JPS63317558A - Production of high polymer dye - Google Patents

Abstract

PURPOSE:To obtain the titled dye, having excellent characteristics, such as solvent resistance, and suitable as recording or display materials, such as pressure-sensitive paper, heat-sensitive paper, photosensitive and pressure- sensitive paper, fixing type heat-sensitive paper or electrically conductive heat- sensitive paper, by copolymerizing a color former monomer with a developer monomer. CONSTITUTION:The aimed dye obtained by copolymerized (A) a color former monomer [preferably 2-p-vinylbenzoylamino-6-diethylaminofluoran, 2-p-(4'- vinylbenzoylamino)anilino-3-methyl-6-dibutylaminofluoran, etc.] with (B) a developer monomer (e.g. styrenesulfonylaminosalicylic acid or vinylbenzyloxyphthalic acid) at a ratio so as to preferably provide >=2mol. of the latter based on the former.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a dye that utilizes a color-forming reaction caused by contact between a color former and a color developer, and particularly relates to a method for producing a polymer dye.

(Prior art) Pressure-sensitive paper, thermal paper,
Recording materials and display materials such as light-sensitive pressure-sensitive paper, fixing type thermal paper, and electrically conductive thermal paper have been developed.

The present inventors have already discovered that color forming agents having a vinyl group or vinylidene group can be polymerized and are currently filing a patent, and have confirmed that they have favorable characteristics such as reduced capri and increased sensitivity.

On the other hand, research is also underway on polymer dyes, focusing on their diffusion resistance, film-forming ability, and edibility.

For example, in the US patent, 233.3λg, ≠31.30
/, 2, same≠, 6/ri, TataO1 same≠31/≠Tako issue is detailed, but (1) it is necessary to make it into a dye through chemical treatment after a polymerization reaction (2) the hue is different. (3) When the molecular weight is increased, the chemical processing is difficult to proceed and the brightness is lost. (4) There are still points to be improved, such as the auxochrome is limited to azo bonds. .

It has been discovered that the above-mentioned drawbacks can be improved by skillfully using a color former monomer and a color developer monomer, and the present invention has been completed.

(Object of the Invention) An object of the present invention is to provide a polymer dye with improved properties and a method for producing the polymer dye.

(Structure of the Invention) The object of the present invention was achieved by completely copolymerizing the dye monomer and the developer monomer.

The color former monomer refers to a color former having, for example, a vinyl group or a vinylidene group (hereinafter referred to as a vinyl group).

The color former having a vinyl group of the present invention has at least one active hydrogen atom such as a hydroxy group or an amine/group.
It is synthesized by reacting a compound with an active group such as an acid halide, ester, halide, or isocyanate having a vinyl group. Alternatively, a vinyl monomer having an active group such as a hydroxy group, a amino group, an epoxy group, or an ester, and a group such as an acid, an acid halide, or an ester can be used.
It is synthesized by reaction with a color former. These unit operations themselves are well known (known techniques, and can be used).

On the other hand, the color developer of the present invention refers to a color developer having a vinyl group.

The color developer having a vinyl or ru group is preferably a derivative of phenols, benzoic acids, sulfonic acids, amides, or imides having at least one acidic group.

Even if the vinyl group of the present invention is directly bonded to the aromatic ring or active hydrogen-containing site of the color former or color developer, alkylene, arylene, oxaalkylene, ester, carbonyl,
They may be bonded via a divalent group such as amide or ether. Examples of the above-mentioned vinyl groups include acryloxy, methacryloxy, vinylbenzoyloxy, vinylphenoxyacetoxy, methacryloxyethoxy, acryloxyethoxy, vinylbenzenesulfonyloxy, iriruoxy, acrylamide, methacrylamino,
β-acrylamide ethyl, β-N-ethyl-N-acrylamide ethyloxy, vinyloxyethoxy, vinylanilinocarbonyloxy, β-methacryloxypropoxy, β-acryloxypropoxy, vinylbenzyloxy, β-methacryloylminoethoxy, chloro Ethylvinyl, β-acryloylaminoethoxy, β-p
-Vinylbenzoyloxyethoxy, γ-vinylphenoxy, β-hydroxypropoxy, β-methacrylic dipropoxy, β, γ-dimethacrylic dipropoxy, glycidyloxy, vinyl, vinylphenoxy, β-vinylphenoxyethoxy, etc. It can take various forms.

That is, a color former having a vinyl group is a combination of at least seven of these groups and a color former nucleus (for example, phthalides, leucos), and at least one of these groups and an acidic group t.
It can be said that the combination with the mother nucleus (for example, phenols, benzoic acids, and sulfonic acids) is a color developer with vinyl base.

In addition, in the invention, it is desirable to use one or more other monomers in the copolymerization of the color former monomer and the color developer monomer.

This monomer has particle size, solubility, dispersibility, adhesiveness, Tg1
Used to control properties such as color development and storage stability. For example, acrylamide, methacrylamide, acrylanilide, diacrylic acid, sodium acrylic acid, sodium acrylic acid propanesulfonate, esters such as 6-bis-acrylaminohexane, (meth)acrylic esters such as methyl methacrylate, ( Butyl meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)
Cyclohexyl acrylate, (meth)acrylic acid cellosolve ester, phenoxyethyl (meth)acrylate, allyl (meth)acrylate, cinnamoyloxyethyl (meth)acrylate, diethylene glycol (meth)acrylate, triethylene glycol ethyl ether (meth) Acrylate, phenoxypropyl (meth)
Acrylate, phenyl (meth)acrylate, styrene, vinyltoluene, divinylbenzene, vinylbenzene butyl sulfonate, vinyl phenol, vinylbenzoic acid, vinylpyridine, vinylmethylpyridine, vinylmethylhemethylpyridine , vinyl aromatics such as acrylonitrile, vinyl acetate, vinyl carbazole, chloromethyl vinyl ether, diallyl phthalate, vinyl dioxolane, fish water maleic acid, and epichlorohydrin.

Methods for the yfL polymerization reaction include radical polymerization, ionic polymerization, etc., and various polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and solvent-free polymerization can be used.

For example, the vinyl-based color formers or developers described above can be polymerized if initiated by a radical initiator.

As a catalyst, a perFltm salt-reducing agent, an oily or aqueous azo compound, a peroxide, a metal catalyst, etc. can be used. The polymerization reaction is preferably carried out under an inert gas atmosphere, and in the case of heating, the temperature is 720°C or less,
However, it is preferably less than yo''c.

In addition, when using a solvent, water, ester, ether,
Polar solvents such as halides, ketones, amides, alcohols,
Non-polar solvents such as hydrocarbons and aromatics can be used alone or in combination.

Furthermore, during the polymerization reaction, various color formers or color developers may be present to improve hue and color development efficiency.

In the polymerization reaction as described above, emulsification method, deaeration method,
It is convenient to operate with reference to ordinary polymerization reactions with respect to reaction temperature control, handling of the metal catalyst, post-treatment method after the completion of the polymerization reaction, purification method of the obtained polymer compound, etc. For example, general operating methods are detailed in 5orensen 1 Polymer Synthesis Experimental Methods, Tokyo Kagaku Doujin, 15'A Otsu.

As the color former layer according to the present invention, the above-mentioned functional group t
triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leucoolamine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, fluorene compounds, spiropyran Examples include system compounds.

Preferred examples of the color former layer according to the present invention are as follows.

/) j-p-vinylbenzoylamino-ot-diethyl-minofluoran 12-p-(4u-vinylbenzoylamino)anilino-3-methyl-6-cyptylaminofluoranj) J-p(1-vinylbenzylamino) ) Ayurif-3
-quamino 6-N-ethyl-isoamyl-isoamyl-4-vinylbenzylidene-amino-6-dinithylaminofluoran-β-(p-vinylbenzoylamino)ethyl-3-chloro-6-ethyl Aminofluorane 6)-1β-<p-vinylbenzoylaminoethylamino)ethyl-6-dinithylaminofluoran? ) 2-p-vinylbenzenesulfonyl-mino-3-yneamyl-6-diethyl-minofluorane) 2-anilino-3-methyl-AN-ethylhe β-p-vinylbenzoylaminoethylamino-fluorane 9) (p- Vinylbenzoylamino)benzoylleucomethylene blue 10) 4t-diethylami/phenyl-≠'-N-ethylhevinylbenzylaminophenyl phthalide l/)λ-p-vinylbenzoyloxy≠-diethylaminophenyl-at-p-vinylbenzoyl Oxy-
Hiro'-methyl-j'-γnylinophenyl phthalide/2) x-p-vinylphenylureido A-diethylaminofluoran/3) 2-p-vinylanilino-3-methyl-6-diethylminofluoranha 0--anilino -Hiro-γ-p-vinylbenzoylminophthyl-6-diethylminofluoran/j) λ-β-hydroxy-γ-p-vinylphenoxyp-Opyramino-6-diethylminofluoran/4)j-(4'-diethyl) minnow-methacryloxyphenyl)-3-Ci-ethyl-2-methylindol-3-yl)phthalide 17)j-[Hiroshi-diethylami/-1-p-vinylbenzyloxyphenyl)-j-
(/-dithyl-2-methylindol-3-yl)phthalide/I) 3-[goodiethylamine-,2-(≠-vinylbenzoyloxy)phenyl"J-3-CI-ethyl-
2-methylindole-J-ik)phthalide/9)3-[μmdiethylamino-λ-(vinyl-t-
t-diethyloxy)phenyl)-3-(/-ethyl-
d-Methyl-indol-3-yl]phthalide 20) 3-[Goodiethylami/-2-(β-acryloxyethoxy)phenyl"J-3-CI-ethyl-2-
Methylindol-3-yl)phthalide, 2t) 3-C-dibutylamino-β-acrylamidoethoxyphenyl)-3-(/-ethyl-λ-methylindol-3-yl)phthalide, 2,2) 3-(11t-diethylamino-2-vinylbenzyloxyphenyl)-j-C1,2-dimethylindol-3-yl)phthalide, z3)J-(Hiro-diethylamino-λ-β, γ-dimethacryoxypropoxyphenyl) )-3-(/-ethyl-2-phenylindol-3-yl)phthalide, 2≠)3-[≠-diethylamino-2-(β-acryloxypropyloxy)phenyl)-J-(/-ethyl- -Methylindol-3-yl) ≠ -Dinza7talide 2K) 3-C≠-diethylami/-1-vinylbenzenesulfonyloxy)phenyl J-j-(/-ethyl-2
-Methylindol-3-yl)-Hiro-azaphthalide JA)j-(4'-diethylamino)-,2-(β-vinylphenoxy)phenylJ-3-C/-ethyl-,2
-iso-pentylindol-3-yl)-≠-Zaftarid,! 7) 2-acrylamino-6-diethylminofluorane, 2r) 2-acrylamino-6-dibutylamide/fluoran) no-acrylamino-6-N-cyclohexyl-
N-methylaminofluorane 30), 2-acrylamino-3-riol 1. -diethyl-minofluoran 3/) no-acrylamino-3-methyl-6-diethyl-minofluoran 3.2) J-methacrylamino-3-ethyl-6-dibutylami/fluoran 33) λ-p-methacrylaminoanilino-6 2-1)-acrylaminoanilino-6-dibutyl-fluoran/fluoran.

3K) 2-β-acrylaminoethylamino-6-dibutylamino/fluoran 34) 2-β-acrylaminopropylamino-3-chloro-6-diethylami/fluoran 37), 2-anilino-3-β-acrylamino Ether-6-diethylminofluoranejJ') 2-p-chloroanilino-3-β-methacrylaminopropyl-6-dibutylaminofluorane3) noanilino-3-methyl-6-N-p-acrylamino/anilino- N-ethylaminofluorane 1 Ito), 2-dibenzylamino-AN-acrylaminoheethylfluoran 1/) 2-hexylamino-AN-methacrylamino-~-methylfluoran ψλ) 3. 3-bis(p-dimethylami/phenyl)-
A-N-ethylhe β-methacryloxyethyl ryomino 7-talide≠3) 3,3-bis(p-diethylaminophenyl)-
Examples include 6-N-ethylvinylbinylamide/phenylphthalide.

The color developer monomer may be a compound having an addition polymerizable group and a phenolic hydroxyl group, a carboxyl group, a sulfo group, etc., especially phenol horn, salicylic acids, or a combination thereof with a metal compound, or a gold salt.

Specific examples include /) styrenesulfonylaminosalicylic acid, 2) vinylbenzyloxyphthalic acid 3
) Zinc β-methacryloxyethoxysalicylate tLL
) Vinyloxyethyloxybenzoic acid I'd j) β-Methacryloxyethoxysalicylic acid 6) β-Methacryloxyethyl orseinate 7) β-Methacryloxyethoxyphenol d) β-Methacryloxyethyl-β-resorcinate ta) Human Oxy Styrene sulfonic acid-h-ethyl ester 1O) β-methacryloxypropyl-p
-Hydroxybenzoate //) Methacryloxymethylphenol /, 2) Methacrylamide propane sulfonic acid /3) β-methacryloxyethoxy-
dihydroxybenzene / γ-styrenesulfonyloxy-β-methacryloxypropanecarboxylic acid
/j) γ-acryloxypropyl-α-human axyethyloxysalicylic acid /6) β-hydroxyethoxycarbonylphenol /7) β-methacryloxyethyl-p-hydroxycinnamate /r) 3,3; Distyrene sulfone Acid midophenol / methacryloxyethoxy 7tardz 20) Methacrylic acid, 21) Meccryloxyethoxyhydrooxynaphtho 6. 22>
3-β-methacryloxyethoxyphenol J3)β
-Methacryloxyethyl-p-hydroxycinnamate 2≠) β' -methano I/Ooxyethyl-β resorcinate, 2J) β-methacryloxyethyloxycarbonylhydroxybenzoic acid, 26) N,N-di-β
-Methacryloxyethylaminosalicyl r1i! ,
27) N,N-diβ-methacryloxyethylamide/sulfonylsalicylic acid, etc., and metal salts thereof, such as zinc salts, are preferred.

In the copolymerization of these color former monomers and color developer monomers, it is convenient to copolymerize them with other vinyl or vinylidene monomers. For example, the monomer may include amide, ether, ester, or γ-romatics having an addition-polymerizable group. These can be copolymerized under the same conditions as the monofunctional monomers already mentioned.

Preferred compounds include polyvinylbenzene, which is obtained by reacting polyamines, polyols, amino alcohols, etc. with allyl halide, (meth)acrylic acid chloride, or (meth)acrylic acid ester.

For example, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate,
Trimethyl0-propane di(meth)acrylate, pentaerythritol tri(meth)acrylate, diglycidyl(meth)acrylate, β(meth)acrylamidoethyl(meth)acrylate, 6-di(meth)acrylamidohexane, divinylbenzene, butane Diol diglycidyl ether, t l J + j-t!
J subinyloxyethoxybenzene, l,3-di β-
(Meth) Ori-oxyethoxybenzene, polyethylene glycol poly(meth) acrylate, Ori-ru (meth)
Acrylates, glycidyl (meth)acrylates, etc. are examples. These are used in the polymer in an amount of about 60% by weight or less, preferably less than /θ weight t%.

In addition, the color former monomer is 40 wt%, and the color developer monomer is 40 wt%, preferably about 7 wt. A composition that is particularly desirable from the viewpoint of resistance.

Furthermore, if necessary, these colored copolymers can be decolored by contacting them with (1) a desensitizer +2)
It is also possible to change the color density to kK by applying ss.
(3) It has characteristics such as the ability to add plant additives to the polymerization reaction solution and use it as a coating solution.

Examples of the color former monomer and color developer monomer copolymer in the present invention include the following: Ethyl-methylindole-3
-yl)phthalide/zinc β-methacryloxyethoxysalicylate/diethylene glycol dimethacrylate/acrylic copolymer, z)J-(≠-diethylamino-2-methacryloxyphenyl)-3-(/-ethyl-1-methylindo 3-yl) phthalide/vinyloxyethyloxybenzoic acid/vinylbenzoic acid/divinylbenzene sulfonic acid/
Butoxyethyl acrylate copolymer 3) 3-[≠-diethylaminophenyl)-3-(/-ethyl-λ-methylindol-3-yl)phthalide/β-methacryloxyethyl -β-resorcinate/butyl methacrylate/methacrylic acid/β-ethyl dipropoxy acrylate copolymer≠)3-(≠-diethylamino-2-vinylbenzyloquinphenyl)-3-(/,,2-dimethylindole -3-yl)phthalide/chloroOmethylstyrene/methacryloquine ethoxysalicylic acid/methacrylic acid/
Methyl methacrylate/2-ethylhexyl acrylate copolymer j),! -acrylamino-6-dinithylaminofluorane/2-acrylamino-6-cyptylaminofluorane) 2-acrylamino-6-hecyclohexylhemethylaminofluorane/β-methacrylate O xib O
Biru p-human O-oxybenzoate/γ-butquinpropyl methacrylate/styrene copolymer, 4) j-(≠-diethylamino-(γ-acryloxib O-pyroxy) phenyl, l-3-(/-ethyl-2) -Methylindol-3-yl)≠-Ryzaftalide/methacryloxyethoxyphthalylk?/butoxyethyl methacrylate copolymer 7) J-(:4(-diethylamino-2-(β-aclJoxyethoxy)phenyl)- 3-(/-ethyl-2-methylindole-3-
yl) phthalide/β-methacryloxethyl-p-hydroquienshede/vinyltoluene/2-ethylhexyl acrylate copolymer 1) 3-[≠-diethylamino),2-(β-vinylphenoxy)phenylcou 3-CI -ethyl-,2-is
o-pentylindol-3-yl)-≠-azaphthalide/β'-methacryloxyethyl-β-renyl inert/2-ethylhexyl methacrylate/vinyl acetate 10) j-p-vinylbenzoyloxy −≠
-diethylminophenylx'-p-vinylbenzoyloxy-≠'-methyl-j'-anilinophenyl phthalide/vinylbenzoic acid/β-methacryloxyethoxyphenol/ethyl acrylate/butyl methacrylate copolymer//), 2 -β-acrylamino/butyramino-3-
Chloro-6-diethyl-minofluoran, -ichiryo-nilino-3-β-acrylaminoethyl-6-diethyl-minofluoran/methacrylic acid/methacryloxyethoxyhydroxynaphthoic acid/noethylhexyl acrylate copolymer/j), 2-p -methacrylaminoanilino-
6-Dimethylaminofluorane/2-p-acrylaminoanilino-6-diphthylaminofluorani//λ-
β-acrylamine ethylamino-6-dibutylaminofluoran/methacryloquine propane sulfonic acid/sulfostyrene-maleic anhydride/β-hydroxyethyloxysalicylic acid methacrylate copolymer/3), 2-anilino-3-methyl-, 4-N-Ethyl-β-p-vinylbenzoyl-minoethyl-mino-fluoran/β-methacryloxyethyl-p-hydroxycinnamate/acrylamide/methacrylic acid/β
- Methacryloxyethyl cinnamate too! ! , @body/1j-(≠-dibutyl-2-β-acryloxyethoxyphenyl)-3-CI=ethyl-methylindol-3-yl)azaphthalide/3-(≠-diethylamino-β-methacryloxy ethoxyphenyl)-3-(/-ethyl-1-methylindole-3-
azaphthalide/β-acryl oxypropion [f/methacrylamidopro)ξsulfone Q/styrene sulfonc/hexyl acrylate copolymer/l>3
-C≠-diethylamino-2-β,γ-dimethacryoxypropoxyphenyl) -3-(/-ethyl-phenylindo-yl)phthalide/vinylbenzyloxy7-talic acid/triethylene glycol dimethacrylate/phenoxyethyl methacrylate copolymer/A) j-(dardiethyl-2-(vinyloxyethyloxy)phenyl-3-CI-ethyl-2-methyl-indol-3-yl)phthalide/styrene/,
2-acrylic acid-6-diethylamide/fluoran/
β-methacryloxyethyloxycarbonylhydroxybenzoic acid/butyl methacrylate/styrene/methacrylic acid copolymer/7) 2-p-chloroanilino-3-β-methacrylaminopropyl-6-dibutyl ryominofluoran/Koryoji 1J No 3 -Methyl-6-N-p-acrylicyl-aminoanili/-h-ethyl-ryomi/fluoran/≠-diethylaminophenyl-μ'-N-ethyl-vinylbenzylaminophenyl phthalide/β-methacryloxyethoxy-3,≠- Dicarboxybenzene/acrylic butyl/acrylic co-M combination/f) 3.3-bis(p-dimethylaminophenyl)-
6-N-Ethylhew β-methacryloxyethylaminophthalide/p-vinylbenzoylleucomethylene blue/β-methacryloxyethyl orseinate/methacrylic acid/2-ethylhexyl acrylate/β-hydroxyethyl methacrylate copolymer/R )2-anilino-≠-γ-p-vinylbenzoylaminoptyl-6-diethylaminofluorane/3,6-
Cymethacryloxyethoxyfluorane/λ-β-hydroxy-γ-p-vinylphenoxybrobylamino-6
-diethylaminofluoran/styrene sulfone zinc minosalicylate/pentaerythritol triacrylate copolymer 10) 2-acrylamino-3-chloro-6-diethylamide/fluoran/. 2-acrylic γmino-3-methyl-6-diethylaminofluorane/maleic anhydride β-
Hydroxyethoxycarbonylphenol reactant/β-
Methacroxyethyl-2,4A-dihydroxybenzoate/triethylene glycol ethyl ether methacrylate copolymer λ/)2-pC'l'-vinylbenzylamino)anilino-3-chloro-6-N-ethyl-N-isoamylamino Fluorane/vinyltoluene/β-methacryloxyethoxy-dihydroxybenzene/diethylene glycol methacrylate/methacrylic acid copolymer j, 2), 2-β-(p-vinylbenzoylrymino)ethylamino-3-rioo-1, -diethylaminofluorane/acrylic acid/styrenesulfonic acid-styrenesulfone-N-ethylamide/acrylic esterimide copolymerjj)j-(4<-diethylamino-,2-(vinyloxyethyloxy)phenyl]-3-( /-ethyl-2
-Methyl-indol-3-yl)phthalide/β-methacrylamidopropoxybenzenesulfonic acid/triethylene glycol dimethacrylate copolymer 24')j-(4'-diethylamino-1-methacryloxyphenyl)-j-(/ -ethyl-2-methylindol-3-yl)phthalide/vinylbenzyloxy7
Tal t11/2-ethylhexyl acrylate/β-methacryloxyethyl-22-cyano-cinnamate/ethyl acrylate copolymer 2j) 3.4-bis-β-methacryloxyethoxyfluoran phthalide/β-methacryloxy Ethoxy-3,≠
-dicarboxybenzene/dimethacrylokydimethylbenzene copolymer 21s) 2-vinylbenzylideneamino-6-diethylaminofluoran/3-methacryloxyethoxy-
6-methoxyfluorane/3,3'-diallylbisphenol S/styrenesulfonaminosalicylic acid/human O-oxyethyl methacrylate/acrylic rg/divinylbenzene copolymer j7) J-(≠-dibutylamino!-β-acryloxy ethoxyphenyl)-3-(/
-ethyl-2-methylindol-3-yl)azaphthalide/3-(≠-diethylamino-λ-β-methacryloxyethoxyphenyl)-3-(/-ethyl-λ-methylindol-3-yl)azaphthalide/methacryl Roxymethylphenol/maleic anhydride/vinyl acetate copolymer j,? )3-(≠-diethylminnow!-(≠-vinylbenzoyloxy)phenyl)-3-(/-ethyl-2
-Methylindol-3-yl) azaphthalide/vinylphenol/vinylbenzoic acid lead copolymer 2)--β-(p-vinylbenzoylminoethylamino)ethylamino-6-diethylaminofluorane/
Vinyltoluene/butoxyethyl acrylate/p-vinylbenzenesulfonic acid sodium copolymer, zinc chloride reactant 30) Cohexyl minnow 6-N-methacrylic minnow Methylfluoran/β-hexyloxyethyl methacrylate//-p- Vinylbenzyloxy-3, dicarboxybenzene copolymer zinc salt 3-)Hiro-diethylamino-2-Cβ-acryloxyethoxy)phenyl 3-3-(/-ethyl-2-methylindol-3-yl)azaphthalide/ Vinylmethylimidazole copolymer rhodan zinc reactant 3, di≠-diallylamino-(β-acryloxyethoxy)phenyl-3-(/-octyl-2-phenylindol-3-yl)diazaphthalide/zinc styrene sulfonate Examples include copolymers.

These polymer dyes are conventionally known colorless dyes, such as C
It is also possible to use it in combination with low-molecular colorless dyes exhibiting various tan hues, such as VL%BI and MB, which are disclosed in the above-mentioned patents, to achieve deeper hues and color changes.

Specific examples of these various existing colorless dyes, such as phthalides, are U.S. Reissue Patent No. 23.0λ≠, U.S. Patent No. 3. 9/, /// issue, same 3゜≠ri/, //2 issue, same 3. ≠9/, //6, 3, jOri, /7≠, specific examples of fluorans are U.S. Pat. No. 3,6λ≠, 107, U.S. Pat. ．． θ／／No. 3
1≠62.121, 3.61/, 3ri 0, 3゜ri 20,310, 3. No. 377, specific examples of subirojibirans are given in U.S. Patent No. 3. ri7/.

Pyridine-based and pyrazine-based compounds are disclosed in US Pat. No. 3.77J, tA2tA, US Pat. za33゜end6
No. 9, U.S. Patent≠, x4Lg, No. 3/♂, fluorenization @ patent application No. 1. /-, 24tOPg No. 7, etc.

Some examples of colorless dyes include triarylmethane compounds such as 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (i.e., crystal violet lactone), 3°3-his( p-dimethylaminophenyl) phthalide, 3-(p-dimethylaminophenyl)-3-<! , 3-') methylindole-3-
yl) phthalide, 3-<p-dimethylaminophenyl)
-3-(2-methylindol-3-yl)phthalide,
etc., and diphenylmethane compounds include ≠, j
' -Bis-dimethylaminobenzhydrin benzyl ether, hehalophenyl leukoolami 7, N-2
. -Chloroanilino)lactam, Ni-benzylamino-6-diethylaminofluorane, -One-anilino-6-diethylami/fluorane, -Ichiryo-nilino-3-methyl-6-diethylγminofluorane, Noanilino-3-methyl-6-cyclohexylmethylamine / Fluoran,! -〇-Taroanilino 6-diethylminofluorane 1,2-m-tarolonilino 6-diethylmininofluorane, λ-(3
9 μm dichloro-nilianilino-diethylaminofluorane, λ-octylamino-6-diethylaminofluoran, λ-dihexylamino-6-diethylaminofluoran, λ-m-trifluoromethyl-6-diethylaminofluorane, 2- butylamino-3-chloro-6-diethylaminofluorane, d-ethoxyethylamino-3-chloro-6-diethylaminofluorane,
2-p-Chloroanilino-3-methyl-6-cyptyl aminofluorane, λ-chloroanilino-3-methyl-6-dioctyl-6-dioctylominofluorane, λ-anilino-3-chloro-
6-dinitylaminofluorane, λ-rephenylamino-6-ethylaminofluorane-monoanilino 3-
Methyl-6-diphenylminofluorane, -1phenyl-6-diethylaminofluorane, 2-anilino-3
-Methyl-A-N-ethyl-isoamyl-minofluorane, 3-methyl-j-chloro-6-
Diethylaminofluorane, 2-anilino-3-methyl-6-dinithylamino-7-methylfluoran, 2-anilino-3-methoxy-6-sibutylaminofluorane, λ-〇-chlorodilinos-6-dibutylamino Fluoran, λ-p-chlorodilinos-3-nitoxy-4-N
-ethylheisoamylaminofluorane, -10-
riOroanilino-6-p-butylanilinofluorane,
2-anilino-3-pentadecyl-6-diethylaminofluorane, -anilino-3-ether-6-dibutyl-minofluorane, 2-anilino-3-methyl-j'.

j′-dichlorofluorane,! -〇-Toluidino 3-
Methyl-6-diitubrobylaminohiro'.

j′-dimethylaminofluorane, -ichiryojisuno 3-
Ethyl A-N-ethylheisoamylaminofluorane, 2-anilino-3-methyl-,4-N-ethyl-
N-γ-methoxypropyl-minofluoran, -1-anilino-3-chloro-6-to-12-methyl-isoamyl-minofluoran, etc. Thiazine compounds include benzoyl leucomethylene blue, p-nido-Opensoyl leucomethylene blue, etc. , spiro-based compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3.3'-cyclorosespiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho- Examples include (3-methoxy-benzo)subiobiran and 3-propyl-spiro-dibenzopyran, and it is desirable to use two or more of them in combination.

A color developer can also be used in combination with the polymer dye.

Examples include common known compounds such as phenol derivatives, salicylic acid derivatives, aromatic carboxylic acid gold R14
, acid clay, bentonite, novolac resin, metal-treated novolac resin, μ-tert-butylphenol,
j-phenylphenol, λ,! -Bis(Hiro-hydroxyphenyl)propane (bisphenol A), 44.4
! ' -isopropylidene bis(2-methylphenol), /ll-bis-(3-chloro-μm hydroxyphenyl)cyclohexane, /, l-bis(3-chloro'
-ψ-humanOxyphenyl)-2-ethylbutane, ≠,
≠'-Secondary-isooctylidene diphenol, Hiro-tert-octylphenol, 4t.

≠'-5ec-butylidene diphenol, l-chlorophenylphenol, 4! , μ'-isohentylidene diphenol, e, l -methylcyclohexylidene diphenol, ψ, ψ' -dihydroxydiphenyl sulfide, /, ≠-bis-μ'-hydroxycumylbenzene, /, 3-bis≠'- Hydroxycumylbenzene, ≠
, 4! '-thiobis(6-tert-phthyl-3-methylphenol), ≠, <z'-dihydroxydiphenyl sulfone, human quinone monobenzyl ether, +-
Hydroxybenzophenone, 2. Pi-dihydroxybenzophenone, polyvinylbenzyloxyluponylphenol, λ, ≠, ≠'-trihydroxybenzophenone, 2,2', 11,4A'-tetrahydroxybenzophenone, ≠-dimethyl hydroxyphthalate, ≠−
Methyl hydroxybenzoin.

-1≠, <z'-trihydroxydiphenylsulfone,
i, s-bis-p-human mixiferpentane, /
6-pis p-human mixyphenoxyhexane, tolyl hiro-hydroxybenzoate, μm hydroxybenzoic acid α-phenylbenzyl ester, ≠-phenylpropyl human O-oxybenzoate, ≠- phenethyl human O-oxybenzoate, goo-hydroxybenzoic acid m -p-riO lobenzyl, μm hydroxybenzoic acid H-p-methoxybenzyl, ≠-hydroxybenzoic acid benzyl ester, g-hydroxybenzyl,
Froic acid-m-70 lobenzyl ester, ≠-hydroxybenzoic acid β-7 enethyl ester, gluhydroxy, 2
', l-dimethyl diphenyl sulfone, β-phenethylorseinate, cinnamyl orseinate, orselic acid-0-10 lophenoxyethyl ester, 〇-ethylphenoxyethyl orselinot% O-phenylphenoxy Ethyl orselinate, m-phenylphenoxyethyl orselinate, 2. ≠-dihydroxybenzoic acid-β-3'-1-butyl-j'-hydroxyphenoxyethyl ester, /-1-butyl-≠-p-hydroxyphenylsulfonyloxybenzene, Hiro-N-benzylsulfamoylphenol, ! , ≠-dihydroxybenzoic acid-p-methylbenzyl ester, 2. tA-dihydroxybenzoic acid-β-phenoxyethyl ester, +
21≠-Dihydroxy-ot-methylbenzoic acid benzyl ester, bis-gu-hydroxyphenylacetate methyl, ditolylthiourea, Hiroshi, l-diacetyldiphenylthiourea, 3-7enyl salicylic acid, j-p-α-methylbenzyl- α-Methylbenzylsalicyl tH1j-p-
Methoxyphenoxyethyloxysalicylic acid, j-phenoxyethoxysalicylic acid, j-p-hensyl-α-
Methylbenzylsalicyl rIR%3-xylyl-j-(
α,α-dimethylbenzyl)salicylic acid%3. j-di(α-methylbenzyl)salicylic acid, 2-hydroxy-
Aromatic carboxylic acids such as 7-α-ethylbenzyl-3-naphthoic acid, 3. ,! - acids such as dicyclopentagenylsalicylic acid or zinc groups, p-hydroxybenzoic acid β-phenoxybutyl ester, p-hydroxybenzoic acid δ-phenoxybutyl ester, 2. ≠, A-) hydroxybenzoic acid β-p-methoxyphenoxyethyl ester, p-hydroxybenzoic acid β-phenoxyethoxyethyl ester, p-hydroxybenzoic acid β-p
-Ptoxyphenoxyisobrobyl ester,! .

IA-Sihydrooxybenzoic acid-β-p-methoxyphenoxyethoxyethyl ester, orselic acid phenoxybutyl ether, β-resorcinic acid-p-methoxyphenoxyethyl ether, orselic acid β-p-methoxyphenoxyethoxyethyl ether, orselic acid β-p-methoxyphenoxyethoxyethyl ether −
0-Methoxyphenoxyethyl ether, orceric acid tolyloxyethyl ester, orceric acid-β-p-
Methoxyphenoxypropyl ester, β-resorcinic acid phenoxyethyl ether, β-resorcinic acid δ-p
- Difficult color developers such as phenols such as methoxyphenoxybutyl ester, non-raphenylphenol-formalin, rose butylphenol-acetylene, and these organic color developers such as zinc, magnesium, aluminum, and calcium. , polyvalent gold v4 salts such as titanium, manganese, tin, and nickel, inorganic acids, acid clay, activated clay, attapulgide, bentonite, coidal silicate, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, zinc rhodan, chloride Zinc, iron stearate, cobalt naphthenate, nickel peroxide,
Inorganic color developers such as ammonium nitrate, aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, stearic acid, benzoic acid, para-tertiary butylbenzoic acid, 7
One or more of tarric acid, gallic acid, etc. may be used without reservation.

When applied to these polymer dye recording materials, it is used in the form of a fine dispersion or fine droplets, or in the form of a film.

Furthermore, in this case, various additives well known in the field of recording materials and polymer resins, such as pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, and fluorescent dyes, may be added. , surfactants and other additives are used. For example, aromatic alkyl or substituted alkyl ethers and/or amides having long-chain alkyl groups as disclosed in JP-A No. 31-372r and Mukaiyo-1r702hiro may be used in combination. Examples of such compounds are 7eneterbiphenyl, benzyloxynaphthalene, pendylbiphenyl, di-m-)lyloxyethane, β-phenoxyethoxyanisole, l-phenoxy-2-p-ethylphenoxyethane, bis-β- (p-methoxyphenoxy)
Ethoxymethane, /-2'-methoxyphenoxy-≠"-ethyloxyphenoxyethane, /, cordiphenoxyethane, /, 4<-diphenoxybutane, bis-
β-(p-ethoxyphenoxy)ethyl ether, l-
Phenoxy-p-chlorophenoxyethane, /-λ
′-Methylphenoxyco μ“-Etheroxyphenoxyethane, /-≠′-Methylphenoxy2-≠“-
Fluorophenoxyethane, l-phenoxy-Jp-
Natoxyphenylthioethane, /, J-bis-p-methoxyphenylthioethane, /-tolyloxy-col-
It is preferable to use an ether such as methoxyphenylthioethane or a compound such as stearamide, methylene bisstearamide, stearaniside, behenic acid amide, stearanilide, and stearyl urea.

Pigments include kaolin, calcined kaolin, talc, zinc oxide, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate, mica, micro Balloon, urea-formalin filler, polyethylene hair takele, cellulose filler, etc. particle size 0. Selected from / or / jμ.

Examples of waxes include paraffin wax, carboxy-modified paraffin wax, cowna wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

Examples of metalstones include polyvalent metal salts of higher fatty acids, ie, zinc stearate, aluminum stearate, calcium stearate, zinc oleate, and the like.

Hindered phenols include compounds having at least one bulky group adjacent to the phenolic hydroxyl group, such as polybutylated bisphenol A, 1/, /,!
-) Lys-J-i-butyl-μ-hydroxy-4-methylphenylbutanato.

Examples of ultraviolet absorbers include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives, etc. For example, α-cyano-β-phenylbutyl cinnamate, 0-benzotriazolylphenol, 0-benzotriazolyl-p- Chlorophenol, O-benzotriazolyl-2
,≠-dibutylphenol, 0-benzotriazolyl-
Examples include p-chlorophenol.

(Examples of the Invention) Examples are shown below, but the present invention is not limited only to these examples.

Example / J-(Hiro-diethylamifoucault β-methacryloxyethoxyphenyl)-3-(/-ethyl-,2-methylindol-3-yl)phthalide 0°5no,≠-β-methacryloxyethoxyphthal acid i, oy, divinylbenzene 0. /p, coethylhexyl methacrylate (7
, J was weighed into a flask equipped with a nitrogen gas inlet tube, and acetonitrile /ja/ and dimethylacetamide were added. −
and passed nitrogen gas for 1.2 minutes. Next, azobisdimethylisovaleronitrile/jη was added, and the mixture was kept at 0C to 6J0C for t hours while slowly passing nitrogen gas, and then poured into uooal of methanol to precipitate a high molecular compound. It showed a clear blue color.

When heated to 1200C, official i increased more.

Example λ Monomer J-(4!-diethylaminocovinylbenzyloxyphenyl)-j-(/.

013 parts of λ-dimethylindol-3-yl) phthalide, methacryloxyethoxysalicylic acid/,! parts, 0.2 parts of methacrylic acid, 0.2 parts of methyl methacrylate, 2-
A copolymer was obtained in the same manner as in Example except that 0.3 parts of ethylhexyl acrylate was used.

Example 3, ≠ 3-(Hiro-diethylamino-11 methacryloxyphenyl)-J-(/-ether-λ-methylia)'-
j-(l)phthalide/vinyloxyethyloxybenzoic acid/divinylbenzenesulfonic acid/butoxyethyl acrylate [Example 3, weight ratio 0.2:2. θ:o, 2:/
, o].

J-[44-diethylamino-co(γ-acryloxypropyloxy)phenyl]-J-(/-ethyl-comethylindol-3-yl)≠-azaphthalide/methacryloxyethoxyphthalic acid/butoxyethoxyethyl methacrylate [Practice] gal, weight ratio 0.1. :/, Konio, T] was used, but a polymer dye was obtained in the same manner.

The compound of Example 3 had good solvent resistance. The color of the compound in the experimental gal became more vivid (by kneading it with zinc white).

Claims (1)

[Claims] A method for producing a polymer dye characterized by copolymerizing a color former monomer and a color developer monomer.