TWI587914B - Ceramic microparticle dispersant, ceramic microparticle dispersion composition, and ceramic microparticle dispersion sheet - Google Patents

Description

Ceramic microparticle dispersant, ceramic microparticle dispersion composition, and ceramic microparticle dispersion sheet

The present invention relates to a novel ceramic microparticle dispersant, a ceramic microparticle dispersion composition, and a ceramic microparticle dispersion sheet.

The present application claims priority to Japanese Patent Application No. 2015-086675, filed on Apr. 21, 2015, and the Japanese Patent Application No. 2015-217370, filed on In this article.

In various fields, a material in which a finely divided substance is uniformly dispersed in a resin or a solvent is sought. If the substance is micronized, aggregates are generally formed. Therefore, when the fine particles are dispersed in a resin or a solvent, the aggregate must be crushed by some methods. As a method of crushing the aggregate, there are mechanical dispersion or interfacial chemical methods. As one of the interface chemistry methods, a method of using a polymer dispersant is known.

Various polymer dispersants have been proposed since the beginning. For example, Patent Document 1 proposes a copolymer comprising: a block chain (A) containing a group consisting of a repeating unit selected from a repeating unit having a tertiary amino group and a quaternary ammonium salt group; a polymer of at least one repeating unit; and a block chain (B) comprising a copolymer comprising a repeating unit having a polyoxyalkylene chain and a repeating unit having an acidic group. It is described that the copolymer can be used for pigment dispersion in paints, printing inks, inkjet inks, pigment dispersions for color filters, and the like.

Patent Document 2 proposes a copolymer comprising: a block chain (A) comprising at least 1 selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group. a repeating unit; and a block chain (B) comprising a repeating unit having an acidic group and the following formula (I)

(wherein R ¹ represents a hydrogen atom or a C1 to C3 alkyl group, R ² represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group), and the copolymerization ratio of the repeating unit represented by the formula (I) is embedded In the segment chain (B), it is 90% by mass or more. It is described that the copolymer can be used for pigment dispersion in paints, printing inks, inkjet inks, pigment dispersions for color filters, and the like.

Patent Document 3 proposes a copolymer comprising: a block chain (A) comprising at least 1 selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group. a repeating unit; and a block chain (B) comprising the following formula (I): wherein R ¹ represents a hydrogen atom or the like, R ² and R ³ each independently represent a hydrogen atom, and Q represents an alkyl group. The oxygen-saturated heterocyclic group as a substituent, n represents a repeating unit represented by any one of 0 to 6 and the following formula (II): wherein R ⁴ represents a hydrogen atom or the like, and R ⁵ represents saturation. a repeating unit represented by an aliphatic hydrocarbon group or the like, and a copolymerization ratio of the repeating unit represented by the above formula (II) is 90% by weight in the block chain (B) excluding the repeating unit represented by the above formula (I) the above. It is described that the copolymer can be used for dispersion of various organic pigments in paints, printing inks, inkjet inks, pigment dispersions for color filters, and the like, and metal oxides, metal hydroxides, metal carbonates, and metal sulfates. Dispersion of inorganic particles such as salts, metal silicates, metal nitrides, or dispersion of carbon nanotubes.

Patent Document 4 proposes a dispersing agent for inorganic particles comprising a block copolymer comprising: a polymer block (a) comprising a repeating unit selected from a group having a tertiary amino group and having four stages At least one repeating unit of the group consisting of repeating units of the ammonium salt structure; and a polymer block (b) comprising a repeating unit selected from the group consisting of having a crosslinkable functional group, and having a trapped light At least one repeating unit of the group consisting of repeating units of the structure of the function of radicals generated under oxidation.

In recent years, with the miniaturization and high performance of electronic equipment, components used in the electronics industry have also required miniaturization and high performance. In the manufacturing steps of the above members, the micronized ceramic particles must be dispersed in water or various solvents. However, the smaller the particle diameter of the ceramic particles, the more difficult it is to disperse. Among the ceramic fine particles, in particular, boron nitride fine particles or niobium carbide fine particles are difficult to disperse. Patent Document 5 proposes a mechanical dispersion method in which fine particles such as tantalum carbide are dispersed using a rotor stator homogenizer. However, a polymer dispersant capable of dispersing boron nitride fine particles or niobium carbide fine particles well has not been found.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: WO2011/129078

Patent Document 2: WO2012/001945

Patent Document 3: WO2012/063435

Patent Document 4: WO2014/109308

Patent Document 5: WO2014/132445

An object of the present invention is to provide a novel ceramic fine particle dispersant which can disperse ceramic fine particles such as tantalum carbide or boron nitride in a dispersion medium such as an organic solvent. Further, an object of the present invention is to provide a composition comprising the above ceramic fine particle dispersant, ceramic fine particles, and a dispersion medium.

In order to achieve the above object, the research was repeated, and the present invention including the following aspects was completed.

(1) A ceramic fine particle dispersant comprising a block polymer (wherein an acidic group is not contained), the block polymer comprising: a block chain (A) having the 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 each independently represent an alkyl group or an aralkyl group. Or a heteroarylalkyl group, Z- represents a repeating unit represented by a counteranion; and a block chain (B) having the formula [III] [Chemical 4]

(In the formula [III], R ³¹ represents a hydrogen atom or an alkyl group, X ³ represents -NH- or -O-, and R ³³ represents an alkyl group, an aralkyl group or a heteroarylalkyl group).

(2) The ceramic fine particle dispersing agent according to (1), wherein the block chain (A) further comprises 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, and R ²² and R ²³ each independently represent an alkyl group or an aralkyl group. Or a repeating unit represented by a heteroaralkyl group.

(3) The ceramic fine particle dispersing agent according to (1), wherein the block chain (B) further comprises the formula [IV] [Chemical 6]

(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, m represents an integer of any of 1 to 100, and R ⁴³ represents a hydrogen atom. Or a repeating unit represented by an alkyl group.

The ceramic fine particle dispersing agent according to any one of (1) to (3), wherein the ceramic fine particles are boron nitride fine particles or cerium carbide fine particles.

(5) A composition containing the ceramic fine particle dispersant according to any one of (1) to (4), a dispersion medium, and ceramic fine particles.

(6) The composition according to (5), wherein the dispersion medium is a thermoplastic resin.

(7) The composition according to (5), which further comprises a vulcanizing agent;

(8) A sheet obtained by heat-forming a composition according to (7).

The ceramic fine particle dispersant of the present invention can disperse ceramic fine particles such as lanthanum carbide or boron nitride in a dispersion medium.

(ceramic microparticle dispersant)

The ceramic fine particle dispersant of the present invention includes a block polymer each having at least one of the block chain (A) and the block chain (B) described below.

Further, the block polymer of the present invention does not have an acidic group such as a -COOH group, a -SO ₃ H group or a -PO(OH) ₂ group.

The number average molecular weight (Mn) of the block polymer in the present invention is preferably from 2,000 to 200,000, more preferably from 2,000 to 50,000, still more preferably from 3,000 to 20,000. Further, the molecular weight distribution of the block polymer of the present invention is preferably from 1.0 to 2.5, more preferably from 1.0 to 2.0, in terms of a weight average molecular weight/number average molecular weight (Mw/Mn) ratio.

Further, the weight average molecular weight and the number average molecular weight are based on standard polymethyl methacrylate measured by gel permeation chromatography (GPC) using N,N-dimethylformamide as a solvent. The molecular weight is converted to a value obtained.

The block polymer of the present invention may contain other block chains in addition to the block chain (A) and the block chain (B), and the block chain (A) and (in the block polymer of the present invention) The total content of B) is usually from 1 to 100% by weight, preferably from 10 to 100% by weight, particularly preferably 100% by weight. The weight ratio of the block chain (A) to the block chain (B) is not particularly limited, and is preferably 5/95 to 95/5.

(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 in R ¹¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, and the like. The base of carbon number is 1~6.

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

In the formula [I], Y ¹ represents a divalent linking group.

Examples of the divalent linking group in Y ¹ include an alkylene group, an alkyl-O-alkylene group, and the like.

Examples of the alkylene group include a methylene group, an ethyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a butane-2,3 group. -diyl, pentane-1,5-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, hexane-1,6-diyl, octane a group having a carbon number of 1 to 10 such as a 1,8-diyl group or a decane-1,10-diyl group.

The alkyl-O-alkylene group means a group in which an alkyl group and an alkylene group are bonded via an -O- bond. Examples of the alkylene-O-alkylene group include a group having 2 to 10 carbon atoms such as ethyl-O-extended ethyl group and ethyl-O-trimethylene group.

R ¹² to R ¹⁴ each independently represent an alkyl group, an aralkyl group or a heteroarylalkyl group.

Examples of the alkyl group in R ¹² to R ¹⁴ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, and a n-pentyl group. The base of the hexyl group is 1 to 6 carbon atoms.

Examples of the aralkyl group in R ¹² to R ¹⁴ include an aryl group having 6 to 10 carbon atoms such as a benzyl group, a phenethyl group or a 3-phenylpropyl group bonded to an alkyl group having 1 to 6 carbon atoms. The basis.

Examples of the heteroarylalkyl group in R ¹² to R ¹⁴ include pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-ylmethyl and the like having at least one N, O or S as A hetero atom, a group of 5 to 10 heteroaryl groups bonded to an alkyl group having 1 to 6 carbon atoms.

Z- represents a counter anion.

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

The ratio of the repeating unit represented by the formula [I] contained in the block chain (A) is preferably from 10 to 100% by weight, more preferably from 50 to 100% by weight, based on the total weight of the block chain (A). . If embedded When the ratio of the repeating unit represented by the formula [I] contained in the segment chain (A) is less than 10% by weight, the dispersion property tends to be lowered.

The repeating unit other than the repeating unit represented by the above formula [I] is 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 in R ²¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, and the like. The base of carbon number is 1~6.

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 in Y ² include an alkylene group, an alkylene-O-alkylene group, and the like.

Examples of the alkylene group include a methylene group, an ethyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a butane-2,3 group. -diyl, pentane-1,5-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, hexane-1,6-diyl, octane a group having a carbon number of 1 to 10 such as a 1,8-diyl group or a decane-1,10-diyl group.

The alkyl-O-alkylene group means a group in which an alkylene group and an alkylene group are bonded via -O-. Make Examples of the alkyl-O-alkylene group include a group having a carbon number of 2 to 10 such as ethyl-O-extended ethyl group and ethyl-O-trimethylene group.

R ²² and R ²³ each independently represent an alkyl group, an aralkyl group or a heteroaralkyl group.

Examples of the alkyl group in R ²² and R ²³ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, and a n-pentyl group. The base of the hexyl group is 1 to 6 carbon atoms.

Examples of the aralkyl group in R ²² and R ²³ include an aryl group having 6 to 10 carbon atoms such as a benzyl group, a phenethyl group or a 3-phenylpropyl group bonded to an alkyl group having 1 to 6 carbon atoms. The basis.

Examples of the heteroarylalkyl group in R ²² and R ²³ include pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-ylmethyl and the like having at least one N, O or S as A hetero atom, a group of 5 to 10 heteroaryl groups bonded to an alkyl group having 1 to 6 carbon atoms.

(block chain (B))

The block chain (B) has a repeating unit represented by the formula [III].

The ratio of the repeating unit represented by the formula [III] contained in the block chain (B) is preferably from 0.1 to 100% by weight, more preferably from 10 to 100% by weight, based on the total weight of the block chain (B). .

In the formula [III], R ³¹ represents a hydrogen atom or an alkyl group.

Examples of the alkyl group in R ³¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, and the like. The base of carbon number is 1~6.

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

In the formula [III], R ³² represents an alkyl group, an aralkyl group or a heteroarylalkyl group.

Examples of the alkyl group in R ³² include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, and the like. The base of carbon number is 1~6.

Examples of the aralkyl group in 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 is bonded to an alkyl group having 1 to 6 carbon atoms.

Examples of the heteroarylalkyl group in R ³² include pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-ylmethyl and the like having at least one N, O or S as a hetero atom. A group of 5 to 10 heteroaryl groups bonded to an alkyl group having 1 to 6 carbon atoms.

The repeating unit other than the repeating unit represented by the above formula [III] may be a repeating unit represented by the following formula [IV].

In the formula [IV], R ⁴¹ represents a hydrogen atom or an alkyl group.

Examples of the alkyl group in R ⁴¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, and the like. The base of carbon number is 1~6.

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

In the formula [IV], R ⁴² represents an alkylene group.

Examples of the alkylene group in R ⁴² include a methylene group, an ethyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a butane. -2,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, hexane-1,6-di A group having a carbon number of 1 to 10 such as a octane group, an octane-1,8-diyl group or a decane-1,10-diyl group.

The alkyl-O-alkylene group means a group in which an alkyl group and an alkylene group are bonded via an -O- bond. Examples of the alkylene-O-alkylene group include a group having 2 to 10 carbon atoms such as ethyl-O-extended ethyl group and ethyl-O-trimethylene group.

In the formula [IV], m represents any one of 1 to 100.

In the formula [IV], R ⁴³ represents a hydrogen atom or an alkyl group.

Examples of the alkyl group in R ⁴³ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, and the like. The base of carbon number is 1~6.

(other repeating units which may be contained in the block chains (A) and (B), and other repeating units in the block which may be contained)

Examples of the repeating unit which may be contained in the block chain (A) and (B) and the repeating unit which may be contained in other blocks may be derived from (meth)acrylic monomers and aromatics other than the above. A repeating unit such as a vinyl monomer or a conjugated diene monomer.

The (meth)acrylic monomer, the aromatic vinyl monomer, and the conjugated diene monomer which are the raw materials of the above-mentioned repeating unit can be exemplified as follows.

Examples of the (meth)acrylic monomer include (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, Glycidyl methacrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, etc. (meth) acrylate compound; 2-methoxyethyl (meth) acrylate, methoxy polyethylene glycol (unit number of ethylene glycol is 2~ 100) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, etc., which may be used alone or in combination of two Use above.

Examples of the aromatic vinyl monomer include styrene, o-methyl styrene, p-methyl styrene, p-tert-butyl styrene, α-methyl styrene, and p-t-butoxy styrene. , third butoxystyrene, p-(1-ethoxyethoxy)styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinyl anthracene a heteroaryl compound such as 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylthiophene or 4-vinylthiophene, etc., which can be used alone One type or two or more types are used in combination.

Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, and 2-tert-butyl-1,3-butylene. Diene, 2-phenyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentene Diene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-octadiene, 4,5-diethyl-1,3-octyl Diene, 3-butyl-1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1,3-tricycloquinone Diene, myrcene, chloroprene, etc. may be used alone or in combination of two or more.

(Manufacturing method of ceramic fine particle dispersing agent)

The method for producing the ceramic fine particle dispersant of the present invention will be described below.

(1) A method for producing a block polymer 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 the formula [Im] can be polymerized by a known living polymerization method, and a compound represented by the formula [IIIm] can be added to the reaction system to carry out a known living polymerization method.

[11]

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

Formula [HIm] In the R ^31, X ^3, R ³² of formula [III] in the R ^31, the same as X ^3, R ^32.

The obtained block polymer can be purified by a general purification method.

(2) a block chain (A) comprising a repeating unit represented by the formula [I], and a block chain having a repeating unit represented by the formula [III] and a repeating unit represented by the formula [IV] (B) Method for producing block polymer

The compound represented by the above formula [Im] can be polymerized by a known living polymerization method, and the compound represented by the above formula [IIIm] and the compound represented by the following formula [IVm] are added to the reaction system, and are known. Manufactured by living polymerization.

[Chemistry 13]

Formula [IVm] In the ^{R 41, X 4, R 42} , R 43 in the formula [IV] in the ^{R 41, X 4, R 42} , the same as R ^43.

The obtained block polymer can be purified by a general purification method.

(3) a block chain (A) comprising a repeating unit represented by the formula [I] and a repeating unit represented by the formula [II], and a repeating unit represented by the formula [III] and represented by the formula [IV] Method for producing block polymer of block chain (B) of repeating unit

First, a compound represented by the following formula [IIm] is polymerized by a known active polymerization method, and a compound represented by the above formula [IIIm] and a compound represented by the above formula [IVm] are added to the reaction system, and are known. Active polymerization. Then, it can be produced by subjecting a part of the tertiary amine group in the obtained polymer to four stages by a known method.

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

In the case of a repeating unit or other block chain other than the above formulas [I] to [IV], living compound may be added by adding a compound which is a raw material according to the above method.

As a known living polymerization method, a living anionic polymerization method or a living cationic polymerization method can be mentioned.

As a well-known four-stage method, the quaternization method using a quaternization agent is mentioned.

Examples of the quaternization agent include benzyl chloride, benzyl bromide, benzyl iodide, etc., or methyl chloride, ethyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate. A general quaternizing agent such as an ester.

The obtained block polymer can be purified by a general purification method.

The block polymer obtained as described above can be used as a ceramic fine particle dispersant either directly or dissolved or dispersed in a solvent.

Examples of the solvent include water; an aliphatic hydrocarbon solvent such as hexane, decane, dodecane or tetradecane; an alicyclic hydrocarbon solvent such as cyclohexane; an aromatic hydrocarbon solvent such as toluene or xylene; and acetone. a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; an ester solvent such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate or propylene glycol methyl ether acetate; Alcohol, n-propanol, isopropanol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerol and other alcoholic solvents; tetrahydrofuran, two Alkane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), 1-methoxy-2-propane An ether solvent such as an alcohol. The solvent may be used singly or in combination of two or more. The amount of the solvent to be used can be appropriately set depending on the viewpoint of the viscosity of the dispersant or the like. The amount of the solvent which may be contained in the dispersing agent of the present invention is preferably from 5 to 95% by weight.

The ceramic fine particle dispersant of the present invention is suitable for uniformly dispersing ceramic fine particles in a dispersion medium.

(ceramic microparticle dispersion composition)

The composition of the present invention comprises ceramic fine particles, the ceramic fine particle dispersant of the present invention, and a dispersion medium. In the composition of the present invention, it is preferred that the ceramic fine particles are uniformly dispersed in the dispersion medium.

(ceramic microparticles)

The type of the ceramic fine particles to be dispersed by the ceramic fine particle dispersant of the present invention is not particularly limited, and is preferably cerium carbide (SiC) fine particles or boron nitride (BN) fine particles, and more preferably boron nitride (BN) fine particles. Among the ceramic fine particles, the cerium carbide fine particles or the boron nitride fine particles are particularly difficult to uniformly disperse the fine particles in the dispersion medium, and therefore the ceramic fine particle dispersing agent of the present invention is useful.

The primary particle diameter of the ceramic fine particles is not particularly limited, but is preferably 1000 nm or less, more preferably 500 nm or less.

The amount of the ceramic fine particles contained in the composition of the present invention is preferably from 1 to 90% by weight, more preferably from 5 to 50% by weight, still more preferably from 5 to 30% by weight. Further, the amount of the ceramic fine particle dispersant of the present invention used in the composition of the present invention is preferably from 1 to 200 parts by weight, more preferably from 1 to 100 parts by weight, based on 100 parts by weight of the ceramic fine particles, and further preferably 1 to 50 parts by weight.

(dispersion medium)

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

Examples of the liquid dispersion medium include water; an aliphatic hydrocarbon solvent such as hexane, decane, dodecane or tetradecane; an alicyclic hydrocarbon solvent such as cyclohexane; an aromatic hydrocarbon solvent such as toluene or xylene; and acetone. a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; an ester solvent such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate or isobutyl acetate; methanol, ethanol, n-propanol , an alcohol solvent such as isopropyl alcohol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol or glycerin; tetrahydrofuran, two An ether solvent such as an alkane, an ethylene glycol monomethyl ether (methyl cellosolve), an ethylene glycol monoethyl ether (ethyl cellosolve), or an ethylene glycol monobutyl ether (butyl cellosolve). 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 in view of the viscosity of the composition and the like. The amount of the liquid dispersion medium which may be contained in the composition of the present invention is preferably from 5 to 95% by weight.

Examples of the solid dispersion medium include a thermoplastic resin, a thermosetting resin, and a photocurable resin. 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 can also be obtained by using a curable component as a solid dispersion medium.

Examples of the thermoplastic resin include polyoxyxylene resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, fluororesin, and ABS (acrylonitrile-butadiene-styrene). -butadiene-styrene) resin, AS (acrylonitrile-styrene) resin, acrylic resin, polyamine, polyacetal, polycarbonate, modified polyphenylene ether, polyparaphenylene Butylene formate, polyethylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polyfluorene, polyether oxime, amorphous polyarylate, liquid crystal polymer, polyetheretherketone, thermoplastic polysiloxane Amine, polyamidoximine, and the like. The thermoplastic resin may be heated and melted, or dissolved in a solvent, and kneaded or mixed with the ceramic fine particles and the ceramic fine particles with a dispersing agent.

The composition comprising a thermoplastic resin may further contain a vulcanizing agent. Examples of the vulcanizing agent include benzammonium peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and tributyl peroxide. Cumene, dibutyl butyl peroxide, p-methylbenzhydryl peroxide, and the like.

The sheet-shaped material can be produced by heat-forming a dispersion composition containing the ceramic fine particle dispersant of the present invention, a thermoplastic resin, a vulcanizing agent, and ceramic fine particles. The conditions for the heat molding can be appropriately set in accordance with the properties of the thermoplastic resin or the ceramic fine particles.

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

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

Examples of the monomer or oligomer used in the photocurable resin or the thermosetting resin include monofunctional (meth)acrylate monomers, monoethylenically unsaturated compounds such as styrene and acrylonitrile. Diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol Di(meth)acrylate, triethyl (meth)acrylate, PEG (polyethylene glycol) #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, pentaerythritol tri ( a polyfunctional (meth) acrylate monomer such as methyl acrylate, pentaerythritol tetra(meth) acrylate, trimethylolpropane triacrylate or trimethylolpropane tetraacrylate; (meth)acrylic acid Amino acid ester; epoxy (meth) acrylate, and the like.

Among these, dipentaerythritol hexa(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane is preferred. A polyfunctional (meth) acrylate monomer such as tetraacrylate. Further, these may be used alone or in combination of two or more.

As a polymerization initiator, those who start polymerization by light irradiation (photopolymerization initiator), and those who start polymerization by heating (thermal polymerization initiator) are mentioned. Specific examples of the polymerization initiator include an organic peroxide, an imidazole derivative, a bisimidazole derivative, an N-arylglycine derivative, an organic azide compound, a titanocene, and an aluminate. Compound, N-alkoxypyridinium salt, 9-oxosulfur Derivatives, etc.

Examples of the organic peroxide include hydrogen peroxide, tert-butyl peroxide, hydrogen peroxide, menthane, cumene hydroperoxide, hydrogen peroxide, diisopropylbenzene, and the like; and oxidized lauric acid Peroxy esters such as tributyl acrylate, tert-butyl peroxybenzoate, and tert-butyl peroxy citrate; 1,5-dibutylbutyl-3,3,5-trimethylcyclohexane Peroxy ketals such as alkanes; peroxy ketones such as ethyl acetoxyacetate; dinonyl peroxides such as benzamidine peroxide.

Other examples include benzoin, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxyphenylacetophenone, 2-ethylhydrazine.醌, 1,3-bis(t-butyldioxycarbonyl)benzophenone, 4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone, 3-phenyl-5-iso Oxazolinone, 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 Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)-butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), bis(2,4-cyclopentadiene-1- Base)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium) (trade name Irgacure 784, manufactured by Ciba Specialty Chemicals Co., Ltd.), diisopropyl peroxide Benzene, tert-butyl peroxybenzoate, tert-butylhexyne-3, and the like. These polymerization initiators may be used alone or in combination of two or more.

The composition of the present invention can be prepared by appropriately mixing the ingredients.

[Examples]

Hereinafter, the present invention will be described in detail using examples, but the technical scope of the present invention is not limited to the examples.

<Manufacture of Dispersant>

(Example 1-1)

300 g of tetrahydrofuran and 0.3 g of lithium chloride were placed in a 1000 mL flask, and the mixture was cooled to -60 °C. After adding 9.5 g of n-butyllithium (15.4 wt% concentration of hexane solution), and then adding two different 2.1 g of propylamine and stirred for 10 minutes. After adding 23.2 g of N,N-dimethylaminoethyl methacrylate (hereinafter abbreviated as DMAEMA) to the reaction system over 5 minutes, the mixture was stirred for 15 minutes. A part of the sample was sampled, and it was confirmed by GC (gas chromatography) that the monomer disappeared. 53.5 g of butyl methacrylate (hereinafter abbreviated as BMA) was added dropwise over 30 minutes in the reaction system. A part of the sample was sampled, and after confirming the disappearance of the monomer by GC measurement, 2.0 g of methanol was added to terminate the reaction.

The obtained block polymer was analyzed by GPC (mobile phase N,N-dimethylformamide, PMMA standard), and the weight average molecular weight (Mw) was 5,500, and the molecular weight distribution (Mw/Mn) was 1.24. .

The reaction solution was diluted with ethyl acetate, washed with water three times, and then subjected to solvent replacement by propylene glycol methyl ether acetate (hereinafter, abbreviated as PGMEA). 0.8 equivalent of benzyl chloride (hereinafter, abbreviated as BzCl) relative to DMAEMA was added. Further, a mixed solution of PGMEA and 1-methoxy-2-propanol (hereinafter abbreviated as PGME) in a weight ratio of 7 to 3 was added so that the concentration of the block polymer was 35% by weight. Thereafter, it was aged at 80 ° C for 5 hours to obtain Dispersant A.

(Example 2-1)

To a 500 mL flask, 190 g of tetrahydrofuran and 0.3 g of lithium chloride were added, and the mixture was cooled to -60 °C. After adding 5.8 g of n-butyllithium (15.4% by weight of a hexane solution), 1.1 g of diisopropylamine was further added and stirred for 10 minutes. After adding 15.1 g of DMAEMA to the reaction system over 5 minutes, the mixture was stirred for 15 minutes. A part was sampled, and it was confirmed by GC measurement that the monomer disappeared. A mixture of 17.1 g of BMA and 17.1 g of methoxypolyethylene glycol monomethacrylate (manufactured by PME-200 Oil Co., Ltd.) (hereinafter sometimes abbreviated as PEGMA) was added dropwise to the reaction system over 30 minutes. A part of the sample was sampled, and after confirming the disappearance of the monomer by GC measurement, 1.5 g of methanol was added to terminate the reaction.

The obtained block polymer was analyzed by GPC (mobile phase N,N-dimethylformamide, PMMA standard), and the weight average molecular weight (Mw) was 5,600. The cloth (Mw/Mn) was 1.20.

The reaction solution was diluted with ethyl acetate, washed with water three times, and then solvent-replaced by PGMEA. 0.8 equivalents of BzCl was added relative to DMAEMA. Further, a mixed solution of PGMEA and PGME in a weight ratio of 7 to 3 was added so that the concentration of the block polymer became 35% by weight. Thereafter, it was aged at 80 ° C for 5 hours to obtain a dispersant B.

<Manufacture of Composition>

(Example 1-2)

9 parts by weight of the boron nitride particles (manufactured by Showa Denko Co., Ltd., UHP-S1), 2.7 parts by weight of the dispersant A obtained in Example 1-1, and 88.3 parts by weight of methyl ethyl ketone. This mixed solution was placed in a disperser and dispersed under the following conditions to obtain a composition A. After the dispersion was started, the average particle diameter of the boron nitride particles was measured under the following conditions for a fixed period of time. The average particle size was fixed within 2 hours after the start of dispersion. The average particle diameter of the boron nitride fine particles at the time point 2 hours after the start of dispersion was 470 nm.

[Dispersion conditions]

Dispersing machine: RBM type batch Ready Mill manufactured by Aimex Co., Ltd.

Number of revolutions: 1500rpm

Amount of slurry: 30g

Dispersed beads filling amount: zirconia beads (bead diameter 0.1mm) 90g

[Measurement conditions of average particle size]

The dispersion obtained by sampling the composition was diluted 10-fold with methyl ethyl ketone, and the average particle diameter was measured using a particle size analyzer (manufactured by Malvern, Zetasizer Nano S).

(Example 2-2)

Composition B was obtained in the same manner as in Example 1-2, except that Dispersant B obtained in Example 2-1 was used instead of Dispersant A obtained in Example 1-1. After the dispersion was started, the average particle diameter of the boron nitride particles was measured under the following conditions for a fixed period of time. At the beginning The average particle size was fixed within 2 hours after dispersion. The average particle diameter of the boron nitride fine particles at the time point 2 hours after the start of dispersion was 420 nm.

(Example 3)

The composition B obtained in Example 2-2 (250 parts by weight, containing 22.5 parts by weight of boron nitride particles), polyoxyxylene resin (100 parts by weight: manufactured by KE-971-U Shin-Etsu Chemical Co., Ltd.), and vulcanized The agent (2 parts by weight: manufactured by C-8 Shin-Etsu Chemical Co., Ltd.) was put into an electrothermal high-temperature rolling machine (manufactured by Ikeda Machinery Co., Ltd.). The mixture was kneaded at 50 ° C for 1 hour to obtain a composition C. The obtained composition C was press-formed at 170 ° C for 10 minutes to obtain a sheet having a film thickness of 1 mm. The thermal conductivity (W/m‧K) of the obtained sheet was 0.465.

(Method for measuring thermal conductivity)

The thermal conductivity (W/m‧K) can be measured by the density (kg/m ³ ) measured by the underwater displacement method, the specific heat (j/kg ‧ K) measured by a differential scanning calorimeter (DSC), and It is calculated by multiplication of the thermal diffusivity (m ² /S) measured by the laser flashing thermal property measuring device.

(Example 4)

The composition B obtained in Example 2-2 (500 parts by weight, containing 45 parts by weight of boron nitride particles), polyoxyxylene resin (100 parts by weight: manufactured by KE-971-U Shin-Etsu Chemical Co., Ltd.), and vulcanized The agent (2 parts by weight: manufactured by C-8 Shin-Etsu Chemical Co., Ltd.) was put into an electrothermal high-temperature rolling machine (manufactured by Ikeda Machinery Co., Ltd.). The mixture was kneaded at 50 ° C for 1 hour to obtain a composition D. The obtained composition was press-formed at 170 ° C for 10 minutes to obtain a sheet having a film thickness of 1 mm. The thermal conductivity (W/m‧K) of the obtained sheet was 0.612.

(Comparative Example 1)

25 parts by weight of boron nitride particles (manufactured by Showa Denko Co., Ltd., UHP-S1), polyoxynoxy resin (100 parts by weight: KE-971-U Shin-Etsu Chemical Co., Ltd.) and vulcanizing agent (2,5-two) Methyl-2,5-bis(t-butylperoxide) hexane, 2 parts by weight: C-8, manufactured by Shin-Etsu Chemical Co., Ltd.) was put into an electrothermal high-temperature roller press (manufactured by Ikeda Machinery Co., Ltd.). The mixture was kneaded at 50 ° C for 1 hour to obtain a composition. The obtained composition was at 170 ° C The film was formed by press molding for 10 minutes to obtain a sheet having a film thickness of 1 mm. The thermal conductivity (W/m‧K) of the obtained sheet was 0.457.

(Comparative Example 2)

50 parts by weight of boron nitride particles (manufactured by Showa Denko Co., Ltd., UHP-S1), polyoxynoxy resin (100 parts by weight: manufactured by KE-971-U Shin-Etsu Chemical Co., Ltd.), and a vulcanizing agent (2 parts by weight: C) -8 Shin-Etsu Chemical Co., Ltd. manufactured) was put into an electrothermal high-temperature rolling machine (manufactured by Ikeda Machinery Co., Ltd.). The mixture was kneaded at 50 ° C for 1 hour to obtain a composition. The obtained composition was press-formed at 170 ° C for 10 minutes to obtain a sheet having a film thickness of 1 mm. The thermal conductivity (W/m‧K) of the obtained sheet was 0.552.

Claims (7)

A ceramic microparticle dispersant comprising a block polymer (wherein an acidic group is not included), the block polymer comprising: a block chain (A) having the 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 each independently represent an alkyl group or an aralkyl group. Or a heteroaralkyl group, Z ^- represents a repeating unit represented by a counter anion; and a block chain (B) having the 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 aralkyl group or a heteroarylalkyl group), and the ceramic is represented by a repeating unit. The microparticles are boron nitride microparticles or niobium carbide microparticles. The ceramic microparticle dispersant of claim 1, wherein the block chain (A) further comprises 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, and R ²² and R ²³ each independently represent an alkyl group or an aralkyl group. Or a repeating unit represented by a heteroaralkyl group. The ceramic microparticle dispersant of claim 1, wherein the block chain (B) further comprises 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, m represents an integer of any of 1 to 100, and R ⁴³ represents a hydrogen atom. Or a repeating unit represented by an alkyl group. A composition comprising the ceramic fine particles dispersed according to any one of claims 1 to 3 Agent, dispersion medium and ceramic microparticles. The composition of claim 4, wherein the dispersion medium is a thermoplastic resin. The composition of claim 4, which further comprises a vulcanizing agent. A sheet obtained by heat-forming a composition as claimed in claim 6.