JPH11277896A - Ink jet recording transfer medium, manufacture of image-transferred matter and cloth to be transferred - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form images with improved ink absorptiveness, high density, and fine vividness, and enhance washing fastness of transferred images in the case of transferring images on cloth by blending thermoplastic resin fine particles, a thermoplastic resin binder, inorganic fine particles, and a coupling agent. SOLUTION: In order to manufacture an ink jet recording transfer medium, a release layer and a transfer layer are laminated on a base material. In this instance, it needs to blend thermoplastic resin fine particles, a thermoplastic resin binder, inorganic fine particles, and a coupling agent in the transfer layer. As concrete examples of thermoplastic resin fine particles, there are polyethylene, polyvinyl acetate, or the like, whose particle diameter is suitable to be in the range of 0.05-100 μm is terms of ink absorptiveness and the vividness of images. Inorganic fine particles are suitable to be white, and as concrete examples, there are given silica, aluminum silicate, hydrotalcite, or the like, and as a concrete example of such a coupling agent, there is given a coupling agent such as silane, titanate, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer medium used for forming an image on a transfer object by transfer, an image transfer product using the transfer medium, and a transfer cloth.
More specifically, a transfer medium for ink jet recording in which an ink jet recording method is used when an image is formed on a transfer layer constituting a transfer medium, using the transfer medium, transferring an image onto a transfer target to form a transfer image The present invention relates to a method for producing an image transfer product to be formed, and a transferred fabric obtained by the production method.

[0002]

2. Description of the Related Art Ink jet recording methods include various ink discharge methods, for example, an electrostatic suction method, a method of applying mechanical vibration or displacement to ink by using a piezoelectric element, and heating and bubbling of ink. There is known a method of utilizing such a method, and ink droplets are generated and fly by these ink discharge methods, and a part or all of them are attached to a recording material to perform recording. Such an ink jet recording method is attracting attention as a simple method that generates little noise and can perform high-speed printing and color printing. In recent years, an ink jet printer that can easily perform color printing using this method has been widely used.

[0003] In recent years, with the spread of ink jet printers capable of easily performing color printing, demands for performing color printing on various recording materials using the ink jet printer have been increasing.
In response to such demands, a printing method using a transfer medium (transfer paper) does not require any form on the recording material side, that is, an image is printed on a recording material that cannot be directly printed by a printer. It is a technique that has received special attention because it can be formed.

Several transfer media of the type in which an image is formed using an ink jet recording method have been proposed. JP-A-8-207426 discloses an ink jet recording method in which a transfer image can be stuck to a recording material only by heating by forming an ink receiving layer from a thermoplastic resin, a crystalline plasticizer and a tackifier. Suggest a seat. JP-A-8-207450 discloses a sheet comprising a support layer and a thermal transfer layer, wherein the thermal transfer layer includes a granular thermoplastic polymer resin, porous inorganic fine particles, and a binder (binder). A transfer medium capable of ink-jet recording and capable of thermal transfer has been proposed.
Further, U.S. Pat. S. P. 5,501,902 also proposes an ink-jet transfer medium having a constitution in which a cationic resin, an ink viscosity modifier and the like are added in addition to the above constitution.

However, these prior arts have a sufficient performance in an ink jet recording step on a transfer medium and an image transfer from the transfer medium to a recording material, but have a sufficient performance after the image is transferred to the recording material. The performance for the robustness of the transferred image was not satisfactory. Specifically, when the image transfer product is washed, the dye forming the image, the transfer layer material carrying the image flows out into water, or causes such as fluffing on the surface of the fabric. Therefore, there is a problem that the image density is reduced.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to make it possible to form a good transferred image by transferring an image formed by using an ink jet printing method to a transfer target such as a cloth. In particular, the present invention is to provide a transfer medium for performing high-absorbency ink, high-density and high-clarity images can be formed, and further, when an image is transferred to a transfer target such as cloth. An object of the present invention is to provide an excellent transfer medium for ink jet recording capable of forming a good transfer image having high washing fastness, a method for producing an image transfer product having the above-described characteristics, and a cloth to be transferred.

[0007]

The above object is achieved by the present invention described below. That is, the present invention relates to a transfer medium for ink jet recording in which a release layer and a transfer layer are provided on a base material, wherein the transfer layer comprises a thermoplastic resin fine particle, a thermoplastic resin binder, an inorganic fine particle, and a coupling agent. A transfer medium for ink jet recording, a method for manufacturing an image transfer product using the transfer medium, and a transferred fabric.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to preferred embodiments of the present invention.

First, the operation of the present invention will be described below. The transfer medium for ink jet recording of the present invention comprises a release layer and a transfer layer provided on a substrate. In this configuration, the transfer layer is required to have the following three functions.

First, a function of favorably absorbing ink for ink-jet recording, forming a high-quality image, and maintaining the formed image satisfactorily.

Second, it is possible to transfer an image adhered to a recording medium (recording material) such as a cloth or a film on a recording medium such as a cloth in good condition. Function to do.

Third, when the color material in the transfer layer is firmly fixed in the layer after being transferred to the transfer object such as a cloth or a film, and the transfer object, such as a cloth, is washed, A function that can prevent image deterioration that may occur when the transfer target on which an image is formed is wet with water or sweat.

According to the present invention, there is provided an ink-jet recording transfer medium having a transfer layer satisfying all the above functions. That is, in the present invention, by using the thermoplastic resin fine particles, the thermoplastic resin binder, the inorganic fine particles and the coupling agent as the material constituting the transfer layer, it is possible to achieve all of the above-mentioned required performance. Can be. Hereinafter, the role (function) of each material will be specifically described.

In the present invention, the fine particles of the thermoplastic resin used for forming the transfer layer refer to fine particles made of a water-insoluble thermoplastic resin. More preferably, porous thermoplastic resin fine particles are used. If such a thermoplastic resin fine particle is contained in the transfer layer, it is present in the transfer layer in a state before forming a transfer image, without being formed into a film and remaining in a shape as fine particles. As a result, the transfer layer becomes a porous layer, and when the ink is supplied to the transfer layer by the ink jet recording method, the ink is favorably absorbed and held in the gaps between the fine particles. Further, in this case, if porous thermoplastic resin fine particles are used, the ink is absorbed in the voids of the fine particles, so that the ink absorbency of the transfer layer can be further improved.

On the other hand, when the image is adhered to the object to be transferred and the image is transferred, for example, by heating and pressing from the support side of the transfer medium, the fine particles of the thermoplastic resin in the transfer layer are bonded to the thermoplastic resin. Since the particles are melted and transferred together with the adhesive, these particles are also formed into a film, and the color material can be fixed in a good state on a transfer target such as a cloth or a film. In this case, since the thermoplastic resin is present in a fine particle state in the transfer layer before melting, for example, when the thermoplastic resin is transferred to a fabric, these fine particles enter between the fibers and surround the fibers. Is melted in a state of surrounding and then fixed, so that even if the fabric expands and contracts, a clear transfer image can be obtained without seeing the color of the underlying fiber.

The present invention includes a thermoplastic resin binder for binding the thermoplastic resin fine particles to form a transfer layer. The thermoplastic resin binder has a function of adhering the transfer layer to the transfer target at the time of transfer. However, when the transfer layer is formed of only these materials, the transfer layer excessively penetrates the cloth, and the color material sinks, resulting in a problem that the image density is reduced. In addition, the same factor causes a problem in that the image of the fabric surface becomes fluffy when washed and the image density is reduced.

The present inventors have studied these problems, and as a result, it has been found that by adding inorganic fine particles to the transfer layer, the transfer layer can be prevented from excessively penetrating into the cloth, and the above problem can be improved. Was found. In other words, by adding inorganic particles having no melting property to heat to the transfer layer,
At the time of transfer, the thermoplastic resin forming the transfer layer is prevented from penetrating too much into the fabric, and a film is formed on the surface of the fabric to obtain a clear image with high density. Further, when a transfer image is formed on a fabric using the transfer medium for inkjet recording of the present invention, the transferred fabric adheres to the fiber on the surface of the fabric, so that the transferred fabric has high robustness without being fluffed even by washing. Can be provided.

However, as described above, since the inorganic fine particles do not melt with heat and have no adhesiveness to the transfer receiving body, if added excessively, the inorganic fine particles fall off due to friction during washing or the like. On the contrary, there is a problem that the robustness is deteriorated. Therefore, as a result of further study on this problem, the addition of the coupling agent in addition to the above three constituent materials can prevent the inorganic fine particles from falling off, and can obtain a transfer image having higher washing fastness. I found that.

The coupling agent used in the present invention has a function of linking the inorganic material and the organic material through a chemical reaction or by increasing the affinity of the two in a mixed system of the inorganic material and the organic material. It is a material. Specifically, for example, there are coupling agents such as silane-based, titanate-based, and aluminate-based coupling agents, and the structure of these coupling agents is silica, titanium, or aluminum as a central element. Those having a group (methoxy group, ethoxy group, etc.) that can bind to the particle surface, those having a functional group (amino group, vinyl group, epoxy group, etc.) that reacts with organic substances, or those that increase the affinity with organic substances Some have a group (isopropyl group, octyl group, etc.).

In a more preferred embodiment of the present invention,
A coupling agent having a functional group reactive with a thermoplastic resin is used, and as a thermoplastic resin fine particle or a thermoplastic resin binder, a heat reactive with the reactive group of the coupling agent is used. Use a plastic resin. In the case of such an aspect, the inorganic fine particles and the fine particles of the thermoplastic resin or the binder are chemically reacted and bonded, so that the bond between the inorganic fine particles and the thermoplastic resin becomes stronger,
In the transfer-receiving fabric and the like obtained by using the transfer medium for ink jet recording of the present invention, higher washing fastness is obtained.

Further, in a more preferred embodiment of the present invention, the transfer layer has at least a two-layer structure. For example, a layer containing a coupling agent having a functional group reactive with a thermoplastic resin and a layer containing a thermoplastic resin having a reactivity with the coupling agent are separately formed, and at least these It is preferable that the transfer layer is composed of two layers. That is, when the inorganic fine particles, the reactive coupling agent, and the reactive thermoplastic resin are present in the same layer, the three react before the transfer layer is transferred to the object. If the three react, the plasticity of the thermoplastic resin may be impaired, which may hinder transfer to the transfer target. On the other hand, if the layer containing the coupling agent and the layer containing the thermoplastic resin are formed as separate layers, it is possible to eliminate the possibility of the above three reactions at the stage before the transfer. Can be. When the transfer layer has the two-layer structure described above, the inorganic fine particles may be added to either layer. However, according to the study of the present inventors, the coupling was performed in a state where the inorganic fine particles had been reacted with the coupling agent in advance. It was found that a higher effect was obtained when the layer was formed together with the agent.

In another embodiment of the present invention, it is effective to use a coupling agent having no reactivity with a thermoplastic resin. In this case, the coupling agent reacts with the inorganic fine particles to increase the affinity of the surface of the inorganic fine particles with the thermoplastic resin. When such a coupling agent is used, the adhesiveness between the inorganic fine particles and the thermoplastic resin is enhanced, so that the inorganic fine particles can be effectively prevented from falling off. Further, in this case, since a strong bond does not occur between the thermoplastic resin and the inorganic fine particles, the plasticity of the thermoplastic resin is not impaired, and therefore, the transfer property to the transfer object is prevented. Nor.

Further, as another embodiment of the present invention, it is effective to provide a layer composed of a uniform film containing no resin particles between the transfer layer and the release layer. There are two advantages of providing such a layer. First, the formation of the transfer layer becomes easier. That is, in the transfer medium for ink jet recording of the present invention, a porous transfer layer having ink absorbency is provided on the release layer. Thus, when a porous layer is provided on a layer having low adhesion, such as a release layer, the adhesion between the layers is poor, and the transfer layer may peel off during handling. In contrast, the transfer layer has a two-layer structure,
By providing a uniform coating layer on the release layer side, the adhesion between the release layer and the transfer layer can be improved,
Such a problem is less likely to occur.

Second, the washing fastness of the transferred image is further improved. That is, when the transfer layer has a two-layer configuration, when the transfer layer on which the image is formed is transferred to a transfer target such as a cloth,
Since the transfer layer adjacent to the release layer constitutes the outermost surface of the transferred image, the uniform coating layer covers the surface. As a result, the color material forming the image is brought into close contact with the cloth in a more concealed state, and thus it is considered that the robustness of the transferred image is increased. Also, the presence of the uniform coating can more effectively prevent the inorganic fine particles from falling off. In the present invention, it is more effective to use a resin having high reactivity or affinity with the functional group of the coupling agent as a material for forming the uniform coating layer.

In the above case, it is more preferable to use the same thermoplastic resin for the uniform coating layer and the porous layer containing fine resin particles for absorbing and retaining the ink.
That is, by using the same material, the adhesion between the two layers can be increased, so that the robustness of the transferred image is further improved. In addition, since the difference in the refractive index between the two layers is reduced, the transfer layer after transfer becomes transparent, so that a clear image can be obtained.

The transfer medium for ink jet recording of the present invention has a release layer in addition to the transfer layer having the above-described structure. The presence of the release layer makes it possible to efficiently and easily transfer the transfer layer having the above-described excellent properties onto a recording material such as a cloth to form an image. For example, after transferring the transfer layer on which an image is formed to the surface of the fabric, when the base material holding the transfer layer is to be removed, the transferred transfer layer peels off from the fabric together with the base material. It is possible to effectively prevent the image from being disturbed due to the transfer or part of the transfer layer remaining on the substrate.

Next, specific materials used for the transfer medium for ink jet recording of the present invention will be described.

First, as the material used for the fine particles of the thermoplastic resin constituting the transfer layer, any fine particles made of a non-water-soluble thermoplastic resin can be used. Examples of such a thermoplastic resin include polyethylene, polypropylene, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, poly (meth) acrylic acid, poly (meth) acrylate, polyacrylic acid derivatives, and polyacrylic acid. Amides, polyethers, polyesters, polycarbonates, cellulosic resins, polyacrylonitriles, polyimides, polyamides, polyvinyl chloride, polyvinylidene chloride, polystyrene, thiochol, polysulfone, polyurethane, polystyrene, and other copolymers of these resins. Can be In the present invention, among these, polyethylene, polypropylene, poly (meth) acrylic acid, poly (meth) acrylate, polyvinyl acetate, polyvinyl chloride, polyurethane, polyamide, and copolymers thereof are more preferable. It is preferably used.

In the transfer medium for ink jet recording of the present invention, polyamide, especially nylon 6 and nylon 1
It is preferable to use thermoplastic resin fine particles composed of the copolymer (2). That is, when these fine particles are used, the coloring of the dye becomes good, and a clearer image can be obtained.

The fine particles used in the present invention have a particle size of 0.00 from the viewpoints of ink absorption and image clarity.
It is preferably in the range of 5 μm to 100 μm, more preferably in the range of 0.2 to 50 μm, and even more preferably in the range of 5 to 20 μm. That is, when the particle size of the thermoplastic resin particles is smaller than 0.05 μm, when formed as a transfer layer, the gap between the particles is too small, and it is difficult to obtain sufficient ink absorbency. or,
If the particles are too small, the surface smoothness will be too high, and when transferred, the transfer layer will be less likely to penetrate between the fibers of the fabric, making it easier for the transferred image to be formed as a uniform continuous coating on the fabric surface. In some cases, a good transfer image may not be obtained, for example, the transfer image may be easily peeled off from the cloth, or when the cloth is expanded or contracted, the transfer layer may crack and the underlying fibers may be seen. On the other hand, if the particle size is larger than 100 μm, the resolution of the image is lowered, and a clear image cannot be obtained.

It is preferable to use porous fine particles as the thermoplastic resin fine particles composed of the above-mentioned materials used in the present invention. If porous fine particles are used in the present invention, the ink absorbency of the transfer layer can be further improved, so that more ink can be absorbed with a thin layer thickness. Further, reducing the thickness of the transfer layer not only makes it easier to transfer the image, but also allows the texture of the image after transfer to be softened when transferred to a cloth or the like, to obtain a more preferable transferred product. Becomes possible.

Further, as the thermoplastic resin fine particles used in the present invention, it is preferable to use a material which can be easily transferred at home or the like after forming an image with a general-purpose ink jet printer. In this respect, the thermoplastic resin used preferably has a melting point in the range of 70 ° C to 200 ° C, more preferably in the range of 80 ° C to 180 ° C,
More preferably, it is preferable to use one in the range of 100 ° C to 150 ° C. When a material having a melting point lower than 70 ° C. is used, there is a possibility that the fine particles may be melted and formed into a continuous film depending on conditions during distribution or storage. Since the drying temperature after coating must be lower than the melting point of the thermoplastic fine particles, it is preferable to use a drying temperature of 70 ° C. or higher from the viewpoint of production efficiency. On the other hand, the melting point is 20
When a resin having a temperature higher than 0 ° C. is used, high energy is required for transfer, and a transfer image is easily formed on a material to be transferred such as a cloth, which is one of the objects of the present invention. It becomes difficult.

Further, in the present invention, it is preferable to use a resin having a low melt viscosity in consideration of the adhesion of the transfer layer to the cloth when the cloth is used as the material to be transferred. That is, when a resin having a high heat-melt viscosity is used, the adhesion between the transfer layer and the fabric is poor, and the transfer layer formed as a film tends to peel off. On the other hand, if a material having a low hot melt viscosity is used, the transfer layer can easily enter between the fibers of the fabric,
Even if the fabric expands and contracts, the color of the underlying fiber is not visible,
A good transfer image is obtained. In order to minimize the texture of the transferred fabric as much as possible, it is preferable to use a material that can provide a highly flexible coating.

Next, the thermoplastic resin binder constituting the transfer layer of the transfer medium for ink jet recording of the present invention together with the above-mentioned thermoplastic resin fine particles will be described. The binder is added for the purpose of forming the transfer layer by binding the above-mentioned thermoplastic fine particles to each other, and for the purpose of bonding the transfer layer on which the image is formed at the time of transfer to the cloth. In the present invention, a conventionally known water-insoluble thermoplastic resin is used for the binder as well as the thermoplastic resin fine particles. Specifically, those mentioned above as the material for the fine particles can be used.

In the present invention, the ratio of the fine particles of the thermoplastic resin to the binder is 1/2 to 50 / weight ratio.
1, and more preferably 1 /
Range of 2 to 20/1, more preferably 1/2 to 15 /
1 range. If the ratio of the fine particles of the thermoplastic resin is too large, adhesion between the fine particles or between the fine particles and the release layer becomes insufficient, and a transfer layer having sufficient strength cannot be formed.
On the other hand, if the proportion of the thermoplastic resin particles is too small, it becomes difficult to obtain a transfer layer capable of forming an image having excellent ink absorbency and image clarity.

Next, the inorganic fine particles used in the transfer layer together with the thermoplastic resin fine particles and the binder will be described. As described above, by adding inorganic fine particles to the transfer layer, the thermoplastic resin forming the transfer layer is prevented from excessively penetrating into the cloth when transferred onto the material to be transferred. Since a transfer layer film can be formed on the surface, a clear transfer image with high density can be formed. Furthermore, since voids are created by adding inorganic particles to the transfer layer, the ink absorbency of the transfer layer is further improved, and a clearer image can be formed.

The inorganic fine particles used for such purpose may be white inorganic particles which do not have heat melting property and are specifically, for example, silica, aluminum silicate, magnesium silicate, hydrosilicone, and the like. Examples include talcite, calcium carbonate, titanium oxide, clay, talc, (basic) magnesium carbonate, and the like. Among these, it is preferable to use a material having a high dyeing property, since the dye is better fixed on the fabric surface.

When a material having a higher porosity among inorganic particles is used, the ink absorbency of the transfer layer becomes higher, and a clearer image can be obtained. As the particle size of the inorganic particles used in the present invention, it is preferable to use particles having a particle size close to the particle size of the thermoplastic resin fine particles described above. This is because if particles having different particle sizes are added to the transfer layer, the smaller particles are filled between the larger particles, which may result in lowering the porosity in the transfer layer. Because there is.

Next, the coupling agent added to the transfer layer together with the above-mentioned inorganic fine particles will be described.

As described above, the coupling agent used in the present invention is added for the purpose of preventing the inorganic fine particles from falling off due to the force of friction or the like in the image after transfer and deteriorating the image. Specifically, a material having reactivity or affinity with the inorganic fine particles and the thermoplastic resin can be used, and more specifically, a silane-based, titanate-based, or aluminate-based material can be used. Coupling agents can be used.

The silane coupling agent has an organic functional group such as amino type, ureide type, vinyl type, methacryl type, epoxy type, mercapto type and isocyanate type, and has a reactivity with a thermoplastic resin. Has functional groups. In the present invention, a more optimal material may be selected from these materials according to the types of the fine particles of the thermoplastic resin and the binder used in the transfer layer. In particular,
It is preferable to use the following combinations.

For example, an isocyanate-based coupling agent is preferably used for a resin having a hydroxyl group, an amino group, a carboxyl group, a mercapto group, or the like.
The epoxy-based coupling agent is preferably used for a resin having a carboxyl group, a mercapto group, a double bond, and an isocyanate group. Further, amino-based coupling agents are chlorine-based, fluorine-based resin, chlorosulfone group,
It is preferably used for a resin having a carboxyl group, an ester group, an epoxy group, a methylol group, and a sulfone group.

Titanium-based coupling agents include those having an organic functional group such as an isostearoyl group, a dodecylbenzenesulfone group, dioctyl pyrophosphate, and dioctyl phosphate, but have no reactivity with a thermoplastic resin. However, by reacting with the inorganic particles, the affinity of the surface of the inorganic particles with the thermoplastic resin can be increased. In the case of these titanium-based coupling agents, as in the case of the silane-based coupling agent, it is preferable to select and use a more optimal material according to the thermoplastic resin used in the transfer layer. . In particular, it is preferable to use a combination of those having similar polarities of the thermoplastic resin used and the polarities of the organic functional groups of the coupling agent since the affinity can be further increased. For example, when using a thermoplastic resin such as polyethylene or polypropylene, the organic functional group has a small polarity such as an isostearoyl group, and when using a polyamide or the like, a polar group such as an N-aminoethyl / aminoethyl group is used. It is better to use a large one.

As the aluminate coupling agent,
There is acetoalkoxyaluminum diisopropylate, which, like the titanate-based coupling agent described above, can also increase the affinity of the surface of the inorganic fine particles with the thermoplastic resin. As a method for adding these coupling agents, there are a dry method, a wet method, an integral blend method and the like.

In the transfer layer of the present invention, various additives may be added in addition to the above-mentioned materials. In particular, when a cationic material is added to the transfer layer, higher washing fastness can be obtained. That is, the coloring material generally used for the ink used in the ink jet printer is an anionic aqueous dye. Then, the coloring material is taken in together when the thermoplastic resin fine particles are melted by the heat at the time of transfer, and is fixed as a coating on a recording material such as a cloth. However, the formed film may not be completely uniform, and in such a case, the dye may exude when the image transfer product is immersed in water. On the other hand, if a cationic material is added to the transfer layer, the dye can be insolubilized and elution of the dye can be prevented.

Specific examples of the cationic material that can be used at this time include the following materials.

Cationized modified products of resins such as polyvinyl alcohol, hydroxyethylcellulose and polyvinylpyrrolidone; amine monomers such as allylamine, diallylamine, allylsulfone, dimethylallylsulfone and diallyldimethylammonium chloride; dimethylaminoethyl (meth) acrylate; Diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylammonostyrene, methylethylaminostyrene, N
Polymers and copolymers of acrylic monomers having primary to tertiary amine to quaternary ammonium bases in side chains, such as -methylacrylamide, N-dimethylacrylamide, N, N-dimethylaminoethylmethacrylamide, and quaternized compounds thereof Product, dicyanamide, etc.
Examples of the resin include a resin having a quaternary amine to a quaternary ammonium base.

Further, adding fine particles of a thermoplastic resin or a plasticizer of a binder to the transfer layer is effective in improving transferability. By adding a plasticizer, the melt viscosity of the transfer layer at the time of transfer, that is, at the time of heating is reduced, so that the adhesion of the transfer layer to the fabric can be further improved, and the transferability is improved. As the plasticizer used at this time, any conventionally known plasticizer can be used. Specifically, for example, phthalate esters such as diethyl phthalate, dioctyl phthalate, dimethyl phthalate, dibutyl phthalate, phosphate esters such as tributyl phosphate and triphenyl phosphate, octyl adipate, adipic acid such as isononyl adipate Ester, dibutyl sebacate, sebacic acid ester such as dioctyl sebacate, acetyl tributyl citrate, acetyl triethyl citrate, dibutyl maleate, diethylhexyl maleate, dibutyl fumarate, trimellitic acid plasticizer, polyester plasticizer, Epoxy plasticizers, stearin plasticizers, paraffin chloride, toluenesulfonamide and derivatives thereof, p-oxybenzoic acid-2-ethylhexyl ester and the like can be mentioned.

For the purpose of improving the ink permeability, a surfactant may be added to the transfer layer. That is, by adding a surfactant to the transfer layer, the wettability of the child surface is improved, so that when an image is formed by an ink jet recording method, the permeability of the water-based ink into the transfer layer is increased. As the surfactant used at this time, a commonly used nonionic surfactant can be used, and more specifically, surfactants such as ether-based, ester-based, ether-ester-based, and fluorine-containing surfactants can be used. Agents can be used.

The preferable thickness of the transfer layer of the transfer medium for ink jet recording of the present invention constituted as described above is 15 to 250 μm, more preferably 40 to 200 μm.
μm, more preferably in the range of 50 to 150 μm.
In the transfer layer, the layer thickness of a portion having a space for absorbing and retaining ink, which can form an image by inkjet recording, is preferably 10 to 150 μm, more preferably 30 to 120 μm, and still more preferably 40 to 100 μm.
m. If the layer thickness of the transfer layer of the transfer medium is too thick, when transferred to a flexible material to be transferred such as cloth,
The flexibility of the transfer portion is inferior, and the texture of that portion deteriorates. On the other hand, if the thickness of the transfer layer is too thin, the strength of the layer is weakened, which causes deterioration in washing fastness and the like. In addition, if the layer thickness of the portion having a gap for absorbing and holding the ink is reduced, the ink is not sufficiently absorbed and held, so that it is difficult to form a high-definition image.

The release layer that constitutes the ink jet recording medium of the present invention together with the transfer layer having the above-described structure includes:
This has the effect of increasing the releasability of the transfer layer and the substrate during transfer when transferring the transfer layer to a recording medium such as a fabric.

At this time, as a material used for the release layer, first, as a heat-fusible material, waxes such as carnauba wax, paraffin wax, microcrystalline wax, caster wax, stearic acid,
Higher fatty acids such as palmitic acid, lauric acid, aluminum stearate, lead stearate, barium stearate, zinc stearate, zinc valmitate, methylhydroxystearate, glycerol monohydroxystearate, glycerol monohydroxystearate, and metals thereof Derivatives such as salts and esters, polyamide resins, petroleum resins, rosin derivatives, chroman-indene resins, terpene resins, novolak resins, styrene resins, olefin resins such as polyethylene, polypropylene, polybutene, and polyolefin oxides, and vinyl ethers And the like. In addition, a silicone resin, a fluorosilicone resin, a fluoroolefin vinyl ether terpolymer, a perfluoroepoxy resin, a thermosetting acrylic resin having a perfluoroalkyl group in a side chain, a vinylidene fluoride-based curable paint, or the like may be used. Can be.

The base material for holding the release layer and the transfer layer as described above, which is used in the transfer medium for ink jet recording of the present invention, can be transported by a printer and can be used for thermal transfer. Any substrate can be used as long as it has the necessary heat resistance. Specifically, for example, polyester, diacetate, triacetate,
Examples include synthetic resins such as acrylic polymers, polycarbonate, polyvinyl chloride, polyimide, cellophane, and celluloid, and flexible substrates such as paper, cloth, and nonwoven fabric. In the transfer medium for ink jet recording of the present invention, in particular, by using a flexible substrate, even if the shape of the portion to be transferred of the transfer object is a curved surface, Since the transfer layer of the transfer medium can be transferred along the transfer medium, a good transfer image can be formed even on a transfer target having a shape other than a flat surface, which is preferable.

The thickness of the substrate is not particularly limited, but is preferably in a range that can be transported by a general-purpose ink jet printer, for example, 30 μm to 2 μm.
It is preferable to use one having a range of 00 μm.

The method for forming the release layer and the transfer layer on the substrate is not particularly limited. For example, a coating material is prepared by dissolving or dispersing a suitable material for forming the transfer layer in an appropriate solvent. And a method of coating by a method such as applying the coating liquid, a method of forming a film from a suitable material for forming a transfer layer, a method of laminating the film on a substrate, and an extrusion method. A molding method and the like can be given. Examples of the coating method of the coating liquid include a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, a bar coater method, a size press method, a shim sizer method, a spray coat method, a gravure coat method and a curtain coater method. Is mentioned.

The transfer medium for ink jet recording of the present invention produced by the method as described above comprises an image forming step of forming a desired image on a transfer layer of the transfer medium for ink jet recording by an ink jet recording method, and an image forming step. The transfer layer side of the transfer medium on which the image is formed is superimposed on the surface of the transfer object, and the transfer layer is transferred to the transfer object surface by heating from the back opposite to the transfer layer side. And a transfer step of forming an image transfer product of the present invention.

That is, first, an image is formed on the transfer layer of the transfer medium for ink jet recording of the present invention by an ink jet recording method, and then the formed image is superimposed on a transfer object such as a cloth or a film. The transfer layer is transferred onto the substrate by heating from the back side of the transfer medium opposite to the transfer layer side, and then the substrate is peeled off to form an image on the cloth.
At this time, a commercially available printer can be used as it is as the inkjet printer. Further, the coloring material constituting the ink used in the image forming step is not particularly limited, and a conventionally known anionic coloring material can be used.

As described above, in the method for producing an image transfer product of the present invention, an image is formed on a transfer layer, and the image is transferred to an object to be transferred such as cloth to form an image. Since it is not a method of directly forming an image by printing an image on a cloth, it is not necessary to change a coloring material in accordance with a type of a fiber material constituting a recording material such as a cloth. Therefore, if a transfer image is formed on a cloth by using the cloth for the transfer receiving body and the method for manufacturing an image transfer product as described above, a transferred cloth on which a good image is formed can be obtained by a simple method. . The fabric that can be used in the transferred fabric of the present invention is not particularly limited, and examples of materials constituting the fabric include cotton, hemp, silk, wool, rayon, polyester, nylon, acrylic, acetate, and triacetate. , Polyurethane and the like, and blended fibers thereof. Further, the fabric formed from these materials can use any form such as a woven fabric, a knitted fabric, and a nonwoven fabric.

[0059]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

The materials used in the examples and comparative examples are shown below.

Thermoplastic resin fine particles (thermoplastic resin fine particles a): Porous nylon resin fine particles. Orgasol 3501EXD NAT (Elf at Chem Co., Ltd., particle size 10 μm) (thermoplastic resin fine particles b): ethylene resin Fine particles ・ AC polyethylene A-6 (AlliedSignal, particle size 6 μm)

Binder resin (thermoplastic resin binder a): Ethylene-acrylic acid emulsion Hitech E-8778 (manufactured by Toho Chemical Industry Co., Ltd.)
(Solid content: 25%) (thermoplastic resin binder b): urethane emulsion Taketake W-635c (manufactured by Takeda Pharmaceutical Co., Ltd.)
(Solid content: 35%) (thermoplastic resin binder c): ethylene resin emulsion (ethylene-based emulsion) Chemipearl W-300 (manufactured by Mitsui Petrochemical Co., Ltd., particle size: 6 μm, solid content: 40%)

Coupling agent (coupling agent a): silane coupling agent (reactive group: epoxy group) SH-6040 (manufactured by Toray Dow Corning KK)
% As an aqueous solution) (coupling agent b): silane coupling agent (reactive group: amino group) SH-6020 manufactured by Toray Dow Corning Co., Ltd.
% As an aqueous solution) (coupling agent c): titanium coupling agent (organic functional group: isostearoyl group) KR-TTS (manufactured by Ajinomoto Co., Inc. as 5% IPA solution) (coupling agent d): Titanium coupling agent (organic functional group: N-aminoethyl / aminoethyl group) KR-44 (manufactured by Ajinomoto Co., Inc. as a 5% IPA solution)

Inorganic fine particles (inorganic fine particles a): Silica Mizukasil P-78A (manufactured by Mizusawa Chemical Industry Co., Ltd., particle size 3 μm)

Various additives (cationic resin a): acrylic cationic resin EL polymer NWS-16 (Shin-Nakamura Chemical Co., Ltd.)
(Plasticizer a): N-ethyl-o, p
-Toluenesulfonamide-Topsizer No. 3 (Fujiamide Chemical Co., Ltd.)
(Surfactant a): Fluorinated surfactant Surflon S-131 (manufactured by Seimi Chemical Co., Ltd., solid content 30%)

Substrate (substrate a provided with release layer): Release paper (having release layer of silicone resin) ST60OKT-T (manufactured by Lintec Corporation)

Using the above materials, a coating liquid having the following composition was prepared. At this time, as for the addition of the coupling agent and the inorganic fine particles, the inorganic fine particles are added to a solution in which the coupling agent is dissolved in water or isopropyl alcohol (IPA) in advance, and a sufficiently stirred mixture is added to the paint. This was performed by a wet method. Next, using a bar coater, the coating liquid prepared as described above is coated and dried under the following conditions using a bar coater to form a transfer layer. Each of the transfer layers having a release layer and a transfer layer Transfer media of Examples and Comparative Examples were produced. Table 1 collectively shows the structures of the transfer layers of the transfer media of Examples 1 to 6 and Comparative Examples 1 to 5.

Example 1 <Composition of the first layer of the transfer layer> 100 parts by weight of thermoplastic resin fine particles a 400 parts by weight of thermoplastic resin binder a (100 parts by weight of solid content) 15 parts by weight of inorganic fine particles a Coupling agent a 15 parts by weight Cationic resin a 50 parts by weight (solids content 15 parts by weight) Surfactant a 8 parts by weight (solids content 2.4 parts by weight) Plasticizer a 20 parts by weight Isopropyl alcohol (IPA) 200 parts by weight <Coating conditions>-Drying conditions: 70 ° C / 10 minutes-Coating film thickness: 60 µm

Example 2 <Composition of the first layer of the transfer layer> 100 parts by weight of thermoplastic resin fine particles b 170 parts by weight of thermoplastic resin binder b (50 parts by weight of solid content) 10 parts by weight of inorganic fine particles a Coupling agent b 10 parts by weight Cationic resin a 33 parts by weight (solids content 10 parts by weight) Surfactant a 6 parts by weight (solids content 1.2 parts by weight) Isopropyl alcohol (IPA) 100 parts by weight (coating Conditions) ・ Drying conditions: 70 ° C./10 minutes ・ Coating film thickness: 80 μm

Example 3 <Composition of Transfer Layer First Layer (Surface Layer Side)> 100 parts by weight of thermoplastic resin fine particles a 400 parts by weight of thermoplastic resin binder a (100 parts by weight of solid content) Cationic resin a 50 parts by weight (solids content 15 parts by weight)-Surfactant a 8 parts by weight (solids content 2.4 parts by weight)-Plasticizer a 20 parts by weight-IPA 100 parts by weight (coating conditions)-Drying conditions: 70 ° C / 10 minutes ・ Coating thickness: 60 μm

<Composition of Transfer Layer Second Layer (Release Layer Side)> Inorganic fine particles a 15 parts by weight Coupling agent a 15 parts by weight Binder c 150 parts by weight (60 parts by weight) IPA 50 parts by weight Part (coating condition) ・ Drying condition: 70 ° C./10 minutes ・ Coating film thickness: 20 μm

Example 4 <Composition of the first layer of the transfer layer> 100 parts by weight of thermoplastic resin fine particles a 400 parts by weight of thermoplastic resin binder a (100 parts by weight of solid content) 50 parts by weight of cationic resin a Solid content 15 parts by weight) Surfactant a 8 parts by weight (solids content 2.4 parts by weight) Plasticizer a 20 parts by weight IPA 100 parts by weight (coating conditions) Drying condition: 70 ° C / 10 minutes Coating film thickness: 60 μm

<Composition of the second layer of the transfer layer> 100 parts by weight of thermoplastic resin binder c (coating condition) Drying condition: 70 ° C./5 minutes Coating film thickness: 5 μm

<Composition of Third Layer of Transfer Layer> 15 parts by weight of inorganic fine particles a 15 parts by weight of coupling agent a 150 parts by weight (60 parts by weight) of thermoplastic resin binder c 50 parts by weight of IPA Processing conditions) Drying conditions: 70 ° C / 10 minutes Coating film thickness: 20 μm

Example 5 <Composition of transfer layer> 100 parts by weight of thermoplastic resin fine particles b 170 parts by weight of thermoplastic resin binder b (50 parts by weight of solid content) 10 parts by weight of inorganic fine particles a Coupling agent c 10 parts by weight Cationic resin a 33 parts by weight (solid content 10 parts by weight) Surfactant a 6 parts by weight (solids content 1.2 parts by weight) IPA 100 parts by weight (coating conditions) Drying condition: 70 ° C / 10 minutes ・ Coating thickness: 80 μm

Example 6 <Composition of the transfer layer> 100 parts by weight of thermoplastic resin fine particles a 250 parts by weight of thermoplastic resin binder b (100 parts by weight of solids) 15 parts by weight of inorganic fine particles a Coupling agent d 15 parts by weight ・ Cation resin a 33 parts by weight (solid content 10 parts by weight) ・ Surfactant a 8 parts by weight (solids content 2.4 parts by weight) ・ Plasticizer a 20 parts by weight ・ IPA 200 parts by weight (coating) Conditions) ・ Drying conditions: 70 ° C./10 minutes ・ Coating film thickness: 60 μm

Comparative Example 1 <Composition of Transfer Layer> 100 parts by weight of thermoplastic resin fine particles a 400 parts by weight of thermoplastic resin binder a 100 parts by weight of solid content 100 parts by weight of inorganic fine particles a 15 parts by weight of cationic resin a 50 parts by weight (solids content 15 parts by weight)-Surfactant a 8 parts by weight (solids content 2.4 parts by weight)-Plasticizer a 20 parts by weight-IPA 200 parts by weight (coating conditions)-Drying conditions: 70 ° C / 10 minutes ・ Coating thickness: 60 μm

Comparative Example 2 <Composition of Transfer Layer> 100 parts by weight of thermoplastic resin fine particles a 400 parts by weight of thermoplastic resin binder a (100 parts by weight of solid content) 50 parts by weight of cationic resin a (solid content of 15 parts) 8 parts by weight of surfactant a (2.4 parts by weight of solid content) 20 parts by weight of plasticizer a 100 parts by weight of IPA (coating conditions) Drying condition: 70 ° C./10 minutes Thickness: 60 μm

Comparative Example 3 <Composition of Transfer Layer> 100 parts by weight of fine particles of thermoplastic resin b 170 parts by weight of fine binder of thermoplastic resin b (50 parts by weight of solid content) 10 parts by weight of inorganic fine particles a Resin a 33 parts by weight (solids content 10 parts by weight) Surfactant a 6 parts by weight (solids content 1.2 parts by weight) IPA 100 parts by weight (coating conditions) Drying condition: 70 ° C./10 minutes coating Working thickness: 80 μm

Comparative Example 4 <Composition of Transfer Layer> 100 parts by weight of thermoplastic resin fine particles a 250 parts by weight of thermoplastic resin binder b (100 parts by weight of solid content) 15 parts by weight of inorganic fine particles a Cationic resin a 33 parts by weight (solids content 10 parts by weight)-Surfactant a 8 parts by weight (solids content 2.4 parts by weight)-Plasticizer a 20 parts by weight-IPA 100 parts by weight (coating conditions)-Drying conditions: 70 ° C / 10 minutes ・ Coating thickness: 60 μm

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

[0084]

[Table 4]

The ink jet color printer BJC-600J (manufactured by Canon Inc.) was applied to the transfer media obtained in Examples 1 to 6 and Comparative Examples 1 to 5 prepared as described above.
Was used to perform printing in a back-printed film mode to form an image. After printing, 100% cotton T-shirt (HA
The transfer layer side of the transfer medium on which an image is formed is laminated on a TES shirt side on BESY (manufactured by NES), and a thermal transfer machine (heat plate surface temperature 200 ° C. transfer pressure 80 g) is applied from the substrate side
/ Cm ² ) to form an image transfer. With respect to the transfer images of the image transfer products thus created, (1) image quality,
(2) Washing fastness and (3) transferability were evaluated.

(1) Image Quality Two-color patches were printed side by side, and evaluation was made based on the bleeding at the boundary. As for the image, 100% duty yellow and cyan, blue and red were used adjacent to all the pixels, and the bleeding at the boundary of each color was visually observed.
The evaluation was performed in the following four stages. A: no bleeding at the boundary between all colors B: bleeding only at the boundary between secondary colors (between blue and red) C: between the secondary and primary colors (blue and red) D: Blind spots were found at the boundary even in the cyan area.

(2) Washing fastness The T-shirt, which is an image transcript produced by the above method, was washed for 10 minutes and rinsed for 10 minutes 10 times each using a home two-layer washing machine. Next, after dehydration, it was dried with a dryer. The degree of decolorization of the transfer portion of each T-shirt thus washed and dried was visually observed, and the washing fastness of each sample was evaluated according to the following criteria. The image formed on the T-shirt has 100% duty black, cyan, magenta and yellow patches (15
mm × 15 mm). A: There was no bleaching B: A little bleaching C: It was fairly bleaching

(3) Transferability The degree of peeling of the transfer portion of each T-shirt after washing and drying in the above-described washing fastness evaluation test was visually observed.
The transferability of each sample was evaluated according to the following criteria. A: The transfer layer was not peeled off B: The transfer layer was partially peeled off C: The transfer layer was entirely peeled off The evaluation results of Examples and Comparative Examples are shown in Table 2. .

(4) Preservation of Transfer Medium Further, Examples 1 to 6 and Comparative Example 1 prepared as described above were prepared.
Each of the transfer media (sheets) in Nos. 1 to 5 was placed in a polypropylene bag, left in a high-temperature bath at 60 ° C./50% for 2 days, and then used to print an image on a T-shirt in the same manner as described above. Transfer was performed to obtain each T-shirt as an image transfer product. next,
For each of the obtained T-shirts, (2) washing fastness and (3) transferability were evaluated in the same manner as described above, and (3) sheet preservability was evaluated.

[0090]

[Table 5]

[0091]

As described above, according to the present invention,
Provided is a transfer medium for ink jet recording excellent in sheet preservability, which can easily and stably form a good transfer image on a transfer target such as a cloth by using an ink jet recording method. In particular, by using such a transfer medium, it is possible to form a transfer image having high ink absorbency, high density, and high clarity. Is soft and has excellent texture and high washing fastness.

Claims (8)

[Claims] 1. In a transfer medium for ink jet recording having a release layer and a transfer layer provided on a substrate, the transfer layer contains thermoplastic resin fine particles, a thermoplastic resin binder, inorganic fine particles, and a coupling agent. A transfer medium for ink jet recording, comprising: 2. The transfer medium for inkjet recording according to claim 1, wherein the coupling agent has a functional group reactive with the thermoplastic resin fine particles or the thermoplastic resin binder. 3. A transfer layer comprising: a layer containing a coupling agent;
3. The transfer medium for ink jet recording according to claim 2, wherein the transfer medium is separated into at least two layers including a layer containing a thermoplastic resin reactive to the coupling agent. 4. The transfer medium for ink-jet recording according to claim 1, wherein the coupling agent has no reactivity with the thermoplastic resin fine particles, the thermoplastic resin binder, or other materials in the transfer layer. 5. The transfer layer comprises at least two layers,
The transfer medium for ink jet recording according to any one of claims 1 to 4, wherein the lowermost layer of the transfer layer which is in contact with the release layer is a uniform coating layer containing no resin particles. 6. The transfer medium according to claim 5, wherein the transfer layer and the uniform coating layer contain the same thermoplastic resin. 7. An image forming step of forming a desired image on a transfer layer of an ink jet recording transfer medium by an ink jet recording method, and covering a transfer layer side surface of the transfer medium on which an image is formed by the image forming step. Overlaid on the surface of the transfer body,
Transferring the transfer layer to the surface of the transfer-receiving member by heating from the back surface opposite to the transfer layer side to form a transfer image. A method for producing an image transfer product, comprising using the transfer medium for inkjet recording according to claim 1. 8. A transferred fabric having a transferred image formed on the fabric, wherein the transferred image is formed by the method for producing an image transferred product according to claim 7.