JPH09157508A - Water-base polyester resin dispersion and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a eater-base polyester resin dispersion which gives an ink which gives a high-quality record and forms a dried film excellent in water resistance by using, as the disperse phase, a resin comprising a specific polyester resin and a resin formed from am ethylenically unsatd. monomer, pref. the disperse phase having been colored with a colorant. SOLUTION: This resin dispersion a water-base medium and fine polyester resin particles from dispersed therein and comprising 5-99wt.% polyester resin formed from a polycarboxylic acid component contg. 1-100mol% cyclohexenedicarboxylic acid and a polyhydric alcohol component and 95-1wt.% resin obtd. by polymerizing an ethnically unsatd. monomer. Pref. the resin particles have been colored with a dye or pigment, pref. with a hydrophobic and/or org.-solvent-sol. dye. A recording material mainly comprising the dispersion enable high-quality image record and setting and has both a high reliability and an excellent storage stability.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous dispersion of a resin which is widely used in paints, water-based paints, paper coating agents, coating materials for films and various recording materials. The present invention relates to a water dispersion of a polyester resin and a water dispersion of a colored polyester resin, which can be suitably used as an ink recording material used in various printing machines, non-impact printers, etc., from writing instruments, markers, marking pens, etc. It is a thing.

[0002]

2. Description of the Related Art Recently, countermeasures for environmental problems are required in all fields, and recording materials and inking materials used in printing machines, non-impact printers, markers, writing instruments, etc. are also required to be solvent-free and water-based. Is coming. Aqueous recording materials mainly composed of aqueous solutions of water-soluble dyes,
Those mainly composed of a fine dispersion of pigment are widely used. Recording materials using water-soluble dyes are mainly acidic dyes, direct dyes, aqueous solutions of water-soluble dyes classified into some food dyes, etc., and glycols, alkanolamines, surface tension, etc. as moisturizers are prepared. For this purpose, those added with a surfactant, alcohol, a resin component as a binder component and the like are used. Recording materials using these water-soluble dyes are most commonly used because of their high reliability against clogging in the writing tip or in the recording system.
However, since the recording material using such a water-soluble dye is an aqueous solution of the dye, it easily bleeds on the recording paper. Further, since it is prepared so as to quickly penetrate into the recording paper in order to increase the apparent drying speed, it is unavoidable that the recording quality is deteriorated due to the blurring of the ink. It is also obvious that the water resistance is poor because it is a water-soluble dye. Furthermore, it is difficult to say that a water-soluble dye that has simply penetrated into recording paper and that has been dry-fixed is "dyed", and the light fastness is very low.

As a measure for solving the problems of the recording material using the water-soluble dye as described above, addition of resin fine particles such as emulsion and latex has been studied for a long time. Japanese Patent Application Laid-Open No. 55-18418 describes that "components such as rubber and resin are finely divided by an emulsifier (particle size of about 0.01 to
There is a proposal regarding a recording material for inkjet recording to which a latex which is a kind of colloidal solution dispersed in water in the form of several μm) is added. The latex preferably used is styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, polychloroprene latex, vinylpyridine-styrene-butadiene latex, butyl rubber latex, polybutadiene latex, polyisoprene latex, polysulfide rubber latex, etc. And synthetic resin latexes such as acrylic ester latex, styrene-butadiene resin latex, vinyl acetate latex, vinyl chloride latex, vinylidene chloride latex, and the like.

In the proposal, the particle diameter of the latex particles that can be added is said to be in the range of about 0.01 to several μm. However, if the particle size is less than 0.2 μm, the effect of preventing ink smearing on the recording paper is insufficient, and high recording quality cannot be obtained. The particle size is 1.0
If it is more than μm, the nozzle is frequently clogged and it becomes difficult to use it from the viewpoint of reliability. Therefore, it is considered that the practically usable range is approximately 0.2 to 1.0 μm. When such resin fine particles are added to the ink, attention must be paid to sedimentation or floating due to the difference in specific gravity between the particles and the medium. In the case of water-based ink, it is difficult for the specific gravity of the medium to deviate significantly from 1.0. In fine particles of about 0.2 μm or larger, the effect of gravity is larger than the diffusing force of particles due to Brownian motion, and therefore the difference between the particle specific gravity and the medium specific gravity is 0.1 in such a region.
Hereafter, it is necessary to suppress it to preferably about 0.07 or less. The specific gravity of the synthetic rubber-based latex exemplified in the patent proposal is in the range of about 0.9 to 1.0, and although such a condition is satisfied to some extent, most synthetic rubbers have an unsaturated double bond in the molecule. There is a problem in light resistance and weather resistance. Further, when vulcanization is carried out to reduce unsaturated bonds, the fixing of particles onto recording paper is hindered, resulting in a problem in recording quality.

Further vulcanization results in a specific gravity of 1.1.
As a result, the problem of sedimentation occurs. Further, since such a synthetic rubber latex has a low glass transition temperature, it is easy to form a film at room temperature, the nozzle is likely to be clogged when dried at the nozzle tip, and the dried product is soft and somewhat sticky. Therefore, its removal is very difficult. The synthetic resin latex exemplified in the patent has a specific gravity of 1.
In the case of a synthetic resin containing one or more halogen atoms, particularly in the case of a synthetic resin containing a halogen element, the specific gravity is close to 1.3 to 1.5, so that sedimentation occurs in the particle size range where the anti-bleeding effect is exhibited. Furthermore, as can be said for all of these latexes, many of the emulsifiers used in the production of the latex are apt to promote foaming of the ink and lower the surface tension more than necessary, which is problematic. JP-A-54-146
No. 109 proposes a recording material using a water-soluble dye to which vinyl polymer fine particles swelled with a solvent and colored with an oily dye are added. Polymers preferably used are mainly (meth) acrylic acid ester-based copolymer fine particles, and have a glass transition temperature of 30 or less.
It is stated that it is preferable that the temperature is not higher than ° C.
There is no description about the particle size in the proposal. It is obvious that the fine particles swollen with a solvent at such a low glass transition temperature have film-forming properties when dried at room temperature,
It is easily inferred that nozzle clogging will frequently occur when such an ink is used.

(Recording Material Using Pigment Dispersion) In order to improve the drawbacks of a recording material using a water-soluble dye, it has been proposed to use carbon black or an organic pigment as a recording material. In the recording material using such a pigment dispersion, the water resistance of the ink is greatly improved. However, these pigments have a high specific gravity of 1.5 to 2.0, and attention must be paid to the sedimentation of dispersed particles. In order to stably disperse the pigment having such a high specific gravity, the average particle diameter is about 0.
It is necessary to finely disperse the ink to 1 μm or less, resulting in a high dispersion cost and a very expensive ink. Further 0.1μ
If the particle size is less than m, the effect of preventing blurring is insufficient and high quality recorded characters and images cannot be obtained. Further, there is a problem that the physical properties of the ink such as surface tension and foaming property are limited by the dispersant used for dispersion.

(Recording Material Using Colored Resin Particles) An ink jet recording ink has been proposed in which a water-dispersible resin is colored with an oil-soluble dye or a hydrophobic dye.
These are proposals relating to "ink using colored polymer particles as a recording agent". For example, JP-A-54-
58504 proposes an ink in which a mixture of a hydrophobic dye solution and vinyl polymer fine particles is oil-in-water dispersed. It is disclosed in the text that the vinyl polymer fine particles are swelled in the solvent of the dye solution by being mixed with the hydrophobic dye solution and further colored by the dye. Since the hydrophobic dye is used as the recording agent, the obtained image is said to have water resistance. According to the proposal, water is used as a continuous phase, and colored vinyl polymer particles swollen with a solvent are used as a dispersed phase so that water has control of ink viscosity and has a somewhat high viscosity (low volatility) as a solvent. It is allowed to use things. JP-A-55-13947
1, JP-A-3-250069 proposes an ink using emulsion-polymerized or dispersion-polymerized particles dyed with a dye. The purpose of the proposal is to prevent bleeding by using colored particles as a dispersoid and water (transparent) as a medium, as in Japanese Patent Laid-Open No. 54-58504. It is necessary to fix it on the recording paper by forming a film. It has been suggested that the desirable particle size is in the submicron region from the viewpoint of the necessity of film formation and ensuring of dispersion stability.

In both proposals, the water-dispersible resin is a vinyl polymer. In these vinyl polymers, it is difficult to perform high-concentration coloring because the dye has a low solubility in the resin. In Japanese Patent Laid-Open No. 54-58504, it is accepted that the polymer fine particles are swollen with a solvent to improve the dyeing property. In this case, however, there is a problem of nozzle clogging due to dry film formation at the nozzle tip. Occurs. JP-A-4-
In 185672, in the ink composed of colored resin particles and an aqueous medium, a water-soluble compound is dissolved in the aqueous medium so that the specific gravity difference between the colored resin particles and the aqueous medium becomes 0.0
It is proposed that the particle size be 4 or less to prevent the sedimentation of particles. Here, it is said that inorganic salts are preferably used as the water-soluble compound. However, when such an inorganic salt is dissolved in an aqueous medium, the ionic strength in the system increases and the stability of the dispersion system decreases, so that the colored resin particles agglomerate and the fluid properties of the inkjet ink cannot be maintained.

Japanese Unexamined Patent Publication No. 4-185673, Japanese Unexamined Patent Publication No. 4-18
In 5674, the effective specific gravity is lowered by swelling the colored resin particles with a solvent in the ink composed of the colored resin particles and the aqueous medium, and the specific gravity difference between the colored resin particles and the aqueous medium is 0.04 or less. Is proposed. In such a case, it is difficult to avoid nozzle clogging as described above. JP-A-63-132083 has a solid content of 30% by weight by containing a substance which is solid at room temperature.
There is a proposal regarding an inkjet recording ink adjusted so that the viscosity at that time is 3 times or more the viscosity at a solid content of 10% by weight. In this proposal, by using a solvent having a low vapor pressure, the ink is quickly dried on the recording paper, the solid content concentration rapidly increases, and the viscosity increases accordingly,
It is said that bleeding can be suppressed. Here, the "solid substance at room temperature" is clearly defined in the text as "a substance that can be dissolved and contained in the ink", and a dispersoid (a substance unnecessary for a medium), which is the subject of the present invention, Is a completely different thing. A large number of water-soluble polymers are exemplified as specific examples in the present text. In the case of an ink containing a water-soluble polymer component like this ink, there is a concern that the adjustment range of the physical properties of the ink is narrowed and that the nozzle is frequently clogged due to drying.

As described above, recording materials mainly used for ink jet recording have been mainly reviewed. However, the sedimentation of particles and the clogging caused by dry film formation are caused by writing instruments, markers, marking pens, other types of printers, printing machines. Also occurs when such an aqueous recording material is used. The present inventors have conducted intensive studies in view of such circumstances, and as a result, found that an aqueous dispersion of a polyester resin can be colored with an oily or hydrophobic dye at an extremely high concentration, and proposed JP-A-6-340835. The proposal is that when an aqueous dispersion of colored polyester resin fine particles is used as an ink for writing instruments or a recording material for various printers, the recording quality on recording paper is good, and the water resistance of the dried film-forming product is excellent. It was made as a result of finding that the characteristics such as

However, in the subsequent research, when such an aqueous dispersion of colored polyester resin particles is used, good recording cannot be performed due to clogging of the writing point in the region above the glass transition temperature of the resin. Etc., the trouble was discovered. In such a case, as a conventional means, an unsaturated polyester resin in which an unsaturated monomer such as fumaric acid or maleic acid is introduced is used, and a so-called vinyl-based monomer having an ethylenically unsaturated bond is used for crosslinking. The method is taken. By using such means, the clogging property is certainly improved, but the polyester resin using the aliphatic unsaturated monomer is liable to cause hydrolysis, and the dispersion using the aqueous medium, which is the main object of the present invention, In the case of (1), hydrolysis of the resin causes problems such as a decrease in film forming temperature, an increase in viscosity, a decrease in the fastness of the film formed product, and a deterioration in storage stability of the dispersion.

[0012]

As described above, the fine particle dispersion type recording material using pigments, colored resin particles and the like overcomes the problems of the water-soluble dye type recording material and has a high recording quality. Although it has the potential to be realized, it often leaves problems in terms of reliability such as particle settling and clogging caused by dry film formation, and replaces all water-soluble dye type recording agents. Has not reached.

[0013]

SUMMARY OF THE INVENTION In view of the above situation, the inventors of the present invention have conducted intensive research and, as a result, have arrived at the next invention. That is, the present invention provides a polyester resin 5 to 99 obtained from a polyhydric carboxylic acid containing 1 to 100 mol% of cyclohexenedicarboxylic acid as a dispersoid and a polyhydric alcohol.
%, A polyester resin aqueous dispersion, characterized in that fine particles comprising 95 to 1% by weight of a resin obtained by polymerization of a monomer having an ethylenically unsaturated bond are finely dispersed in an aqueous medium, A polyester resin aqueous dispersion characterized in that the polyester resin contains 20 to 2000 eq./ton of ionic groups, wherein the polyester resin fine particles are colored with a dye and / or a pigment. Which is a polyester resin water dispersion, wherein the coloring material for coloring the polyester resin is a hydrophobic and / or organic solvent-soluble dye, wherein the cyclohexene is in a water-based medium. Obtained from polyhydric carboxylic acids containing 1 to 100 mol% of dicarboxylic acid and polyhydric alcohol, having an ionic group of 20 to 2
A method for producing a polyester resin water dispersion, which comprises polymerizing a monomer having an ethylenically unsaturated bond with a water-soluble initiator in the presence of polyester resin fine particles containing 000 eq./ton. is there.

The main dispersoid of the water dispersion of the present invention comprises a polyester resin. The polyester resin is composed of a polyester resin and a so-called vinyl polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond. The polyester resin in the present invention is obtained by condensation of polyvalent carboxylic acids and polyvalent alcohols. Examples of the polycarboxylic acid used in the polyester resin include dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and diphenic acid. Aromatic dicarboxylic acids such as group dicarboxylic acids, p-oxybenzoic acid, p- (hydroxyethoxy) benzoic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and aromatic unsaturated polycarboxylic acids such as phenylenediacrylic acid, Aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, unsaturated polycarboxylic acids such as citraconic acid, and cyclohexanedicarboxylic acid , Cyclohexenedicarboxylic acid, dimer acid, etc. The dicarboxylic acids and the like, also can be exemplified other trimellitic acid as a polycarboxylic acid, trimesic acid, and the like trivalent or higher polyvalent carboxylic acids such as pyromellitic acid.

Examples of the polyvalent alcohols used in the polyester resin include aliphatic polyvalent alcohols, alicyclic polyvalent alcohols, aromatic polyvalent alcohols and the like.
Examples of the aliphatic polyhydric alcohols include ethylene glycol
, Propylene glycol, 1,3-propanedioe
2,3-butanediol, 1,4-butanediol
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylol heptane, diethylene glycol, dipropylene glycol,
2,2,4-trimethyl-1,3-pentanediol,
Polyethylene glycol, polypropylene glycol,
Aliphatic diols such as polytetramethylene glycol,
Examples thereof include trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, and other triols and tetraols. As the alicyclic polyvalent alcohols, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, spiroglycol, hydrogenated bisphenol A and ethylene oxide of hydrogenated bisphenol A Adducts and propylene oxide adducts,
Examples thereof include tricyclodecanediol and tricyclodecane dimethanol.

As the aromatic polyhydric alcohols, paraxylene glycol, metaxylene glycol, orthoxylene glycol, 1,4-phenylene glycol, 1,
Examples thereof include an ethylene oxide adduct of 4-phenylene glycol, bisphenol A, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct. Further, as a polyester polyol, ε
Examples thereof include lactone-based polyester polyols obtained by ring-opening polymerization of lactones such as caprolactone.

In the present invention, among these, cyclohexene dicarboxylic acid is used as a polycarboxylic acid component in an amount of 1-10.
It is essential to use polyhydric carboxylic acids containing 0 mol%. As the cyclohexene dicarboxylic acid, cis-2-cyclohexene-1,2-dicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic acid (cis-Δ4-tetrahydroxyorthophthalic acid) are preferable. The content of cyclohexenedicarboxylic acid is 5 to 70 mol% based on the total acid components.
Is preferred and 10 to 50 mol% is more preferred, and 20 to 3
A compounding amount of 0 mol% is more preferable. In the present invention, it is preferable to use an acid component composed of 10 to 50 mol% of cyclohexenedicarboxylic acid and 50 to 90 mol% of cyclohexanedicarboxylic acid or dimer acid. Such a polyester resin has an ionic group of 20 to 2000 eq./ton (equivalent / 1
It is preferably contained in the range of 0 ⁶ g). The ionic groups that may be introduced into the polyester resin include alkali metal sulfonates or ammonium sulfonates, alkali metal carboxylates or ammonium carboxylates, sulfuric acid groups, phosphoric acid groups, phosphonic acid groups, phosphinic acid groups. Alternatively, anionic groups such as ammonium salts and alkali metal salts thereof, or cationic groups such as primary to tertiary amine groups can be used.
The ionic group can be introduced by using an ionic group-containing monomer.

In order to introduce a cationic group, 2-aminopropane 1,3 diol, nitrile monoalkanol, nitrile dialkanol and nitrile trialkanol can be preferably used. In order to introduce a sulfonate alkali metal base or ammonium sulfonate base into polyester, sulfoterephthalic acid, 5
-Alkali metals of mono- or polyvalent carboxylic acids having a sulfonic acid group, such as sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid and metasulfobenzoic acid. A salt, an ammonium salt or the like may be copolymerized with the polyester. Alkali metal ions such as Li, Na and K, alkaline earth metal ions, ammonium ions, 1
Examples thereof include salts with primary to quaternary alkylammonium ions and alkanolamines.

The ionic group contained in the polyester resin used in the present invention is preferably an organic amine salt of a carboxylic acid group. Such an ionic group can be obtained by introducing a carboxyl group into the polyester resin and then neutralizing it with a base. As the base, alkali metals, ammonia, and other organic amines can be used, and in the present invention, it is particularly preferable to use organic amines. As a method of introducing a carboxyl group into the polyester resin, in the vacuum polymerization method, a method of introducing a polyvalent carboxylic acid anhydride such as trimellitic anhydride, phthalic anhydride, pyromellitic anhydride into the system at the final stage of polymerization of the polyester Can be illustrated. Further, in the vacuum polymerization method, the carboxyl group remaining at the end of the polyester can be used as it is.

As the organic amine, alkylamine, alkanolamine, alkylalkanolamine, aromatic amine, cyclic amine, alkylenediamine and the like can be used, and alkanolamine is particularly preferable. As the alkanolamine, monoalkanolamine,
Examples thereof include dialkylmonoalkanolamine, dialkanolamine, monoalkyldialkanolamine, and trialkanolamine, preferably trialkanolamine, and more preferably 2,2 ′,
2 ″ -nitrile triethanol, tripropanolamine, triisopropanolamine, tributanolamine, trihexanolamine can be used. The content of these ionic groups relative to the polyester resin,
20 to 2000 eq./ton (equivalent / 10 ⁶ g) is required, and preferably 20 to 1000 eq./ton (equivalent / 10).
⁶ g), more preferably 50-500 eq./ton (equivalent /
10 ⁶ g), even more preferably 50-200 eq./to
n (equivalent / 10 ⁶ g). The ionic group has a function of imparting dispersion stability to the polyester resin fine particles that impart water dispersibility to the polyester resin, and when the content of the ionic group is less than the predetermined amount, sufficient water dispersibility is obtained. In some cases, the polyester resin may become water-soluble and the desired water dispersion may not be obtained if the content of the ionic group is too large.

The polyester resin can be obtained by a conventional method such as a vacuum polymerization method or a reduced pressure polymerization method. The former is a method used for polymerizing polyethylene terephthalate or the like, which is used for fibers, films, plastic bottles and the like, and a polyester having a relatively high molecular weight can be obtained. The latter is a method used when polymerizing an unsaturated polyester resin such as an alkyd resin, and a polyester having a relatively low molecular weight is obtained. In addition to these conventional methods, the polyester resin can be obtained by an acid chloride method or the like. The number average molecular weight of the polyester resin in the present invention is preferably 1,000 to 20,000, more preferably 1,500 to 10,000, and further preferably 2,000 to 5,000. If the molecular weight is low, the resulting coating film may have insufficient physical properties. If the molecular weight is too high, dry film formation may be hindered. The glass transition temperature of the polyester resin in the present invention is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, even more preferably 50 ° C. or higher, and further more preferably 60 to.
80 ° C. range. If the glass transition temperature is too low, the dried coating film becomes tacky, which may be inconvenient for some applications. If the glass transition temperature is too high, dry film formation may be hindered. The above is the polyester resin in the present invention.

The dispersoid in the aqueous dispersion of the present invention comprises 5 to 99% by weight of the polyester resin having the above-mentioned specific composition and 1 to 95% by weight of the resin obtained by the polymerization of the monomer having an ethylenically unsaturated bond. Consists of. Further, in the present invention, the dispersoid particles, the unsaturated bond contained in the cyclohexene dicarboxylic acid contained in the polyester resin of the specific composition described above, a cross-linked structure by polymerization of a monomer having an ethylenically unsaturated bond. It is preferable to have Here, as the monomer having an ethylenically unsaturated bond, so-called vinyl-based monomer, for example, alkyl (meth) acrylate having an alkyl group having 1 to 10 carbon atoms, methoxyethyl (meth) acrylate, (meth) ) (Meth) acrylic acid esters such as hydroxyethyl acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, methyl vinyl ketone, phenyl vinyl ketone, methyl isopropenyl ketone Such as unsaturated ketones, vinyl formate, vinyl acetate, vinyl propionate, vinyl butanoate, and other vinyl esters, methyl vinyl ether, ethyl vinyl ether, etc.
Ter, vinyl ethers such as propyl vinyl ether, vinyl halides and vinylidene halides,
Acrylamide and its alkyl-substituted form are mentioned.

Further, styrene, alkyl substitution products of styrene, halogen substitution products of styrene, allyl alcohol and its esters or ethers, vinyl aldehydes such as acrolein and methacrolein, acrylonitrile, methacrylonitrile and vinylidene cyanide. And vinyl monomers, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid and itaconic acid, and salts thereof, unsaturated hydrocarbon sulfones such as vinyl sulfonic acid, acrylic sulfonic acid and parastyrene sulfonic acid. Acids and salts thereof, phosphoric acid esters having a double bond, and salts thereof, pyridine, vinylpyrrolidone, vinylimidazole, vinylcarbazol, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) Kurire - door, and the like. In addition to these, siloxanes, lactones, lactams,
A ring-opening polymerization type monomer such as an epoxy compound may be used in combination.

In the present invention, the dispersoid fine particles made of a resin are preferably colored with a dye. As the coloring matter, either a pigment or a dye may be used. More specifically, as a pigment, C.I. I. Pigment Yellow 3, 1
3, 14, 15, 16, 17, 185, C.I. I. Pig
ment Red 47, 48, 58, 81, 95, 1
22, 184, 185, C.I. I. PigmentBio
let 23, C.I. I. Pigment Blue 1
5, 16 and carbon blacks can be preferably used. Further, the dye is not particularly limited as long as it can dye the crosslinked polyester resin firmly. When the polyester resin contains an anionic group, it is a cationic dye such as a basic dye, and when it contains a cationic group, it is an anionic dye such as an acid dye, a direct dye or a reactive dye. Can be dyed. Further, disperse dyes, oil dyes, some vat dyes, reactive disperse dyes and the like used for dyeing polyester fibers can be used.

Examples of the acid dye in the present invention include C.I. I. Known acid dyes classified as Acid Color can be used. In addition, some C.I. I. A dye classified as Direct Color can also be used as an acid dye. These are azo, anthraquinone, quinophthalone, triallylmethane, xanthene, phthalocyanine, and other dye skeletons to which about 1 to 4 anionic groups (mostly sodium sulfonate groups) are introduced. For process color use, C.I. I. Acid Yell
Of ow, Hue is Green Yellow,
Alternatively, a dye classified as Bright Greenish Yellow may be C.I. as magenta. I. Acid
Of Red, Hue is Bluish Red or B
dyes classified as light Blue Red,
And / or C.I. I. H in Acid Violet
ue is Reddish Violet, or Brig
A dye classified as ht Reddish Violet is C.I. I. H in Acid Blue
ue is Greenish Blue, or Bright
t Greenish Blue, and / or C.I.
I. Hue is Bluish in Acid Green
Green or Bright Bluish G
Dyes classified as reen are preferably used alone or appropriately mixed.

The basic dyes in the present invention include acridine type, methine type, polymethine type, azo type, azomethine type, xanthene type, thioxanthene type, oxazine type,
Known basic dyes such as thioxazine type, triallylmethane type, cyanine type, anthraquinone type and phthalocyanine type can be used. Especially for the three primary colors of process color, C.I. I. Basic Yel
low 11, 12, 13, 21, 23, 24, 33,
40, 51, 54, 63, 71 and 87 are C.I. I. Basic Red 13, 14, 45, 1
9, 26, 27, 34, 35, 36, 38, 39, 4
2, 43, 45, 46, 50, 51, 52, 53, 5
6, 59, 63, 65, 66, 71, C.I. I. Basi
c Violet 7, 11, 14, 15, 16, 1
8, 19, 20, 28, 29, 30, 33, 34, 3
5, 36, 38, 39, 41, 44 are C.I. I. Basic Blue 3, 22, 33, 4
1, 45, 54, 63, 65, 66, 67, 75, 7
7,85,87,88,109,116 are preferably used. Such an ionic dye can be used in the range of 1 to 98 mol%, preferably 20 to 90 mol% based on the ionic group equivalent contained in the polyester resin.

In the present invention, it is preferably colored with "a dye which is insoluble or slightly soluble in water and soluble in an organic solvent". The "dye that is insoluble in water or sparingly soluble in water and soluble in an organic solvent" in the present invention is an oil-soluble dye,
Disperse dyes and some bath dyes can be exemplified. These are "Solve" in the color index.
nt Dye "," Disperse Dye "," V
at Dye ”. Chemically, anthraquinone dye, azo dye, disazo dye, triazo dye, phthalocyanine dye, indigo dye, methine dye, nitro dye, quinophthalone dye, quinoline dye, cyanomethine dye, A triphenylmethane dye, a xanthene dye, etc. can be used. More specifically, as an oil-soluble dye, C.I. I. Solvent Yellow 96 C.I. I. Solvent Yellow 162 C.I. I. Solvent Red 49 C.I. I. Solvent Blue 25 C.I. I. Solvent Blue 35 C.I. I. Solvent Blue 38 C.I. I. Solvent Blue 64 C.I. I. Solvent Blue 70 C.I. I. Solvent Black 3 etc. can be illustrated.

As a disperse dye, C.I. I. Disperse Yellow 33 C.I. I. Disperse Yellow 42 C.I. I. Disperse Yellow 54 C.I. I. Disperse Yellow 64 C.I. I. Disperse Yellow 198 C.I. I. Disperse Red 60 C.I. I. Disperse Red 92 C.I. I. Disperse Violet 26 C.I. I. Disperse Violet 35 C.I. I. Disperse Violet 38 C.I. I. Disperse Blue 56 C.I. I. Disperse Blue 60 C.I. I. At least one dye selected from Disperse Blue 87 is preferably used.

These are particularly excellent in light fastness, hue and saturation, and are preferable as the three primary colors for process color. In addition, known dyes and pigments may be used in combination for fine adjustment of hue. Further, dyes used in sublimation type thermal transfer recording, which have been developed recently, can be used for such purpose. Such a dye is blended in the range of 0.2 to 30% by weight, more preferably 2 to 25% by weight, still more preferably 5 to 20%, based on the polyester resin.
%, Still more preferably 10 to 20% by weight. If the blending amount is too small, a sufficient coloring density cannot be obtained. On the contrary, if the blending amount is too large, the stability of the water dispersion is impaired.

The present invention is an aqueous fine dispersion in which the resin component is finely dispersed in an aqueous medium in the form of fine particles. The method for producing the polyester resin fine particles in the present invention is not particularly limited,
It can be obtained using a known mechanical or surface chemistry dispersion method. That is, a method in which a polyester resin solution is mechanically emulsified in the presence of an emulsification aid such as a surfactant with a high-speed stirrer such as a homogenizer and the solvent is removed can be used. Alternatively, a method of directly pulverizing and finely dispersing the resin by using a jet mill, a freezer mill, a ball mill, an attritor, a sand mill or the like can be used. In the present invention, when the polyester resin is an ionic group-containing polyester resin, the polyester resin has a self-emulsifying property, so that the fine particles can be produced by the phase inversion self-emulsification method. By using these fine particles as seeds and performing a seed polymerization operation, polyester resin particles composed of a polyester resin and a vinyl polymer obtained by polymerization of a monomer having an ethylenically unsaturated bond can be obtained.

Hereinafter, a method for producing the polyester fine particles to be the seed particles by the above operation will be described. The fine particle dispersion of the polyester resin is prepared by mixing the ionic group-containing polyester resin and the water-soluble organic compound in advance and then adding water, or the ionic group-containing polyester resin, the water-soluble organic compound and water are mixed and heated all at once. It can be obtained by a method or the like. At that time, a surfactant or the like can be used together. Ethanol as the water-soluble organic compound,
Isopropanol, butanol, ethylene glycol,
Propylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, tertiary butyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane and the like can be used. The water-soluble organic compound is preferably one that can be removed by azeotropic distillation after the ionic group-containing polyester resin is dispersed in water.

As a preferable method for obtaining an aqueous dispersion of fine colored polyester resin fine particles in the present invention, a polyester resin having a predetermined amount of a carboxyl group is first polymerized, and the polyester resin, dye, water-soluble organic compound and base are sufficiently added. A method of mixing and dissolving in water, adding water thereafter to disperse the water, and removing the water-soluble organic compound by azeotropic distillation or the like as required can be exemplified. Further, a colored aqueous dispersion can be obtained in the same manner by adding a dye into the system and treating at a high temperature after obtaining an aqueous dispersion of a polyester resin. The water dispersion means a state generally called an emulsion or colloidal dispersion. The ionic group dissociates in the aqueous medium and forms an electric double layer at the interface between the polyester resin and water. When the polyester resin is present as fine microparticles in the aqueous system, an electrostatic repulsive force is generated between the microparticles due to the action of the electric double layer, and the microparticles are stably dispersed in the aqueous medium. The particle size of the polyester resin fine particles can be controlled by the ionic group content, the ratio of the polyester resin and the water-soluble organic compound at the time of emulsification, and other emulsification conditions such as the rotation speed and the temperature.

In the present invention, the polyester particles thus obtained are used as seed particles, and the polyester particles are dispersed in an aqueous medium and the above-mentioned monomer having an ethylenically unsaturated double bond, so-called vinyl. Fine particles of a polyester resin (polyester composite resin) are obtained by swelling the polyester resin with a monomer of 5 to 99 wt% and vinyl monomer of 1 to 95 wt% and further polymerizing. If the vinyl monomer and the unsaturated bond of cyclohexenedicarboxylic acid have a high copolymerizability and the compounding amounts of both are appropriate, both of them become particles of a graft body or a crosslinked resin. The reaction initiator is not particularly limited and a known initiator may be used.
For example, an organic peroxide-based initiator such as benzoylperoxide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2-azobis (2-methyl-butyronitrile), 2,2′-azobisisobutyl Nitrile,
Azo initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), ammonium persulfate, potassium persulfate, etc. The water-soluble initiator and the like can be used.

When an oily organic peroxide type initiator is used, firmly crosslinked resin fine particles can be obtained.
When a water-soluble initiator is used, the vicinity of the surface of the particles is crosslinked at a high density, and the core of the particles has a relatively low crosslink density.
Resin fine particles having a shell structure can be obtained. When a water-soluble initiator is used, emulsion polymerization partially occurs because the semi-soluble micelles produced by the polyester resin oligomers present in the dispersion medium also serve as polymerization sites, resulting in semi-soluble micelles. Grow into emulsion-polymerized fine particles, and the semi-dissolved components in the aqueous dispersion are removed. Further, in the case of an amphoteric initiator such as azobisisobutyl nitrile, the inside of the particle is firmly cross-linked, and an aqueous dispersion from which the semi-dissolved component is removed can be obtained. In this way, the inside of the particle is crosslinked, and the aqueous dispersion in which the semi-soluble component is reduced exhibits good redispersibility. In the present invention, known reaction accelerators such as cobalt type, vanadium type, manganese type, tertiary amine type, quaternary ammonium salt type and mercaptan type can be used in combination.

The average particle size of the polyester resin fine particles in the present invention is preferably in the range of 0.01 to 1.0 μm, more preferably 0.03 to 0.5 μm, and even more preferably 0.05 to 0. The range of 4 is more preferable 0.1
A range of up to 0.3 μm is even more preferred. Of the present invention,
The pH of the (colored water dispersion) in which the finely dispersed polyester resin fine particles are colored is preferably 4 or higher, more preferably 6 or higher, even more preferably 7.5 or higher, and 7.5-9. A range of 0.5 is even more preferred. The viscosity of the colored aqueous dispersion of the present invention is preferably in the range of 1.5 to 30 centipoise, more preferably 1.8 to 15 centipoise, still more preferably 2.0 to 10 centipoise, and 3.0 to 6. A range of 0 centipoise is even more preferred. The surface tension of the colored water dispersion of the present invention is not particularly limited, but at 25 ° C.,
Preferably 10 to 72, more preferably 20 to 70,
Further preferably, it is 30 to 60 dyn / cm.
The zeta potential of the colored polyester resin fine particles of the present invention is not particularly limited, but is in the range of 20 to 70 mV, preferably 30 to 60 mV.

In the present invention, an ultraviolet absorber, an antioxidant and the like can be added for the purpose of improving light resistance and heat resistance. As the ultraviolet absorber and the light stabilizer, a salicylate compound, a benzophenone compound, a benzotriazole compound, etc. can be used. Examples of the metal deactivator include N-salicyloyl-N'-aldehyde hydrazine, N-salicyloyl-N'-acetylhydrazine, N, N'-diphenyl-oxamide, N, N'-di (2-hydroxyphenyl) oxamide and the like. Can be used. As an ozone deterioration inhibitor, 6-ethoxy-2,2,4-trimethyl-
1,2 dihydroquinoline, N-phenyl-N'-isopropyl-p-phenylenediamine and the like can be used. As the radical chain inhibitor (primary antioxidant), a phenol compound, an amine compound, an ascorbic acid compound or the like can be used. Sulfur compounds can be used as the peroxide decomposer (secondary antioxidant), and citric acid, phosphoric acid, etc. can be used as the synergist. In the present invention, it is preferable to use at least one UV absorber selected from benzotriazole type, benzophenone type, and benzosalicylate type. The blending amount of these antioxidants is 0.01 to 5.0% by weight, preferably 0.02 to 1.0% by weight, and more preferably 0.1 to 5.0% by weight based on the polyester resin.
It is about 05 to 0.5% by weight.

Further, in the present invention, light resistance and heat resistance can be improved by using a singlet oxygen quencher together. As the singlet oxygen quencher, nickel complex compounds such as diazabiscyclooctane and carotene can be used. Examples of the nickel complex compound include 2,2′-thio-bis (4-octylphenyl) nickel, nickel acetylacetonate, bis (dithiobenzyl) nickel, bis (4,4′-dimethoxydithiobenzyl) nickel, Bis (dithiobenzyl) nickel tetrabutylammonium salt, Bis (4,4′-dimethoxydithiobenzyl) nickel tetotabutylammonium salt,
2,2'-thio-bis (4-tert-octylphenolate) -tert-butylamine-nickel salt, 2,
2'-thio-bis (4-tert-octylphenole-
G) -tertiary octylamine nickel salt, 3,5
-Di-tert-butyl-4-hydroxybenzyl monoethylphosphonate nickel, nickel dimethyldicarbamate, nickel diethyldicarbamate, nickel dibutyldicarbamate, nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel dibutyldithiocarbamate Etc. are preferably used. The content of these singlet oxygen quenchers is 0.01 to 5.0% by weight, preferably 0.02 to 1.
It is 0% by weight, more preferably about 0.05 to 0.5% by weight.

The aqueous medium may contain various water-soluble additives. As the additive, a water-soluble organic compound can be exemplified. As the water-soluble organic compound, methanol, ethyl alcohol, propanol, isopropanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, neopentyl glycol, polypropylene glycol, Butyl cellosolve, tertiary butyl cellosolve, diethylene glycol, triethylene glycol, polyethylene glycol, thiodiglycol, glycerin, 2,2 ', 2''-nitrile triethanol, ethylenediamine, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Examples thereof include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, alkylene glycol monoalkyl ether, N-methylpyrrolidone, and the like. The water-soluble organic compound is 50% of the aqueous medium.
It can be added as appropriate within the range not exceeding. A fluorine-based or silicone-based antifoaming agent can be added to the aqueous medium of the present invention. Furthermore, various fungicides and fungicides, and if necessary, inorganic and organic pigments may be added to the extent that transparency is not impaired.

The present invention will be more specifically described with reference to the following examples, but the present invention is not limited to the examples shown here. .

Example 1 << Polymerization of Polyester Resin >> 120 parts by weight of 1,4-cyclohexanedicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic acid were placed in an autoclave equipped with a thermometer and a stirrer. 50 parts by weight, 112 parts by weight of ethylene glycol, 78 parts by weight of tricyclodecane dimethanol, 0.1 parts by weight of tetrabutoxy titanate were charged and heated at 150 to 220 ° C. for 180 minutes to carry out an esterification reaction. It was Next, after raising the temperature to 240 ° C., the system pressure is gradually reduced to 30 mm after 10 minutes, and the pressure is adjusted to 10 mmHg.
The reaction was continued for 20 minutes. After that, the atmosphere in the autoclave was replaced with nitrogen gas and the pressure was adjusted to atmospheric pressure. 200 to 220 ℃
15.4 parts by weight of trimellitic anhydride was added and the reaction was carried out for 60 minutes to obtain a copolyester resin (A1).

The composition ratio (NMR analysis) of the copolyester resin (A1) is as follows: 1,4-cyclohexanedicarboxylic acid 65 mol%, cis-4-cyclohexene-1,2-dicarboxylic acid 27 mol%, trimellitic acid terminal 8 mol %, Ethylene glycol 50 mol%, tricyclodecane dimethanol 50 mol%, average molecular weight 3300, acid value (ionic group amount) 360 eq./ton, glass transition temperature 68 ° C.

<< Preparation of Aqueous Dispersion of Colored Polyester >> Polyester resin (A1) 2 was placed in a four-necked 10 liter separable flask equipped with a thermometer, a condenser and a stirring blade.
00 parts by weight, methyl ethyl ketone 100 parts by weight, tetrahydrofuran 50 parts by weight, (resin / solvent ratio = 4/3)
20 parts by weight of copper phthalocyanine oil dye Neopenblue FF4012 (manufactured by BASF) as a cyan dye, 9 parts by weight of triethanolamine as a base (3 in terms of resin)
00 eq./ton) was charged and dissolved at 70 ° C. Then 7
500 parts by weight of ion-exchanged water at 0 ° C. was added to emulsify and disperse in water. Further, the distillation temperature is 103 ° C in a distillation flask.
It was distilled until reaching to obtain a colored polyester resin fine particle water dispersion (B1). The average particle size of the obtained colored polyester resin fine particles was 0.13 μm.

<< Seed Polymerization >> In a four-necked 10 liter separable flask equipped with a thermometer, a condenser and a stirring blade, 1000 parts by weight of an aqueous dispersion of colored polyester resin fine particles (B1) whose non-volatile content was adjusted to 20 wt%. Parts, 100 parts by weight of distilled styrene in which 3% by weight of azobisisobutyronitrile was dissolved, and the mixture was gently stirred for about 2 hours until styrene droplets that could be visually confirmed disappeared. Then, the temperature was raised to 80 ° C., the temperature was kept for 5 hours, and then cooled to room temperature.
A colored crosslinked polyester resin fine particle water dispersion (C1) comprising a polyester resin and a polystyrene resin was obtained.
The dispersed particle diameter of (C1) was 0.15 μm.

<< Preparation of Recording Agent >> A recording agent was obtained by mixing and preparing samples so as to have the following constitution. Recording agent: Colored polyester fine particles (C1) (non-volatile content) 20 wt% Glycerin 15 wt% Ethanol 2 wt% Water 63 wt% << Evaluation >> The obtained trial recording agent (D1) was used as a drawing pen (0.5 mm width) manufactured by Lottling Co. ), A line was drawn on the recycled paper, and the recording quality was visually evaluated. Recording quality (visual): Whisker-like noise per line length of 1 cm (feathering) Less than 1 ◎ 1-2, ○ 2-4 △ 4 or more × The thickness of the line was calculated from the line width of the line and the line width that was actually ruled to obtain the blur width.

The lined paper was immersed in ion-exchanged water for 5 minutes, and water resistance was evaluated by the presence or absence of bleeding of the coloring material. Water resistance (visual inspection) ◯: No bleeding of color components is observed Δ: Some color components are bleeding, but the recording on the recording paper remains (the characters are legible). ×: The color component is bleeding and the recording on the recording paper is lost (characters cannot be read). A pen containing a recording material is put in a 40 ° C, 50% RH environment for 96 times.
The pen tip was evaluated for clogging resistance by leaving it for a certain period of time and then performing scoring again. Clogging resistance ◯: Even if left without a cap, it will return to the scribeable state. . Δ: It does not recover without the cap, but recovers when left capped. ×: Does not recover even if capped.

Similarly, a pen charged with a recording material was allowed to stand in an environment of 60 ° C. for 30 minutes, and the heat resistance was evaluated by whether or not the pen could be restored to a scoring-enabled state again. Heat resistance ◯: Even when left without a cap, it returns to a state where marking can be performed again. Δ: It does not recover without the cap, but recovers when left capped. ×: Does not recover even if capped. The obtained recording agent was sealed in a glass sample bottle, and
The storage stability was evaluated by the state after left at 1 ° C for 1 month. ○: No particular change. Or, increase in viscosity within 10% compared with the initial stage Δ: Change in viscosity exceeds 10%. X: Sedimentation of fine particles, or gelation of the whole occurs. The results are shown in Table 1. Shown in

[0046]

[Table 1] In addition, Table 1. Among them, CHEA: cyclohexenedicarboxylic acid FA: fumaric acid St: styrene DVB: divinylbenzene MMA: methyl methacrylate AIBN: azobisisobutylnitrile KPS: potassium persulfate.

[0047]

Comparative Example 1 << Polymerization of Polyester Resin >> In an autoclave equipped with a thermometer and a stirrer, 94 parts by weight of dimethyl terephthalate, 95 parts by weight of dimethyl isophthalate, 89 parts by weight of ethylene glycol, 80 parts of neopentyl glycol were added. Parts by weight and 0.1 parts by weight of tetrabutoxy titanate were charged and heated at 120 to 230 ° C. for 120 minutes to carry out a transesterification reaction. Next, 6.7 parts by weight of 5-sodium sulfoisophthalic acid was added, the reaction was continued at 220 to 230 ° C. for 60 minutes, and the temperature was further raised to 250 ° C., then the system pressure was 1 to 10 mmH.
As a result of continuing the reaction for 60 minutes, a copolyester resin (A2) was obtained.

Copolymerized polyester resin (A2) Composition ratio (NMR analysis) Terephthalic acid 48.5 mol%, isophthalic acid 49 mol%, 5-sodium sulfoisophthalic acid 2.5 mol%, ethylene glycol 61 mol%, neopentyl glycol 39 mol%, average molecular weight 2700, sodium sulfonate group content (ionic group amount) 118 eq./ton glass transition temperature 58 ° C The sodium sulfonate group amount is the sulfur concentration in the resin determined by fluorescent X-ray analysis measurement. Use as a reference.

<< Preparation of Aqueous Dispersion of Colored Polyester >> A polyester resin (A2) 2 was placed in a four-necked 10-liter separable flask equipped with a thermometer, a condenser, and a stirring blade.
00 parts by weight, methyl ethyl ketone 100 parts by weight, tetrahydrofuran 50 parts by weight, (resin / solvent ratio = 4/3)
As a cyan dye, 20 parts by weight of a copper phthalocyanine oil dye Neopenblue FF4012 [manufactured by BASF] was charged and dissolved at 70 ° C. Next, deionized water 5 at 70 ° C
00 parts by weight was added to emulsify and disperse in water. Further distill in a distillation flask until the distillate temperature reaches 103 ° C,
A colored polyester resin fine particle water dispersion (B2) was obtained.
The average particle diameter of the obtained colored polyester resin fine particles was 0.10 μm. << Preparation of Recording Agent >> A recording agent was obtained by mixing and preparing samples so as to have the following constitution. Recording agent; Colored polyester fine particles (B2) (non-volatile content) 20 wt% Glycerin 15 wt% Ethanol 2 wt% Water 63 wt%

<Evaluation> The same evaluation as in Example 1 was performed.
The results are shown in Table 1. Shown in

Comparative Example 2 << Polymerization of Polyester Resin >> Polymerization was carried out in the same manner as in Example 1 to obtain a polyester resin shown below. Copolymerized polyester resin (A3) Composition ratio (NMR analysis) 1,4-cyclohexanedicarboxylic acid 65 mol%, fumaric acid 27 mol%, trimellitic acid terminal 8 mol%, ethylene glycol 50 mol%, tricyclodecane dimethanol 50 mol%, Average molecular weight 3200, acid value (ionic group weight) 500 eq./ton, glass transition temperature 68 ° C

<< Preparation of Colored Polyester Aqueous Dispersion >> The same procedure as in Example 1 was carried out to obtain a colored polyester resin fine particle water dispersion (B3). The average particle diameter of the obtained colored polyester resin fine particles was 0.09 μm. << Seed Polymerization >> In a four-necked 10-liter separable flask equipped with a thermometer, a condenser, and a stirring blade, 1000 parts by weight of an aqueous dispersion of colored polyester resin fine particles (B1) whose nonvolatile content was adjusted to 20 wt%, azo 100 parts by weight of distilled styrene in which 3 wt% of bisisobutyronitrile was dissolved was charged, and the mixture was gently stirred for about 2 hours until the visually visible styrene droplets disappeared. Then, the temperature was raised to 80 ° C., the temperature was maintained for 5 hours, and then the temperature was cooled to room temperature to obtain a colored crosslinked polyester resin fine particle water dispersion (C3) composed of a polyester resin and a polystyrene resin. The dispersed particle size of (C3) was 0.10 μm.

<< Preparation of Recording Agent >> A recording agent was obtained by mixing and preparing samples so as to have the following constitution. Recording material: Colored polyester type fine particles (C3) (non-volatile content) 20 wt% Glycerin 15 wt% Ethanol 2 wt% Water 63 wt% << Evaluation >> The same evaluation as in Example 1 was performed below. The results are shown in Table 1.
Shown in

[0053]

Example 2 << Polymerization of Polyester Resin >> Polymerization was carried out in the same manner as in Comparative Example 1 to obtain a polyester resin shown below. Copolymerized polyester resin (A4) composition ratio (NMR analysis) 1,4-cyclohexanedicarboxylic acid 20 mol%, dimer acid 50 mol%, cis-4-cyclohexene-1,2-dicarboxylic acid 27 mol%, 5-sodium sulfoisophthalic acid 3 mol %, Ethylene glycol 98 mol%, polyethylene glycol # 20000 2 mol%, average molecular weight 3500, sodium sulfonate group content (ionic group amount) 98 eq./ton glass transition temperature 68 ° C.

<< Preparation of Colored Polyester Aqueous Dispersion >> Polyester resin (A4) 2 was placed in a four-necked 10 liter separable flask equipped with a thermometer, a condenser and a stirring blade.
00 parts by weight, 100 parts by weight of methyl ethyl ketone, 200 parts by weight of tetrahydrofuran, (resin / solvent ratio = 2 /
3) 15 parts by weight of Oleosol Fast Pink FB (CI Solvent Red 218) [manufactured by Taoka Chemical Industry Co., Ltd.] as a magenta dye was charged and dissolved at 70 ° C. Next, 500 parts by weight of ion-exchanged water at 70 ° C. was added to emulsify and disperse in water. Further, the mixture was distilled in a distillation flask until the distillate temperature reached 103 ° C. to obtain a colored polyester resin fine particle water dispersion (B4). The average particle diameter of the obtained colored polyester resin fine particles was 0.32 μm. << Seed Polymerization >> A four-necked 10 liter separable flask equipped with a thermometer, a condenser, and a stirring blade was added, and 1000 parts by weight of an aqueous dispersion of colored polyester resin fine particles (B4) whose nonvolatile content was adjusted to 20 wt%, azo. 20 parts by weight of distilled styrene having 3% by weight of bisisobutyronitrile dissolved therein,
80 parts by weight of divinylbenzene was charged, and the mixture was gently stirred for about 2 hours until the visually identifiable monomer droplets disappeared. Then, the temperature was raised to 80 ° C., the temperature was maintained for 5 hours and then cooled to room temperature to obtain a colored crosslinked polyester resin fine particle water dispersion (C4) comprising a polyester resin and a polystyrene / polydivinylbenzene resin. The dispersed particle size of (C4) was 0.34 μm.

<< Preparation of Recording Agent >> A recording agent was obtained by mixing and preparing samples so as to have the following constitution. Recording material: Colored polyester fine particles (C4) (calculated as nonvolatile content) 20 wt% Glycerin 15 wt% Ethanol 2 wt% Water 63 wt% << Evaluation >> The same evaluation as in Example 1 was performed below. The results are shown in Table 1.
Shown in

[0056]

Example 3 << Preparation of Colored Polyester Aqueous Dispersion >> 200 parts by weight of a polyester resin (A1) was placed in a four-necked 10 liter separable flask equipped with a thermometer, a condenser, and a stirring blade.
100 parts by weight of methyl ethyl ketone, 50 parts by weight of tetrahydrofuran, (resin / solvent ratio = 4/3) 10 parts by weight of Eisen / spiron / yellow GRLH special [Hodogaya Chemical Co., Ltd.] as a cyan dye, and 6 parts by weight of triethanolamine as a base. (200eq./ton in resin equivalent)
Was charged and melted at 70 ° C. Next, 500 parts by weight of ion-exchanged water at 70 ° C. was added to emulsify and disperse in water. Further, distillation was carried out in a distillation flask until the distillate temperature reached 103 ° C. to obtain a colored polyester resin fine particle water dispersion (B5). The average particle diameter of the obtained colored polyester resin fine particles was 0.25 μm. << Seed polymerization >> 1000 parts by weight of an aqueous dispersion (B5) of a colored polyester resin fine particle having a nonvolatile content adjusted to 20 wt% was placed in a four-necked 10-liter separable flask equipped with a thermometer, a condenser, and a stirring blade. Methyl methacrylate 10 in which 3 wt% of bisisobutyronitrile was dissolved
0 part by weight was charged, and the mixture was gently stirred for about 2 hours until the visually recognizable monomer droplets disappeared. Then the temperature is 80
The temperature was raised to 0 ° C., the temperature was maintained for 5 hours, and then the temperature was cooled to room temperature to obtain a colored crosslinked polyester resin fine particle water dispersion (C5) composed of a polyester resin and a polymethylmethacrylate resin. The dispersed particle size of (C5) was 0.27 μm.

<< Preparation of Recording Agent >> A recording agent was obtained by mixing and preparing samples so as to have the following constitution. Recording agent: Colored polyester fine particles (C5) (non-volatile content) 20 wt% Glycerin 15 wt% Ethanol 2 wt% Water 63 wt% << Evaluation >> The same evaluation as in Example 1 was performed below. The results are shown in Table 1.
Shown in

[0058]

Example 4 <Emulsion polymerization treatment> Coloring obtained in Example 3 in which a nonvolatile content concentration was adjusted to 20 wt% in a four-necked 10-liter separable flask equipped with a thermometer, a condenser, and a stirring blade. 1000 parts by weight of the polyester resin fine particle water dispersion (B5) and 10 parts by weight of methyl methacrylate were charged, and the mixture was gently stirred for about 2 hours until the visually identifiable monomer droplets disappeared. Then, 100 parts by weight of deionized water in which 0.5 part by weight of potassium persulfate was dissolved was added, the temperature was raised to 80 ° C., the temperature was maintained for 5 hours, and then cooled to room temperature, which consisted of polyester resin and polymethylmethacrylate resin. An aqueous dispersion of colored crosslinked polyester resin fine particles (C6) was obtained. The dispersed particle size of (C6) was 0.25 μm. << Preparation of Recording Agent >> A recording agent was obtained by mixing and preparing samples so as to have the following constitution. Recording agent: Colored polyester fine particles (C6) (non-volatile content) 20 wt% Glycerin 15 wt% Ethanol 2 wt% Water 63 wt% << Evaluation >> The same evaluation as in Example 1 was performed below. The results are shown in Table 1.
Shown in

[0059]

Comparative Example 3 A recording material having the following composition was prepared and evaluated in the same manner. The results are shown in Table 2. Shown in Water-soluble dye C.I. I. Direct Blue 86 purified product 2 wt% glycerin 5 wt% water 93 wt% Dye purification operation mainly means removal of sodium sulfate which is an inorganic impurity. This trial recording agent is a so-called typical water-soluble dye type recording agent containing no resin particles.

[0060]

As described above, the polyester resin colored water dispersion of the present invention has excellent characteristics as a recording agent having a high recording quality, and can be used for various non-impacts such as writing instruments and drawing inks. It can be widely used for printers, gravure printing, flexographic printing, offset printing and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C09D 11/10 PTS C09D 11/10 PTS 167/02 PLA 167/02 PLA (72) Inventor Yozo Yamada 2-1-1 Katata, Otsu, Shiga Prefecture, Toyobo Co., Ltd.

Claims (5)

[Claims] 1. A polyester resin obtained from a polyhydric carboxylic acid containing 1 to 100 mol% of cyclohexenedicarboxylic acid and a polyhydric alcohol as a dispersoid, in an amount of 5 to 99% by weight,
A polyester resin aqueous dispersion, wherein polyester resin fine particles comprising 95 to 1% by weight of a resin obtained by polymerization of a monomer having an ethylenically unsaturated bond are finely dispersed in an aqueous medium. 2. The polyester resin has an ionic group of 2
The polyester resin aqueous dispersion according to claim 1, which contains 0 to 2000 eq./ton. 3. The polyester resin aqueous dispersion according to claim 1, wherein the polyester resin fine particles are colored with a dye and / or a pigment. 4. The colored polyester resin aqueous dispersion according to claim 1, wherein the coloring material for coloring the polyester resin is a hydrophobic and / or organic solvent-soluble dye. 5. In an aqueous medium, obtained from polyhydric carboxylic acids containing 1 to 100 mol% of cyclohexenedicarboxylic acid and a polyhydric alcohol, and containing 20 to 2000 ionic groups.
A process for producing a polyester resin aqueous dispersion, which comprises polymerizing a monomer having an ethylenically unsaturated bond with a water-soluble initiator in the presence of eq./ton-containing polyester resin fine particles.