WO2014119739A1 - Marking sheet for clothing and method for thermal transfer using same - Google Patents

Abstract

This marking sheet for clothing comprises a support (1) and, disposed on one surface thereof in the following order from the support side, a colored layer (2), a water-soluble resin layer (3) containing polyethyleneimine, and a heat-fusible adhesive layer (4). The water-soluble resin layer (3) can serve also as a colorant migration prevention layer (5) which prevents any colorant contained in the garment from migrating to the colored layer (2). Alternatively, a colorant migration prevention layer (5) may be disposed separately. This marking sheet for clothing, even when used after bonded to a garment, e.g., cloth, retains the property of preventing colorant migration, suffers neither lifting nor peeling, and does not impair the texture thereof.

Description

Marking sheet for clothing and thermal transfer method using the same

The present invention relates to a marking sheet that is adhered to clothing such as fabric by heat.

Conventionally, a marking sheet in which a colored layer made of a vinyl chloride resin or a polyurethane resin is provided on a support such as release paper and a thermal adhesive layer is laminated on the colored layer has been used. These marking sheets are cut into a desired shape with a cutting machine, etc., and then thermally bonded to a clothing fabric such as sportswear through a heat bonding layer with a heat lami roll or a heat press to attach a bib to the clothing. It is used for.

In recent years, these fabrics for sportswear and so on have been colored with chemical fibers because of their good texture such as touch, ease of washing, and design. A marking sheet that is thermally bonded to a fabric is also required to have a texture that follows a flexible fabric and an adhesive during use.

When the above-mentioned marking sheet is thermally bonded to a colored chemical fiber fabric, the coloring material of the fabric, mainly the dye, passes through the thermal bonding layer and moves to the colored layer of the marking sheet, and the original marking sheet There is a problem that the appearance of the hue is mixed with the hue of the fabric and the appearance is impaired. This problem is prominent when the clothing fiber is a polyester fabric.

In order to prevent the migration of the coloring material from the fabric to the marking sheet, a barrier layer having a function of preventing the migration of the coloring material between the colored layer of the marking sheet and the fabric may be provided by coating (patent Documents 1 and 3) and providing a barrier layer of plastic film or metal foil (Patent Document 2) have been proposed.

Japanese Patent Laid-Open No. 7-26479 JP-A-8-134783 JP-A-8-156429

However, the barrier layer using the above-described coating or the barrier layer using a plastic film or a metal layer has insufficient adhesion between the barrier layer and the colored layer. As a result, there is a problem that floating or peeling is likely to occur when the marking film is used.
In addition, when the water-resistant agent is added and crosslinked as a dye transfer prevention layer (Patent Document 3), the marking sheet itself has a hard feel and there is a problem that the texture of the flexible fabric is impaired. This problem is particularly noticeable when the dye migration prevention layer is thick.

Therefore, the present invention prevents the coloring material of the adherend from being transferred to the colored layer of the marking sheet even when the marking sheet is adhered to an adherend such as a fabric (coloring material migration preventing property). An object of the present invention is to provide a marking sheet for clothing that does not cause the marking sheet to float or peel (adhesiveness) and does not impair the texture of a flexible adherend (texture).

The present inventors diligently studied a material that has extremely good adhesion to the colored layer and does not cause curing due to crosslinking even by thermal bonding, and does not impair the texture of clothing.
As a result of intensive studies, by laminating a water-soluble resin layer containing polyethyleneimine on the colored layer of the clothing marking sheet of the present invention, the colored layer, while having colorant migration prevention and texture, It has been found that the adhesiveness to the adherend via the hot-melt adhesive layer can be remarkably improved, that is, the adhesiveness during use of the clothing marking sheet can be greatly improved. It came to be completed.

That is, the marking sheet for clothing of the present invention that solves the above problems includes a hot-melt adhesive layer, a colored layer, and one or more intermediate layers between the hot-melt adhesive layer and the colored layer, The intermediate layer adjacent to the hot-melt adhesive layer is a water-soluble resin layer containing polyethyleneimine.
Further, the marking sheet for clothing of the present invention is a marking sheet having a colorant migration preventing property, and a water-soluble resin containing a colored layer and polyethyleneimine in order from the support side on one side of the support. It is a clothing marking sheet characterized by having a layer and a heat-meltable adhesive layer.

Further, the clothing marking sheet of the present invention is characterized in that the water-soluble resin layer is a colorant migration preventing layer having a colorant migration preventing property.

Moreover, the marking sheet for clothing of the present invention is characterized by having a colorant migration preventing layer having a colorant migration preventing property between the water-soluble resin layer and the hot-melt adhesive layer. .

The clothing marking sheet of the present invention is characterized in that the colorant migration preventing layer contains a polyvinyl alcohol resin.

The clothing marking sheet of the present invention is characterized in that the polyethyleneimine has a number average molecular weight of 1800 or more.

The clothing marking sheet of the present invention is characterized in that the content of polyethyleneimine contained in the water-soluble resin layer is less than 25 parts by weight with respect to 100 parts by weight of the resin of the water-soluble resin layer. Is.

The clothing marking sheet of the present invention is characterized in that the colored layer is a resin colored layer capable of inkjet printing.

Further, the thermal transfer method for a clothing marking sheet of the present invention is a method for thermally transferring a colored layer of a desired shape onto an adherend using the above-described clothing marking sheet, wherein the thermal marking property of the clothing marking sheet is as follows. The colored layer, the intermediate layer, and the hot-melt adhesive layer are transferred to the adherend by overlapping and heat-bonding such that the surface of the adhesive layer and the surface of the adherend are in contact with each other.

The thermal transfer method for a clothing marking sheet of the present invention includes a step of peeling the support when the clothing marking sheet includes a support on the outermost side in contact with the colored layer. The step of peeling the support is performed before or after the step of heat bonding.
Moreover, the thermal transfer method of the marking sheet for clothes of this invention includes the process of carrying out the inkjet printing of a desired character and a pattern on the surface of the said colored layer before the process of heat-bonding.

According to the present invention, there is provided a marking sheet for clothing that has good adhesion without peeling off the adherend and the marking sheet at the time of use, while having a colorant migration preventing property and without damaging the softness and texture. can do.

The figure which shows embodiment of the marking sheet for clothing of this invention The figure which shows an example of the process of the thermal transfer method using the marking sheet for clothing of this invention The figure of other examples of the process of the thermal transfer method using the marking sheet for clothes of the present invention The figure of another example of the process of the thermal transfer method using the marking sheet for clothes of this invention

The clothing marking sheet of the present invention comprises a heat-meltable adhesive layer, a colored layer, and one or more intermediate layers between the heat-meltable adhesive layer and the colored layer, and the heat-meltable adhesive layer includes The adjacent intermediate layer is a water-soluble resin layer containing polyethyleneimine. At least one of the intermediate layers has a colorant migration preventing property. Moreover, the marking sheet for clothing of this invention may be provided with the support body which touches a colored layer.
Hereinafter, each layer which comprises the marking sheet for clothing of this invention is demonstrated concretely.

As a support used in the marking sheet for clothing of the present invention, regardless of whether it is transparent or opaque, for example, paper, coated paper, laminated paper, synthetic paper such as PP, various plastic films can be used. Since there are cases where a heat lami roll or a hot pressing process may be included, paper or polyester film having heat resistance to such an extent that shrinkage and warpage are hardly generated at the heat bonding temperature is preferable.

In addition, if necessary, the surface of the support in contact with the colored layer may be subjected to a release treatment, or the surface of the support is subjected to sandblasting, embossing, or shaping to make the colored layer surface matt. Or a mat-like coating film may be provided to make the surface uneven.

The thickness of the support is not particularly limited, but a thickness of about 10 μm to 1000 μm can be used from the viewpoint of increasing costs and preventing workability.

The colored layer is a part of a bib or a patch that is thermally bonded to an adherend, and a resin binder in which a coloring material such as a dye or pigment is dissolved or dispersed can be used. A white pigment such as titanium oxide can also be used as the colorant.
As the resin binder, those having film properties can be used, for example, vinyl chloride resin, vinyl acetate resin, vinylidene chloride resin, polyester resin, polyurethane resin, polyolefin resin, acrylic resin, rubber resin. 1 type, or 2 or more types of resin can be used. Those which do not melt due to heat during heat bonding are good. A curing agent may be used to improve the film strength, water resistance and oil resistance.

In particular, polyurethane resins and vinyl chloride resins are preferred because they are flexible and do not impair the texture of the adherend, and are excellent in water resistance, weather resistance, etc. In addition, mechanical properties, abrasion resistance, low temperature properties From the viewpoint of environmental problems, polyurethane resins are more preferable.

The polyurethane-based resin is produced by a polyaddition reaction of polyol and polyisocyanate, and may be a film formed by a solvent casting method or a film formed by heat extrusion, and may be a polyester type or a polyether type.

The thickness of the colored layer is preferably so thin that the coating strength is not insufficient, and thin enough not to deteriorate the cutting property, die cut property, texture or productivity. Is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more. The upper limit is 500 μm or less, more preferably 300 μm or less, and even more preferably 150 μm or less.

The colored layer is colored with a coloring material as described above, but can also be printed by an ink jet printing method. By performing ink jet printing on the colored layer, for example, by performing ink jet printing of a desired color on the white colored layer, clothing marking sheets of various colors and special colors can be obtained, and gradation such as photographic gradation It is also possible to print a certain design. Thereby, even if it does not have the stock of the clothing marking sheet of various colors, it is sufficient if there is a clothing marking sheet of a single color, for example, a white colored layer, and the stock quantity can be reduced. Moreover, when the marking sheet for clothes of this invention presupposes printing to a colored layer, a colored layer may be transparent or semi-transparent, and may become a colored layer afterwards. In addition, in order to carry out the inkjet printing of the colored layer of this invention, it can print using what is called a solvent ink by which the ink pigment was disperse | distributed with the organic solvent with the inkjet output machine. If it is resin used for the colored layer illustrated above, such inkjet printing is possible, without performing a special process.

Next, the intermediate layer provided between the colored layer and the hot-melt adhesive layer will be described. The intermediate layer may be a single layer or two or more layers, but at least one layer is a layer having a colorant migration preventing property. The layer in contact with the colored layer is a water-soluble resin layer containing polyethyleneimine.

Accordingly, the water-soluble resin layer containing polyethyleneimine and the colorant migration preventing layer can be separately laminated, or the water-soluble resin layer itself having polyethyleneimine has the colorant migration preventing property. In both cases, the water-soluble resin layer containing polyethyleneimine has an effect of improving the adhesiveness with the colored layer. A preferred embodiment as the structure of the intermediate layer is shown in FIG.

The marking sheet for clothing shown in FIG. 1 (a) is an embodiment in which the intermediate layer is a single layer and the water-soluble resin layer containing polyethyleneimine also serves as a colorant migration preventing layer. On the surface, a colored layer 2, a water-soluble resin layer 3 containing polyethyleneimine, and a heat-meltable adhesive layer 4 are provided in this order from the support.

(B) of FIG. 1 is provided with at least two layers of a colorant migration preventing layer 5 and a water-soluble resin layer 3 as an intermediate layer. The colored layer 2 is formed on the support 1 in order from the support. And a water-soluble resin layer 3 containing polyethyleneimine, a colorant migration preventing layer 5 and a hot-melt adhesive layer 4.

(C) of FIG. 1 is an embodiment that does not have a support, and has a colored layer 2, a polyethyleneimine-containing water-soluble resin layer 3 that also serves as a coloring material migration preventing layer, and a heat-meltable adhesive layer 4. A separator 6 is provided on the heat-meltable adhesive layer 4. In this embodiment, a coloring material migration preventing layer may be separately provided between the water-soluble resin layer 3 and the hot-melt adhesive layer 4.

First, a case where the water-soluble resin layer containing polyethyleneimine and the colorant migration preventing layer are laminated separately will be described ((b) in FIG. 1). In this case, the colorant migration preventing layer is provided between the water-soluble resin layer containing polyethyleneimine and the hot-melt adhesive layer. As the coloring material migration preventing layer, a known material can be used, but it is preferable to use a resin having a solubility (degree) parameter, a so-called SP value (according to IUPAC GOLD BOOK), of 11 or more, which is a characteristic inherent to the resin, In particular, a layer containing a polyvinyl alcohol resin which is a resin excellent in colorant migration prevention property is preferable.

The reason why the polyvinyl alcohol resin is particularly excellent in colorant migration prevention is considered as follows.
In order to color a hydrophobic fiber such as a polyester fiber, a hydrophobic colorant such as a disperse dye is used because it is difficult to color with a water-soluble colorant. However, the polyester fiber itself is originally a material with poor adhesion, and the hydrophobic colorant for coloring the fiber also has poor adhesion, with the heat when the marking sheet is heat bonded and the change over time after bonding, It is considered that the hydrophobic coloring material sublimates and migrates, passes through the thermal adhesive layer, and the colored layer is contaminated.

On the other hand, the polyvinyl alcohol resin is a resin having particularly high hydrophilicity among the resins, and has an SP value of 12.6. By using such a resin having a high SP value, it is possible to prevent the coloring material from moving further to the coloring layer side by repelling the hydrophobic coloring material transferred through the thermal adhesive layer.

Furthermore, in order to improve the colorant migration preventing property, among the polyvinyl alcohol resins, those having a high degree of saponification can be suitably used.

When the degree of saponification of the polyvinyl alcohol resin is increased, the number of hydroxyl groups is increased and the hydrophilicity is further increased, and for the reason described above, the colorant migration preventing property of the hydrophobic colorant is increased. In addition, hydroxyl groups increase and hydrophilicity increases (for example, the water contact angle becomes smaller), but water resistance itself is good due to the increase of intermolecular and intramolecular hydrogen bonds due to the increase of hydroxyl groups in the molecule. It is thought that there is also an effect that can be made. In terms of water resistance itself, the polyvinyl alcohol resin itself has an effect that the crystallinity can be increased by heat at the time of coating film formation and the water resistance can be improved.

The saponification degree of the polyvinyl alcohol resin suitably used is 85 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 97 mol% or more. Is substantially 100 mol% (completely saponified product).

By making the saponification degree 85 mol% or more, the colorant migration preventing property can be improved, and the use of polyvinyl alcohol resins having different saponification degrees can be adjusted as appropriate.

The degree of polymerization of the polyvinyl alcohol resin preferably used is in the range of 400 to 2000, and is usually represented by the solution viscosity of an aqueous solution (4% by weight, 20 ° C.).
When the degree of polymerization is 400 or less, the film strength becomes weak, and when the degree of polymerization is 2000 or more, it becomes difficult to dissolve, and at the same time, the solution viscosity increases and it becomes difficult to apply, so the degree of polymerization can be appropriately selected within the above range.

The colorant migration preventing layer may contain a water-soluble resin such as polyacrylic acid methyl ester, polyacrylic acid ethyl ester, carboxymethyl cellulose resin, methyl cellulose resin, hydroxyethyl cellulose resin, and starch in addition to the polyvinyl alcohol resin. However, the polyvinyl alcohol resin is preferably 70% by weight or more based on the entire resin of the water-soluble resin layer from the viewpoint of the colorant migration preventing function. More preferably, it is 80 weight% or more, More preferably, it is 90 weight% or more.

The water-soluble resin layer containing polyethyleneimine is a layer that prevents the colored layer after thermal transfer from being peeled off from the adherend by firmly adhering to the colored layer. The heat-meltable adhesive layer, the water-soluble resin layer, In the case where a colorant migration preventing layer is provided between them, the colorant migration preventing function may or may not have a function, but a layer having good adhesion to the laminated colorant migration preventing layer may be used. preferable. Water-soluble resins, water-alcohol mixed solvent-soluble resins, and water-based emulsion resins can be used as water-soluble resins. Specifically, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, water-soluble nylon resins (water-soluble resins) Polyamide resin), methyl cellulose resin, ethyl cellulose resin, carboxymethyl cellulose resin, hydroxyethyl cellulose resin, hydroxypropyl cellulose resin, hydroxypropyl methylcellulose resin, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, polyvinyl acetal resin, polyester resin series One or two kinds of emulsion, polyvinyl acetate resin emulsion, acrylic resin emulsion and the like can be mixed and used.

The reason why the adhesive strength with the colored layer can be improved by providing a water-soluble resin layer containing polyethyleneimine on the colored layer is considered as follows.

When polyethyleneimine is contained in the water-soluble resin layer, the familiarity (affinity) between the amino group in the molecular structure of polyethyleneimine, which is water-soluble, and the resin constituting the water-soluble resin layer is good. In the case where the resin is a hydroxyl group-containing hydrophilic resin, it is considered that the resin is more familiar because it is electrically attracted by hydrogen bonding. On the other hand, since the ethylene chain in the molecular structure of polyethyleneimine is hydrophobic, it blends well with the hydrophobic colored layer, and as a result, it is considered that the adhesion between the colored layer and the water-soluble resin layer is improved. It is done.

“Familiarity” between polyethyleneimine with improved adhesion and resin in water-soluble resin layer means “physical gel” in which the amino group of polyethyleneimine and the resin in water-soluble resin layer are weak bonds such as hydrogen bonds. It is thought that this is a state that causes Unlike a “chemical gel” that is a strong bond such as a covalent bond, a physical gel does not cause so-called curing / crosslinking. Since no curing / crosslinking has occurred, it is considered that the water-soluble resin layer, that is, the marking sheet for clothing, is hard and does not impair the texture. The fact that the composition is not cured / crosslinked is presumed from the fact that the coating solution of the water-soluble resin layer containing the polyethyleneimine of the present invention can be reused without gelation even if stored for a long period of time.

Polyethyleneimine contained in the water-soluble resin layer may have a molecular weight of 300 or more, preferably 1,500 or more, more preferably 10,000 or more, and even more preferably 50,000 or more. The upper limit of the molecular weight is preferably 100,000 or less. By setting the molecular weight to 300 or more, the adhesive force between the colored layer and the water-soluble resin layer can be improved, and by setting the molecular weight to 100,000 or less, the solution viscosity increases and workability deteriorates. It can be avoided that polyethyleneimine is expensive and expensive.
As a method for measuring the molecular weight of polyethyleneimine, those having a molecular weight of less than 50,000 are those based on the number average molecular weight (Mn) due to an increase in boiling point, and those having a molecular weight of 50,000 or more are those based on the viscosity method. It was.

As for the amount of polyethyleneimine added, the lower limit is 100 parts by weight of the resin of the water-soluble resin layer, and the lower limit is 1 part by weight or more, preferably 2 parts by weight or more, more preferably 3 parts by weight or more. The upper limit is less than 25 parts by weight, preferably less than 20 parts by weight, more preferably less than 15 parts by weight. By making the addition amount 1 part by weight or more, the adhesive force between the colored layer and the water-soluble resin layer can be improved. Further, when the amount is less than 25 parts by weight, the water-soluble resin layer itself can be provided with a colorant migration preventing property, and particularly when the amount is less than 20 parts by weight, the colorant migration preventing property can be improved.

In the clothing marking sheet of the present invention, when the water-soluble resin layer containing polyethyleneimine and the colorant migration preventing layer are separated, the water-soluble resin layer containing polyethyleneimine and the colorant migration preventing layer As for the thickness of the coating film, the lower limit is 0.4 μm or more, preferably 0.7 μm or more, and the upper limit is 2.0 μm or less, preferably 1.7 μm or less.

When the water-soluble resin layer containing polyethyleneimine is 0.4 μm or more, the adhesiveness with the colored layer can be improved, and when the coloring material migration preventing layer is laminated by setting it to 2.0 μm or less But there is no loss of texture. Further, when the colorant migration preventing layer is 0.4 μm or more, the colorant migration preventing property can be improved, and when it is 2.0 μm or less, it is laminated on the water-soluble resin layer containing the polyethyleneimine. Even if it does, the texture will not be impaired.

By making the intermediate layer into a multilayer structure in this way, the water-soluble resin layer containing polyethyleneimine can be made into a thin film while maintaining good texture, adhesiveness, and colorant migration prevention property, The amount of polyethyleneimine used can be relatively reduced and the cost can be reduced.

Next, the case where the water-soluble resin layer itself containing polyethyleneimine has the colorant migration preventing property ((a) in FIG. 1) will be described. In this case, as the water-soluble resin constituting the water-soluble resin layer, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, water-soluble nylon resin (water-soluble polyamide resin), methyl cellulose resin, ethyl cellulose resin, carboxymethyl cellulose resin, hydroxyethyl cellulose resin It is preferable to use a water-soluble resin such as hydroxypropylcellulose resin, hydroxypropylmethylcellulose resin, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, and polyvinyl acetal resin, and polyvinyl alcohol resin is particularly preferable. When a polyvinyl alcohol resin is used, the preferred saponification degree, polymerization degree, and content of the polyvinyl alcohol resin contained in the water-soluble resin layer are the same as described for the colorant migration preventing layer.

In addition, the molecular weight and addition amount of polyethyleneimine contained in the water-soluble resin layer are also in the same range as the molecular weight and addition amount in the case of a structure in which the water-soluble resin layer and the colorant migration prevention layer are laminated separately. is there.

The film thickness of the water-soluble resin layer containing polyethyleneimine is 0.4 μm or more, preferably 0.7 μm or more, more preferably 1.0 μm or more as the lower limit. The upper limit of the film thickness is 3.0 μm or less, preferably 2.5 μm or less, more preferably 2.0 μm or less. By setting the film thickness to 0.4 μm or more, it is possible to improve the adhesion to the colored layer and the colorant migration prevention property. By setting the film thickness to 3.0 μm or less, application of repellency, craters, etc. Defects can be reduced.
In addition, when the water-soluble resin layer containing polyethyleneimine also serves as the colorant migration preventing layer, the adhesiveness of the colored layer and the colorant can be obtained by providing only one intermediate layer between the colored layer and the heat-meltable adhesive layer. Since the migration preventing property can be obtained, the thickness of the entire clothing marking sheet can be reduced, and a thermal transfer product having a good texture can be obtained without impairing the texture of the adherend.

As described above, the case where the structure of the intermediate layer is shown in FIGS. 1A and 1B has been described, but the same applies to the case where the support is not provided as shown in FIG. In any case, both the film thickness of the water-soluble resin layer containing polyethyleneimine and the film thickness in the case where there is a resin layer containing polyvinyl alcohol are both thin, so that the texture as a marking sheet for clothing should be improved. In addition, the adhesiveness to the colored layer and the colorant migration preventing property can be improved despite the thin film. The colorant migration preventing property can be imparted wherever the layer having the colorant migration preventing property is disposed.

In addition, a water-proofing agent can be added to the water-soluble resin layer containing polyethyleneimine and the layer containing polyvinyl alcohol resin for the purpose of improving water resistance and the like within a range that does not impair adhesiveness and texture.

As water-proofing agents that can be added, organic titanium compounds, glyoxal, methylolated melamine, dimethylolurea, etc. can be used. The ratio of the group or reaction site (mol) with respect to 1 mol of the reactive group of the resin is the addition amount of the reactive group or reaction site (mol) of the water resistant agent (when 1 mol: 1 mol is equivalent ratio), the lower limit Is 0.2 mol or more, preferably 0.5 mol or more, still more preferably 0.8 mol or more, and the upper limit is 2.0 mol or less, preferably 1.5 mol or less, and even more preferably 1.2 mol or less.

Next, the hot melt adhesive layer will be described. The heat-meltable adhesive layer is laminated on a water-soluble resin layer containing polyethyleneimine or a coloring material migration preventing layer (resin layer containing polyvinyl alcohol), and each layer containing the colored layer of the clothing marking sheet of the present invention is adhered. It is a layer for heat-bonding to the clothing.
As the heat-meltable adhesive layer, a material having good adhesiveness can be selected according to the type of adherend, and a material that does not block at room temperature and has no tack is preferably used. A so-called hot-melt adhesive that is melt-bonded by heat at the time of thermal bonding can be suitably used.

Examples of the resin that can be used as the hot-melt adhesive layer include one or more of ethylene vinyl acetate, polyolefin, synthetic rubber, acrylic, polyurethane, polyamide, and polyester resins. . In addition, a resin having flexibility that follows the elongation of the fabric when adhered to the fabric and further having water resistance is preferably used. Among the above resins, polyurethane resins and polyester resins are particularly preferable. It can be used suitably.

The film thickness of the heat-meltable adhesive layer varies depending on the fabric to be adhered, but can be bonded if it is 10 μm or more. In order to improve the adhesive strength, it is preferable that the film thickness is thick. However, if the film thickness is too large, inconvenience occurs in cutting property, die cutting property, productivity, and the like, and therefore 200 μm or less is preferable.

The interface between the heat-meltable adhesive layer and the water-soluble resin layer or the resin layer containing polyvinyl alcohol needs to be firmly bonded without being peeled even after being bonded to the fabric adherend. For this reason, when the adhesive strength is insufficient, a layer for improving adhesiveness may be provided between the heat-meltable adhesive layer and the water-soluble resin layer or the resin layer containing polyvinyl alcohol. Surface treatment such as corona discharge treatment can also be performed on the resin layer or the resin layer containing polyvinyl alcohol.

Although the manufacturing method of the marking sheet for clothing of the present invention is not particularly limited, for example, it can be manufactured by the following manufacturing method. First, a known release treatment is performed on a support such as paper or a plastic film as necessary to form a colored layer by a coating method or a heat extrusion method. In the case of forming a film by a coating method, the above-described resin binder and coloring material are dispersed or dissolved in an organic solvent, applied and dried to form a colored layer. In the case of forming a film by a hot extrusion method, a colored layer is formed on a support by kneading and extruding a binder resin or a component that becomes the binder resin and a pigment. In this case, a master badge previously kneaded and pelletized may be used.

Next, on the laminated colored layer, a water-soluble resin containing polyethyleneimine is dissolved in water or an alcohol solvent, or an emulsion paint containing polyethyleneimine is applied and dried. Furthermore, when laminating a layer containing a polyvinyl alcohol resin, a solution obtained by dissolving a polyvinyl alcohol resin or the like with water or an alcohol-based solvent on a water-soluble resin layer containing polyethyleneimine is applied and dried. A layer containing an alcohol resin is laminated. As a coating method for forming the water-soluble resin layer, known methods such as a bar coater method, a roll coater method, a die coater method, and a gravure coater method can be used.

Next, a hot-melt adhesive resin that is hot-melted by a hot melt coater, an extrusion method or the like is directly applied to the laminated water-soluble resin layer, and a hot-melt adhesive layer is laminated. Alternatively, a film obtained by forming a heat-melt adhesive resin on another support in advance and the water-soluble resin layer surface of the laminated sheet are heat-laminated, and a heat-melt adhesive layer is formed on the water-soluble resin layer. You may laminate.

The clothing marking sheet of the present invention may be provided with other layers in addition to the above-mentioned layers without departing from the effects and configurations of the present invention. Examples of the other layers include an easy adhesion layer that increases adhesion between the layers, an antistatic layer, and an ultraviolet blocking layer.

In addition, during film formation in each of the above steps, additives such as an antioxidant, a dispersant, an antistatic agent, a leveling agent, an antifoaming agent, an antiblocking agent, and a tackifier do not impair the effects of the present invention. It can be added to each layer as appropriate.

A method for thermally transferring the marking sheet for clothing of the present invention to an adherend will be described with reference to FIGS.
First, it is appropriately selected whether the support is peeled off at the beginning of the transfer step or finally the support is peeled off. Referring to FIG. 2, after peeling the support 1 (from (a) to (b) of FIG. 2), the clothing marking sheet is cut into a desired shape as necessary (including half-cut) or Die-cut ((c)), pile up so that the heat-meltable adhesive layer 4 of the clothing marking sheet and the surface of the adherend 8 are in contact with each other, and pass through a hot ram roll or hot press to 120 ° C to 230 ° C, 0 The film is thermally bonded under a condition of about 0.01 to 1.0 MPa ((d)), and each layer from the colored layer to the heat-meltable adhesive layer is transferred to the adherend ((e)). The cutting step (c) may be omitted. In the case of the process shown in FIG. 3, cutting and thermal bonding are performed in the state where the support 1 is present, and the support 1 is peeled off after the thermal bonding. The conditions for thermal bonding are the same.

Further, as shown in FIG. 4, the support 1 of the clothing marking sheet is peeled off (FIGS. 4A to 4B), and on the exposed surface of the colored layer 2, a desired region, a desired character, Ink-jet printing of the desired design etc. ((c)), and cutting (including half-cutting) or die-cutting into the desired shape and contour when the printed area, characters, designs, etc. are required, The surface of the heat-meltable adhesive layer and the surface of the adherend are stacked so that they are in contact with each other and passed through a hot lami roll, or heat-bonded under conditions of 120 ° C. to 230 ° C. and about 0.01 to 1.0 MPa ( (D)) Each layer from the colored layer printed with characters, designs and regions to the heat-meltable adhesive layer is transferred to the adherend ((e)). As indicated by the dotted line in FIG. 4 (a), in order to facilitate the handling of the marking sheet in each process up to thermal bonding, a separator 6 or a protective film is provided on the thermal bonding layer 4 as necessary. Etc. may be attached. The same applies to the thermal transfer method of FIGS.

Hereinafter, the present invention will be further described with reference to examples. “Parts” and “%” are based on weight unless otherwise specified.

[Example 1]
Using a substrate obtained by laminating a white polyurethane resin layer (colored layer) having a thickness of 30 μm on a support having a thickness of 145 μm that has been subjected to a release treatment, the following water-soluble resin layer coating solution is applied to one side of the white polyurethane resin layer. Application and drying were performed to form a water-soluble resin layer having a thickness of 1.5 μm. The amount of polyethyleneimine added in the following water-soluble resin layer coating solution is 3.9 parts in terms of solid content with respect to the polyvinyl alcohol resin.
Heat melting of a water-soluble resin layer of a sheet in which a water-soluble resin layer is laminated on the base material, and a sheet of a separately prepared release paper having a thickness of 150 μm and a 55 μm-thick polyester heat-melting adhesive layer laminated thereon The adhesive sheet was bonded to the adhesive layer at 170 ° C. with a hot lami roll to produce a clothing marking sheet of Example 1.

<Water-soluble resin layer coating solution>
・ Polyvinyl alcohol resin 100 parts by weight (Gohsenol A300: Nippon Synthetic Chemical Industry Co., Ltd., saponification degree 97.0-98.5 mol%, solid content 100%)
・ 13 parts by weight of polyethyleneimine (Wako Pure Chemical Industries, molecular weight 70,000, solid content 30%)
1100 parts by weight of water

[Example 2]
The marking sheet for clothing of Example 2 is the same as Example 1 except that the amount of polyethyleneimine of Example 1 is changed to 9.8 parts in terms of solid content and added to the polyvinyl alcohol resin. Was made.

[Example 3]
The marking sheet for clothing of Example 3 in the same manner as in Example 1 except that the amount of polyethyleneimine of Example 1 was changed to 14.8 parts in terms of solid content and added to the polyvinyl alcohol resin. Was made.

[Example 4]
The marking sheet for clothing of Example 4 in the same manner as in Example 1 except that the amount of polyethyleneimine of Example 1 was changed to 19.8 parts in terms of solid content and added to the polyvinyl alcohol resin. Was made.

[Example 5]
The marking sheet for clothing of Example 5 is the same as Example 1 except that the amount of polyethyleneimine of Example 1 is changed to 24.8 parts in terms of solid content with respect to the polyvinyl alcohol resin and added. Produced.

[Example 6]
A clothing marking sheet of Example 6 was prepared in the same manner as in Example 2 except that polyethyleneimine having a different molecular weight (Wako Pure Chemical Industries, Ltd., molecular weight 10,000) was used as the polyethyleneimine.

[Example 7]
A clothing marking sheet of Example 7 was produced in the same manner as Example 2 except that polyethyleneimine having a different molecular weight (Wako Pure Chemical Industries, Ltd., molecular weight 1,800) was used as the polyethyleneimine.

[Example 8]
The clothing of Example 8 is the same as Example 2 except that the polyvinyl alcohol resin of Example 2 is changed to Gohsenol C500 (Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 95.0 to 97.0 mol%, solid content: 100%). A marking sheet was prepared.

[Example 9]
The apparel of Example 9 is the same as Example 2 except that the polyvinyl alcohol resin of Example 2 is changed to Gohsenol AL06R (Nippon Synthetic Chemical Industry Co., Ltd., saponification degree 91.0-94.0 mol%, solid content 100%). A marking sheet was prepared.

[Example 10]
After applying and drying the same water-soluble resin layer coating liquid as in Example 1 on one side of the white polyurethane resin layer of the same substrate as in Example 1, to form a water-soluble resin layer having a thickness of 0.5 μm, Further, on the water-soluble resin layer, the following polyvinyl alcohol resin layer coating solution was applied and dried to laminate a 1.0 μm-thick polyvinyl alcohol resin layer. Further, in the same manner as in Example 1, The marking sheet for clothes of Example 10 was produced by bonding the heat-meltable adhesive layer.

<Polyvinyl alcohol resin layer coating solution>
・ 100 parts by weight of polyvinyl alcohol resin (Gohsenol NH18: Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 98.0-99.0 mol%, solid content: 100%)
・ 1100 parts by weight of water

[Comparative Example 1]
A clothing marking sheet of Comparative Example 1 was produced in the same manner as Example 2 except that polyethyleneimine was not added.

[Comparative Example 2]
A clothing marking sheet of Comparative Example 2 was produced in the same manner as in Example 2 except that adipic acid dihydrazide (solid content: 100%) was used instead of the polyethyleneimine of Example 2.

[Comparative Example 3]
A silane coupling agent (KBM403, 3-glycidoxypropyltrimethoxysilane, Shin-Etsu Silicone) was added in place of polyethyleneimine in Example 2 in the same manner as in Example 2 except that 0.1 part in terms of nonvolatile content was added. Thus, a clothing marking sheet of Comparative Example 3 was produced.

[Comparative Example 4]
Except that 9.8 parts of water-dispersible polyisocyanate (DNW5500, solid content 80%, NCO content 13-14%, DIC) was added in place of polyethyleneimine in Example 2 in terms of solid content, this was carried out. In the same manner as in Example 2, a clothing marking sheet of Comparative Example 4 was produced.

The clothing marking sheets obtained in Examples 1 to 10 were thermally bonded to a polyester fiber fabric “polyester tricot EN155 red” colored in red under a hot press condition of “190 ° C. for 30 seconds 0.04 MPa”. However, a polyester fibrous fabric that was able to be thermally transferred satisfactorily and to which each clothing marking sheet was thermally transferred was obtained.

[Colorant migration prevention]
Regarding the clothing marking sheets obtained in Examples 1 to 10 and Comparative Examples 1 to 4, each clothing marking sheet was placed on a polyester fiber fabric “polyester tricot EN155 red” colored red as a transfer fabric. The adhesive was thermally bonded under a hot press condition of 190 ° C. for 30 seconds 0.04 MPa ”, the support was peeled off, and the transferability of the red colorant to the white polyurethane layer was measured with a color meter ZE2000 (Nippon Denshoku) L ^* , ΔE was calculated by measuring a ^* and b ^* .
△ "E" is 0-10 or less,
△ E is more than 10 and 20 or less.
The case where ΔE exceeded 20 was designated as “x”.
The results are shown in Table 1.

[Texture]
With respect to each clothing marking sheet after the thermal transfer, the texture was examined by tactile sensation.
“◎” indicates that the texture is not impaired.
“○” is what was felt a little harder,
Those that were clearly felt to be hard were marked with “x”.
The results are shown in Table 1.

[Adhesiveness]
About each marking sheet for clothes after the said heat transfer, the adhesiveness was investigated by the tape adhesion test, putting a goblet eye with a cutter from the white polyurethane layer side.
If the tape was not peeled even after several tapes, “◎”
“○” indicates that the tape is peeled off slightly after several times of tape bonding.
The thing peeled off by several times of tape adhesion was set as "x".
The results are shown in Table 1.

The marking sheets for clothing of Examples 1 to 4, Example 6, Example 8, and Example 10 were all excellent in colorant migration prevention, texture, and adhesion.

The clothing marking sheet of Example 5 had good texture and adhesiveness, but had lower colorant migration preventiveness than those of other examples, and colorant migration was observed. This seems to be because the amount of polyethyleneimine added is slightly higher.

The garment marking sheet of Example 7 was excellent in colorant migration prevention and texture, but its adhesion was slightly inferior to that of the other examples, and peeling was observed although it was very slight. This seems to be due to the slightly lower molecular weight of polyethyleneimine.

The clothing marking sheet of Example 9 had good texture and adhesiveness, but had a lower colorant migration preventing property than those of other examples, and the migration of the colorant was observed. It seems that the saponification degree of the used polyvinyl alcohol resin is slightly lower than the others.

On the other hand, the clothing marking sheet of Comparative Example 1 was poor in adhesion because polyethyleneimine was not added to the water-soluble resin layer.

The marking sheets for clothing of Comparative Examples 2 to 4 are additives that are known as crosslinking agents or curing agents (adipic acid dihydrazide, silane coupling agent, water-dispersible polyisocyanate, without adding polyethyleneimine to the water-soluble resin layer. ), But the adhesiveness was poor.

The clothing marking sheet of Comparative Example 3 to which a silane coupling agent as a curing agent is added and the clothing marking sheet of Comparative Example 4 to which a water-dispersible polyisocyanate that is also a curing agent is added are a resin of a water-soluble resin layer. Although the same polyvinyl alcohol resin having the colorant migration preventing property as in Example 2 was used, the colorant migration property was lower than that in Example 2.

Furthermore, although the marking sheet for clothing of Comparative Example 4 to which water-dispersible polyisocyanate is added has a thin water-soluble resin layer, the texture is not significantly impaired, but the texture is less than others. It was inferior. This is presumably because the water-soluble resin layer is hardened by a crosslinking reaction with polyisocyanate.

DESCRIPTION OF SYMBOLS 1 ... Support body, 2 ... Colored layer, 3 ... Water-soluble resin layer (intermediate layer), 4 ... Hot-melt adhesive layer, 5 ... Colorant transfer prevention layer (intermediate layer) , 6... Separator, 7... Printed layer, 8.

Claims (12)

1. A marking sheet for clothing comprising a hot-melt adhesive layer, a colored layer, and one or more intermediate layers disposed between the hot-melt adhesive layer and the colored layer, the hot-melt adhesive A marking sheet for clothing, wherein the intermediate layer adjacent to the layer is a water-soluble resin layer containing polyethyleneimine.
2. The clothing marking sheet according to claim 1,
   The said water-soluble resin layer is a coloring material transfer prevention layer which prevents that the coloring material contained in a to-be-adhered body transfers to the said coloring layer, The marking sheet for clothing characterized by the above-mentioned.
3. A clothing marking sheet according to claim 1,
   A clothing comprising a coloring material migration preventing layer for preventing a coloring material contained in an adherend from moving to the colored layer between the water-soluble resin layer and the heat-meltable adhesive layer. Marking sheet.
4. A marking sheet for clothing according to claim 2 or 3,
   The said coloring material transfer prevention layer contains polyvinyl alcohol resin, The marking sheet for clothing characterized by the above-mentioned.
5. A clothing marking sheet according to any one of claims 1 to 4,
   The number average molecular weight of the said polyethyleneimine is 1800 or more, The marking sheet for clothing characterized by the above-mentioned.
6. A clothing marking sheet according to any one of claims 1 to 5,
   The marking sheet for clothing, wherein the content of polyethyleneimine contained in the water-soluble resin layer is less than 25 parts by weight with respect to 100 parts by weight of the resin of the water-soluble resin layer.
7. A clothing marking sheet according to any one of claims 1 to 6,
   The colored layer includes a resin capable of inkjet printing and a coloring material, and is a marking sheet for clothing.
8. In the marking sheet having the colorant migration preventing property, on one side of the support, in order from the support side, a colored layer, a water-soluble resin layer containing polyethyleneimine, and a hot-melt adhesive layer Characteristic marking sheet for clothing.
9. A method for thermally transferring a colored layer having a desired shape onto an adherend using the clothing marking sheet according to any one of claims 1 to 8, wherein the surface of the heat-meltable adhesive layer of the clothing marking sheet And the surface of the adherend are stacked and thermally bonded so that the colored layer, the intermediate layer, and the heat-meltable adhesive layer are transferred to the adherend. Thermal transfer method.
10. It is a thermal transfer method of the marking sheet for clothes according to claim 9,
    The said marking sheet for clothing is equipped with a support body in the outermost side which touches the said colored layer, and has the process of peeling the said support body, The thermal transfer method of the marking sheet for clothing characterized by the above-mentioned.
11. It is a thermal transfer method of the marking sheet for clothes according to claim 9 or 10,
    The method for peeling off the support is performed before or after the step of heat bonding.
12. It is the thermal transfer method of the marking sheet for clothes according to any one of claims 9 to 11,
    A method for thermal transfer of a marking sheet for clothing, comprising a step of inkjet printing desired characters and designs on the surface of the colored layer before the step of heat bonding.

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