JPH02273292A - Image receiving medium for sublimation type thermal transfer recording - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image receiving medium for sublimation type thermal transfer recording, which is used in combination with a thermal transfer recording medium having a transfer layer containing a heat sublimable dye.

[Conventional technology]

In recent years, the demand for full-color printers has increased year by year, and the recording methods for these full-color printers include electrophotography,
There are inkjet methods, thermal transfer methods, etc., but the thermal transfer method is often used because it is easy to maintain and is noiseless.

This thermal transfer method uses a thermal transfer recording medium (color ink sheet) in which a colorant is dispersed in a heat-fusible substance or an ink layer in which a sublimable dye is dispersed in a resin binder is provided on a substrate. An image-receiving medium (image-receiving sheet) is placed on the ink layer surface, and thermal energy controlled by an electric signal from a laser or a thermal head is applied from the recording medium side to heat-melt transfer or sublimation the ink in that area onto the image-receiving sheet. This is a recording method that forms an image by transferring the image.

This thermal transfer recording method is roughly divided into a heat-melting transfer type and a sublimation transfer type depending on the type of recording medium used.The latter, in principle, uses dyes that respond to heat energy from a thermal head, etc. Since it sublimates in a monomolecular form, it has the advantage that intermediate tones can be easily obtained and the gradation can be controlled at will, and is considered to be the most suitable method for full-color printers.

However, this sublimation type thermal transfer recording method uses a color ink sheet as a recording supply and selectively performs heating recording based on image signals. ) are used one by one, and even if there are unused portions after that, they are discarded, which has the disadvantage of high running costs.

Therefore, in order to improve this drawback, from the viewpoint of the printing method, the speed of the image receiving sheet should be increased by n times the speed of the ink sheet (n>
1), a 0x mode method is used in which printing is repeated with both sheets running. Note that this 0x mode method uses a relative velocity method that gradually shifts the overlap between the part of the ink layer used in the previous time and the part used in the next time.
Printing is performed multiple times using one ink sheet.

Furthermore, from a material standpoint, attempts have been made to replace the conventional synthetic paper with paper such as gravure paper for the image receiving substrate.

[Problem to be solved by the invention]

However, in the conventional sublimation thermal transfer recording method, an image receiving medium has been used in which a dye-receiving layer made of thermoplastic polyester resin, etc., which exhibits strong dyeability against sublimation dyes, is formed on a substrate. , such image-receiving media do not have sufficient hardness, abrasion resistance, peelability, etc. Especially in the 0x mode method, strong frictional force is applied between the transfer recording medium and the image-receiving medium, so it is difficult to prevent fusion during recording. It may cause damage or damage. Specifically, in the 0x mode method, the ratio between the moving speed of the transfer recording medium [V4] and the moving speed of the image receiving medium [v2] is changed, and the larger the ratio of n=(V21/EV,), the more Number of pages that can be printed on one sheet of transfer recording medium (
n) also becomes large, which is preferable. However, during printing, friction occurs because the speeds of the transfer recording medium and the image receiving medium are different, and the larger n is, the greater the force is, which makes it easier for fusion and damage to occur.
The image-receiving medium that can print even if the image size is large is considered to be a preferable image-receiving medium.

In addition, conventional image-receiving media have the disadvantage that when paper is used as the substrate, the adhesion between the transfer recording medium and the image-receiving medium is insufficient, resulting in spots where the dye is not transferred (so-called white spots).

Therefore, the present invention can also be used in the 0x mode method, which requires images with high density 1, high light fastness, and high storage stability, and even higher releasability than normal dye-sublimation thermal transfer recording methods. Excellent removability. The first objective is to provide an image receiving medium for sublimation type thermal transfer recording, and the second objective is to provide an image receiving medium for sublimation type thermal transfer recording that does not cause white spots even when the substrate is paper. .

[Means to solve the problem]

According to the present invention, in an image receiving medium for sublimation type thermal transfer recording having a dye receiving layer on a substrate which can be dyed with a sublimation dye, the receiving layer is a copolymer containing vinyl chloride and a polymerizable unsaturated carboxylic acid as monomer units. An image receiving medium for sublimation type thermal transfer recording is provided, which is characterized in that the image receiving medium is mainly composed of an isocyanate compound, and an elastic layer is provided between the substrate and the dye-receiving layer. Further, the dye-receiving layer has a layer mainly composed of a copolymer containing vinyl chloride and a polymerizable unsaturated carboxylic acid as monomer units and an isocyanate compound, and a layer mainly composed of a vinyl chloride-based resin. An image receiving medium for sublimation thermal transfer recording is provided which is formed by laminating layers in that order.

Specifically, the image receiving medium for sublimation thermal transfer recording of the present invention comprises a copolymer containing vinyl chloride and a polymerizable unsaturated carboxylic acid as monomer units (hereinafter simply referred to as a vinyl chloride resin containing a C0OH group) on a substrate. Since it has a structure with a dye-receiving layer mainly composed of an isocyanate compound, it has excellent dyeability, peelability, light resistance, and storage stability due to the vinyl chloride resin. The hardening reaction between the group and the isocyanate compound further increases the hardness.
It has improved abrasion resistance and # properties, and by providing an elastic layer between the substrate and the dye-receiving layer, it has good adhesion even when paper is used as the substrate. , there will be no white spots.

Furthermore, the dye-receiving layer has a structure in which a layer mainly composed of a vinyl chloride resin containing a COOH group and an isocyanate compound, and a layer mainly composed of a vinyl chloride resin are laminated in that order, thereby further improving the surface resistance. Friction properties are significantly improved.

Next, the present invention will be explained with reference to the drawings.The specific structure and operation of the present invention are as follows.

In the first @, the image receiving medium of the present invention is composed of an image receiving substrate A and a dye receiving layer B. That is, the image-receiving medium of the present invention has a structure in which a dye-receiving layer B mainly consisting of a vinyl chloride resin containing a COOH group and an isocyanate compound is coated on an image-receiving substrate A. Further, 1 indicates a thermal head, and the sublimation thermal transfer recording medium has a heat-resistant layer 2. It is composed of a transfer substrate 3 and a dye transfer M4.

Due to the heating from the thermal head 1, the heat sublimable dye is sublimated and diffused from the dye transfer layer 4 of the sublimation heat transfer recording medium,
The sublimated dye is transferred to the dye receiving fiB of the image receiving medium.

The sublimation dye transferred to the image-receiving medium diffuses into the dye-staining resin forming the dye-receiving layer 8 and dyes the medium.

In the image receiving medium of the present invention, since the dye receiving medium M8 is mainly composed of a vinyl chloride resin containing a C0OH group and an isocyanate compound, there is no heat fusion during recording due to the vinyl chloride resin component contained. An image with good releasability, high image density, high light resistance, and high storage stability can be obtained. Furthermore, the hardness, abrasion resistance, and releasability are further improved by the curing reaction between the C0OH group contained and the isocyanate compound. Even in the 0x mode method, fusion, breakage, etc. do not occur.

Further, in the present invention, a case where six elastic layers C are provided in which elastic layers C can be provided between the image receiving medium A and the dye receiving layer B is shown in FIG. In this case, since there is one elastic layer C, even if paper such as gravure paper is used as the substrate A, pressure can be applied uniformly during recording, and the adhesion to the transfer recording medium is good.

A high-density image with no white spots can be obtained.

Furthermore, in the present invention, the dye-receiving layer.

It is also possible to have a laminated structure of a layer mainly composed of a vinyl chloride resin containing a C0OH group and an isocyanate compound (cured receptor layer) and a layer mainly composed of a vinyl chloride resin (surface dye receptor layer).

A case where the dye-receiving layer has a laminated structure is shown in FIG. 3, for example. That is, in FIG. 3, the dye-receptive layer B in FIG. 2 consists of a cured receptor layer B1 mainly composed of a vinyl chloride resin containing a COOH group and an isocyanate compound, and a vinyl chloride layer laminated thereon. It differs from the case shown in FIG. 2 in that it consists of a laminate with a surface dye-receiving layer B2 whose main component is a resin. In this case, the dye sublimated from the dye transfer layer 4 of the sublimation thermal transfer recording medium is mainly dyed into the surface dye-receiving layer B2 of the image-receiving medium. The abrasion resistance of the material is significantly improved. This seems to be because the mold release agent such as silicone oil in the surface dye-receiving layer B2 is more likely to be concentrated in the vicinity of the surface due to the presence of the cured receptor layer B1, thereby increasing the effect.

Dye receiving layer B of the present invention (cured receiving layer B in case of laminated structure)
The vinyl chloride resin containing Coo) 1 group used in and contains a polymerizable unsaturated carboxylic acid as a subcomponent. In this case, the monopolymerizable unsaturated carboxylic acid is
Examples include acrylic acid, methacrylic acid, and maleic acid. Also.

In addition to vinyl chloride and a polymerizable unsaturated carboxylic acid, this copolymer also contains other comonomers, such as vinyl alcohol derivatives such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, and acrylic acid. (Meth) such as butyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.
Acrylic acid derivatives; maleic acid derivatives such as diethyl maleate and dibutyl maleate; methyl vinyl ether,
Vinyl ether derivatives such as ethyl vinyl ether and butyl vinyl ether; olefins such as ethylene and propylene may also be included.

The monomer ratio in the copolymer is 60 to 90 for vinyl chloride.
Weight 2, polymerizable unsaturated carboxylic acid 0.5-5% by weight.

In addition, the amount of components other than vinyl chloride and polymerizable unsaturated carboxylic acid is preferably about 5 to 39.5 weight 2.

Preferred specific examples of this copolymer include the following.

vinyl chloride/maleic acid copolymer, Vinyl chloride/acrylic acid copolymer.

Vinyl chloride/vinyl acetate/maleic acid copolymer, vinyl chloride/vinyl acetate/acrylic acid copolymer.

Ethylene/vinyl chloride/maleic acid copolymer.

Ethylene/vinyl chloride/acrylic acid copolymer, vinyl chloride/vinyl propionate/acrylic acid copolymer.

Vinyl chloride/vinyl propionate/maleic acid copolymer, etc.

Among these, vinyl chloride/vinyl acetate/maleic acid copolymer is preferably used, and its commercially available products include 5, for example, VMCHlVMCC manufactured by Union Carbide Co.
Denkabinyl 1000C110 manufactured by Denki Kagaku Kogyo Co., Ltd.
Examples include 0OC3, 100OCK.

Further, as the isocyanate compound used in the dye-receiving JejB (cured receptor layer B in the case of a laminated structure) of the present invention, tolylene diisocyanate, hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, triphenylmethane triisocyanate, etc. Various isocyanate compounds are used, and adducts of these with hexanetriol and the like can also be used. The ratio of the vinyl chloride resin containing a C0OH group to the isocyanate compound is preferably in the range of 0.2 to 2.0 in terms of NCO/C0OH molar ratio.

In addition, examples of the vinyl chloride resin used in the surface dye-receiving layer B2 in the case of a laminated structure include polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, etc.
It is preferable that the vinyl chloride component is 80 double fluorite or more. Commercially available products include 5, for example, manufactured by Union Carbide (7).
VYHHlVYNS, VYHD, VYLF, etc. and Denkabinir 10100O manufactured by Denki Kagaku Kogyo Co., Ltd.

1000A, 100OL, 100OD, MHElo
o, ME120, etc.

Note that the dye receiving layer B of the present invention (cured receiving layer B□ in the case of a laminated structure) contains a conventionally known dyeable resin, such as a polyester resin, a polycarbonate resin, a styrene resin, a silicone resin, etc. Especially in the case of a single layer structure, it is preferable to include a vinyl chloride resin.

Furthermore, a release agent such as amino-modified silicone, epoxy-modified silicone, alkyd-modified silicone, etc. can be contained in the dye-receiving layer B (in the case of a laminated structure, the surface dye-receiving layer at). By using these silicones,
The effect of preventing heat fusion with the transfer recording medium is further improved. The amount added is preferably 10% by weight or less based on the amount of resin in the receiving layer.

Incidentally, a filler can also be contained in the dye-receiving layer. Examples of fillers include white pigments such as silica, titanium oxide, and calcium carbonate, and the amount added is preferably 5 to 60% by weight 2 based on the amount of resin in the receptor layer. , a surfactant, an ultraviolet absorber, an antioxidant, etc. can also be included as appropriate.

Further, in the image receiving medium of the present invention, an elastic layer C is provided on the substrate A.
In the case where the core layer is provided, examples of the material constituting the core layer include those having rubber elasticity such as butadiene rubber, urethane rubber, styrene-butadiene rubber, silicone rubber, chloroprene rubber, and acrylic rubber.

The substrate A in the image receiving medium of the present invention may be synthetic paper, baryta paper, art paper, coated paper, gravure paper, plastic film, etc. alone or in a laminate thereof;
Preferably used. The image receiving medium of the present invention comprises dye-receiving NB
(In the case of a laminated structure, the hardening-receptive NB coating) contains C0OH groups, which improves its adhesion, so it has sufficient adhesive strength even with baryta paper, plastic films, etc., which had low adhesion with conventional dye-receiving layers. can be kept and used satisfactorily.

In addition, in conventional image-receiving media, when paper such as gravure paper is used as a substrate, the adhesion with the transfer recording medium is insufficient, resulting in
White spots may occur in the image or the image intensity may decrease, but especially in the present invention, when an elastic layer is provided between the substrate and the dye-receiving layer, pressure is not applied uniformly during recording. , high image density without white spots can be obtained.

The thickness of the first elastic layer and the dye-receiving layer is preferably about 1 to 10 degrees.

〔Effect of the invention〕

Since the image receiving medium for sublimation type thermal transfer recording of the present invention has the above structure, the image receiving medium of claim (1) has the following features: (a) There is no thermal fusion during recording, the peelability is good, and the n-time mode (b) Images with high image density, high light resistance, and high preservability can be obtained; (c) Even when using baryta paper or plastic film as a substrate, It has the outstanding effect of maintaining sufficient adhesive strength.

In addition, in the image receiving medium of claim (2), (d) even when paper such as gravure paper is used as the substrate, the adhesion with the transfer recording medium is good and high density images without white spots can be obtained. It will be done.

This effect is added.

Furthermore, in the image receiving medium according to claim (3).

(e) Friction resistance is further improved.

This effect is added.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples. Note that all parts shown below are based on weight.

Example 1 A mixture having the following composition was thoroughly mixed and dispersed to prepare a dye-receiving layer coating liquid [liquid A].

[Liquid A]

Vinyl chloride/vinyl acetate/maleic acid 10 parts Copolymer (trade name VMCH; manufactured by Union Carbide) Toluene 40 parts Methyl ethyl ketone 40 parts Next, [Liquid A] was mixed with a wire bar into synthetic paper about 150 mm thick. (Product name Yupo FPG-150; manufactured by Oji Yuka Synthetic Paper Co., Ltd.)
After drying at a drying temperature of 75° C. for 1 minute to form a dye-receiving layer with a thickness of about 5 cm, the dye-receiving layer was further stored at 80° C. for 3 hours to harden, thereby producing an image-receiving medium of the present invention.

On the other hand, as a sublimation transfer recording medium, a coating liquid for an ink layer (i.e., a dye transfer layer) having the following formulation was applied onto a PET film with a thickness of 6 lines on which a silicone cured resin film (thickness: about 1 ts) was provided as a backing plate. Apply [Liquid B] to a thickness of about 2 coats,
A transfer recording medium was obtained.

[Liquid B]

Methyl ethyl ketone 45 parts Toluene 45 parts The obtained transfer recording medium and image receiving medium are superimposed so that the ink layer of the transfer recording medium and the dye receiving layer of the image receiving medium face each other,
Images were recorded from the back side of the transfer recording medium by changing the heating energy using a thermal head. Here, recording was performed under the condition that the speed ratio between the transfer recording medium and the image receiving medium was n:10.

The recording density of the thermal head was 6 dots/mm, and the recording output was 0.42 W/dot.

Example 2 An image receiving medium of the present invention was produced in the same manner as in Example 1, except that the following [Liquid C] was used instead of [Liquid A].

[Liquid C]

Toluene 40 parts Methyl ethyl ketone 40 parts Subsequently, image recording was carried out in the same manner as in Example 1. Comparative Example 1 Except that the following CD liquid] was used as the coating liquid for the dye-receiving layer.
An image receiving medium for comparison was prepared in the same manner as in Example 1, and images were recorded.

[Liquid D]

Methyl ethyl ketone 40 parts Comparative Example 2 A comparative image receiving medium was prepared in the same manner as Comparative Example I, except that the following [Liquid H] was used instead of [Liquid D] in Comparative Example 1, and image recording was performed. Ta.

[H liquid]

Toluene 40 parts Methyl ethyl ketone 40 parts or more The surfaces of the transfer recording medium and image receiving medium after image recording were visually observed. The results are shown in Table 1.

Table 1: 40 parts of toluene Example 3 A mixture having the following composition was thoroughly mixed and dispersed, and the coating liquid for the elastic layer [liquid H] and the coating liquid for the dye-receiving layer [liquid G] were applied at tAW! did.

[H liquid]

50 parts of water [Liquid G] 40 parts of toluene 40 parts of methyl ethyl ketone Next, [Liquid H] was coated on about 60 μm thick Clavia paper (manufactured by Honshu Paper Industries) using a wire bar. After forming the elastic layer, [Liquid G] was applied onto the elastic layer using a wire bar to form a dye-receiving layer having a thickness of about 3 mm, thereby producing an image-receiving medium of the present invention.

The obtained image-receiving medium and a transfer recording medium similar to that obtained in Example 1 were placed one on top of the other so that the ink layer of the transfer recording medium and the dye-receiving layer of the image-receiving medium faced each other, and thermal radiation was applied from the back side of the transfer recording medium. Record an image by changing the heating energy of the head, change the speed ratio of the transfer recording medium and the image receiving medium to observe the presence or absence of thermal fusion, and observe the image after recording (presence or absence of white spots), Light resistance and storage stability tests were conducted. The recording density of the thermal head is 6 dots/I.
The recording output was 0.42υ/dot.

Example 4 Example 3 except that the following [Liquid H] and [Liquid 1] were used instead of [Liquid H] and [Liquid G], respectively.
An image receiving medium of the present invention was produced in the same manner as described above.

[H liquid]

Silicone rubber (product name DX35-203A; manufactured by Toray Silicone Co., Ltd.) [1 liquid] Next, apply [K liquid] on the cured receptor layer to a thickness of about 2/Jm.
An image-receiving medium of the present invention was prepared in the same manner as in Example 3, except that a surface dye-receiving layer was formed.

[J liquid]

Toluene: 40 parts Methyl ethyl ketone: 40 parts Subsequently, images were recorded in the same manner as in Example 3, and H detection for the presence or absence of thermal fusion and a light resistance test were conducted.

Example 5 In place of the dye-receiving layer coating liquid [G liquid] in Example 3, the following cured receptor layer coating liquid [J liquid] and surface dye-receiving layer coating liquid [K liquid] were used, and the elastic layer was first coated. [Liquid J] was applied on top to form a cured receptor layer with a thickness of about 2 pa, and then image recording was performed in the same manner as in Example 3 using 40 parts of toluene and 40 parts of methyl ethyl ketone [Liquid K] 40 parts of toluene and 40 parts of methyl ethyl ketone. Observation of the presence or absence of heat fusion, light resistance test, etc. were carried out.

Comparative Example 3 A comparative image receiving medium was prepared in the same manner as in Example 3, except that the following [Liquid L] was used as the coating liquid for the dye-receiving layer, and no elastic layer was provided. Whether there is fusion or not! [Liquid L] 40 parts of toluene 40 parts of methyl ethyl ketone Comparative Example 4 The same procedure as in Comparative Example 3 was used except that the following [Liquid N] was used in place of [Liquid CL] in Comparative Example 3. Create an image receiving medium for comparison, record images, and observe the presence or absence of thermal fusion.
Light resistance tests etc. were conducted.

[M liquid]

Methyl ethyl ketone 40 parts Comparative Example 5 Except for using the above [liquid] as the coating liquid for the dye-receiving layer.
A comparative image receiving medium was prepared in the same manner as in Example 3, and an image was recorded thereon, and a W4 test for the presence or absence of heat fusion, a light resistance test, etc. were conducted.

The above results are shown in Table 2. The test method was as follows.

(i) Heat fusion: The moving speed ratio of the transfer medium and the image receiving medium [■2/v1]: The peeling state wA is observed by changing n from 1 to IO.

(ii) Light resistance: The recorded sample is exposed to light for 24 hours using a xenon fade meter, and changes are observed.

(in) Preservability: Observe changes after recording the sample after leaving it in the dark at 60°C for 100 hours.

toluene 40 copies Table 2 There is.

A... Image receiving substrate, B... Dye receiving layer, 8. ...Cured receiving layer, B2...Surface dye receiving layer, C...Elastic layer, ■...Thermal head, 2...Heat-resistant layer of transfer recording medium, 3...Transfer of transfer recording medium Substrate, 4... Dye transfer layer of transfer recording medium.

From the above results, the image receiving medium for sublimation thermal transfer recording of the present invention has no thermal adhesion during recording, has good releasability, does not generate adhesion even in the n-fold mode, and has good light resistance and storage stability. It can be seen that images with excellent quality can be obtained. Furthermore, it can be seen that the image-receiving medium for sublimation type thermal transfer recording of the present invention in which an elastic layer is provided between the substrate and the dye-receiving layer does not cause white spots even when paper is used as the substrate.

[Brief explanation of drawings]

1 to 3 are schematic sectional views showing the image receiving mechanism of the image receiving medium for sublimation thermal transfer recording according to the present invention, and also include a schematic sectional view of the sublimation thermal transfer recording medium.

Claims (3)

[Claims] (1) In an image-receiving medium for sublimation type thermal transfer recording having a dye-receiving layer on a substrate to which a sublimation dye can be dyed, the receptive layer is made of a copolymer containing vinyl chloride and a polymerizable unsaturated carboxylic acid as monomer units and an isocyanate. 1. An image-receiving medium for sublimation thermal transfer recording, characterized in that the main component is a compound. (2) The image-receiving medium for sublimation thermal transfer recording according to claim (1), further comprising an elastic layer provided between the substrate and the dye-receiving layer. (3) The dye-receiving layer consists of a layer mainly composed of vinyl chloride and a copolymer containing a polymerizable unsaturated carboxylic acid as a monomer unit and an isocyanate compound, and a layer mainly composed of a vinyl chloride resin, which are laminated in that order. The image-receiving medium for sublimation type thermal transfer recording according to claim 1 or 2, wherein the image-receiving medium is made of: