JPH02103183A - Image recording receiving sheet - Google Patents

Abstract

PURPOSE:To obtain a transfer image of high accuracy improved in gradation reproducibility in thermal transfer recording and to also obtain a transfer image improved in transfer efficiency in thermal pressure-sensitive recording by containing polymer microspheres in the heat insulating layer having a void structure provided on a base material. CONSTITUTION:The heat-meltable ink layer of a thermal transfer film is superposed on the heat insulating layer of a receiving sheet provided with said heat insulating layer composed of polymer microspheres and thermal recording is performed by a thermal head through the non-ink layer of the thermal transfer film. By this method, heat-meltable ink is melted to penetrate into the void structure part in the heat insulating layer. Further, the heat of the thermal head is stored in said heat insulating layer. Therefore, even when energy to be applied is reduced, thermal recording becomes possible and a transfer image good in gradation reproducibility is obtained. In thermal pressure-sensitive recording, the inner phase oil containing dye or pigment enclosed in a microcapsule is discharged by destructing the microcapsule under pressure but easily penetrates into the void structure part of the heat insulating layer part of the receiving sheet and a transfer image improved in transfer efficiency can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application in the Prison Industry The present invention is applicable to image transfer and pressure-sensitive recording using a thermal edge device such as a thermal printer, or photosensitive and pressure-sensitive recording using photocurable pear microcapsules. 〇(5) Conventional technology regarding transfer sheet for Kenml record In recent years, thermal printer, thermal facsimile 48
Thermal transfer recording, which is used to form transferred images on plain paper, has been actively developed. This thermal transfer recording is easy to maintain because the mechanism of the device is quantitative, and the price and maintenance are low. Also, it is possible to record clearly and accurately with low energy consumption, and it uses multi-colored ink sheets. It has been widely used recently because it allows color recording to be performed relatively quickly.

In particular, with regard to color thermal transfer recording, high-definition recording with good gradation reproducibility is required for CA D/CAM, color copying machines, video printers, etc.In terms of equipment, improvement of thermal heads, In thermal transfer films, a wide range of improvements have been made in the materials, physical properties, layer structure, etc. of fI&S infusion inks, as well as recording methods.

Also, is the transfer paper flat? Improvements have been made in 1IIN, ink oil absorption, air permeability, etc. ◎ For example, for transfer paper, there are the following public technologies @ JP-A-6
No. 0-256487 discloses that image-receiving paper coated with a hot bath-fusible substance having a melting point higher than that of the hot-fusible ink provides gradation.

@-As in 182487/1987, oil absorption (based on JISK5101<) ao*/1 is applied to the surface of the image-receiving sheet.
It is disclosed that by providing a receiver 117m containing an oil-absorbing pigment of ooIi or more, it is possible to stably obtain a clear recorded image without unevenness in density.

On the other hand, for photosensitive and pressure-sensitive recording using photocurable microcapsules, the recording method is as follows. ◎It consists of a transfer sheet with microcapsules on a support and a transfer sheet, typically plain paper. Ru. At least one of the membrane and the inner phase of the microcapsules on the transfer sheet is composed of a substance that changes its appearance when exposed to light, heat, or light and heat. Due to this property, a line image is formed on the transfer sheet in an imagewise manner.The internal phase of the microcapsules contains a coloring agent, which corresponds to oil-based ink. When combined with a transfer sheet, pressure, heat, or pressure is applied to the microcapsules in the image area, thereby destroying the microcapsules, and the internal phase, that is, the ink, is transferred to the image-receiving sheet to obtain a recorded image.

As an example, Japanese Patent Application Laid-Open No. 62-39844 discloses that a photocurable resin MM and colored dyes and pigments are enclosed in microcapsules, and imagewise 4-dimensional imagewise y! forming a seedling, hardening the microcapsules by applying a superimposed compound on the exposed portion, and then destroying the unhardened microcapsules by applying pressure in combination with a transfer sheet; A plain paper transfer type photosensitive and pressure sensitive recording sheet is disclosed in which an image is obtained by transferring a released colorant to a transfer sheet.

JP-A No. 62-39845 uses microcapsules consisting of a heat bath meltable substance as a film material and an inner phase of a photocurable resin or a colored dye and pigment dissolved or dispersed in a photocurable resin and an organic solvent. Discloses a photosensitive thermal transfer recording sheet in which an image is obtained by combining a transfer sheet and plain paper as a transfer sheet and applying pressure and heat.
O Problems to be Solved by the Invention There are various problems in the patent bulletin cited in the above-mentioned prior art.0 For example, in the heat transfer record, heat 11I! - When the dye material is applied to image receiving paper (transfer sheet), the resulting transferred image will not have long-term storage stability, especially thermal stability. In the case of an image-receiving sheet (transfer sheet) provided with a heat-melting ink, the heat-melting ink depends on the melt viscosity of the ink and the oil absorption amount of the pigment, and there is room for improvement in obtaining high-definition transferred images. ◇ On the other hand, in light- and pressure-sensitive recording, plain paper has conventionally been used as a transfer sheet. However, the image quality obtained with plain paper was insufficient in terms of a degree, color, resolution, etc., and it was not possible to obtain high-quality images.Especially in color images, cyan , magenta, yellow, and other colors are generally transferred using pegs and mixed, making it impossible to obtain high-quality color images.Means for Solving the Problems The Inventors et al. As a result of conducting research, the present invention provides a transfer sheet for image recording that can obtain high-definition recording with good gradation reproducibility. The transfer sheet for image recording is 21i! @
A heat insulating layer having voids is coated on top, and the cut Kt- mainly contains polymeric microspheres8.
Characteristics: The polymer microspheres used in the heat insulation layer are made of hollow resin particles or particles with a different phase structure.The hollow resin particles are made of styrene resin, acrylic resin, or styrene-acrylic resin. The particles with a different phase structure are made of a polyethyl acrylate-polystyrene copolymer resin, a butyl polyacrylate-polystyrene copolymer resin, or a polymethyl methacrylate-polystyrene copolymer resin. ◎ The image recording transfer sheet used in the present invention is capable of obtaining high-precision RtA with gradation reproducibility and transferred images with excellent transfer efficiency in thermal transfer recording, photosensitive pressure sensitive ML recording, and color image recording. Can be done.

In addition, the same effect8 can be obtained in the recording of Nanakuro uTum, and it is also possible to use Inkjetsu Ha4000 type receiving paper C, which requires ink absorbency.Hereinafter, the present invention will be specifically described. Describe the transfer sheet for image recording of the present invention in terms of thermal transfer recording.0 Insulation of the transfer sheet in which a heat insulating layer made of lamellar Miku4 spheres is provided on the heat-melting ink layer side of the heat transfer film and on the base material. When the applied energy of the thermal head is applied to the thermal transfer film, thermal recording is performed with the thermal head from the non-ink layer side of the thermal transfer film by overlapping the layer sides.
The heat-melting ink melts and penetrates into the W+ heated no hollow void structure.◎Furthermore, the heat insulating layer is equipped with fIL narrow voids, so the heat from the thermal head is stored in this insulating layer. .

For this reason, the applied energy required for thermal recording can be reduced to 0. In other words, even if the applied energy is reduced, the transfer record will be 9 north, and by recording stepwise from the lowest to the highest applied energy. , it is possible to obtain a transfer with good gradation reproducibility @ Also, the recording becomes high definition ◇ In photosensitive and pressure sensitive recording, the inner phase oil containing the dye and pigment encapsulated in the microcapsules is released into the microcapsules by pressure. It is released when it breaks, but it easily penetrates into the void structure of the heat insulating layer of the transfer sheet, making it possible to obtain an efficient transferred image. ◇Also, when applying pressure, heat may also be used. As in the case of thermal transfer paper, thermal efficiency improves due to heat storage in the heat insulating layer, and the viscosity of the capsule contents further decreases, resulting in an improvement in transfer efficiency.

In the present invention, hollow resin particles and particles with a different phase structure are suitable for the purpose of the present invention as the polymer microspheres used in the heat insulating layer of the transfer sheet for image recording.

Hollow resin particles are resin particles that have voids inside, and have a particle size on the order of submicrons to several 1000mA. 18, the layer formed on the base material has heat insulation properties due to the air contained therein, and can also have oil absorption properties because it can change the pores to non-porosity. Particles with a different phase structure can be used as seeds. Composite polymer emulsion particles in which two or more polymer molecules coexist in one particle are produced by the emulsification method, and the shapes are like American sugar, snowmen, wild strawberries, and stars. these! 11! The method uses polymer A made by emulsion polymerization.
By using the particles as seeds and carrying out seed emulsion polymerization of monomer B therein, A/BO)'4i composite particles consisting of two types of polymer molecules are finally produced. Different types of polymers form a different phase structure with phase separation. Since particles with a different phase structure exhibiting such a unique morphology have a high S, the coating layer on the base material has a void structure, making it a coating layer with heat insulation properties. In addition, the pores have an oil-absorbing function.To give specific examples of hollow resin particles and particles with different phase structure, hollow resin particles include styrene-based resins such as polystyrene and poly(r-methylstyrene). , polymethyl methacrylate, polyethyl methacrylate, etc., styrene-acrylic copolymer resins, etc. Also, examples of particles with different phase structure include polyacrylic ether-polystyrene copolymer resins, Examples include polybutyl acrylate-polystyrene copolymer resin, polymethyl methacrylate-polystyrene copolymer resin, and the like.

In the present invention, the particle size of these particles is an outer diameter of 10 sf+& or less, preferably 5 ms or less, and more preferably 3-tsuru or less.

The heat insulating layer of the image recording transfer sheet used in the present invention mainly consists of a combination of polymeric microspheres and a binder.

The mixing ratio of polymer microspheres and binder is 5 to 100 parts by weight of binder to 100 parts by weight of polymer microspheres in terms of heat insulation and oil absorption properties! Jik part, preferably 10 to 10 parts per 100 jt of polymeric microspheres.
50 parts by weight, and more preferably, considering dusting to a supercalender during the production of lightly coated paper, 0 polymer microspheres and a binder of 15 to 100 parts by weight per 100 parts of polymer microspheres. In the combination, inorganic pigments and organic pigments (spherical particles that are not hollow resin particles) 8 may be used in combination within the range that does not impair the heat insulation properties in order to make the oil absorption properties more effective in addition to the heat insulation properties. .

Specifically, examples of inorganic pigments include clay talc, calcium carbonate, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, satin white, silicon oxide, zeolite, magnesium hydroxide, basic magnesium carbonate, alumina, and synthetic pigments. silica, calcium silicate,
Examples include diatomaceous earth, aluminum hydroxide, etc.; organic pigments include benzoguanamine, polyethylene, polystyrene, urea-formalin resin, and polyamide resin; Examples of molecules that can be used for synthetic resin latex and M bath additives include starches such as oxidized starch, etherified starch, and dextrin, carboxymethyl cellulose, and hydroxyethyl cellulose.
Cellulose brocade conductor, casein, gelatin, soy protein,
Polyvinyl alcohol and its derivatives, maleic anhydride VJ4 resin, maleic anhydride and ethylene, styrene,
A copolymer of two or more components with inbutadiene, vinyl acetate, etc. is used. As the synthetic resin latex, c. Conjugated diene polymer latex such as ordinary styrene-butadiene copolymer, methylmethacrylate-butadiene copolymer, polymer or copolymer of acrylic acid ester and methacrylic acid ester, etc. Acrylic polymer latex, vinyl-based polymers such as ethylene-vinyl acetate copolymer
1. Polymer latex modified with functional groups such as carboxyl groups of various M combinations of these M monomers are used.Resins soluble in organic solvents include polyacrylonitrile, boribi, etc. 2-nyl chloride, polyvinyl acetate, melamine resin, phenolic resin, polyurethane, polyamide resin, alkyd a! 1) In the composition of the heat insulating layer, if necessary, dispersants, thickeners, flow-through agents, antifoaming agents, antifoaming agents, etc.
There is no problem in adding additives, colorants, preservatives, pH adjusters, etc.8 as appropriate, as long as the properties are not impaired.

As the base material used in the present invention, opaque, translucent, or transparent supports are used, and paper, synthetic paper 1, paper, nonwoven fabric, glass, metal, cellophane, wood, synthetic resin film, etc. are used.

Regarding the price increase method of the present invention, the above-mentioned combinations of configurations include water-based coating and bath agent coating. , gravure coater m can be applied. Drying after coating is carried out by various methods such as gas heater, electric heater, steam heater, h-air 7111 heat, etc. to obtain a hollow sheet. ~6011/n? degree is coated onto the support. Preferably, the dry coating weight is 2
~4011/rr? It is possible to set the necessary amount t at one time, and it is also possible to obtain the required amount by checking twice or more. The transfer sheet has poor smoothness and may reduce the quality of the resulting image. It is also possible to improve the finish of the image by giving 8.

■Function The image recording transfer sheet of the present invention has a heat insulating layer with a void structure on the base material.The heat insulating layer is made of polymeric microspheres, so thermal transfer is achieved due to the void structure and l#T thermal effect. In recording, we were able to obtain a high-definition transferred image with good gradation reproducibility, and in light- and pressure-sensitive recording, we were able to obtain a transferred image8 with good transfer efficiency. I will explain it specifically. In addition, "part" indicates a heavy filtration part.

(Creation of thermal transfer film) 8 heat-resistant layers were placed on one side of a polyester film with a 6μ thick groove, and on the other side, heat-melt ink with the following composition was applied using a hot melt coater to a thickness of 3゜0μ. Coating was performed to obtain a heat transfer film.

Carbon black 13 parts by weight Lunaba wax 40 paraffin wax (155°F) 40 ethylene-vinyl acetate copolymer
2 petroleum resin
5 (Preparation of light-sensitive pressure-sensitive recording transfer sheet) Production of hardened microcapsules containing cyan dye: 1096 parts of ethylene-maleic anhydride copolymerized water *100 parts, 10 parts of urea, 1 m of resorcinol, and 200 parts of water.
Mix part 8 to make a bath solution and hydroxylate) Using the IJ cum water bath strainer, add rAir to H3 and 5.

Separately, add 14.5 parts to 165.6 parts of epoxy acrylate light-curing resin (trade name: Lipoxy, manufactured by Showa Kobunshi Koji Seisaku).
IllS cyanide Orazole Blue was seeded in advance, and then 0.8 part of 2,2-dimethoxy-2-phenylacetophenone (trade name: Irgakier 651, exhibited by Civer-Geigy) was added at 4 yuan. was emulsified and dispersed in the above-mentioned water mixture to form an oil-in-water emulgene with oil droplets of 4 to 8 microns. Next, 2.5 grams of 37% formaldehyde aqueous solution was added, the temperature of the solution was maintained at 55° C., stirring was continued for 4 hours, and then the mixture was cooled to room temperature to complete microencapsulation.

Furthermore, under light shielding, 30 parts of this microcapsule, 20 parts of wheat starch as stilt, and 1 part of paraffin wax were mixed together.
Blended with 0W6 and 10 parts of SBB latex, 50 tsubo° breakage
A photosensitive pressure-sensitive recording transfer sheet was obtained by coating I/Ze base paper using a Mayer par.

Example 1 A heat-insulating layer-forming liquid consisting of the following formulation was applied to a base paper of tsubo i5011/lri using an air knife coater Knee J10
#/rI? A transfer sheet for image recording was obtained by applying a smooth coating on the surface using a super calender.
Tt, the polyacrylic-polystyrene copolymer is a particle with a different phase structure with a particle size of LOsm, and the shape; Copolymer 15 parts 1 0M-4000 (Kuraray IA) Comparative example 1 Example 2 in which thermal transfer recording paper (Mitsubishi Paper Industries, trade name: TTR-T) was used as a transfer sheet for image recording sickles ~1
3 and Comparative Examples 2 to 4 Transfer sheets for image recording were prepared in the same manner as in Example 1 by changing the polymeric microspheres as listed in Section 1.

Regarding the combination of polymer cross-sphere and binder,
The amount of binder per polymeric microsphere 4A10.0 weight is listed in 1. All of the particles with a different phase structure used in Examples 11 to 13 had a flat-shaped form. In Comparative Example 4, urea resin particles, which were non-hollow resin particles, were used.

Example 14 In the same manner as in Example 1, a transfer sheet for recording an 111i image was prepared using the following formulation.

Comparative Example 5 General plain paper (Xerox paper) 8 was used as a double transfer sheet for image recording.

Evaluation 1, Thermal Transfer Recording: The hot melting ink side of the thermal transfer film and Examples 1 to 1
4 and the upper side of the heat insulation layer value of the transfer sheet for image recording prepared in Comparative Examples 1 to 4 were overlapped and evaluated by the following test method. ◎The results are listed in Table 2. ) Using a tear-maru head printing device,
Changed the printing energy from 0.27 to 2.08J [solid printing was performed].

If there is a direct inclination between the IM degree obtained by printing and the printed Calo energy, 0. IM object is X, O・Δ
, expressed as ×.

■ Using the same equipment as Takazue's Note ■, the energy of 0.27 fiJ
℃ half printing is carried out, and the slight ++a due to fine transfer is O1 for the bad one, and X for the bad one, 0, Δ
, 〇■ Expressed with
The peeling of the acid layer was observed and the contact of the CML skin was evaluated.

2. Evaluation of photosensitive and pressure sensitive recording image quality was carried out using the photosensitive and pressure sensitive recording transfer sheet described in EI.
Then, the sheets were stacked on the transfer sheets for image recording of Examples 1 to 14 and Comparative Examples 1 to 4', passed through rubber rolls, and pressed.
The image quality of the obtained images was evaluated. Table 2 shows the results.
◎ (Image Preparation) The cyan reflection was measured using a reflection art meter Macbash RD-918 (manufactured by Macbeth).

■ Color of the image The 8 cedar trees in the obtained image are expressed as 0, Mu, × (marked in the margin below), where the color of the cedar is 80° for the bright color and 8x for the scary one.From the results in Table 2, the polymer microsphere 100 When there is a lot of binder base per X section (Comparative Example 3), the smell is inferior to the mechanical transfer recording (11 tonality, high citrus method), and when there is little (Comparative Example 2), it is bad! The - contact '4 column is inferior to 0, and in the photosensitive and pressure sensitive recording 16, the setting of 'umi* is low in Comparative Example 3.4, 0 ratio 4I2, and Ii in Example 2! Although the concentration of 1I11i1 is high, it causes peeling of the coating, which is not preferable.

(Q: Effect of discovery The -l recording transfer sheet of the present invention can obtain a high-grained shoulder with gradation reproducibility in thermal transfer recording and photosensitive pressure-sensitive recording, and transfer II!l113!8 with excellent transfer efficiency.・It has an extremely high level of industrial significance.

Claims (5)

[Claims] (1) A transfer sheet for image recording comprising a heat insulating layer having a void structure coated on a base material, wherein the heat insulating layer mainly contains polymeric microspheres. (2) The image recording transfer sheet according to claim 1, wherein the polymeric microspheres are made of hollow resin particles. (3) The image recording transfer sheet according to claim 2, wherein the hollow resin particles are made of a styrene resin, an acrylic resin, or a styrene-acrylic copolymer resin. (4) The image-recording transfer sheet according to claim 1, wherein the polymeric microspheres are composed of particles with a different phase structure. (5) Claim 4, wherein the particles with a different phase structure are made of polyethyl acrylate-polystyrene copolymer resin, polybutyl acrylate-polystyrene copolymer resin, or polymethyl methacrylate-polystyrene copolymer resin. Transfer sheet for image recording as described.