JPH0248439B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a transfer printing sheet that can transfer and print a beautiful and clear pattern on a subject with a single touch, similar to that obtained by direct printing. BACKGROUND ART Conventionally, as transfer printing paper, water transfer type and alcohol transfer type are known. Water transfer type transfer printing paper is made by printing a predetermined pattern on the water glue layer of a transfer sheet (paper with water glue applied to the entire surface of one side), then varnishing the printed layer, and then A release paper is placed over the varnish layer to prevent blocking. For the transfer operation, first remove the release paper, then
Wet the entire area with water to swell the water glue layer, and
This is done by shifting the transfer paper side or the printing layer side while applying the transfer paper side to the subject. In addition, alcohol transfer type transfer printing paper is
Water glue layer of double paper transfer sheet (consisting of opaque paper with the release side of thin, translucent paper that has been subjected to release processing, and water glue applied to the surface of the translucent paper) A predetermined pattern is printed on top, then an alcohol-activated adhesive is applied over the printed layer in a larger area than the outline of the pattern, and then a release paper is placed over it to prevent blocking. be. To perform the transfer operation, remove the release paper and opaque paper from the transfer printing paper, wet the subject side with alcohol, place the subject against the surface coated with alcohol-activated adhesive, and wait until the adhesive is formed. This is done by applying water to the translucent paper side to swell the water glue layer, and then removing the translucent paper. Incidentally, although not transfer printing paper, stickers are also widely used for the purpose of attaching patterns to objects. Stickers are made by printing a predetermined pattern on the surface of tack paper (release paper coated with adhesive on one side and then pasting film or paper on top of the adhesive layer), and then If necessary, a polypropylene film or the like is laminated on top of the printed layer to protect the printed layer, and then a die is punched out using a die.When using the sticker, the sticker is removed from the release paper and then removed. By pressing the adhesive coated side onto the subject, one-touch attachment is possible. A further development of this sticker is the punched letter sticker. The cut-out character sticker is
A printing layer is placed on top of the adhesive layer of release paper coated with adhesive on the entire surface of one side, then punched out using a mold that has the outline shape of the characters, and unnecessary parts other than the characters are manually removed. Then, a transparent sheet coated with a low-tack adhesive called an application is placed over the printed layer. When using, peel off the release paper, press the adhesive coated side to the subject, and then peel off the application.
The letters are attached. Problems to be Solved by the Invention However, in the case of the above-mentioned conventional water transfer type transfer printing paper, it is difficult to wet the transfer printing paper with water or to slide the transfer paper side or the printing layer side during the transfer operation. Because of the requirement, it cannot be applied to subjects that are exposed to water.When sliding, the printing film is soft due to water, so it is difficult to separate from the transfer sheet, and there is a risk that the printing film may collapse. It takes a long time to reach a certain level of adhesive strength, and the finish is not necessarily beautiful because the varnish layer that protects the printed film must be made slightly larger than the outline of the printed layer. There was a problem. In addition, since the above-mentioned conventional alcohol transfer type transfer printing paper requires moistening with alcohol or water during the transfer operation, it cannot be applied to subjects that are susceptible to alcohol or water. It takes a long time to develop adhesive strength, and the alcohol-activated adhesive layer must be made slightly larger than the outline of the printed layer (otherwise, the printed film will break in the protruding areas). The finish is not necessarily beautiful,
Since printing had to be done in reverse, there were problems such as the risk of misidentification. Furthermore, with ordinary stickers, there are problems such as a lack of beauty as the sheet remains with a larger area than the printed pattern, and it is difficult to obtain a sheet material that satisfactorily meets the physical properties required by the subject. In the case of character stampers, the cost of the molds increases as a large number of molds are required to cut out the characters, and the work to remove the parts other than the characters after punching with the molds is done by hand. There were problems such as poor quality, high labor costs, and because the letters were punched out using a die, it could not be applied to small or complex letters. The present invention has been made to fundamentally solve these conventional problems. Means for Solving the Problems The transfer printing sheet of the present invention has a predetermined pattern of printed layer B made of an adhesive composition containing a surfactant on the release property surface of a release sheet A having release properties. , and then, on the printed layer B, a monochrome or multicolor ink printing layer C is provided so as to draw substantially the same pattern as above, and further, the printed layer C
It has a structure in which a removable protective sheet D covering a wider area than the pattern is provided from above, and by finding such a specific structure, the above problems can be solved at once. I came to the conclusion. As the release sheet A having mold releasability in the present invention, a sheet such as paper or a plastic sheet, one side of which is treated with a release agent, is used. As a release agent, long chain alkyl acrylate copolymer, long chain alkyl vinyl ester copolymer, long chain alkyl vinyl ether copolymer, long chain alkyl acrylamide copolymer, long chain alkyl allyl ester copolymer, maleic acid Copolymers of long-chain alkyl derivatives, polymers converted into long-chain alkyl esters, polymers converted into long-chain alkyl carbamates, polyethyleneimine derivatives, compounds containing perfluorinated alkyl groups (including fluororesins), silicones, paraffins, etc. can be exemplified. In addition, it is also possible to use a sheet in which the sheet itself is made of a material that has release properties, or a sheet in which a release agent is internally added during sheet manufacture. In the present invention, the above-mentioned release sheet A
First, a printed layer B of a predetermined pattern, such as letters, figures, patterns, etc., is provided on the releasable surface of the adhesive composition containing a surfactant. As the adhesive composition, a pressure-sensitive adhesive (pressure-sensitive adhesive) composition is preferably used, but a heat-sensitive adhesive composition or a rewetting adhesive composition may also be used in some cases. Adhesive compositions consist mainly of adhesive elements, and optionally contain adhesion agents, softeners, anti-aging agents, fillers, vulcanizing agents, crosslinking agents, coloring agents, and other additives. It consists of a mixture of ingredients in a suitable ratio. Main adhesive elements include natural rubber, isoprene rubber, styrene-butadiene rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer, butyl rubber, polyisobutylene, silicone rubber, polyvinyl isobutyl ether, chloroprene rubber, and nitrile rubber. , graft rubber, recycled rubber and other elastomers: α, β-
Polymers or copolymers of ethylenically unsaturated compounds, such as olefins (ethylene, propylene, butylene, etc.), styrenic monomers (styrene, α-methylstyrene, vinyltoluene, etc.), acrylonitrile or methacrylonitrile, vinyl esters ( vinyl acetate, vinyl propionate, etc.), vinyl ethers (vinyl isobutyl ether, etc.), unsaturated carboxylic acid monomers (acrylic acid, methacrylic acid, their esters,
Hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol mono- or pentaacrylate, crotonic acid or its ester, maleic acid, itacon Polymers or copolymers of compounds such as citraconic acid, citraconic acid, their esters or anhydrides, diallyl phthalate, divinylbenzene, acrylamide, methacrylamide, vinyl alcohol, vinyl chloride, etc.: epoxidized polybutadiene, etc. can be exemplified. Among these, acrylic adhesives, that is, acrylic esters or methacrylic esters (X) having an alkyl group having 4 to 12 carbon atoms;
Unsaturated carboxylic acids (Y) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic acid monoester, maleic anhydride, itaconic acid, itaconic acid monoester, itaconic anhydride, and acrylic acid with short chain alkyl groups. Acrylic pressure-sensitive adhesives copolymerized with unsaturated compounds (Z) such as esters or methacrylates, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, vinyl acetate, diallyl phthalate, etc., have properties such as adhesive properties, weather resistance, and transparency. It is particularly practical because of its excellent properties. Tackifiers include rosin, ester gum,
Ester gum H, polyterpene resin, petroleum resin,
Examples include styrene resins, alkylphenol resins, terpenephenol resins, and ethylene-vinyl acetate copolymer resins. As softeners, various plasticizers, polybutene,
Liquid tackifier resin, polyisobutylene low polymer,
Examples include polyvinyl isobutyl ether low polymer, lanolin, depolymerized rubber, process oil, and vulcanized oil. As the filler, various fillers are used, including titanium oxide, zinc white, silica, aluminum hydroxide, calcium carbonate, barium sulfate, clay, talc, mica, iron oxide, various rocks, and starch. As anti-aging agents, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, mercaptobenzimidazole, 1,1-bis(4-hydroxyphenol)
Various anti-aging agents are used, including cyclohexane and phenyl-β-naphthylamine. In addition, certain polymers such as cellulose derivatives, phenolic resins, urea resins, melamine resins, epoxy resins, gelatin, etc. can also be blended. The surfactants to be incorporated into the adhesive composition as described above include soaps, alkyl sulfates, alkylbenzene sulfonates, dialkyl sulfosuccinates, naphthalene sulfonates or polymers thereof,
Anionic surfactants such as polyoxyethylene alkyl ether sulfonates and polyoxyethylene alkyl ether phosphates; polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyoxyethylene alkyl esters, polyoxyethylene and Examples include nonionic surfactants such as oxypropylene block polymers and sorbitan monoalkylate; cationic surfactants such as alkyltrimethylammonium chloride and quaternary ammonium type surfactants. In addition, organosilicon compounds, that is, various silicone oils with a dialkylsiloxane structure, epoxidized silicone oils,
Fluorine-based compounds such as carboxy-modified silicone oil and various other modified silicone oils, i.e., sulfonates, carboxylates, ethylene oxide adducts, trimethylammonium salts, phosphate esters, and oligomers thereof containing perfluoroalkyl groups. , urethane derivatives, etc. are also used. Two or more of these surfactants are often used in combination. Among these surfactants, at least one surfactant selected from the group consisting of dialkyl sulfosuccinates, organosilicon compounds, and fluorine compounds is used as at least a part of the surfactant to be blended. is particularly preferred for the purposes of the present invention. The blending amount of the surfactant is desirably selected from the range of 0.00001 to 20% by weight, more preferably selected from the range of 0.0001 to 5% by weight, based on the total amount of the adhesive composition. If the amount of surfactant blended is too small, when printing on release sheet A, repelling or dents may occur on the printed surface, making it impossible to obtain stable quality. On the other hand, if the blending amount is too large, adhesive coating may The water resistance and solvent resistance as a film are poor, and the adhesive strength with the subject and the ink film provided on the top surface is reduced. Printing of the adhesive composition onto the release sheet A may be performed by various types of plano-concave printing, but silk screen printing (screen printing) is often used. When performing silk screen printing, antifoaming agents and other additives are often mixed in to prevent foaming during the printing process, which can easily cause repellency and dents on the printed surface. However, by incorporating a specific amount of surfactant as described above, this type of trouble can be avoided. When printing the adhesive composition on the release sheet A by silk screen printing, the viscosity of the adhesive composition can vary widely, but usually the viscosity is 1 to 300%.
It is often adjusted to poise (BH type rotational viscometer display, 25℃). If it is less than 1 poise, repelling, dents, etc. are likely to occur, while if it exceeds 300 poise,
Since the adhesive composition is difficult to be applied from the plate and the printing surface is difficult to obtain smoothness, printing work efficiency tends to decrease. The printed layer B can be formed into a multilayer of two or more layers. When forming multiple layers, adhesive compositions having different adhesive properties can also be used. After providing the print layer B in a predetermined pattern of the surfactant-containing adhesive composition on the releasable surface of the release sheet A as described above,
On the adhesive composition print layer B, a monochrome or multicolor ink print layer C is provided so as to draw substantially the same pattern as above. Inks include non-colorant inks, colorant-containing inks, ultraviolet curable inks, electron beam curable inks, and functional (conductive,
Various conventionally used inks can be used, including temperature-sensitive, fluorescent, luminous, reflective, aromatic, magnetic, OCR, desensitized, resist, transfer printing, etc.) inks. When printing, overprinting may be performed. A three-dimensional effect can be obtained by forming the printing layer thickly over the entire pattern or partially. Note that it is also desirable that the uppermost printed layer be an overcoat layer made of colorless ink, and this layer plays the role of imparting gloss to the printed layer and protecting the printed layer after transfer. In the present invention, a removable protective sheet D covering a wider area than the pattern is further provided on the printed layer C by pasting or other means. By installing this protective sheet D, the production of the intended transfer printing sheet is completed. As the protective sheet D, the surface of a transparent film or sheet made of polyolefin, polyvinyl chloride, polyester, polyamide, polyurethane, polyimide, cellulose derivative, polyacetal, etc. may be coated with an adhesive having mild adhesive strength as necessary. It is preferable to use a material coated on the entire surface or partially. It is also possible to strengthen the body by stacking a plurality of protective sheets D. In special cases, paper can also be used as the protective sheet D. The transfer printing sheet of the present invention has a layer configuration of A/B/C/D, and as detailed above, each layer is normally formed in order from the A side, but ultimately this It is sufficient that a layered structure is formed, and the order of formation is not limited. In order to facilitate the transfer operation, the adhesion strength Fab between the release sheet A and the surfactant-containing adhesive composition printed layer B, the ink printed layer C and the protective sheet D
The adhesion strength Fcd between the subject and the adhesive composition printed layer B containing a surfactant, Fbx, should satisfy the following relationship: Fbx>Fcd>Fab. FIG. 1 is a schematic cross-sectional view showing a state in which a printed layer B of a predetermined pattern made of an adhesive composition containing a surfactant is provided on a release sheet A. FIG. 2 is a partially cutaway perspective view showing an example of the transfer printing sheet of the present invention, and FIG. 3 is a schematic cross-sectional view thereof.
FIG. 4 is an exploded view. In the figure, A is a release sheet having mold releasability, B is a printed layer of an adhesive composition containing a surfactant, C is a monochromatic or multicolored ink printed layer, and D is a protective sheet. Transfer printing is performed on the subject using the transfer printing sheet created in this way. The material of the subject is
metals, plastics, wood and bamboo, ceramics,
Any material can be used, including paper, woven fabric, non-woven fabric, leather, and inorganic materials. It can also be applied to the raw surface of ceramics before quenching. The transfer operation can be carried out simply by first gently peeling off the release sheet A, then adhering and pressing the adhesive composition printed layer B side to the subject, and then peeling off the protective sheet D. Next, the present invention will be explained in more detail with reference to Examples. Hereinafter, "parts" and "%" are expressed on a weight basis. Example 1 500 parts of xylene was charged into a flask equipped with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen gas blowing device, and the temperature was raised to 110°C while continuing stirring and nitrogen gas blowing.
Then, while maintaining the temperature at 105 to 110°C, a mixed solution consisting of 300 parts of 2-ethylhexyl acrylate, 250 parts of butyl acrylate, 30 parts of methacrylic acid, and 20 parts of hydroxyethyl acrylate was added dropwise from the dropping funnel over a period of 3 hours. 5 parts of t-butyl hydroperoxide (polymerization initiator) was added dropwise from the funnel over 3.5 hours. Furthermore, at the same temperature, 3
By continuing the reaction for a period of time, the number average molecular weight
18000, an acrylic copolymer with a non-volatile content of 50% was obtained. Next, to 100 parts of the acrylic copolymer obtained above, 0.5 parts of KM85 manufactured by Shin-Etsu Silicone Co., Ltd., which is an emulsion type silicone, 50 parts of isophorone as a solvent, and Shin-Etsu Silicone Co., Ltd., which is dimethyl silicone oil, were added. Mixed with 0.2 parts of KF69 from Manufacturer Co., Ltd., it has a surfactant effect containing two types of silicone.
A surfactant-containing adhesive composition having both antifoaming and leveling effects was obtained. 8E Ivory manufactured by Fuji Shiko Co., Ltd. was prepared as release sheet A, and a pattern was silk screen printed on the surface with release properties using the adhesive composition obtained above, and then dried at 70°C for 5 minutes to remove the interface. An activator-containing adhesive composition printed layer B was formed. Next, from above the printed layer B of the surfactant-containing adhesive composition, a silk screen ink white (vinyl gloss manufactured by Tanaka Ink Chemical Industry Co., Ltd.) is used to accurately overlap the above printed pattern, and the silk screen is applied. Printing was performed and dried at 70° C. for 10 minutes to form a printed layer C of ink. Next, the adhesive-treated side of a protective sheet D called an application (polypropylene film coated with a pressure-sensitive adhesive with mild adhesiveness) is placed on top of the ink-printed layer C and pressed with a rubber roller. A desired transfer printing sheet was obtained. The release sheet is peeled off from the thus obtained transfer printing sheet, and the peeled side (the side on which the surfactant-containing adhesive composition printed layer B is provided) is
After pasting it on an ABS board and pressing it down several times with your fingers, I gently peeled off the protective sheet D and found that the ABS
Only the pattern consisting of B/C remained on the plate, and the transfer was completed. After removing the protective sheet D, it was left at room temperature for 7 days, and its adhesion to the ABS board that was the subject, water resistance, moisture resistance, etc. were examined. The results are shown in Table 1. Example 2 For 100 parts of the acrylic copolymer obtained in Example 1,
0.5 parts of KM85 manufactured by Shin-Etsu Silicone Co., Ltd., which is an emulsion type silicone, 50 parts of isophorone as a solvent, and a dialkyl sulfosuccinate surfactant (Neocol SWC manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as a surfactant. One part was mixed to obtain an adhesive composition, and an experiment was conducted in the same manner as in Example 1. The results are also shown in Table 1. Example 3 For 100 parts of the acrylic copolymer obtained in Example 1,
0.5 part of emulsion type silicone KM85 manufactured by Shin-Etsu Silicone Co., Ltd., 50 parts of isophorone as a solvent, and a block polymer of polyoxyethylene and polyoxypropylene (Epan 420 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as a surfactant. An adhesive composition was obtained by mixing one part of the following, and an experiment was conducted in the same manner as in Example 1. The results are also shown in Table 1.

[Table] Printability was determined by silk screen printing the adhesive composition and visually checking the printed surface after drying at 70° C. for 5 minutes. The finish quality was determined by printing white ink on the printed adhesive composition layer, drying it at 70° C. for 10 minutes, and then visually evaluating the appearance of surface cracks, blisters, dents, etc. Adhesion was tested by making an X mark on the adhesive ink layer with a razor blade and peeling it off using cellophane adhesive tape. Water resistance was determined by immersing the transfer-printed object in water at room temperature for 48 hours, and visually evaluating the condition immediately after pulling it up. Moisture resistance is for transfer-printed objects at 40°C and 95°C.
It was left under conditions of %RH for 24 hours, and the condition immediately after removal was visually judged. Comparative Example 1 An experiment was conducted in the same manner as in Example 1, except that the surfactant was omitted when preparing the adhesive composition, but printability of the adhesive: Many repellents Finishing after printing: Many dents To the subject The results were that the adhesion was weak, the water resistance was peeling, and the moisture resistance was blistering. Example 4 A flask equipped with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen gas blowing device was charged with 340 parts of water and Neogen R (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier, followed by stirring and nitrogen gas blowing. The temperature was raised to 80℃ while continuing to heat up, and then 315 parts of 2-ethylhexyl acrylate and butyl acrylate were added while maintaining the temperature between 78 and 82℃.
A mixed solution consisting of 250 parts of methacrylic acid, 29 parts of methacrylic acid, 5 parts of hydroxyethyl acrylate, and 1 part of diallyl phthalate was added dropwise from the dropping funnel over 3 hours.
From another funnel, 150 parts of 2% ammonium persulfate solution (polymerization initiator) was dropped over 3.5 hours. By continuing the reaction for 3 hours at the same temperature, an acrylic copolymer with a number average molecular weight of 152,000 and a non-volatile content of 50% was obtained. Next, to 100 parts of the acrylic copolymer obtained above, 0.2 parts of Nopco 8034 (manufactured by San Nopco Co., Ltd.) as an antifoaming agent and 3 parts of hydroxyethyl cellulose were added.
% aqueous solution and 10 parts of a 1% aqueous solution of a fluorosurfactant as a surfactant were mixed to obtain a surfactant-containing adhesive composition. Hereinafter, an experiment was conducted in the same manner as in Example 1. However, the ink printing by silk screen printing was multicolored overprinting, and the top layer was performed using colorless ink. The results are shown in Table 2. Example 5 For 100 parts of the acrylic copolymer obtained in Example 2,
Nopco 8034 (manufactured by San Nopco Co., Ltd.) as an antifoaming agent
An adhesive composition was obtained by mixing 0.2 parts of hydroxyethyl cellulose, 20 parts of a 3% aqueous solution of hydroxyethyl cellulose, and 1 part of a dialkyl sulfosuccinate surfactant as a surfactant, and the following experiment was conducted in the same manner as in Example 4. Ivy. The results are also shown in Table 2. Example 6 For 100 parts of the acrylic copolymer obtained in Example 2,
Nopco 8034 (manufactured by San Nopco Co., Ltd.) as an antifoaming agent
An adhesive composition was obtained by mixing 0.2 parts of hydroxyethyl cellulose, 20 parts of a 3% aqueous hydroxyethyl cellulose solution, and 3 parts of polyoxyethylene nonyl phenol ether as a surfactant, and an experiment was conducted in the same manner as in Example 4. The results are also shown in Table 2.

[Table] Comparative Example 2 An experiment was conducted in the same manner as in Example 4, except that the surfactant was omitted when preparing the adhesive composition. Printability of the adhesive: A lot of repellency. Finish quality after printing: dents. High Adhesion to the subject Weak Water resistance Peeling and blistering Moisture resistance No peeling was obtained. Effects of the Invention The present invention provides excellent effects as listed below. With just one touch, you can transfer and print a clear and beautiful pattern on your subject that looks just like it was printed directly. Even if the adhesive composition is printed on a release sheet, even if the printing is done by silk screen printing, for example, the printed surface will not have cracks, cracks, shrinkage, etc.
Does not cause dents etc. Since the protective sheet can be peeled off and removed immediately after being attached to the object, the time required for transfer is extremely short, and furthermore, no skill is required for the transfer operation. Since the printed layer of the adhesive composition and the printed layer of ink or paint have substantially the same pattern, there is no overflow of the adhesive composition. Since there is no need to moisten the transfer printing sheet or subject with water or alcohol in advance, it can be applied to subjects that are susceptible to water or alcohol. Since only the layers formed by printing are transferred, it is possible to design a product that meets the performance requirements of the subject, such as outdoor weather resistance, flexibility, and heat resistance. Since it is a transfer printed sheet obtained only by printing, there is no need for punching or extra space, and the manufacturing method is simplified and the design is superior.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view showing a state in which a printed layer B of a predetermined pattern made of an adhesive composition containing a surfactant is provided on a release sheet A. FIG. 2 is a partially cutaway perspective view showing an example of the transfer printing sheet of the present invention, FIG. 3 is a schematic sectional view thereof, and FIG. 4 is an exploded view thereof. A...Release sheet having mold releasability, B...Printed layer made of surfactant-containing adhesive composition, C...Printed layer made of ink, D...Protection sheet.

Claims (1)

[Claims] 1. A printed layer B of a predetermined pattern made of an adhesive composition containing a surfactant is provided on the releasable surface of a release sheet A having a releasable property, and then a printed layer B is formed on the printed layer B. , a monochrome or multicolor printing layer C of ink is provided so as to draw substantially the same pattern as the above, and a removable protective sheet D covering a wider area than the pattern is further provided over the printing layer C. A transfer printing sheet having a structure. 2. The transfer printing sheet according to claim 1, wherein the blending amount of the surfactant is 0.00001 to 20% by weight based on the total amount of the adhesive composition. 3. At least one surfactant selected from the group consisting of dialkyl sulfosuccinates, organosilicon compounds, and fluorine compounds is used as at least a part of the surfactants blended into the adhesive composition. A transfer printing sheet according to claim 1.