JPH09157363A - Water-base polyester resin dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problems with a recording material contg. a water-sol. dye and obtain a recording material enhanced in reliability and record quality by finely dispersing, in a water-base medium, fine particles contg. a polyester resin produced by using a polycarboxylic acid component contg. a specific polycarboxylic acid. SOLUTION: A water-base polyester resin dispersion is formed by emulsifying, in deionized water, fine particles of a resin colored with a hydrophobic and/or org.-solvent-sol. dye. The resin mainly comprises a polyester resin which has a content of ionic groups (org. amine carboxylate groups) of 20-2,000eq. /ton and a number average mol.wt. of 1,000-20,000 and is obtd. by reacting a polyhydric alcohol component with a polycarboxylic acid component contg. 5-70mol% cyclohexenedicarboxylic acid (e.g. cis-2-cyclohexene-1,2-dicarboxylic acid), pref. comprising 10-50mol% cyclohexenedicarboxylic acid and 90-50mol% cyclohexanedicarboxylic acid or dimer acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion of a resin that is widely used in paints, water-based paints, paper coating agents, coating materials for films, and various recording materials. From a marking pen, etc.
The present invention relates to an aqueous dispersion of a polyester resin and an aqueous dispersion of a colored polyester resin which can be suitably used as an ink recording material used in various printing machines, non-impact printers and the like.

[0002]

2. Description of the Related Art In recent years, environmental measures have been required in all fields, and recording materials and inking materials used for printing machines, non-impact printers, markers, writing instruments, etc. are also required to be solvent-free and water-based. There is. As an aqueous recording material, a material mainly composed of an aqueous solution of a water-soluble dye and a material mainly composed of a fine dispersion of a 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 at the writing point or recording system. However, since the recording material using the water-soluble dye is an aqueous solution of the dye, it easily bleeds on the recording paper. Further, since it is necessary to increase the apparent drying speed, the recording quality is adjusted so as to quickly penetrate the recording paper, so that the recording quality is unavoidably 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 above problems of the recording material using the water-soluble dye, the addition of resin fine particles such as emulsion and latex has been studied for a long time.
In JP-A-55-18418, a latex which is "a kind of colloidal solution in which components such as rubber and resin are dispersed in water in the form of fine particles (particle diameter of about 0.01 to several μm) by an emulsifier" is added. There is a description of the recording agent for inkjet recording. The particle size of the latex particles in the above invention is 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 bleeding on the recording paper is insufficient, and high recording quality cannot be obtained. Further, if the particle size is 1.0 μm or more, the nozzle is frequently clogged, which makes it difficult to use from the viewpoint of reliability. Therefore, the practically usable range is about 0.2 to
It is considered to be 1.0 μm. When the 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 the case of fine particles of about 0.2 μm or more, the effect of gravity is greater than the diffusing force of the particles due to Brownian motion. In this case, therefore, the difference between the particle specific gravity and the medium specific gravity is suppressed to 0.1 or less, preferably 0.07 or less. There is a need.

The specific gravity of the synthetic rubber latex exemplified in the above invention is about 0.9 to 1.0, and although the above conditions are 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 the unsaturated bonds, the fixing of the particles on the recording paper is hindered and a problem occurs in the recording quality. Further excessive vulcanization causes a specific gravity of 1.1 or more, which causes a problem of sedimentation. Further, since the synthetic rubber-based 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 tip of the nozzle, and the dried product is soft and slightly sticky. Therefore, its removal is very difficult. Regarding the synthetic resin latex exemplified in the above invention, the specific gravity is 1.1 or more, and particularly in the case of a synthetic resin containing a halogen element, the specific gravity reaches 1.3 to 1.5, so that the particle size for exhibiting the bleeding prevention effect is obtained. Sedimentation occurs in all areas. Furthermore, these latexes are generally problematic because many of the emulsifiers used in the production of the latex tend to promote bubbling of the ink and reduce the surface tension more than necessary.

JP-A-54-146109 describes 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 are exemplified, and it is described that a glass transition temperature of 30 ° C. or lower is a preferable condition. There is no description about the particle size in the invention. At the low glass transition temperature, it is obvious that the fine particles swollen with a solvent have a film forming property when dried at room temperature, and when the above ink is used, it is easy for nozzle clogging to frequently occur. By analogy.

(Recording Material Using Pigment Dispersion) In order to improve the drawbacks of a recording material using a water-soluble dye, there is a description that carbon black or an organic pigment is used as a recording material. In a recording material using such a pigment, 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 above high specific gravity pigment, it is necessary to finely disperse the average particle diameter to approximately 0.1 μm or less, which increases the dispersion cost. Further, if the particle size is 0.1 μm or less, the effect of preventing bleeding is insufficient and high quality recorded characters and images cannot be obtained. Further, there is a problem that the use of the dispersant limits the physical properties of the ink such as surface tension and foaming property.

(Recording Material Using Colored Resin Particles) An invention for coloring a water-dispersible resin with an oil-soluble dye or a hydrophobic dye is described as an ink jet recording ink. These relate to “ink using colored polymer particles as a recording agent”. For example, JP
No. 4-58504 describes 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 swell in the solvent of the dye solution when mixed with the hydrophobic dye solution and are further colored by the dye. Since the hydrophobic dye is used as the recording material, the obtained image is said to have water resistance. In the above invention, water is used as the continuous phase, and colored vinyl polymer particles swollen with a solvent are used as the dispersed phase to give water control of the ink viscosity, and a solvent having a somewhat high viscosity (low volatility) is used. Allowed to use.

Japanese Patent Laid-Open Nos. 55-139471 and 3-2
50069 describes an ink using emulsion-polymerized or dispersion-polymerized particles dyed with a dye. The gist of the invention is to prevent bleeding by using colored particles as a dispersoid and water (transparent) as a medium, as in JP-A-54-58504. In this case, however, since no solvent is contained, the particles form a film. By doing so, it is necessary to fix the recording paper. 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 any invention, 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, but in this case, the problem of nozzle clogging occurs due to dry film formation at the nozzle tip. .

Japanese Patent Laid-Open No. 4-185672 discloses an ink composed of colored resin particles and an aqueous medium, in which a water-soluble compound is dissolved in the aqueous medium to reduce the specific gravity difference between the colored resin particles and the aqueous medium to 0.04 or less. It is described to prevent settling of particles. It is said that inorganic salts are preferable as the water-soluble compound. However, when the inorganic salt is dissolved in an aqueous medium, the ionic strength in the system increases,
Since the stability of the dispersion system is lowered, the colored resin particles are aggregated, and the fluid characteristics of the ink jet ink cannot be maintained.
In JP-A-4-185673 and JP-A-4-185674, an effective specific gravity is lowered by swelling colored resin particles with a solvent in an ink composed of colored resin particles and an aqueous medium, thereby reducing the color resin particles and the aqueous medium. The specific gravity difference of 0.
It is described that the value is 04 or less. In this case, it is difficult to avoid the nozzle clogging as described above.

In JP-A-63-132083, by containing a substance which is solid at room temperature, the viscosity at a solid content of 30% by weight is adjusted to be three times or more the viscosity at a solid content of 10% by weight. There is a description regarding the ink for inkjet recording. According to the present invention, by using a solvent having a low vapor pressure, the ink is quickly dried on the recording paper, the solid content concentration is rapidly increased, the viscosity is increased accordingly, and bleeding is 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 completely different.
A large number of water-soluble polymers are exemplified as specific examples in the present text. As described above, in the ink containing the water-soluble polymer component, the adjustment range of the physical properties of the ink is narrowed, and the nozzle clogging due to drying is likely to occur frequently. Above, we have mainly reviewed recording materials used for inkjet recording, but the sedimentation of particles and the clogging caused by dry film formation are caused by the aqueous recording in writing instruments, markers, marking pens, other types of printers, printing machines. It also occurs when materials are used.

The present inventors, as a result of continuing research in view of such circumstances, have found that an aqueous dispersion of a polyester resin can be colored with an oily or hydrophobic dye at an extremely high concentration (Japanese Patent Laid-Open No. 6-340835). According to the invention, when an aqueous dispersion of fine colored polyester resin 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 of (1) are expressed. However, in the subsequent research, when such an aqueous dispersion of colored polyester resin particles was used, there were problems such as clogging of the writing tip in the region above the glass transition temperature of the resin and good recording could not be performed. found.
As a conventional means in such a case, a method of using an unsaturated polyester resin into which an unsaturated monomer such as fumaric acid or maleic acid has been introduced and crosslinking with a so-called vinyl monomer having an ethylenically unsaturated bond Is taken. Although the clogging property is certainly improved by using such means,
Polyester resin using an aliphatic unsaturated monomer is liable to cause hydrolysis, and in a dispersion using an aqueous medium, which is the main object of the present invention, the hydrolysis of the resin causes a decrease in film forming temperature and an increase in viscosity. However, it causes problems such as deterioration of the fastness of the film-forming product and deterioration of storage stability of the dispersion.

[0013]

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 realizes high recording quality. However, there are many problems that remain in terms of reliability such as sedimentation of particles and clogging caused by dry film formation, and all of the water-soluble dye type recording agents have not been replaced.

[0014]

As a result of continuing the research in view of such circumstances, the present inventors have arrived at the next invention. That is, the present invention is characterized in that, as the dispersoid, fine particles containing at least a polyester resin obtained from a polyhydric carboxylic acid containing 1 to 100 mol% of cyclohexenedicarboxylic acid and a polyhydric alcohol are finely dispersed in an aqueous medium. A polyester resin water dispersion, wherein the polyester resin contains 20 to 2000 equivalents / ton of an ionic group, wherein the fine particles are colored with a dye and / or a pigment. The polyester resin water dispersion is characterized in that the coloring material for coloring the fine particles is a hydrophobic and / or organic solvent-soluble dye.

The main dispersoid of the water dispersion of the present invention comprises a polyester resin. The fine particles containing the polyester resin of the present invention may contain a so-called vinyl-based polymer obtained by polymerization of a monomer having an ethylenically unsaturated bond, in addition to the polyester resin. 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, p-oxybenzoic acid, p- (hydroxyethoxy) benzoic acid, hexahydrophthalic acid, tetrahydrophthalic acid and other aromatic oxycarboxylic acids, phenylenediacrylic acid and other aromatic unsaturated polycarboxylic acids Acids, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and other aliphatic dicarboxylic acids, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid and other unsaturated polycarboxylic acids and cyclohexanedicarboxylic acid , Cyclohexenedicarboxylic acid, dimer acid, etc. Alicyclic dicarboxylic acids, etc., and 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 polyhydric alcohols used in the polyester resin include aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, aromatic polyhydric 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 aromatic polyhydric alcohols, para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol
And ethylene oxide adduct of 1,4-phenylene glycol, bisphenol A, ethylene oxide adduct of bisphenol A, and propylene oxide adduct. Further, examples of the polyester polyol include lactone polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone.

In the present invention, among these, cyclohexene dicarboxylic acid is used as a polyvalent carboxylic acid component in an amount of 1 to 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 cyclohexene dicarboxylic acid is 5 to 70 mol%, preferably 10 to 50 mol%, and more preferably 20 to 30 mol%, based on all the acid components. In the present invention, cyclohexenedicarboxylic acid 1
It is preferable to use an acid component composed of 0 to 50 mol% and cyclohexanedicarboxylic acid or dimer acid of 50 to 90 mol%.

The polyester resin of the present invention preferably contains an ionic group in the range of 20 to 2000 equivalents / ton. As the ionic group that can be introduced into polyester,
Anionic group such as alkali metal sulfonate or ammonium sulfonate, alkali metal carboxylate or ammonium carboxylate, sulfuric acid group, phosphoric acid group, phosphonic acid group, phosphinic acid group or their ammonium salts and alkali metal salts Or a cationic group such as a primary to tertiary amine group. The ionic group is introduced by using an ionic group-containing monomer. To introduce a cationic group, 2
-Aminopropane 1,3-diol, nitrile monoalkanol, nitrile dialkanol and nitrile trialkanol are preferably used.

To introduce an alkali metal sulfonate or ammonium sulfonate into polyester, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4
-Sulfophthalic acid, 4-sulfonaphthalene-2,7 dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid,
The polyester may be copolymerized with an alkali metal salt or ammonium salt of a mono- or polyvalent carboxylic acid having a sulfonic acid group such as metasulfobenzoic acid. Li, Na,
Alkali metal ions such as K, alkaline earth metal ions,
Examples thereof include salts with ammonium ions, primary to quaternary alkylammonium ions, alkanolamines and the like.

The ionic group contained in the polyester resin of the present invention is preferably an organic amine salt of a carboxylic acid group. The ionic group is 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, organic amines are particularly preferably used. 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 mentioned. 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. Examples of the alkanolamine include monoalkanolamine, dialkylmonoalkanolamine, dialkanolamine, monoalkyldialkanolamine, trialkanolamine and the like, preferably trialkanolamine, and more preferably 2,2 ′, 2 ′. Examples include'-nitrile triethanol, tripropanolamine, triisopropanolamine, tributanolamine, and trihexanolamine.

The content of the ionic group is required to be 20 to 2000 equivalents / ton, preferably 20 to 1000 equivalents / ton, and more preferably 5 to the polyester resin.
It is 0 to 500 equivalents / ton, particularly preferably 50 to 200 equivalents / ton. The ionic group has a function of imparting dispersion stability to the polyester resin fine particles which 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. If the content of the ionic group is too large, the polyester resin may become water-soluble and the desired water dispersion may not be obtained.

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 etc. used for fibers, films, plastic bottles, etc.
A relatively high molecular weight polyester 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 1,000 to 20,000, preferably 15
00-10,000, more preferably 2000-5000
It is. If the molecular weight is low, the resulting coating film may have insufficient physical properties. Conversely, 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 20 ° C. or higher, and preferably 4
The temperature is 0 ° C or higher, more preferably 50 ° C or higher, and particularly preferably 60 to 80 ° C. 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.

In the present invention, it is preferable that the dispersoid fine particles made of a resin containing a specific polyester resin as a main component are 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, 13, 14, 1
5, 16, 17, 185, C.I. I. Pigment R
ed 47, 48, 58, 81, 95, 122, 18
4, 185, C.I. I. PigmentViolet 2
3, C.I. I. Pigment Blue 15, 16,
Carbon blacks and the like can be preferably used. The dye is not particularly limited as long as it can dye the polyester resin firmly. When the polyester resin contains an anionic group, it is dyed with a cationic dye such as a basic dye, and when it contains a cationic group, it is dyed with an anionic dye such as an acid dye, a direct dye or a reactive dye. can do. 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 sparingly 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 32, 96, 16
2, C.I. I. Solvent Red 49, 118,
218, C.I. I. Solvent Blue 25, 3
5, 38, 64, 70, C.I. I. Solvent Bl
ack 3 etc. can be illustrated. Further, as a disperse dye, C.I.
I. Disperse Yellow 33, 42, 5
4, 64, 198, C.I. I. Disperse Red
60, 92, C.I. I. Disperse Violet
t 26, 35, 38, C.I. I. Disperse B
At least one dye selected from lue 56, 60, 87 is preferably used. These are particularly excellent in fastness to light, hue, and saturation, and process color
It is preferable as the three primary colors. 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. The dye is blended in the range of 0.2 to 30% by weight, preferably 2 to 25% by weight, more preferably 5 to 20% by weight, and particularly preferably 10 to 20% by weight, based on the polyester resin. Is blended with. 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, and it can be obtained by using a known mechanical or surface chemical dispersion method. That is, a method of mechanically emulsifying a solution of a polyester resin with a high-speed stirrer such as a homogenizer in the presence of an emulsification aid such as a surfactant and removing the solvent 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.

The method for producing the polyester fine particles will be described below. 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. Examples of the water-soluble organic compound include ethanol, isopropanol, butanol,
Ethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, tar
Char-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 preferred method for obtaining an aqueous dispersion of a preferred polyester resin 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 mixed and dissolved. Then, water can be added to disperse the mixture in water, and the water-soluble organic compound can be removed by azeotropic distillation or the like, if necessary. 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 rotation speed and temperature. The average particle diameter of the polyester resin fine particles in the present invention is in the range of 0.01 to 1.0 μm, preferably 0.03 to 0.5 μm,
The range of 0.05 to 0.4 is more preferable, and the range of 0.1 to 0.
The range of 3 μm is particularly preferable. The pH of the colored aqueous dispersion of the present invention is 4 or more, preferably 6 or more, more preferably 7.5 or more, and particularly preferably 7.5 to 9.5. The viscosity of the colored aqueous dispersion of the present invention is 1.5 to 30 centipoise, preferably 1.8 to 15 centipoise, and 2.0 to 1
0 centipoise is more preferable, and 3.0 to 6.0 centipoise is particularly preferable. The surface tension of the colored water dispersion of the present invention is not particularly limited, but it is 1 at 25 ° C.
0 to 72 dyn / cm, preferably 20 to 70 d
yn / cm, more preferably 30 to 60 dyn / cm. The zeta potential of the colored polyester fine particles of the present invention is not particularly limited, but is 20 to 70 mV, and 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. A sulfur-based compound can be used as the peroxide decomposing agent (secondary antioxidant), and citric acid, phosphoric acid, or the like can be used as the complementing agent. In the present invention, at least one selected from benzotriazole type, benzophenone type and benzosalicylate type
It is preferred to use some types of UV absorbers. The blending amount of these antioxidants is 0.01 to polyester resin.
It is 5.0% by weight, preferably 0.02-1.0% by weight, more preferably 0.05-0.5% 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. The nickel complex compound is 2, 2'-
Thio-bis (4-octylphenyl) nickel, nickel acetylacetonate, bis (dithiobenzyl) nickel, bis (4,4'-dimethoxydithiobenzyl)
Nickel, tetrabutylammonium salt of bis (dithiobenzyl) nickel, tetotabutylammonium salt of bis (4,4′-dimethoxydithiobenzyl) nickel,
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, relative to the binder resin.
To 1.0% by weight, and more preferably 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. Water-soluble organic compounds include methanol, ethanol, 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,
Examples thereof include ethylenediamine, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, alkylene glycol monoalkyl ether, and N-methylpyrrolidone. The water-soluble organic compound can be appropriately added within a range not exceeding 50% of the aqueous medium. A fluorine-based or silicone-based antifoaming agent can be added to the aqueous medium of the present invention. Further, various fungicides and fungicides, and if necessary, inorganic or organic pigments may be added to the extent that transparency is not impaired.

The polyester particles obtained as described above are used as seed particles, and the polyester particles are dispersed in an aqueous medium to obtain the above-mentioned monomer having an ethylenically unsaturated double bond, that is, a so-called vinyl monomer. Then, the polyester resin is swelled so as to be 5 to 99% by weight of the polyester resin and 1 to 95% by weight of the vinyl monomer, and further polymerized to obtain particles of the polyester composite resin. 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.

Examples of the vinyl-based monomer include alkyl (meth) acrylate whose alkyl group has 1 to 10 carbon atoms, methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and (meth) acrylic. (Meth) acrylic acid esters such as phenyl acid acid, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, methyl vinyl ketone, phenyl vinyl ketone,
Unsaturated ketones such as methyl isopropenyl ketone, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate vinyl butanoate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether, halogenated Vinyl and vinylidene halides, acrylamide and its alkyl substitution products, styrene, styrene alkyl substitution products, styrene halogen substitution products, allyl alcohol and its esters or ethers, acrolein, vinyl aldehydes such as methacrolein, Acrylonitrile, methacrylonitrile, vinyl monomers such as vinylidene cyanide, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid and itaconic acid, and salts thereof, vinyl sulfonic acid, Acrylic acid, unsaturated hydrocarbon sulfonic acids and salts thereof such as p-styrene sulfonic acid, phosphoric acid esters having a double bond, and salts thereof, pyridine, vinyl pyrrolidone, vinyl imidazo -
, Vinylcarbazol, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like can be used.

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'-Azobisisobutylnitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile)
And the like, and water-soluble initiators such as ammonium persulfate and potassium persulfate.

[0042]

BEST MODE FOR CARRYING OUT THE INVENTION In a preferred embodiment of the polyester resin aqueous dispersion according to the present invention, cyclohexene dicarboxylic acid 10 to 50 is used as a preferable polycarboxylic acid.
Fine particles containing at least a polyester resin obtained by condensation of the polyvalent carboxylic acid with a polyhydric alcohol containing 100% by mol of cyclohexanedicarboxylic acid or 50 to 90 mol% of dimer acid are finely dispersed in an aqueous medium. It was done. The above polyester resin contains an organic amine, particularly an alkanolamine, as a part of the ionic group, and its preferable content is 50 to 200 equivalents / ton, and is colored with a hydrophobic and / or organic solvent-soluble dye. What is described is a more preferable form.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

[0044]

【Example】

(Example 1) << Polymerization of polyester resin >> In an autoclave equipped with a thermometer and a stirrer, 120 parts by weight of 1,4-cyclohexanedicarboxylic acid cis-4-cyclohexene-1,2-dicarboxylic acid 50 Parts by weight Ethylene glycol 112 parts by weight Tricyclodecane dimethanol 78 parts by weight Tetrabutoxy titanate 0.1 parts by weight were charged and the esterification reaction was carried out by heating at 150 to 220 ° C. for 180 minutes. Next, after raising the temperature to 240 ° C., the system pressure is gradually reduced to 30 mmHg and 10 mmHg is reached.
The reaction continued for minutes. After that, the atmosphere in the autoclave was replaced with nitrogen gas to bring the pressure to atmospheric pressure. Maintaining the temperature at 200 to 220 ° C., 15.4 parts by weight of trimellitic anhydride was added and the reaction was carried out for 60 minutes to obtain a copolymerized polyester resin (A1). Copolymerized polyester resin (A1) composition ratio (NMR analysis) 1,4-cyclohexanedicarboxylic acid 65 mol% cis-4-cyclohexene-1,2-dicarboxylic acid 27 mol% trimellitic acid terminal 8 mol% ethylene glycol 50 mol% tricyclo Decane dimethanol 50mol% Average molecular weight 3300 Acid value (ionic group amount) 360 equivalents / ton Glass transition temperature 68 ° C

<< Preparation of Polyester Aqueous Dispersion >> Thermometer,
In a four-necked 10-liter separable flask equipped with a condenser and a stirring blade, 200 parts by weight of A1 above, 100 parts by weight of methyl ethyl ketone, and 50 parts of tetrahydrofuran.
Parts by weight (resin / solvent ratio = 4/3) and 9 parts by weight of triethanolamine as a base (300 equivalents / ton in terms of resin) were 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 polyester resin fine particle water dispersion (B1). The average particle size of the obtained B1 fine particles is 0.13 μm.
Met.

<< Evaluation of Polyester Aqueous Dispersion >> The pH of the obtained polyester aqueous dispersion was adjusted to 7.0 (adjusted using an aqueous triethanolamine solution and an aqueous citric acid solution).
It was stored in an environment of ° C for 30 days, and the stability was evaluated by the presence or absence of abnormality such as pH change, viscosity change, and sediment. The results are shown in Table 1 below.

<Evaluation of solvent resistance of coating film> 20 parts by weight of styrene obtained by dissolving 1.5 parts by weight of azobisisobutyronitrile as a crosslinking agent in 400 parts by weight of the obtained polyester aqueous dispersion (nonvolatile content 25%). Parts, 10 parts by weight of divinylbenzene, and 20 parts by weight of methyl methacrylate were added, and the mixture was gently stirred until the monomer droplets disappeared. Next, an aluminum plate was coated with an applicator so as to have a dry film thickness of 10 μm, and dried and cured in a dry oven at 80 ° C. to obtain a coating film. The solvent resistance of the obtained coating film was evaluated based on the state of the coating film after being immersed in methyl ethyl ketone for 5 minutes. The results are shown in Table 1 below. In Table 1, CHEA: cyclohexenedicarboxylic acid FA: fumaric acid storage stability ○: no abnormality (no sediment, viscosity change within ± 20%, pH change within ± 0.5) △: no sediment, viscosity change ± 20% Above or pH change ± 0.5 or more x: Sediment is present. Solvent resistance of coating film: No abnormality or slight swelling x: Dissolution or extreme swelling.

Comparative Example 1 Polymerization of Polyester Resin In an autoclave equipped with a thermometer and a stirrer, dimethyl terephthalate 94 parts by weight dimethyl isophthalate 95 parts by weight ethylene glycol 89 parts by weight neopentyl glycol 80 1 part by weight and 0.1 part by weight of tetrabutoxy titanate were charged and heated at 120 to 230 ° C. for 120 minutes to carry out a transesterification reaction. Then, 6.7 parts by weight of 5-sodium sulfoisophthalic acid was added, the reaction was continued at 220 to 230 ° C. for 60 minutes, further heated to 250 ° C., and the reaction was continued for 60 minutes at a system pressure of 1 to 10 mmHg. 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 Sulfonic acid Content of sodium group (amount of ionic group) 118 equivalent / ton Glass transition temperature 58 ° C. The amount of sodium sulfonate group is based on the sulfur concentration in the resin obtained by fluorescent X-ray analysis measurement.

<< Preparation of Polyester Aqueous Dispersion >> Thermometer,
In a four-necked 10 liter separable flask equipped with a condenser and a stirring blade, 200 parts by weight of the above A2, 100 parts by weight of methyl ethyl ketone, and 50 parts of tetrahydrofuran.
Part by weight (resin / solvent ratio = 4/3) 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 polyester resin fine particle water dispersion (B2). The average particle diameter of the obtained B2 fine particles was 0.10 μm. << Evaluation >> The following evaluation was performed in the same manner as in Example 1. The results are shown in Table 1 below.

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 (Amount of ionic group) 500 equivalents / ton Glass transition temperature 68 ° C

<< Preparation of Polyester Aqueous Dispersion >> Example 1
In the same manner as described above, polyester resin fine particle water dispersion (B
3) was obtained. The average particle size of the obtained B3 fine particles is 0.0
It was 9 μm. << Evaluation >> The following evaluation was performed in the same manner as in Example 1. The results are shown in Table 1 below.

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% ethyleneglycol -Mol 98 mol% polyethylene glycol # 20000 2 mol% average molecular weight 3500 sodium sulfonate group content (ionic group content) 98 equivalents / ton glass transition temperature 68 ° C

<< Preparation of Polyester Aqueous Dispersion >> Thermometer,
200 parts by weight of A4, 100 parts by weight of methyl ethyl ketone, and 20 parts of tetrahydrofuran were placed in a four-necked 10 liter separable flask equipped with a condenser and a stirring blade.
0 parts by weight and 15 parts by weight (resin / solvent ratio = 2/3) were 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,
An aqueous dispersion of fine polyester resin particles (B4) was obtained. The obtained B4 fine particles had an average particle diameter of 0.32 μm. << Evaluation >> The following evaluation was performed in the same manner as in Example 1. The results are shown in Table 1 below.

[0054]

[Table 1]

(Example 3) << Preparation of Colored Polyester Aqueous Dispersion >> 200 parts by weight of A1 obtained in Example 1 was placed in a four-necked 10 liter separable flask equipped with a thermometer, a condenser and a stirring blade. Parts, 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 yellow dye, and triethanolamine 6 as a base. Parts by weight (200 eq./in terms of resin)
ton) 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, it was distilled in a distillation flask until the distillate temperature reached 103 ° C., and the colored polyester resin fine particle water dispersion (B
5) was obtained. The average particle size of the obtained colored B5 fine particles was 0.25 μm.

(Example 4) The dye in Example 3 was used as magenta dye, Oleosol Fast Pink FB (C.I.
I. SolventRed 218) [made by Taoka Chemical Co., Ltd.] 2
A colored polyester resin fine particle water dispersion (B6) was obtained under the same conditions except that 0 part by weight was used. Coloring B obtained
The average particle size of the 6 fine particles was 0.26 μm.

(Example 5) Similarly, as a cyan dye, a copper phthalocyanine-based oily dye Neopen Blue FF4 was used as a cyan dye.
012 [manufactured by BASF] 20 parts by weight, but otherwise under the same conditions as the colored polyester resin fine particle water dispersion (B
7) was obtained. The average particle size of the obtained colored B7 fine particles was 0.25 μm.

(Example 6) Similarly, a dye was used as a black dye, and Oleosol Fast Black RL (C.I.
LventBlack 27) [manufactured by Taoka Chemical Co., Ltd.] was used to obtain a colored polyester resin fine particle water dispersion (B8) under the same conditions as above. The average particle size of the obtained colored B8 fine particles was 0.25 μm.

<< Preparation of Recording Agent >> Using the colored polyester aqueous dispersions (B5 to B8) obtained in Examples 3 to 6, samples were mixed and prepared so as to have the following constitution to obtain 4 recording agents. . Recording agent Colored polyester fine particles (non-volatile content) 20 wt% (choose one from B5 to B8 above) Glycerin 15 wt% Ethanol 2 wt% Water 63 wt%

<< Evaluation >> The obtained trial recording agent was placed in a drawing pen (0.5 mm width) manufactured by Lottling Co., and a line was marked on the recycled paper to visually evaluate the recording quality. With all the recording agents, good marking was possible without bleeding or feathering. The lined paper was dipped in ion-exchanged water for 5 minutes, and water resistance was evaluated by the presence or absence of bleeding of the coloring material. It was confirmed that any of the recording agents showed no bleeding of the color component and showed good water resistance.

[0061]

As described above, the polyester resin aqueous dispersion of the present invention is useful as an aqueous resin base for paints because it has excellent storage stability and can form a good crosslinked coating film. When colored, it has excellent characteristics as a recording material having high recording quality.
It can be widely used for various non-impact printers, gravure printing, flexographic printing, offset printing, etc. from drawing inks and the like.

Front page continued (72) Inventor Yozo Yamada 1-1-1 Katata, Otsu City, Shiga Prefecture Inside Toyobo Co., Ltd.

Claims (4)

[Claims] 1. Fine particles containing at least a polyester resin obtained from a polyhydric carboxylic acid containing 1 to 100 mol% of cyclohexenedicarboxylic acid and a polyhydric alcohol as a dispersoid are finely dispersed in an aqueous medium. Polyester resin water dispersion. 2. The polyester resin has an ionic group of 2
The polyester resin water dispersion according to claim 1, which contains 0 to 2000 equivalents / ton. 3. The aqueous dispersion of polyester resin according to claim 1, wherein the fine particles are colored with a dye and / or a pigment. 4. The polyester resin aqueous dispersion according to claim 1, wherein the coloring material for coloring the fine particles is a hydrophobic and / or organic solvent-soluble dye.