JP6031125B2 - Dispersant for inorganic particles, composition containing the dispersant, curable composition, cured product, and thin film - Google Patents

Description

The present invention relates to a dispersant for inorganic particles capable of uniformly dispersing inorganic particles in a solvent, a resin or the like, and a composition containing the dispersant 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 thin film obtained by curing the curable composition.
This application claims priority based on Japanese Patent Application No. 2013-004098 filed in Japan on January 11, 2013 and Japanese Patent Application No. 2013-006985 filed in Japan on January 18, 2013. , The contents of which are incorporated herein.

  By uniformly dispersing the inorganic particles in the medium, the characteristics of various materials can be changed. For example, the refractive index of the transparent resin can be changed by dispersing zirconium oxide in the transparent resin. Inorganic particles tend to aggregate and generally have low dispersibility in media such as solvents and resins. Therefore, a dispersant is used to disperse the inorganic particles in a solvent, a resin or the like.

  Examples of such dispersants include ionic or nonionic surfactant-based dispersants, polymer-based dispersants such as polyvinyl alcohols, polyacrylic acid and acrylic acid copolymers, stearic acid amide, and ethylene bisamide. And amide dispersants. Patent Document 1 proposes a polymer dispersant comprising a block polymer having two types of blocks having a polymerization initiator fragment of atom transfer polymerization (ATRP) and different polarities.

JP 2002-534542 A

Since the dispersant generally has a small molecular weight, if a large amount of the dispersant is used to disperse the inorganic particles, the hardness of a material made of a polymer compound, such as a resin, may be lowered.
In addition, a resin material containing inorganic particles dispersed in a resin is required to have weather resistance, in particular, characteristics such as being hardly yellowed by light such as UV. By adding a hindered amine light stabilizer and the like in addition to the dispersant for dispersing the inorganic particles, uniform dispersion of the inorganic particles and improvement of light resistance can be realized. However, adding a large amount of dispersant and light stabilizer tends to cause adverse effects such as a decrease in the mechanical strength of the resin material, so even if higher light resistance is required, they are added in a large amount to the resin. Can not do it.

  An object of the present invention is to uniformly disperse inorganic particles in a solvent, a resin, etc., and to improve the properties of a composition containing the dispersed inorganic particles and a cured product thereof (dispersed inorganic particles And the like, and the hardness of resin cured products containing dispersed inorganic particles can be improved, etc.) A dispersant for inorganic particles, and the dispersant and inorganic particles are contained. It is to provide a composition. Furthermore, an object of the present invention is to provide a curable composition containing the dispersant for inorganic particles and a curable component, a cured product obtained by curing the curable composition, and a thin film obtained by curing the curable composition. Is to provide.

  As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention have a compound 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. Polymer comprising at least one repeating unit selected from the group consisting of a combination block (a), a repeating unit having a crosslinkable functional group, and a repeating unit having a structure having a function of capturing radicals generated by oxidation by light The block copolymer containing the block (b) was found to have excellent properties as a dispersant for inorganic particles, and the present invention was completed.

That is, this invention includes the following forms.
[1] Polymer block (a) 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, and a repeating having a crosslinkable functional group It comprises a block copolymer containing a unit and a polymer block (b) containing at least one repeating unit selected from the group consisting of repeating units having a structure having a function of capturing radicals generated by oxidation by light. Dispersant for inorganic particles.
[2] The dispersant for inorganic particles according to [1], wherein the repeating unit having a crosslinkable functional group is a repeating unit represented by the formula (I).

（式（Ｉ）中、Ｒ^１は、水素原子またはＣ１〜Ｃ３アルキル基を表し、Ｒ^２およびＲ^３は、それぞれ独立に、水素原子またはＣ１〜Ｃ６アルキル基を表し、Ｑは、置換基としてアルキル基を有していてもよい含酸素飽和ヘテロ環基、またはＣ２〜Ｃ２０アルケニル基を表し、ｎ１はＣＲ^２Ｒ^３の繰り返し数を表し且つ０〜６のいずれかの整数である。）

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

[3] The dispersant for inorganic particles according to [1], wherein the repeating unit having a structure having a function of trapping radicals generated by oxidation by light is a repeating unit represented by the formula (I ′).

（式（Ｉ’）中、Ｒ^０は、水素原子またはＣ１〜Ｃ３アルキル基を表し、Ｐ^１、Ｐ^２、Ｐ^３およびＰ^４は、それぞれ独立にＣ１〜Ｃ６のアルキル基を表し、Ｐ^１、Ｐ^２、Ｐ^３およびＰ^４のＣ１〜Ｃ６のアルキル基は、相互に結合して環を形成していてもよく、Ｘは２価の連結基を表し、Ｙは、水素原子、オキシル基またはＣ１〜Ｃ６のアルキル基を表し、ｎ２は、０または１を表し、ｒは、Ｃ１〜Ｃ３アルキル基を表し、ｍは、０または１を表す。）

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

[4] A polymer block (a) containing a repeating unit having a quaternary ammonium salt structure, a 2,2,6,6-tetraalkylpiperidine structure, a 2,2,5,5-tetraalkylpyrrolidine structure, A block copolymer comprising a polymer block (b) containing a repeating unit having a 2,2,6,6-pentaalkylpiperidine structure or a 1,2,2,5,5-pentaalkylpyrrolidine structure. Item 10. The inorganic particle dispersant according to Item 1.
[5] The dispersant for inorganic particles according to any one of [1] to [4], wherein the repeating unit having a quaternary ammonium salt structure is a repeating unit represented by the formula (II).

（式（ＩＩ）中、Ｒ^４は、水素原子またはＣ１〜Ｃ３アルキル基を表し、Ｒ^５、Ｒ^６およびＲ^７は、それぞれ独立に、Ｃ１〜Ｃ６アルキル基またはＣ６〜Ｃ１０アリールＣ１〜Ｃ６アルキル基を表し、Ｘは、Ｃ１〜Ｃ１０アルキレン基またはＣ１〜Ｃ１０アルキレン−Ｏ−Ｃ１〜Ｃ１０アルキレン基を表し、Ｚ⁻は、カウンターアニオンを表す。）

(In formula (II), R ⁴ represents a hydrogen atom or a C1-C3 alkyl group, and R ⁵ , R ⁶ and R ⁷ are each independently a C1-C6 alkyl group or a C6-C10 aryl C1-C6 alkyl group. represents a group, X represents a C1 -C10 alkylene radical or a C1 -C10 alkylene -O-C1 -C10 alkylene group, Z ^- represents a counter anion).

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

（式（ＩＩＩ）中、Ｒ^８は、水素原子またはＣ１〜Ｃ３アルキル基を表し、Ｒ^９は、Ｃ１〜Ｃ２０アルキル基またはＣ６〜Ｃ１０アリールＣ１〜Ｃ６アルキル基を表す。）

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

[7] A composition comprising inorganic particles, the dispersant for inorganic particles according to any one of [1] to [6], and a dispersion medium.
[8] A curable composition comprising inorganic particles, the dispersant for inorganic particles according to any one of [1] to [6], and a curable component.
[9] A cured product obtained by curing the curable composition according to [8].

[10] A thin film obtained by curing the curable composition according to [8].

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

  The dispersant for inorganic particles of the present invention comprises a block copolymer containing a polymer block (a) and a polymer block (b).

The polymer block (a) includes 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 the repeating unit has a quaternary ammonium salt structure. Preferred repeating units having a quaternary ammonium salt structure include repeating units represented by the formula (II).

式（ＩＩ）中、Ｒ^４は、水素原子またはＣ１〜Ｃ３アルキル基を表し、Ｒ^５、Ｒ^６およびＲ^７は、それぞれ独立に、Ｃ１〜Ｃ６アルキル基またはＣ６〜Ｃ１０アリールＣ１〜Ｃ６アルキル基を表し、Ｘは、Ｃ１〜Ｃ１０アルキレン基またはＣ１〜Ｃ１０アルキレン−Ｏ−Ｃ１〜Ｃ１０アルキレン基を表し、Ｚ^-は、カウンターアニオンを表す。なお、Ｃ１、Ｃ３、Ｃ６、Ｃ１０などは、当該基を構成する炭素原子の数を表す。

In formula (II), R ⁴ represents a hydrogen atom or a C1-C3 alkyl group, and R ⁵ , R ⁶ and R ⁷ are each independently a C1-C6 alkyl group or a C6-C10 aryl C1-C6 alkyl group. X represents a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group, and Z ⁻ represents a counter anion. 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 linear or branched. Examples of the C1-C3 alkyl group include methyl, ethyl, n-propyl, i-propyl and the like. Examples of the C1-C6 alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and the like.
Examples of the C1-C10 alkylene group include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-2,3-diyl, pentane-1,5- Examples include 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.
C6-C10 aryl C1-C6 alkyl groups include benzyl, phenethyl, 3-phenyl-n-propyl, 1-phenyl-n-hexyl, naphthalen-1-ylmethyl, 2-naphthalen-2-ylethyl, 1-naphthalene 2-yl-n-propyl, inden-1-ylmethyl and the like.
Examples of Z ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ^— .

  The proportion 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 contained in the polymer block (a) is preferably 10 to 100% by mass. It is. When the proportion 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 contained in the polymer block (a) is low, a dispersant for inorganic particles The dispersion performance tends to decrease.

  The polymer block (a) may contain a repeating unit having no tertiary amino group or quaternary ammonium salt structure. Examples of the repeating unit include a repeating unit derived from a (meth) acrylic acid monomer, a repeating unit derived from an aromatic vinyl monomer, and a repeating unit derived from a conjugated diene monomer.

  The polymer block (a) comprises 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 a tertiary amino group or quaternary ammonium salt structure. The repeating unit which does not have may be connected at random, or may be connected alternately.

  The polymer block (a) polymerizes, for example, a monomer having a tertiary amino group and / or a monomer having a quaternary ammonium salt structure and a monomer not having a tertiary amino group or quaternary ammonium salt structure as necessary. Or by polymerizing a monomer having a tertiary amino group and, if necessary, another monomer copolymerizable therewith, and then quaternizing all or part of the tertiary amino group Can do.

  Examples of the monomer having a quaternary ammonium salt structure include a monomer represented by the formula (IIm1). The symbols in formula (IIm1) have the same meaning as the symbols in formula (II). Specific examples of the monomer having a quaternary ammonium salt structure include (meth) acryloyloxyethyltrimethylammonium fluoride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium bromide, (meth) acryloyloxy. Ethyltrimethylammonium iodide, (meth) acryloyloxypropyltrimethylammonium fluoride, (meth) acryloyloxypropyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium bromide, (meth) acryloyloxypropyltrimethylammonium iodide, (meth) ) Acryloyloxybutyltrimethylammonium fluoride, (meth) acryloyloxy Tilt trimethyl ammonium chloride, (meth) acryloyloxy-butyl bromide, and (meth) acryloyloxy-butyl trimethyl ammonium iodide. These can be used alone or in combination of two or more.

  Examples of the monomer having a tertiary amino group include a monomer represented by the formula (IIm2). The symbols in formula (IIm2) have the same meaning as the symbols in formula (II). Specific examples of the monomer having a tertiary amino group include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. , Diethylaminobutyl (meth) acrylate, dimethylaminoethoxyethyl (meth) acrylate, dimethylaminoethoxypropyl (meth) acrylate, diethylaminobutoxybutyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

  Other monomers that can be used to obtain the polymer block (a) include (meth) acrylic acid; (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid n-propyl, (meta ) I-propyl acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, (Meth) acrylic acid esters such as (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid 1-ethylcyclohexyl, (meth) acrylic acid benzyl; styrene; o-methylstyrene, p-methylstyrene, pt-butylstyrene, α-methylstyrene, pt-butoxystyrene, mt-butoxystyrene , Styrene derivatives such as p- (1-ethoxyethoxy) styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid; 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2 -Vinylheteroaryl such as vinylthiophene and 4-vinylthiophene; vinylnaphthalene, vinylanthracene, etc .; 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene 2-phenyl-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 Conjugated dienes such as 3-butyl-1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1,3-tricyclodecadiene, myrcene, chloroprene, etc. Is mentioned. These can be used alone or in combination of two or more.

The polymer block (b) of the present invention has 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 radicals generated by oxidation by light. Is included.
A case where the polymer block (b) includes a repeating unit having a crosslinkable functional group is a first embodiment, and the repeating unit having a structure in which the polymer block (b) has a function of capturing radicals generated by oxidation by light. The case where it contains is demonstrated below as a 2nd aspect.

(First aspect)
In the first embodiment of the present invention, the polymer block (b) contains a repeating unit having a crosslinkable functional group. The crosslinkable functional group is preferably nonpolar or low polarity. Examples of the nonpolar or low polarity crosslinkable functional group include a group containing a carbon-carbon double bond such as ethenyl and 2-propen-2-yl, and an oxygen-containing saturated heterocyclic group such as oxiranyl and oxetanyl. The non-polar or low-polar 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. Examples of the repeating unit having a non-polar or low-polar crosslinkable functional group in the dispersant for inorganic particles of the present invention include the repeating unit represented by the formula (I).

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

The C1-C3 alkyl group or the C1-C6 alkyl group is as already described in the description of the formula (II).
The oxygen-containing saturated heterocyclic group in Q is a saturated heterocyclic group containing at least one oxygen atom as an atom constituting a ring. In addition to oxygen atoms, other heteroatoms such as nitrogen atoms and sulfur atoms may be included as atoms constituting the ring. In the oxygen-containing saturated heterocyclic group, the number of atoms constituting the ring is preferably 3 to 8, more preferably 3 to 6.
Specific examples of the oxygen-containing saturated heterocyclic group include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, morpholinyl, thiomorpholinyl and the like. Of these, oxiranyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl are preferred.
In the oxygen-containing saturated heterocyclic group in Q, a C1-C6 alkyl group may be preferably substituted on the atoms constituting the ring. The C1-C6 alkyl group is as already described in the description of the formula (II).

  As the C2-C20 alkenyl group in Q, ethenyl, 1-propenyl, 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, decenyl, pentadecenyl, eicosenyl, tricosenyl and the like. Of these, C2-C6 alkenyl groups are preferred, and ethenyl is more preferred.

  In the first embodiment of the present invention, the ratio of the repeating unit represented by the formula (I) contained in the polymer block (b) is preferably 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 a cured product obtained by curing the curable composition tends to decrease.

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

In formula (III), R ⁸ represents a hydrogen atom or a C1-C3 alkyl group, and R ⁹ represents a C1-C20 alkyl group or a C6-C10 aryl C1-C6 alkyl group.
The C1-C3 alkyl group and the C6-C10 aryl C1-C6 alkyl group are as described above in the description of the formula (II).
Examples of the C1-C20 alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, hexyl, Examples include heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and eicosyl. Of these, C1-C6 alkyl groups are preferred.

  In the first embodiment 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 within the above range, the hardness of a cured product obtained by curing the curable composition tends to be improved.

  In the first embodiment of the present invention, the polymer block (b) may contain repeating units having no quaternary ammonium salt structure other than the repeating units represented by the formulas (I) and (III). Good. Examples of the repeating unit include a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a conjugated diene monomer.

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

  In the first embodiment of the present invention, the polymer block (b), for example, polymerizes a monomer having a non-polar or low-polar crosslinkable functional group and, if necessary, another monomer copolymerizable therewith. Can be obtained by:

  Monomers having non-polar or low-polar crosslinkable functional groups include glycidyl (meth) acrylate, oxetan-2-ylmethyl (meth) acrylate, oxetane-3-ylmethyl (meth) acrylate, and (meth) acrylic acid. (2-methyloxetane-2-yl) methyl, (meth) acrylic acid (3-methyloxetane-3-yl) methyl, (meth) acrylic acid (2-ethyloxetane-2-yl) methyl, (meth) acrylic Acid (3-ethyloxetane-3-yl) methyl, (meth) acrylic acid (3-propyloxetane-3-yl) methyl, (meth) acrylic acid 2- (oxetane-2-yl) ethyl, (meth) acrylic Acid 2- (oxetane-3-yl) ethyl, (meth) acrylic acid (tetrahydrofuran-2-yl) methyl, (meth) acrylic (Tetrahydrofuran-3-yl) methyl, (meth) acrylic acid (2-methyltetrahydrofuran-2-yl) methyl, (meth) acrylic acid (3-methyltetrahydrofuran-3-yl) methyl, (meth) acrylic acid (5 -Methyltetrahydrofuran-2-yl) methyl, (meth) acrylic acid (4-methyltetrahydrofuran-2-yl) methyl, (meth) acrylic acid (3-methyltetrahydrofuran-2-yl) methyl, (meth) acrylic acid ( 2-methyltetrahydrofuran-3-yl) methyl, (meth) acrylic acid (5-methyltetrahydrofuran-3-yl) methyl, (meth) acrylic acid (4-methyltetrahydrofuran-3-yl) methyl, (meth) acrylic acid 2- (Tetrahydrofuran-3-yl) ethyl, (meth) acrylic acid Xylan-2-ylmethyl, (3-methyloxiran-2-yl) methyl (meth) acrylate, (2-methyloxiran-2-yl) methyl (meth) acrylate, and allyl (meth) acrylate, 2-methyl-2-propenyl methacrylate), (E) -buten-2-yl (meth) acrylate, (Z) -buten-2-yl (meth) acrylate, 3-butenyl (meth) acrylate , (Meth) acrylic acid 3-methyl-3-butenyl, (meth) acrylic acid (E) -penten-3-yl, (meth) acrylic acid (Z) -penten-3-yl, (meth) acrylic acid 3 -Methyl-2-butenyl and the like. Of these, allyl (meth) acrylate is preferred.

  In the first embodiment of the present invention, other monomers that can be used to obtain the polymer block (b) include methyl (meth) acrylate, ethyl (meth) acrylate, and t-butyl (meth) acrylate. , N-butyl (meth) acrylate, benzyl (meth) acrylate, and the like. Furthermore, examples of the other monomer that can be used for obtaining the polymer block (b) include the same monomers as those exemplified as the other monomer that can be used for obtaining the polymer block (a).

(Second embodiment)
In the second embodiment of the present invention, the polymer block (b) contains a repeating unit having a structure having a function of capturing radicals generated by oxidation by light. Examples of the structure having a function of capturing radicals generated by oxidation by light include structures found in hindered amine light stabilizers, for example, structures in which a bulky alkyl group is bonded to a nitrogen atom. Specifically, 2,2,6,6-tetraalkylpiperidine structure, 2,2,5,5-tetraalkylpyrrolidine structure, 1,2,2,6,6-pentaalkylpiperidine structure, 1,2, Examples include 2,5,5-pentaalkylpyrrolidine structure.

  2,2,6,6-tetraalkylpiperidine structure, 2,2,5,5-tetraalkylpyrrolidine structure, 1,2,2,6,6-pentaalkylpiperidine structure, 1,2,2,5,5 -As the repeating unit having a pentaalkylpyrrolidine structure or the like, the repeating unit represented by the formula (I ') is preferable.

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

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

  The divalent linking group in X is not particularly limited, but is preferably a single bond, a C1-C6 alkylene group or a C2-C6 alkyleneoxy group, more preferably a single bond or a C1-C6 alkyleneoxy group, A single bond is preferable.

  Examples of the C1-C6 alkylene group include methylene, ethylene, propylene, methylethylene, butylene, 1,2-dimethylethylene, pentylene, 1-methylbutylene, 2-methylbutylene and the like.

  Examples of the C2-C6 alkyleneoxy group include ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy, 1,4-butyleneoxy and 1,6-hexyleneoxy. Can be mentioned.

  In the second embodiment of the present invention, the proportion of the repeating unit represented by the formula (I ′) contained in the polymer block (b) is preferably 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 embodiment of the present invention, the polymer block (b) preferably further contains a repeating unit represented by the formula (III).

In formula (III), R ⁸ represents a hydrogen atom or a C1-C3 alkyl group, and R ⁹ represents a C1-C20 alkyl group or a C6-C10 aryl C1-C6 alkyl group.
The C1-C3 alkyl group and the C6-C10 aryl C1-C6 alkyl group are as described above in the description of the formula (II).
Examples of the C1-C20 alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, t-pentyl, Examples include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and eicosyl. Of these, C1-C6 alkyl groups are preferred.

  In the second embodiment 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 within the above range, the dispersibility of the inorganic particles tends to be improved.

  In the second embodiment of the present invention, the polymer block (b) may further include a repeating unit having a crosslinkable functional group. The crosslinkable functional group is preferably nonpolar or low polarity. Examples of the nonpolar or low polarity crosslinkable functional group include a group containing a carbon-carbon double bond such as ethenyl and 2-propen-2-yl, and an oxygen-containing saturated heterocyclic group such as oxiranyl and oxetanyl. The non-polar or low-polar 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. As a preferable repeating unit having a crosslinkable functional group in the dispersant for inorganic particles of the present invention, a repeating unit represented by the formula (IV) may be mentioned.

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

The C1-C3 alkyl group or the C1-C6 alkyl group is as already described in the description of the formula (II).
The oxygen-containing saturated heterocyclic group in Q is a saturated heterocyclic group containing at least one oxygen atom as an atom constituting a ring. In addition to oxygen atoms, other heteroatoms such as nitrogen atoms and sulfur atoms may be included as atoms constituting the ring. In the oxygen-containing saturated heterocyclic group, the number of atoms constituting the ring is preferably 3 to 8, more preferably 3 to 6.
Specific examples of the oxygen-containing saturated heterocyclic group include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, morpholinyl, thiomorpholinyl and the like. Of these, oxiranyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl are preferred.
In the oxygen-containing saturated heterocyclic group in Q, a C1-C6 alkyl group may be preferably substituted on the atoms constituting the ring. The C1-C6 alkyl group is as already described in the description of the formula (II).

  As the C2-C20 alkenyl group in Q, ethenyl, 1-propenyl, 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, decenyl, pentadecenyl, eicosenyl, tricosenyl and the like. Of these, C2-C6 alkenyl groups are preferred, and ethenyl is more preferred.

  In the second embodiment 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, the hardness of a cured product obtained by curing the curable composition tends to increase.

  In the second embodiment of the present invention, the polymer block (b) contains a tertiary amino group or a quaternary ammonium salt structure other than the repeating units represented by the formula (I ′), the formula (III) and the formula (IV). The repeating unit which does not have may be further contained. Examples of the repeating unit include a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a conjugated diene monomer.

  In the second embodiment of the present invention, the polymer block (b) may be one in which the above-mentioned repeating units are randomly connected or alternately connected.

  In the second embodiment of the present invention, the polymer block (b), for example, polymerizes a monomer having a function of scavenging radicals generated by light oxidation and, if necessary, another monomer copolymerizable therewith. Can be obtained.

  The following compounds can be exemplified as monomers having a function of capturing radicals generated by oxidation with light.

  Monomers having non-polar or low-polar crosslinkable functional groups include glycidyl (meth) acrylate, oxetan-2-ylmethyl (meth) acrylate, oxetane-3-ylmethyl (meth) acrylate, and (meth) acrylic acid. (2-methyloxetane-2-yl) methyl, (meth) acrylic acid (3-methyloxetane-3-yl) methyl, (meth) acrylic acid (2-ethyloxetane-2-yl) methyl, (meth) acrylic Acid (3-ethyloxetane-3-yl) methyl, (meth) acrylic acid (3-propyloxetane-3-yl) methyl, (meth) acrylic acid 2- (oxetane-2-yl) ethyl, (meth) acrylic Acid 2- (oxetane-3-yl) ethyl, (meth) acrylic acid (tetrahydrofuran-2-yl) methyl, (meth) acrylic (Tetrahydrofuran-3-yl) methyl, (meth) acrylic acid (2-methyltetrahydrofuran-2-yl) methyl, (meth) acrylic acid (3-methyltetrahydrofuran-3-yl) methyl, (meth) acrylic acid (5 -Methyltetrahydrofuran-2-yl) methyl, (meth) acrylic acid (4-methyltetrahydrofuran-2-yl) methyl, (meth) acrylic acid (3-methyltetrahydrofuran-2-yl) methyl, (meth) acrylic acid ( 2-methyltetrahydrofuran-3-yl) methyl, (meth) acrylic acid (5-methyltetrahydrofuran-3-yl) methyl, (meth) acrylic acid (4-methyltetrahydrofuran-3-yl) methyl, (meth) acrylic acid 2- (Tetrahydrofuran-3-yl) ethyl, (meth) acrylic acid Xylan-2-ylmethyl, (3-methyloxiran-2-yl) methyl (meth) acrylate, (2-methyloxiran-2-yl) methyl (meth) acrylate, and allyl (meth) acrylate, 2-methyl-2-propenyl methacrylate), (E) -buten-2-yl (meth) acrylate, (Z) -buten-2-yl (meth) acrylate, 3-butenyl (meth) acrylate , (Meth) acrylic acid 3-methyl-3-butenyl, (meth) acrylic acid (E) -penten-3-yl, (meth) acrylic acid (Z) -penten-3-yl, (meth) acrylic acid 3 -Methyl-2-butenyl and the like. Of these, allyl (meth) acrylate is preferred.

  In the second embodiment of the present invention, other monomers that can be used to obtain the polymer block (b) include methyl (meth) acrylate, ethyl (meth) acrylate, and t-butyl (meth) acrylate. , N-butyl (meth) acrylate, benzyl (meth) acrylate, and the like. Furthermore, examples of the other monomer that can be used for obtaining the polymer block (b) include the same monomers as those exemplified as the other monomer that can be used for obtaining the polymer block (a).

  The mass ratio of the polymer block (a) and the polymer block (b) of the present invention is not particularly limited, but is preferably 20/80 to 80/20, more preferably 40/60 to 60/40. . In addition, since the polymer block (a) is more polar than the polymer block (b), the affinity with a polar solvent or a functional group having polarity is relatively high. On the other hand, the polymer block (b) has a relatively high affinity with a nonpolar solvent or a nonpolar functional group. Generally, the surface of inorganic particles has a functional group such as a hydroxyl group. According to the polarity strength of the inorganic particle surface and the polarity strength of the dispersion medium, the mass ratio of the polymer block (a) and the polymer block (b) is set, and the inorganic particle dispersant according to the present invention is inorganic. The ability to break up and disperse the particles can be adjusted.

The block copolymer constituting the dispersant for inorganic particles of the present invention may contain a 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. Specific examples include polymer blocks containing repeating units derived from (meth) acrylic acid monomers, aromatic vinyl monomers, conjugated diene monomers, and the like. Examples of (meth) acrylic acid monomers, aromatic vinyl monomers, conjugated diene monomers and the like are the same as those already described.

The block copolymer according to the present invention has a number average molecular weight of preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 30,000. . Further, the molecular weight distribution of the block copolymer according to the present invention is preferably a ratio of weight average molecular weight / number average molecular weight, and is preferably 1.0 to 2.5, more preferably 1.0 to 2.0.
The weight average molecular weight and the number average molecular weight are values obtained by converting data measured by gel permeation chromatography (GPC) using N, N-dimethylformamide as a solvent to the molecular weight of standard polymethyl methacrylate.

  The block copolymer is not particularly limited by the production method. The block copolymer is, for example, 1) polymerizing a monomer for obtaining a polymer block (a) to obtain a polymer block (a), and subsequently adding a monomer for obtaining a polymer block (b) A method comprising growing a molecular chain of the polymer block (b) from the end of the polymer block (a); and 2) polymerizing a monomer for obtaining the polymer block (b) to obtain a polymer block (b And subsequently growing a molecular chain of the polymer block (a) from the end of the polymer block (b) by adding a monomer to obtain the polymer block (a); or 3 ) Polymerizing the monomer for obtaining the polymer block (a) to obtain the polymer block (a), separately polymerizing the monomer for obtaining the polymer block (b) to obtain the polymer block (b), Obtained polymer block Click the polymer block and (b) (a) can be obtained by a method comprising to couple.

  The block copolymer is preferably a method comprising sequentially growing molecular chains as in 1) or 2) above. Such sequential polymerization is preferably performed by a living polymerization method. Examples of the living polymerization method include a living radical polymerization method and a living anion polymerization method. Among these, the living anion polymerization method is preferable because the composition and molecular weight can be strictly controlled.

  In sequential polymerization, switching from the polymerization of the monomer to obtain the previous polymer block to the polymerization of the monomer to obtain the next polymer block has completely eliminated the monomer to obtain the previous polymer block. It can be done at the time, or it can be done when there is a little remaining. A taper portion may be formed between the two polymer blocks depending on the remaining amount of the monomer for obtaining the previous polymer block. The progress of the polymerization reaction can be confirmed by detecting the remaining amount of the monomer by gas chromatography or liquid chromatography. Further, after completion of addition of the monomer for obtaining the previous polymer block, although depending on the kind of the monomer and the solvent, stirring is performed for 1 minute to 1 hour, and then addition of the monomer for obtaining the next polymer block is started. You can also.

  The anionic polymerization initiator used in the living anionic polymerization for obtaining the block copolymer according to 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, cesium and the like. Examples of the organic alkali metal compound include alkylated products, allylated products, arylated products, and lithium amide compounds of the above alkali metals. Specifically, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, ethyl sodium, lithium biphenyl, lithium naphthalene, lithium triphenyl, sodium naphthalene, potassium naphthalene, methyl 2-lithioisobutyrate, 2- Ethyl lithioisobutyrate, isopropyl 2-lithioisobutyrate, α-methylstyrene sodium dianion, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, 1,4-dilithio-2-butene, 1,6 -Dilithiohexane, polystyryl lithium, cumyl potassium, cumyl cesium, lithium dimethylamide, lithium diethylamide, lithium dibutylamide, lithium dipropylamide, lithium diisopropylamide, lithium Diheptyl amide, lithium dihexyl amide, and the like lithium dioctyl amide. These anionic polymerization initiators can be used alone or in combination of two or more.

  The usage-amount of an anionic polymerization initiator is 0.0001-0.2 mol normally with respect to 1 mol of total amounts of the monomer to be used, Preferably it is 0.0005-0.1 mol. By using an anionic polymerization initiator in this range, the target polymer can be produced with high yield. The polymerization temperature is not particularly limited as long as it does not cause side reactions such as transfer reaction and termination reaction, and the monomer is consumed and the polymerization is completed. The concentration of the monomer relative to the polymerization solvent is not particularly limited, but is preferably 1 to 40% by mass, more preferably 2 to 15% by mass.

  It is generally 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, a monomer having a tertiary amino group is polymerized, and then the tertiary amino group is quaternized by a known method. Quaternization can be carried out using substances known as alkylating agents for tertiary amines. Specifically, benzyl chloride, benzyl bromide and benzyl iodide; alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide; sulfuric acid such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate An alkyl etc. can be mentioned.

The solvent that can be used for the living anionic polymerization is not particularly limited as long as it does not participate in the polymerization reaction and is compatible with the polymer. Specifically, polar solvents such as ether compounds such as diethyl ether, tetrahydrofuran, dioxane and trioxane, tertiary amines such as tetramethylethylenediamine and hexamethylphosphoric triamide, aliphatic and aromatic such as hexane and toluene Nonpolar solvents or low polarity solvents such as aliphatic or alicyclic hydrocarbon compounds can be exemplified. These solvents can be used alone or in combination of two or more. In the production method of the present invention, polymerization can be accurately controlled even when a nonpolar solvent or a low polarity solvent is used in combination with a polar solvent. For example, the nonpolar solvent or the low polarity solvent , 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, a dialkyl zinc such as diethyl zinc, a dialkyl magnesium such as dibutyl magnesium, or an organic metal such as triethyl aluminum can be used as a polymerization stabilizer or as a purification agent for a monomer or a solvent, if necessary. .

  In the living anion polymerization, an additive such as an alkali metal salt or an alkaline earth metal salt can be added at the start of the polymerization or during the polymerization, if necessary. Specific examples of such additives include mineral salts and halides such as sodium, potassium, barium and magnesium sulfates, nitrates and borates. More specifically, lithium And barium chloride, bromide, iodide, lithium borate, magnesium nitrate, sodium chloride, potassium chloride and the like. Among these, lithium halides such as lithium chloride, lithium bromide, lithium iodide, and lithium fluoride are preferable, and lithium chloride is particularly preferable.

  The block copolymer obtained as described above can be used as it is, or dissolved in a solvent and used as a dispersant for inorganic particles. The dispersant 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 dispersant for inorganic particles according to the present invention, and a dispersion medium. In the composition of the present invention, it is preferable 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 silica, diatomaceous earth, aluminum oxide (alumina), zinc oxide, titanium dioxide (titania), zirconium oxide (zirconia), calcium oxide, magnesium oxide, iron oxide, copper oxide, and tin oxide. , Chromium oxide, antimony oxide, yttrium oxide, cerium oxide, samarium oxide, lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, ferrites, etc .; calcium hydroxide, magnesium hydroxide, aluminum hydroxide Metal hydroxides such as basic magnesium carbonate; metal carbonates such as heavy calcium carbonate, light calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalicite; metal sulfate such as calcium sulfate, barium sulfate, gypsum fiber Metal silicates such as calcium silicate (wollastonite, zonotlite), kaolin, clay, talc, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, glass flakes; aluminum nitride, nitride Metal nitrides such as boron and silicon nitride; metal titanates such as potassium titanate, calcium titanate, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate; zinc borate, aluminum borate, etc. Metal borates; Metal phosphates such as tricalcium phosphate; Metal sulfides such as molybdenum sulfide; Metal carbides such as silicon carbide; Carbons such as carbon black, graphite, and carbon fibers; Simple metals such as gold and silver Is mentioned. The particles composed of these substances can be dispersed alone or in combination of two or more. Of these, metal oxides are preferable, and zirconium oxide (zirconia) is more preferable.
The amount of inorganic particles contained in the composition of the present invention is preferably 1 to 80% by mass, more preferably 5 to 50% by mass. Moreover, the amount of the dispersant for inorganic particles according to the present invention used in the composition of the present invention is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the inorganic particles. More preferably, it is 10-50 mass parts.

In the composition of the present invention, a liquid medium or a solid medium can be used as the dispersion medium.
Examples of liquid dispersion media include water; aliphatic hydrocarbons such as hexane, decane, dodecane, and tetradecane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones: Esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate; methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, etc. Alcohols: tetrahydrofuran, dioxane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol And the like ethers such as chromatography mono butyl ether (butyl cellosolve). Among these, from the viewpoint of 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 can be used singly 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 from the viewpoint of an appropriate composition viscosity and the like. The amount of the liquid dispersion medium that can be contained in the composition of the present invention is preferably 10 to 50% by mass.

  Examples of the solid dispersion medium include thermoplastic resins, thermosetting resins, and photocurable resins. 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 preferable to use a curable component as a solid dispersion medium to obtain a curable composition.

  Examples of the thermoplastic resin include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, fluorine resin, ABS resin, AS resin, acrylic resin, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, Examples include polyethylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polysulfone, polyether sulfone, amorphous polyarylate, liquid crystal polymer, polyether ether ketone, thermoplastic polyimide, and polyamideimide. The thermoplastic resin can be kneaded or mixed with the inorganic particles and the dispersant for inorganic particles after being melted by heating or dissolved in a solvent.

  A thermosetting resin changes from a liquid to a solid by applying heat. Examples of the thermosetting resin include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, thermosetting polyimide, and the like. Further, examples of the thermosetting resin include those containing at least a monomer and, if necessary, an oligomer and a thermal polymerization initiator.

  In addition, the photocurable resin changes from a liquid to a solid when irradiated with light (such as ultraviolet rays). Examples of the photocurable resin include those containing at least a monomer and, if necessary, an oligomer and a photopolymerization initiator.

Monomers or oligomers used in the photocurable resin or thermosetting resin include monofunctional (meth) acrylate monomers, monoethylenically unsaturated compounds such as styrene and acrylonitrile; diethylene glycol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, triethylene di (meth) acrylate, PEG # 200 di (meth) acrylate, PEG # 400 Di (meth) acrylate, PEG # 600 di (meth) acrylate, neopentyl di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythrito Polyfunctional (meth) acrylate monomers such as urtri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane tetraacrylate; urethane (meth) acrylate; epoxy (meth) acrylate It is done.
Among these, polyfunctional (meth) acrylate monomers such as dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane triacrylate, and trimethylolpropane tetraacrylate Is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

As the polymerization initiator, there are one that initiates a polymerization reaction by irradiation of light (photopolymerization initiator) and one that initiates a polymerization reaction by heating (thermal polymerization initiator). Specific examples of the polymerization initiator include organic peroxides, imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. .
Examples of organic peroxides include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, and diisopropylbenzene hydroperoxide; t-butyl peroxylaurate, t-butyl peroxide Peroxyesters such as oxybenzoate and t-butylperoxydecanoate; Peroxyketals such as 1,5-di-t-butylperoxy-3,3,5-trimethylcyclohexane; Ethyl acetoacetate peroxide Ketone peroxides such as diacyl peroxides such as benzoyl peroxide.
Others, benzoin, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxyphenylacetophenone, 2-ethylanthraquinone, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 4, 4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1, 2-diphenylethane-1-one (trade name Irgacure 651, manufactured by Ciba Specialty Chemicals), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name Irgacure 184, Ciba Specialty Chemica) Ruz Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), bis ( η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium) (trade name Irgacure 784, Ciba Specialty Chemicals ( Co., Ltd.), dicumyl peroxide, t-butyl perbenzoate, t-butylperoxyhexyne-3 and the like. These polymerization initiators can be used alone or in combination of two or more.

In the curable composition of the first aspect of the present invention, the content of inorganic particles is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional monomer, and the content of the polymerization initiator is Preferably it is 0.5-10 mass parts with respect to 100 mass parts of polyfunctional monomers, and content of the dispersing agent for inorganic particles of the first aspect of the present invention is 100 mass parts of inorganic particles. Preferably it is 1-200 mass parts. When the curable composition containing each component is cured at such a ratio, a cured product having high hardness can be obtained.
In the curable composition of the second aspect of the present invention, the content of inorganic particles is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional monomer, and the content of the polymerization initiator is The content of the dispersant for inorganic particles according to the second aspect of the present invention is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer. Preferably it is 1-200 mass parts. When the curable composition containing each component is cured at such a ratio, a cured product having excellent light resistance can be obtained.

  The composition or curable composition according to the present invention can be prepared by appropriately mixing the respective components. In the preparation of the curable composition, the dispersant for inorganic particles according to the present invention, the inorganic particles and the liquid dispersion medium are mixed to prepare the liquid composition of the present invention, which can be mixed with the curable component. Good.

The curable composition according to the present invention can be formed into a desired shape such as a film according to the use, and then irradiated with light and / or heated to obtain a cured product.
The heating is not particularly limited by the method, and can be performed using 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. Of these, ultraviolet rays are preferably used.
Irradiation with visible light can be performed using, for example, an incandescent bulb or a fluorescent lamp. Irradiation with ultraviolet rays can be performed using, for example, 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 rays to be irradiated is not particularly limited, but is preferably 150 nm to 400 nm, more preferably 200 nm to 380 nm. The atmosphere during the light irradiation may be an air atmosphere, but an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or a low oxygen concentration atmosphere is preferable. Although the temperature at the time of light irradiation is not specifically limited, Preferably it is 10-200 degreeC.

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

When the dispersant for inorganic particles according to the first aspect of the present invention is used, the curable composition according to the present invention has a functional group in the curable component and the dispersant for inorganic particles according to the present invention at the time of curing. Since the dispersant for inorganic particles binds to the solid dispersion medium that is a high molecular weight resin component by reacting with the crosslinkable functional group, the dispersant for inorganic particles does not bleed out, and the conventional curable composition A cured product having a higher hardness than the product can be obtained. In particular, when a curable composition is molded into a film and cured, a film with 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 according to the present invention can obtain a cured product having excellent light resistance. In particular, when a curable composition is formed into a film and cured, a film having excellent light resistance can be obtained.

  The present invention will be described in more detail with reference to examples. However, the technical scope of the present invention is not limited to these examples.

Comparative Example 1
Tetrahydrofuran 239.6g and lithium chloride 0.3g were put into a 500 mL flask, and it cooled to -60 degreeC. To this was added a hexane solution (concentration: 15.4% by mass) containing 5.3 g of n-butyllithium, and then 1.4 g of diisopropylamine was added, followed by stirring for 10 minutes. To this, 18.1 g of N, N-dimethylaminoethyl methacrylate (hereinafter abbreviated as DMAEMA) was added dropwise over 5 minutes. After completion of the dropwise addition, the mixture was stirred until DMAEMA was no longer detected by gas chromatography. Subsequently, 42.2 g of methyl methacrylate (hereinafter abbreviated as MMA) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred until no MMA was detected by gas chromatography. Thereafter, 2.0 g of methanol was added to make the living activity disappear. A block copolymer having a polymer block of DMAEMA and a polymer block of MMA, a number average molecular weight (Mn) of 5480, and a molecular weight distribution (Mw / Mn) of 1.15 was obtained. The number average molecular weight and the weight average molecular weight are values obtained by converting data measured by gel permeation chromatography using N, N-dimethylformamide as a solvent, with the molecular weight of standard polymethyl methacrylate.

  80 mL of ethyl acetate was added to the liquid containing the block copolymer. It was then washed 3 times with water. Thereafter, the obtained polymer was dissolved in propylene glycol 1-monomethyl ether 2-acetate (PGMEA). 0.8 mol of benzyl chloride (hereinafter abbreviated as BzCl) was added to 1 mol of DMAEMA. A mixed solution consisting 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 aged at 80 degreeC for 5 hours, and obtained the dispersing agent A for inorganic particles.

Example 1
Tetrahydrofuran 114.4g and lithium chloride 0.1g were put into a 200 mL flask, and it cooled to -60 degreeC. To this was added a hexane solution (concentration: 15.4% by mass) containing 2.1 g of n-butyllithium, then 0.5 g of diisopropylamine was added and stirred for 10 minutes. To this, 7.4 g of DMAEMA was added dropwise over 5 minutes. After completion of the dropwise addition, the mixture was stirred until DMAEMA was no longer detected by gas chromatography. Next, a mixed solution of 7.2 g of MMA and 9.6 g of allyl methacrylate (hereinafter abbreviated as AMA) was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred until MMA and AMA were not detected by gas chromatography. Thereafter, 0.8 g of methanol was added to make the living 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. It was then washed 3 times with water. Thereafter, the obtained polymer was dissolved in PGMEA. 0.8 mole of BzCl was added to 1 mole of DMAEMA. A mixed solution composed of 70% by mass of PGMEA and 30% by mass of PGMA was added so that the solid content concentration was 35%. Then, it aged at 80 degreeC for 5 hours, and obtained the dispersing agent B for inorganic particles.

Example 2
Tetrahydrofuran 101.6g and lithium chloride 0.1g were put into a 200 mL flask, and it cooled to -60 degreeC. To this was added a hexane solution (concentration: 15.4% by weight) containing 2.1 g of n-butyllithium, and then 0.6 g of diisopropylamine was added and stirred for 10 minutes. To this, 7.3 g of DMAEMA was added dropwise over 5 minutes. After completion of the dropwise addition, the mixture was stirred until DMAEMA was no longer detected by gas chromatography. Next, a mixture of 9.6 g of allyl methacrylate (hereinafter abbreviated as AMA) and 7.2 g of 2,2,6,6-tetramethyl-4-piperidyl methacrylate (hereinafter abbreviated as TMPMA) 15 g Added dropwise over a period of minutes. After completion of the dropwise addition, the mixture was stirred until AMA and TMPMA were no longer detected by gas chromatography. Thereafter, 0.8 g of methanol was added to make the living activity disappear. A block copolymer having a polymer block of DMAEMA and a copolymer block of AMA / TMPMA, 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. It was then washed 3 times with water. Thereafter, the obtained polymer was dissolved in PGMEA. 0.8 mole of BzCl was added to 1 mole of DMAEMA. A mixed solution composed of 70% by mass of PGMEA and 30% by mass of PGMA 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 C for inorganic particles.

Comparative Example 2
45.0 parts by mass of zirconia particles (Nippon Denko Corporation, PCS60; primary particle size 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 the mixture was placed in a disperser (150 g of zirconia beads having a beads diameter of 0.1 mm, manufactured by Imex Co., Ltd.) and dispersed for 3 hours to obtain dispersion A. The median diameter of the inorganic particles in dispersion A was 67 nm.

Example 3
Dispersion B was prepared in the same manner as in Comparative Example 2 except that inorganic particle dispersant A was changed to inorganic particle dispersant B. The median diameter of the inorganic particles in dispersion B was 45 nm.

Example 4
Dispersion C was prepared in the same manner as in Comparative Example 2 except that inorganic particle dispersant A was changed to inorganic particle dispersant C. The median diameter of the inorganic particles in dispersion C was 44 nm.

  From the above results, it can be seen that the dispersants B and C for inorganic particles according to the present invention have higher ability to loosen and disperse the aggregation of inorganic particles than the dispersant A for inorganic particles.

Comparative Example 3
125 parts by mass of dispersion A, 50 parts by mass of dipentaerythritol hexaacrylate, 2 parts by mass of a photopolymerization initiator (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, Irgacure 907), And 325 mass parts of methyl ethyl ketone was mixed, and the curable composition was obtained.
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 then light of 400 mJ / cm ² was applied using a high-pressure mercury lamp. Irradiated to obtain a cured film A. The Martens hardness of the cured film A was 251.2 N / mm. The Martens hardness was measured using a picodenter.

Example 5
A cured film was obtained in the same manner as in 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 can be seen that a higher degree of cured product is obtained when the inorganic particle dispersant B is used than when the inorganic particle dispersant A is used.

Comparative Example 4
Dispersion A 125 parts by mass, polyfunctional urethane acrylate (GX-8781K; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), photopolymerization initiator (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane -1-one, Irgacure 907) 2 parts by mass, and methyl ethyl ketone 325 parts by mass were mixed to obtain a curable composition.
The obtained curable composition was applied onto a polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 188 μm using a # 12 bar coater, and dried at 80 ° C. for 3 minutes using a hot air circulation dryer. I let you. Next, a concentrating high-pressure mercury lamp (UV light mainly composed of 365 nm, 313 nm, and 254 nm wavelengths, manufactured by Eye Graphics, 1 lamp type, 120 W / cm, lamp height 9.8 cm, conveyor speed 5.7 m / Min) was irradiated with UV light with an integrated dose of 400 mJ / cm @ 2 (254 nm) to form a cured film having a thickness of 2 .mu.m, and a laminated film A was obtained. 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 laminated film C was obtained by forming a cured film in the same manner as in Comparative Example 4 except that the dispersion A was changed to the dispersion C. 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)
Measured according to JIS K 7105. Nippon Denshoku Industries Co., Ltd. haze meter NDH-300A was used as a measuring device. The total light transmittance (TT) is a ratio (%) of incident light that has been transmitted through the sample. The transmitted light includes diffuse light and parallel light. The total light transmittance is the sum of diffuse light transmittance (DF) and parallel light transmittance.
(TT) = (DF) + (parallel light transmittance)
The haze rate (Hz) (%) is the ratio (%) of the diffused light transmittance to the total light transmittance.
(Hz) = (DF) / (TT) × 100

(Refractive index)
J. et al. A. The refractive index for light of 589 nm was measured using a high-speed spectroscopic ellipsometer M-2000D manufactured by Woollam.

(Measurement method of Martens hardness)
Martens hardness was measured using a surface coating property tester Picodenter HM500 manufactured by Fischer Instruments.

(Light resistance [Yellow Index: YI])
The YI of the laminated film immediately after production was measured. This value was defined as “YI 0 hour”. 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 manufactured laminated film for 180 hours. Thereafter, YI of the laminated film was measured. This value was defined as “YI 180 hours”. YI indicates the degree to which the hue leaves the yellow direction from colorless or white. In accordance with JIS K7373: 2006, measurement was performed using a spectrocolorimeter (NIPPON DENSHOKU SD5000).

  As Table 1 shows, the case where the inorganic particle dispersant C is used is superior to the case where the inorganic particle dispersant A is used in that a cured product having excellent light resistance and high hardness can be obtained. Recognize. In addition, the refractive index is higher in the case of using the dispersant C for inorganic particles because the dispersibility of the zirconia particles is better.

Example 7
A 200 mL flask was charged with 50.8 g of tetrahydrofuran and 0.05 g of lithium chloride, and cooled to -60 ° C. To this was added a hexane solution (concentration: 15.4 wt%) containing 1.05 g of n-butyllithium, then 0.3 g of diisopropylamine was added, and the mixture was stirred for 10 minutes. To this, 3.65 g of DMAEMA was added dropwise over 5 minutes. After completion of the dropwise addition, the mixture was stirred until DMAEMA was no longer detected by gas chromatography. Subsequently, a mixed liquid of 4.8 g of methyl methacrylate (hereinafter abbreviated as MMA) and 7.2 g of TMPMA was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was stirred until MMA and TMPMA were no longer detected by gas chromatography. Thereafter, 0.4 g of methanol was added to make the living activity disappear. A block copolymer having a polymer block of DMAEMA and a copolymer block of MMA / TMPMA, a number average molecular weight (Mn) of 5600, and a molecular weight distribution (Mw / Mn) of 1.18 was obtained.

  40 mL of ethyl acetate was added to the liquid containing the block copolymer. It was then washed 3 times with water. Thereafter, the obtained polymer was dissolved in PGMEA. 0.8 mole of BzCl was added to 1 mole of DMAEMA. A mixed solution composed of 70% by mass of PGMEA and 30% by mass of PGMA was added so that the solid content concentration was 35%. Then, it aged at 80 degreeC for 5 hours, and obtained the dispersing agent D for inorganic particles.

  A curable composition and a cured film were prepared using the dispersant D for inorganic particles in the same manner as described above. The light resistance of the cured film was better when the inorganic particle dispersant D was used than when the inorganic particle dispersant A was used.

Claims (3)

And inorganic particles, a dispersing agent for non-machine particles, a composition comprising a dispersion medium,
The dispersant for inorganic particles is a repeating unit having a tertiary amino group and formula (II):

(In formula (II), R ⁴ represents a hydrogen atom or a C1-C3 alkyl group, R ⁵ , R ⁶ and R ⁷ each independently represent a C1-C6 alkyl group, and X represents C1-C10 An alkylene group, Z ⁻ represents a counter anion.) And a polymer block (a) containing a repeating unit represented by formula (2) and a repeating unit containing a repeating unit having a 2,2,6,6-tetraalkylpiperidine structure. A block copolymer containing a combined block (b) and having a weight average molecular weight / number average molecular weight ratio of 1.0 to 2.0,
A composition wherein the dispersion medium is a ketone . The polymer block (b) is
Formula (III)

2. In Formula (III), R < ⁸ > represents a hydrogen atom or a C1-C3 alkyl group, and R < ⁹ > represents the C1-C20 alkyl group. Composition . The composition according to claim 1 or 2 , wherein the inorganic particles are zirconium oxide.