JP3352824B2 - Magenta color dye for sublimation transfer recording, ink composition for sublimation transfer recording, and transfer sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye for sublimation transfer recording (hereinafter abbreviated as "sublimation dye") used for a color hard copy or the like by a sublimation thermal transfer recording method, and an ink composition for sublimation transfer recording containing the dye. And a transfer sheet.

[0002]

2. Description of the Related Art A thermal transfer recording system using a sublimation dye uses a thin condenser paper having a thickness of several microns or a transfer sheet obtained by applying a transferable dye made of an ink to a PET film. This is one of the thermal transfer printing methods in which the image is selectively heated and transferred to a recording sheet as a recording material, and is currently used as a means for image recording (hard copy) various image recording information.

[0003] The sublimation dye used here is required to be rich in color, excellent in color mixing, strong in dyeing power, and relatively high in stability. The recording method described above has a large characteristic not found in other printing methods in that the amount of dye to be transferred depends on thermal energy and the dye concentration after dyeing can be controlled in an analog manner.

The azo dyes proposed in the prior art (Japanese Patent Application Laid-Open No. 61-227092) generally have a high molar extinction coefficient and potentially have the transferability necessary for the transfer image density. There are many. However, on the other hand, the dye is crystallized on the ribbon due to insufficient solubility in the solvent, making it impossible to prepare a high-concentration ink or having poor compatibility with the ribbon binder, and significantly impairing the thermal transfer efficiency of the dye. The problem is that the dyeing ability of the dye after the transfer is insufficient, so that the one that adheres to the image surface becomes dirty or the quality of the image itself deteriorates, and the durability of the most important dye itself, especially the light resistance In many cases, they have problems such as inferior properties and cannot withstand long-term storage, and very few dyes have solved all these problems.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a magenta color dye for sublimation transfer recording excellent in solubility, dyeing power, durability and light fastness, and an ink composition for sublimation transfer recording containing the dye. , And a transfer sheet.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, generally, the transfer speed of a sublimation dye at the time of transfer is determined by the interaction between the dye molecules. , And that are related to the interaction between the dye molecules and the binder resin used in the ink, that is,
The best dyes are those that have high solubility of the sublimation dye in the ink solvent, low melting point, and small enough that the interaction with the binder resin used in the ink does not impair the storage stability after the production of the transfer sheet. The inventors have found that a magenta colorant represented by the following general formula (1) is suitable as a sublimation dye satisfying the above-mentioned conditions, and have completed the present invention.

That is, the present invention provides the following general formula (1)

[0008]

Embedded image [Wherein, R ¹ represents a hydrogen atom, a C ₁ -C ₄ alkyl group, C ₁
~ C ₆ alkoxy group or a halogen atom,
R ² and R ³ are the same or independently a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₂ -C ₅ alkylcarbonylamino group, a C ₂ -C ₅ alkoxy group; A carbonylamino group, a C ₁ -C ₄ alkylsulfonylamino group,
Or a halogen atom, and R ⁴ and R ⁵ are the same or independently a hydrogen atom, a substituted or unsubstituted alkyl group, C ₃ -C ₆
Alkenyl group, C ₇ -C ₁₀ aralkyl group, C ₆ -C ₁₀
Indicates an aryl group. And a magenta colorant for sublimation transfer recording. The present invention was a temperature comprising the above dye, binder resin and organic solvent and / or water
It is a flower transfer recording ink composition, further comprising a substrate sheet and a dye-carrying layer formed on one surface of the substrate sheet,
A transfer sheet wherein the dye contained in the dye-supporting layer is the above-described dye.

Hereinafter, the present invention will be described in detail.

The sublimation dye according to the present invention has the above general formula (1)
In the general formula (1), R ¹ is
Hydrogen atom, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, C ₁ -C ₄ alkyl groups such as tert- butyl group, a methoxy group, an ethoxy group , N-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, se
C ₁ -C ₆ alkoxy groups such as c-butoxy group, tert-butoxy group, n-hexyloxy group, fluorine, chlorine,
Shows a halogen atom such as bromine and iodine.

In the general formula (1), R ² and R ³ are the same or independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- C ₁ such as butyl group and tert-butyl group
Alkyl group -C _4, a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, isobutoxy group, sec- butoxy group, tert- butoxy group, C ₁ ~ such as n- hexyloxy group an alkoxy group having C _6, a methyl group, an ethylcarbonylamino group, n- propyl carbonyl group, isopropylamino carbonyl amino group, n- butylcarbonyl alkylcarbonylamino group C ₂ -C _5, such as an amino group, methoxycarbonylamino Group, ethoxycarbonylamino group, n-
C such as a propoxycarbonylamino group, an isopropoxycarbonylamino group and an n-butoxycarbonylamino group
₂ -C ₅ alkoxycarbonyl group, methylsulfonylamino group, ethylsulfonylamino group, n- propylsulfonyl group, isopropylsulfonyl amino group, n- butylsulfonyl C ₁ -C ₄ alkylsulfonylamino group such as an amino group Or a halogen atom such as fluorine, chlorine, bromine and iodine.

In the general formula (1), R^Four, R^FiveEach
Hydrogen atoms, methyl groups, ethyl groups,
n-propyl group, isopropyl group, n-butyl group, iso-
Butyl group, sec-butyl group, tert-butyl group, n
-Pentyl group, n-hexyl group, n-heptyl group, n-
C such as octyl group₁~ C₈Alkyl group, allyl group, 2
-Methyl-2-propenyl group, 2-butenyl group, 3-bu
C such as a thenyl group and a 3-methyl-2-butenyl group;_Three~ C₆of
C such as alkenyl group, benzyl group, phenethyl group, etc.₇~ C
_TenAralkyl, phenyl, p-tolyl, m-
Ryl, o-tolyl, p-chlorophenyl, m-c
C such as lolophenyl group and o-chlorophenyl group₆~ C_Ten
And the like. Of these, the alkyl group is substituted
The substituent may be, for example, methoxy
Group, ethoxy group, n-propoxy group, isopropoxy
Group, n-butoxy group, isobutoxy group, sec-butoxy
Si group, tert-butoxy group, n-hexyloxy group, etc.
C₁~ C₆Alkoxy, methoxymethoxy, meth
Xyethoxy group, ethoxyethoxy group, methoxypropo
Xy, ethoxypropoxy, propoxypropoxy
C such as a group_Two~ C₆An alkoxyalkoxy group, phenoxy
Group, m-methylphenoxy group, o-methylphenoxy group
Group, p-chlorophenoxy group, m-chlorophenoxy group
C, o-chlorophenoxy group, etc.₆~ C₁₂Aryl
Oxy group, thiophenoxy group, p-methylthiophenoxy
Si group, m-methylthiophenoxy group, o-methylthiophene
C such as an enoxy group₆~ C₁₂Thioaryloxy group,
Tylcarbonylamino group, ethylcarbonylamino group,
n-propylcarbonylamino group, isopropylcarbo
C such as nilamino group and n-butylcarbonylamino group_Two
~ C_FiveAn alkylcarbonylamino group, methoxycarbo
Nilamino group, ethoxycarbonylamino group, n-pro
Poxycarbonylamino group, isopropoxycarbonyl
C such as amino group and n-butoxycarbonylamino group_Two~
C_FiveAlkoxycarbonylamino group, methyl carbonyl
Group, ethylcarbonyl group, n-propylcarbonyl
Group, isopropylcarbonyl group, n-butylcarbonyl
C such as a group_Two~ C_FiveAlkylcarbonyl group, methylcarbo
Xy group, ethyl carboxy group, n-propyl carboxy
Group, isopropylcarboxy group, n-butylcarboxy
C such as a group_Two~ C_FiveAlkyl carboxy group, methoxy
Boxoxy, ethoxycarboxy, n-propoxy
Boxoxy group, isopropoxycarboxy group, n-butoxy
C such as carboxy group_Two~ C_FiveAn alkoxycarboxy group,
Methoxycarbonyl methoxy group, ethoxycarbonyl
Toxyl group, ethoxycarbonylmethoxy group, n-propo
Xycarbonylmethoxy group, isopropoxycarbonyl
C such as methoxy group and n-butoxycarbonylmethoxy group
_Three~ C₆An alkoxycarbonylalkoxy group, fluorine,
Examples include halogen atoms such as chlorine, bromine and iodine, and cyano groups.
I can do it.

The magenta colorant represented by the general formula (1) according to the present invention can be prepared by diazotizing an aniline (a) having a dicyanoethenyl group represented by the following reaction formula, ) And diazo coupling.

[0014]

Embedded image In the present invention, it is also possible to produce an ink composition for sublimation transfer recording using the dye produced by the above method, and to supply the ink composition in the form of an ink.

As a method for producing an ink composition for sublimation transfer recording using the dye of the present invention, a dye is prepared by using an appropriate resin,
What is necessary is just to mix with a solvent etc. In this case, the amount of the dye in the ink composition for sublimation transfer recording is usually 1 to 10% by weight, preferably 2 to 5% by weight.

The resin used in producing the above ink composition may be a resin used in ordinary printing inks, such as rosin, phenol, xylene, petroleum, vinyl, polyamide and alkyd. , Nitrocellulose, oil-based resins such as alkyl celluloses,
Alternatively, aqueous resins such as maleic acid, acrylic acid, casein, shellac and glue can be used. In this case, the amount of the resin in the ink composition for sublimation transfer recording is preferably usually 1 to 20% by weight based on the total weight of the ink composition.

Solvents used in producing the ink composition include alcohols such as methanol, ethanol, propanol and butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, and aromatics such as benzene, toluene and xylene. And general solvents such as esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, hydrocarbons such as ligroin, cyclohexane and kerosene, and dimethylformamide. When an aqueous resin is used, water or a mixture of water and the above-mentioned solvents can be used.

As a substrate on which the ink is applied, thin paper such as condenser paper and glassine paper, and a plastic film having good heat resistance such as polyester, polyamide and polyimide are suitable. 2-50 to improve heat transfer efficiency from recording head to dye
A thickness of about μm is appropriate. The dye-carrying layer provided on the surface of the substrate can be prepared by applying the above-described ink to the substrate.

A heat-resistant lubricating layer for preventing fusion with the thermal recording head may be provided on the surface of the substrate opposite to the dye-carrying layer.

Examples of the recording material include polyolefin resins such as polyethylene and polypropylene; halogenated resins such as polyvinyl chloride and polyvinylidene chloride;
Copolymerization of vinyl resins such as polyvinyl alcohol, polyvinyl acetate and polyacrylic ester, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, and olefins such as ethylene and propylene with other vinyl monomers Cellulosic resins such as system resins, ionomers, cellulose diacetate, and cellulose triacetate;
Examples thereof include fibers, woven fabrics, films, sheets, and molded products made of a resin such as polycarbonate, polysulfone, and polyimide. Particularly preferred are woven fabrics, sheets or films made of polyethylene terephthalate.

Further, in the present invention, the resin obtained by adding acidic fine particles such as silica gel to the resin is coated on a plain paper, impregnated, or laminated with a resin film, or specially treated by acetylation. By using processed paper as a recording material, good recording with excellent image stability under high temperature and high humidity can be performed. In addition, films of various resins or synthetic paper made therefrom can also be used.

Further, after the transfer recording, for example, a polyester film is hot-pressed and laminated on the transfer recording surface, so that the coloring of the dye can be improved and the storage stability of the recording can be improved.

As a thermal transfer method, a transfer sheet is prepared by applying the ink composition obtained by the above method on an appropriate substrate, and the sheet is superimposed on a recording material. A method of heating and pressurizing with a head can be used, in which case the dye on the sheet is transferred onto the recording material.

[0024]

The present invention will be described below in detail with reference to examples. Parts in Examples are parts by weight. % Indicates% by weight.

Example 1 151 parts of p-nitrobenzaldehyde, 73 parts of malononitrile and 700 parts of ethanol were mixed and reacted at 70 ° C. for 2 hours. The reaction mass was filtered at room temperature, washed with ethanol and water, and dried to obtain 181 parts of 4- (2,2-dicyanoethenyl) nitrobenzene.

Then, 200 parts of water, 200 parts of ethanol
And 151 parts of iron powder and 9 parts of 35% hydrochloric acid, and the mixture was heated to 70 ° C. Next, 180 parts of 4- (2,2-dicyanoethenyl) nitrobenzene was mixed and reacted for 3 hours. After the reaction, the reaction product was separated by filtration, and the filter cake was dissolved in 40 parts of N, N-dimethylimidazolidinone and filtered again. The filtrate was poured into 400 parts of water, and the resulting crystals were separated by filtration, dried and dried to give 4- (2,2-dicyanoethenyl) aniline.
31 parts were obtained.

Next, 318 parts of 98% sulfuric acid and 24 parts of sodium nitrite were mixed and cooled to 0 ° C. 4- (2,2
-Dicyanoethenyl) aniline (60 parts) at 0 ° C.
Allowed to react for hours. 97 parts of 3- (N, N-diallylamino) acetanilide was added and reacted at 0 ° C. for 1 hour, and further 770 parts of 32% sodium hydroxide was added and reacted for 1 hour. The reaction mass was filtered, washed with water and washed with methanol to obtain 72 parts of a compound represented by the following formula (A).

[0028]

Embedded image The absorption maximum wavelength (λma) of the compound in toluene
x) was 535 nm.

Further, using the compound of the formula (A), an ink composition was prepared by the following method, a transfer sheet and a recording material were prepared, and recording and transfer were performed. (1) Preparation of ink composition Dye of the above formula (A) 3 parts Polybutyral resin 4.5 parts Methyl ethyl ketone 46.25 parts Toluene 46.25 parts The dye mixture having the above composition is mixed with glass beads using a paint conditioner. The ink composition was prepared by mixing for 30 minutes. (2) Preparation of transfer sheet The above ink was applied to a 9 μm thick polyethylene terephthalate film whose back surface was heat-treated using a gravure calibrator (plate depth 30 μm) so that the dry coating amount was 1.0 g / m ^2. Coated and dried. (3) Preparation of recording material Polyester resin 0.8 part (Vylon 103 Toyobo; Tg = 47 ° C.) EVA polymer plasticizer 0.2 part (Elvaloy 741p Mitsui Polychemicals; Tg =
Amino modified silicone 0.04 parts (KF-857 Shin-Etsu Chemical Co., Ltd.) Epoxy modified silicone 0.04 parts (KF-103 Shin-Etsu Chemical Co., Ltd.) Methyl ethyl ketone / toluene / cyclohexane (weight ratio 4: 4: 2) 9.0 parts were mixed to prepare a coating solution. Synthetic paper (Oji Yuka, YUPO FPG # 150) and bar coater (RK Pri)
nt Coat Instruments manufactured by N
o. Using 1), the coating liquid was applied at a rate of 4.5 g / m ² when dried, and dried at 100 ° C. for 15 minutes. (4) Transfer Recording The transfer sheet and the recording material are superposed on each other with the ink-coated surface and the coating liquid-coated surface facing each other. Recording was performed under the condition of 0.0 millisecond, and a magenta color recording having a maximum transfer density of 2.86 was obtained.

The maximum transfer density was measured using a densitometer RD-514 manufactured by Macbeth Co., USA (filter: Ratten No. 58).

The maximum transfer density was calculated by the following equation.

Maximum transfer density = 1 log ₁₀ (I ₀ / I) I ₀ = intensity of light reflected from a standard white reflector I = intensity of light reflected from a test object Light resistance test of the obtained recording Was carried out using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ± 2 ° C., with little change in color after 40 hours of irradiation and stability of images under high temperature and high humidity. It was excellent.

The fastness of the obtained recorded image was measured at 50 ° C.
The image was determined by the sharpness of the image after being left in the atmosphere for 48 hours, and the coloring when the surface was rubbed with white paper.
The sharpness of the image did not change, the white paper was not colored, and the fastness of the recorded image was good.

Example 2 In the same manner as in Example 1, a compound represented by the following formula (B) was synthesized. The maximum absorption wavelength (λmax) of this compound in toluene was 535 nm.

[0035]

Embedded image Preparation of ink, preparation of a transfer sheet and a recording material, and transfer recording were performed in the same manner as in Example 1, and a magenta color record having a maximum transfer density of 2.67 was obtained.

All of these records were subjected to a light resistance test in the same manner as in Example 1. As a result, the records hardly changed, and the stability of images under high temperature and high humidity was excellent.

A fastness test was conducted in the same manner as in Example 1. However, the sharpness of the image did not change, and the white paper was not colored.
The fastness of the recorded image was good.

Examples 3 to 22 Magenta dyes shown in Table 1 were produced in the same manner as in Example 1, and ink preparation, transfer sheet and recording material preparation, and transfer recording were performed in the same manner. The light fastness test and the fastness test were all carried out in the same manner as in Example 1 for the recordings of Example 1. The maximum transfer density and test results of the obtained recording are as shown in Table 1.

All of these records were subjected to a light resistance test in the same manner as in Example 1. As a result, the records showed little change, and were excellent in image stability under high temperature and high humidity.

A fastness test was conducted in the same manner as in Example 1. However, the sharpness of the image did not change, and the white paper was not colored.
The fastness of the recorded image was good.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3] Light resistance ○: Almost no fading occurs after irradiation for 40 hours.

Fastness ○: The sharpness of the image does not change,
Preparation of ink, preparation of a transfer sheet and a recording material, and transfer recording were carried out in the same manner as in Example 1 for the dye compounds shown in Table 2 without coloring white paper. Further, a light resistance test and a fastness test were performed in the same manner as in Example 1. Table 2 shows the maximum transfer density of the obtained recording and the test results.

As can be seen from this table, the maximum transfer density,
No resin satisfying the conditions of light fastness and fastness at the same time was obtained, and further, the poor compatibility of the dye with the binder resin resulted in an unclear image, markedly colored white paper, and poor.

[0046]

[Table 4] Lightfastness: Discoloration is observed after irradiation for 40 hours.

Fastness ×: The image became unclear and the white paper was markedly colored.

[0048]

The magenta dye represented by the general formula (1) of the present invention can control the transfer amount of the dye by changing the thermal transfer time and the energy applied to the thermal recording head, so that the gradation recording can be performed. And is suitable for full-color recording.

Further, since it is stable against heat, light, moisture, chemicals, etc., it does not decompose during transfer recording, and the obtained record has excellent storage stability.

Further, since the dye of the present invention has good solubility in organic solvents and good dispersibility in water, it is easy to prepare a high-concentration ink which is uniformly dissolved or dispersed. It is a dye of practical value that can provide good transfer density recording.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Keisuke Takuma, Inventor 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. Dai Nippon Printing Co., Ltd. (72) Inventor Hiroshi Eguchi 1-1-1, Ichigaya Kagacho, Shinjuku-ku, Tokyo Dainippon Printing Co., Ltd. (72) Inventor Kazuya Yoshida 1-1, Ichigaga-cho, Shinjuku-ku, Tokyo No. 1 Inside of Dai Nippon Printing Co., Ltd. (56) References JP-A-59-11362 (JP, A) JP-A-3-256793 (JP, A) JP-A-62-111190 (JP, A) JP-A-2 -67189 (JP, A) JP-A-5-584 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/38-5/40 CAPLUS (STN) REGISTRY (STN) MARPAT ( STN)

Claims (3)

(57) [Claims] 1. A compound of the general formula (1) [Wherein, R ¹ represents a hydrogen atom, a C ₁ -C ₄ alkyl group, C ₁
~ C ₆ alkoxy group or a halogen atom,
R ² and R ³ are the same or independently a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₂ -C ₅ alkylcarbonylamino group, a C ₂ -C ₅ alkoxy group; A carbonylamino group, a C ₁ -C ₄ alkylsulfonylamino group,
Or a halogen atom, and R ⁴ and R ⁵ are the same or independently a hydrogen atom, a substituted or unsubstituted alkyl group, C ₃ -C ₆
Alkenyl group, C ₇ -C ₁₀ aralkyl group, C ₆ -C ₁₀
Represents an aryl group. And a magenta colorant for sublimation transfer recording. 2. A sublimation transfer recording, characterized by containing a sublimation transfer recording magenta dye, a binder resin and organic solvent and / or water of the general formula according to claim 1 (1) Ink composition. 3. A sublimation represented by the general formula (1) according to claim 1, comprising a base sheet and a dye supporting layer formed on one surface of the base sheet, wherein the dye contained in the dye supporting layer is represented by the general formula (1).
A transfer sheet, which is a magenta color dye for transfer recording.