JP5704691B2 - Polymerizable diamond and resin composition containing the same - Google Patents

Description

  The present invention relates to a polymerizable nanodiamond and a method for producing the same.

  Since diamond has the highest hardness among existing materials, diamond has been put to practical use in a process of smoothly polishing an object surface using diamond fine particles as an abrasive. Moreover, it has been put into practical use to improve the lubricity and wear resistance of an object surface by forming a thin film made of diamond fine particles on the object surface. Diamond has such excellent mechanical properties, and is also a material with excellent electrical, thermal, and optical properties, and is expected to be used in a wider range of fields. .

  In particular, if the nanoparticles are kept in a dispersed state without aggregating and aggregating in the medium, the contact area with the medium becomes very large, and therefore, it is expected that the mixing effect will be stronger than in the conventional microparticle mixing system. . (Non-Patent Document 1)

  From the above viewpoint, various composites of nanodiamonds and organic polymers have been studied, for example, composites of nanodiamonds and polymethylmethacrylate (PMMA). (Patent Document 1)

  However, the familiarity between nanodiamonds and polymers is insufficient, and nanodiamonds are not sufficiently dispersed. Therefore, in view of the vast surface area of nanoparticles, the present situation is that they do not function sufficiently.

Eiji Osawa, “Scientific Perspectives for Nanotechnology,” Contemporary Chemistry, 2005, April, No. 409, pages 38-42

JP 2004-51937 A

  The present invention provides a surface-modified nanodiamond capable of improving the compatibility with a polymer by modifying a polymerizable functional group on the surface of the nanodiamond having a very large surface area, and a method for producing the same. For the purpose.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have made it possible to react with a polar group on the surface of the nanodiamond, a functional group that reacts with the polar group, and a compound having a polymerizable functional group to react with the polymer. A method for producing diamond has been found and the present invention has been completed.

That is, the present invention relates to (1) a functional group that reacts with diamond particles (a) having an average particle size of 100 nm or less having one or more polar groups selected from a hydroxyl group, an amino group, or a carboxyl group on the surface; A surface-modified diamond obtained by reacting a compound (b) having a polymerizable functional group (hereinafter sometimes simply referred to as a “surface modifier”);
(2) The diamond according to the above (1), wherein the functional group of the compound (b) that reacts with the surface polar group of the diamond particle (a) is an isocyanate group,
(3) The above-described (1) or (2), wherein the polymerizable functional group of the compound (b) is a vinyl group, a (meth) acrylate group, a glycidyl group, an isocyanate group, an amine group, a carboxyl group or a silanol group. diamond,
(4) Light and / or thermosetting resin composition containing diamond according to any one of (1) to (3) (5) Curing obtained by curing the curable composition according to (4) (6) A film comprising the cured product described in (5)

  The surface-modified nanodiamond of the present invention is improved in compatibility with a polymer and chemically bonded to a compound having a polymerizable functional group, so that it has excellent mechanical properties, electrical properties, and thermal properties that have not existed before. A composite having optical characteristics and the like can be formed.

It is a FT-IR figure of the nano diamond which surface-modified 2-isocyanatoethyl methacrylate which concerns on Example 1 of this invention. It is a thermogravimetric measurement figure of the nano diamond which surface-modified 2-isocyanatoethyl methacrylate which concerns on Example 1 of this invention. It is a pyrolysis GC-MS figure of the nano diamond which surface-modified 2-isocyanatoethyl methacrylate which concerns on Example 1 of this invention. It is a FT-IR figure of the nano diamond which surface-modified isophorone diisocyanate which concerns on Example 2 of this invention. It is a thermogravimetric measurement figure of the nano diamond which surface-modified IPDI which concerns on Example 2 of this invention. It is a pyrolysis GC-MS figure of the nano diamond which surface-modified IPDI which concerns on Example 1 of this invention.

The present invention is described in detail below. In the following, the particle size and particle size mean the volume average particle size measured by dynamic light scattering particle size distribution measurement, and may be referred to as the average particle size below.
The diamond particles used in the present invention are hydrophilic diamond particles having a primary particle size of 3 to 5 nm obtained by chemically purifying a recovered soot obtained by a detonation method of detonating an oxygen-deficient explosive with nitric acid or sulfuric acid. As a raw material.

  Diamond particles obtained by the detonation method are mainly composed of 75 to 90% by weight of carbon atoms, the rest being 1-2% by weight of hydrogen atoms, 1 to 3% by weight of nitrogen atoms, and 5 to 23% by weight of oxygen. Including atoms, primary particles are strongly agglomerated. That is, hydrogen atoms, nitrogen atoms, and oxygen atoms are localized in the surface layer portion of the diamond particle, these atoms are very various, many functional groups such as methyl group, nitrile group, hydroxyl group, amino group, carbonyl group, It constitutes a carboxyl group or an aldehyde group. Among these groups, the diamond particles that can be used in the present invention have one or more polar groups selected from a hydroxyl group, an amino group, and a carboxyl group.

  The surface-modified nanodiamond particles of the present invention can be obtained by the production method described below. Whether the polymer is suitable for the polymerizable nanodiamond particles obtained by the production method is measured by the following FT-IR measurement, thermogravimetry (TGA). ), The result of pyrolysis GC-MS measurement can be used as an index.

  The surface-modified nanodiamond particles of the present invention are obtained by reacting nanodiamond particles obtained by the detonation method with a surface modifier in a dispersion in which the nano-diamond particles are previously dispersed in an appropriate dispersion medium.

  In the present invention, the surface modifier is not particularly limited as long as it is a compound having an isocyanate group that reacts with the surface polar group of nanodiamond and having a functional group polymerizable with a polymer. used.

The polymerizable functional group is preferably at least one selected from vinyl group, (meth) acrylate group, glycidyl group, isocyanate group, amine group, carboxyl group or silanol group.
Specific examples of surface modifiers that can be used include 2-isocyanatomethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, and 2-isocyanatobutyl (meth) acrylate. 2-isocyanatoethoxyethyl (meth) acrylate, 2-isocyanatopropoxypropyl (meth) acrylate, 2-isocyanatophenyl (meth) acrylate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate, 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl methacrylate, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, monomethyltriisocyanatesilane, tetraisocyanate Nate silane, isophorone diisocyanate, tolylene diisocyanate, methylene bisphenyl diisocyanate, hexamethylene diisocyanate and the like.

  The dispersion medium for modifying the surface of the compound capable of being polymerized on the nanodiamond particles is not particularly limited as long as the dispersion medium dissolves the surface modifier and does not react with the isocyanate group and does not decompose. An organic solvent or the like is used. Among these, an aprotic polar organic solvent in which nanodiamond particles are well dispersed is preferable in order to efficiently modify the surface of the compound with nanodiamond particles.

  Here, a case where N-methyl-2-pyrrolidone is used as a dispersion medium will be described as a typical example, but a dispersion medium other than N-methyl-2-pyrrolidone can be similarly implemented.

First, nano diamond particles are put into N-methyl-2-pyrrolidone, and the raw nano diamond particles are sufficiently dispersed. The dispersion method is 1 to 48 hours, preferably 2 to 24 hours, more preferably about 5 to 20 hours with stirring in an ultrasonic bath. If the added nanodiamond particles cannot be sufficiently dispersed, coarse particles may be removed by centrifugation.
The average particle diameter of the produced nanodiamond dispersion is 100 nm or less, preferably 3 to 100 nm, more preferably 3 to 50 nm, and particularly preferably 3 to 40 nm. When the average particle size is 100 nm or more, the surface polar groups that react with the isocyanate groups of the surface modifier may be inhibited by aggregation.

  The concentration of the nanodiamond particles is 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of N-methyl-2-pyrrolidone. is there.

  In addition, when there exists a possibility that the water | moisture content which exists in a dispersion may react with a surface modifier, it is effective to use, after adding desiccants, such as molecular sieves, to a dispersion, and leaving still for 2 to 3 days.

  Next, a surface modifier is mixed in the dispersion. The amount of the surface modifier used is 0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 1 part by weight of the nanodiamond particles.

  Subsequently, the reaction is started with stirring. In order to accelerate the reaction at this time, a catalyst such as dibutyltin dilaurate may be added. If there is a risk of polymerization between surface modifiers such as vinyl group and (meth) acrylate group, a polymerization inhibitor such as hydroquinone. May be added.

  The reaction temperature is 20 to 150 ° C., preferably 30 to 100 ° C., more preferably 40 to 80 ° C., the reaction time is 0.5 to 24 hours, preferably 1 to 15 hours, more preferably about 2 to 10 hours. is there.

  After completion of the reaction, a low-polar solvent such as toluene is added in an amount of 2 to 5 times based on the weight of the dispersion medium, and the surface-modified nanodiamond particles are aggregated or precipitated, and then solid-liquid separated by means such as filtration, Furthermore, after washing with an organic solvent in which a surface modifier such as N-methyl-2-pyrrolidone or methyl ethyl ketone is dissolved, the product is dried under reduced pressure to obtain the desired surface-modified nanodiamond particles. In addition, it is also possible to use a centrifuge as a means for solid-liquid separation.

The curable resin composition used in the present invention is not particularly limited as long as it is a resin composition that can be cured by light irradiation and / or heating. For example, a curable resin composition having an unsaturated double bond, an epoxy group, Examples thereof include a curable resin composition having a cyclic ether such as an oxetanyl group.

The curable resin composition having an unsaturated double bond is not particularly limited, and examples thereof include resins having a vinyl group, a vinyl ether group, an allyl group, a maleimide group, a (meth) acryl group, and the like. A resin having a (meth) acrylic group is preferred from the viewpoint of properties and versatility. In addition, in this specification, a (meth) acryl group means an acryl group or a methacryl group.

Examples of the resin having a (meth) acryl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, and acryloyl. Half-ester, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, which is a reaction product of morpholine, hydroxyl group-containing (meth) acrylate and acid anhydride of polycarboxylic acid compound , Di (meth) acrylate of ε-caprolactone adduct of trimethylolpropane polyethoxytri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, and neopentyl glycol hydroxypivalate (For example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate, dipentaerythritol and ε-caprolactone reaction product, dipenta Examples include erythritol poly (meth) acrylate, epoxy (meth) acrylate that is a reaction product of a mono- or polyglycidyl compound and (meth) acrylic acid, and the like.

There is no restriction | limiting in particular as a glycidyl compound used for the epoxy (meth) acrylate which is a reaction material of a mono- or polyglycidyl compound and (meth) acrylic acid, For example, bisphenol A, bisphenol F, bisphenol S, 4,4'- Biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert- Butylphenol ), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di-4 -Phenols having a fluorene skeleton such as hydroxyphenylfluorene, phenolized polybutadiene, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol Examples thereof include glycidyl etherified products of polyphenols such as A.

The epoxy (meth) acrylate which is a reaction product of these mono- or polyglycidyl compounds and (meth) acrylic acid can be obtained by esterifying an equivalent amount of (meth) acrylic acid to the epoxy group. This synthesis reaction can be performed by a generally known method. For example, resorcin diglycidyl ether with an equivalent amount of (meth) acrylic acid, a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) and a polymerization inhibitor (for example, methoquinone, Hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene and the like) and, for example, an esterification reaction is performed at 80 to 110 ° C. The (meth) acrylated resorcin diglycidyl ether thus obtained is a resin having a radically polymerizable (meth) acryloyl group.

It does not specifically limit as a curable resin composition which has the said cyclic ether, For example, an epoxy resin, an alicyclic epoxy resin, an oxetane resin, a furan resin etc. are mentioned. Of these, epoxy resins, alicyclic epoxy resins, and oxetane resins are preferred from the viewpoint of reaction rate and versatility. The epoxy resin is not particularly limited. For example, a novolak type such as a phenol novolak type, a cresol novolak type, a biphenyl novolak type, a trisphenol novolak type, a dicyclopentadiene novolak type; a bisphenol A type, a bisphenol F type, 2, 2 Examples thereof include bisphenol types such as' -diallyl bisphenol A type, hydrogenated bisphenol type, and polyoxypropylene bisphenol A type. Other examples include glycidylamine.

As a commercially available product of the above epoxy resin, for example, as a phenol novolak type epoxy resin, Epicron N-740, N-770, N-775 (all of which are manufactured by Dainippon Ink and Chemicals), Epicoat 152, Epicoat 154 ( As mentioned above, all are Japan Epoxy Resin Co., Ltd.). Examples of the cresol novolac type include epiclone N-660, N-665, N-670, N-673, N-680, N-695, N-665-EXP, N-672-EXP (all of which are large. As a biphenyl novolak type, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); As a trisphenol novolak type, for example, EP1032S50, EP1032H60 (all of these are manufactured by Japan Epoxy Resin); Examples of the dicyclopentadiene novolak type include XD-1000-L (manufactured by Nippon Kayaku Co., Ltd.), HP-7200 (manufactured by Dainippon Ink &Chemicals); and bisphenol A type epoxy resin, for example, Epicoat 828 and Epicoat 834. , Epicoat 1001, Epicoat 1004 (above, any Japan Epoxy Resin Co., Ltd.), Epicron 850, Epicron 860, Epicron 4055 (all of which are manufactured by Dainippon Ink & Chemicals, Inc.); ), Epicron 830 (manufactured by Dainippon Ink and Chemicals); 2,2′-diallyl bisphenol A type, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.); Hydrogenated bisphenol type, for example, ST- 5080 (manufactured by Tohto Kasei Co., Ltd.); Examples of the polyoxypropylene bisphenol A type include EP-4000 and EP-4005 (all of which are manufactured by Asahi Denka Kogyo Co., Ltd.).

Examples of commercially available oxetane resins include etanacol EHO, etanacol OXBP, etanacol OXTP, etanacol OXMA (all of which are manufactured by Ube Industries, Ltd.). Moreover, it does not specifically limit as said alicyclic epoxy resin, For example, Celoxide 2021, Celoxide 2080, Celoxide 3000 (above, all are the Daicel UCB company make) etc. are mentioned. These curable resin compositions having a cyclic ether group may be used alone or in combination of two or more.

Examples of the photoreaction initiator contained in the present invention include a cationic polymerization type and a radical polymerization type, but there is no particular limitation. Examples of radical polymerization photoinitiators include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one and other acetophenones; 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, etc. Anthraquinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide be able to. Preferable examples include 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone.

In addition, as the cationic polymerization type photoinitiator, benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, trisphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexaphosphate Fluoroborate, 4,4′-bis [bis (2-hydroxyethoxyphenyl) sulfonio] phenyl sulfide bishexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium Hexafluorophosphate, 4-methylphenyl [4- (1 -Methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate and the like.
In the present invention, the photoreaction initiator may be used alone or in combination of two or more. As a compounding quantity of the said photoinitiator, it is 0.01-10 weight part with respect to 100 weight part of said curable compounds, Preferably it is 0.1-5 weight part. If it is less than 0.01 part by weight, the ability to initiate photopolymerization may be insufficient and the effect may not be obtained. If it exceeds 10 parts by weight, due to an abrupt photopolymerization reaction, due to internal stress during curing, It may cause a decrease in adhesive strength.

The thermosetting agent is not particularly limited as long as it is for reacting and crosslinking an unsaturated double bond or an epoxy group in the curable compound by heating. For example, acid anhydrides, amines, phenols, Examples include imidazoles, dihydrazines, Lewis acids, Bronsted acid salts, polymercaptons, isocyanates, and blocked isocyanates.

Specific examples of acid anhydrides that can be used include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, biphenyltetracarboxylic anhydride Aromatic carboxylic acid anhydrides, such as azelaic acid, sebacic acid, dodecanedioic acid anhydrides, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic acid anhydride, het acid anhydride And alicyclic carboxylic acid anhydrides such as hymic acid anhydrides.

Specific examples of amines that can be used include aromatics such as diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene, m-xylylenediamine, and the like. Aliphatic amines such as aliphatic amines, ethylenediamine, diethylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, polyetherdiamine, guanidines such as dicyandiamide, 1- (o-tolyl) biguanide, adipine Hydrazide compounds such as acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin] And the like.

Specific examples of phenols that can be used include bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, tetramethylbisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, Dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ) Ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenyl Methane, le Zorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenolized polybutadiene, phenol, cresols, ethylphenols, butylphenols , Novolak resins, xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolak resins, biphenyl skeleton-containing phenol novolak resins, fluorenes Various novolak resins such as skeleton-containing phenol novolak resins, furan skeleton-containing phenol novolak resins, brominated bisphenols Le A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolak, chlorinated bisphenol S, halogenated phenols such as chlorinated bisphenol A, represented by the following formula 1

(Wherein, x, y, z, l, m and n are average polymerization degrees, and x = 3 to 7, y = 1 to 4, z = 5 to 15, and l + m = 2 to 200 integers. And m / (l + m) ≧ 0.04, and n is not particularly limited.
And a phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer represented by

(In the formula, l, m, and n are average polymerization degrees, respectively, and each represents an integer of 1 + m = 2 to 200, and m / (l + m) ≧ 0.04, and n is not particularly limited.) 2
And a phenolic hydroxyl group-containing polyamide represented by

The phenolic hydroxyl group-containing polyamides described above can be synthesized, for example, by the following method. That is, an excess amount of diamine is added to a dicarboxylic acid component containing a dicarboxylic acid having a phenolic hydroxyl group, and these are added, for example, by using a condensing agent in the presence of a phosphite ester and a pyridine derivative to form N-methyl. A polyamide containing a phenolic hydroxyl group is obtained by heating and stirring and condensation reaction in an inert solvent such as nitrogen in an organic solvent such as -2-pyrrolidone. Moreover, block copolymers with polybutadiene, polybutadiene-acrylonitrile, etc. can be synthesized, for example, by the following method. That is, a polyamide oligomer containing a phenolic hydroxyl group obtained by the method described above is produced. As a result, a polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends and a polybutadiene having carboxyl groups at both ends were added to the obtained phenolic hydroxyl group-containing polyamide oligomer solution having amino groups at both ends, It can be obtained by polycondensation. Moreover, dicarboxylic acid is made excessive with respect to diamine to synthesize a polyamide having both carboxylic acid groups at both ends, and a polybutadiene-acrylonitrile copolymer having both amino groups at both ends or amino groups at both ends. Polybutadiene can also be reacted. The dicarboxylic acid component and the diamine need only contain at least one or both of them containing a phenolic hydroxyl group. As long as this condition is satisfied, a dicarboxylic acid or diamine not containing a phenolic hydroxyl group is used in combination. be able to.

Specific examples of the dicarboxylic acid having a phenolic hydroxyl group that can be used for the phenolic hydroxyl group-containing polyamide derivative include 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyphthalic acid, 3-hydroxyphthalic acid, and 2-hydroxyterephthalate. Specific examples of dicarboxylic acids in which an acid or the like does not have a phenolic hydroxyl group include phthalic acid, isophthalic acid, terephthalic acid, dicarboxyl naphthalene, succinic acid, fumaric acid, glutaric acid, adipic acid, 1,3-cyclohexane Examples include dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3'-methylene dibenzoic acid and the like.

Specific examples of diamines containing phenolic hydroxyl groups that can be used include 3,3′-diamine-4,4′-dihydroxyphenylmethane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) difluoromethane, 3,4-diamino-1,5-benzenediol, 3,3'-dihydroxy-4,4'-diaminobisphenyl, 3, 3'-diamino-4,4'-dihydroxybiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) ketone, 2,2-bis (3-amino-4-hydroxyphenyl) sulfide, 2,2 -Bis (3-amino-4-hydroxyphenyl) ether, 2,2-bis (3-amino-4-hydroxyphenyl) sulfone, 2,2-bis 3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) methane, etc., and phenol Specific examples of diamines that do not contain a functional hydroxyl group include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, diaminonaphthalene, piperazine, hexanetylenediamine, tetramethylenediamine, m-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 2,2'-bis (4-aminophenyl) propane, 3,3'-diaminodiphenylsulfone, 3,3'-diamino And diphenyl and the like, and 3,4'-diaminodiphe Ether is preferred, but the invention is not limited to these.

Also, polybutadiene-acrylonitrile copolymer having various functional groups at both ends can be obtained from Goodrich from Hycar.
It is marketed as CTBN and can be used to block these with the phenolic hydroxyl group-containing polyamide.

Specific examples of imidazoles that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole) (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl, 4 -Methylimidazole (1 ')) ethyl-s-triazine, 2,4-dia No-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl Various imidazoles such as 3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the imidazoles Examples thereof include salts with polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid.

As a compounding quantity of these thermosetting agents, it is 0.5-50 weight part with respect to 100 weight part of said curable compounds, Preferably it is 1-40 weight part. If it is less than 0.5 part by weight, the cured product properties such as adhesiveness and chemical resistance deteriorate due to insufficient curing. On the other hand, when the amount exceeds 50 parts by weight, the thermosetting agent component is excessively excessive, and the heat resistance and the like are reduced. In addition, the said thermosetting agent can also be used in mixture of 2 or more types.

The resin composition of the present invention may contain a curing accelerator as necessary. Examples of the curing accelerator include phosphorus compounds such as triphenylphosphine, for example, triethylamine, tetraethanolamine, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), N, N -Tertiary amine compounds such as dimethylbenzylamine, 1,1,3,3-tetramethylguanidine or 2-ethyl-4-methylimidazole, N-methylpiperazine, such as 1,8-diazabicyclo [5. 4.0] -7-undecenium tetraphenylborate and the like.

If necessary, other additives can be added to the resin composition of the present invention. For example, natural waxes, synthetic waxes and plasticizers such as metal salts of long chain aliphatic acids, release agents such as acid amides, esters and paraffins, stress relaxation agents such as nitrile rubber and butadiene rubber, trioxide Inorganic flame retardants such as antimony, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, calcium aluminate, tetrabromobisphenol A, anhydrous tetrabromo Brominated flame retardants such as phthalic acid, hexabromobenzene, brominated phenol novolak, silane coupling agents, titanate coupling agents, coupling agents such as aluminum coupling agents, fused silica, crystalline silica, low α Wire silica, glass flake, glass beads, glass balloon, talc, Lumina, calcium silicate, aluminum hydroxide, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite or rare earth cobalt, gold, silver, nickel, copper, lead, iron powder, iron oxide, sand iron, etc. Metal powder and inorganic fillers or conductive particles such as graphite, carbon, petal, chrome lead, colorants such as dyes and pigments, carbon fiber, glass fiber, boron fiber, silicon carbide fiber, alumina fiber, silica alumina fiber Inorganic fibers such as aramid fibers, polyester fibers, cellulose fibers, carbon fibers and other organic fibers, oxidation stabilizers, light stabilizers, moisture resistance improvers, thixotropy imparting agents, diluents, antifoaming agents, and other various types These resins, tackifiers, antistatic agents, lubricants, ultraviolet absorbers and the like can be blended.

The curable resin composition of the present invention contains a curable compound having a reactive functional group, a photoreaction initiator and / or a thermosetting agent, a surface-modified nanodiamond, and a curing accelerator and other additives as necessary. The resin varnish which has electroconductivity can be obtained by mixing uniformly in. Examples of the solvent include organic solvents such as toluene, ethanol, n-propanol, cellosolve, cyclopentanone, cyclohexanone, tetrahydrofuran, N-methyl-2-pyrrolidone, and dimethylformamide, but are not particularly limited. The amount of the solvent used is preferably adjusted to have an appropriate viscosity depending on the purpose of use of the resin composition, but is usually 50 to 2000 parts by weight with respect to 100 parts by weight of the solid content.

The curable resin composition of the present invention can be preferably used as a visible light transmissive film. The coating film of the curable resin composition of the present invention applied to the substrate is cured or dried to form a coating film, and the conditions or methods for this curing or drying are appropriately determined according to the type of resin component used. You can choose. Usually, a coating film is obtained by evaporating a solvent from a coating film at room temperature or under heating. Moreover, this hardening method etc. can be performed by a conventionally known method. The coating amount of the curable resin composition can be appropriately selected from a wide range according to the use, but generally the film thickness after curing is about 0.005 to 2 mm, particularly about 0.01 to 1 mm. It is preferable that the amount is as follows.

Examples of the base resin used for the base material include thermosetting resins and thermoplastic resins, and specifically, silicone resins, acrylic resins, polyimide resins, phenol resins, melamine resins, urea resins, urethane resins, and the like. It is done. Also, polyimide film, PET (polyethylene terephthalate) film, polyester film, polyparabanic acid film, polyether ether ketone film, polyphenylene sulfide film, aramid film,
Various synthetic fibers, natural fibers, glass fibers, metal fibers and other woven fabrics and non-woven fabrics can be appropriately selected and used.

There is no restriction | limiting in particular as a coating method of the curable resin composition of this invention, For example, well-known coating methods, such as a spin coater, a dip coater, a spray coater, a bar coater, a roll coater, a comma coater, can be mentioned.

Hereinafter, the present invention will be described by way of examples. However, these are merely examples of embodiments, and the technical scope of the present invention is not construed as being limited thereto. In Examples, “part” means “part by weight” and “%” means “% by weight”.
In addition, implementation items and test methods in this example are as follows.

(A) (Thermogravimetry (TGA))
Using a differential thermothermal gravimetric simultaneous measurement device (TG / DTA6200, manufactured by SSI Nanotechnology Co., Ltd.) under conditions of a temperature range of 40 to 700 ° C. and a heating rate of 10 ° C./min under a nitrogen stream (flow rate 200 ml / min). The measurement was performed.

(B) (Infrared spectroscopy measurement (FT-IR measurement)
Measurement was performed at 150 ° C. under 133 Pa using an infrared spectrophotometer (FT / IR-6300V type, manufactured by JASCO Corporation).

(C) (Pyrolysis GC-MS)
Pyrolysis GC-MS is measured by Curie Point Pyrolyzer (manufactured by Nippon Analytical Industries), GC-MS (TRACE GC-TRACE DSQ, THERMO
FISHER SIENTIFIC) was used and the measurement was performed at 590 ° C.

(Example 1)
In a four-necked 300 ml glass reactor equipped with a stirrer, a heating device, a reflux device and a dropping device, 120 ml of 0.5% nanodiamond dispersion previously dispersed in N-methyl-2-pyrrolidone is weighed. I took it. The particle size distribution of 0.5% nanodiamond / N-methyl-2-pyrrolidone was measured using a dynamic light scattering particle size distribution analyzer (Nanotrack particle size analyzer UPA-EX, manufactured by Nikkiso Co., Ltd.). As a result, the average particle size was 8.5 nm.

  To this, 2.74 g of 2-isocyanatoethyl methacrylate (made by Showa Denko) as a surface modifier is added while stirring, dibutyltin dilaurate as a catalyst is added, and hydroquinone as a polymerization inhibitor is added to 2-isocyanato. 1000 ppm was added with respect to ethyl methacrylate. Next, a modification reaction was performed on the nanodiamond particle surface at 60 ° C. while sending dry air into the reaction solution at a flow rate of 30 ml / min. The reaction time was 5 hours.

  The reaction product was taken out into a 500 ml beaker, 350 ml of toluene was added, and nanodiamond particles whose surface was modified with 2-isocyanatoethyl methacrylate were aggregated. (A) The agglomerated nanodiamond particles were subjected to solid-liquid separation by suction filtration, the particles were taken out into a 100 ml beaker, and 80 ml of a N-methyl-2-pyrrolidone / toluene mixed solution was added. (B) Then, it wash | cleaned for 10 minutes in an ultrasonic bath, and solid-liquid separation was again performed by suction filtration. After performing the operations (a) and (b) three times, the washing solvent was changed to methyl ethyl ketone, and the same operations as (a) and (b) were performed four times, followed by drying under reduced pressure for 12 hours. A surface-modified diamond of the present invention was obtained.

FIG. 1 shows the FT-IR measurement results of nanodiamond particles obtained by modification with 2-isocyanatoethyl methacrylate obtained in Example 1 above. Moreover, the control of FIG. 1 is a FT-IR measurement result before surface modification. Comparing the results after the surface modification with the control from FIG. 1, the peak near 3400 cm ⁻¹ derived from the amino group N—H and the peak near 3000 cm ⁻¹ derived from the alkyl group and the methacrylate group C—H are clearly increased. It can be seen that the surface of the nanodiamond particles is chemically modified.

  FIG. 2 shows the results of thermogravimetric analysis. From FIG. 2, the weight reduction rate is clearly different from the control, and the weight percentage of inorganic components of the nanodiamond particles surface-modified with 2-isocyanatoethyl methacrylate was 71.5%.

  FIG. 3 shows the result of pyrolysis GC-MS. Compared with the control from FIG. 3, a decomposition product derived from 2-isocyanatoethyl methacrylate, which is a surface modifier, was confirmed. As described above, from the results of FT-IR measurement, thermogravimetry, and pyrolysis GC-MS, nanodiamond particles having a polymerizable compound bonded to the surface could be confirmed.

(Example 2)
In a four-necked 300 ml glass reactor equipped with a stirrer, a heating device, a reflux device and a dropping device, 120 ml of 0.5% nanodiamond dispersion previously dispersed in N-methyl-2-pyrrolidone is weighed. I took it. In this, 4.77 g of surface modification agent isophorone diisocyanate (hereinafter referred to as IPDI) was added while stirring, and the surface was modified on the nanodiamond particle surface at 150 ° C. while feeding nitrogen gas into the reaction solution at a flow rate of 30 ml / min. Reaction was performed. The reaction time was 5 hours.

  The reaction product was taken out into a 500 ml beaker, 350 ml of toluene was added, and the nanodiamond particles surface-modified with IPDI were aggregated. (A) The agglomerated nanodiamond particles were subjected to solid-liquid separation by suction filtration, the particles were taken out into a 100 ml beaker, and 80 ml of a N-methyl-2-pyrrolidone / toluene mixed solution was added. (B) Then, it wash | cleaned for 10 minutes in an ultrasonic bath, and solid-liquid separation was again performed by suction filtration. After performing the operations (a) and (b) three times, the cleaning solvent was changed to MEK, and the same operations as (a) and (b) were performed four times, followed by drying under reduced pressure for 12 hours. Obtained.

In FIG. 4, the FT-IR measurement result of the nano diamond particle by IPDI modification obtained in said Example 2 was shown. Comparing the results after the surface modification with the control from FIG. 4, the peak near 3400 cm ⁻¹ derived from the amino group N—H, the peak near 3000 cm ⁻¹ derived from the alkyl group and the methacrylate group C—H increased. In addition, a peak around 2300 cm ⁻¹ derived from the isocyanate group NCO appears, and it can be seen that the nanodiamond particle surface is chemically modified.

  FIG. 5 shows the results of thermogravimetric analysis. FIG. 5 clearly shows a difference in the weight reduction rate compared with the control, and the inorganic component weight% of the nanodiamond particles surface-modified with IPDI was 91.3%.

  FIG. 6 shows the result of pyrolysis GC-MS. Compared with the control from FIG. 6, a decomposition product derived from IPDI as the surface modifier was confirmed. As described above, from the results of FT-IR measurement, thermogravimetry, and pyrolysis GC-MS, nanodiamond particles having a polymerizable compound bonded to the surface could be confirmed.

(Example 3)
1.6 parts by weight of the surface-modified diamond prepared in Example 1, 74 parts by weight of KAYARAD OPP-1 (Nippon Kayaku Co., Ltd.) as a monomer, and 24 of KAYARAD R-551 (manufactured by Nippon Kayaku Co., Ltd.) A part by weight was mixed in n-propanol, and after removing n-propanol with an evaporator, 0.5 part by weight of Irgakia 184 (manufactured by Ciba Specialty Chemicals) was mixed as an initiator to obtain a composite cured product. When the light transmittance of the obtained cured product was measured, it was 73.8%, the familiarity with the polymer was improved, and the transparency was maintained.

(Comparative example)
The same operation was performed except that the surface-modified diamond was changed to the unmodified diamond in Example 3. When the light transmittance was measured, it was 12.7%, and since the familiarity with the polymer was not sufficient, the transparency could not be maintained.

  Unlike the polymer composite mixed by the conventional method, the surface-modified diamond of the present invention improves the familiarity of the nanodiamond and the polymer, and can be firmly bonded. Therefore, excellent mechanical properties, electrical properties, Polymer composites with thermal properties, optical properties, etc. can be produced.

Claims (4)

Vinyl which is a polymerizable functional group and an isocyanate group which reacts with diamond particles (a) having an average particle diameter of 100 nm or less having one or more polar groups selected from a hydroxyl group, an amino group or a carboxyl group on the surface and an average particle diameter of 100 nm or less. Surface-modified diamond obtained by reacting a compound (b) having at least one of a group, (meth) acrylate group, glycidyl group, amino group , carboxyl group or silanol group. A light and / or thermosetting resin composition comprising the diamond according to claim 1 and containing a resin having an unsaturated double bond, an epoxy group, and a cyclic ether .
A cured product obtained by curing the curable composition according to claim 2. A film comprising the cured product according to claim 3.

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