CN101134811A - Polymeric azo compound - Google Patents
Polymeric azo compound Download PDFInfo
- Publication number
- CN101134811A CN101134811A CNA2007101367037A CN200710136703A CN101134811A CN 101134811 A CN101134811 A CN 101134811A CN A2007101367037 A CNA2007101367037 A CN A2007101367037A CN 200710136703 A CN200710136703 A CN 200710136703A CN 101134811 A CN101134811 A CN 101134811A
- Authority
- CN
- China
- Prior art keywords
- compound
- pigment
- acid
- azo compound
- polymeric azo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a novel macromolecule azo compound with good solubility which is used for polymerizing initiator and pigment, comprising a polymerization initiator formed by the macromolecule azo compound, pigment whose surface is grafted macromolecule free radical obtained by the macromolecule azo compound and a pigment combination containing the pigment. Wherein, the macromolecule azo compound is represented by the formular (I), in the formular, R<12>, R<13>, R<22> and R<23> represent alkyl with 1-10 carbon atoms or cyan respectively, a and b represent 0-4 respectively, A<11> and A<12> are macromolecule chains, Y<11> and Y<12> are -CO-O-, -O-CO-, -NH-, CO-, -CO-NH-, -O- or -S- respectively.
Description
Technical field
The present invention relates to have ad hoc structure polymeric azo compound, contain polymerization starter that this polymeric azo compound forms, the pigment of the high molecular free radical that obtains by this polymeric azo compound at surface grafting and the color compositions that contains this pigment.
Background technology
Azo-2-carboxylic acid and polyalkylene glycol polycondensation and the known energy of compound that obtains are as the polymeric azo polymerization starter.For example, in patent documentation 1, disclose and contained 4, the polymerization starter of the polycondensation compound of 4 '-azo two (4-cyanopentanoic acid) and polyalkylene glycol.
In addition, if the known polymeric azo compound that will have azo bond in main chain heats with carbon black, then pass through high molecular free radical grafting on black carbon surface of the thermolysis generation of polymeric azo compound.For example, in patent documentation 2, disclosing bonding has the grafting carbon black of the grafted chain with polyalkylene oxide chain, in patent documentation 3, the carbon black that the functional group that decomposition by the radical initiator that is made of azonitrile compound produces is arranged at surface bond is disclosed, the polymer graft black carbon that the polycondensation compound of 4 '-azo two (4-cyanopentanoic acid) and polyalkylene glycol or polydimethylsiloxane obtains is disclosed by 4 in non-patent literature 1.
In patent documentation 4, disclose and contained the hard coat resin combination that has carried out the surface-treated colloid silica by silane coupling agent, but this resin combination can't obtain enough dispersivenesses.
Patent documentation 1: the spy opens the 2003-12784 communique
Patent documentation 2: the spy opens flat 9-324133 communique
Patent documentation 3: the spy opens flat 11-323176 communique
Patent documentation 4: the spy opens the 2006-63244 communique
Non-patent literature 1: polymer collection of thesis Vol.49, No.11, pp.865-870
Summary of the invention
The purpose of this invention is to provide a kind of favorable solubility, as the novel high polymer azo-compound of polymerization starter and pigment, contain polymerization starter that this polymeric azo compound forms, the pigment of the high molecular free radical that obtains by this polymeric azo compound at the surface grafting of pigment and the color compositions that contains this pigment.
The present invention is by providing by the polymeric azo compound shown in the following general formula (I), thereby realizes above-mentioned purpose.
(in the formula, R
12, R
13, R
22And R
23Represent that independently of one another carbonatoms is 1～10 alkyl or cyano group, a and b are 0～4 number independently of one another, A
11And A
12Be macromolecular chain, Y
11And Y
12Be independently of one another-CO-O-,-O-CO-,-NH-CO-,-CO-NH-,-O-or-S-.)
In addition, the present invention is by providing the polymerization starter that is made of above-mentioned polymeric azo compound, thereby realizes above-mentioned purpose.
In addition, the present invention is the grafting pigment of the high molecular free radical that produces in the thermolysis by the radical initiator that is made of above-mentioned polymeric azo compound of the surface grafting of pigment by a kind of feature, thereby realizes above-mentioned purpose.
In addition, the present invention is by providing the color compositions that contains above-mentioned grafting pigment, solvent and adhesive resin, thereby realizes above-mentioned purpose.
If use the polymerization starter that contains polymeric azo compound of the present invention to have the radical polymerization of the compound of vinyl or propenyl, then can obtain only to have the segmented copolymer of different polymkeric substance at the terminal bonding of main polymer chain, at surface grafting the dispersing of pigments height of the high molecular free radical that obtains by this polymeric azo compound.
Embodiment
Below, to novel high polymer azo-compound of the present invention, contain polymerization starter that this polymeric azo compound forms, the pigment of the high molecular free radical that obtains by this polymeric azo compound at the surface grafting of pigment and the color compositions that contains this pigment, be elaborated based on preferred implementation.
In above-mentioned general formula (I), as by R
12, R
13, R
22And R
23The carbonatoms of expression is 1～10 alkyl, can list methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, isobutyl-, amyl group, isopentyl, tert-pentyl, hexyl, cyclohexyl, cyclohexyl methyl, cyclohexyl ethyl, heptyl, different heptyl, uncle's heptyl, n-octyl, iso-octyl, uncle's octyl group, 2-ethylhexyl, n-nonyl, positive decyl etc.
In above-mentioned general formula (I), as by A
11And A
12The macromolecular chain of expression, have no particular limits, can list for example polyoxyethylene (polyoxylene) chain, polymethylene chain, polyether chain, polyester chain, polysiloxane chain, poly-(methyl) acrylate chains, polystyrene-vinyl-acetic ester chain, polyamide chains, polyimide chain, polyurethane chain, polyureas chain, poly-peptide chain etc.
As by the polymeric azo compound shown in the general formula of the present invention (I), can list following illustrative material.
In general formula (I), be to pass through Y
11, Y
12Import macromolecular chain A
11, A
12Chain polymer (below, sometimes only be designated as " chain polymer "), can list: have and make the polymeric azo compound that has the compound of hydroxyl and azodicarboxy acid compound reaction resulting structures at an end, have an end that makes at chain polymer and have the compound of epoxy group(ing) and the polymeric azo compound of azodicarboxy acid compound reaction resulting structures, have an end that makes at chain polymer and have the compound of hydroxyl and the polymeric azo compound of azo dicarboxylic anhydride reaction resulting structures, have and make the polymeric azo compound that has amino compound and azodicarboxy acid compound reaction resulting structures at an end of chain polymer, have an end that makes at chain polymer and have the compound of epoxy group(ing) and the polymeric azo compound of azo diol compound reaction resulting structures, have an end that makes at chain polymer and have the compound of carboxyl and the polymeric azo compound of azo diol compound reaction resulting structures, have the compound that has alcohol radical endways that makes compound with carboxyl or alcohol radical and epoxy compounds and acid anhydrides cross reaction and obtain and the polymeric azo compound of azodicarboxy acid compound reaction resulting structures, have the compound that has carboxyl endways that makes compound with carboxyl or alcohol radical and epoxy compounds and acid anhydrides cross reaction and obtain and the polymeric azo compound of azodicarboxy acid compound reaction resulting structures, have an end that makes at chain polymer and have the compound of anhydride group and the polymeric azo compound of azo diol compound reaction resulting structures, have an end that makes at chain polymer and have the compound of hydroxyl and the polymeric azo compound of azo two carboxylic acid halides reaction resulting structures, have and make the polymeric azo compound that has amino compound and azo two acetyl halide compounds reaction resulting structures at an end of chain polymer, have an end that makes at chain polymer and have the compound of acid halide group and the polymeric azo compound of azo diol compound reaction resulting structures, have an end that makes at chain polymer and have the compound of cyclic ester structure and the polymeric azo compound of azo diol compound reaction resulting structures, has the polymeric azo compound that makes azodicarboxy acid compound and cyclic ester compound ring-opening polymerization resulting structures, has the polymeric azo compound that makes azodicarboxy acid compound and cyclic amide compound ring-opening polymerization resulting structures, has the polymeric azo compound that makes azodicarboxy acid compound and cyclic ether compound ring-opening polymerization resulting structures, has the polymeric azo compound that makes azodicarboxy acid compound and epoxy compounds generation anionoid polymerization resulting structures, has the macromolecular compound that makes azo diol compound and cyclic ester compound ring-opening polymerization resulting structures, has the compound that makes azodicarboxy acid compound and epoxy compounds and acid anhydrides cross reaction resulting structures, has compound that makes azo diol compound and acid anhydrides and epoxy compounds cross reaction resulting structures etc., wherein, be preferably and have the polymeric azo compound that makes the compound that in an end of chain polymer, has hydroxyl and azodicarboxy acid compound reaction resulting structures.
The above-mentioned compound (A) that has hydroxyl in an end of chain polymer is by 1.5～2.5 normal compounds (A) that have hydroxyl in an end of chain polymer are obtained with the reaction of 1 normal azodicarboxy acid compound (B) with the polymeric azo compound that azodicarboxy acid compound (B) esterification obtains.The above-mentioned compound (A) that has hydroxyl in an end of chain polymer can use a kind or will be used in combination more than 2 kinds, can select, and makes its total satisfy aforementioned proportion.
As the above-mentioned compound (A) that in an end of chain polymer, has hydroxyl, can list for example polyalkylene glycol monoalkyl ether, the polypropylene glycol monoalky lether, the block of oxyethane and propylene oxide or random affixture and an end are the ethylene glycol of alkoxyl group or the condenses of propylene glycol, at least one end is the polyester of hydroxyl, have at least one end hydroxyl ethylenically unsaturated monomer monomer or multipolymer, the thermoplastic resin that has hydroxyl endways, has the thermosetting resin of hydroxyl etc. endways, owing to can when pigment is carried out grafting, give good dispersiveness, therefore preferred polyalkylene glycol monoalkyl ether, the polypropylene glycol monoalky lether, the block of oxyethane and propylene oxide or random affixture and an end are the ethylene glycol of alkoxyl group or the condenses of propylene glycol.
As above-mentioned thermoplastic resin, can list polymethylmethacrylate, Vinyl toluene acrylate polyvinyl butyral, the polyvinyl acetal, Polyvinylpyrolidone (PVP), polyvinyl alcohol, polyvinyl chloride, vinylchlorid-vinyl acetate copolymer, vinylchlorid-ethylene copolymer, vinylchlorid-vinylidene chloride-vinyl acetate terpolymers, vinylchlorid-maleate copolymer, vinylchlorid-alkylmethacrylate polymer, vinylchlorid-acrylonitrile copolymer, vinylchlorid-various vinyl ether co-polymers, styrene-acrylate, the ethylene-vinyl acetate ester copolymer, ethene-(methyl) ethyl acrylate copolymer, vinylbenzene-butadienecopolymer, polystyrene, polycarbonate, polymeric amide, polyamidoimide, polyetherimide, urethane, polyester, polycaprolactone, butyrolactone, poly(lactic acid), polyacrylonitrile, synthesized polymer materials such as vinylbenzene-copolymer-maleic anhydride, as thermosetting resin, can list Resins, epoxy, polyimide, resol etc.
As above-mentioned azodicarboxy acid compound (B), can list compound by following general formula (I-1) expression.
(in the formula, R
12, R
13, R
22, R
23, a is identical with above-mentioned general formula (I) with b.)
As polymeric azo compound by above-mentioned general formula (I) expression, preferred Y
11Be-O-CO-, Y
12Be-compound of CO-O-, by A
11And A
12The macromolecular chain of expression is the cheap and manufacturing easily of the compound of polyether chain and polyester chain, is preferred therefore.
A
11And A
12Polyether chain can import by Aethoxy Sklerol, as polyether alcohols, can list use methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, 2-butanols, isopropylcarbinol, the trimethyl carbinol, amylalcohol (amyl alcohol), tertiary amyl alcohol, hexanol, hexalin, amylalcohol (pentanol), octanol, uncle's octanol, 2-ethylhexanol, decyl alcohol, dodecyl alcohol, lauryl alcohol, oleyl alcohol, stearyl alcohol, monoalkyl alcohol such as docosyl alcohol are with oxyethane, propylene oxide, epoxiess such as glycidyl ether, the trimethylene oxide class, the compound that cyclic ether compound ring-opening polymerizations such as tetrahydrofuran (THF) (oxolane) class oxane class obtain, and use above-mentioned monoalkyl alcohol the above-mentioned cyclic ether more than 2 kinds to be carried out the compound of block or random addition gained.
At A
11And A
12Be in the compound of polyether chain, because solvability height, the molecular weight of controlled polymerization initiator easily, and can obtain the high grafting pigment of dispersiveness by the compound of following formula general formula (II) expression, so be preferred.
(in the formula, R
12, R
13, R
22, R
23, a is identical with above-mentioned general formula (I) with b, R
11And R
21Represent that independently of one another carbonatoms is 1～24 alkyl, Z
11, Z
12, Z
21And Z
22Represent that independently of one another carbonatoms is 1～4 alkylidene group, m, n, s and t are 0～1000 number independently of one another, m+n's and, s+t's and be more than 2 independently of one another.)
In above-mentioned general formula (II), as by Z
11, Z
12, Z
21And Z
22The carbonatoms of expression is 1～4 alkylidene group, can list methylene radical, ethylidene, trimethylene, propylidene, 1,1-propylidene, isopropylidene, tetramethylene, butylidene, isobutylene, ethyl ethylidene, dimethyl ethylidene etc.; As by R
11And R
21The carbonatoms of expression is 1～24 alkyl, can list methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, isobutyl-, amyl group, isopentyl, tert-pentyl, hexyl, cyclohexyl, cyclohexyl methyl, cyclohexyl ethyl, heptyl, different heptyl, uncle's heptyl, n-octyl, iso-octyl, uncle's octyl group, 2-ethylhexyl, n-nonyl, positive decyl, lauryl, stearyl, docosyl etc.As by R
11And R
21The carbonatoms of expression is in 1～24 the alkyl, because being 1～4 alkyl, carbonatoms can obtain the high grafting pigment of dispersiveness, in addition, having esterification reactive high of the compound of hydroxyl and azodicarboxy acid compound at an end of chain polymer, is preferred therefore.
As polymeric azo compound by above-mentioned general formula (II) expression, preferred R
12And R
22Be methyl, R
13And R
23Be cyano group, a and b are 2 compounds, in addition, because synthetic easily and cost is low, are preferred by the compound of following general formula (II-1) expression therefore.
(in the formula, R
11, R
21, n, m, s be identical with above-mentioned general formula (II) with t.)
At above-mentioned general formula (II) with (II-1), m and n and and s and t's and be 20～100 compound, owing to can obtain dispersed high grafting pigment, in addition, having esterification reactive high of the compound of hydroxyl and azodicarboxy acid compound at an end of chain polymer, is preferred therefore.
A
11And A
12Polyester chain can import by polyesterols, as the polyesterols compound, material, monoprotic acid or the monohydroxy-alcohol compound that the polylactone that can list material that the hydroxyl of an end of the dehydration polycondensate, low-molecular-weight diol compound of monohydroxy acid and polyester polyalcohols that diprotic acid obtains, this polyester polyalcohols obtained by the monoprotic acid esterification, the lactone ring-opening polymerization is obtained, the terminal carboxyl(group) of this polylactone are obtained by the esterification of monohydroxy-alcohol compound and the reactant of esterification of cyclic ether and dibasic acid anhydride.
As above-mentioned monohydroxy acid, can list oxyacetic acid, lactic acid, 3-hydroxybutyric acid, 3-hydroxyl-3-methylbutyric, 2-Hydroxyoctanoic acid, 15-hydroxyl pentadecane carboxylic acid, phenylglycollic acid, benzyl acid, Whitfield's ointment, cresotinic acid, o-hydroxy propionic acid, phloretic acid etc.; As low-molecular-weight diol, can list ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propylene glycol, 2-butyl-2-ethyl-1,3-propylene glycol, 1,4-butyleneglycol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexylene glycol, 1,7-heptanediol, 3,5-heptanediol, 1,8-ethohexadiol, 2-methyl-1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol; As diprotic acid, can list oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, the dodecyl diacid, 2-methylsuccinic acid, 2-methyl hexanodioic acid, 3-methyl hexanodioic acid, 3-methyl pimelic acid, 2-methyl pimelic acid, 3,8-dimethyl sebacic acid, 3,7-dimethyl sebacic acid, phthalic acid, terephthalic acid, m-phthalic acid, phthalic acid, aromatic dicarboxylic acid classes such as naphthalic acid, 1,2-suberane dicarboxylic acid, 1,3-suberane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,4-dicarboxyl methylene radical hexanaphthene; As monoprotic acid, can list acetate, propionic acid, butyric acid, isopropylformic acid, valeric acid, caproic acid, sad, 2-thylhexoic acid, n-nonanoic acid, sad, neodecanoic acid, undeeanoic acid, laurostearic acid, tridecylic acid, TETRADECONIC ACID, pentadecanoic acid, palmitic acid, margaric acid, stearic acid; As lactone, can list γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, γ-butyrolactone, α-ethanoyl-γ-butyrolactone, δ-caprylolactone, γ-undecane lactone, δ-lauryl lactone, rac-Lactide, glycollide etc.; As the monohydroxy-alcohol compound, can list methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, 2-butanols, isopropylcarbinol, the trimethyl carbinol, amylalcohol, tertiary amyl alcohol, hexanol, hexalin, enanthol, octanol, uncle's octanol, 2-ethylhexanol, decyl alcohol; As cyclic ester, can list epoxiess such as oxyethane, propylene oxide, glycidyl ether, trimethylene oxide class, tetrahydrofuran derivatives, oxane class etc.; As dibasic acid anhydride, can list succinyl oxide, maleic anhydride, citraconic anhydride, itaconic anhydride, trimellitic acid 1,2-anhydride, the pyromellitic acid acid anhydride, 2,2 '-3,3 '-benzophenone tetracarboxylic anhydride, 3,3 '-4,4 '-benzophenone tetracarboxylic anhydride, ethylene glycol bisthioglycolate (three trimellitates dewater), glycerine three (three trimellitates dewater), Tetra hydro Phthalic anhydride, methyl tetrahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, norbornene dicarboxylic anhydride, methyl norbornene dioic anhydride, the trialkyl Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, trialkyl Tetra Hydro Phthalic Anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, the interior methylene radical six hydrogen phthalic anhydrides (Methyl HymicAnhydride) of methyl etc.
In addition, at A by the polymeric azo compound of above-mentioned general formula (I) expression
11And A
12Be in the material of polyester chain, by the favorable solubility of the compound of following general formula (III) expression, therefore the water tolerance excellence is preferred.
(in the formula, R
12, R
13, R
22, R
23, a is identical with above-mentioned general formula (I) with b, Z
13And Z
23Represent that independently of one another carbonatoms is 1～18 alkylidene group, R
31And R
41Represent that independently of one another hydrogen atom or carbonatoms are 1～24 alkyl, p and u are 1～1000 number independently of one another.)
In above-mentioned general formula (III), as by Z
13And Z
23The carbonatoms of expression is 1～18 alkylidene group, can list methylene radical, ethylidene, trimethylene, propylidene, 1,1-propylidene, isopropylidene, tetramethylene, butylidene, isobutylene, ethyl ethylidene, dimethyl ethylidene, pentamethylene, hexa-methylene, heptamethylene, eight methylene radical, 1,4-pentane, two bases, decamethylene, 11 methylene radical, 1,4-undecane, two bases, ten dimethylenes, 1,11-heptadecane, two bases, octadecane two bases etc. are as by R
31And R
41The carbonatoms of expression is 1～24 alkyl, can list in the above-mentioned general formula (II) as R
11And R
21Illustrative group.As by R
31And R
41The carbonatoms of expression is 1～24 alkyl, carbonatoms is 1～4 group owing to can obtain dispersed high grafting pigment, in addition, having esterification reactive high of the compound of hydroxyl and azodicarboxy acid compound at an end of chain polymer, is preferred therefore.
In above-mentioned general formula (III), p and u are 20～100 material owing to can obtain dispersed high grafting pigment, in addition, having esterification reactive high of the compound of hydroxyl and azodicarboxy acid compound at an end of chain polymer, is preferred therefore.
The reaction that obtains polymeric azo compound of the present invention can be carried out according to conventional methods, and preferably in inactive gas atmosphere such as nitrogen, argon gas, ℃ following reaction is 30 minutes～10 hours in room temperature～50.
In the reaction that obtains polymeric azo compound of the present invention, as required, can use appropriate solvent.As this solvent, can list ketones such as methylethylketone, Methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK), pimelinketone; Ether solvents such as ether, diox, tetrahydrofuran (THF), 1,2-glycol dimethyl ether, 1,2-diethoxyethane, dipropylene glycol dme; Esters solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate; Cellosolve kind solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol methyl ether acetate; Alcoholic solvents such as methyl alcohol, ethanol, XOR n-propyl alcohol, XOR propyl carbinol, amylalcohol; Solvent of ether ester type such as glycol monomethyl methyl acetic acid ester, glycol monomethyl ethylhexoate, propylene glycol methyl acetic acid ester; BTX kind solvents such as benzene,toluene,xylene; Aliphatic hydrocarbon kind solvents such as hexane, heptane, octane, hexanaphthene; Terpenes hydrocarbon ils such as turps, D-limonene, firpene; Solvent oil, ス ワ ゾ-Le #310 (コ ス モ Guia Hill oil (strain)), ソ Le ベ Star ソ #100 paraffin class solvents such as (worker's Network ソ Application chemistry (strain)); Halogenated aliphatic hydrocarbon kind solvents such as tetracol phenixin, chloroform, trieline, methylene dichloride, 1,2-ethylene dichloride; Halogenated aromatic varsols such as chlorobenzene; Trivalin SF kind solvent, aniline, triethylamine, pyridine, acetate, acetonitrile, dithiocarbonic anhydride, N, N-dimethyl formamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), water etc., these solvents can use a kind, or use with the form of mixed solvent more than 2 kinds.
In the reaction that obtains polymeric azo compound of the present invention, as required, can also add condensing agent.As this condensing agent, there is no particular limitation, can use the material that uses in the present esterification, can list for example N, carbodiimide classes such as N-dicyclohexylcarbodiimide, 1-ethyl-3-(dimethylaminopropyl) carbodiimide, DIC; 2,4, aryl sulfonyl chloride classes such as 6-triisopropylphenylsulfonyl chloride, Tosyl chloride; 2,4,6-tri isopropyl benzenesulfonyl Orazamide, 2,4, arylsulfonamides such as 6-tri isopropyl benzenesulfonyl triazolylamide; The azodicarboxylate; Organic sulfonic acid halide; Diphenyl phosphate azide, diethoxy phosphoryl chloride, nitrine phosphoric acid diethoxy ester, propyl phosphonous acid acid anhydride, diphenyl phosphoryl chloride; Metal alkoxides such as dimethoxy magnesium, diethoxy magnesium, diisopropoxy aluminium, three tert.-butoxy aluminium; Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide; Alkaline-earth metal such as calcium hydroxide, magnesium hydroxide oxyhydroxide; Alkaline-earth metals oxide such as calcium oxide, magnesium oxide; Amination basic metal such as lithium amide; Lime carbonate, zinc chloride, aluminum chloride, oxo phosphorus chloride, tetramethyl ammonium chloride, the vitriol oil, Vanadium Pentoxide in FLAKES, Tripyrophosphoric acid, diacetyl oxide, carbonyl dimidazoles, Tosyl chloride, deacidite etc.In addition, as the condensation auxiliary agent, can also use organic basess such as triethylamine, pyridine, benzylamine, benzyl methylamine, γ-dimethyl aminopyridine, xylidine, tributylamine, 4-piperidyl pyridine.
Polymerization starter of the present invention is made of polymeric azo compound of the present invention, can make for example ethylenically unsaturated monomer polymerization or copolymerization.As above-mentioned ethylenically unsaturated monomer, there is no particular limitation, can use known material.Can list for example unsaturated fatty hydrocarbons such as ethene, propylene, butylene, iso-butylene, vinylchlorid, vinylidene chloride, vinylidene, tetrafluoroethylene; (methyl) vinylformic acid, methylene-succinic acid, toxilic acid, citraconic acid, fumaric acid, interior methylene radical six hydrogen phthalic acids (Hymic acid), Ba Dousuan, iso-crotonic acid, vinyl-acetic ester, allyl acetate, styracin, Sorbic Acid, (methyl) Hydroxyethyl acrylate maleic acid ester, (methyl) Propylene glycol monoacrylate maleic acid ester, Dicyclopentadiene (DCPD) maleic acid ester or have 1 carboxyl and the unsaturated polyprotonic acids such as multifunctional (methyl) acrylate of (methyl) acryl more than 2; (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid-2-hydroxypropyl acrylate, (methyl) glycidyl acrylate, following compound N o.1～No.4, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) stearyl acrylate ester, (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) dimethylaminoethyl acrylate, 1,6 hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, three ((methyl) acryloxy ethyl) chlorinated isocyanurates, the ester of unsaturated monoprotic acid such as polyester (methyl) origoester acrylate and polyvalent alcohol or polyphenol; The metal-salt of unsaturated polyprotonic acids such as (methyl) zinc acrylate resin, (methyl) vinylformic acid magnesium; Maleic anhydride, itaconic anhydride, methyl tetrahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, trialkyl Tetra Hydro Phthalic Anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, trialkyl Tetra Hydro Phthalic Anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methyl in the acid anhydrides of unsaturated polyprotonic acid such as methylene radical six hydrogen phthalic anhydrides; The acid amides of unsaturated monoprotic acid such as two (methyl) acrylamides of (methyl) acrylamide, methylene-bis (methyl) acrylamide, diethylenetriamine three (methyl) acrylamide, xylyl and polyamine; Unsaturated aldehydes such as propenal; Unsaturated nitriles such as (methyl) vinyl cyanide, cyano group allyl group; Unsaturated aromatics such as vinylbenzene, 4-vinyl toluene, 4-ethyl styrene, 4-hydroxy styrenes, 4-chloro-styrene, Vinylstyrene, vinyl benzoic acid, vinylphenol, vinyl sulfonic acid, 4-vinylbenzenesulfonic acid; Beta-unsaturated ketones such as methyl vinyl ketone; Vinyl alcohol such as unsaturated amine compounds such as vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl piperidines, allyl alcohol, crot(on)yl alcohol; Vinyl ether such as ethyl vinyl ether, N-butyl vinyl ether; Vinyl thioether, vinyl imidazole, Yi Xi oxazolin, vinylcarbazole, vinyl adjoin vinyl epoxy compoundss such as the vinyl monomer of vinyl urethane compound, hydroxyl of the vinyl monomer of pyrrolidone, vinyl pyridine, hydroxyl and polyisocyanate compounds and polyepoxides etc.
Compound N o.1
Compound N o.2
Compound N o.3
Compound N o.4
As using polymerization starter of the present invention to make the method for ethylenically unsaturated monomer polymerization or copolymerization, can list for example solution polymerization, block polymerization, outstanding turbid polymerization, letex polymerization etc.
Above-mentioned polymerization or copolymerization preferably in the inactive gas atmosphere, were carried out under 20～150 ℃ 30 minutes～20 hours, in addition, as required, can use catalyzer, polymerization retarder, chain-transfer agent, solvent etc.
The usage quantity of polymerization starter of the present invention is also different according to the kind of employed ethylenically unsaturated monomer, with respect to the 1mol ethylenically unsaturated monomer, is generally 0.1～100mol%, is preferably 1.0～10mol%.Polymeric azo compound of the present invention can use or use close multiple of decomposition temperature separately.
Grafting pigment of the present invention is to use the free-radical generating agent that is made of polymeric azo compound of the present invention, by with its thermolysis and the high molecular free radical that is generated is grafted on the pigment that the surface of pigment obtains, as its manufacture method, so long as utilize the delocalization πDian Zi that exists in surface of pigments that the free-radical generating agent chemical bonding is got final product, specifically, can list the free-radical generating agent thermolysis that will constitute by polymeric azo compound and the method for the high molecular free radical that generates at present known surface of pigments chemical bonding (grafting).Wherein, so-called " grafting " is meant the irreversible addition of polymkeric substance to the such matrix of pigment.
In the thermolysis of the above-mentioned free-radical generating agent that will constitute by polymeric azo compound and the high molecular free radical that generates be grafted in the method for present known surface of pigments, the grafting reaction is preferably under the inactive gas atmosphere, in appropriate solvent, under 40～150 ℃, carried out 30 minutes～48 hours.
In above-mentioned grafting reaction, the usage quantity of polymeric azo compound is 1～1000 mass parts with respect to the pigment optimization of 100 mass parts, more preferably 10～100 mass parts.
As above-mentioned known pigment, for example can use nitroso compound, nitro-compound, azo-compound, two azo-compounds, cluck ton compound, quinoline compound, anthraquinone compounds, coumarin compound, phthalocyanine compound, isoindoline ketone compound, isoindoline compounds, quinoline a word used for translation ketone compound, anthanthrone compound, perillone compound, perylene compound, diketo pyrrolo-to adjoin and cough up compound, thioindigo compound, dioxazine compound, triphenyl methane compound, quinophthalone compound, naphthalene tetracarboxylic acid; The metal complex of azoic dyestuff, cyanine dyes; Pigment lake; Carbon black that obtains by oven process, channel process, hot method or acetylene black, Ketjen black or carbon black such as dim; Above-mentioned carbon black has been carried out material after acid and the basic surface processing; Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, the little volume of carbon, carbon nanohorn (carbonnanohorns), carbon aerosol, soccerballene; Nigrosine, Pigment black 7, titanium are deceived; Hydrophobic resin; Metal oxides such as chromic oxide, nickel oxide, ferric oxide, Indium sesquioxide, titanium oxide, zinc oxide, calcium oxide, potassium oxide, silicon oxide, aluminum oxide; Layered clay mineral, milori blue (miloriblue), lime carbonate, magnesiumcarbonate, cobalt class, manganese class, talcum, kaolin, yellow prussiate, various metal sulfate, sulfide, selenide, phosphoric acid salt ultramarine, dark purple, ultramarine, sky blue green grass or young crops, tie up organic or inorganic pigment such as sharp Dean (ピ リ ジ ア Application) pigment, emerald.These pigment can use separately, or multiple mixing is used.
As above-mentioned known pigment, commercially available pigment can also be used, for example Pigment red 1,2,3,9,10,14,17,22,23,31,38,41,48,49,88,90,97,112,119,122,123,144,149,166,168,169,170,171,177,179,180,184,185,192,200,202,209,215,216,217,220,223,224,226,227,228,240,254 can be listed; Pigment Orange 13,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,65,71; Pigment Yellow 73 1,3,12,13,14,16,17,20,24,55,60,73,81,83,86,93,95,97,98,100,109,110,113,114,117,120,125,126,127,129,137,138,139,147,148,150,151,152,153,154,166,168,175,180,185; Pigment Green 7,10,36; Pigment Blue 15,15:1,15:2,15:3,15:4,15:5,15:6,22,24,56,60,61,62,64; Pigment violet 1,19,23,27,29,30,32,37,40,50 etc.
The median size of grafting pigment of the present invention is 30～300nm and since addition less just can, dispersed high, so be preferred.As the method that grafting pigment is disperseed or pulverizes, can list the use mortar, ball mill, mould grinding machine (plasto mill), ball mill, vibromill, roller mill, rod mill, tuber grinder, the taper thread grinding machine, the Hai Siwen ball mill, pin type runner milling, hammer mill, the cutter hammer mill, buhrstone mill, jet-propelled runner milling, reverse jet-propelled runner milling, the jet-propelled runner milling of spiral, jet-propelled mixing machine (ジ エ Star ト マ イ ザ one), micronizer mill, nanometer mixing machine (Na ノ マ イ ザ one), マ ジ ヤ Star Network ミ Le, little spraying gun, pulverising mill (ミ Network ロ Application ミ Le), rotary knife cutter, impact grinding type runner milling, compression cut-off type runner milling, the method of Henschel mixing tank etc.
Grafting pigment of the present invention can be at printing ink, coating, makeup, tackiness agent, the electroconductibility imparting agent, conductive paper, the pigment of resin, the electrofax material, weighting agent, toughener, coating material, battery material, electrode materials, electronic material, antistatic material, the electromagnetic shielding material, the cable semi-conductor, planar heat producing body, sorbent material, catalyzer, the properties-correcting agent of plastics or rubber, lubricant, nonlinear optical material, fiber, carbon nanotube, plated material, various recording mediums, use in the extensive uses such as sealing agent.
Grafting pigment of the present invention can pass through to disperse grafting pigment of the present invention and adhesive resin in solvent, thereby as color compositions.
In color compositions of the present invention, the content of above-mentioned grafting pigment is preferably 10～100 quality %, more preferably 50～90 quality % in the shared all solids composition in color compositions.
In addition, as required, can and adjust agent, surface tension with viscosity modifier, pH and adjust agent, tackifier, thixotropy imparting agent, flow agent, defoamer, binding property imparting agent, sequestrant, wetting Agent for Printing Inks, permeate agent, mould inhibitor, rust-preventive agent, sanitas, anti-drying dose, quick-drying agent, fixing salt, oxidation inhibitor, UV light absorber, thermo-stabilizer, fire retardant, lubricant, processing aid, anti-hard caking agent, ionogen, catalyzer, dispersion agent, the known pigment etc. of grafting not.
As above-mentioned solvent, so long as can dissolve or disperse the solvent of above-mentioned each composition, just have no particular limits, can use as the illustrated material of solvent in the reaction that obtains above-mentioned polymeric azo compound.These solvents can use a kind, or use with the form of the mixed solvent more than 2 kinds.In color compositions of the present invention, the content of above-mentioned solvent can be modulated into and make that shared all solids composition is 0.1～30 quality % in the color compositions.
As above-mentioned adhesive resin, have no particular limits, can use at printing ink, coating, coating material, normally used tackiness agent in the welding resist etc. can use for example photo-curable resin, thermosetting resin, alkali soluble resins, acrylic resin, soluble nylon and polymer latex, melamine resin, resol, Resins, epoxy, Phthalic acid, diallyl ester, petroleum resin, maleic acid resin, resol, Synolac, polyorganosiloxane resin, fluoro-resin, the urethane that reaction by ring-type (ester ring type or aromatic series) isocyanic ester and polyvalent alcohol obtains, gelatin, casein, starch, derivatived cellulose, natural macromolecular materials such as Lalgine, the polyvinyl butyral, Polyvinylpyrolidone (PVP), polyvinyl alcohol, polyolefine, polyvinyl chloride, styrol copolymer, polystyrene, polycarbonate, polymeric amide, polyester etc.
In color compositions of the present invention, the content of above-mentioned adhesive resin in the shared all solids composition, is preferably 1～70 quality % in color compositions, more preferably 3～30 quality %.
In color compositions of the present invention, can use Photoepolymerizationinitiater initiater.
As above-mentioned Photoepolymerizationinitiater initiater; can use existing compound known; for example preferred benzophenone; phenylbiphenylyl ketone; 1-hydroxyl-1-2-benzoyl-cyclohexane; benzyl; benzyl dimethyl ketal; 1-benzyl-1-dimethylamino-1-(4 '-morpholinyl benzoyl) propane; 2-morpholinyl-2-(4 '-methyl mercapto) benzoyl propane; thioxanthone; 1-chlorine-4-propoxy-thioxanthone; isopropyl thioxanthone; diethyl thioxanthone; EAQ; 4-benzoyl-4 '-methyldiphenyl base sulfide; the bitter almond oil camphor butyl ether; 2-hydroxyl-2-benzoyl propane; 2-hydroxyl-2-(4 '-sec.-propyl) benzoyl propane; 4-butylbenzene formyl radical trichloromethane; 4-phenoxy group benzoyl trichloromethane; the benzoyl methyl-formiate; 1; 7-two (9 '-acridyl) heptane; 9-normal-butyl-3; 6-two (2 '-morpholinyl butyryl radicals) carbazole; 2-methyl-1-[4-(methyl sulfenyl) phenyl]-2-morpholinyl propane-1-ketone; 2-methyl-4; 6-two (trichloromethyl)-s-triazines; 2-phenyl-4; 6-two (trichloromethyl)-s-triazines; 2-naphthyl-4,6-two (trichloromethyl)-s-triazines; following compound N o.5; No.6 etc.In these materials, preferred benzophenone, 2-methyl-1-[4-(methyl sulfenyl) phenyl]-2-morpholinyl propane-1-ketone.
Compound N o.5
(in the formula, X
1Expression halogen atom or alkyl, R
5Expression R, OR, COR, SR, CONRR ' or CN; R
6Expression R, OR, COR, SR or NRR '; R
7Expression R, OR, COR, SR or NRR '; R and R ' expression alkyl, aryl, aralkyl or heterocyclic radical; These groups can also be replaced by halogen atom and/or heterocyclic radical; In these groups, the alkylene moiety of alkyl and aralkyl can also be interrupted by unsaturated link(age), ehter bond, thioether bond or ester bond, and in addition, R and R ' be Cheng Huan in the lump, and f is 0～5.)
Compound N o.6
(in the formula, X
1, R
5, R
6, R
7, R is identical with above-claimed cpd No.5 with R '; X
1' expression halogen atom or alkyl; Z represents that Sauerstoffatom or sulphur are former.Son; G and h represent 1～4 number separately; R
5' expression R, OR, COR, SR, CONRR ' or CN; R
6' expression R, OR, COR, SR or NRR '; R
7' represent R, OR, COR, SR or NRR ' respectively; R
8Expression diol residue or two mercaptan residues.)
In color compositions of the present invention, can also and use ethylenically unsaturated monomer, chain-transfer agent, tensio-active agent etc.
As above-mentioned ethylenically unsaturated monomer, can list as stating polymeric azo compound in the use as the polymerization of polymerization starter or the ethylenically unsaturated monomer in the copolymerization and illustrative material.
As above-mentioned chain-transfer agent, can list Thiovanic acid, mercaptosuccinic acid, thiosalicylic acid, 2-thiohydracrylic acid, 3-thiohydracrylic acid, 3-sulfydryl butyric acid, N-(2-mercapto radical propionyl group) glycine, 2-sulfydryl nicotinic acid, 3-[N-(2-mercaptoethyl) formamyl] propionic acid, 3-[N-(2-mercaptoethyl) amino] propionic acid, N-(3-mercapto radical propionyl group) L-Ala, 2-sulfydryl ethyl sulfonic acid, 3-sulfydryl propanesulfonic acid, 4-sulfydryl fourth sulfonic acid, dodecyl (4-methylthio group) phenyl ether, 2-mercaptoethanol, 3-sulfydryl-1,2-propylene glycol, 1-sulfydryl-2-propyl alcohol, 3-sulfydryl-3-butanols, mercapto-phenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-sulfydryl-3-pyridol, 2-mercaptobenzothiazole, Thiovanic acid, trimethylolpropane tris (3-mercaptopropionic acid ester), tetramethylolmethane four sulfhydryl compounds such as (3-mercaptopropionic acid esters); Disulphide with this sulfhydryl compound oxidation acquisition; Iodo-alkyl compounds such as iodo acetate, iodo propionic acid, 2-ethylene iodohydrin, 2-iodo ethyl sulfonic acid, 3-iodo propanesulfonic acid.
As above-mentioned tensio-active agent, can use tensio-active agents such as nonionogenic tensides such as cationic tensio-active agent, polyethylene glycol alkyl ether, cithrol, sorbitan fatty acid esters, glycerine monofatty ester, amphoterics, polysiloxane-based tensio-active agent such as anionic species tensio-active agents such as fluorochemical surfactants such as perfluoralkyl phosphate, perfluoroalkyl carboxylate, higher fatty acid alkali salt, alkylsulfonate, alkyl-sulphate, higher amines halate, quaternary ammonium salt, they can also be used in combination.
In color compositions of the present invention, can also improve the characteristic of cured article by further use thermoplastic organic polymer.As this thermoplastic organic polymer, can list for example polystyrene, polymethylmethacrylate, methyl methacrylate-ethyl acrylate copolymer, poly-(methyl) vinylformic acid, vinylbenzene-(methyl) acrylic copolymer, (methyl) vinylformic acid-methylmethacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester etc.
In addition, in color compositions of the present invention, as required, can also add thermal polymerization inhibitors such as methyl-phenoxide, quinhydrones, pyrocatechol, tert-butyl catechol, phenothiazine; Catalyzer; Lubricant; Stablizer; Fire retardant; Softening agent; Adhesion promotor; Weighting agent; Defoamer; Dispersion agent; Flow agent; The additive that silane coupling agent etc. are commonly used.
Pigmental resin composition of the present invention can be coated with method, various printing, the known means of impregnating by spin-coating method, slot coated method, rolling method, curtain, is useful on the support substrate such as metal, paper, plastics.In addition, can also temporarily after implementing on the support substrate such as film, be transferred on other support substrate, to the not restriction of its usability methods.
Embodiment
Below, the present invention will be described in more detail by enumerating embodiment, but the present invention is not limited to these embodiment.In addition, in the following embodiments, " % " is meant quality %.Production Example 1～3 shows the synthetic of surface decoration pigment 1～3, embodiment 1-1～1-6 shows synthesizing by the polymeric azo compound 1～6 of above-mentioned general formula (II) expression, embodiment 1-7 shows synthetic by the polymeric azo compound 7 of above-mentioned general formula (III) expression, and embodiment 2 shows and uses the Raolical polymerizable of polymeric azo compound as polymerization starter.Embodiment 3-1～3-14 shows the synthetic of grafting pigment 1～14, comparative example 3-1～3-5 shows the synthetic of comparison grafting pigment 15～19, embodiment 4-1～4-14 shows the preparation of color compositions No.1～No.14, comparative example 4-1～4-7 shows the preparation of comparison color compositions No.15～No.21, embodiment 5-1～5-8 shows and contains the 3-1 by embodiment, the grafting pigment 1 that 3-4 and 3-6～3-11 obtain, 4 and 6～11 the hard coating agent and the manufacturing of hardcoat film, embodiment 6-1～6-8 shows and contains the 3-1 by embodiment, the grafting pigment 1 that 3-4 and 3-6～3-11 obtain, the preparation of 4 and 6～11 water-based paint compositions, embodiment 7-1～7-3 shows the preparation of the alkali development resin composition that contains the grafting pigment 10～12 that is obtained by embodiment 3-10～3-12.
Synthesizing of [Production Example 1] surface decoration pigment 1
(daily output chemical industry society makes to mix 80g Virahol dispersoid silica dioxide gel; Particle diameter 20nm, solids component 30%, moisture 0.5%), 4.8g vinyltrimethoxy silane, 40g Virahol and 5g ion exchanged water, the 1%HCl aqueous solution that adds 3.6g, stirred 8 hours down at 50 ℃, heat up in a steamer and desolvate, obtain to have the surface decoration pigment 1 of the silicon dioxide microparticle form of vinyl on the surface.
Synthesizing of [Production Example 2] surface decoration pigment 2
(daily output chemical industry society makes to mix 80g methyl alcohol dispersoid silica dioxide gel; Particle diameter 20nm; solids component 30%; moisture 0.5%), the γ of γ-methacryloxypropyl trimethoxy silane of 8g, 0.8g-sulfydryl propyl trimethoxy silicane, 40g Virahol and 5g ion exchanged water; the 1%NaCl aqueous solution that adds 2g; stirred 8 hours down at 50 ℃; heat up in a steamer and desolvate, obtain to have the surface decoration pigment 2 of the silicon dioxide microparticle form of methacryloyl on the surface.
Synthesizing of [Production Example 3] surface decoration pigment 3
(Japanese エ ア ロ ジ Le society makes with the P-25 of 24g; A median size is 10nm) and the 140g trimethyl carbinol in ball mill, disperseed 30 minutes.The 1%HCl aqueous solution that adds 4.8g vinyltrimethoxy silane, 5g ion exchanged water and 5g again stirred 8 hours down at 50 ℃, heated up in a steamer and desolvated, and obtained to have on the surface surface decoration pigment 3 of the titanium oxide microparticle form of vinyl.
Synthesizing of [embodiment 1-1] polymeric azo compound 1
＜step 1〉DMAP hydrochloride synthetic
In 1,4-diox of 20.0g, dissolve 1.88g (15.4mmol) dimethyl aminopyridine (DMAP), under nitrogen atmosphere, at 1, the 4-dioxane solution (0.14g/g) that keeps splashing under the room temperature hydrogenchloride of 4.10g.The white solid that filtration is separated out after cleaning with 1,4 — diox and tetrahydrofuran (THF), carries out drying, obtains the DMAP hydrochloride (yield 83%) of 2.03g as target compound.
＜step 2〉polymeric azo compound 1 synthetic
Remain on 35 ℃ and at 1 of 20.0g, dissolve 20.2g (10.1mmol) the ユ ニ オ Star Network M-2000 (poly glycol monomethyl ether that Japanese grease society makes in the 4 — dioxs, molecular weight 2000), add 1.75g (6.25mmol) 4 under nitrogen atmosphere, 4 '-azo two (4-cyano group enanthic acid) and 0.0373g (0.310mmol) DMAP also make its dissolving.Then, behind the DMAP hydrochloride that in the step 1 that adds 0.0360g (0.227mmol) embodiment 1, obtains, under 35 ℃, splash into 1, the 4 — diox of 2.63g (12.8mmol) dicyclohexylcarbodiimide and 0.5g, stirred 8 hours.1, the 4 — diox that adds 10ml filters the white solid of separating out, and splashes into 200g and is cooled to 5 ℃ normal hexane, carry out redeposition, cross filter solid, carry out drying, thereby obtained polymeric azo compound 1 (the receipts amount is 19.3g, and yield is 90%, and purity is 87%) as target compound.
(embodiment 1-2～1-6) polymeric azo compound 2～6 is synthetic
Except the compound that the pol yalkylene glycol monoalkyl ether among the embodiment 1-1 is replaced with in the table 1 record, with embodiment 1-1 synthetic macromolecule azo-compound 2～6 similarly.Synthetic result (receipts amount, yield, purity) at the polymeric azo compound of gained shown in the table 1 2～6.
Table 1
| Polymeric azo compound | Pol yalkylene glycol monoalkyl ether (P) | (P) molecular weight | Receipts amount (g) | Yield (%) | Purity (%) |
| Polymeric azo compound 2 (embodiment 1-2) | The polyoxyethylene glycol mono allyl ether | 1500 | 8.10 | 92 | 70 |
| Polymeric azo compound 3 (embodiment 1-3) | The polyethyleneglycol lauryl ether | 2400 | 12.0 | 90 | 56 |
| Polymeric azo compound 4 (embodiment 1-4) | The polyethyleneglycol lauryl ether | 1600 | 8.85 | 95 | 65 |
| Polymeric azo compound 5 (embodiment 1-5) | Polyoxyethylene glycol: polypropylene glycol=85/15 multipolymer | 2000 | 10.1 | 89 | 89 |
| Polymeric azo compound 6 (embodiment 1-6) | Polyoxyethylene glycol: polypropylene glycol=70/30 multipolymer | 2000 | 10.2 | 90 | 87 |
Synthesizing of [embodiment 1-7] polymeric azo compound 7
In the 50ml four-hole boiling flask, add 18.00g number-average molecular weight (Mn) and be 3000, weight-average molecular weight (Mw) is 4200 have poly--ε-caprolactone, the 20.00g diox of butoxy and stir at an end, displacement nitrogen makes its dissolving by heating.Put cold after, add to mix 4 of 2.10g, 4 '-azo two (4-cyano group enanthic acid) (ACPA), the DMAP of 0.022g and make its dissolving.In addition, the DMAP hydrochloride that adds 0.022g makes it outstanding turbid, and then, dicyclohexylcarbodiimide (DCC) and the 0.50g diox of dissolving 1.54g are installed on the four-hole boiling flask in dropping funnel, carries out dripping below 35 ℃ to make to react.Add the 20ml diox, heating (＜35 ℃) leaches white precipitate by filtration.Filtrate is splashed in the cold hexane of 200g, carry out redeposition by stirring.It is filtered, drying, thus acquisition is as the polymeric azo compound 7 (the receipts amount is 16.3g, and yield is 82%, and purity is 87%) of target compound.
Qualification result at the polymeric azo compound of gained shown in the table 2 1～7.
Table 2
| H 1NMR(ppm) | C 13NMR(ppm) | |
| Compound 1 DMSO-d6) | 1.62(s)，1.65(s)，2.35-2.52 (m)，3.4-3.7(m)，4.17(t) | 22.3， 28.5，32.3， 57.9，63.5，68.1， 69.5-70.5，71.2，117.8，171.0 |
| Compound 2 (DMSO-d6) | 1.62(s)，1.65(s)，2.35-2.52 (m)，3.4-3.7(m)，3.95(d)， 4.17(t)，5.13(d)，5.22(d)， 5.88(m) | 22.8，28.5，32.3，63.5，68.1，69.5- 70.5，71.2，117.8，132.5，171.0 |
| Compound 3 (DMSO-d6) | 0.9-1.7(m)，2.35-2.52(m)， 3.4-3.7(m)，4.17(t) | 14.1，22.7，22.8，26.1，28.5，29.3- 29.6，31.9，32.3.63.5.64.9，68.1， 69.5-70.5，71.2，117.8，171.0 |
| Compound 4 (DMSO-d6) | 0.9-1.7(m)，2.35-2.52(m)， 3.4-3.7(m)，4.17(t) | 14.1，22.7，22.8，26.1，28.5，29.3- 29.6，31.9，32.3，63.5，64.9，68.1， 69.5-70.5，71.2，117.8.171.0 |
| Compound 5 (DMSO-d6) | 1.04(s)，1.62(s)，1.65(s)， 2.3-2.52(m)，3.2-3.7(m)， 4.17(t) | 17.1，22.8，28.5，32.3，57.9.63.5， 66.3，68.1，69.5-70.5，71.4，74.4， 117.8，171.0 |
| Compound 6 (DMSO-d6) | 1.04 (s)，1.62(s)，1.65(s)， 2.3-2.52(m)，3.2-3.7(m)， 4.17(t) | 17.1，22.8，28.5，32.3，57.9，63.5， 66.3，68.1，69.5-70.5，71.4.74.4， 117.8.171.0 |
| Compound 7 (CDCl) | 0.84(t)，1.30-1.35(m)， 1.52-1.62(m)，1.66(s)，2.24 (t)，2.3-2.46(m)，4.00(t) | 13.6，19.0，23.6，24.4，25.4，28.1， 28.9，30.5，33.0，34.0，62.3，64.0， 64.8，71.7，117.4，171.2，173.4 |
[embodiment 2] use the Raolical polymerizable of polymeric azo compound as polymerization starter
19g (8.95mmol) is dissolved in the 80g toluene by polymeric azo compound 1 and 40g (0.400mol) methyl methacrylate that embodiment 1-1 obtains, in nitrogen atmosphere, stirred 8 hours down at 80 ℃.Be cooled to room temperature, reaction solution is splashed in the 400ml normal hexane, carry out redeposition.Filter and drying, thereby obtain 55g block polymer (Mn=13000).
[embodiment 3-1～3-14 (synthesizing of grafting pigment 1～14) and comparative example 3-1～3-5 (relatively grafting pigment 15～19 is synthetic)]
Blending ratio according to table 3 record, mix 24.0g surface decoration pigment or commercially available pigment, 90.0g propylene glycol-1-monomethyl ether-2-acetic ester and polymeric azo compound, in nitrogen atmosphere, stirring is 8 hours under 74～77 ℃, thereby obtains grafting pigment 1～14 and the propylene glycol-1-monomethyl ether-2-acetate solution that compares grafting pigment 15～19 as target compound respectively.
Table 3
| Grafting pigment | Pigment | Azo-compound | |
| Grafting pigment 1 (embodiment 3-1) | Finishing pigment 1 | Polymeric azo compound 1 | 9.0g |
| Grafting pigment 2 (embodiment 3-2) | Finishing pigment 1 | Polymeric azo compound 1 | 6.9g |
| Grafting pigment 3 (embodiment 3-3) | Finishing pigment 1 | Polymeric azo compound 1 | 4.5g |
| Grafting pigment 4 (embodiment 3-4) | Finishing pigment 1 | Polymeric azo compound 2 | 9.0g |
| Grafting pigment 5 (embodiment 3-5) | Finishing pigment 1 | Polymeric azo compound 2 | 6.9g |
| Grafting pigment 6 (embodiment 3-6) | Finishing pigment 1 | Polymeric azo compound 5 | 9.0g |
| Grafting pigment 7 (embodiment 3-7) | Finishing pigment 1 | Polymeric azo compound 6 | 9.0g |
| Grafting pigment 8 (embodiment 3-8) | Finishing pigment 2 | Polymeric azo compound 1 | 9.0g |
| Grafting pigment 9 (embodiment 3-9) | Finishing pigment 3 | Polymeric azo compound 1 | 9.0g |
| Grafting pigment 10 (embodiment 3-10) | a 1* | Polymeric azo compound 1 | 9.0g |
| Grafting pigment 11 (embodiment 3-11) | b 2* | Polymeric azo compound 1 | 9.0g |
| Grafting pigment 12 (embodiment 3-12) | b | Polymeric azo compound 2 | 6.9g |
| Grafting pigment 13 (embodiment 3-13) | b | Polymeric azo compound 5 | 9.0 g |
| Grafting pigment 14 (embodiment 3-14) | b | Polymeric azo compound 6 | 9.0g |
| Compare grafting pigment 15 (comparative example 3-1) | Finishing pigment 1 | c 3* | 9.0g |
| Compare grafting pigment 16 (comparative example 3-2) | Finishing pigment 1 | d 4* | 9.0g |
| Compare grafting pigment 17 (comparative example 3-3) | Finishing pigment 1 | AIBN 5* | 9.0g |
| Compare grafting pigment 18 (comparative example 3-4) | Finishing pigment 2 | c | 9.0g |
| Compare grafting pigment 19 (comparative example 3-5) | Finishing pigment 2 | e 6* | 9.0g |
1
*: カ Le ベ-Le (carbon nanotube that GS エ Network レ オ ス society makes)
2
*: Z-25 (flaky graphite that the industrial society of itoite China ink makes)
3
*: VPE-0201 (with the polymeric azo polymerization starter that contains the polyoxyethylene glycol unit that the pure medicine of light society makes, molecular weight 2000)
4
*: VPE-0501 (containing the unitary polymeric azo polymerization starter of polydimethyl silane, molecular weight 5000) with the pure medicine of light society makes
5
*: azobis isobutyronitrile
6
*: VPE-0401 (with the polymeric azo polymerization starter that contains the polyoxyethylene glycol unit that the pure medicine of light society makes, molecular weight 4000)
The preparation of [embodiment 4-1～4-14] color compositions No.1～No.14
Blending ratio according to table 4 record, mix the propylene glycol-1-monomethyl ether-2-acetate solution of 83.5g as the grafting pigment 1～14 that obtains by embodiment 3-1～3-14 of the エ ス レ Star Network PSE-0020 (the styrene acrylic copolymer resins that ponding chemical industry society makes) of adhesive resin and 416.5g, the gained slurry is disperseed in ball mill, thereby obtain color compositions No.1～No.14 respectively.
[comparative example 4-1～4-7] be the preparation of color compositions No.15～No.21 relatively
Except the surface decoration pigment of use table 4 record or comparison grafting pigment 15～19 are replaced grafting pigment, similarly prepare comparison color compositions No.15～No.21 with embodiment 4-1～4-14.
Come the comparison color compositions No.15～No.21 for preparing among color compositions No.1～No.14 of preparing among the foregoing description 4-1～4-14 and the comparative example 4-1～4-7 is estimated by the visual observation dispersiveness.Evaluation is: homodisperse is zero, cohesion takes place be *.The result is shown in the table 4.
Table 4
| Color compositions | Pigment | Dispersed |
| No.1 (embodiment 4-1) | Connect skill pigment 1 | ○ |
| No.2 (embodiment 4-2) | Connect skill pigment 2 | ○ |
| No.3 (embodiment 4-3) | Connect skill pigment 3 | ○ |
| No.4 (embodiment 4-4) | Connect skill pigment 4 | ○ |
| No.5 (embodiment 4-5) | Connect skill pigment 5 | ○ |
| No.6 (embodiment 4-6) | Connect skill pigment 6 | ○ |
| No.7 (embodiment 4-7) | Connect skill pigment 7 | ○ |
| No.8 (embodiment 4-8) | Connect skill pigment 8 | ○ |
| No.9 (embodiment 4-9) | Connect skill pigment 9 | ○ |
| No.10 (embodiment 4-10) | Connect skill pigment 10 | ○ |
| No.11 (embodiment 4-11) | Connect skill pigment 11 | ○ |
| No.12 (embodiment 4-12) | Connect skill pigment 12 | ○ |
| No.13 (embodiment 4-13) | Connect skill pigment 13 | ○ |
| No.14 (embodiment 4-14) | Connect skill pigment 14 | ○ |
| No.15 (comparative example 4-1) | Relatively connect skill pigment 15 | × |
| No.16 (comparative example 4-2) | Relatively connect skill pigment 16 | × |
| No.17 (comparative example 4-3) | Relatively connect skill pigment 17 | × |
| No.18 (comparative example 4-4) | Relatively connect skill pigment 18 | × |
| No.19 (comparative example 4-5) | Relatively connect skill pigment 19 | × |
| No.20 (comparative example 4-6) | Finishing pigment 1 | × |
| No.21 (comparative example 4-7) | Finishing pigment 2 | × |
[embodiment 5-1～5-8 (containing the hard coating agent of the grafting pigment 1,4 that obtains by embodiment 3-1,3-4 and 3-6～3-11 and 6～11 and the manufacturing of hardcoat film)]
The Irgacure184 of dissolving 3.0g (Photoepolymerizationinitiater initiater that Ciba Specialty Chemicals company makes) in 3.0g propylene glycol-1-monomethyl ether-2-acetic ester, add 21g ア ロ ニ Star Network ス M-400 (dipentaerythritol acrylate that the synthetic society in East Asia makes), 9.0g PVC ス コ-ト #230 (1 of Osaka organic chemistry industry society manufacturing, 6-hexanediyl ester), 7.0g grafting pigment and 71g propylene glycol methyl acetic acid ester and mixing, the hard coating of acquisition agent respectively.Gained is applied agent firmly is coated with device #14 by rod and is coated on the A-4300 that thickness is 100 μ m (the easy adhesion process polyester film that society makes spins in Japan), then 80 ℃ dry 1 minute down.Afterwards, in air atmosphere, by the ultraviolet ray of high-pressure mercury light irradiation 300mJ, obtaining respectively to solidify thickness is the hardcoat film of 8 μ m.
[embodiment 6-1～6-8 (containing the manufacturing of the water-based paint compositions of the grafting pigment 1,4 that obtains by embodiment 3-1,3-4 and 3-6～3-11 and 6～11)]
In ball mill, 25g tap water, 0.8g ア デ カ ネ-ト B-940 (defoamer that ADEKA society makes), 0.4g ア デ カ コ-Le W-304 (dispersion agent that ADEKA society makes) and 100g grafting pigment were mixed 15 hours, obtain pigment paste.In dispersal mill, mix gained pigment paste, 100g vinylbenzene-acrylic emulsion (clear and polymer society makes), 2.0g ア デ カ ネ-ト B-940 (defoamer that ADEKA society makes) and the 2.0g nitrogen サ イ ザ-CS-12 (manufacturing of チ Star ソ society make film) of 50g, prepare water-based paint compositions respectively.
[embodiment 7-1～7-3 (containing preparation)] by the alkali development resin composition of the grafting pigment 10～12 that obtains among embodiment 3-10～3-12
＜step 1〉preparation of adhesive resin composition
[4-(2 to mix 17.0g pair, 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane, 4.43g vinylformic acid, 0.06g 2,6-ditertbutylparacresol, 0.11g TBuA acetate and 14.3g propylene glycol-1-monomethyl ether-2-acetic ester stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 7.18g propylene glycol-1-monomethyl ether-2-acetic ester, 4.82g succinyl oxide and 0.25g TBuA acetate, stirred 5 hours down at 100 ℃.In addition, add two [4-(2,3-epoxy group(ing) propoxy-) phenyl]-4-xenyl (cyclohexyl) methane and the 2.18g propylene glycol-1-monomethyl ether-2-acetic ester of 5.08g, stirred 12 hours down at 120 ℃, stirred 2 hours down at 80 ℃, after stirring 2 hours under 40 ℃.Thereby add 13.1g propylene glycol-1-monomethyl ether-2-acetic ester and obtain adhesive resin composition (Mw=4200 as target compound with the form of propylene glycol-1-monomethyl ether-2-acetate solution, Mn=2100, acid number (solids component) is 55mgKOH/g).
＜step 2〉preparation of alkali development resin composition
Mix adhesive resin composition that 83.5g obtains by step 1 and 416.5g propylene glycol-1-monomethyl ether-2-acetate solution by the grafting pigment 10～12 that obtains among embodiment 3-10～3-12, by dispersion gained slurry in ball mill, thereby obtain alkali development resin composition respectively.
＜step 3〉preparation of alkali developing photosensitive resin composition
The alkali development resin composition that obtains by step 2 with respect to 44g, add 6.3g Viscoat 295,2.1g benzophenone and 78g propylene glycol-1-monomethyl ether-2-acetic ester respectively, fully stir, thereby obtain alkali developing photosensitive resin composition respectively.
Claims (10)
1. one kind by the polymeric azo compound shown in the following general formula (I),
In the formula, R
12, R
13, R
22And R
23Represent that independently of one another carbonatoms is 1～10 alkyl or cyano group, a and b are 0～4 number independently of one another, A
11And A
12Be macromolecular chain, Y
11And Y
12Be independently of one another-CO-O-,-O-CO-,-NH-CO-,-CO-NH-,-O-or-S-.
2. polymeric azo compound according to claim 1, wherein, in described general formula (I), by A
11And A
12The macromolecular chain of expression is a polyether chain.
3. polymeric azo compound according to claim 1, wherein, in described general formula (I), by A
11And A
12The macromolecular chain of expression is a polyester chain.
4. according to each described polymeric azo compound in the claim 1～3, wherein, Y
11Be-O-CO-, Y
12Be-CO-O-.
5. polymeric azo compound according to claim 1, wherein, the compound of being represented by described general formula (I) is the compound of being represented by following general formula (II);
In the formula, R
12, R
13, R
22, R
23, a is identical with described general formula (I) with b, R
11And R
21Represent that independently of one another carbonatoms is 1～24 alkyl, Z
11, Z
12, Z
21And Z
22Represent that independently of one another carbonatoms is 1～4 alkylidene group, m, n, s and t are 0～1000 number independently of one another, m+n's and, s+t's and be more than 2 independently of one another.
6. polymeric azo compound according to claim 5, wherein, in described general formula (II), R
12And R
22Be methyl, R
13And R
23Be cyano group, a and b are 2.
7. polymeric azo compound according to claim 1, wherein, the compound of being represented by described general formula (I) is the compound of being represented by following general formula (III);
In the formula, R
12, R
13, R
22, R
23, a is identical with described general formula (I) with b, Z
13And Z
23Represent that independently of one another carbonatoms is 1～18 alkylidene group, R
31And R
41Represent that independently of one another hydrogen atom or carbonatoms are 1～24 alkyl, p and u are 1～1000 number independently of one another.
8. the polymerization starter that constitutes by each described polymeric azo compound in the claim 1～7.
9. a grafting pigment is characterized in that, the high molecular free radical that produces in the thermolysis by the free-radical generating agent that is made of each described polymeric azo compound in the claim 1～7 of the surface grafting of pigment.
10. color compositions, it contains the described grafting pigment of claim 9, solvent and adhesive resin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP202088/2006 | 2006-07-25 | ||
| JP2006202088 | 2006-07-25 | ||
| JP173022/2007 | 2007-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101134811A true CN101134811A (en) | 2008-03-05 |
Family
ID=39159153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101367037A Pending CN101134811A (en) | 2006-07-25 | 2007-07-25 | Polymeric azo compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101134811A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768373A (en) * | 2010-01-08 | 2010-07-07 | 武汉科技学院 | Method for preparing water soluble vinyl-sulfone polyurethane class high molecular reactive dye with diazo coupling method |
| CN103080184A (en) * | 2010-08-24 | 2013-05-01 | 佳能株式会社 | Polyester, pigment composition, and toner |
| CN103483519A (en) * | 2012-09-17 | 2014-01-01 | 湛江师范学院 | Synthesis of hyperbranched azo polymer and modification method of same |
| CN103554489A (en) * | 2013-10-18 | 2014-02-05 | 仲恺农业工程学院 | Azobenzene polymer, preparation method and application thereof |
| CN110372851A (en) * | 2019-07-18 | 2019-10-25 | 重庆韩拓科技有限公司 | A kind of synthetic method of the carpenter's glue flame-proof polyol of three-functionality-degree high cohesion energy |
-
2007
- 2007-07-25 CN CNA2007101367037A patent/CN101134811A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768373A (en) * | 2010-01-08 | 2010-07-07 | 武汉科技学院 | Method for preparing water soluble vinyl-sulfone polyurethane class high molecular reactive dye with diazo coupling method |
| CN103080184A (en) * | 2010-08-24 | 2013-05-01 | 佳能株式会社 | Polyester, pigment composition, and toner |
| CN103080184B (en) * | 2010-08-24 | 2014-11-05 | 佳能株式会社 | Polyester, pigment composition, and toner |
| US9097999B2 (en) | 2010-08-24 | 2015-08-04 | Canon Kabushiki Kaisha | Polyester, pigment composition, and toner |
| CN103483519A (en) * | 2012-09-17 | 2014-01-01 | 湛江师范学院 | Synthesis of hyperbranched azo polymer and modification method of same |
| CN103483519B (en) * | 2012-09-17 | 2015-03-25 | 湛江师范学院 | Synthesis of hyperbranched azo polymer and modification method of same |
| CN103554489A (en) * | 2013-10-18 | 2014-02-05 | 仲恺农业工程学院 | Azobenzene polymer, preparation method and application thereof |
| CN110372851A (en) * | 2019-07-18 | 2019-10-25 | 重庆韩拓科技有限公司 | A kind of synthetic method of the carpenter's glue flame-proof polyol of three-functionality-degree high cohesion energy |
| CN110372851B (en) * | 2019-07-18 | 2021-10-19 | 重庆韩拓科技有限公司 | Synthesis method of flame-retardant polyol for wood glue with three functionality degrees and high cohesive energy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3728343B1 (en) | Styrene maleamide block copolymer pigment dispersant | |
| CN1422291B (en) | Process of microgel synthesis and products produced therefrom | |
| JP5968530B2 (en) | Comb copolymer having ionic bonding groups | |
| TWI667268B (en) | Aromatic dispersant, method for obtaining the same and use thereof | |
| KR101252371B1 (en) | Pigment dispersions, block polymers and manufacturing method therefor | |
| JP5734821B2 (en) | Block copolymer, dispersant and pigment dispersion composition | |
| DE60026375T2 (en) | PFROPOPOPOLYMERISATES WITH AMID-FUNCTIONAL GROUPS AS DISPERSIBLE FOR PIGMENTS | |
| KR20010089741A (en) | Pigment composition containing atrp polymers | |
| WO2008107326A1 (en) | Polyamine-polyacrylate dispersant | |
| CN103502305A (en) | Photochromic polymer | |
| CN105037666A (en) | Alkoxysilyl group-containing block copolymer, method for producing the same, resin-treated pigment, and pigment dispersion | |
| CN101134811A (en) | Polymeric azo compound | |
| US20130096268A1 (en) | Monodisperse polymers containing (alkyl)acrylic acid moieties, precursors and methods for making them and their applications | |
| CN101889062B (en) | Pigment-free aqueous polymeric dispersions labelled with fluorescent dyes, production of said polymer dispersions and their use | |
| TWI664208B (en) | Polymers with multiple aromatic imide anchor groups and method for obtaining the same | |
| KR102151724B1 (en) | Aqueous polymer dispersing agent, color mill base comprising the same and manufacturing method therof | |
| EP3535307B1 (en) | Novel monomers and polymers | |
| JP2008056806A (en) | Pigment dispersant, pigment paste, and printing ink composition | |
| CN112334504B (en) | Dispersing agent composition, coloring composition and color filter | |
| CN112334505B (en) | Dispersing agent composition, coloring composition and color filter | |
| KR102719032B1 (en) | Styrene maleamide block copolymer pigment dispersant | |
| JP2007112932A (en) | Block resin | |
| JP2022158617A (en) | Coloring composition, and coating layer | |
| CN117043210A (en) | Block copolymer, dispersant and coloring composition | |
| TW200811218A (en) | Polymeric azo compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20080305 |