JP2005096156A - Transfer material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transfer material which does not require an after-treatment process and shows a successful suitability for deep-drawing process and a successful releasability of a release layer. <P>SOLUTION: This transfer material is structured of at least the release layer 3, a pattern layer 4 and an adhesive layer 6, laminated in that order on a base sheet 1. The release layer 3 is composed mainly of an acrylic resin with an average molecular weight of 150,000 to 500,000, an acrylic-styrene copolymer resin or an acrylic-urethane copolymer resin and an ultraviolet absorbing agent which is copolymerized or mixed with the former. Thus the release layer 3 does not require the after-treatment process as it is formed of a one-pack type solvent ink. In addition, the release layer 3 shows superb moldability and suitability for deep drawing process as it is formed of the acrylic resin and is successfully releasable like a conventional release layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a transfer material capable of imparting a pattern excellent in light resistance and chemical resistance to the surface of a resin molded product.

  Conventionally, there is a molding simultaneous transfer method as a method of decorating the surface of a transfer object. The simultaneous molding transfer method is a method in which a transfer material in which a transfer layer composed of a release layer, a design layer, an adhesive layer, etc. is formed on a base sheet is sandwiched in a molding die, resin is injected into the die, and cooled. In this method, a transfer material is adhered to the surface of the molded product at the same time as the resin molded product is obtained, and then the base sheet is peeled off, and the transfer layer is transferred to the surface of the transfer object to decorate.

In order to improve the light resistance and chemical resistance of the surface of the transfer molded product obtained by such a method, an ultraviolet curable resin or a two-component curable resin is used as the release layer (for example, Patent Document 1). ~ 2).
JP-A-10-58895 JP 2003-53910 A

  However, when an ultraviolet curable resin is used as the release layer, a step of irradiating ultraviolet rays after molding is required as a post-processing step. In addition, there is a problem that the release layer has a large hardness and lacks stretchability, so that it is not suitable for deep drawing.

  In addition, when a two-component curable resin is used as the release layer, a heat treatment step is required as a post-treatment step after the release layer is formed. Further, since the two-component curable resin usually uses an isocyanate curing agent, there is a problem that the peelability from the base sheet is poor.

  Accordingly, an object of the present invention is to provide a transfer material that solves the above-described problems, does not require a post-processing step, and has good deep drawing processability and release layer peelability.

  In order to achieve the above object, the transfer material of the present invention is configured as follows.

  According to the first aspect of the present invention, the release layer, the design layer, and the adhesive layer are sequentially laminated on the base sheet, and the release layer has an average molecular weight of 150,000 to 500,000. Provided is a transfer material comprising a copolymer resin or an acrylic-urethane copolymer resin as a main component, and an ultraviolet absorber copolymerized or mixed.

  According to the second aspect of the present invention, the molecular structure of the acrylic resin, acrylic-styrene copolymer resin or acrylic-urethane copolymer resin constituting the release layer is a three-dimensional structure. Provide transfer material.

  According to the third aspect of the present invention, there is provided the transfer material according to the first or second aspect, wherein the ultraviolet absorber is represented by the following chemical formula.

  In the transfer material of the present invention, at least a release layer, a design layer, and an adhesive layer are sequentially laminated on a substrate sheet, and the release layer has an average molecular weight of 150,000 to 500,000. A resin or an acrylic-urethane copolymer resin was used as a main component, and an ultraviolet absorber was copolymerized or mixed. Therefore, since the release layer is made of a one-component type solvent-based ink, a post-treatment step is not necessary. Further, since it is an acrylic resin, it has excellent moldability and is suitable for deep drawing. Moreover, like the conventional peeling layer, the peelability is good.

  Embodiments of the present invention will be described in detail with reference to the drawings.

  1 and 2 are sectional views showing an embodiment of the transfer material of the present invention. 1 is a base sheet, 2 is a release layer, 3 is a release layer, 4 is a design layer, 5 is an anchor layer, and 6 is an adhesive layer.

  In the transfer material of the present invention, the release layer 3, the design layer 4, and the adhesive layer 6 are sequentially laminated on the base sheet 1, and the release layer 3 has an average molecular weight of 150,000 to 500,000. -A styrene copolymer resin or an acrylic-urethane copolymer resin as a main component, and an ultraviolet absorber is copolymerized or mixed (see Fig. 1).

  As the base sheet 1, a biaxially stretched base sheet 1 such as polyethylene terephthalate (PET), stretched polypropylene (OPP), poly-4-methylpentene-1 (PMP), polyethylene naphthalate (PEN) can be used. Further, an unstretched substrate sheet 1 such as amorphous polyethylene terephthalate (A-PET) or crystalline polypropylene (CPP) can be used. In addition, it is a sheet that can be molded by heating, and has a chemical structure made of a linear or branched polymer. Examples include the following. A thermoplastic resin sheet such as an acrylonitrile-styrene-butadiene copolymer (ABS) film, a polycarbonate (PC) film, an acrylic film, or a polypropylene (PP) film can be used.

  Moreover, when the surface of the base sheet 1 has fine irregularities, the irregularities are copied to the transfer layer, and surface shapes such as matte and hairline can be expressed.

  When the peelability of the transfer layer from the base sheet 1 is good, the transfer layer may be provided directly on the base sheet 1. In order to improve the peelability of the transfer layer from the base sheet 1, the release layer 2 may be formed over the entire surface before providing the transfer layer on the base sheet 1 (see FIG. 2). The release layer 2 is released from the transfer layer together with the base sheet 1 when the base sheet 1 is peeled off after transfer. As the material of the release layer 2, melamine resin release agent, silicone resin release agent, fluororesin release agent, cellulose derivative release agent, urea resin release agent, polyolefin resin release agent Paraffin type release agents and composite release agents thereof can be used. Examples of the method for forming the release layer 2 include a coating method such as a roll coating method and a spray coating method, a printing method such as a gravure printing method and a screen printing method.

  The release layer 3 is formed on the base sheet 1 or the release layer 2. The peeling layer 3 is a layer that peels from the base sheet 1 or the release layer 2 and becomes the outermost surface of the transfer object when the base sheet 1 is peeled after transfer. In the present invention, the material of the release layer 3 is mainly composed of an acrylic resin having an average molecular weight of 150,000 to 500,000, an acrylic-styrene copolymer resin or an acrylic-urethane copolymer resin, and an ultraviolet absorber. It is important to use a copolymerized or mixed one.

  In the present invention, the resin constituting the release layer 3 is excellent from the base sheet 1 by using an acrylic resin, an acrylic-styrene copolymer resin or an acrylic-urethane copolymer resin as a main component. Peelability and excellent moldability during processing can be obtained.

  In addition, as the resin constituting the release layer 3, one having an average molecular weight of 150,000 to 500,000 is used. Since the resin used in the present invention is a one-component type ink, the chemical resistance is lacking unless the average molecular weight is less than 150,000. On the other hand, if the average molecular weight exceeds 500,000, the printability is deteriorated. When the average molecular weight is 1,000,000 or more, the viscosity of the resin itself becomes too high, making it unsuitable as an ink. Even if it can be prepared as an ink, it does not function as the release layer 3 even if it is formed by printing because the solid content is less than 10%.

  Specific examples of such a resin include those represented by the following chemical formula. In the chemical formula, U represents a urethane chain.

  Further, the resin constituting the release layer 3 is copolymerized or mixed with an ultraviolet absorber. The ultraviolet absorber is intended to prevent a photodegradation reaction of an organic compound or a polymer compound having a functional group that absorbs light such as a halogen, a carbonyl group, a benzene ring, or an unsaturated group. Therefore, photodegradation of the release layer 3 can be prevented by copolymerizing or mixing the ultraviolet absorber with the polymer skeleton of the resin constituting the release layer 3.

  As the ultraviolet absorber, a 2-hydroxytriazole-based one represented by the following chemical formula may be used. By using the ultraviolet absorber having such a composition, the acrylic resin, acrylic-styrene copolymer resin or acrylic-urethane copolymer resin constituting the release layer 3 and the ultraviolet absorber can be easily copolymerized. In addition to preventing the ultraviolet absorber from bleeding out from the surface of the release layer 3, it does not evaporate or sublime at high temperatures.

  Moreover, you may use ultraviolet absorbers, such as 2-hydroxybenzophenone series and a cyanoacrylate type.

  The acrylic resin, acrylic-styrene copolymer resin or acrylic-urethane copolymer resin constituting the release layer 3 preferably has a three-dimensional molecular structure. Since the ink of acrylic resin, acrylic-styrene copolymer resin or acrylic-urethane copolymer resin is usually a one-component thermoplastic ink, chemical resistance may not be sufficient. Therefore, by making a part or all of the molecular structure of these resins into a three-dimensional structure, this can be avoided, and more excellent chemical resistance can be provided.

  Examples of the method for forming the release layer 3 include a coating method such as a gravure coating method, a roll coating method, and a comma coating method, and a printing method such as a gravure printing method and a screen printing method.

  The design layer 4 is usually formed on the release layer 3 as a printing layer. As a material for the printing layer, a resin such as polyvinyl resin, polyamide resin, polyester resin, acrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin is used as a binder. A colored ink containing a pigment or dye of an appropriate color as a colorant may be used. As a method for forming the printing layer, a normal printing method such as a gravure printing method, a screen printing method, or an offset printing method may be used. In particular, the offset printing method and the gravure printing method are suitable for performing multicolor printing and gradation expression. In the case of a single color, a coating method such as a gravure coating method, a roll coating method, or a comma coating method may be employed. The print layer may be provided entirely or partially depending on the pattern to be expressed.

  The design layer 4 may be composed of a metal thin film layer or a combination of a printed layer and a metal thin film layer. The metal thin film layer is for expressing the metallic luster as the pattern layer 4 and is formed by a vacuum deposition method, a sputtering method, an ion plating method, a plating method, or the like. Metals such as aluminum, nickel, gold, platinum, chromium, iron, copper, tin, indium, silver, titanium, lead, and zinc, and alloys or compounds thereof are used depending on the metallic luster color to be expressed.

  The adhesive layer 6 adheres each of the above layers to the surface of the transfer object. As the adhesive layer 6, a heat-sensitive or pressure-sensitive resin suitable for the material of the transfer object is appropriately used. For example, when the material of the transfer object is an acrylic resin, an acrylic resin may be used. In addition, when the material of the material to be transferred is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, or polystyrene blend resin, acrylic resin, polystyrene resin, polyamide having affinity with these resins A series resin or the like may be used. Further, when the material of the transfer object is a polypropylene resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone indene resin can be used. Examples of the method for forming the adhesive layer 6 include a coating method such as a gravure coating method, a roll coating method, and a comma coating method, a printing method such as a gravure printing method, and a screen printing method.

  Moreover, you may provide the anchor layer 5 in order to improve the close_contact | adherence adhesiveness of these each layer as needed (refer FIG. 2). As the material of the anchor layer 5, two-component cured urethane resin, thermosetting urethane resin, melamine resin, cellulose ester resin, chlorine-containing rubber resin, chlorine-containing vinyl resin, acrylic resin, epoxy resin, vinyl A copolymer resin may be used. As a method for forming the anchor layer 5, there are a coating method such as a gravure coating method, a roll coating method and a comma coating method, a printing method such as a gravure printing method and a screen printing method.

  Next, various characteristics of the transfer material of the present invention will be described. Table 1 is a table showing the results of testing the releasability and printability of the transfer material of the present invention and the transfer material shown in the prior art.

  In Table 1, the coating in the test column is the case where the peeling layer 3 is formed with a dry film thickness of 5 μm by the lip coating method, and the printing suitability is the printability when the pattern layer 4 is printed on the peeling layer 3. The adhesion indicates the interlayer adhesion between the release layer 3 and the design layer 4, and the release weight indicates the result of the tape peel test. The acrylic layer in the 3rd column of the release layer is a conventionally used acrylic resin (average molecular weight 95000), the ultraviolet curable type is an ultraviolet curable resin, the two component curable type is a two component curable resin, and the high molecular weight is an average molecular weight of 300,000. Acrylic resin, polymer + three-dimensional structure is an acrylic resin having an average molecular weight of 300,000 and the molecular structure is a three-dimensional structure. ○ in the result column indicates good, Δ indicates somewhat difficult, and × indicates defective.

  As is apparent from the results shown in Table 1, the release layer 3 of the transfer material according to the present invention can form the pattern layer 4 and the like without any difference from the conventional release layer 3 made of an acrylic resin. It was provided with peelability.

  Table 2 is a table showing the results of testing the main physical properties of the transfer material of the present invention and the transfer material shown in the prior art.

In Table 2, light resistance 1 in the test column is 500 hours after a carbon arc fade meter (FOM) test (ΔE ≦ 3), light resistance 2 is a test with a QUV irradiation amount of 150 MJ, and alkali resistance is 0.1 N NaOH. After application, test after 4 hours at 50 ° C, acid resistance is 0.1N-H ₂ SO ₄ applied at room temperature, test after 24 hours, Brabus resistance at room temperature for 2 days at 80 ° C Test after 7 days, heat resistance at 100 ° C. after 20 days, moisture resistance at 50 ° C. after 77 days, vacuum formability on base sheet with release layer 3 formed Tests for vacuum forming 1 are shown respectively. The column for release layer 3 is the same as in Table 1. In the result column, “◎” indicates very good, “◯” indicates good, “Δ” indicates somewhat difficult, and “×” indicates poor.

  As is clear from the results shown in Table 2, the transfer material in the present invention showed good results in all test items.

  A method for decorating the surface of an object to be transferred using the transfer method using the transfer material having the above-described layer structure will be described.

  First, the adhesive layer 6 side of the transfer material is brought into close contact with the surface of the transfer object. Next, using a transfer machine such as a roll transfer machine or an up-down transfer machine provided with a heat-resistant rubber-like elastic body such as silicon rubber, a heat-resistant rubber-like condition set at a temperature of about 80 to 270 ° C. and a pressure of about 490 to 1960 Pa. Heat and pressure are applied from the substrate sheet 1 side of the transfer material through the elastic body. By doing so, the adhesive layer 6 adheres to the surface of the transfer object.

  Finally, when the base sheet 1 is peeled off after cooling, peeling occurs at the boundary surface between the base sheet 1 and the release layer 3 and transfer is completed. When the release layer 2 is provided on the base sheet 1, when the base sheet 1 is peeled off, peeling occurs at the boundary surface between the release layer 2 and the release layer 3, and the transfer is completed.

  Next, a method for decorating the surface of a resin molded product, which is a transfer target, using the above-described transfer material and utilizing a simultaneous molding transfer method by injection molding will be described.

  First, a transfer material is fed into a molding die composed of a movable die and a fixed die. At that time, a single sheet of transfer material may be fed one by one, or a necessary part of a long transfer material may be intermittently fed. When a long transfer material is used, it is preferable to use a feeding device having a positioning mechanism so that the registration of the pattern layer 4 of the transfer material and the molding die coincide. In addition, when the transfer material is intermittently fed, if the transfer material is fixed by the movable mold and the fixed mold after the position of the transfer material is detected by the sensor, the transfer material can always be fixed at the same position. This is convenient because the positional shift of the symbol layer 4 does not occur.

  After the molding die is closed, the molding resin melted from the gate is injected and filled in the die, and at the same time as the transfer object is formed, the transfer material is adhered to the surface. Examples of the molding resin include general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, AS resin, and AN resin. Also, general engineering resins such as polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, acrylic resins, polycarbonate modified polyphenylene ether resins, polybutylene terephthalate resins, ultrahigh molecular weight polyethylene resins, polysulfone resins, polyphenylene sulfide resins Super engineering resins such as polyphenylene oxide resins, polyarylate resins, polyetherimide resins, polyimide resins, liquid crystal polyester resins, and polyallyl heat-resistant resins can also be used. Furthermore, composite resins to which reinforcing materials such as glass fibers and inorganic fillers are added can also be used.

  After the resin molded product, which is the transfer target, is cooled, the molding die is opened and the resin molded product is taken out. Finally, the transfer is completed by removing the base sheet 1.

  A transfer material for an automobile interior audio cover panel having a metallic gloss pattern was obtained as follows.

  A three-dimensional structure acrylic resin (average molecular weight) in which a biaxially stretched polyethylene terephthalate film having a thickness of 38 μm is used as a base sheet, a release layer is provided thereon by a gravure printing method, and then an ultraviolet absorber represented by the following chemical formula is copolymerized. 250,000) were formed by gravure printing to provide a release layer (dry film thickness of about 3 to 4 μm). The reason why the same resin has a two-layer structure is that one layer (dry film thickness of about 1.5 to 2 μm) is inferior in light resistance and wear resistance.

  Next, an anchor layer (dry film thickness of about 1.5 to 2 μm) is formed with a two-component urethane resin by gravure printing, and then an aluminum metal thin film layer (film thickness of about 60 nm) is formed by vacuum deposition. Then, an adhesive layer (dry film thickness of about 3 to 4 μm) made of vinyl chloride-vinyl acetate copolymer resin was formed by a gravure printing method to obtain a transfer material.

  The transfer material obtained as described above was supplied between silicon rolls maintained at 240 ° C. and transferred to a polycarbonate molded product, and a molded product excellent in light resistance and chemical resistance was obtained on the outermost layer. The obtained molded product had a good finish without impairing the appearance after 500 hours with a carbon arc fade meter (FOM) and after a chemical resistance test.

  A transfer material for an automotive interior switch panel having a wood grain pattern was obtained as follows.

  An acrylic-styrene copolymer resin in which a biaxially stretched polyethylene terephthalate film having a thickness of 25 μm is used as a base sheet, a release layer is provided thereon by a gravure printing method, and then the same ultraviolet absorber as in Example 1 is copolymerized. (Average molecular weight 170,000) was formed by a gravure printing method to provide a release layer.

  Next, a pattern layer (dry film thickness of about 10 μm) composed of 6 layers by gravure printing using an ink made of an acrylic-vinyl chloride copolymer resin containing pigments such as carbon black, iron oxide, monoazo yellow, and titanium oxide. Then, an adhesive layer (dry film thickness of about 2 to 3 μm) was formed by a gravure printing method using a vinyl chloride-vinyl acetate copolymer resin to obtain a transfer material.

  The transfer material obtained as described above was supplied into an injection mold by a transfer material supply device, heated and vacuum sucked to inject and integrate a heat-resistant ABS resin at a resin temperature of 260 ° C. After cooling, the base sheet was peeled off, and a molded product having excellent light resistance and chemical resistance was obtained as the outermost layer. The obtained molded product had a good finish without impairing the appearance after 500 hours with a carbon arc fade meter (FOM) and after a chemical resistance test.

  In the following manner, a transfer material for an automobile interior center cluster having a metallic gloss pattern was obtained.

  A polyester film that can be molded into a three-dimensional shape with a thickness of 50 μm is used as a base sheet, and a release layer made of an aminoalkyd-based cured resin is formed thereon by a gravure printing method. A copolymerized acrylic-urethane copolymer resin (average molecular weight 370,000) was formed by a reverse coating method to provide a release layer (dry film thickness of about 5 μm).

  Next, an anchor layer (dry film thickness of about 2 to 3 μm) is formed with a two-component urethane resin by a gravure printing method, and then a chromium metal thin film layer (film thickness of about 40 nm) is formed by a vacuum evaporation method. Then, an adhesive layer (dry film thickness of about 4 to 6 μm) made of vinyl chloride-vinyl acetate copolymer resin was formed by a gravure printing method to obtain a transfer material.

  The transfer material obtained as described above was supplied into an injection mold by a transfer material supply device, heated and vacuum sucked to inject and integrate PC / ABS resin at a resin temperature of 265 ° C. After cooling, the base sheet was peeled off to obtain a molded product having excellent light resistance and chemical resistance as the outermost layer. The obtained molded product had a good finish without impairing the appearance after 500 hours with a carbon arc fade meter (FOM) and after a chemical resistance test.

  A car interior switch base transfer material having a wood grain pattern was obtained as follows.

  A biaxially stretched polyethylene terephthalate film having a thickness of 25 μm is used as a base sheet, a release layer is provided thereon by a gravure printing method, and then an ultraviolet absorber represented by the following chemical formula (2- (2-hydroxy-5-methylphenyl) An acrylic resin (average molecular weight 400,000) mixed with benzotriazole was formed by a gravure printing method to provide a release layer.

  Next, a pattern layer (dry film thickness of about 10 μm) composed of 6 layers by gravure printing using an ink made of an acrylic-vinyl chloride copolymer resin containing pigments such as carbon black, iron oxide, monoazo yellow, and titanium oxide. Then, an adhesive layer (dry film thickness of about 2 to 3 μm) was formed by a gravure printing method using a vinyl chloride-vinyl acetate copolymer resin to obtain a transfer material.

  The transfer material obtained as described above was supplied into an injection mold by a transfer material supply device, heated and vacuum sucked to inject and integrate a heat-resistant ABS resin at a resin temperature of 260 ° C. After cooling, the base sheet was peeled off, and a molded product having excellent light resistance and chemical resistance was obtained as the outermost layer. The obtained molded product had a good finish without impairing the appearance after 500 hours with a carbon arc fade meter (FOM) and after a chemical resistance test.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used in automobile interior and exterior, building materials, mobile phones, home appliances, particularly three-dimensional molded products that require light resistance and chemical resistance, and is industrially useful.

It is sectional drawing which shows one Example of the transfer material of this invention. It is sectional drawing which shows one Example of the transfer material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base sheet 2 Release layer 3 Peeling layer 4 Design layer 5 Anchor layer 6 Adhesive layer

Claims (3)

A release layer, a design layer, and an adhesive layer are sequentially laminated on the base sheet, and the release layer has an average molecular weight of 150,000 to 500,000 acrylic resin, acrylic-styrene copolymer resin, or acrylic-urethane copolymer. A transfer material comprising a systemic resin as a main component and a UV absorber copolymerized or mixed. The transfer material according to claim 1, wherein the molecular structure of the acrylic resin, acrylic-styrene copolymer resin or acrylic-urethane copolymer resin constituting the release layer is a three-dimensional structure. The transfer material according to claim 1, wherein the ultraviolet absorber is represented by the following chemical formula.

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