

A cured film was obtained by the same method as Comparative Example 3 except that the dispersion A was changed to the dispersion B. The Martens hardness of the cured film B was 290.4 N/mm.

From the above results, it is understood that a cured product having a high hardness can be obtained in the case where the dispersant B for inorganic particles is used as compared with the case of using the dispersant A for inorganic particles.

Comparative example 4

125 parts by mass of the dispersion A, 50 parts by mass of a polyfunctional acrylate (GX-8781K; manufactured by Dai-Il Pharmaceutical Co., Ltd.), a photopolymerization initiator (2-methyl-1-(4-methylphenylthio) )-2- 2 parts by mass of morphyl propane-1-one, Irgacure 907), and 325 parts by mass of methyl ethyl ketone were mixed to obtain a curable composition.

The obtained curable composition was applied to a polyethylene terephthalate film (Cosmoshine A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 188 μm using a #12 bar coater, and a hot air circulation type dryer was used at 80 ° C. Dry for 3 minutes. Next, a concentrating type high-pressure mercury lamp (UV light having a wavelength of 365 nm, 313 nm, and 254 nm as a main component, manufactured by Eye Graphics, Inc., 1 lamp type, 120 W/cm, lamp height 9.8 cm, conveyor belt speed 5.7 m) /min) UV light having a cumulative irradiation amount of 400 mJ/cm ² (254 nm) was irradiated to form a cured film having a thickness of 2 μm, thereby obtaining a laminated film A. The haze, total light transmittance, refractive index, and yellow index of the laminated film A were measured. The results are shown in Table 1.

Example 6

A cured film was formed in the same manner as in Comparative Example 4 except that the dispersion A was changed to the dispersion C, whereby the laminated film C was obtained. The haze, total light transmittance, refractive index, and yellow index of the laminated film C were measured. The results are shown in Table 1.

(haze and total light transmittance)

The measurement was carried out in accordance with JIS K 7105. Haze Meter NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd. was used as the measuring device. Furthermore, the total light transmittance (TT) is the ratio (%) of the light that is transmitted through the sample among the incident light. As transmitted light, there are diffused rays and parallel rays. The total light transmittance is the sum of the diffused light transmittance (DF) and the parallel light transmittance.

(TT)=(DF)+(parallel light transmittance)

Further, the haze ratio (Hz) (%) is a ratio (%) of the diffused light transmittance to the total light transmittance.

(Hz)=(DF)/(TT)×100

(refractive index)

The refractive index with respect to light of 589 nm was measured using a High-speed spectrum ellipsometer M-2000D manufactured by J.A. Woollam.

(Method for measuring Martens hardness)

The Martens hardness was tested using a surface film property tester Picodentor HM500 manufactured by Fischer Instruments.

(light resistance [yellow index: YI])

The YI of the laminated film immediately after the production was measured. Define this value as "YI0 hours". Next, light having a wavelength range of 300 to 700 nm and an irradiation intensity of 500 w/cm ^{2 was} irradiated from above the produced laminated film for 180 hours. Then, the YI of the laminated film was measured. Define this value as "YI 180 hours". Further, YI is a degree indicating that the hue is deviated from colorless or white to yellow. The measurement was carried out using a spectrophotometer (NIPPON DENSHOKU SD5000) in accordance with JIS K7373:2006.

As shown in Table 1, it is understood that a cured product having excellent light resistance and high hardness can be obtained in the case of using the dispersant C for inorganic particles in the case of using the dispersant A for inorganic particles. Moreover, when the dispersing agent C for inorganic particles is used, since the dispersibility of the zirconia particles is good, the refractive index becomes high.

Example 7

To a 200 mL flask, 50.8 g of tetrahydrofuran and 0.05 g of lithium chloride were added, and the mixture was cooled to -60 °C. A hexane solution (concentration: 15.4% by mass) containing 1.05 g of n-butyllithium was added thereto, and then 0.3 g of diisopropylamine was added thereto, followed by stirring for 10 minutes. It took 5 minutes to add DMAEMA 3.65 g to it. After the completion of the dropwise addition, the mixture was stirred until DMAEMA could not be detected by gas chromatography. Next, a mixture of 4.8 g of methyl methacrylate (hereinafter abbreviated as MMA) and 7.2 g of TMPMA was added dropwise over 10 minutes. After the completion of the dropwise addition, the mixture was stirred until gas chromatography could not detect MMA and TMPMA. Then, 0.4 g of methanol was added to make the activity disappear. A copolymer block having a polymer block of DMAEMA and MMA/TMPMA, a block copolymer having a number average molecular weight (Mn) of 5,600 and a molecular weight distribution (Mw/Mn) of 1.18 was obtained.

To the liquid containing the block copolymer, 40 mL of ethyl acetate was added. Next, it was washed three times with water. Then, the obtained polymer was dissolved in PGMEA. 0.8 mole of BzCl was added relative to DMAEMA 1 molar. A mixed liquid composed of 70% by mass of PGMEA and 30% by mass of PGME was added so that the solid content concentration was 35%. Thereafter, the mixture was aged at 80 ° C for 5 hours to obtain a dispersant D for inorganic particles.

A curable composition and a cured film were produced in the same manner as described above using the dispersant D for inorganic particles. In the case where the dispersant A for inorganic particles is used, the cured film using the dispersant D for inorganic particles is excellent in light resistance.

Claims (10)

A dispersing agent for inorganic particles, comprising a block copolymer comprising a polymer block (a) and a polymer block (b), wherein the polymer block (a) contains a repeat selected from the group consisting of a tertiary amino group At least one repeating unit of the group consisting of a repeating unit having a quaternary ammonium salt structure, the polymer block (b) containing a repeating unit selected from the group consisting of a crosslinkable functional group and a structure having a function of capturing a radical At least one repeating unit of the group consisting of repeating units, the radical being produced by oxidation of light. The dispersing agent for inorganic particles according to the first aspect of the invention, wherein the repeating unit having a crosslinkable functional group is the formula (I) (In the formula (I), R ¹ represents a hydrogen atom or a C1 to C3 alkyl group, and R ² and R ³ each independently represent a hydrogen atom or a C1 to C6 alkyl group, and Q represents an oxygen group which may have an alkyl group as a substituent. A repeating unit represented by a saturated heterocyclic group or a C2 to C20 alkenyl group, and n1 represents a repeating number of CR ² R ³ and is an integer of 0 to 6). The dispersing agent for inorganic particles according to the first aspect of the invention, wherein the repeating unit having a structure for capturing a radical is a repeating unit represented by the formula (I'), and the radical is oxidized by light. produce (In the formula (I'), R ⁰ represents a hydrogen atom or a C1 to C3 alkyl group, and P ¹ , P ² , P ³ and P ⁴ each independently represent a C1 to C6 alkyl group, P ¹ , P ² , P ³ And the alkyl groups of C1 to C6 of P ⁴ may be bonded to each other to form a ring, X represents a divalent linking group, Y represents a hydrogen atom, an oxy group or an alkyl group of C1 to C6, n2 represents 0 or 1, and r represents C1. ~C3 alkyl, m represents 0 or 1). The dispersing agent for inorganic particles according to claim 1 is composed of a block copolymer containing a polymer block (a) and a polymer block (b), wherein the polymer block (a) contains four a repeating unit of the ammonium salt structure, the polymer block (b) contains a 2,2,6,6-tetraalkylpiperidine structure, a 2,2,5,5-tetraalkylpyrrole structure, 1,2 , a repeating unit of a 2,6,6-pentaalkylpiperidine structure or a 1,2,2,5,5-pentapyrrolidinium structure. The dispersing agent for inorganic particles according to any one of claims 1 to 4, wherein the repeating unit having a quaternary ammonium salt structure is a repeating unit represented by the formula (II) (In the formula (II), R ⁴ represents a hydrogen atom or a C1 to C3 alkyl group, and R ⁵ , R ⁶ and R ⁷ each independently represent a C1 to C6 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group, and X represents C1 ~ C10 alkylene group or a C1 ~ C10 alkylene group -O-C1 ~ C10 alkylene group, Z ^- represents a counter anion (counteranion)). The dispersing agent for inorganic particles according to any one of claims 1 to 5, wherein the polymer block (b) further contains a repeating unit represented by the formula (III) (In the formula (III), R ⁸ represents a hydrogen atom or a C1 to C3 alkyl group, and R ⁹ represents a C1 to C20 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group). A composition comprising an inorganic particle, a dispersing agent for inorganic particles according to any one of claims 1 to 6, and a dispersion medium. A curable composition comprising an inorganic particle, a dispersing agent for inorganic particles according to any one of claims 1 to 6, and a curable component. A cured product obtained by hardening a hardenable composition of claim 8 of the patent application. A film obtained by hardening a hardenable composition of claim 8 of the patent application.