JP2018030051A - Inorganic particle dispersant and inorganic particle dispersion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel inorganic particle dispersant capable of dispersing excellently boron nitride fine particles into an organic solvent.SOLUTION: An inorganic particle dispersant includes a block copolymer containing a block chain having a repeating unit expressed by figure [I].SELECTED DRAWING: None

Description

  The present invention relates to a novel inorganic particle dispersant and inorganic particle dispersion composition.

  In various fields, there is a demand for materials in which finely divided substances are uniformly dispersed in a resin or a solvent. When the substance is made into fine particles, aggregates are generally formed. Therefore, when the fine particles are dispersed in a resin or a solvent, the aggregates must be crushed by some method. Examples of a method for crushing the aggregate include mechanical dispersion and a surface chemical method. As one of surface chemical methods, a method using a polymer dispersant is known.

  Conventionally, various polymer dispersants have been proposed. For example, in Patent Document 1, a block chain (A) composed of a polymer 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 base, A copolymer containing a repeating unit having an oxyalkylene chain and a block chain (B) composed of a copolymer containing a repeating unit having an acidic group has been proposed. The copolymer is described as being useful for pigment dispersion in paints, printing inks, inkjet inks, pigment dispersions for color filters, and the like.

  In Patent Document 2, a block chain (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 base, a repeating unit having an acidic group, and Formula (I)

(In the formula, R ¹ represents a hydrogen atom or a C1-C3 alkyl group, and R ² represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.) B) and a copolymer having a copolymerization ratio of the repeating unit represented by the formula (I) of 90% by mass or more in the block chain (B) has been proposed. The copolymer is described as being useful for pigment dispersion in paints, printing inks, inkjet inks, pigment dispersions for color filters, and the like.

In Patent Document 3, a block chain (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 base, and the following formula (I) (formula In the formula, R ¹ represents a hydrogen atom, R ² and R ³ each independently represent a hydrogen atom, and Q represents an oxygen-containing saturated heterocyclic group which may have an alkyl group as a substituent. N represents an integer of 0 to 6, and the following formula (II) (wherein R ⁴ represents a hydrogen atom or the like, and R ⁵ represents A block chain (B) containing a repeating unit represented by the following formula (II), wherein the copolymerization ratio of the repeating unit represented by the following formula (II) is: 90% by weight or less in the block chain (B) excluding the repeating unit represented by Copolymers have been proposed are. The copolymer is used for the dispersion of various organic pigments in paints, printing inks, inkjet inks, pigment dispersions for color filters, metal oxides, metal hydroxides, metal carbonates, metal sulfates, metal It is described that it is useful for dispersion of inorganic particles such as silicate and metal nitride, and dispersion of carbon nanotubes.

  In Patent Document 4, a 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 crosslinkable functional group A block copolymer comprising a repeating unit having a polymer block (b) containing at least one repeating unit selected from the group consisting of repeating units having and a repeating unit having a function of capturing radicals generated by oxidation by light There has been proposed a dispersant for inorganic particles comprising:

  In recent years, with the miniaturization and high performance of electronic devices, there is a demand for miniaturization and high performance of members used in the electronic industry. In the manufacturing process of the member, it is necessary to disperse the finely divided inorganic particles in water or various solvents. However, dispersion becomes more difficult as the particle size of the inorganic particles becomes smaller. Among inorganic particles, especially boron nitride fine particles and silicon carbide fine particles are difficult to disperse. Patent Document 5 proposes a mechanical dispersion method in which fine particles such as boron nitride fine particles and silicon carbide are dispersed using a rotor / stator homogenizer. However, a polymer dispersant capable of satisfactorily dispersing the boron nitride fine particles has not been known.

WO2011 / 129078 brochure WO2012 / 001945 brochure WO2012 / 063435 Pamphlet WO2014 / 109308 brochure WO2014 / 132445 brochure

  An object of the present invention is to provide a novel inorganic particle dispersant capable of dispersing inorganic particles such as boron nitride in a dispersion medium such as an organic solvent. Moreover, the objective of this invention is providing the composition containing the said inorganic particle dispersing agent, an inorganic particle, and a dispersion medium.

  As a result of repeated studies to achieve the above object, the present invention including the following aspects has been completed.

（式〔Ｉ〕中、Ｒ^１１は、水素原子またはアルキル基を示し、Ｘ^１は、−ＮＨ−または−Ｏ−を示し、Ｙ^１は、二価の連結基を示し、Ｒ^１２〜Ｒ^１４は、それぞれ独立に、アルキル基、アリールアルキル基またはヘテロアリールアルキル基を示し、Ｚ⁻はカウンターアニオンを示す。）で表される繰り返し単位を有するブロック鎖（Ａ）と、式〔III〕

（式〔III〕中、Ｒ^３１は、水素原子またはアルキル基を示し、Ｘ^３は、−ＮＨ−または−Ｏ−を示し、Ｒ^３２は、アルキル基、アリールアルキル基またはヘテロアリールアルキル基を示す。）で表される繰り返し単位を有するブロック鎖（Ｂ）を含み、ブロック鎖（Ａ）とブロック鎖（Ｂ）の総重量に対してブロック鎖（Ａ）を２５〜７５重量％含有するブロック共重合体（ただし、酸性基を含まない）を含有する無機粒子分散剤や、
〔２〕ブロック鎖（Ａ）が、さらに、式〔II〕

（式〔II〕中、Ｒ^２１は、水素原子またはアルキル基を示し、Ｘ^２は、−ＮＨ−または−Ｏ−を示し、Ｙ^２は、二価の連結基を示し、Ｒ^２２、Ｒ^２３は、それぞれ独立に、アルキル基、アリールアルキル基またはヘテロアリールアルキル基を示す。）で表される繰り返し単位を含む〔１〕に記載の無機粒子分散剤や、
〔３〕ブロック鎖（Ｂ）が、さらに、式〔IV〕

（式〔IV〕中、Ｒ^４１は、水素原子またはアルキル基を示し、Ｘ^４は、−ＮＨ−または−Ｏ−を示し、Ｒ^４２は、アルキレン基を示し、ｍは、１〜１００のいずれかの整数を示し、Ｒ^４３は、水素原子またはアルキル基を示す。）で表される繰り返し単位を含む〔１〕に記載の無機粒子分散剤や、
〔４〕〔１〕〜〔３〕のいずれかに記載の無機粒子分散剤と、分散媒と、無機粒子とを含有する組成物や、
〔５〕分散媒が、熱可塑性樹脂である〔４〕に記載の組成物に関する。 That is, the present invention
[1] Formula [I]

(In the formula [I], R ¹¹ represents a hydrogen atom or an alkyl group, X ¹ represents —NH— or —O—, Y ¹ represents a divalent linking group, and R ^{12 to} R ^14. are each independently an alkyl group, an arylalkyl group or heteroarylalkyl group, Z ^-. the block chain (a) having a repeating unit represented by showing a counter anion), formula (III)

(In the formula [III], R ³¹ represents a hydrogen atom or an alkyl group, X ³ represents —NH— or —O—, and R ³² represents an alkyl group, an arylalkyl group or a heteroarylalkyl group. And a block chain containing 25 to 75% by weight of the block chain (A) with respect to the total weight of the block chain (A) and the block chain (B). Inorganic particle dispersant containing a polymer (but not containing an acid group),
[2] The block chain (A) further has the formula [II]

(In the formula [II], R ²¹ represents a hydrogen atom or an alkyl group, X ² represents —NH— or —O—, Y ² represents a divalent linking group, R ²² , R ²³ Each independently represents an alkyl group, an arylalkyl group or a heteroarylalkyl group.) The inorganic particle dispersant according to [1], comprising a repeating unit represented by:
[3] The block chain (B) is further represented by the formula [IV]

(In the formula [IV], R ⁴¹ represents a hydrogen atom or an alkyl group, X ⁴ represents —NH— or —O—, R ⁴² represents an alkylene group, and m represents any one of 1 to 100. And R ⁴³ represents a hydrogen atom or an alkyl group.) The inorganic particle dispersant according to [1], which includes a repeating unit represented by:
[4] A composition containing the inorganic particle dispersant according to any one of [1] to [3], a dispersion medium, and inorganic particles,
[5] The composition according to [4], wherein the dispersion medium is a thermoplastic resin.

  The inorganic particle dispersant of the present invention can disperse inorganic particles such as boron nitride in a dispersion medium.

(Inorganic particle dispersant)
The inorganic particle dispersant of the present invention contains a block copolymer containing at least one block chain (A) and block chain (B) described below. The inorganic particle dispersant of the present invention may contain a polymer or the like known as an inorganic particle dispersant in addition to the block copolymer.
Further, the block copolymer of the present invention does not have an acidic group such as a —COOH group, a —SO ₃ H group, and a —PO (OH) ₂ group.

Although the number average molecular weight (Mn) of the block copolymer in this invention is not specifically limited, 2,000-200,000, 2,000-50,000, 3,000-20,000, 5,000-20 , 7,000, 20,000 to 20,000, 10,000 to 20,000, and the like can be selected. The molecular weight distribution of the block copolymer according to the present invention is selected from 1.0 to 2.5, 1.0 to 2.0, etc., in the ratio of weight average molecular weight / number average molecular weight (Mw / Mn). be able to.
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 based on the molecular weight of standard polymethyl methacrylate.

The block copolymer of the present invention may contain other block chains in addition to the block chain (A) and the block chain (B), but the block chain (A) and The total content of (B) is usually 1 to 100% by weight, preferably 50 to 100% by weight, particularly preferably 100% by weight.
The ratio of the block chain (A) to the total weight of the block chain (A) and the block chain (B) is 25 to 75% by weight, 30 to 75% by weight, 35 to 75% by weight, 40 to 75% by weight, 25 to 25% by weight. 70%, 30-70%, 35-70%, 40-70%, 25-65%, 30-65%, 35-65%, 40-65%, 25-60% %, 30-60 wt%, 35-60 wt%, 40-60 wt%, 25-55 wt%, 30-55 wt%, 35-55 wt%, 40-55 wt%, 25-50 wt%, 30-50 weight%, 35-50 weight%, 40-50 weight%, 25-45 weight%, 30-45 weight%, 35-45 weight%, 40-45 weight%, etc. can be selected. When the ratio of the block chain (A) in the total weight of the block chain (A) and the block chain (B) is more than 75% by weight, the dispersion performance tends to be lowered.

(Block chain (A))
The block chain (A) has a repeating unit represented by the formula [I].

In the formula [I], R ¹¹ represents a hydrogen atom or an alkyl group.
Examples of the alkyl group for R ¹¹ include 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, and n-hexyl. Can be mentioned.

In the formula [I], X ¹ represents —NH— or —O—.

In formula [I], Y ¹ represents a divalent linking group.
Examples of the divalent linking group for Y ¹ include an alkylene group and an alkylene-O-alkylene group.
Examples of the alkylene group include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-2,3-diyl, pentane-1,5-diyl and pentane. A group having 1 to 10 carbon atoms such as -1,4-diyl, 2-methylbutane-1,4-diyl, hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl; Can be mentioned.
An alkylene-O-alkylene group means a group in which an alkylene group and an alkylene group are bonded through an —O— bond. Examples of the alkylene-O-alkylene group include groups having 2 to 10 carbon atoms such as ethylene-O-ethylene group and ethylene-O-trimethylene group.

R ^{12 to} R ¹⁴ each independently represents an alkyl group, an arylalkyl group, or a heteroarylalkyl group.
Examples of the alkyl group for R ^{12 to} R ¹⁴ include carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, and n-hexyl. The group of 1-6 can be mentioned.
Examples of the arylalkyl group in R ^{12 to} R ¹⁴ include a group in which an aryl group having 6 to 10 carbon atoms such as benzyl group, phenethyl group, and 3-phenylpropyl group and an alkyl group having 1 to 6 carbon atoms are bonded. it can.
The heteroarylalkyl group in R ^{12 to} R ¹⁴ has at least one N, O, or S as a hetero atom such as a pyridin-2-ylmethyl group, a pyridin-3-ylmethyl group, a pyridin-4-ylmethyl group And a group in which a heteroaryl group having 5 to 10 members and an alkyl group having 1 to 6 carbon atoms are bonded.

Z ⁻ represents a counter anion.
Examples of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

  The proportion of the repeating unit represented by the formula [I] contained in the block chain (A) is 10 to 100% by weight, 20 to 100% by weight, 30 to 100% by weight with respect to the total weight of the block chain (A). %, 40 to 100% by weight, 50 to 100% by weight, 60 to 100% by weight, 70 to 100% by weight, and the like can be selected. When the proportion of the repeating unit represented by the formula [I] contained in the block chain (A) is less than 10% by weight, the dispersion performance tends to be lowered.

  Examples of the repeating unit other than the repeating unit represented by the formula [I] include a repeating unit represented by the following formula [II].

In the formula [II], R ²¹ represents a hydrogen atom or an alkyl group.
Examples of the alkyl group for R ²¹ include 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, and n-hexyl. Can be mentioned.

In the formula [II], X ² represents —NH— or —O—.

In the formula [II], Y ² represents a divalent linking group.
Examples of the divalent linking group for Y ² include an alkylene group and an alkylene-O-alkylene group.
Examples of the alkylene group include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-2,3-diyl, pentane-1,5-diyl and pentane. A group having 1 to 10 carbon atoms such as -1,4-diyl, 2-methylbutane-1,4-diyl, hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl; Can be mentioned.
An alkylene-O-alkylene group means a group in which an alkylene group and an alkylene group are bonded via —O—. Examples of the alkylene-O-alkylene group include groups having 2 to 10 carbon atoms such as ethylene-O-ethylene group and ethylene-O-trimethylene group.

R ²² and R ²³ each independently represents an alkyl group, an arylalkyl group, or a heteroarylalkyl group.
Examples of the alkyl group for R ²² and R ²³ include carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, and n-hexyl. The group of 1-6 can be mentioned.
Examples of the arylalkyl group for R ²² and R ²³ include a group in which an aryl group having 6 to 10 carbon atoms such as benzyl group, phenethyl group, and 3-phenylpropyl group and an alkyl group having 1 to 6 carbon atoms are bonded. it can.
The heteroarylalkyl group for R ²² and R ²³ has at least one N, O, or S as a hetero atom, such as a pyridin-2-ylmethyl group, a pyridin-3-ylmethyl group, or a pyridin-4-ylmethyl group. And a group in which a heteroaryl group having 5 to 10 members and an alkyl group having 1 to 6 carbon atoms are bonded.

(Block chain (B))
The block chain (B) has a repeating unit represented by the formula [III].
The proportion of the repeating unit represented by the formula [III] contained in the block chain (B) is 0.1 to 100% by weight, 1 to 100% by weight, 10 to 10% by weight based on the total weight of the block chain (B). 100% by weight, 20-100% by weight and the like can be selected.

In the formula [III], R ³¹ represents a hydrogen atom or an alkyl group.
Examples of the alkyl group in R ³¹ include 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and the like. Can be mentioned.

In the formula [III], X ³ represents —NH— or —O—.

In the formula [III], R ³² represents an alkyl group, an arylalkyl group or a heteroarylalkyl group.
^Examples of the alkyl group for R ³² include 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, and n-hexyl. Can be mentioned.
^Examples of the arylalkyl group for R ³² include a group in which an aryl group having 6 to 10 carbon atoms such as a benzyl group, a phenethyl group, or a 3-phenylpropyl group and an alkyl group having 1 to 6 carbon atoms are bonded.
The heteroarylalkyl group for R ³² has at least one N, O, or S as a hetero atom, such as a pyridin-2-ylmethyl group, a pyridin-3-ylmethyl group, a pyridin-4-ylmethyl group, and the number of members. The group which 5-10 heteroaryl groups and the C1-C6 alkyl group couple | bonded can be mentioned.

  Examples of the repeating unit other than the repeating unit represented by the formula [III] include a repeating unit represented by the following formula [IV].

In the formula [IV], R ⁴¹ represents a hydrogen atom or an alkyl group.
The alkyl group in R ^41, methyl, ethyl, n- propyl, i- propyl, n- butyl, s- butyl, i- butyl, t- butyl, n- pentyl, carbon atoms such as n- hexyl 1-6 Can be mentioned.

In the formula [IV], X ⁴ represents —NH— or —O—.

In the formula [IV], R ⁴² represents an alkylene group.
As the alkylene group for R ⁴² , methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-2,3-diyl, pentane-1,5- 1 to 10 carbon atoms such as diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl The group of is mentioned.

  In formula [IV], m represents an integer of 1 to 100.

In the formula [IV], R ⁴³ represents a hydrogen atom or an alkyl group.
^Examples of the alkyl group for R ⁴³ include 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, and n-hexyl. Can be mentioned.

(Other possible repeating units in the block chains (A) and (B) and other possible repeating units in the block)
Other repeating units that can be contained in the block chains (A) and (B), and other repeating units that can be contained in the block include (meth) acrylic acid-based monomers other than those described above, aromatic vinyl-based monomers, Examples thereof include repeating units derived from conjugated diene monomers.
Examples of the (meth) acrylic acid-based monomer, aromatic vinyl-based monomer, and conjugated diene-based monomer that are the raw materials for the repeating unit include the following.
Examples of (meth) acrylic acid monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth ) N-butyl acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, glycidyl (meth) acrylate, (meta ) (Meth) acrylate compounds such as cyclohexyl acrylate, 2-ethylhexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate , Methoxypolyethylene glycol (ethylene glycol has 2 to 100 units) (meth) acrylate, Toxipolyethylene glycol (the number of ethylene glycol units is 2 to 100) (meth) acrylate, phenoxypolyethylene glycol (the number of ethylene glycol units is 2 to 100) (meth) acrylate, and the like can be exemplified, and these are used alone. Or a mixture of two or more.

  Examples of the aromatic vinyl monomer include styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, α-methylstyrene, pt-butoxystyrene, mt-butoxystyrene, p- (1 -Ethoxyethoxy) styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinylanthracene, 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylthiophene And heteroaryl compounds such as 4-vinylthiophene, and the like. These can be used alone or in admixture of two or more.

  Conjugated diene monomers include 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, 3-butyl-1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1,3-tri Examples thereof include cyclodecadiene, myrcene, chloroprene, and the like. These can be used alone or in combination of two or more.

(Method for producing block copolymer)
The manufacturing method of the block copolymer of this invention is demonstrated below.

(1) A method for producing a block copolymer comprising a block chain (A) having a repeating unit represented by the formula [I] and a block chain (B) having a repeating unit represented by the formula [III] The compound represented by [Im] is polymerized by a known living polymerization method, and the compound represented by the formula [IIIm] is added to the reaction system to perform the known living polymerization method.

In the formula ^{[Im], R 11, X 1, Y} 1, R 12, R 13, R 14 and Z, ^R 11 in the formula ^{[I], X 1, Y 1, R} 12, R 13, R ¹⁴ and Z are the same.

In the formula ^{[IIIm], R 31,} X 3, R ³² are the same as ^{R 31,} X ^{3, R 32} in the formula [III].
The obtained block copolymer can be purified by a general purification method.

(2) A block chain (A) having a repeating unit represented by the formula [I], and a block chain (B) having a repeating unit represented by the formula [III] and a repeating unit represented by the formula [IV] The compound represented by the above formula [Im] is polymerized by a known living polymerization method, and the compound represented by the above formula [IIIm] and the following formula [IVm] in the reaction system It can manufacture by adding the compound represented and performing well-known living polymerization.

In the formula ^{[IVm], R 41, X 4, R} 42, R 43 are the same as ^R 41 in the formula ^{[IV], X 4, R 42, R} 43.
The obtained block copolymer can be purified by a general purification method.

(3) a block chain (A) having a repeating unit represented by the formula [I] and a repeating unit represented by the formula [II], a repeating unit represented by the formula [III] and a formula represented by the formula [IV] First, the compound represented by the following formula [IIm] is polymerized by a known living polymerization method, and the above formula [IIIm] ] And the compound represented by the above formula [IVm] are added to carry out known living polymerization. Subsequently, it can manufacture by quaternizing a part of tertiary amino group in the obtained copolymer by a well-known method.

In the formula ^{[IIm], R 21, X 2, Y 2} , R 22, R 23 are the same as ^{R 21, X 2, Y 2} , R 22, R 23 in the formula [II].

Even when a repeating unit other than the above formulas [I] to [IV] and other block chains are contained, living polymerization can be performed by adding a compound as a raw material according to the above method.
Known living polymerization methods include living anionic polymerization methods and living cationic polymerization methods.
A known quaternization method includes a quaternization method using a quaternizing agent.
As the quaternizing agent, benzyl chloride, benzyl bromide, benzyl iodide and the like, methyl chloride, ethyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate and the like are common. A quaternizing agent can be mentioned.
The obtained block copolymer can be purified by a general purification method.

The block copolymer obtained as described above can be used as an inorganic particle dispersant as it is or after being dissolved or dispersed in a solvent.
Solvents include water; aliphatic hydrocarbon solvents such as hexane, decane, dodecane, and tetradecane; alicyclic hydrocarbon solvents such as cyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like Ketone solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, propylene glycol methyl ether acetate, etc .; methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, diethylene glycol, Alcohol solvents such as triethylene glycol, propylene glycol, glycerin; tetrahydrofuran, dioxane, ethylene glycol monomethyl ether (methyl cellosolve), ethyl Glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), and ether solvents such as 1-methoxy-2-propanol can be exemplified. A solvent can be used individually by 1 type or in combination of 2 or more types. The amount of the solvent used can be appropriately set from the viewpoint of appropriate dispersant viscosity and the like. The amount of the solvent that can be contained in the dispersant of the present invention is preferably 5 to 95% by weight.
The inorganic particle dispersant of the present invention is suitable for uniformly dispersing inorganic particles in a dispersion medium.

(Inorganic particle dispersion composition)
The composition of the present invention contains inorganic particles, the inorganic particle dispersant of 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.

(Inorganic particles)
The kind of inorganic particles that can be dispersed with the inorganic particle dispersant of the present invention is not particularly limited, but silica, diatomaceous earth, aluminum oxide (alumina), zinc oxide, titanium dioxide (titania), zirconium oxide (zirconia), calcium oxide. , Magnesium oxide, iron oxide, copper oxide, tin oxide, chromium oxide, antimony oxide, yttrium oxide, cerium oxide, samarium oxide, lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, ferrites and other metal oxides Metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate; metal carbonates such as heavy calcium carbonate, light calcium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalisite; Calcium sulfate , Metal sulfates such as barium sulfate and gypsum fiber; calcium silicate (wollastonite, zonotlite), kaolin, clay, talc, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, glass Metal silicates such as flakes; metal nitrides such as aluminum nitride, boron nitride, silicon nitride; metal titanates such as potassium titanate, calcium titanate, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate Metal borate such as zinc borate and aluminum borate; Metal phosphate such as tricalcium phosphate; Metal sulfide such as molybdenum sulfide; Metal carbide such as silicon carbide; Carbon black, graphite, carbon fiber, etc. Carbon; gold, silver Such as how simple metal, and the like. The particles composed of these substances can be dispersed alone or in combination of two or more. Of these, boron nitride is more preferred.

  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.

  The amount of inorganic particles contained in the composition of the present invention is 1 to 90% by weight, 5 to 80% by weight, 5 to 70% by weight, 5 to 60% by weight, 5 to 50% by weight, 5 to 40% by weight, 5-30 weight% etc. can be selected. Moreover, the amount of the inorganic particle dispersant according to the present invention used in the composition of the present invention is 1 to 200 parts by weight, 1 to 100 parts by weight, 1 to 50 parts by weight, etc. with respect to 100 parts by weight of the inorganic particles. Can be selected.

(Dispersion medium)
In the composition of the present invention, a liquid medium or a solid medium can be used as the dispersion medium.
Examples of the liquid dispersion medium include water; aliphatic hydrocarbon solvents such as hexane, decane, dodecane, and tetradecane; alicyclic hydrocarbon solvents such as cyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; acetone, methyl ethyl ketone, and methyl isobutyl. Ketone solvents such as ketone; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate; methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, Alcohol solvents such as propylene glycol and glycerin; tetrahydrofuran, dioxane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl acetate) Cellosolve), and ether-based solvents such as ethylene glycol monobutyl ether (butyl cellosolve) and the like. 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 5 to 95% by weight.

  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, a curable composition may be used as a solid dispersion medium to form a curable composition.

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

The composition containing a thermoplastic resin may further contain a vulcanizing agent. As vulcanizing agents, benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, Examples thereof include p-methylbenzoyl peroxide.
A sheet-like material can be produced by thermoforming the dispersion composition containing the inorganic particle dispersant, the thermoplastic resin, the vulcanizing agent, and the inorganic particles of the present invention. The conditions for the heat molding can be appropriately set according to the properties of the thermoplastic resin and the inorganic particles.

  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 rutri (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 ( 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.) Product), 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.

  The composition according to the present invention can be prepared by appropriately mixing each component.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, the technical scope of this invention is not limited to these illustrations.

<Manufacture of inorganic particle dispersant>
[Example 1]
190 g of tetrahydrofuran (hereinafter abbreviated as THF) and 0.3 g of lithium chloride were added to the flask and cooled to −60 ° C. After adding 5.8 g of n-butyllithium (15.4 wt% hexane solution), 1.1 g of diisopropylamine was further added and stirred for 10 minutes. Into the reaction system, 15.1 g of dimethylaminoethyl methacrylate (hereinafter abbreviated as DMAEMA) was added dropwise over 5 minutes, followed by stirring for 15 minutes. A part was sampled, and the disappearance of the monomer was confirmed by gas chromatography (hereinafter abbreviated as GC) measurement.
Next, a mixture of 17.1 g of n-butyl methacrylate (hereinafter abbreviated as nBMA) and 17.1 g of methoxypolyethylene glycol monomethacrylate (PME-200 manufactured by NOF Corporation) (hereinafter abbreviated as PEGMA) After dropwise addition over 30 minutes, the mixture was stirred for 15 minutes. A part was sampled, and after confirming the disappearance of the monomer by GC measurement, 1.5 g of methanol was added to stop the reaction.
When the obtained polymer was analyzed by gel permeation chromatography (hereinafter abbreviated as GPC) (mobile phase N, N-dimethylformamide, PMMA standard), the weight average molecular weight (Mw) was 5600, and the molecular weight distribution (Mw / Mn) was 1.20.
The reaction solution was diluted with ethyl acetate, washed with water three times, and then solvent-substituted with 2-methoxy-1-methylethyl acetate (hereinafter abbreviated as PGMEA). 0.8 equivalent of benzyl chloride (hereinafter abbreviated as BzCl) was added to DMAEMA. Further, PGMEA was added so that the copolymer concentration was 35% by weight. Then, the inorganic particle dispersing agent a was obtained by ageing | curing | ripening at 80 degreeC for 5 hours. The synthesized block copolymer contains 42% by weight of the block chain (A).

[Comparative Example 1]
To the flask, 403.3 g of THF and 2.1 g of lithium chloride were added. After cooling to −60 ° C., 17.1 g of n-butyllithium (15.4 wt% hexane solution) was added. Furthermore, 4.1 g of diisopropylamine was added and stirred for 15 minutes. Next, 3.8 g of methyl isobutyrate was added and the mixture was further stirred for 15 minutes. A mixture of 49.8 g of nBMA and 49.8 g of PEGMA was dropped into the reaction system over 45 minutes, and then stirred for 15 minutes. A part was sampled, and the disappearance of the monomer was confirmed by measuring GC.
Next, 10.9 g of DMAEMA was added dropwise, and the reaction was continued for 30 minutes after the addition. After sampling a part and confirming the disappearance of the monomer by measuring GC, the reaction was stopped by adding 6.7 g of methanol.
When the obtained polymer was analyzed by GPC (mobile phase N, N-dimethylformamide, PMMA standard), the molecular weight (Mw) was 4600, and the molecular weight distribution (Mw / Mn) was 1.12.
The reaction solution was diluted with THF and hexane, washed twice with water, and then the solvent was distilled off. The solvent was replaced with PGMEA. 0.8 equivalents of BzCl was added to DMAEMA. Further, PGMEA was added so that the copolymer concentration was 35% by weight. Then, the inorganic particle dispersing agent b was obtained by ageing | curing | ripening at 80 degreeC for 5 hours. The synthesized block copolymer contains 14% by weight of the block chain (A).

[Example 2]
75.0 g of THF and 0.1 g of lithium chloride were added to the flask and cooled to −60 ° C. After adding 5.8 g of n-butyllithium (15.4 wt% hexane solution), 0.3 g of diisopropylamine was further added and stirred for 10 minutes. Further, 0.3 g of methyl isobutyrate was added and stirred for 10 minutes. A mixture of nBMA 6.0 g and PEGMA 6.0 g was dropped into the reaction system over 15 minutes. A part was sampled and monomer disappearance was confirmed by GC measurement. DMAEMA 3.0g was dripped over 5 minutes in the reaction system, Then, it stirred for 15 minutes. A part was sampled, and after confirming the disappearance of the monomer by GC measurement, 0.5 g of methanol was added to stop the reaction.
When the obtained polymer was analyzed by GPC (mobile phase N, N-dimethylformamide, PMMA standard), the weight average molecular weight (Mw) was 5000 and the molecular weight distribution (Mw / Mn) was 1.20.
The reaction solution was diluted with ethyl acetate, washed with water three times, and then the solvent was replaced with PGMEA. 0.8 equivalents of BzCl was added to DMAEMA. Further, PGMEA was added so that the copolymer concentration was 35% by weight. Then, the inorganic particle dispersing agent c was obtained by ageing | curing | ripening at 80 degreeC for 5 hours. The synthesized block copolymer contains 30% by weight of the block chain (A).

[Example 3]
75.0 g of THF and 0.1 g of lithium chloride were added to the flask and cooled to −60 ° C. After adding 5.8 g of n-butyllithium (15.4 wt% hexane solution), 0.3 g of diisopropylamine was further added and stirred for 10 minutes. Further, 0.3 g of methyl isobutyrate was added and stirred for 10 minutes. In the reaction system, a mixture of 3.0 g of nBMA and 3.0 g of PEGMA was added dropwise over 10 minutes. A part was sampled and monomer disappearance was confirmed by GC measurement. After dropping 9.1 g of DMAEMA into the reaction system over 10 minutes, the mixture was stirred for 15 minutes. A part was sampled, and after confirming the disappearance of the monomer by GC measurement, 0.5 g of methanol was added to stop the reaction.
When the obtained polymer was analyzed by GPC (mobile phase N, N-dimethylformamide, PMMA standard), the weight average molecular weight (Mw) was 4500, and the molecular weight distribution (Mw / Mn) was 1.22.
The reaction solution was diluted with ethyl acetate, washed with water three times, and then the solvent was replaced with PGMEA. 0.8 equivalents of BzCl was added to DMAEMA. Further, PGMEA was added so that the copolymer concentration was 30% by weight. Then, the inorganic particle dispersing agent d was obtained by ageing | curing | ripening at 80 degreeC for 5 hours. The synthesized block copolymer contains 71% by weight of the block chain (A).

<Production of dispersion composition>
[Distribution condition]
Dispersing machine: RBM type batch-type ready mill rotating speed manufactured by Imex Corporation: 1500 rpm
Slurry amount: 30g
Dispersed bead filling amount: 90 g of zirconia beads (bead diameter 0.1 mm)

[Measurement conditions for average particle size]
The dispersion sampled from the dispersion composition was diluted 10 times from the dispersion medium, and then the average particle size was measured using a particle size analyzer (manufactured by Malvern, Zetasizer Nano S).

[Example 4]
9 parts by weight of boron nitride particles (manufactured by Showa Denko KK, UHP-S1), 2.7 parts by weight of the inorganic particle dispersing agent a obtained in Example 1, and 88.3 parts by weight of methyl ethyl ketone were mixed. The mixed solution was put into a disperser and dispersed under the above conditions to obtain a dispersion composition. After the start of dispersion, the average particle diameter of the boron nitride particles was measured under the following conditions at regular intervals. The average particle diameter of the boron nitride fine particles at the time point of 2 hours after the start of dispersion was 420 nm.

[Comparative Example 2]
9 parts by weight of boron nitride particles (manufactured by Showa Denko KK, UHP-S1), 2.7 parts by weight of the inorganic particle dispersant b obtained in Comparative Example 1, and 88.3 parts by weight of methyl ethyl ketone were mixed. The mixed solution was put into a disperser and dispersed under the above conditions to obtain a dispersion composition. After the start of dispersion, the average particle diameter of the boron nitride particles was measured under the following conditions at regular intervals. The average particle diameter of the boron nitride fine particles at 4 hours after the start of dispersion was 4300 nm.

[Example 5]
9 parts by weight of boron nitride particles (manufactured by Showa Denko KK, UHP-S1), 2.6 parts by weight of the inorganic particle dispersant c obtained in Example 2, and 88.4 parts by weight of methyl ethyl ketone were mixed. The mixed solution was put into a disperser and dispersed under the above conditions to obtain a dispersion composition. After the start of dispersion, the average particle diameter of the boron nitride particles was measured under the following conditions at regular intervals. The average particle diameter of the boron nitride fine particles at the time point of 2 hours after the start of dispersion was 660 nm.

[Example 6]
9 parts by weight of boron nitride particles (manufactured by Showa Denko KK, UHP-S1), 3 parts by weight of the inorganic particle dispersant d obtained in Example 3, and 88 parts by weight of methyl ethyl ketone were mixed. The mixed solution was put into a disperser and dispersed under the above conditions to obtain a dispersion composition. After the start of dispersion, the average particle diameter of the boron nitride particles was measured under the following conditions at regular intervals. The average particle diameter of the boron nitride fine particles at the time point of 2 hours after the start of dispersion was 590 nm.

Claims (5)

Formula [I]

(In the formula [I], R ¹¹ represents a hydrogen atom or an alkyl group, X ¹ represents —NH— or —O—, Y ¹ represents a divalent linking group, and R ^{12 to} R ^14. are each independently an alkyl group, an arylalkyl group or heteroarylalkyl group, Z ^-. the block chain (a) having a repeating unit represented by showing a counter anion), formula (III)

(In the formula [III], R ³¹ represents a hydrogen atom or an alkyl group, X ³ represents —NH— or —O—, and R ³² represents an alkyl group, an arylalkyl group or a heteroarylalkyl group. And a block chain containing 25 to 75% by weight of the block chain (A) with respect to the total weight of the block chain (A) and the block chain (B). An inorganic particle dispersant containing a polymer (however, an acid group is not included). The block chain (A) further has the formula [II]

(In the formula [II], R ²¹ represents a hydrogen atom or an alkyl group, X ² represents —NH— or —O—, Y ² represents a divalent linking group, R ²² , R ²³ Each independently represents an alkyl group, an arylalkyl group, or a heteroarylalkyl group.) The inorganic particle dispersant according to claim 1, comprising a repeating unit represented by: The block chain (B) further has the formula [IV]

(In the formula [IV], R ⁴¹ represents a hydrogen atom or an alkyl group, X ⁴ represents —NH— or —O—, R ⁴² represents an alkylene group, and m represents any one of 1 to 100. And R ⁴³ represents a hydrogen atom or an alkyl group.) The inorganic particle dispersant according to claim 1, comprising a repeating unit represented by: The composition containing the inorganic particle dispersing agent of any one of Claims 1-3, a dispersion medium, and an inorganic particle. The composition according to claim 4, wherein the dispersion medium is a thermoplastic resin.