JPH021382A - Dyeable resin for image-receiving material for sublimation transfer - Google Patents

Abstract

PURPOSE:To improve developed color density of images and durability by providing a dyeable layer comprising as a main constituent a modified polyester resin having halogen atoms in a resin skeleton thereof a base to produce an image-receiving material for sublimation transfer. CONSTITUTION:A dyeable layer comprising a dyeable resin containing as a main constituent a modified polyester resin having halogen atoms in a resin skeleton thereof is provided on a base to obtain an image-receiving material for sublimation transfer. The halogen atoms are introduced into the modified polyester resin preferably by a method wherein 3-bromo-1,2-propanediol, 3- chloro-1,2-propanediol, tetrachlorophthalic anhydride or the like is copolymerized with other comonomers for forming the polyester. The modified polyester resin shows enhanced color development sensitivity for dyes and enhanced fastness upon being dyed, so that high-quality images can be obtained.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a dyeable resin for sublimation transfer image-receiving paper used in combination with a thermal transfer sheet containing a sublimation dye.
It improves its color development and dye fastness.

(Prior art) In the conventional transfer method, a thermal transfer sheet coated with a sublimable disperse dye is heated with a thermal hend, etc., and the sublimable dye is transferred onto a sublimation transfer receiver paper facing the thermal transfer sheet, thereby recording an image. This is what you get.

By using the coloring materials as cyan, magenta, yellow, and blank if necessary, and sequentially recording by heat transfer overlapping,
Full color images can be obtained.

The dyeing resin used in the dyeing layer of the above-mentioned sublimation transfer image-receiving paper has conventionally been disclosed in JP-A-57-107885, JP-A-60-64899, and JP-A-61-258790.
As shown in Japanese Patent Application Laid-Open No. 62-105689, those containing saturated polyester as a main ingredient are known.

In addition, with the aim of improving the dye density and the stability of printed image quality, a dyeing layer made of saturated polyester resin or the like was impregnated with finely powdered oxide as a dye adsorbent. -5411188 Publication, Jikai Showa 6
0-101089, JP-A-59-133098, etc.

(Problems to be Solved by the Invention) Conventionally, when a saturated polyester is used alone as a dyeing layer, a high quality image with good gradation can be obtained, but the color density is not sufficient. In addition, regarding the stability of images, there are problems in that in hot and humid conditions, dyes that have been dyed may migrate and contaminate other transfer objects, and that the clarity of images decreases during storage due to poor light resistance. There was a point.

(Means for Solving the Problems) In order to solve the above problems, the present invention provides a dyeing layer of a sublimation transfer image receptor having a dyeing layer provided on a base material and a cough base layer.
This is a dyeable resin for a sublimation transfer image receptor, which is mainly composed of a dyeable resin, and the dyeable resin mainly contains a modified polyester resin having a halogen atom in the resin skeleton.

Methods for introducing halogen atoms into the modified polyester resin of the present invention include 3-bromo-1,2-propanediol, 3-chloro-12-propanediol, het's acid anhydride, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride. There is a method of copolymerizing compounds such as , alkylene oxide adduct of tetrabromobisphenol A, Megafanok (F-528: manufactured by Dainippon Ink Chemical 9@) together with other polyester copolymer components, but preferably,
3-bromo-1,2-propanediol, 3-chloro-
1,2-propanediol and tetrachlorophthalic anhydride.

Alternatively, there is a method of introducing the polyester glycol by reacting an organic diisocyanate at the end thereof and extending the chain with the glycol component of the halogen-containing polyester comonomer or the diamine compound described below.

The above-mentioned diamine compound is 4,4'-methylenedi2.
6-dibromoaniline, 4,4'-methylenedi-2-bromo6-chloroaniline, 4,4'-methylenedi-6bromo-2-toluidine, 4-chloro-O-phenylenediamine, 4-chloro-m-phenylenediamine, 2.6-
Examples include dichloro-p-phenylenediamine, 2,5-dichloro-p-phenylenediamine, and 2-chloro-p-phenylenediamine, 4-chloro-m-phenylenediamine, and preferably 4,4'-methylenedi-2-bromine. 6-chloroaniline, 2,6-dichloro-p-phenylenediamine.

Furthermore, there is a method in which the following monofunctional compound is added to the polyester glycol terminal via an organic diisocyanate. Examples of the above-mentioned -functional compound include p-fluoroaniline, 0-fluoroaniline, 2,3-dichloroaniline, and the like, with 2,3-dichloroaniline being preferred.

Examples of the organic diisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3'-dimethoxy-44'-biphenylene diisocyanate, p-xylylene diisocyanate, m-
Xylylene diisocyanate, 1,3-diisocyanate methylcyclohexanone, 1,4-diisocyanate methylcyclohexanone, 4,4'-diisocyanate dicyclohexane, 4,4'-diisocyanate cyclohexylmethane, isophorone diisocyanate, 2
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2,4-naphthalene diisocyanate, 3.
Examples include 3'-dimethyl-44'-biphenylene diisocyanate, 4,4'-diisocyanate diphenyl ether, and 1,5'-naphthalene diisocyanate. Among these, p-xylylene diisocyanate, m-xylylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, and isophorone diisocyanate are preferred.

It is appropriate that the concentration of halogen atoms in the modified polyester resin of the present invention is 30 to 3,000 eq/l Obg.

-The halogen atom in S has high electronegativity, and when introduced into the molecular skeleton, it is thought that it creates a part with low electron density within the molecule, and dye molecules tend to stably adsorb to this low-density part within the molecule. . Therefore, if the halogen atom density in the resin is lower than the above concentration range, sufficient improvement in coloring sensitivity and color fastness will not be achieved. Furthermore, if the temperature exceeds the above 01° range, the solvent solubility of the resin decreases, making it impossible to coat it on the substrate.

In addition to the halogen atom-containing acid component, the carboxylic acid component of the modified polyester resin in the present invention includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-nartaric acid, p-oxybenzoic acid,
Aromatic oxycarboxylic acids such as P-(hydroquinetogysi)benzoic acid, succinic acid, adipic acid, azelaic acid,
Sebacic acid, aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, Te1-
Mention may be made of unsaturated aliphatic acids such as lahydrophthalic acid and 1,4-cyclohexanedicarboxylic acid, and alicyclic dicarboxylic acids, tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid. Among these acid components, it is preferable that the aromatic dicarboxylic acid is present in an amount of 70 mol % or more based on the total acid components.

In addition to the above-mentioned diols having halogen atoms, glycol components of the modified polyester resin include ethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,3.4-trimethyl-1,3-bentanediol, 3- Methyl-pentane-1,5-diol, 14-cyclohexane dimetatool, ethylene oxide additive of bisphenol A,
Ethylene oxide and propylene oxide adducts of hydrogenated bisphenol A, polyethylene glycol,
Polypropylene glycol, polytetramethylene glycol, 2,2-diethyl-1,3-propanediol,
Examples include 2-n-butyl-2-ethyl-1,3-propanediol.

Among the above glycol components, preferably ethylene glycol, neopentyl glycol, 3-methylpentane-1
, 5-diol, ethylene oxide adduct of bisphenol A, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, and the like. Furthermore, trimethyloles such as trimethylolethane, I.limethylolpropane, glycerin, and pentaerythritol, and tetraols may be used in combination with the above glycol component.

In addition to the above-mentioned copolymerization components, various lactone compounds can be used as copolymerization components in the modified polyester resin of the present invention. Examples of the lactone compound include δ-valerolactone, ε-caprolactone, β-propiolactone, β-2,2-dimethylpropiolactone, and the like. These lactone compounds may be randomly copolymerized in the modified polyester resin of the present invention, and if necessary, the bronch copolymerized modified polyester resin can be prepared by ring-opening addition polymerization to the terminal groups of the modified polyester resin. You can also get it.

The number average molecular weight of the modified polyester resin of the present invention is 2,
000 to 0.000, preferably 5,000 to 50
,000 range. If the molecular weight is less than 2.000, the durability of the dyed layer decreases, and if it exceeds 100,000, the viscosity of the solution becomes too high, making it difficult to pump out, which is not preferred.

As the substrate to which the dyeable resin of the present invention is applied, sheet-like materials such as synthetic paper, nonwoven fabric, and film can be used.

In the present invention, various lubricating substances may be blended in addition to the modified polyester resin of the present invention for the purpose of improving the releasability from the thermal transfer sheet.

The above-mentioned lubricating substances include fluororesins, silicone resins, organic sulfonate compounds, organic phosphate compounds,
Examples include interfacial lubricants such as organic carboxylate compounds.

Further, the modified polyester resin in the present invention may contain an ultraviolet absorber, a radical scavenger, etc., if necessary, for the purpose of improving the light resistance of recorded images. As the above-mentioned compounds, benzophenone KM 4, quinone compounds, etc. are used.

(Function) A site with low electron density is generated in the halogen atom molecular skeleton of the modified polyester resin of the present invention, and such a site becomes a stable adsorption point for sublimable dye molecules, so that the coloring sensitivity to the dye is improved. , dyeing fastness is improved, and high-quality images can be obtained.

(Example) Below, the present invention will be specifically explained with reference to Examples.6 Below, production examples of various modified polyester resins used as Examples in the present invention and their performance evaluation results are shown. In the production examples, "parts" simply indicate parts by weight, and "molecular weight" simply indicate number average molecular weight. Regarding the performance evaluation method, image density and image durability were evaluated, and the measurement methods thereof are as shown below, and the evaluation results are shown in Table 2.

1. Production example of modified polyester resin 1 In an autoclave equipped with a meter and a stirrer, dimethyl terephthalic acid 4.
85 parts, dimethyl isophthalic acid 485 parts, ethylene glycol 443 parts, neopentyl glycol 400 parts, 3
- Promo 1,2-propylene glycol 5 parts and tetrabutoxy titanium) 0.68 parts were charged, 150
Heated at ~230°C for 120 minutes to perform transesterification,
Next, the temperature of the reaction system was raised to 250'C in 30 minutes, and the pressure in the system was gradually reduced to 0.3 m + 1 g or less after 45 minutes, and the reaction was continued under these conditions for an additional 60 minutes, producing a pale yellow transparent modified polyester resin A. Obtained. The molecular weight of the obtained resin was 15,000. Table 1 shows modified polyester resins B-H obtained by a similar manufacturing method. The resin composition was analyzed by 'H-nmr, and the molecular weight was analyzed by GPC.

The concentration of halogen groups contained was determined from elemental analysis values.

Production Example 2 of Modified Polyester Resin 485 parts of dimethyl terephthalic acid, 485 parts of dimethyl isophthalic acid, 409 parts of ethylene glycol, 485 parts of neopentyl glycol, and 0.68 parts of tetrabutoxy titanate were placed in the same autoclave as in Production Example 1.
Heat at 0-230°C for 120 minutes to perform transesterification. The reaction system was then heated to 250'C for 30 minutes,
The pressure of the system was gradually reduced to 0.3 mmt1g or less after 45 minutes, and the reaction was continued under these conditions for an additional 30 minutes to form molecules i12.
A polyester diol (■) of ooO was obtained.

1,100 parts of the above polyester diol was placed in a reaction vessel equipped with a thermometer, a stirrer, and an N-flow cooler, and 70 parts of toluene was added.
After charging and dissolving the isophorone diisocyanate 5
9 parts, and 0.03 parts of dibutyltin diurarate.
The reaction was carried out at 0 to 100°C for 2 hours.

Next, 65 parts of toluene was charged and diluted, and then 3 parts of 2,6-dichlorop-phenylenediamine were added and heated at 80 to 90°C.
After reacting for an hour, the temperature was lowered to 70°C, 135 parts of methyl ethyl ketone was added, and the reaction was further carried out for 2 hours to obtain modified polyester resin J. The molecular weight of the obtained modified polyester M was 40.000.

Production Example 3 of Modified Polyester Resin In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 1100 parts of the polyester diol used in Production Example 2,
After charging and dissolving 66 parts of toluene, 24.5 parts of isophorone diisocyanate and 0.05 parts of dibutyltin dilaurate.
1 part was added thereto and reacted at 90-100'C for 2 hours. Next, 100 parts of toluene and 166 parts of methyl ethyl ketone were charged and the reaction temperature was cooled to 40"C.
Add 9.5 parts and react at 40'C for 1 hour.
A modified polyester resin K of 2.500% was obtained.

Modified polyester resins J and K in Production Example 2.3 above
are shown in Table 1. The resin composition is determined by 'It-nmr.
Molecular weight was analyzed by GPC. The concentration of contained norogen was determined from elemental analysis values.

2. Method for evaluating image density The image receptor sheet and the heat transfer couple sheet are stacked one on top of the other so that the dyeing layer and the coloring material layer are in contact with each other, and the output of the thermal head is set to 0. 7
W/dot, head heating time 8IIs, dot density 3
The cyan and magenta dyes in the color material layer were transferred to the dyed layer by heating with a dot/rail. The density of the resulting transferred image was measured using a Macbeth densitometer.

3. Evaluation method of image durability ■ Evaluation method of moisture resistance and heat resistance Synthetic paper (Yupo PPG-150 manufactured by Oji Yuka Co., Ltd.
) at 50°C and relative humidity (RH) 80
% atmosphere for one week to perform aging. After aging, the degree of transfer of dye #4 onto the synthetic paper was visually observed, and those with a clearly low degree of transfer and those with a high degree of O transfer were rated as ×.

(2) Exposure was carried out for 10 hours under the conditions based on the evaluation method JIS LO842 manufactured by Hiroshi. The image density after the above test was measured using a Macbeth densitometer, and the dye density retention rate (%) was compared with the density before the light fastness test.
).

Using modified polyester resins B-F, J, and K, a dyed layer was provided by the same method as in Example 1, and Example 2 was obtained, respectively.
~8.

Comparative Examples 1 and 2 Using modified polyester resins G and H, dyed layers were provided in the same manner as in Example 1, and Comparative Examples 1 and 2 were prepared, respectively.
And so.

Example 1 Modified polyester resin A is dissolved in a solution of toluene:methyl ethyl ketone = 50:50 to make a 40% solution. To this solution, epoxy modified silicone oil (manufactured by Shin-Etsu Chemical: KF-102) was added by weight of 10% of resin A.
17mm 150μm synthetic paper (manufactured by Oji Yuka: Yuboppc1
No. 50) was coated using a wire bar to obtain a dry coating film of 4 μm. The sheet was dried in an atmosphere at 100°C for 30 minutes to obtain a dyed layer.

Examples 2 to 8 As is clear from Table 2, modified polyester resins containing halogen atoms have excellent performance in terms of dye density, light resistance, and heat resistance.

(Effect of the invention) Conventionally, it has been difficult to satisfy both coloring sensitivity and dyeing fastness with dyeing resins for sublimation transfer image receptors, but by using modified polyester resins containing halogen atoms, The above drawbacks are largely overcome, and it is possible to obtain high-quality images with excellent color density and durability.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Scope of Claims] The dyeing layer of a sublimation transfer image receptor having a base material and a dyeing layer provided on the base material is mainly made of a dyeable resin,
A dyeable resin for a sublimation transfer image receptor, characterized in that the dyeable resin has a modified polyester resin having a halogen atom in its resin skeleton as a main component.