WO2018074349A1

WO2018074349A1 - Dispersing agent for inorganic nitrides and inorganic nitride dispersion composition

Info

Publication number: WO2018074349A1
Application number: PCT/JP2017/037141
Authority: WO
Inventors: 俊明岡戸; 祥太大隅
Original assignee: 日本曹達株式会社
Priority date: 2016-10-19
Filing date: 2017-10-13
Publication date: 2018-04-26
Also published as: TW201823288A

Abstract

The present invention addresses the problem of providing a dispersing agent for inorganic nitrides which is capable of well dispersing microparticles of an inorganic nitride such as boron nitride in a dispersion medium such as an organic solvent and which has a high heat resistance. The dispersing agent according to the present invention for inorganic nitrides comprises a block copolymer which comprises: block chain (A) containing a repeating unit having a carboxyl group; and block chain (B) containing at least one member selected from the group consisting of a repeating unit represented by formula [II] (in formula [II]: R²¹ represents a hydrogen atom or a C_1-6 alkyl group; X² represents -NH- or -O-; and R²² represents a hydrocarbon group) and a repeating unit represented by formula [III] (in formula [III]; R³ ¹ represents a hydrogen atom or a C_1-6 alkyl group; X³ represents -NH- or -O-; and R³ ² represents a group having an etheric oxygen atom), provided that the block copolymer is free from a tertiary amino group or a quaternary ammonium base.

Description

Dispersant for inorganic nitride, inorganic nitride dispersion composition

The present invention relates to a novel inorganic nitride dispersant and inorganic nitride dispersion composition. This application claims priority to Japanese Patent Application No. 2016-205454 filed on Oct. 19, 2016, the contents of which are incorporated herein by reference.

A material in which finely divided substances are uniformly dispersed in a resin or solvent is required in various fields. 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)

(Wherein 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, etc., 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 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.
Moreover, in patent document 6, it is a dispersing agent contained in the epoxy resin composition containing a boron nitride particle and an epoxy resin, Comprising: The dispersing agent which is a copolymer formed by at least 2 types of acrylic monomers is mentioned. Proposed.

WO2011 / 129078 brochure WO2012 / 001945 brochure WO2012 / 063435 Pamphlet WO2014 / 109308 brochure WO2014 / 132445 brochure JP 2008-266406 A

There has been a demand for a novel inorganic nitride dispersant that can satisfactorily disperse inorganic nitride fine particles such as boron nitride in a dispersion medium such as an organic solvent. Moreover, since the material which disperse | distributed inorganic nitride particle | grains to various dispersion media using the dispersing agent may be processed on heating conditions, the dispersing agent for inorganic nitrides which was excellent in heat resistance was calculated | required.

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

That is, the present invention relates to the following inventions.
(1) A block comprising at least one selected from the group consisting of a block chain (A) containing a repeating unit having a carboxyl group, a repeating unit represented by the formula [II] and a repeating unit represented by the formula [III] A dispersant for inorganic nitride containing a block copolymer containing a chain (B). However, the block copolymer does not contain a tertiary amino group or a quaternary ammonium base.

(In the formula [II], R ²¹ represents a hydrogen atom or a C1-6 alkyl group, X ² represents —NH— or —O—, and R ²² represents a hydrocarbon group.)

(In the formula [III], R ³¹ represents a hydrogen atom or a C1-6 alkyl group, X ³ represents —NH— or —O—, and R ³² represents a group having an etheric oxygen atom. )
(2) The inorganic nitride dispersant according to (1), wherein the hydrocarbon group of R ²² in formula [II] is an alkyl group, an arylalkyl group, a heteroarylalkyl group, a cycloalkyl group, or an allyl group .
(3) The inorganic nitride dispersant according to (1), wherein the group having an R ³² etheric oxygen atom in formula [III] is formula [III-1] or formula [III-2].

(In the formula [III-1], R ³³ represents an alkylene group, m represents an integer of 1 to 100, R ³⁴ represents a hydrogen atom or an alkyl group, and * represents a bonding position. .)

(In the formula [III-2], R ³⁵ and R ³⁶ each independently represent a hydrogen atom or a C1-C6 alkyl group, and Q may contain a C1-C6 alkyl group as a substituent. Represents an oxygen-saturated heterocyclic group, and n represents an integer of 0 to 6. * represents a bonding position.)
(4) The dispersant for inorganic nitride according to (1), wherein the repeating unit having a carboxyl group is a repeating unit represented by the formula [I].

(In the formula [I], R ¹¹ represents a hydrogen atom or a C1-6 alkyl group.)
(5) The ratio of the block chain (A) to the total weight of the block chain (A) and the block chain (B) is 15% by weight or more and 70% by weight or less, according to any one of (1) to (4) An inorganic nitride dispersant.
(6) The inorganic nitride dispersant according to any one of (1) to (5), wherein the block copolymer has a number average molecular weight (Mn) of 2,000 to 100,000.
(7) The inorganic nitride dispersant according to any one of (1) to (6), wherein the inorganic nitride is any of boron nitride, aluminum nitride, silicon nitride, or gallium nitride.
(8) A composition containing the dispersant for inorganic nitride according to any one of (1) to (6), a dispersion medium, and an inorganic nitride.
(9) The composition according to (8), wherein the inorganic nitride is any of boron nitride, aluminum nitride, silicon nitride, or gallium nitride.
(10) Fine particles having the inorganic nitride dispersant described in any one of (1) to (6) attached to the surface of the inorganic nitride particles.
(11) The fine particles according to (10), wherein the inorganic nitride particles are any of boron nitride fine particles, aluminum nitride fine particles, silicon nitride fine particles, or gallium nitride fine particles.

The inorganic nitride dispersant of the present invention can disperse inorganic nitride particles such as boron nitride in a dispersion medium. The inorganic nitride dispersant of the present invention is excellent in heat resistance.

(Dispersant for inorganic nitride)
The dispersant for inorganic nitride of the present invention includes 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 known polymer dispersant in addition to the block copolymer.
The block copolymer of the present invention preferably contains no tertiary amino group or quaternary ammonium base.

The number average molecular weight (Mn) of the block copolymer used in the present invention can be 2,000 to 100,000, 2,000 to 50,000, and 2,000 to 30,000. The molecular weight distribution of the block copolymer according to the present invention is 1.0 to 2.5, 1.0 to 2.4, 1.0 in terms of the ratio of weight average molecular weight / number average molecular weight (Mw / Mn). -2.3, 1.0-2.2, 1.0-2.1, 1.0-2.0, and the like can be selected.
The weight average molecular weight and 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 15 wt% to 70 wt%, 15 wt% to 65 wt%, 15 wt% to 60 wt%, 15 wt%. % To 55%, 15% to 50%, 20% to 70%, 20% to 65%, 20% to 60%, 20% to 55%, 20% to For example, 50% by weight can be selected.

(Block chain containing a repeating unit having a carboxyl group (A))
The block chain (A) includes a repeating unit having a carboxyl group (—COOH group). The repeating unit having a carboxyl group is not particularly limited as long as the repeating unit has a carboxyl group, but is preferably a repeating unit represented by the formula [I].

In the formula [I], R ¹¹ represents a hydrogen atom or a C1-6 alkyl group.
Examples of the C1-6 alkyl group for R ¹¹ include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and the like. Can do.

The proportion of the repeating unit having a carboxyl group contained in the block chain (A) is 10 to 100% by weight, 20 to 100% by weight, 30 to 100% by weight, 40 to 40% by weight based on the total weight of the block chain (A). 100% by weight, 50 to 100% by weight, 60 to 100% by weight, 70 to 100% by weight, 80 to 100% by weight, 90 to 100% by weight, 100% by weight and the like can be selected. Of these, 100% by weight is preferred.

(Block chain (B))
The block chain (B) contains at least one selected from the group consisting of a repeating unit represented by the formula [II] and a repeating unit represented by the formula [III].
The block chain (B) has a repeating unit represented by the formula [II], a repeating unit represented by the formula [III], or a repeating unit represented by the formula [II] and the formula [III]. One of those having both. Here, each of the repeating unit represented by the formula [II] and the repeating unit represented by the formula [III] may be one kind or two or more kinds.

In the formula [II], R ²¹ represents a hydrogen atom or a C1-6 alkyl group.
Examples of the C1-6 alkyl group for R ²¹ include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and the like. Can do.

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

In the formula [II], R ²² represents a hydrocarbon group. Preferred examples of the hydrocarbon group for R ²² include an alkyl group, an arylalkyl group, a heteroarylalkyl group, a cycloalkyl group, and an allyl group.
Examples of the alkyl group for R ²² include C1-6 groups 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 ²² include a group in which a C6-10 aryl group such as a benzyl group, a phenethyl group, or a 3-phenylpropyl group is bonded to a C1-6 alkyl group.
The heteroarylalkyl group for R ²² includes at least one N, O, or S as a heteroatom, such as a pyridin-2-ylmethyl group, a pyridin-3-ylmethyl group, a pyridin-4-ylmethyl group, and the number of members And a group in which a 5 to 10 heteroaryl group and a C1 to 6 alkyl group are bonded.
Examples of the cycloalkyl group for R ²² include C3-6 cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

In the formula [III], R ³¹ represents a hydrogen atom or a C1-6 alkyl group.
Examples of the C1-6 alkyl group for R ³¹ include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and the like. Can do.

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

In the formula [III], R ³² represents a group having an etheric oxygen atom. The group having an etheric oxygen atom is not particularly limited as long as it has an etheric oxygen atom, but is preferably a formula [III-1] or a formula [III-2] described below.

In the formula [III-1], R ³³ represents an alkylene group. ^Examples of the alkylene group for R ³³ include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-2,3-diyl, pentane-1,5- C1-10 groups such as diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl Is mentioned.
In the formula [III-1], m represents an integer of 1 to 100.

In the formula [III-1], R ³⁴ represents a hydrogen atom or an alkyl group.
^Examples of the alkyl group for R ³⁴ include C1-6 groups 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-1], * represents a bonding position with X ³ .

In the formula [III-2], R ³⁵ and R ³⁶ each independently represent a hydrogen atom or a C1-C6 alkyl group. Examples of the C1-6 alkyl group for R ³⁵ and R ³⁶ include 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-2], Q represents an oxygen-containing saturated heterocyclic group which may have a C1-C6 alkyl group as a substituent. The oxygen-containing saturated heterocyclic group may have a substituent on any carbon atom on the ring. The oxygen-containing saturated heterocyclic group means a 3- to 8-membered saturated heterocyclic ring which contains at least one oxygen atom and may further contain one heteroatom selected from N and S, preferably 3 A 6-membered saturated heterocycle.
Here, examples of the oxygen-containing saturated heterocyclic group include an oxiranyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group.

In the formula [III-2], n represents an integer of 0 to 6.

In the formula [III-2], * represents a bonding position with X ³ .

The proportion of the repeating unit represented by the formula [II] and / or the formula [III] contained in the block chain (B) is 10 to 100% by weight, 20 to 100% with respect to the total weight of the block chain (B). Wt%, 30-100 wt%, 40-100 wt%, 50-100 wt%, 60-100 wt%, 70-100 wt%, 80-100 wt%, 90-100 wt%, 100 wt% etc. You can choose.

(Other possible repeating units in the block chains (A) and (B) and other possible repeating units in the block copolymer)
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 copolymer include (meth) acrylate monomers other than those mentioned above, aromatic Examples thereof include repeating units derived from vinyl monomers and conjugated diene monomers.

(Method for producing block copolymer)
An example of the method for producing the block copolymer of the present invention will be described below.
A mixture of the compound represented by the formula [IIm] and the compound represented by the formula [IIIm] is added to a solvent containing a polymerization initiator at a low temperature to perform living anion polymerization. After confirming the disappearance of the compound represented by the formula [IIm] and the compound represented by the formula [IIIm], the compound represented by the formula [Im] is dropped into the reaction system to perform living anion polymerization. After completion of the reaction, the protecting group P is deprotected to obtain the block copolymer of the present invention. The obtained block copolymer can be purified by a general purification method.

Wherein ^{[Im], R 11} is the same as ^{R 11} in the formula [I]. In the formula [Im], P represents a protecting group for a carboxyl group.

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

Wherein ^[IIIm], R 31, ^{X 3,} and ^{R 32} are the same as ^R 31, ^{X 3} of the formula [III], and ^{R 32.}

The block copolymer obtained as described above can be used as a dispersant for inorganic nitride 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 nitride dispersant of the present invention is suitable for uniformly dispersing inorganic nitride particles in a dispersion medium.

(Inorganic nitride dispersion composition)
The composition of the present invention comprises inorganic nitride particles, a dispersant for inorganic nitride of the present invention, and a dispersion medium. In the composition of the present invention, the inorganic nitride is preferably uniformly dispersed in the dispersion medium.

(Inorganic nitride particles)
The kind of inorganic nitride that can be dispersed with the inorganic nitride dispersant of the present invention is not particularly limited, and examples thereof include boron nitride, aluminum nitride, silicon nitride, and gallium nitride. 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 nitride particles is not particularly limited, but is preferably 1000 nm or less, more preferably 500 nm or less.

The amount of the inorganic nitride 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, and 5 to 40% by weight. %, 5 to 30% by weight, and the like can be selected. The amount of the inorganic nitride dispersant used in the composition of the present invention is 1 to 200 parts by weight, 1 to 100 parts by weight, 1 to 100 parts by weight with respect to 100 parts by weight of the inorganic nitride particles. For example, 50 parts by weight 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, 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, fluororesin, 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 polymer, polyether ether ketone, thermoplastic polyimide, and polyamideimide. The thermoplastic resin can be kneaded or mixed with the inorganic nitride and the dispersant for inorganic nitride after being melted by heating or dissolved in a solvent.

The composition containing a thermoplastic resin may further contain a vulcanizing agent. Examples of the vulcanizing agent include 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 nitride dispersant, the thermoplastic resin, the vulcanizing agent, and the inorganic nitride 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 nitride particles.

Thermosetting resin changes from liquid to solid when heated. 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. *

Also, 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 (registered trademark) 184, Ciba Special Manufactured by T Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure (registered trademark) 369, 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 (registered trademark)) 784, manufactured by Ciba Specialty Chemicals), 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.

By bringing the inorganic nitride dispersant of the present invention into contact with the inorganic nitride, the inorganic nitride dispersant of the present invention can be adhered to the surface of the inorganic nitride particles. The inorganic nitride particles having the inorganic nitride dispersant adhered to the surface can be used in various applications as surface-treated fine particles.

[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 nitride dispersant>
Example 1
To the flask, 100 g of tetrahydrofuran (hereinafter referred to as THF) and 0.1 g of lithium chloride were added and cooled to −60 ° C. After adding 2.2 g of n-butyllithium (15.4 wt% hexane solution), 0.5 g of diisopropylamine was further added and stirred for 10 minutes. Further, 0.5 g of methyl isobutyrate was added and stirred for 10 minutes. A mixture of n-butyl methacrylate (hereinafter referred to as nBMA) 9.0 g and methoxypolyethylene glycol monomethacrylate (PME-200 manufactured by NOF Corporation) (hereinafter referred to as PEGMA) 9.0 g was dropped into the reaction system over 10 minutes. Thereafter, the mixture was stirred for 5 minutes. A part was sampled and monomer disappearance was confirmed by GC measurement. Subsequently, 3.7 g of 2-ethoxyethyl methacrylate (hereinafter referred to as EEMA) was added dropwise, and the reaction was continued for 1 hour after the addition. A part was sampled, and after confirming disappearance of the monomer by GC measurement, 0.4 g of methanol was added to stop the reaction.
The reaction solution was diluted with THF and hexane, washed twice with water, and then the solvent was distilled off. After solvent substitution with 2-methoxy-1-methylethyl acetate (hereinafter PGMEA), water was added. After reacting for 6 hours under heating and refluxing, water was distilled off and PGMEA was added so that the polymer concentration was 50% by weight to obtain Dispersant A (nBMA / PEGMA-methacrylic acid (hereinafter referred to as MA) = 45/45). -10% by weight). When analyzed by GPC (mobile phase THF, PMMA standard), the molecular weight (Mw) was 5200, and the molecular weight distribution (Mw / Mn) was 1.13.

Example 2
To the flask, 100 g of THF and 0.1 g of lithium chloride were added and cooled to −60 ° C. After adding 2.2 g of n-butyllithium (15.4 wt% hexane solution), 0.5 g of diisopropylamine was further added and stirred for 10 minutes. Further, 0.5 g of methyl isobutyrate was added and stirred for 10 minutes. A mixture of nBMA 8.0 g and PEGMA 8.0 g was dropped into the reaction system over 10 minutes, followed by stirring for 5 minutes. A part was sampled and monomer disappearance was confirmed by GC measurement. Next, 7.4 g of EEMA was added dropwise, and the reaction was continued for 1 hour after the addition. 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.
The reaction solution was diluted with THF and hexane, washed twice with water, and then the solvent was distilled off. After solvent substitution with PGMEA, water was added. After reacting for 6 hours under heating and refluxing, water was distilled off and PGMEA was added to a polymer concentration of 30% by weight to obtain Dispersant B (nBMA / PEGMA-MA = 40 / 40-20% by weight). When analyzed by GPC (mobile phase THF, PMMA standard), the molecular weight (Mw) was 5300, and the molecular weight distribution (Mw / Mn) was 1.13.

Example 3
To the flask, 100 g of THF and 0.1 g of lithium chloride were added and cooled to −60 ° C. After adding 2.2 g of n-butyllithium (15.4 wt% hexane solution), 0.5 g of diisopropylamine was further added and stirred for 10 minutes. Further, 0.5 g of methyl isobutyrate was added and stirred for 10 minutes. A mixture of 7.0 g of nBMA and 7.0 g of PEGMA was dropped into the reaction system over 10 minutes, followed by stirring for 5 minutes. A part was sampled and monomer disappearance was confirmed by GC measurement. Next, 11.0 g of EEMA was added dropwise, and the reaction was continued for 1 hour after the addition. 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.
The reaction solution was diluted with THF and hexane, washed twice with water, and then the solvent was distilled off. After solvent substitution with PGMEA, water was added. After reacting for 6 hours under heating and refluxing, water was distilled off and PGMEA was added to a polymer concentration of 40% by weight to obtain Dispersant C (nBMA / PEGMA-MA = 35 / 35-30% by weight). When analyzed by GPC (mobile phase THF, PMMA standard), the molecular weight (Mw) was 4000 and the molecular weight distribution (Mw / Mn) was 1.26.

Comparative Example 1
To the flask, 100 g of THF and 0.1 g of lithium chloride were added and cooled to −60 ° C. After adding 2.2 g of n-butyllithium (15.4 wt% hexane solution), 0.5 g of diisopropylamine was further added and stirred for 10 minutes. Further, 0.5 g of methyl isobutyrate was added and stirred for 10 minutes. A mixture of nBMA 7.0 g, PEGMA 7.0 g, and EEMA 11.0 g was dropped into the reaction system over 10 minutes, followed by stirring for 30 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.
The reaction solution was diluted with THF and hexane, washed twice with water, and then the solvent was distilled off. After solvent substitution with PGMEA, water was added. After reacting for 6 hours under heating and refluxing, water was distilled off and PGMEA was added so that the polymer concentration was 33 wt% to obtain Dispersant D (nBMA / PEGMA / MA = 35/35/30 wt%). When analyzed by GPC (mobile phase THF, PMMA standard), the molecular weight (Mw) was 4400, and the molecular weight distribution (Mw / Mn) was 1.20.

Example 4
94 g of THF and 0.25 g of lithium chloride were added to the flask and cooled to −60 ° C. After adding 1.5 g of n-butyllithium (15.4 wt% hexane solution), 0.4 g of diisopropylamine was further added and stirred for 10 minutes. Furthermore, 0.4 g of methyl isobutyrate was added and stirred for 10 minutes. A mixture of nBMA (3.75 g) and PEGMA (3.75 g) was dropped into the reaction system over 10 minutes, followed by stirring for 5 minutes. A part was sampled, and the disappearance of the monomer was confirmed by measuring GC. Subsequently, 12.4 g of t-butyl methacrylate (hereinafter abbreviated as TBMA) was added dropwise, and the reaction was continued for 1 hour after the addition. 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.
After the solvent of the reaction solution was distilled off, the solvent was replaced with toluene, diluted with ethanol, and 2.0 g of sulfuric acid was added. After reacting at 80 ° C. for 6 hours, it was diluted with THF. After washing three times with water, the solvent was distilled off, and THF was added to obtain a polymer concentration of 31% by weight to obtain Dispersant E (nBMA / PEGMA-MA = 25 / 25-50% by weight). When analyzed by GPC (mobile phase THF, PMMA standard), the molecular weight (Mw) was 3100, and the molecular weight distribution (Mw / Mn) was 1.26.

<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).

[Measurement conditions for heat resistance test]
The weight reduction rate of the powder obtained by drying the dispersion composition was measured using thermogravimetry (TGA / DSC, 10 ° C./min, nitrogen gas atmosphere manufactured by METLER TOLEDO).

Example 5
9 parts by weight of boron nitride particles (manufactured by Showa Denko KK, UHP-S1 average primary particle size (D50) 500 nm), 2.0 parts by weight of dispersant A obtained in Example 1, and 89.0 parts by weight of methyl ethyl ketone Mixed. The mixed solution was put into a disperser and dispersed under the above conditions to obtain a dispersion composition A1. After the start of dispersion, the average particle diameter of the boron nitride particles was measured under the above conditions at regular intervals. The average particle diameter of the boron nitride fine particles at 4 hours after the start of dispersion was 4200 nm. The weight reduction rate in the range of 150 to 250 ° C. of the powder obtained by drying the dispersion composition A1 was 0%. Further, no weight reduction was confirmed up to 300 ° C.

Example 6
9 parts by weight of boron nitride particles (manufactured by Showa Denko KK, UHP-S1 average primary particle size (D50) 500 nm), 2.5 parts by weight of the dispersant B obtained in Example 2, and 88.5 parts by weight of methyl ethyl ketone Mixed. The mixed solution was put into a disperser and dispersed under the above conditions to obtain dispersion composition B1. After the start of dispersion, the average particle diameter of the boron nitride particles was measured under the above conditions at regular intervals. The average particle diameter of the boron nitride fine particles at 1 hour after the start of dispersion was 1900 nm. The weight reduction rate in the range of 150 to 250 ° C. of the powder obtained by drying the dispersion composition B1 was 0%. Further, no weight reduction was confirmed up to 300 ° C.

Example 7
9 parts by weight of boron nitride particles (manufactured by Showa Denko KK, UHP-S1 average primary particle size (D50) 500 nm), 3.3 parts by weight of the dispersant C obtained in Example 3, and 87.7 parts by weight of methyl ethyl ketone Mixed. The mixed solution was put in a disperser and dispersed under the above conditions to obtain a dispersion composition C1. After the start of dispersion, the average particle diameter of the boron nitride particles was measured under the above conditions at regular intervals. The average particle diameter of the boron nitride fine particles at 1200 hours after the start of dispersion was 1200 nm. The weight reduction rate in the range of 150 to 250 ° C. of the powder obtained by drying the dispersion composition C1 was 0%. Further, no weight reduction was confirmed up to 300 ° C.

Comparative Example 2
9 parts by weight of boron nitride particles (manufactured by Showa Denko KK, UHP-S1 average primary particle size (D50) 500 nm), 3.0 parts by weight of the dispersant D obtained in Comparative Example 1, and 88 parts by weight of methyl ethyl ketone were mixed. . The mixed solution was put in a disperser and dispersed under the above conditions to obtain a dispersion composition D1. After the start of dispersion, the average particle diameter of the boron nitride particles was measured under the above conditions at regular intervals. The average particle diameter of the boron nitride fine particles at 1 hour after the start of dispersion was 7400 nm, and after 2 hours, they aggregated and could not be recovered.

Example 8
9 parts by weight of boron nitride particles (manufactured by Showa Denko KK, UHP-S1 average primary particle size (D50) 500 nm), 2.5 parts by weight of the dispersant E obtained in Example 4, and 88.5 parts by weight of methyl ethyl ketone Mixed. The mixed solution was put in a disperser and dispersed under the above conditions to obtain a dispersion composition E1. After the start of dispersion, the average particle diameter of the boron nitride particles was measured under the above 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 820 nm. Further, the weight reduction rate in the range of 150 to 250 ° C. of the powder obtained by drying the dispersion composition E1 was 0%. Further, no weight reduction was confirmed up to 300 ° C.

Claims

A block chain (B) containing a repeating unit having a carboxyl group and a block chain (B) containing at least one selected from the group consisting of a repeating unit represented by the formula [II] and a repeating unit represented by the formula [III] An inorganic nitride dispersant containing a block copolymer. However, the block copolymer does not contain a tertiary amino group or a quaternary ammonium base.

(In the formula [II], R 21 represents a hydrogen atom or a C1-6 alkyl group, X 2 represents —NH— or —O—, and R 22 represents a hydrocarbon group.)

(In the formula [III], R 31 represents a hydrogen atom or a C1-6 alkyl group, X 3 represents —NH— or —O—, and R 32 represents a group having an etheric oxygen atom. )
The inorganic nitride dispersant according to claim 1, wherein the hydrocarbon group of R 22 in formula [II] is an alkyl group, an arylalkyl group, a heteroarylalkyl group, a cycloalkyl group, or an allyl group.
The dispersant for inorganic nitride according to claim 1, wherein the group having an etheric oxygen atom of R 32 in formula [III] is formula [III-1] or formula [III-2].

(In the formula [III-1], R 33 represents an alkylene group, m represents an integer of 1 to 100, R 34 represents a hydrogen atom or an alkyl group, and * represents a bonding position. .)

(In the formula [III-2], R 35 and R 36 each independently represent a hydrogen atom or a C1-C6 alkyl group, and Q may contain a C1-C6 alkyl group as a substituent. Represents an oxygen-saturated heterocyclic group, and n represents an integer of 0 to 6. * represents a bonding position.)
The inorganic nitride dispersant according to claim 1, wherein the repeating unit having a carboxyl group is a repeating unit represented by the formula [I].

(In the formula [I], R 11 represents a hydrogen atom or a C1-6 alkyl group.)
The ratio of the block chain (A) to the total weight of the block chain (A) and the block chain (B) is 15% by weight or more and 70% by weight or less, for the inorganic nitride according to any one of claims 1 to 4. Dispersant.
The inorganic nitride dispersant according to any one of claims 1 to 5, wherein the block copolymer has a number average molecular weight (Mn) of 2,000 to 100,000.
The inorganic nitride dispersant according to any one of claims 1 to 6, wherein the inorganic nitride is any one of boron nitride, aluminum nitride, silicon nitride, and gallium nitride.
A composition comprising the inorganic nitride dispersant according to any one of claims 1 to 6, a dispersion medium, and an inorganic nitride.
The composition according to claim 8, wherein the inorganic nitride is any of boron nitride, aluminum nitride, silicon nitride, or gallium nitride.
Fine particles having the inorganic nitride dispersant attached to any one of claims 1 to 6 on the surface of the inorganic nitride particles.
The fine particles according to claim 10, wherein the inorganic nitride particles are any of boron nitride fine particles, aluminum nitride fine particles, silicon nitride fine particles, or gallium nitride fine particles.