JPS6399208A - Production of high polymer color former - Google Patents

Abstract

PURPOSE:To obtain a color former suitable as a color former useful for recording materials such as photosensitive pressure-sensitive recording paper, electrically conductive heat-sensitive recording paper, etc., or display material, having function to color by contact especially with an acidic substance, by copolymerizing a vinyl group-containing color former with another monomer. CONSTITUTION:A vinyl group-containing color former [e.g. 2-p-vinyl-benzoyl- amino-6-diethylaminofluoran, 3-3-bis(p-diethylaminophenyl)-6-N-ethyl-N- vinylbenzylaminophenyl phthalide, etc.] is copolymerized with at least one other monomer (e.g. acrylamide, diethylene glycol diacrylate, etc.) by radical polymerization, solution polymerization, emulsion polymerization, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a polymer compound, and more particularly, to a method for producing a polymer coloring agent that has the function of coloring upon contact with an acidic substance.

The polymer coloring agent according to the present invention can be used for light-sensitive pressure-sensitive paper, pressure-sensitive paper,
It is a compound useful as a color former for use in recording materials such as thermal paper and electrically conductive thermal recording paper, or display materials.

(Prior art) Triphenylmethanephthalide-based compounds, fluoran-based compounds, fetchazidi/based compounds, indolyl-7-thallide-based compounds, leucoauramine-based compounds, and rhodamine lactam-based compounds are used as color formers that color when they come into contact with electron-accepting compounds. , triphenylmethane-based compounds, triazene-based compounds, and other various compounds have been investigated.

For example, U.S. patents JuP/l//, J≠ri//12, J
φrilll≦, 310ri17≠, 362u107.3t
λ77r7, J61A10//, 34/Ltxrxr,
5trisyo, 3yxozto.

J? ! 917/,! 97/rat, 377!4A2 da,
JrJ-Jrt? , 14211-6311, etc.

When these are used for recording materials, various recording systems have been developed, such as pressure-sensitive systems, heat-sensitive systems, electrically conductive heat-sensitive systems, and photosensitive pressure-sensitive systems. However, in these systems, the water solubility of the color former,
Properties such as lipophilicity and hydrophobicity greatly affect the properties of recording materials. In the past, attempts have been made to introduce lipophilic groups or add bis-containing compounds in order to increase lipophilicity, achieve high concentration of solubility in oil, or reduce capri. However, for example, when a lipophilic group is introduced, the molecular weight increases, resulting in a disadvantage that the color density per unit weight decreases. If it is made into a screw body, the manufacturing method will be difficult, and it will be difficult to use the raw materials manually and make N-manufactured materials.

Another problem is that when low-molecular-weight color formers that exhibit different hues are used together, it is difficult for both to develop a uniform color. For example, when color is developed by applying heat, the color tone varies depending on the ease of melting, and when color is developed using dissolution/diffusion, the color tone varies depending on the ease of dissolution.

The present inventor has conducted various studies to overcome the drawbacks of these prior art techniques, and as one solution, he has conceived the idea of completely copolymerizing a plurality of color formers to form a polymer compound, and has devised the present invention. It has arrived.

(Object of the Invention) An object of the present invention is to provide a method for producing a polymeric color former, especially a copolymer. In addition, 3 color formers with vinyl groups are used.
．． ! - Provided is a polymeric coloring agent characterized in that it is copolymerized with one or more other monomers that produce a different color hue when brought into contact with zinc di-α-methylbenzylsalicylate.

(Structure of the invention) Is the purpose of the present invention a vinyl group? This was achieved by developing a complete method for producing a polymer color former characterized by copolymerizing a color former with at least one other monomer.

It has been thought that color formers, such as fluoranated adducts, which have a large conjugated system cannot be used to form polymers due to the stabilization of polymerization initiation radicals by the π-electron system. However, after synthesizing a derivative with a vinyl group and attempting to polymerize it, it was discovered that the polymerization unexpectedly proceeded easily and produced a polymeric liquid fluoran compound in a short time. In this field, where even the formation of color formers with vinyl groups has never been considered, the fact that their polymerization has been confirmed is completely new knowledge.

The color forming agent having a vinyl group of the present invention is produced by reacting a color forming agent having at least one active hydrogen atom such as hydroxy or amine with a compound having an active group such as an acid halide, ester, halide or isocyanate having a vinyl group. It is synthesized by

For example, acrylic acid chloride, methacrylic acid chloride, glycidyl acrylate, chloroethyl vinyl ether, glycidyloxy IJL/-), acrolein,
Examples of compounds with active groups include methylol acrylamide, chloromethylbenzene acrylamide, formylstyrene, vinylbenzoic acid chloride, vinylbenzenesulfonyl chloride, vinylbenzyl chloride, methyl vinylbenzoate, and vinylphenoxyacetyl chloride. Alternatively, another method may be used in which a color former intermediate having a vinyl group is used as a starting material.

The group having a vinyl group such as a vinyl group or a vinylidene group according to the present invention may be directly bonded to the aromatic ring of the color former or a site having all of its active hydrogens, and the substituent may be alkylene, arylene, oxaalkylene, It may be bonded via a group such as thiaalkylene or a combination of two or more thereof.

For example, acryloxy, methacryloxy, vinylbenzyloxy, vinylphenoxyacetoxy, methacryloxyethoxy, acryloxyethoxy, vinylbenzenesulfonyloxy, allyloxy, acrylamide,
Methacrylamino, β-acrylamidoethyl, β-N
-ethyl-N-acrylamidoethyloxy, vinyloxyethoxy, vinylanilinocarbonyloxy, β-
Methacryloxypropoxy, β-acryloxypropoxy, vinylbenzyloxy, β-methacryloylaminoethoxy, β-acryloylaminoethoxy, β-p-
Examples include vinylbenzoyloxyethoxy, γ-vinylphenoxy, β-hydroxypropoxy, β, γ-dimethacrylokydipropoxy, glycidyloxy, β-vinylphenoxyethoxy, and the like.

The number of vinyl groups is preferably 7 to 2. If there are three or more, the obtained polymer compound is not suitable for forming an insoluble and infusible gel.

Preferred examples of the vinyl group-containing color forming agent according to the present invention are as follows.

/)up-vinylbenzoylamino-6-diethylaminofluorane2)-2-p-(≠'-vinylbenzoylamino)anilino-3-methyl-6-cyptylaminofluorane/3)2-p( <”-vinylbenzylamino)anilino-
3-700-j-N-Ethyl-N-ynamylaminofluoran/ Hiroshi) Corvinylbenzylideneamino-t-diethylaminofluoranej) 2-β-(p-vinylbenzoylamino)ethylamino-3-700- J-diethylaminofluorane t) co-β-(p-vinylbenzoylaminoethylamine) ethylamino-bu-diethylaminofluorane 7) 2-p-vinylbenzenesulfonylamino-3-yamyl-6-diethylaminofluorane r) 2- Anilino-3-methyl-A -N-ethyl-N-β-p-vinylbenzoylaminoethylamino-
(p-vinylbenzoylamino)benzoylleucomethylene blue IO) ≠-diethylaminophenyl-411 N
-Ethyl-N-vinylbenzylaminophenyl 7thallide//)J-p-vinylbenzoyloxy-μmdiethylaminophenyl-J/p-vinylbenzoyloxy-≠'-methyl-! '-Anilinophenyl 7-thallide l) Cole-vinylphenylureido 6-diethylaminofluorane/j) 2-p-vinylanilino-3-methyl-6-diethylaminofluorane l≠) J-7 Nilino≠-γ-p -vinylbenzoylaminobutyl-6-diethylaminofluorane/l) 2-β-hydroxy-γ-p-vinylphenoxy-propylamino-4-diethylaminofluorane#)J-(≠-diethylaminocomethacryloxyphenyl)- J-(/-Ethyl-2-methylindol-3-yl)phthalide/7) J-[”≠-diethylaminol-p-vinylbenzyloxyphenyl]-J
-(/-ethyl-cotatylindol-3-yl)phthalide it) 3-(<t-diefk7mi/-2-(
lI-vinylbenzoyloxy)phenyl)-3-(/
-Ether-2-methylindol-3-yl)phthalide/ri)J-(44-diethylaminocor(vinyloxyethyloxy)phenyl)-J-(/-ethyl-comethylindol-3-yl) Phthalide 20) J-(goodiethylamino-(β-acryloxyethoxy)phenyl]-3-(/-ethyl-methylindol-3-yl)phthalide x/) J-(≠-dibutylamino-2 -β-acrylamidoethoxyphenyl)-3-(/-ethyl-2-methylindol-3-yl)phthalylλJ)J-(u-jethylaminocovinylbenzyloxyphenyl)-S
-(/,2-dimethylindol-3-yl)7talidoco3)3-(dargetylamino-2-β,r-dimethacryoxypropoxyphenyl)-3-(/-ethyl-phenylindole-3 -yl)7thalide 2g) 3-(:≠-jethylaminocor(β-acryloxypropyloxy)phenyl]-3-(/-ethyl-λ-methylindol-3-yl)μm azaphthalide Jj)j -(≠-diethylamino-covinylbenzenesulfonyloxy)phenyl)-J-(i-ethyl-comethylindol-3-yl)-μm azaphthalidome) J-(Hiro-diethylamino)-2-(β-hinylphenoxy ) phenyl)-J-(/-ethyl-2-i
So--! Methylindole-3-yl)-Daaza 7
Thallidocore) co-acrylamino-diethylaminofluorane 2-2-acrylamino-6-dibutylaminofluorane 27) 2-acrylamino-j-N-cyclohexyl-
N-Methylaminofluorane 30) No-acrylamino-3-chloro-4-diethylaminofluorane 3/) 2-Acrylamino-3-methyl-6-diethylaminofluorane 3) Co-methacrylamino-3-ethyl-6 -dibutylaminofluoran JJ) up-p-methacrylaminoanilino-6-diethylaminofluoran 341) J-p-acrylaminoanilino-2-dibutylaminofluoran 3-licor β-acrylaminoethylamino-6- Dibutylaminofluorane 3) Co-β-acrylaminopropylamino-J
-40 low-diethylaminofluorane 37), 2-
Anilino-3-β-acrylaminoethyl-6-diethylaminofluorane j, r) 2-p-chloroanilino-
3-β-methacrylaminopropyl-6-dibutylaminofluorane JP) co-anilino 3-methyl-7-N-p-acrylaminoanilino-N-ethylaminofluorane≠Q) 2-dibenzylamino-AN -acrylamino-N-ethylfluorane 4t/)! -hexylamino-4-N-methacrylamino-N-methylfluorane 1) J, J-bis(p-dimethylaminophenyl)-1
-N-ethyl-N-β-methacryloxyethylamino 7
Talide μJ) 3.3-bis(p-diethylamino 7-enyl)-AN-ethyl-N-vinylvinylaminophenyl 7-thallide and the like.

It is convenient to copolymerize two or more of these vinyl group-containing color formers with other vinyl or vinylidene monomers to freely control particle size, solubility, tackiness, dispersion stability, color development, etc. be able to. However, in the case of copolymerization, at least the coloring agent component is a component that colors when it comes into contact with an acidic substance!
It is preferable to blend it so that it is contained in an amount of 10% or more.

Examples of such copolymerization partners include acrylamide, cellosolve acrylate, styrene, methyl methacrylate, acrylonitrile, vinylcarbazole, octyl acrylate, sodium acrylamide propane sulfonate, butyl methacrylate, ethyl acrylate,
These include divinylbenzene, vinyl dioxolane, epichlorohydrin, allyl methacrylate, cinnamoyloxyethyl methacrylate, vinylbenzophenone, ethylene glycol diacrylate, diethylene glycol diacrylate, and the like.

Polymerization reaction methods include radical polymerization, ionic polymerization,
Various methods can be selected, including solution polymerization, emulsion polymerization, suspension polymerization, and solvent-free polymerization.

More specifically, radical polymerization can be initiated by a radical initiator. persulfate-ringing agent,
Oil-based or water-based azo compounds, oxides, metal catalysts, etc. can be used.The polymerization reaction is preferably carried out under an inert gas atmosphere, and when heating, the temperature should be kept at 0C or less. It is preferable that the temperature is less than or equal to 0'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, the colorless dyes mentioned above may be co-present to improve the 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 regarding reaction temperature control, methods for handling metal catalysts, post-treatment methods after the completion of the polymerization reaction, and methods for purifying the obtained super-polymeric compound. For example, for general operating instructions, see 5o
Rensen's Polymer Synthesis Experimental Method'Tokyo Kagaku Doujin, is familiar with lt6.

These color formers include conventionally known color formers such as CVL, B
It is also possible to aim at deepening the hue, changing color, etc. by using it in combination with a low-molecular coloring agent showing various hues disclosed in the above-mentioned patents, such as LMB.

(Examples of the invention) Example/J-(4C-diethylamifoucault β-methacryloxyethoxyphenyl)-J-(i-ethyl-!-methylindol-3-yl)phthalide O1j? , 2-acrylamino-3-diethylaminofluorane 0.22 and butyl methacrylate O8! f was used as a monomer. These are 20ml of tetrahydro 7 run, methyl ethyl ketone! d into a flask equipped with a nitrogen gas inlet tube, and nitrogen gas was passed through the flask for 21 minutes using a scale. Next, azobisdimethylisovaleronitrile/JFr9f was added, and while slowly passing nitrogen gas, 4
After holding it for a while, pouring it into methanol of ≠00rrl causes the polymer compound to precipitate. Yield/f0 Practical Example The same operation as Section 1 was performed. However, as a monomer, butyl methacrylate 0.3? , styrene o, iy,
5-p-vinylbenzoylamino-3-methyl-t-diethylaminofluorane 0°3f and J-(a-dietheraminol-β-methacryloxyethoxyphenyl)-3-(/-octyl-λ-methylindole 3-
il) phthalide 0.31. The reaction time was changed to t hours, and the post-treatment was carried out in the same manner as in Example 1, and a polymer compound was obtained as a precipitate by pouring into methanol at ≠oomt.

Yield o, ry0 Also, these copolymers have 3. ! -Zinc-α-methylbenzylsalicylate When it came into contact with Zinc Zirton Clay, it developed a clear color, and the color image had good storage stability.

Claims (1)

[Claims] A method for producing a polymeric color former, which comprises copolymerizing a color former having a vinyl group with at least one other monomer.