CN101134811A - Polymer azo compound - Google Patents

Abstract

The present invention provides a new polymer azo compound with good solubility and can be used as a polymerization initiator and a pigment. The polymer azo compound containing the polymer azo compound is grafted on the surface of the pigment A macromolecular radical pigment obtained from an azo compound and a pigment composition containing the pigment. Wherein, the polymeric azo compound is represented by the above general formula (I), wherein R ¹² , R ¹³ , R ²² and R ²³ each independently represent an alkyl or cyano group with 1 to 10 carbon atoms, a and b are each independently a number from 0 to 4, A ¹¹ and A ¹² are polymer chains, Y ¹¹ and Y ¹² are each independently -CO-O-, -O-CO-, -NH-CO-, -CO-NH-, -O- or -S-.

Description

Polymer azo compound

technical field

The present invention relates to a high molecular weight azo compound having a specific structure, a polymerization initiator containing the high molecular weight azo compound, a pigment having a high molecular free radical obtained by grafting the high molecular weight azo compound on the surface, and the pigment containing the high molecular weight azo compound pigment composition.

Background technique

Compounds obtained by polycondensation of azodicarboxylic acid and polyalkylene glycol are known to be useful as polymeric azo polymerization initiators. For example, Patent Document 1 discloses a polymerization initiator containing a polycondensation compound of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol.

In addition, it is known that when a polymeric azo compound having an azo bond in the main chain is heated together with carbon black, polymeric radicals generated by thermal decomposition of the polymeric azo compound are grafted on the surface of the carbon black. . For example, Patent Document 2 discloses a grafted carbon black bonded with a graft chain having a polyalkylene oxide chain, and Patent Document 3 discloses a grafted carbon black composed of an azonitrile compound bonded to the surface. The carbon black of the functional group produced by the decomposition of the free radical initiator, disclosed in the non-patent literature 1 by 4,4'-azobis (4-cyanovaleric acid) and polyalkylene glycol or polydiethylene glycol Polymer-grafted carbon black obtained by polycondensation of methylsiloxane compounds.

Patent Document 4 discloses a resin composition for a hard coat layer containing colloidal silica surface-treated with a silane coupling agent, but sufficient dispersibility cannot be obtained from this resin composition.

Patent Document 1: JP-A-2003-12784

Patent Document 2: Japanese Unexamined Patent Publication No. 9-324133

Patent Document 3: Japanese Unexamined Patent Publication No. 11-323176

Patent Document 4: JP-A-2006-63244

Non-Patent Document 1: Collection of Polymer Papers Vol.49, No.11, pp.865-870

Contents of the invention

The object of the present invention is to provide a kind of good solubility, the novel macromolecular azo compound that is used as polymerization initiator and pigment, the polymerization initiator that contains this macromolecular azo compound, graft on the surface of pigment by this high molecular weight azo compound A polymer free radical pigment obtained from a molecular azo compound and a pigment composition containing the pigment.

The present invention achieves the above object by providing a polymeric azo compound represented by the following general formula (I).

(In the formula, R ¹² , R ¹³ , R ²² and R ²³ each independently represent an alkyl or cyano group with 1 to 10 carbon atoms, a and b are each independently a number of 0 to 4, A ¹¹ and A ¹² is a polymer chain, Y ¹¹ and Y ¹² are each independently -CO-O-, -O-CO-, -NH-CO-, -CO-NH-, -O- or -S-.)

Furthermore, the present invention achieves the above-mentioned object by providing a polymerization initiator composed of the above-mentioned high molecular weight azo compound.

Furthermore, the present invention achieves the above object by a grafted pigment characterized by grafting polymeric radicals generated by thermal decomposition of a radical initiator composed of the aforementioned polymeric azo compound onto the surface of the pigment.

Furthermore, the present invention achieves the above object by providing a pigment composition comprising the above-mentioned grafted pigment, a solvent, and a binder resin.

If radical polymerization of a compound having a vinyl group or acrylic group is carried out using a polymerization initiator containing the polymeric azo compound of the present invention, block copolymerization in which a different polymer is bonded only at the end of the polymer main chain can be obtained A pigment whose surface is grafted with a polymeric radical obtained from the polymeric azo compound has high dispersibility.

Detailed ways

Hereinafter, the novel high molecular weight azo compound of the present invention, the polymerization initiator containing the high molecular weight azo compound, the pigment obtained by grafting the high molecular weight radical obtained from the high molecular weight azo compound on the surface of the pigment, and the pigment containing the same The pigment composition is described in detail based on a preferred embodiment.

In the above general formula (I), examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹² , R ¹³ , R ²² and R ²³ include methyl, ethyl, propyl, and isopropyl. , butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-amyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, tert Heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc.

In the above general formula (I), the polymer chains represented by A ¹¹ and A ¹² are not particularly limited, and examples thereof include polyoxyethylene chains, polymethylene chains, polyether chains, poly Ester chains, polysiloxane chains, poly(meth)acrylate chains, polystyrene-vinyl acetate chains, polyamide chains, polyimide chains, polyurethane chains, polyurea chains, polypeptide chains, etc.

Examples of the polymeric azo compound represented by the general formula (I) of the present invention include those exemplified below.

In the general formula (I), it is a chain polymer in which polymer chains A ¹¹ and A ¹² are introduced via Y ¹¹ and Y ¹² (hereinafter, sometimes simply referred to as "chain polymer"). Examples include: Polymer azo compound having a structure obtained by reacting a compound having a hydroxyl group at one end with an azodicarboxylic acid compound, and a polymer having a structure obtained by reacting a compound having an epoxy group at one end of a chain polymer with an azodicarboxylic acid compound High molecular azo compounds, high molecular azo compounds having a structure obtained by reacting a compound having a hydroxyl group at one end of a chain polymer with azodicarboxylic anhydride, compounds having an amino group at one end of a chain polymer A high molecular azo compound having a structure obtained by reacting with an azodicarboxylic acid compound, a high molecular azo compound having a structure obtained by reacting a compound having an epoxy group at one end of a chain polymer with an azodiol compound, having A polymeric azo compound having a structure obtained by reacting a compound having a carboxyl group at one end of a chain polymer with an azodiol compound, a compound having a carboxyl group or an alcohol group, an epoxy compound, and an anhydride A compound having an alcohol group at the end and a polymeric azo compound having a structure obtained by reacting an azodicarboxylic acid compound, a compound having a carboxyl group at the end obtained by reacting a compound having a carboxyl group or an alcohol group with an epoxy compound and an acid anhydride, and A high molecular azo compound having a structure obtained by reacting an azodicarboxylic acid compound, a high molecular azo compound having a structure obtained by reacting a compound having an anhydride group at one end of a chain polymer with an azodiol compound, a high molecular azo compound having a structure obtained by making A polymeric azo compound having a structure obtained by reacting a compound having a hydroxyl group at one end of a chain polymer with an azodicarbonyl halide, and a compound having an amino group at one end of a chain polymer reacting with an azodicarbonyl halide compound A polymeric azo compound having a structure, a polymeric azo compound having a structure obtained by reacting a compound having an acid halide group at one end of a chain polymer with an azodiol compound, having a A high molecular azo compound with a structure obtained by reacting a compound with a cyclic ester structure and an azodiol compound, a high molecular azo compound with a structure obtained by ring-opening polymerization of an azodicarboxylic acid compound and a cyclic ester compound, and a high molecular azo compound with a structure that allows High molecular weight azo compound having a structure obtained by ring-opening polymerization of an azodicarboxylic acid compound and a cyclic amide compound; a high molecular azo compound having a structure obtained by ring-opening polymerization of an azodicarboxylic acid compound and a cyclic ether compound; Polymer azo compounds with a structure obtained by anionic polymerization of azodicarboxylic acid compounds and epoxy compounds, macromolecular compounds with structures obtained by ring-opening polymerization of azodiol compounds and cyclic ester compounds, A compound having a structure obtained by cross-reacting an acid compound with an epoxy compound and an acid anhydride, a compound having a structure obtained by cross-reacting an azodiol compound with an acid anhydride and an epoxy compound, etc., among them, preferably having a A polymer azo compound with a structure obtained by reacting a compound having a hydroxyl group with an azodicarboxylic acid compound.

The polymeric azo compound obtained by esterifying the compound (A) having a hydroxyl group at one end of the chain polymer with the azodicarboxylic acid compound (B) is obtained by making 1.5 to 2.5 equivalents of Obtained by reacting a compound (A) having a hydroxyl group at one terminal with 1 equivalent of an azodicarboxylic acid compound (B). The compound (A) having a hydroxyl group at one end of the chain polymer may be used alone or in combination of two or more, and may be selected so that the total thereof satisfies the above ratio.

Examples of the compound (A) having a hydroxyl group at one end of the chain polymer include polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, and blocks of ethylene oxide and propylene oxide. or monomers of random adducts and condensates of ethylene glycol or propylene glycol having an alkoxy group at one end, polyesters having at least one hydroxyl group at one end, ethylenically unsaturated monomers having at least one hydroxyl group at one end, or Copolymers, thermoplastic resins having a hydroxyl group at the end, thermosetting resins having a hydroxyl group at the end, etc., because they can impart good dispersibility when grafting the pigment, polyethylene glycol monoalkyl ether and polypropylene glycol monoalkyl ether are preferred. Alkyl ether, block or random adduct of ethylene oxide and propylene oxide, and condensate of ethylene glycol or propylene glycol with an alkoxy group at one end.

Examples of the thermoplastic resin include polymethyl methacrylate, vinyl toluene acrylate polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, vinyl chloride- Vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride -acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, styrene acrylate, ethylene-vinyl acetate copolymer, ethylene-(meth)ethyl acrylate copolymer, styrene-butadiene copolymer , polystyrene, polycarbonate, polyamide, polyamideimide, polyetherimide, polyurethane, polyester, polycaprolactone, butyrolactone, polylactic acid, polyacrylonitrile, styrene-malay Synthetic polymer materials such as acid anhydride copolymers, and examples of thermosetting resins include epoxy resins, polyimides, and phenolic resins.

Examples of the azodicarboxylic acid compound (B) include compounds represented by the following general formula (I-1).

(In the formula, R ¹² , R ¹³ , R ²² , R ²³ , a, and b are the same as the above general formula (I).)

As the polymer azo compound represented by the above-mentioned general formula (I), it is preferable that Y ¹¹ is -O-CO-, Y ¹² is a compound of -CO-O-, and the polymer chains represented by A ¹¹ and A ¹² are poly Compounds of ether chains and polyester chains are inexpensive and easy to manufacture, and thus are more preferable.

The polyether chains of A ¹¹ and A ¹² can be introduced by polyether alcohols, as polyether alcohol compounds, can enumerate the use of methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, isobutanol, tert-butanol, amyl alcohol, tert-amyl alcohol, hexanol, cyclohexanol, pentanol, octanol, tert-octanol, 2-ethylhexanol, decanol, dodecyl alcohol , lauryl alcohol, oleyl alcohol, stearyl alcohol, behenyl alcohol and other monoalkyl alcohols, epoxides such as ethylene oxide, propylene oxide, glycidyl ether, oxetanes, tetrahydrofuran ( Compounds obtained by ring-opening polymerization of cyclic ether compounds such as oxolanes and oxanes, and compounds obtained by block or random addition of two or more of the above-mentioned cyclic ethers using the above-mentioned monoalkyl alcohol.

Among the compounds in which A ¹¹ and A ¹² are polyether chains, the compound represented by the following general formula (II) has high solubility, is easy to control the molecular weight of the polymerization initiator, and can obtain a grafted pigment with high dispersibility, Therefore it is more preferable.

(In the formula, R ¹² , R ¹³ , R ²² , R ²³ , a and b are the same as the above general formula (I), R ¹¹ and R ²¹ each independently represent an alkyl group with 1 to 24 carbon atoms, Z ¹¹ , Z ¹² , Z ²¹ and Z ²² each independently represent an alkylene group with 1 to 4 carbon atoms, m, n, s and t each independently represent a number from 0 to 1000, the sum of m+n, s+ The sum of t is 2 or more independently.)

In the above general formula (II), examples of the alkylene group having 1 to 4 carbon atoms represented by Z ¹¹ , Z ¹² , Z ²¹ and Z ²² include methylene, ethylene, trimethylene , propylene, 1,1-propylene, isopropylene, tetramethylene, butylene, isobutylene, ethylethylene, dimethylethylene, etc.; as a result of R ¹¹ and R The alkyl group having 1 to 24 carbon atoms represented by ²¹ includes methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, and isopentyl Base, tert-pentyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, n-decyl, lauryl, stearyl, behenyl, etc. Among the alkyl groups having 1 to 24 carbon atoms represented by R ¹¹ and R ²¹ , due to the alkyl group having 1 to 4 carbon atoms, a grafted pigment with high dispersibility can be obtained, and in addition, in chain polymerization A compound having a hydroxyl group at one terminal of the compound is preferable because of its high reactivity in the esterification reaction with an azodicarboxylic acid compound.

As the polymer azo compound represented by the above-mentioned general formula (II), it is preferable that R ¹² and R ²² are methyl groups, R ¹³ and R ²³ are cyano groups, and a and b are 2 compounds. In addition, by the following general formula The compound represented by (II-1) is more preferable because it is easy to synthesize and low in cost.

(In the formula, R ¹¹ , R ²¹ , n, m, s, and t are the same as the above-mentioned general formula (II).)

In the above general formulas (II) and (II-1), the sum of m and n, and the sum of s and t is 20 to 100 compounds, since grafted pigments with high dispersibility can be obtained, in addition, in the chain A compound having a hydroxyl group at one end of the polymer is preferable because of its high reactivity in the esterification reaction with an azodicarboxylic acid compound.

The polyester chains of A ¹¹ and A ¹² can be introduced from polyester alcohols. Examples of polyester alcohol compounds include dehydration polycondensates of monohydroxy acids, polyester polyols obtained from low-molecular diol compounds and dibasic acids, and the One terminal hydroxyl group of polyester polyol esterified with a monobasic ester, polylactone obtained by ring-opening polymerization of lactones, and one terminal carboxyl group of the polylactone esterified with a monoalcohol compound, Esterification reactant of monobasic acid or monoalcohol compound with cyclic ether and dibasic acid anhydride.

Examples of the monohydroxy acids include glycolic acid, lactic acid, 3-hydroxybutyric acid, 3-hydroxy-3-methylbutyric acid, 2-hydroxyoctanoic acid, 15-hydroxypentadecanecarboxylic acid, mandelic acid, benzyl amino acid, salicylic acid, cresolic acid, o-hydroxyphenylpropionic acid, rhizoric acid, etc.; as low-molecular-weight diols, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl Base-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 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-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octane Diol, 1,9-nonanediol, 1,10-decanediol; as dibasic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, etc. acid, azelaic acid, sebacic acid, dodecyl diacid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpimelic acid, 2- Methylpimelic acid, 3,8-dimethylsebacic acid, 3,7-dimethylsebacic acid, phthalic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid Aromatic dicarboxylic acids, 1,2-cycloheptane dicarboxylic acid, 1,3-cycloheptane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid acid, 1,4-cyclohexanedicarboxylic acid, 1,4-dicarboxymethylenecyclohexane; as the monobasic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, hexanoic acid can be enumerated , octanoic acid, 2-ethylhexanoic acid, nonanoic acid, octanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, seventeen acid, octadecanoic acid ; As the lactones, γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, γ-caprolactone, -butyrolactone, α-acetyl-γ-butyrolactone, δ-octyl lactone, γ-undecyl lactone, δ-laurolactone, lactide, glycolide, etc.; as a monohydric alcohol compound, Examples include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, isobutanol, t-butanol, pentanol, t-amyl alcohol, hexanol, cyclohexanol, heptanol, octanol , tert-octyl alcohol, 2-ethylhexanol, decanol; as cyclic esters, epoxides such as ethylene oxide, propylene oxide, glycidyl ether, oxetanes, tetrahydrofuran, Oxanes, etc.; as dibasic acid anhydrides, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic Acid anhydride, 3,3'-4,4'-benzophenone tetracarboxylic anhydride, ethylene glycol bis(dehydrated trimellitate), glycerol tri(dehydrated trimellitate), phthalic anhydride , Methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, norbornene diacid anhydride, methyl norbornene diacid anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride Acid anhydride, methyl hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl endomethylene hexahydrophthalic anhydride (Methyl HymicAnhydride), etc.

In addition, among those in which ^A11 and ^A12 of the polymeric azo compound represented by the above general formula (I) are polyester chains, the compound represented by the following general formula (III) has good solubility and excellent water resistance , so it is preferred.

(In the formula, R ¹² , R ¹³ , R ²² , R ²³ , a and b are the same as the above general formula (I), Z ¹³ and Z ²³ each independently represent an alkylene group with 1 to 18 carbon atoms, R ³¹ and ^R41 each independently represent a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, and p and u are each independently a number of 1 to 1000.)

In the above general formula (III), examples of the alkylene group having 1 to 18 carbon atoms represented by Z ¹³ and Z ²³ include methylene, ethylene, trimethylene, propylene, 1 , 1-propylene, isopropylene, tetramethylene, butylene, isobutylene, ethylethylene, dimethylethylene, pentamethylene, hexamethylene, heptamethylene base, octamethylene, 1,4-pentanediyl, decamethylene, undecanediyl, 1,4-undecanediyl, dodecamethylene, 1,11-heptadecane Diyl group, octadecanediyl group, etc., as the alkyl group having 1 to 24 carbon atoms represented by R ³¹ and R ⁴¹ , the groups exemplified as R ¹¹ and R ²¹ in the above general formula (II) can be mentioned . As an alkyl group with 1 to 24 carbon atoms represented by R ³¹ and R ⁴¹ , a group with 1 to 4 carbon atoms can obtain a grafted pigment with high dispersibility. In addition, in the chain polymer A compound having a hydroxyl group at one terminal is preferable because of its high reactivity in the esterification reaction with an azodicarboxylic acid compound.

In the above general formula (III), p and u are 20 to 100, because a highly dispersible grafted pigment can be obtained. In addition, a compound having a hydroxyl group at one end of the chain polymer and azodicarboxylic acid Since the reactivity of the esterification reaction of a compound is high, it is preferable.

The reaction to obtain the polymeric azo compound of the present invention can be carried out according to conventional methods, preferably in an inert gas atmosphere such as nitrogen or argon, at room temperature to 50°C for 30 minutes to 10 hours.

In the reaction for obtaining the polymeric azo compound of the present invention, an appropriate solvent may be used as necessary. Examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether and other ether solvents; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, Ester solvents such as n-butyl acetate; cellosolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate; methanol, ethanol, iso-or n-propanol, iso-or n-butyl Alcohol solvents such as alcohol and amyl alcohol; ether ester solvents such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, and propylene glycol methyl acetate; BTX such as benzene, toluene, and xylene Solvents; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; solvent oil, スワゾ-ル#310 (Cosmo Matsuyama Petroleum )), Solbetsuso #100 (Gongkuson Chemical Co., Ltd.) and other paraffin solvents; carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane and other halogenated aliphatic hydrocarbon solvents; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl Sulfoxide, water, and the like can be used alone or as a mixture of two or more solvents.

In the reaction for obtaining the polymeric azo compound of the present invention, a condensing agent may be added as needed. The condensing agent is not particularly limited, and substances currently used in esterification reactions can be used, such as N,N-dicyclohexylcarbodiimide, 1-ethyl-3-(dimethylaminopropyl Carbodiimide, diisopropylcarbodiimide and other carbodiimides; 2,4,6-triisopropylbenzenesulfonyl chloride, p-toluenesulfonyl chloride and other arylsulfonyl chlorides; 2,4 , 6-triisopropylbenzenesulfonyl imidazole amide, 2,4,6-triisopropylbenzenesulfonyl triazole amide and other aryl sulfonamides; azodicarboxylates; organic sulfonyl halides; azide Diphenyl Phosphate, Diethoxy Phosphoryl Chloride, Diethoxy Azido Phosphate, Propyl Phosphonic Anhydride, Diphenyl Phosphoryl Chloride; Dimethoxy Magnesium, Diethoxy Magnesium, Diisopropoxy Aluminum , tri-tert-butoxy aluminum and other metal alkoxides; lithium hydroxide, sodium hydroxide, potassium hydroxide and other alkali metal hydroxides; calcium hydroxide, magnesium hydroxide and other alkaline earth metal hydroxides; calcium oxide, Alkaline earth metal oxides such as magnesium; alkali metal amides such as lithium amide; calcium carbonate, zinc chloride, aluminum trichloride, phosphorus oxochloride, tetramethylammonium chloride, concentrated sulfuric acid, phosphorus pentoxide, Polyphosphoric acid, acetic anhydride, carbonyldiimidazole, p-toluenesulfonyl chloride, basic ion exchange resin, etc. In addition, as condensation aids, triethylamine, pyridine, benzylamine, benzylmethylamine, γ-dimethylaminopyridine, dimethylaniline, tributylamine, 4-piperidylpyridine, etc. can also be used organic base.

The polymerization initiator of the present invention is composed of the polymeric azo compound of the present invention, and can polymerize or copolymerize, for example, an ethylenically unsaturated monomer. It does not specifically limit as said ethylenically unsaturated monomer, A well-known thing can be used. Examples include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, itaconic acid, maleic acid, citron Acid, Fumaric Acid, Hymic Acid, Crotonic Acid, Isocrotonic Acid, Vinyl Acetate, Allyl Acetate, Cinnamic Acid, Sorbic Acid, Hydroxyethyl (meth)acrylate Esters maleate, hydroxypropyl (meth)acrylate maleate, dicyclopentadiene maleate, or polyfunctional ( Unsaturated polyacids such as meth)acrylates; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, the following compound No.1 ~No.4, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, ( Isooctyl methacrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 1, 6 hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate ) acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tris((meth)acryloyloxyethyl)isocyanurate, polyester Esters of unsaturated monobasic acids such as (meth)acrylate oligomers and polyols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; maleic anhydride, coating Canonic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl -3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylendomethylene hexahydrophthalic anhydride Anhydrides of unsaturated polybasic acids such as diacid anhydrides; (meth)acrylamide, methylenebis(meth)acrylamide, diethylenetriaminetri(meth)acrylamide, xylylbis(meth)acrylamide Amides of unsaturated monobasic acids and polyamines such as acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile and cyanated allyl; styrene, 4-methylstyrene, 4- Ethylstyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid and other unsaturated aromatic compounds; Unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl piperidine, etc., vinyl alcohols such as allyl alcohol and crotyl alcohol; ethyl Vinyl ether, N-butyl vinyl ether and other vinyl ethers; vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl-containing Vinyl urethane compounds such as vinyl monomers and polyisocyanate compounds, vinyl epoxy compounds such as hydroxyl-containing vinyl monomers and polyepoxides, and the like.

Compound No.1

Compound No.2

Compound No.3

Compound No.4

As a method of polymerizing or copolymerizing an ethylenically unsaturated monomer using the polymerization initiator of this invention, solution polymerization, block polymerization, suspension polymerization, emulsion polymerization etc. are mentioned, for example.

The above polymerization or copolymerization is preferably carried out in an inert gas atmosphere at 20 to 150°C for 30 minutes to 20 hours, and a catalyst, polymerization inhibitor, chain transfer agent, solvent, etc. can be used as necessary.

The usage-amount of the polymerization initiator of this invention varies with the kind of ethylenic unsaturated monomer used, It is 0.1-100 mol% normally with respect to 1 mol of ethylenic unsaturated monomer, Preferably it is 1.0-10 mol%. The high-molecular azo compound of the present invention may be used alone or in plural with similar decomposition temperatures.

The grafted pigment of the present invention is a pigment obtained by grafting the generated polymeric radicals on the surface of the pigment by thermally decomposing the free radical generating agent composed of the polymeric azo compound of the present invention. Its production method, as long as the free radical generating agent is chemically bonded by utilizing the delocalized π electrons existing on the pigment surface, specifically, the chemical bonding (grafting) of the pigment surface known at present can be made of a polymer A method of generating high-molecular radicals by thermally decomposing a radical generator composed of an azo compound. Here, "grafting" refers to the irreversible addition of a polymer to a substrate such as a pigment.

In the above-mentioned method of grafting the polymer radicals generated by the thermal decomposition of the free radical generating agent composed of polymer azo compounds on the surface of the currently known pigments, the grafting reaction is preferably carried out in an inert gas atmosphere. In a suitable solvent, it is carried out at 40-150° C. for 30 minutes to 48 hours.

In the above-mentioned grafting reaction, the usage-amount of a polymeric azo compound is preferably 1-1000 mass parts with respect to 100 mass parts of pigments, More preferably, it is 10-100 mass parts.

As the above known pigments, for example, nitroso compounds, nitro compounds, azo compounds, disazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindol compounds, Dorinone compounds, isoindoline compounds, quinacridone compounds, dibenzopyrenedione compounds, perillone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, Triphenylmethane compounds, quinophthalone compounds, naphthalene tetracarboxylic acid; metal complexes of azo dyes and cyanine dyes; lake pigments; carbon black or acetylene black obtained by furnace method, tank method, thermal method, Carbon black such as ketjen black or lamp black; the above-mentioned carbon black has been subjected to acidic and alkaline surface treatment; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microvolume, carbon nanohorn ( carbonnanohorns), carbon aerosol, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin; chromium oxide, nickel oxide, iron oxide, indium oxide, titanium oxide, zinc oxide, calcium oxide, potassium oxide, oxide Metal oxides such as silicon and alumina; layered clay minerals, milori blue, calcium carbonate, magnesium carbonate, cobalt, manganese, talc, kaolin, ferrocyanide, various metal sulfates, sulfide Organic or inorganic pigments such as selenide, phosphate ultramarine blue, cyan blue, ultramarine blue, azure blue, Viridian pigment, emerald, etc. These pigments may be used alone or in combination.

As the above-mentioned known pigments, commercially available pigments can also be used, such as 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; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 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; 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 purple 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

The average particle diameter of the grafted pigment of the present invention is 30 to 300 nm, and it is preferable because the addition amount is small and the dispersibility is high. As a method of dispersing or pulverizing the grafted pigment, there may be mentioned the use of a mortar, bead mill, plasto mill, ball mill, vibrating ball mill, roll mill, rod mill, tube mill, cone mill, etc. Mills, Haswin Ball Mills, Needle Mills, Hammer Mills, Knife Hammer Mills, Disc Mills, Jet Mills, Reverse Jet Mills, Spiral Jet Mills, Jet mixer (jetsutomiza), jet mill, nanomixer (nanomiza), majiatsukumill, micro atomizer, micronmill (micronmill), rotary cutter, impact mill, compression cut type Mill, Henschel mixer, etc. method.

The grafted pigment of the present invention can be used in inks, coatings, cosmetics, adhesives, conductivity imparting agents, conductive paper, resin pigments, electrophotographic materials, fillers, reinforcing agents, coating materials, battery materials, electrode materials , electronic materials, antistatic materials, electromagnetic wave shielding materials, cable semiconductors, planar heating elements, adsorbents, catalysts, plastic or rubber modifiers, lubricants, nonlinear optical materials, fibers, carbon nanotubes, electroplating materials, It is used in a wide range of applications such as various recording media and sealants.

The grafted pigment of the present invention can be used as a pigment composition by dispersing the grafted pigment of the present invention and a binder resin in a solvent.

In the pigment composition of the present invention, the content of the grafted pigment is preferably 10 to 100% by mass, more preferably 50 to 90% by mass, of the total solid content of the pigment composition.

In addition, if necessary, a viscosity adjuster, a pH adjuster, a surface tension adjuster, a thickener, a thixotropy imparting agent, a leveling agent, an antifoaming agent, an adhesiveness imparting agent, a chelating agent, a humectant, a penetrating agent, anti-fungal agent, anti-rust agent, preservative, anti-drying agent, quick-drying agent, fixer, antioxidant, ultraviolet absorber, heat stabilizer, flame retardant, lubricant, processing aid, anti-caking agent , electrolytes, catalysts, dispersants, ungrafted known pigments, etc.

The above-mentioned solvent is not particularly limited as long as it can dissolve or disperse the above-mentioned components, and those exemplified as solvents in the reaction for obtaining the above-mentioned polymer azo compound can be used. These solvents may be used alone or as a mixed solvent of two or more. In the pigment composition of the present invention, the content of the above solvent can be adjusted so that the total solid content of the pigment composition is 0.1 to 30% by mass.

As the above-mentioned binder resin, there is no particular limitation, and binders commonly used in inks, paints, coating materials, soldering resists, etc. can be used, and for example, photocurable resins, thermosetting resins, alkali-soluble resins, etc. can be used. , acrylic resin, soluble nylon and polymer latex, melamine resin, phenolic resin, epoxy resin, diallyl phthalate, petroleum resin, maleic acid resin, phenolic resin, alkyd resin, polysiloxane Resin, fluororesin, polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol, natural polymer materials such as gelatin, casein, starch, cellulose derivatives, alginic acid, polyvinyl Butyral, polyvinylpyrrolidone, polyvinyl alcohol, polyolefin, polyvinyl chloride, styrene copolymer, polystyrene, polycarbonate, polyamide, polyester, etc.

In the pigment composition of the present invention, the content of the binder resin is preferably 1 to 70% by mass, more preferably 3 to 30% by mass, based on the total solid content of the pigment composition.

In the pigment composition of the present invention, a photopolymerization initiator can be used.

As the above-mentioned photopolymerization initiator, conventionally known compounds can be used, for example, benzophenone, phenyl biphenyl ketone, 1-hydroxyl-1-benzoylcyclohexane, benzyl, benzyldimethyl Ketal, 1-benzyl-1-dimethylamino-1-(4'-morpholinylbenzoyl)propane, 2-morpholinyl-2-(4'-methylmercapto)benzoylpropane , Thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethylanthraquinone, 4-benzoyl-4'-methyldiphenyl Benzyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4'-isopropyl)benzoylpropane, 4-butylbenzoyl trichloride Methane, 4-phenoxybenzoyl chloroform, methyl benzoylformate, 1,7-bis(9'-acridinyl)heptane, 9-n-butyl-3,6-bis(2 '-morpholinobutyryl)carbazole, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-methyl-4,6 -two (trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl base)-s-triazine, the following compounds No.5, No.6, etc. Among these substances, benzophenone and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one are preferable.

Compound No.5

(wherein, X ¹ represents a halogen atom or an alkyl group, R ⁵ represents R, OR, COR, SR, CONRR' or CN; R ⁶ represents R, OR, COR, SR or NRR'; R ⁷ represents R, OR, COR, SR or NRR'; R and R' represent alkyl, aryl, aralkyl or heterocyclic groups; these groups can also be substituted by halogen atoms and/or heterocyclic groups; in these groups, alkyl and The alkylene part of the aralkyl group can also be interrupted by unsaturated bonds, ether bonds, thioether bonds or ester bonds. In addition, R and R' can also form a ring together, and f is 0-5.)

Compound No.6

(In the formula, X ¹ , R ⁵ , R ⁶ , R ⁷ , R and R' are the same as the above-mentioned compound No.5; X ₁ 'represents a halogen atom or an alkyl group; Z represents an oxygen atom or a sulfur atom. Child; g and h each represents a number from 1 to 4; R ⁵ ' represents R, OR, COR, SR, CONRR' or CN; R ⁶ ' represents R, OR, COR, SR or NRR'; R ⁷ ' represents R, OR, COR, SR or NRR'; ^R represents a diol residue or a dithiol residue.)

In the pigment composition of the present invention, an ethylenically unsaturated monomer, a chain transfer agent, a surfactant, and the like can also be used in combination.

As said ethylenic unsaturated monomer, what was illustrated as an ethylenic unsaturated monomer in the polymerization or copolymerization using the said high molecular weight azo compound as a polymerization initiator is mentioned.

Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl) Glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercapto Propionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3- Mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-3-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2 —Mercapto compounds such as mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate); disulfide obtained by oxidation of the mercapto compound; iodine Iodoalkyl compounds such as acetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.

As the above-mentioned surfactant, fluorine-containing surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates can be used. Cationic surfactants such as high-level amine halide salts and quaternary ammonium salts, non-ionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides Surfactants such as activating agents, amphoteric surfactants, and polysiloxane-based surfactants may also be used in combination.

In the pigment composition of the present invention, the characteristics of a cured product can also be improved by further using a thermoplastic organic polymer. Examples of such thermoplastic organic polymers include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer substances, (meth)acrylic acid-methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, etc.

In addition, in the pigment composition of the present invention, thermal polymerization inhibitors such as anisole, hydroquinone, catechol, tert-butyl catechol, and phenothiazine can also be added as needed; catalyst; lubricant; stabilizer Flame retardants; plasticizers; adhesion promoters; fillers; defoamers; dispersants; leveling agents; silane coupling agents and other commonly used additives.

The pigment resin composition of the present invention can be applied to support substrates such as metal, paper, and plastic by known means such as spin coating, slit coating, roll coating, curtain coating, various printing, and dipping. In addition, it can also be transferred to another support substrate after performing it temporarily on a support substrate such as a film, and there is no limitation on the application method.

Example

Hereinafter, the present invention will be described in more detail by citing examples, but the present invention is not limited to these examples. In addition, in the following Examples, "%" means mass %. Production Examples 1 to 3 show the synthesis of surface decorative pigments 1 to 3, and Examples 1-1 to 1-6 show the synthesis of polymeric azo compounds 1 to 6 represented by the above general formula (II). Examples 1 to 7 show the synthesis of the polymeric azo compound 7 represented by the above general formula (III), and Example 2 shows the radical polymerization reaction using the polymeric azo compound as a polymerization initiator. Examples 3-1 to 3-14 show the synthesis of grafted pigments 1 to 14, Comparative Examples 3-1 to 3-5 show the synthesis of comparative grafted pigments 15 to 19, and Example 4-1 ～4-14 shows the preparation of pigment composition No.1～No.14, comparative example 4-1～4-7 shows the preparation of comparative pigment composition No.15～No.21, embodiment 5- 1 to 5-8 show hard coating agents and hard coating films containing grafted pigments 1, 4 and 6 to 11 obtained in Examples 3-1, 3-4 and 3-6 to 3-11 The manufacture of, embodiment 6-1～6-8 shows the water-based paint that contains grafted pigment 1, 4 and 6～11 obtained by embodiment 3-1, 3-4 and 3-6～3-11 Preparation of the composition, Examples 7-1 to 7-3 show the preparation of the alkali-developable resin composition containing the grafted pigments 10 to 12 obtained in Examples 3-10 to 3-12.

[Manufacturing Example 1] Synthesis of Surface Decorative Pigment 1

80 g of isopropanol-dispersed colloidal silica gel (manufactured by Nissan Chemical Industries; particle diameter 20 nm, solid content 30%, water content 0.5%), 4.8 g of vinyltrimethoxysilane, 40 g of isopropanol, and 5 g of ion-exchanged water were mixed , 3.6 g of 1% HCl aqueous solution was added, stirred at 50° C. for 8 hours, and the solvent was distilled off to obtain Surface Decorative Pigment 1 in the form of silica fine particles having vinyl groups on the surface.

[Production Example 2] Synthesis of Surface Decorative Pigment 2

Mix 80 g of methanol-dispersed colloidal silica gel (manufactured by Nissan Chemical Industries; particle diameter 20 nm, solid content 30%, water content 0.5%), 8 g of γ-methacryloxypropyltrimethoxysilane, and 0.8 g γ-mercaptopropyltrimethoxysilane, 40g isopropanol and 5g ion-exchanged water, add 2g of 1% NaCl aqueous solution, stir at 50°C for 8 hours, distill off the solvent to obtain di Surface decorative pigments in the form of silica particles2.

[Production Example 3] Synthesis of Surface Decorative Pigment 3

24 g of P-25 (manufactured by Nippon Aerosil Corporation; primary average particle size: 10 nm) and 140 g of tert-butanol were dispersed in a bead mill for 30 minutes. Add 4.8 g of vinyltrimethoxysilane, 5 g of ion-exchanged water, and 5 g of 1% HCl aqueous solution, stir at 50° C. for 8 hours, and distill off the solvent to obtain a surface decoration pigment in the form of titanium oxide particles having vinyl groups on the surface. 3.

[Example 1-1] Synthesis of Polymer Azo Compound 1

<Step 1> Synthesis of DMAP hydrochloride

Dissolve 1.88g (15.4mmol) dimethylaminopyridine (DMAP) in 20.0g of 1,4-dioxane, and drop 4.10g of hydrogen chloride into 1,4-dioxane at room temperature under a nitrogen atmosphere. Alkanes solution (0.14g/g). The precipitated white solid was filtered, washed with 1,4-dioxane and tetrahydrofuran, and then dried to obtain 2.03 g of the target DMAP hydrochloride (yield 83%).

<Step 2> Synthesis of Polymer Azo Compound 1

Dissolve 20.2 g (10.1 mmol) of Unioc M-2000 (polyethylene glycol monomethyl ether manufactured by NOF Co., Ltd., molecular weight: 2000) in 20.0 g of 1,4-dioxane while maintaining the temperature at 35° C., under a nitrogen atmosphere 1.75 g (6.25 mmol) of 4,4'-azobis(4-cyanoheptanoic acid) and 0.0373 g (0.310 mmol) of DMAP were added and dissolved. Next, after adding 0.0360 g (0.227 mmol) of DMAP hydrochloride obtained in step 1 of Example 1, 2.63 g (12.8 mmol) of dicyclohexylcarbodiimide and 0.5 g of 1 were added dropwise at 35° C. 4 - Dioxane, stirred for 8 hours. Add 10 ml of 1,4-dioxane, filter the precipitated white solid, drop 200 g of n-hexane cooled to 5°C for reprecipitation, filter the solid, and dry it to obtain the target polymer azo compound 1 (the yield is 19.3 g, the yield is 90%, and the purity is 87%).

(Example 1-2～1-6) Synthesis of Polymer Azo Compounds 2～6

Polymer azo compounds 2 to 6 were synthesized in the same manner as in Example 1-1 except that the polyalkylene glycol monoalkyl ether in Example 1-1 was replaced with the compounds described in Table 1. Table 1 shows the synthesis results (yield, yield, purity) of the obtained polymeric azo compounds 2 to 6.

Table 1

Polymer azo compound Polyalkylene glycol monoalkyl ether (P) Molecular weight of (P) Yield (g) Yield (%) Purity (%) Polymer azo compound 2 (embodiment 1-2) Polyethylene glycol monoallyl ether 1500 8.10 92 70 Polymer azo compound 3 (embodiment 1-3) Polyethylene glycol monolauryl ether 2400 12.0 90 56 Polymer azo compound 4 (embodiment 1-4) Polyethylene glycol monolauryl ether 1600 8.85 95 65 Polymer azo compound 5 (embodiment 1-5) Polyethylene glycol: polypropylene glycol = 85/15 copolymer 2000 10.1 89 89 Polymer azo compound 6 (embodiment 1-6) Polyethylene glycol: polypropylene glycol = 70/30 copolymer 2000 10.2 90 87

[Example 1-7] Synthesis of Polymer Azo Compound 7

In a 50ml four-necked flask, 18.00g of poly-ε-caprolactone with a butoxyl group at one end, 20.00g of dioxane and Stir, replace nitrogen, and dissolve by heating. After standing to cool, 2.10 g of 4,4'-azobis(4-cyanoheptanoic acid) (ACPA) and 0.022 g of DMAP were added and dissolved. In addition, 0.022 g of DMAP hydrochloride was added to make it suspended, and then, 1.54 g of dicyclohexylcarbodiimide (DCC) and 0.50 g of dioxane were dissolved in a dropping funnel, and the four-necked flask was installed. The dropwise addition was performed at 35° C. or lower to allow the reaction to proceed. Add 20ml of dioxane, heat (<35°C), and filter off the white precipitate by filtration. The filtrate was dropped into 200 g of cold hexane, and reprecipitated by stirring. This was filtered and dried to obtain the target polymer azo compound 7 (amount: 16.3 g, yield: 82%, purity: 87%).

Table 2 shows the identification results of the obtained polymeric azo compounds 1 to 7.

Table 2

H ¹ NMR (ppm) C ¹³ NMR (ppm) Compound 1DMSO-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

[Example 2] Radical Polymerization Using High Molecular Azo Compounds as Polymerization Initiators

19 g (8.95 mmol) of the polymeric azo compound 1 obtained in Example 1-1 and 40 g (0.400 mol) of methyl methacrylate were dissolved in 80 g of toluene, and stirred at 80° C. for 8 hours in a nitrogen atmosphere. After cooling to room temperature, the reaction solution was dropped into 400 ml of n-hexane for reprecipitation. Filtration and drying afforded 55 g of block polymer (Mn=13000).

[Examples 3-1 to 3-14 (synthesis of grafted pigments 1 to 14) and comparative examples 3-1 to 3-5 (synthesis of comparative grafted pigments 15 to 19)]

According to the mixing ratio recorded in Table 3, mix 24.0g of surface decoration pigments or commercially available pigments, 90.0g of propylene glycol-1-monomethyl ether-2-acetate and high molecular weight azo compounds, in a nitrogen atmosphere, at 74 ~ By stirring at 77° C. for 8 hours, propylene glycol-1-monomethyl ether-2-acetate solutions of target grafted pigments 1 to 14 and comparative grafted pigments 15 to 19 were respectively obtained.

table 3

grafted pigment pigment Azo compounds Grafted pigment 1 (embodiment 3-1) Surface Modification Pigment 1 Polymer azo compound 1 9.0g Grafted pigment 2 (embodiment 3-2) Surface Modification Pigment 1 Polymer azo compound 1 6.9g Grafted pigment 3 (embodiment 3-3) Surface Modification Pigment 1 Polymer azo compound 1 4.5g Grafted pigment 4 (embodiment 3-4) Surface Modification Pigment 1 Polymer azo compound 2 9.0g Grafted pigment 5 (embodiment 3-5) Surface Modification Pigment 1 Polymer azo compound 2 6.9g Grafted pigment 6 (embodiment 3-6) Surface Modification Pigment 1 Polymer azo compound 5 9.0g Grafted pigment 7 (embodiment 3-7) Surface Modification Pigment 1 Polymer azo compound 6 9.0g Grafted pigment 8 (embodiment 3-8) Surface Modification Pigment 2 Polymer azo compound 1 9.0g Grafted pigment 9 (embodiment 3-9) Surface Modification Pigments 3 Polymer azo compound 1 9.0g Grafted Pigment 10 (Example 3-10) a ^1* Polymer azo compound 1 9.0g Grafted pigment 11 (embodiment 3-11) b2 ^* Polymer azo compound 1 9.0g Grafted pigment 12 (embodiment 3-12) b Polymer azo compound 2 6.9g Grafted pigment 13 (embodiment 3-13) b Polymer azo compound 5 9.0g Grafted pigment 14 (embodiment 3-14) b Polymer azo compound 6 9.0g Comparative grafted pigment 15 (comparative example 3-1) Surface Modification Pigment 1 c ^3* 9.0g Comparative grafted pigment 16 (comparative example 3-2) Surface Modification Pigment 1 d ^4* 9.0g Comparative grafted pigment 17 (comparative example 3-3) Surface Modification Pigment 1 AIBN ^5* 9.0g Comparative grafted pigment 18 (comparative example 3-4) Surface Modification Pigment 2 c 9.0g Comparative grafted pigment 19 (comparative examples 3-5) Surface Modification Pigment 2 e ^6* 9.0g

1 ^* : カルベール (carbon nanotubes manufactured by GS Ecocleos)

2 ^* : Z-25 (flaky graphite manufactured by Ito Graphite Industry Co., Ltd.)

3 ^* : VPE-0201 (a high molecular weight azo polymerization initiator containing polyethylene glycol units manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 2000)

4 ^* : VPE-0501 (a high molecular weight azo polymerization initiator containing a polydimethylsilane unit manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 5000)

5 ^* : Azobisisobutyronitrile

6 ^* : VPE-0401 (a macromolecular azo polymerization initiator containing a polyethylene glycol unit manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 4000)

[Example 4-1～4-14] Preparation of Pigment Composition No.1～No.14

According to the mixing ratio described in Table 4, 83.5 g of Esrec PSE-0020 (styrene-acrylic copolymer resin manufactured by Sekisui Chemical Industry Co., Ltd.) The propylene glycol-1-monomethyl ether-2-acetate solutions of the obtained grafted pigments 1 to 14 were dispersed in a bead mill to obtain pigment compositions No.1 to No.14, respectively.

[Comparative Examples 4-1 to 4-7] Preparation of comparative pigment compositions No.15 to No.21

Comparative pigment compositions No.15 to No.21 were prepared in the same manner as in Examples 4-1 to 4-14, except that the surface decoration pigments described in Table 4 or comparative grafted pigments 15 to 19 were used instead of the grafted pigments. .

The pigment compositions No. 1 to No. 14 prepared in the above-mentioned Examples 4-1 to 4-14 and the comparative pigment compositions No. 15 to No. 21 were evaluated. The evaluations were: ◯ for uniform dispersion, and x for agglomerated one. The results are shown in Table 4.

Table 4

Pigment composition pigment dispersion No.1 (Example 4-1) grafting pigment 1 ○ No.2 (Example 4-2) grafting paint 2 ○ No.3 (Example 4-3) grafting paint 3 ○ No.4 (Example 4-4) grafting paint 4 ○ No.5 (Example 4-5) grafted pigment 5 ○ No.6 (Example 4-6) grafted pigment 6 ○ No.7 (Example 4-7) grafted pigment 7 ○ No.8 (Example 4-8) grafting paint 8 ○ No.9 (Example 4-9) grafted pigment 9 ○ No.10 (Example 4-10) grafting paint 10 ○ No.11 (Example 4-11) Grafting Pigment 11 ○ No.12 (Example 4-12) grafting pigment 12 ○ No.13 (Example 4-13) grafted pigment 13 ○ No.14 (Example 4-14) grafted pigment 14 ○ No.15 (comparative example 4-1) Compare Grafting Pigments 15 x No.16 (comparative example 4-2) Compare grafted pigments 16 x No.17 (comparative example 4-3) Compare grafted pigments 17 x No.18 (comparative example 4-4) Compare grafted pigments 18 x No.19 (comparative example 4-5) Compare grafted pigments 19 x No.20 (comparative example 4-6) Surface Modification Pigment 1 x No.21 (comparative example 4-7) Surface Modification Pigment 2 x

[Examples 5-1 to 5-8 (hard coating agents and hard coating agents containing grafted pigments 1, 4 and 6 to 11 obtained in Examples 3-1, 3-4 and 3-6 to 3-11) Manufacture of coated films)]

Dissolve 3.0 g of Irgacure 184 (a photopolymerization initiator manufactured by Ciba Specialty Chemicals) in 3.0 g of propylene glycol-1-monomethyl ether-2-acetate, add 21 g of Aronicus M-400 (dipentaerythritol hexamethanone manufactured by Toagosei Co., Ltd.) Acrylate), 9.0g ビスコ—ト#230 (1,6-hexanediol diacrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.), 7.0g grafted pigment and 71g propylene glycol methyl acetate were mixed to obtain Hard coating agent. The obtained hard coating agent was coated on A-4300 (adhesion-friendly polyester film manufactured by Toyobo Co., Ltd.) with a film thickness of 100 μm by bar coater #14, and dried at 80° C. for 1 minute. Thereafter, in an air atmosphere, 300 mJ of ultraviolet rays were irradiated by a high-pressure mercury lamp to obtain hard coat films with a cured film thickness of 8 μm, respectively.

[Example 6-1～6-8 (contains the manufacture of the water-based coating composition of grafted pigment 1,4 and 6～11 obtained by embodiment 3-1, 3-4 and 3-6～3-11 )]

In a ball mill, 25g tap water, 0.8g アデカネ-ト B-940 (defoamer manufactured by ADEKA), 0.4g アデカコル W-304 (dispersant manufactured by ADEKA) and 100g grafted pigments were mixed for 15 hours , to obtain a pigment paste. Mix 50 g of the obtained pigment paste, 100 g of styrene-acrylic emulsion (manufactured by Showa High Molecular Co., Ltd.), 2.0 g of ADEKA NET B-940 (defoamer manufactured by ADEKA Co., Ltd.) and 2.0 g in a dispersion mill. Aqueous coating compositions were prepared using Nitrogen Cyza-CS-12 (a film-forming agent manufactured by Chitsuso Co., Ltd.).

[Examples 7-1 to 7-3 (preparation of alkali-developable resin compositions containing grafted pigments 10 to 12 obtained in Examples 3-10 to 3-12)]

<Step 1> Preparation of Adhesive Resin Composition

Mix 17.0g of bis[4-(2,3-epoxypropoxy)phenyl]-4-biphenyl(cyclohexyl)methane, 4.43g of acrylic acid, 0.06g of 2,6-di-tert-butyl p-methyl Phenol, 0.11 g of tetrabutylammonium acetate and 14.3 g of propylene glycol-1-monomethyl ether-2-acetate were stirred at 120°C for 16 hours. After cooling to room temperature, 7.18 g of propylene glycol-1-monomethyl ether-2-acetate, 4.82 g of succinic anhydride and 0.25 g of tetrabutylammonium acetate were added, and stirred at 100° C. for 5 hours. In addition, 5.08 g of bis[4-(2,3-epoxypropoxy)phenyl]-4-biphenyl(cyclohexyl)methane and 2.18 g of propylene glycol-1-monomethyl ether-2-acetic acid were added ester, after stirring at 120°C for 12 hours, at 80°C for 2 hours, and at 40°C for 2 hours. 13.1 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target adhesive resin composition (Mw=4200 , Mn=2100, acid value (solid content) is 55mgKOH/g).

<Step 2> Preparation of Alkaline Developable Resin Composition

Mix 83.5g of the binder resin composition obtained in step 1 and 416.5g of the propylene glycol-1-monomethyl ether-2-acetic acid of the grafted pigments 10-12 obtained in Examples 3-10-3-12 The ester solution and the obtained slurry were dispersed in a bead mill to obtain an alkali-developable resin composition, respectively.

<Step 3> Preparation of Alkaline Developable Photosensitive Resin Composition

With respect to 44g of the alkali-developable resin composition obtained in step 2, 6.3g of trimethylolpropane triacrylate, 2.1g of benzophenone and 78g of propylene glycol-1-monomethyl ether-2-acetate were added respectively, Stir well to obtain an 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.