WO2014119739A1 - Marking sheet for clothing and method for thermal transfer using same - Google Patents
Marking sheet for clothing and method for thermal transfer using same Download PDFInfo
- Publication number
- WO2014119739A1 WO2014119739A1 PCT/JP2014/052299 JP2014052299W WO2014119739A1 WO 2014119739 A1 WO2014119739 A1 WO 2014119739A1 JP 2014052299 W JP2014052299 W JP 2014052299W WO 2014119739 A1 WO2014119739 A1 WO 2014119739A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- clothing
- marking sheet
- water
- soluble resin
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
Definitions
- the present invention relates to a marking sheet that is adhered to clothing such as fabric by heat.
- 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.
- 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.
- the coloring material of the fabric mainly the dye
- the thermal bonding layer moves to the colored layer of the marking sheet
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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 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.
- the marking sheet for clothing of this invention may be provided with the support body which touches a colored layer.
- each layer which comprises the marking sheet for clothing of this invention is demonstrated concretely.
- 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.
- 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 ⁇ m to 1000 ⁇ m 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.
- 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.
- 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.
- 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 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 15 ⁇ m or more.
- the upper limit is 500 ⁇ m or less, more preferably 300 ⁇ m or less, and even more preferably 150 ⁇ m 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.
- ink jet printing 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.
- a colored layer may be transparent or semi-transparent, and may become a colored layer afterwards.
- it can print using what is called a solvent ink by which the ink pigment was disperse
- 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.
- 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.
- a colored layer 2 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.
- 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.
- a coloring material migration preventing layer may be separately provided between the water-soluble resin layer 3 and the hot-melt adhesive layer 4.
- the colorant migration preventing layer is provided between the water-soluble resin layer containing polyethyleneimine and the hot-melt adhesive layer.
- 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 polyvinyl alcohol resin is particularly excellent in colorant migration prevention.
- a hydrophobic colorant such as a disperse dye is used because it is difficult to color with a water-soluble colorant.
- 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.
- the polyvinyl alcohol resin is a resin having particularly high hydrophilicity among the resins, and has an SP value of 12.6.
- 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.
- 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.
- 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.
- 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).
- the saponification degree 85 mol% or more 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.).
- 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.
- 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.
- Water-soluble resins, water-alcohol mixed solvent-soluble resins, and water-based emulsion resins can be used as water-soluble resins.
- 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
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the water-soluble resin layer containing polyethyleneimine and the colorant migration preventing layer 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 ⁇ m or more, preferably 0.7 ⁇ m or more, and the upper limit is 2.0 ⁇ m or less, preferably 1.7 ⁇ m or less.
- 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 ⁇ m or less But there is no loss of texture. Further, when the colorant migration preventing layer is 0.4 ⁇ m or more, the colorant migration preventing property can be improved, and when it is 2.0 ⁇ m or less, it is laminated on the water-soluble resin layer containing the polyethyleneimine. Even if it does, the texture will not be impaired.
- the intermediate layer 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.
- the water-soluble resin layer itself containing polyethyleneimine has the colorant migration preventing property ((a) in FIG. 1)
- 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
- a water-soluble resin such as hydroxypropylcellulose resin, hydroxypropylmethylcellulose resin, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, and polyvinyl acetal resin
- polyvinyl alcohol resin is particularly preferable.
- 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.
- 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 ⁇ m or more, preferably 0.7 ⁇ m or more, more preferably 1.0 ⁇ m or more as the lower limit.
- the upper limit of the film thickness is 3.0 ⁇ m or less, preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the resin that can be used as the hot-melt adhesive layer examples include one or more of ethylene vinyl acetate, polyolefin, synthetic rubber, acrylic, polyurethane, polyamide, and polyester resins. .
- a resin having flexibility that follows the elongation of the fabric when adhered to the fabric and further having water resistance is preferably used.
- 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 ⁇ m 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 ⁇ m 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.
- 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.
- 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.
- the above-described resin binder and coloring material are dispersed or dissolved in an organic solvent, applied and dried to form a colored layer.
- 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.
- a master badge previously kneaded and pelletized may be used.
- 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.
- 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.
- 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.
- 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.
- the other layers include an easy adhesion layer that increases adhesion between the layers, an antistatic layer, and an ultraviolet blocking layer.
- 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.
- 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.
- 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.
- Example 1 Using a substrate obtained by laminating a white polyurethane resin layer (colored layer) having a thickness of 30 ⁇ m on a support having a thickness of 145 ⁇ m 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 ⁇ m. 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.
- 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 ⁇ m, Further, on the water-soluble resin layer, the following polyvinyl alcohol resin layer coating solution was applied and dried to laminate a 1.0 ⁇ m-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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
Landscapes
- Decoration By Transfer Pictures (AREA)
- Decoration Of Textiles (AREA)
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
本発明は、布地などの衣料に熱により接着させるマーキングシートに関する。
The present invention relates to a marking sheet that is adhered to clothing such as fabric by heat.
従来、離型紙等の支持体に、塩化ビニル樹脂やポリウレタン樹脂からなる着色層を設け、更にそれらの着色層の上に熱接着層が積層されたマーキングシートが使用されている。これらのマーキングシートは、カッティングマシン等により所望の図形にカットした後、熱ラミロールや熱プレスにより熱接着層を介してスポーツウエア等の衣料用布地に熱接着させて、衣料にゼッケン等を付けるのに用いられている。
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.
これらのスポーツウエア等の衣料用布地には、肌触り等の風合いの良さ、洗濯のし易さ、デザイン性等の要請から、近年は化学繊維を着色したものが多く用いられており、それらの衣料用布地に熱接着させるマーキングシートにも、柔軟な布地に追従する風合い性や、使用時の接着性が要求されている。
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.
着色された化学繊維の布地に上述したようなマーキングシートを熱接着させた場合、布地の着色材、おもに染料が熱接着層を通過してマーキングシートの着色層に移行し、マーキングシートの元の色相に布地の色相が混じった状態になって外観を損なうという問題が生じている。この問題は、衣料用繊維がポリエステル製布地の場合に顕著に発生している。
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.
このような布地からマーキングシートへの着色材の移行を防止するため、マーキングシートの着色層と布地との間で着色材の移行を防止する機能を持った、バリヤ層を塗布により設けたり(特許文献1、3)、プラスチックフィルムあるいは金属箔のバリヤ層を設けること(特許文献2)が提案されている。
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.
しかし、上記のような塗布によるバリヤ層や、プラスチックフィルムあるいは金属層を用いたバリヤ層では、それらバリヤ層と着色層との接着性が不十分であった。これによりマーキングフィルムの使用時に浮や剥がれが生じやすいという問題があった。
また、染料移行防止層として耐水化剤を添加して架橋させたものでは(特許文献3)、マーキングシート自体が硬い感触になって、柔軟な布地の風合い性が損なわれるという問題がある。この問題は、染料移行防止層の膜厚が厚い場合には特に顕著となる。 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.
また、染料移行防止層として耐水化剤を添加して架橋させたものでは(特許文献3)、マーキングシート自体が硬い感触になって、柔軟な布地の風合い性が損なわれるという問題がある。この問題は、染料移行防止層の膜厚が厚い場合には特に顕著となる。 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.
そこで、本発明は、布地等の被着物に、マーキングシートを接着させて使用しても、被着物の着色材の、マーキングシートの着色層への移行を防止しつつ(着色材移行防止性)、マーキングシートの浮きや剥離が生じることが無く(接着性)、柔軟な被着物の風合いを損なうことのない(風合い性)衣料用マーキングシートを提供することを目的とする。
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).
本発明者らは、着色層との接着性が極めて良好で且つ熱接着によっても架橋による硬化が生じず、衣料の風合い性を損なわない材料について鋭意検討した。
鋭意検討の結果、本発明の衣料用マーキングシートの着色層上に、ポリエチレンイミンを含んだ水溶性樹脂層を積層することにより、着色材移行防止性及び風合い性を有しつつ、着色層と、熱溶融性接着層を介した被着物との接着性を格段に向上させることができ、つまりは衣料用マーキングシートの使用時の接着性を大幅に良好にすることができることを見出し、本発明を完成するに至った。 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.
鋭意検討の結果、本発明の衣料用マーキングシートの着色層上に、ポリエチレンイミンを含んだ水溶性樹脂層を積層することにより、着色材移行防止性及び風合い性を有しつつ、着色層と、熱溶融性接着層を介した被着物との接着性を格段に向上させることができ、つまりは衣料用マーキングシートの使用時の接着性を大幅に良好にすることができることを見出し、本発明を完成するに至った。 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.
すなわち、上記課題を解決する本発明の衣料用マーキングシートは、熱溶融性接着層、着色層、及び、前記熱溶融性接着層と前記着色層との間に1ないし複数の中間層を備え、前記熱溶融性接着層に隣接する中間層が、ポリエチレンイミンを含んだ水溶性樹脂層であることを特徴とする。
また本発明の衣料用マーキングシートは、着色材移行防止性を有したマーキングシートであって、支持体上の一方の面に、前記支持体側から順に、着色層、ポリエチレンイミンを含んだ水溶性樹脂層、及び熱溶融性接着層を有することを特徴とする衣料用マーキングシートである。 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.
また本発明の衣料用マーキングシートは、着色材移行防止性を有したマーキングシートであって、支持体上の一方の面に、前記支持体側から順に、着色層、ポリエチレンイミンを含んだ水溶性樹脂層、及び熱溶融性接着層を有することを特徴とする衣料用マーキングシートである。 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.
また、本発明の衣料用マーキングシートは、前記水溶性樹脂層が、着色材移行防止性を有する着色材移行防止層であることを特徴とするものである。
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.
また、本発明の衣料用マーキングシートは、前記水溶性樹脂層と前記熱溶融性接着層との間に、着色材移行防止性を有する着色材移行防止層を有することを特徴とするものである。
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. .
また、本発明の衣料用マーキングシートは、前記着色材移行防止層が、ポリビニルアルコール樹脂を含むことを特徴とするものである。
The clothing marking sheet of the present invention is characterized in that the colorant migration preventing layer contains a polyvinyl alcohol resin.
また、本発明の衣料用マーキングシートは、前記ポリエチレンイミンの数平均分子量が1800以上であることを特徴とするものである。
The clothing marking sheet of the present invention is characterized in that the polyethyleneimine has a number average molecular weight of 1800 or more.
また、本発明の衣料用マーキングシートは、前記水溶性樹脂層に含まれるポリエチレンイミンの含有量が、水溶性樹脂層の樹脂100重量部に対して、25重量部未満であることを特徴とするものである。
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.
また、本発明の衣料用マーキングシートは、前記着色層がインクジェット印刷可能な樹脂着色層であることを特徴とするものである。
The clothing marking sheet of the present invention is characterized in that the colored layer is a resin colored layer capable of inkjet printing.
また、本発明の衣料用マーキングシートの熱転写方法は、上述した衣料用マーキングシートを用いて、被着物に所望の形状の着色層を熱転写する方法であって、前記衣料用マーキングシートの熱溶融性接着層の表面と前記被着物の表面とが接するように重ねて熱接着して、前記着色層、前記中間層、及び前記熱溶融性接着層を前記被着物に転写することを特徴とする。
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.
本発明の衣料用マーキングシートの熱転写方法は、衣料用マーキングシートが、前記着色層に接する最外側に支持体を備える場合、前記支持体を剥離する工程を有する。支持体を剥離する工程は、熱接着する工程の前又は後に行われる。
また本発明の衣料用マーキングシートの熱転写方法は、熱接着する工程の前に、前記着色層の表面に所望の文字、図柄をインクジェット印刷する工程を含む。 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.
また本発明の衣料用マーキングシートの熱転写方法は、熱接着する工程の前に、前記着色層の表面に所望の文字、図柄をインクジェット印刷する工程を含む。 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.
本発明によれば、着色材移行防止性を有しつつ、柔軟で風合い性を損なうことなく、使用時に被着物とマーキングシートとが剥離することの無い良好な接着性を有する衣料用マーキングシートとすることができる。
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.
本発明の衣料用マーキングシートは、熱溶融性接着層、着色層、及び、前記熱溶融性接着層と前記着色層との間に1ないし複数の中間層を備え、前記熱溶融性接着層に隣接する中間層が、ポリエチレンイミンを含んだ水溶性樹脂層である。中間層の少なくとも一層は着色材移行防止性を有する。また本発明の衣料用マーキングシートは、着色層に接する支持体を備えていてもよい。
以下、本発明の衣料用マーキングシートを構成する各層について具体的に説明する。 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.
以下、本発明の衣料用マーキングシートを構成する各層について具体的に説明する。 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.
本発明の衣料用マーキングシートに用いられる支持体としては、透明、不透明を問わず、例えば、紙、コート紙、ラミ紙、PP製などの合成紙、各種プラスチックフィルムを使用することができるが、熱ラミロールや熱プレスする工程が入る場合があることから、熱接着温度でシュリンクや反りが生じ難い程度の耐熱性がある紙やポリエステル系フィルムが好ましい。
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.
また、必要に応じて、支持体の着色層と接する面に離型処理を施してもよいし、着色層面を艶消し表面にするために、支持体表面をサンドブラスト処理、エンボス処理、賦型処理等をしておくか、マット状塗膜をつけて凹凸面にしておいてもよい。
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.
支持体の厚みとしては特に制限はないが、コストが高くなったり作業性に支障を来たさないようにする観点から、10μm~1000μm程度のものを使用することができる。
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.
着色層は、被着物に熱接着してゼッケンやパッチの部分になるもので、樹脂バインダーに染料や顔料の着色材が溶解あるいは分散されたものを使用することができる。なお着色材には酸化チタンのような白色顔料も使用することができる。
樹脂バインダーとしては、被膜性があるものが使用でき、例えば、塩化ビニル系樹脂、酢酸ビニル系樹脂、塩化ビニリデン系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、ポリオレフィン系樹脂、アクリル系樹脂、ゴム系樹脂等の1種もしくは2種以上の樹脂が使用できる。熱接着時の熱により溶融しないものが良い。被膜強度、耐水性・耐油性を向上させるために硬化剤を使用したものでも良い。 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.
樹脂バインダーとしては、被膜性があるものが使用でき、例えば、塩化ビニル系樹脂、酢酸ビニル系樹脂、塩化ビニリデン系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、ポリオレフィン系樹脂、アクリル系樹脂、ゴム系樹脂等の1種もしくは2種以上の樹脂が使用できる。熱接着時の熱により溶融しないものが良い。被膜強度、耐水性・耐油性を向上させるために硬化剤を使用したものでも良い。 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.
特に、柔軟で被着物の風合い性を損なわない点や、耐水性、耐候性等が優れる点で、ポリウレタン系樹脂、塩化ビニル系樹脂が好ましく、更に、機械的特性、耐磨耗性、低温特性、環境問題の観点からポリウレタン系樹脂がより好ましい。
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.
ポリウレタン系樹脂は、ポリオールとポリイソシネートを重付加反応させて製造され、溶剤キャスト法で成膜したものでも熱押し出し成膜したものでも良く、またポリエステル型でもポリエーテル型のものでも使用できる。
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.
着色層の膜厚は、被膜強度が不十分にならない程度の厚さがあり、且つカッティング性、ダイカット性、風合い性あるいは生産性等が悪くならない程度に薄いことが好ましく、具体的には、下限は好ましくは5μm以上、より好ましくは10μm以上、更により好ましくは15μm以上であり、上限は500μm以下、より好ましくは300μm以下、更により好ましくは150μm以下である。
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.
着色層は、前述のように着色材で着色されたものであるが、インクジェット印刷法により印刷することも可能である。着色層にインクジェット印刷することにより、例えば白色の着色層に所望の色のインクジェット印刷をすることにより、種々の色や特別色の衣料用マーキングシートが得られ、また、写真階調のようなグラデーションのあるデザインを印刷することも可能になる。これにより、多種の色の衣料用マーキングシートの在庫を持たなくても、単色、例えば白色の着色層の衣料用マーキングシートがあればよく、在庫量を減らすことが可能になる。また本発明の衣料用マーキングシートが着色層への印刷を前提にする場合には、着色層は透明や半透明であってもよく、事後的に着色層となるものであってもよい。なお、本発明の着色層をインクジェット印刷するには、インクジェット出力機により、インク顔料を有機溶剤で分散させた、いわゆるソルベントインクを使用して印刷することができる。上記で例示した着色層に用いる樹脂であれば、特別な処理をすることなく、このようなインクジェット印刷が可能である。
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.
次に着色層と熱溶融性接着層との間に設けられる中間層について説明する。中間層は、一層でも二層以上でもよいが、少なくとも一層は着色材移行防止性を有する層である。また着色層に接する層は、ポリエチレンイミンを含んだ水溶性樹脂層である。
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.
従って、ポリエチレンイミンを含有する水溶性樹脂層と着色材移行防止層とを分けて積層する構成をとることができるし、あるいは、ポリエチレンイミンを有する水溶性樹脂層自体が着色材移行防止性を有する構成とすることもでき、両構成の場合とも、ポリエチレンイミンを含有する水溶性樹脂層は、着色層との接着性を良好にする効果を有する。中間層の構成として好適な態様を図1に示す。
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.
図1の(a)に示す衣料用マーキングシートは、中間層が一層でポリエチレンイミンを含んだ水溶性樹脂層が着色材移行防止層を兼ねている実施形態であり、支持体1上の一方の面に、支持体から順に、着色層2、ポリエチレンイミンを含んだ水溶性樹脂層3、及び熱溶融性接着層4を有する。
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.
図1の(b)は、中間層として、着色材移行防止層5と水溶性樹脂層3との少なくとも2層を備えたものであり、支持体1上に、支持体から順に、着色層2、ポリエチレンイミンを含んだ水溶性樹脂層3、着色材移行防止層5及び熱溶融性接着層4を有する。
(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.
図1の(c)は、支持体を有しない実施形態であり、着色層2、着色材移行防止層を兼ねたポリエチレンイミン含有水溶性樹脂層3、及び熱溶融性接着層4を有し、熱溶融性接着層4の上にセパレータ6が設けられている。この実施形態において、水溶性樹脂層3と熱溶融性接着層4との間に別途着色材移行防止層が設けられていてもよい。
(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.
まず、ポリエチレンイミンを含有した水溶性樹脂層と着色材移行防止層とを分けて積層する構成の場合(図1の(b))を説明する。この場合、着色材移行防止層は、ポリエチレンイミンを含んだ水溶性樹脂層と熱溶融性接着層との間に設けられる。着色材移行防止層としては、公知の材料を用いることができるが、樹脂固有の性質である溶解(度)パラメーター、いわゆるSP値(IUPAC GOLD BOOKによる)が11以上の樹脂を用いることが好ましく、特に、着色材移行防止性に優れる樹脂であるポリビニルアルコール樹脂を含む層とすることが好ましい。
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.
ポリビニルアルコール樹脂が、特に着色材移行防止性に優れる理由は以下のように考えられる。
ポリエステル系繊維のような疎水性繊維を着色するためには、水溶性の着色材では着色し難いので、分散染料のような疎水性の着色材が用いられる。しかしポリエステル系繊維自体が、本来接着性が悪い素材であり、繊維を着色するための疎水性の着色材とも接着性が悪く、マーキングシートを熱接着する時の熱や接着後の経時変化で、その疎水性の着色材が昇華・移行して、熱接着層を通過して着色層の汚染が発生すると考えられる。 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.
ポリエステル系繊維のような疎水性繊維を着色するためには、水溶性の着色材では着色し難いので、分散染料のような疎水性の着色材が用いられる。しかしポリエステル系繊維自体が、本来接着性が悪い素材であり、繊維を着色するための疎水性の着色材とも接着性が悪く、マーキングシートを熱接着する時の熱や接着後の経時変化で、その疎水性の着色材が昇華・移行して、熱接着層を通過して着色層の汚染が発生すると考えられる。 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.
一方、ポリビニルアルコール樹脂は、樹脂の中でも特に親水性が高い樹脂であり、SP値12.6となる。このようなSP値が高い樹脂であることにより、熱接着層を通過して移行した疎水性の着色材をはじき、着色材がさらに着色層側に移行するのを防止することができる。
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.
更に、着色材移行防止性を高めるには、ポリビニルアルコール樹脂の中でも、鹸化度が高いものの方が好適に使用できる。
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.
ポリビニルアルコール樹脂の鹸化度が高くなると水酸基が多くなり、更に親水性が高くなって、上述した理由から疎水性の着色材の着色材移行防止性が高くなる。さらに水酸基が多くなって親水性は高くなる(例えば水接触角がより小さくなる)が、分子中に水酸基が増えることにより、分子間や分子内の水素結合も増大することにより耐水性自体は良好にできるという効果もあると考えられる。なお耐水性自体に関して言えば、ポリビニルアルコール樹脂自体が、被膜成膜時などの熱により結晶化度を高められ耐水性を良好に出来るという効果もある。
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.
好適に使用されるポリビニルアルコール樹脂の鹸化度としては、85モル%以上、好ましくは90モル%以上、より好ましくは95モル%以上、更により好ましくは97モル%以上であり、鹸化度の上限としては実質製造上の100モル%(完全鹸化物)である。
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).
鹸化度を85モル%以上とすることにより着色材移行防止性を良好にすることができ、また鹸化度の異なるポリビニルアルコール樹脂を混ぜて使用することは適宜調整できる。
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.
好適に使用されるポリビニルアルコール樹脂の重合度としては400~2000の範囲であり、通常は水溶液(4重量%、20℃)の溶液粘度で表される。
重合度が400以下だと被膜強度が弱くなり、重合度が2000以上だと溶解し難くなると同時に溶液粘度が上がり塗布し難くなるので、重合度は上記の範囲で適宜選択することができる。 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.
重合度が400以下だと被膜強度が弱くなり、重合度が2000以上だと溶解し難くなると同時に溶液粘度が上がり塗布し難くなるので、重合度は上記の範囲で適宜選択することができる。 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.
着色材移行防止層には、ポリビニルアルコール樹脂の他にポリアクリル酸メチルエステル、ポリアクリル酸エチルエステル、カルボキシメチルセルロース樹脂、メチルセルロース樹脂、ヒドロキシエチルセルロース樹脂、デンプン等の水溶性樹脂を含んでいてもよい。ただし、ポリビニルアルコール樹脂は、着色材移行防止機能の観点から、水溶性樹脂層の樹脂全体に対して、70重量%以上であることが好ましい。より好ましくは80重量%以上、さらに好ましくは90重量%以上とする。
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.
ポリエチレンイミンを含有した水溶性樹脂層は、着色層と強固に接着することによって、熱転写後の着色層が被着物から剥がれるのを防止する層であり、熱溶融性接着層と水溶性樹脂層との間に着色材移行防止層が設けられる場合、着色材移行防止機能を有していてもいなくてもよいが、積層される着色材移行防止層との接着性がよいものを使用することが好ましい。水溶性樹脂として、水溶解性樹脂、水・アルコール系混合溶媒溶解性樹脂、および水系エマルジョン樹脂を使用することができ、具体的には、ポリビニルアルコール樹脂、ポリビニルピロリドン樹脂、水溶性ナイロン樹脂(水溶性ポリアミド樹脂)、メチルセルロール樹脂、エチルセルロース樹脂、カルボキシメチルセルロース樹脂、ヒドロキシエチルセルロース樹脂、ヒドロキシプロピルセルロース樹脂、ヒドロキシプロピルメチルセルロース樹脂、ポリアクリル酸メチルエステル、ポリアクリル酸エチルエステル、ポリビニルアセタール樹脂、ポリエステル樹脂系エマルジョン、ポリ酢酸ビニル樹脂系エマルジョン、アクリル樹脂系エマルジョン等の1種あるいは2種を混ぜて使用することができる。
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.
着色層上に、ポリエチレンイミンを含んだ水溶性樹脂層を設けることにより、着色層との接着力を向上できる理由は、以下のように考えられる。
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.
水溶性樹脂層にポリエチレンイミンを含有させると、水溶性であるポリエチレンイミンの分子構造中のアミノ基と、水溶性樹脂層を構成する樹脂とのなじみ(親和性)がよく、特に水溶性樹脂層の樹脂が水酸基含有の親水性樹脂の場合は、水素結合により電気的に引き合ってよりなじみがよいと考えられる。一方、ポリエチレンイミンの分子構造中のエチレン鎖は疎水性のため、疎水性である着色層となじみが良いので、結果的に着色層と水溶性樹脂層との接着性を向上させていると考えられる。
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.
接着性を向上させているポリエチレンイミンと水溶性樹脂層の樹脂との「なじみ」とは、ポリエチレンイミンのアミノ基と水溶性樹脂層の樹脂とが、水素結合等の弱い結合である「物理ゲル」を生じさせている状態であると考えられる。物理ゲルは、共有結合のような強い結合である「化学ゲル」とは異なり、いわゆる硬化・架橋は生じていない。硬化・架橋が生じてないので、水溶性樹脂層つまりは衣料用マーキングシートが硬くなって風合い性を損ねることがないという効果をも発揮されていると考えられる。この硬化・架橋していないことは、本発明のポリエチレンイミンを含んだ水溶性樹脂層の塗布液を長期間保存してもゲル化せず再使用可能なことからも推測される。
“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.
水溶性樹脂層に含有されるポリエチレンイミンは、分子量が300以上、好ましくは1,500以上、より好ましくは10,000以上、更により好ましくは50,000以上のものを使用できる。分子量の上限としては、100,000以下であることが好ましい。分子量を300以上とすることにより着色層と水溶性樹脂層との接着力を良くすることができ、また、分子量100,000以下とすることにより、溶液粘度が高くなり作業性が悪くなることと、ポリエチレンイミンが高価になってコストが高くなってしまうことを回避することができる。
なお、ポリエチレンイミンの分子量の測定方法としては、上記分子量50,000未満のものは沸点上昇による数平均分子量(Mn)によるものとし、50,000以上のものは粘度法による数平均分子量(Mn)とした。 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.
なお、ポリエチレンイミンの分子量の測定方法としては、上記分子量50,000未満のものは沸点上昇による数平均分子量(Mn)によるものとし、50,000以上のものは粘度法による数平均分子量(Mn)とした。 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.
ポリエチレンイミンの添加量としては、水溶性樹脂層の樹脂100重量部に対して、下限はポリエチレンイミンの固型分で1重量部以上、好ましくは2重量部以上、より好ましくは3重量部以上であり、上限としては25重量部未満、好ましくは20重量部未満、より好ましくは15重量部未満である。添加量を1重量部以上とすることにより着色層と水溶性樹脂層との接着力を良くすることができる。また25重量部未満とすることにより、水溶性樹脂層自体に着色材移行防止性を持たせることができ、特に20重量部未満とすることにより着色材移行防止性を良くすることができる。
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.
本発明の衣料用マーキングシートにおいて、ポリエチレンイミンを含んだ水溶性樹脂層と着色材移行防止層とを分けた構成にした場合の、ポリエチレンイミンを含んだ水溶性樹脂層および着色材移行防止層の塗膜厚みとしては、ともに、下限としては0.4μm以上、好ましくは0.7μm以上であり、上限としては2.0μm以下、好ましくは1.7μm以下である。
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.
ポリエチレンイミンを含んだ水溶性樹脂層を0.4μm以上とすることにより、着色層との接着性を良好にすることができ、2.0μm以下とすることにより着色材移行防止層を積層した場合でも風合い性を損なうことが無い。また、着色材移行防止層を0.4μm以上とすることにより、着色材移行防止性を良好とすることができ、2.0μm以下とすることにより上記ポリエチレンイミンを含んだ水溶性樹脂層に積層した場合でも風合い性を損なうことがない。
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.
このように中間層を複層の構造にすることにより、風合い性、接着性、及び着色材移行防止性を良好にしたまま、ポリエチレンイミンを含んだ水溶性樹脂層を薄膜にすることができ、相対的にポリエチレンイミンの使用量を少なくできコストを下げることができる。
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.
次に、ポリエチレンイミンを含有した水溶性樹脂層自体に着色材移行防止性を持たせる場合(図1の(a))について説明する。この場合、水溶性樹脂層を構成する水溶性樹脂としては、ポリビニルアルコール樹脂、ポリビニルピロリドン樹脂、水溶性ナイロン樹脂(水溶性ポリアミド樹脂)、メチルセルロール樹脂、エチルセルロース樹脂、カルボキシメチルセルロース樹脂、ヒドロキシエチルセルロース樹脂、ヒドロキシプロピルセルロース樹脂、ヒドロキシプロピルメチルセルロース樹脂、ポリアクリル酸メチルエステル、ポリアクリル酸エチルエステル、ポリビニルアセタール樹脂等の水溶性樹脂を用いることが好ましく、特にポリビニルアルコール樹脂が好適である。ポリビニルアルコール樹脂を用いる場合、その好適な鹸化度、重合度及び水溶性樹脂層に含まれるポリビニルアルコール樹脂の含有量も、着色材移行防止層について説明したのと同様である。
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.
また、水溶性樹脂層に含有されるポリエチレンイミンの、分子量及び添加量についても、水溶性樹脂層と着色材移行防止層とを分けて積層する構成の場合の、分子量及び添加量と同じ範囲である。
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.
ポリエチレンイミンを含む水溶性樹脂層の膜厚は、下限としては0.4μm以上、好ましくは0.7μm以上、より好ましくは1.0μm以上である。膜厚の上限としては3.0μm以下、好ましくは2.5μ以下、より好ましくは2.0μm以下である。膜厚を0.4μm以上とすることにより、着色層との接着性、および着色材移行防止性を良好にすることができ、膜厚を3.0μm以下とすることによりハジキやクレーター等の塗布欠陥を少なくすることができる。
なおポリエチレンイミンを含む水溶性樹脂層が着色材移行防止層を兼ねる場合には、着色層と熱溶融性接着層との間に一層の中間層を設けるだけで、着色層の接着性と着色材移行防止性を得ることができるので、衣料用マーキングシート全体の厚みを薄くすることができ、被着物の風合いを損なわずに風合いのよい熱転写物を得ることができる。 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.
なおポリエチレンイミンを含む水溶性樹脂層が着色材移行防止層を兼ねる場合には、着色層と熱溶融性接着層との間に一層の中間層を設けるだけで、着色層の接着性と着色材移行防止性を得ることができるので、衣料用マーキングシート全体の厚みを薄くすることができ、被着物の風合いを損なわずに風合いのよい熱転写物を得ることができる。 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.
以上、中間層の構成として図1の(a)、(b)に示す場合について説明したが、図1(c)に示したように支持体を有しない場合についても、同様である。いずれの場合にも、ポリエチレンイミンを含む水溶性樹脂層の膜厚、およびポリビニルアルコールを含む樹脂層がある場合の膜厚も、ともに薄膜のため、衣料用マーキングシートとして風合い性を良好にすることができ、また薄膜にも拘らず着色層との接着性、着色材移行防止性を良好にすることができる。着色材移行防止性を有する層をどこに配置した場合でも、着色材移行防止性を付与することができる。
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.
なお、ポリエチレンイミンを含む水溶性樹脂層およびポリビニルアルコール樹脂を含む層には、接着性や風合い性を損なわない範囲で、耐水性等を向上させる目的等で耐水化剤を添加することもできる。
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.
添加することができる耐水化剤としては、有機チタン化合物、グリオキザール、メチロール化メラミン、ジメチロール尿素等が使用でき、添加量は、水溶性樹脂層の樹脂の反応基(mol)と耐水化剤の反応基あるいは反応部位(mol)との割合が、樹脂の反応基1molに対して、耐水化剤の反応基あるいは反応部位(mol)の添加量が(1mol:1molを当量比とした場合)、下限が0.2mol以上、好ましくは0.5mol以上、更により好ましくは0.8mol以上であり、上限は2.0mol以下、好ましくは1.5mol以下、更により好ましくは1.2mol以下である。
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.
次に熱溶融性接着層について説明する。熱溶融性接着層は、ポリエチレンイミンを含む水溶性樹脂層、あるいは着色材移行防止層(ポリビニルアルコールを含む樹脂層)に積層され、本発明の衣料用マーキングシートの着色層を含む各層を被着物である衣料に熱接着するための層である。
熱溶融性接着層は、被着物の種類に応じて接着性の良い材質を選択することができ、常温でブロッキングせず、タックのないものが好適に使用される。熱接着時の熱により溶融接着する、いわゆるホットメルト系接着剤が好適に使用できる。 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.
熱溶融性接着層は、被着物の種類に応じて接着性の良い材質を選択することができ、常温でブロッキングせず、タックのないものが好適に使用される。熱接着時の熱により溶融接着する、いわゆるホットメルト系接着剤が好適に使用できる。 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.
熱溶融性接着層として使用できる樹脂としては、例えば、エチレン酢酸ビニル系、ポリオレフィン系、合成ゴム系、アクリル系、ポリウレタン系、ポリアミド系、ポリエステル系樹脂などの1種もしくは2種以上が使用される。また、布地に接着させた場合に、布地の伸びに追従するような可とう性を有し、さらに耐水性を有する樹脂が好ましく使用され、上記の樹脂の中でも特にポリウレタン系樹脂、ポリエステル系樹脂が好適に使用できる。
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.
熱溶融性接着層の膜厚としては、被接着物である布地により異なるが、10μm以上あれば接着可能である。接着力を向上させる為には膜厚は厚い方が好ましいが、あまり厚くするとカッティング性、ダイカット性、生産性等に不都合が生ずることから、200μm以下が好ましい。
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.
熱溶融性接着層と水溶性樹脂層またはポリビニルアルコールを含む樹脂層との界面は、布地の被接着物に接着させた後においても剥離することなく強固に接着している必要がある。このため、接着力が不足する場合には熱溶融性接着層と水溶性樹脂層またはポリビニルアルコールを含む樹脂層との間に接着性を向上させるための層を設けても良く、積層前に水溶性樹脂層またはポリビニルアルコールを含む樹脂層に対し、コロナ放電処理等の表面処理を行うことも可能である。
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.
本発明の衣料用マーキングシートの製造方法は特に限定されないが、例えば次の製造方法で製造することができる。まず、紙、プラスチックフィルム等の支持体に、必要に応じて公知の離型処理を施して、着色層を塗工法や熱押し出し法により形成する。塗工法により成膜する場合には、前述のような樹脂バインダーと着色材とを有機溶剤で分散あるいは溶解して塗布、乾燥させて着色層を成膜する。また、熱押し出し法により成膜する場合には、バインダー樹脂あるいはバインダー樹脂となる成分と、顔料とを混練・押し出して支持体上に着色層を成膜させる。この場合に予め混練してペレット化したマスターバッジを使用しても良い。
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.
次に、積層された着色層の上に、ポリエチレンイミンを含んだ水溶性樹脂を水、アルコール系溶媒で溶解して、あるいはポリエチレンイミンを含んだエマルジョン塗料を使用して、塗布、乾燥する。更にポリビニルアルコール樹脂を含む層を積層する場合には、ポリエチレンイミンを含んだ水溶性樹脂層の上に、ポリビニルアルコール樹脂等を、水、アルコール系溶剤で溶解したものを塗布、乾燥させて、ポリビニルアルコール樹脂を含む層を積層する。水溶性樹脂層を形成する塗工方法としては、例えばバーコーター法、ロールコーター法、ダイコーター法、グラビアコーター法等の公知の方法が使用できる。
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.
次に、上記積層された水溶性樹脂層に直接ホットメルトコーターやエクストルージョン法等により熱溶融した熱溶融接着性樹脂を塗布し熱溶融性接着層を積層する。あるいは予め別の支持体に熱溶融接着性樹脂を成膜しておいたものと、上述の積層シートの水溶性樹脂層面とを熱ラミネートし、水溶性樹脂層の上に熱溶融性接着層を積層してもよい。
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.
本発明の衣料用マーキングシートには、本発明の効果および構成を逸脱しない範囲で、上記各層以外に他の層を設けてよい。他の層として、例えば、各層間の接着性を高める易接着層、帯電防止層、紫外線遮断層などが挙げられる。
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.
また、以上の各工程の成膜時において、酸化防止剤、分散剤、帯電防止剤、レベリング剤、消泡剤、ブロッキング防止剤、粘着付与剤等の添加剤を、本発明の効果を阻害しない程度で、各層に適宜添加することもできる。
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.
本発明の衣料用マーキングシートを被着物に熱転写する方法を図2~図4を参照して説明する。
まず転写工程の最初に支持体を剥離するか最後に支持体を剥離するかを適宜選択する。図2を参照して説明すると、支持体1を剥離した後(図2の(a)から(b))、衣料用マーキングシートを必要に応じて所望の形状にカッティング(ハーフカットも含む)あるいはダイカットして((c))、衣料用マーキングシートの熱溶融性接着層4と被着物8の表面とが接するように重ねて、熱ラミロールを通すか熱プレスで、120℃~230℃、0.01~1.0MPa程度の条件で熱接着して((d))、着色層から熱溶融性接着層までの各層を被着物に転写させる((e))。カッティングの工程(c)は省略してもよい。図3に示す工程の場合には、支持体1がある状態でカッティング、熱接着を行い、熱接着後に支持体1を剥離する。熱接着の条件は同様である。 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-meltableadhesive 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.
まず転写工程の最初に支持体を剥離するか最後に支持体を剥離するかを適宜選択する。図2を参照して説明すると、支持体1を剥離した後(図2の(a)から(b))、衣料用マーキングシートを必要に応じて所望の形状にカッティング(ハーフカットも含む)あるいはダイカットして((c))、衣料用マーキングシートの熱溶融性接着層4と被着物8の表面とが接するように重ねて、熱ラミロールを通すか熱プレスで、120℃~230℃、0.01~1.0MPa程度の条件で熱接着して((d))、着色層から熱溶融性接着層までの各層を被着物に転写させる((e))。カッティングの工程(c)は省略してもよい。図3に示す工程の場合には、支持体1がある状態でカッティング、熱接着を行い、熱接着後に支持体1を剥離する。熱接着の条件は同様である。 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
また、図4に示すように、衣料用マーキングシートの支持体1を剥離して(図4(a)から(b))、露出した着色層2の表面に、所望の領域、所望の文字、所望の図柄等をインクジェット印刷し((c))、印刷した領域や文字や図柄等を、カッティング等が必要な場合には所望の形状や輪郭にカッティング(ハーフカットも含む)あるいはダイカットして、熱溶融性接着層の表面と被着物の表面とが接するように重ねて熱ラミロールを通すか熱プレスで、120℃~230℃、0.01~1.0MPa程度の条件で熱接着して((d))、文字や図柄や領域が印刷された着色層から熱溶融性接着層までの各層を被着物に転写させる((e))。なお図4の(a)に点線で示したように、熱接着までの各工程におけるマーキングシートの取り扱い性を容易にするために、必要に応じて、熱接着層4にはセパレータ6や保護フィルムなどを貼着しておいてもよい。図2、図3の熱転写方法でも同様である。
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.
以下、実施例により本発明を更に説明する。なお、「部」、「%」は特に示さない限り、重量基準とする。
Hereinafter, the present invention will be further described with reference to examples. “Parts” and “%” are based on weight unless otherwise specified.
[実施例1]
離型処理された厚み145μmの支持体に厚み30μmの白色ポリウレタン樹脂層(着色層)が積層されたものを基材として、その白色ポリウレタン樹脂層の片面に、下記水溶性樹脂層塗工液を塗布・乾燥して、厚み1.5μmの水溶性樹脂層を形成した。下記水溶性樹脂層塗工液におけるポリエチレンイミンの添加量は、ポリビニルアルコール樹脂に対して、固形分換算で3.9部である。
上記基材に水溶性樹脂層を積層したシートの水溶性樹脂層と、別途作成しておいた、厚み150μmの離型紙に厚み55μmのポリエステル系熱溶融性接着層が積層されたシートの熱溶融性接着層とを、熱ラミロールにより170℃で貼り合せて実施例1の衣料用マーキングシートを作製した。 [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.
離型処理された厚み145μmの支持体に厚み30μmの白色ポリウレタン樹脂層(着色層)が積層されたものを基材として、その白色ポリウレタン樹脂層の片面に、下記水溶性樹脂層塗工液を塗布・乾燥して、厚み1.5μmの水溶性樹脂層を形成した。下記水溶性樹脂層塗工液におけるポリエチレンイミンの添加量は、ポリビニルアルコール樹脂に対して、固形分換算で3.9部である。
上記基材に水溶性樹脂層を積層したシートの水溶性樹脂層と、別途作成しておいた、厚み150μmの離型紙に厚み55μmのポリエステル系熱溶融性接着層が積層されたシートの熱溶融性接着層とを、熱ラミロールにより170℃で貼り合せて実施例1の衣料用マーキングシートを作製した。 [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.
<水溶性樹脂層塗工液>
・ポリビニルアルコール樹脂 100重量部
(ゴーセノールA300:日本合成化学工業社、鹸化度97.0~98.5モル%、固型分100%)
・ポリエチレンイミン 13重量部
(和光純薬工業社、分子量70,000、固型分30%)
水 1100重量部 <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
・ポリビニルアルコール樹脂 100重量部
(ゴーセノールA300:日本合成化学工業社、鹸化度97.0~98.5モル%、固型分100%)
・ポリエチレンイミン 13重量部
(和光純薬工業社、分子量70,000、固型分30%)
水 1100重量部 <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
[実施例2]
実施例1のポリエチレンイミンの量を、ポリビニルアルコール樹脂に対して、固型分換算で9.8部に変えて添加した以外は、実施例1と同様にして、実施例2の衣料用マーキングシートを作製した。 [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.
実施例1のポリエチレンイミンの量を、ポリビニルアルコール樹脂に対して、固型分換算で9.8部に変えて添加した以外は、実施例1と同様にして、実施例2の衣料用マーキングシートを作製した。 [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.
[実施例3]
実施例1のポリエチレンイミンの量を、ポリビニルアルコール樹脂に対して、固型分換算で14.8部に変えて添加した以外は、実施例1と同様にして、実施例3の衣料用マーキングシートを作製した。 [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.
実施例1のポリエチレンイミンの量を、ポリビニルアルコール樹脂に対して、固型分換算で14.8部に変えて添加した以外は、実施例1と同様にして、実施例3の衣料用マーキングシートを作製した。 [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.
[実施例4]
実施例1のポリエチレンイミンの量を、ポリビニルアルコール樹脂に対して、固型分換算で19.8部に変えて添加した以外は、実施例1と同様にして、実施例4の衣料用マーキングシートを作製した。 [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.
実施例1のポリエチレンイミンの量を、ポリビニルアルコール樹脂に対して、固型分換算で19.8部に変えて添加した以外は、実施例1と同様にして、実施例4の衣料用マーキングシートを作製した。 [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.
[実施例5]
実施例1のポリエチレンイミンの量を、ポリビニルアルコール樹脂に対して固型分換算で24.8部に変えて添加した以外は、実施例1と同様にして、実施例5の衣料用マーキングシートを作製した。 [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.
実施例1のポリエチレンイミンの量を、ポリビニルアルコール樹脂に対して固型分換算で24.8部に変えて添加した以外は、実施例1と同様にして、実施例5の衣料用マーキングシートを作製した。 [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.
[実施例6]
ポリエチレンイミンとして分子量の異なるポチエチレンイミン(和光純薬工業社、分子量10,000)を用いた以外は、実施例2と同様にして、実施例6の衣料用マーキングシートを作製した。 [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.
ポリエチレンイミンとして分子量の異なるポチエチレンイミン(和光純薬工業社、分子量10,000)を用いた以外は、実施例2と同様にして、実施例6の衣料用マーキングシートを作製した。 [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.
[実施例7]
ポリエチレンイミンとして分子量の異なるポチエチレンイミン(和光純薬工業社、分子量1,800)を用いた以外は、実施例2と同様にして、実施例7の衣料用マーキングシートを作製した。 [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.
ポリエチレンイミンとして分子量の異なるポチエチレンイミン(和光純薬工業社、分子量1,800)を用いた以外は、実施例2と同様にして、実施例7の衣料用マーキングシートを作製した。 [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.
[実施例8]
実施例2のポリビニルアルコール樹脂をゴーセノールC500(日本合成化学工業社、鹸化度95.0~97.0モル%、固型分100%)に変えた以外は、実施例2と同様にして、実施例8の衣料用マーキングシートを作製した。 [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.
実施例2のポリビニルアルコール樹脂をゴーセノールC500(日本合成化学工業社、鹸化度95.0~97.0モル%、固型分100%)に変えた以外は、実施例2と同様にして、実施例8の衣料用マーキングシートを作製した。 [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.
[実施例9]
実施例2のポリビニルアルコール樹脂をゴーセノールAL06R(日本合成化学工業社、鹸化度91.0~94.0モル%、固型分100%)に変えた以外は、実施例2と同様にして、実施例9の衣料用マーキングシートを作製した。 [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.
実施例2のポリビニルアルコール樹脂をゴーセノールAL06R(日本合成化学工業社、鹸化度91.0~94.0モル%、固型分100%)に変えた以外は、実施例2と同様にして、実施例9の衣料用マーキングシートを作製した。 [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.
[実施例10]
実施例1と同様の基材の白色ポリウレタン樹脂層の片面に、実施例1と同様の水溶性樹脂層塗工液を塗布・乾燥して厚み0.5μmの水溶性樹脂層を形成した後、更にその水溶性樹脂層上に、下記ポリビニルアルコール樹脂層塗工液を塗布・乾燥して厚み1.0μmのポリビニルアルコール樹脂層を積層し、更に実施例1と同様にして、ポリビニルアルコール樹脂層と熱溶融性接着層とを貼り合せて実施例10の衣料用マーキングシートを作製した。 [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.
実施例1と同様の基材の白色ポリウレタン樹脂層の片面に、実施例1と同様の水溶性樹脂層塗工液を塗布・乾燥して厚み0.5μmの水溶性樹脂層を形成した後、更にその水溶性樹脂層上に、下記ポリビニルアルコール樹脂層塗工液を塗布・乾燥して厚み1.0μmのポリビニルアルコール樹脂層を積層し、更に実施例1と同様にして、ポリビニルアルコール樹脂層と熱溶融性接着層とを貼り合せて実施例10の衣料用マーキングシートを作製した。 [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.
<ポリビニルアルコール樹脂層塗工液>
・ポリビニルアルコール樹脂 100重量部
(ゴーセノールNH18:日本合成化学工業社、鹸化度98.0~99.0モル%、固型分100%)
・水 1100重量部 <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
・ポリビニルアルコール樹脂 100重量部
(ゴーセノールNH18:日本合成化学工業社、鹸化度98.0~99.0モル%、固型分100%)
・水 1100重量部 <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
[比較例1]
ポリエチレンイミンを添加しなかった以外は、実施例2と同様にして、比較例1の衣料用マーキングシートを作製した。 [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.
ポリエチレンイミンを添加しなかった以外は、実施例2と同様にして、比較例1の衣料用マーキングシートを作製した。 [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.
[比較例2]
実施例2のポリエチレンイミンの代わりにアジピン酸ジヒドラジド(固型分100%)を用いた以外は、実施例2と同様にして、比較例2の衣料用マーキングシートを作製した。 [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.
実施例2のポリエチレンイミンの代わりにアジピン酸ジヒドラジド(固型分100%)を用いた以外は、実施例2と同様にして、比較例2の衣料用マーキングシートを作製した。 [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.
[比較例3]
実施例2のポリエチレンイミンの代わりにシランカップリング剤(KBM403、3-グリシドキシプロピルトリメトキシシラン、信越シリコーン社)を不揮発分換算で0.1部添加した以外は、実施例2と同様にして、比較例3の衣料用マーキングシートを作製した。 [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.
実施例2のポリエチレンイミンの代わりにシランカップリング剤(KBM403、3-グリシドキシプロピルトリメトキシシラン、信越シリコーン社)を不揮発分換算で0.1部添加した以外は、実施例2と同様にして、比較例3の衣料用マーキングシートを作製した。 [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.
[比較例4]
実施例2のポリエチレンイミンの代わりに水分散性ポリイソシアネート(DNW5500、固型分80%、NCO含有量13~14%、DIC社)を固型分換算で9.8部添加した以外は、実施例2と同様にして、比較例4の衣料用マーキングシートを作製した。 [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.
実施例2のポリエチレンイミンの代わりに水分散性ポリイソシアネート(DNW5500、固型分80%、NCO含有量13~14%、DIC社)を固型分換算で9.8部添加した以外は、実施例2と同様にして、比較例4の衣料用マーキングシートを作製した。 [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.
実施例1~10で得られた衣料用マーキングシートを、赤色に着色されたポリエステル繊維製布地「ポリエステルトリコット EN155赤」に、「190℃30秒間0.04MPa」の熱プレス条件で熱接着させたところ、良好に熱転写でき、各衣料用マーキングシートが熱転写されたポリエステル繊維性布地が得られた。
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.
[着色材移行防止性]
実施例1~10、及び比較例1~4で得られた衣料用マーキングシートに関して、被転写布地として赤色に着色されたポリエステル繊維製布地「ポリエステルトリコット EN155赤」に、各衣料用マーキングシートを「190℃30秒間0.04MPa」の熱プレス条件で熱接着させ、支持体を剥離して、白色ポリウレタン層への赤色着色材の移行性を、カラーメーターZE2000(日本電色社)でL*、a*、b*を測定して△Eを算出した。
△Eが0~10以下だったものを「◎」、
△Eが10を超えて20以下だったものを「〇」、
△Eが20を超えるものを「×」とした。
結果を表1に示す。 [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.
実施例1~10、及び比較例1~4で得られた衣料用マーキングシートに関して、被転写布地として赤色に着色されたポリエステル繊維製布地「ポリエステルトリコット EN155赤」に、各衣料用マーキングシートを「190℃30秒間0.04MPa」の熱プレス条件で熱接着させ、支持体を剥離して、白色ポリウレタン層への赤色着色材の移行性を、カラーメーターZE2000(日本電色社)でL*、a*、b*を測定して△Eを算出した。
△Eが0~10以下だったものを「◎」、
△Eが10を超えて20以下だったものを「〇」、
△Eが20を超えるものを「×」とした。
結果を表1に示す。 [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.
[風合い性]
上記熱転写後の各衣料用マーキングシートに関して、触感により風合い性を調べた。
風合いを損なわないと判断できたものを「◎」、
若干硬くなったと感じられたものを「〇」、
明らかに硬くなったと感じられたものを「×」とした。
結果を表1に示す。 [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.
上記熱転写後の各衣料用マーキングシートに関して、触感により風合い性を調べた。
風合いを損なわないと判断できたものを「◎」、
若干硬くなったと感じられたものを「〇」、
明らかに硬くなったと感じられたものを「×」とした。
結果を表1に示す。 [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.
[接着性]
上記熱転写後の各衣料用マーキングシートに関して、白色ポリウレタン層側からカッターでゴバン目を入れてテープ接着試験により接着性を調べた。
数回のテープ接着でも剥がれが見られなかったものを「◎」、
数回のテープ接着で極僅か剥がれが見られたものを「〇」、
数回のテープ接着で剥がれたものを「×」とした。
結果を表1に示す。 [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.
上記熱転写後の各衣料用マーキングシートに関して、白色ポリウレタン層側からカッターでゴバン目を入れてテープ接着試験により接着性を調べた。
数回のテープ接着でも剥がれが見られなかったものを「◎」、
数回のテープ接着で極僅か剥がれが見られたものを「〇」、
数回のテープ接着で剥がれたものを「×」とした。
結果を表1に示す。 [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.
実施例1~実施例4、実施例6、実施例8、実施例10の衣料用マーキングシートは、何れも、着色材移行防止性、風合い性、接着性が良好だった。
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.
実施例5の衣料用マーキングシートは、風合い性、接着性は良好だったが、他の実施例のものより着色材移行防止性が低く、着色材の移行がみられた。これはポリエチレンイミンの添加量がやや多いためと思われる。
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.
実施例7の衣料用マーキングシートは、着色材移行防止性、風合い性は良好だったが、接着性が他の実施例よりは僅かに劣り、極僅かであるが剥がれが見られた。これはポリエチレンイミンの分子量が若干低めのためと思われる。
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.
実施例9の衣料用マーキングシートは、風合い性、接着性は良好だったが、他の実施例のものよりは着色材移行防止性が低く、着色材の移行がみられた。使用しているポリビニルアルコール樹脂の鹸化度が他のものより若干低いためと思われる。
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.
一方、比較例1の衣料用マーキングシートは、水溶性樹脂層にポリエチレンイミンを添加しなかったので、接着性が悪かった。
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.
比較例2~4の衣料用マーキングシートは、水溶性樹脂層にポリエチレンイミンを添加せずに、架橋剤や硬化剤として知られる添加物(アジピン酸ジヒドラジド、シランカップリング剤、水分散性ポリイソシアネート)を添加したものであるが、いずれも接着性は悪かった。
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.
硬化剤であるシランカップリング剤を添加した比較例3の衣料用マーキングシートや、同じく硬化剤である水分散性ポリイソシアネートを添加した比較例4の衣料用マーキングシートは、水溶性樹脂層の樹脂として実施例2と同じ着色材移行防止性のあるポリビニルアルコール樹脂を用いているにも拘わらず、実施例2のものより着色材移行性が低下した。
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.
さらに水分散性ポリイソシアネートを添加した比較例4の衣料用マーキングシートは、水溶性樹脂層の膜厚が薄いために、風合い性が大幅には損なわれていないものの、他に比べると風合い性が劣るものであった。これは、水溶性樹脂層がポリイソシアネートと架橋反応して硬くなっているためと思われる。
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.
1・・・支持体、2・・・着色層、3・・・水溶性樹脂層(中間層)、4・・・熱溶融性接着層、5・・・着色材移行防止層(中間層)、6・・・セパレータ、7・・・印刷層、8・・・被着物。
DESCRIPTION OFSYMBOLS 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.
DESCRIPTION OF
Claims (12)
- 熱溶融性接着層、着色層、及び、前記熱溶融性接着層と前記着色層との間に配置された1ないし複数の中間層を備えた衣料用マーキングシートであって、前記熱溶融性接着層に隣接する中間層が、ポリエチレンイミンを含んだ水溶性樹脂層であることを特徴とする衣料用マーキングシート。 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.
- 請求項1に記載の衣料用マーキングシートであって、
前記水溶性樹脂層は、被着体に含まれる着色材が前記着色層に移行するのを防止する着色材移行防止層であることを特徴とする衣料用マーキングシート。 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. - 請求項1に記載の衣料用マーキングシートであって、
前記前記水溶性樹脂層と前記熱溶融性接着層との間に、被着体に含まれる着色材が前記着色層に移行するのを防止する着色材移行防止層を有することを特徴とする衣料用マーキングシート。 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. - 請求項2又は3に記載の衣料用マーキングシートであって、
前記着色材移行防止層は、ポリビニルアルコール樹脂を含むことを特徴とする衣料用マーキングシート。 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. - 請求項1ないし4のいずれか一項に記載の衣料用マーキングシートであって、
前記ポリエチレンイミンの数平均分子量が1800以上であることを特徴とする衣料用マーキングシート。 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. - 請求項1ないし5のいずれか一項に記載の衣料用マーキングシートであって、
前記水溶性樹脂層に含まれるポリエチレンイミンの含有量が、水溶性樹脂層の樹脂100重量部に対して、25重量部未満であることを特徴とする衣料用マーキングシート。 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. - 請求項1ないし6のいずれか一項に記載の衣料用マーキングシートであって、
前記着色層は、インクジェット印刷可能な樹脂と着色材とを含むことを特徴とする衣料用マーキングシート。 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. - 着色材移行防止性を有したマーキングシートにおいて、支持体上の一方の面に、前記支持体側から順に、着色層、ポリエチレンイミンを含んだ水溶性樹脂層、及び熱溶融性接着層を有することを特徴とする衣料用マーキングシート。 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.
- 請求項1ないし8いずれか一項に記載の衣料用マーキングシートを用いて、被着物に所望の形状の着色層を熱転写する方法であって、前記衣料用マーキングシートの熱溶融性接着層の表面と前記被着物の表面とが接するように重ねて熱接着して、前記着色層、前記中間層、及び前記熱溶融性接着層を前記被着物に転写することを特徴とする衣料用マーキングシートの熱転写方法。 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.
- 請求項9に記載の衣料用マーキングシートの熱転写方法であって、
前記衣料用マーキングシートは、前記着色層に接する最外側に支持体を備え、前記支持体を剥離する工程を有することを特徴とする衣料用マーキングシートの熱転写方法。 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. - 請求項9又は10に記載の衣料用マーキングシートの熱転写方法であって、
前記支持体を剥離する工程は、熱接着する工程の前又は後に行われることを特徴とする衣料用マーキングシートの熱転写方法。 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. - 請求項9ないし11のいずれか一項に記載の衣料用マーキングシートの熱転写方法であって、
熱接着する工程の前に、前記着色層の表面に所望の文字、図柄をインクジェット印刷する工程を含むことを特徴とする衣料用マーキングシートの熱転写方法。 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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014559780A JP6310863B2 (en) | 2013-02-01 | 2014-01-31 | Marking sheet for clothing and thermal transfer method using the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013018891 | 2013-02-01 | ||
JP2013-018891 | 2013-02-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014119739A1 true WO2014119739A1 (en) | 2014-08-07 |
Family
ID=51262436
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/052299 WO2014119739A1 (en) | 2013-02-01 | 2014-01-31 | Marking sheet for clothing and method for thermal transfer using same |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP6310863B2 (en) |
WO (1) | WO2014119739A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017094855A1 (en) * | 2015-12-02 | 2017-06-08 | 株式会社日本触媒 | Water-soluble film and manufacturing method therefor |
JP2018507436A (en) * | 2015-02-06 | 2018-03-15 | エルジー・ケム・リミテッド | Light conversion film, light conversion element including the same, and display device |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002348787A (en) * | 2001-05-28 | 2002-12-04 | Bando Chem Ind Ltd | Thermoadhesive marking sheet and marked clothing |
JP2003291279A (en) * | 2002-04-03 | 2003-10-14 | Bando Chem Ind Ltd | Laminated sheet for marking sheet and clothing |
JP2008026768A (en) * | 2006-07-25 | 2008-02-07 | Horaisha:Kk | Thermocompression bonding type mark with function of preventing resublimation of sublimation dye |
-
2014
- 2014-01-31 WO PCT/JP2014/052299 patent/WO2014119739A1/en active Application Filing
- 2014-01-31 JP JP2014559780A patent/JP6310863B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002348787A (en) * | 2001-05-28 | 2002-12-04 | Bando Chem Ind Ltd | Thermoadhesive marking sheet and marked clothing |
JP2003291279A (en) * | 2002-04-03 | 2003-10-14 | Bando Chem Ind Ltd | Laminated sheet for marking sheet and clothing |
JP2008026768A (en) * | 2006-07-25 | 2008-02-07 | Horaisha:Kk | Thermocompression bonding type mark with function of preventing resublimation of sublimation dye |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018507436A (en) * | 2015-02-06 | 2018-03-15 | エルジー・ケム・リミテッド | Light conversion film, light conversion element including the same, and display device |
US10407614B2 (en) | 2015-02-06 | 2019-09-10 | Lg Chem, Ltd. | Photoconversion film, and photoconversion element and display device comprising same |
WO2017094855A1 (en) * | 2015-12-02 | 2017-06-08 | 株式会社日本触媒 | Water-soluble film and manufacturing method therefor |
JPWO2017094855A1 (en) * | 2015-12-02 | 2018-10-04 | 株式会社日本触媒 | Water-soluble film and method for producing the same |
Also Published As
Publication number | Publication date |
---|---|
JPWO2014119739A1 (en) | 2017-01-26 |
JP6310863B2 (en) | 2018-04-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2695991B1 (en) | Labeled article and process for making pressure sensitive labels for use in a cold transfer method. | |
KR101638642B1 (en) | Heat transfer methods and sheets for applying an image to a colored substrate | |
WO2015079541A1 (en) | Transparent laser marking sheet, laminate, and method for laser marking | |
JP2010509106A (en) | Improved overlay printing | |
KR102166550B1 (en) | Thermal Laminating Film for Printed Matter | |
JP6310863B2 (en) | Marking sheet for clothing and thermal transfer method using the same | |
JP5717690B2 (en) | Transparent laser marking sheet, laminate, and laser marking method | |
JP2017179195A (en) | Adhesive sheet, adhesive tape, fiber base material sheet, clothing product, and method for producing adhesive sheet | |
JP4996266B2 (en) | Transfer sheet | |
JP5610525B2 (en) | Heat transfer sheet and method for producing the same | |
JP2007223291A (en) | Transfer sheet and forming method of recording image using the said transfer sheet | |
JP5217105B2 (en) | Decorative sheet | |
JP2016078301A (en) | Laminate for decorative molding, method for producing decorative molded article and decorative molded article | |
JP2009297930A (en) | Intermediate transfer recording medium and image recording fiber base material | |
JP7290714B2 (en) | Packaging films and pouch containers | |
WO2006129604A1 (en) | Sublimation transfer print coated leather product and process for producing the same | |
JP2001062970A (en) | Decorative sheet | |
WO2013163513A1 (en) | Hybrid heat transfer label | |
KR102585438B1 (en) | Clear patch ribbon for thermal transfer printing and preparation method of the same | |
JP6628484B2 (en) | Mark material and mark forming method | |
CN213676184U (en) | Environment-friendly multicolor laser transfer film | |
JP4602028B2 (en) | Decorative film and sheet | |
JP2008162106A (en) | Transfer sheet | |
JP5810600B2 (en) | Card manufacturing method | |
KR102038873B1 (en) | Method of heat transfer using thermoplastic polyurethane heating-transfer sheet |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14745401 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014559780 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14745401 Country of ref document: EP Kind code of ref document: A1 |