JP4366596B2 - Transfer sheet and method for producing cosmetic material using the same - Google Patents

Description

  The present invention relates to a transfer sheet for imparting designability to members used in exterior applications including housing members, and a method for producing the transfer decorative material.

Conventionally, when a housing member is taken as an example, a transfer printing method has been widely used as a method for imparting designability and wear resistance to the surface of a crafted member, for example, transfer to a substrate or curved body having an uneven surface. Is generally called lapping transfer or the like. As a transfer method used for this wrapping transfer, for example, a method in which a release layer made of an acrylic resin or the like, a wear-resistant layer (protective layer) and a pattern layer are provided on a film support is known. An adhesive is applied to the transfer sheet and bonded to the member to be transferred, and then the support is peeled off to produce a decorative material by lapping transfer. (For example, see Patent Document 1)
However, according to the above-described conventional configuration, when wrapping transfer is performed to a member to be transferred using the transfer sheet, a solvent contained in the used adhesive (for example, a solvent-based urethane two-component reaction curable resin), Not only does the curing agent penetrate into the transfer sheet, and the penetration strength of the support does not stabilize over time due to the penetration, but if the support is not peeled off immediately after transfer, it cannot be peeled off in some cases. The inconvenience arises.

  Furthermore, according to the above-described conventional configuration, the wear-resistant layer of the transfer sheet is used to give transferability so as to flexibly follow the wrapping shape of the member to be transferred and to adjust the peelability from the support. For example, since the degree of curing is suppressed to a low level by, for example, reducing the addition amount of the curing agent, there is a problem that the surface properties of the finally obtained transfer decorative material are inferior.

  As a method for improving the above problems, a transfer sheet comprising a release layer made of a melamine resin containing a matting agent as necessary on a support, and a protective layer and a pattern printing layer provided thereon in order is used. There has been proposed a method for producing a cosmetic material which is transferred to a substrate to be transferred through an adhesive layer and peeled off at the interface between the release layer and the protective layer (see, for example, Patent Document 2). is not.

JP-A-5-330013 JP-A-9-86094

  In order to solve the above-described problems of the prior art, the object of the present invention is to not only stabilize the peelability with time between the support of the transfer sheet after transfer but also the transfer target in the surface modification method of the object, as well as scratch resistance. It is an object of the present invention to provide a transfer sheet and a transfer method, which can provide a highly protective layer and can be used in outdoor applications, which cannot be achieved by conventional methods, and have excellent design properties.

  In order to achieve the above object, the transfer sheet of the present invention is a transfer sheet obtained by laminating at least a protective layer, a pattern layer, and an adhesive layer on a support, and the protective layer has at least a binder resin having a hydroxyl group or a carboxyl group, A transfer sheet, which is a cured film made of a reactive resin, comprising a curing agent mainly composed of aliphatic isocyanate and alicyclic isocyanate.

  Further, the transfer sheet of the present invention comprises a molar equivalent of a hydroxyl group or a carboxyl group of the binder resin having a hydroxyl group or a carboxyl group, and an isocyanate group of a curing agent mainly comprising at least an aliphatic isocyanate and an alicyclic isocyanate. The transfer sheet is characterized in that the molar equivalent ratio is 5: 1 to 1: 1.

The transfer sheet of the present invention is a transfer sheet characterized in that the ratio of molar equivalents of each isocyanate group in the aliphatic isocyanate and the alicyclic isocyanate is in the range of 1: 1 to 1: 3. is there.
The pattern layer ink has the same composition as the ink used for the protective layer, and a colorant such as a pigment is added. The adhesive layer contains a fluoroethylene / alkyl vinyl ether copolymer and a block isocyanate. It is characterized by containing.

  In addition, the method for producing a decorative material using the transfer sheet of the present invention superimposes the surface of the transfer sheet on which the adhesive layer is laminated and the transfer target, and transfers the protective layer, the pattern layer, and the adhesive layer with heat pressure. After that, the support is peeled off.

  ADVANTAGE OF THE INVENTION According to this invention, the transfer sheet for providing the designability to the member used for exterior uses including a housing member is obtained. Furthermore, the transfer sheet according to the present invention is easy to handle, has a high productivity, and enables the production of a transfer sheet and a transfer member satisfying a high level of water resistance and surface hardness required when used for exterior applications. To do.

Hereinafter, the present invention will be described in detail.
As the support used in the present invention, a polyester film, a polyolefin film such as polyethylene and polypropylene, a polyvinyl chloride resin film, or a laminate film with these other base materials, which has been conventionally used in lapping transfer. Any support can be used. The thickness of the support used may be selected depending on the degree of surface irregularities of the transfer medium, transfer conditions, and the type of support used. However, when polyethylene terephthalate film (PET) is used, it is usually 5. It is preferable to use a 5 to 50 μm sheet.

In the present invention, on the support of the transfer sheet, first, a reactive resin comprising a binder resin having a hydroxyl group or a carboxyl group, and a curing agent containing at least an aliphatic isocyanate and an alicyclic isocyanate as main components. A protective layer made of a cured film is provided.
As the binder resin used for the protective layer, conventionally known thermoplastic resins having a hydroxyl group or a carboxyl group can be used, but it is desirable to select a binder resin component in consideration of use in outdoor applications.

  As binder resins for use in outdoor applications, acrylic resins such as polymethyl methacrylate, styrene acrylic, acrylic polyol, silicone resins such as silicone acrylic copolymers and silicone urethane copolymers, fluoroethylene alkyl vinyl ether copolymers, Examples thereof include fluororesins such as fluoroethylene alkyl vinyl ester copolymers, and these binder resins must be terminated with a resin component having a hydroxyl group or a carboxyl group.

  In addition, the curing agent used in combination needs to contain two components, an aliphatic isocyanate and an alicyclic isocyanate. Examples of the aliphatic isocyanate include hexamethylene diisocyanate (HDI), dimer acid diisocyanate (DDI), norbornene diisocyanate (NBDI), and the like. Examples of the alicyclic isocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI, H12MDI), hydrogenated XDI (H6XDI), and the like. In addition to these two components, a conventionally known curing agent can be used in combination. Examples thereof include melamine resin, benzoguanamine resin, urea resin, amino resin, diamine, aliphatic polyvalent carboxylic acid and its anhydride, epoxy resin, carbodiimide compound and the like.

  The ratio of the molar equivalent of the hydroxyl group or carboxyl group of the binder resin to the molar equivalent of the isocyanate group is preferably 5: 1 to 1: 1. Furthermore, it is desirable that the molar equivalent ratio of each isocyanate group between the aliphatic isocyanate and the alicyclic isocyanate is in the range of 1: 1 to 1: 3. When the molar equivalent of the hydroxyl group or carboxyl group of the binder resin is more than 5 times the molar equivalent of the isocyanate group, the protective layer is not sufficiently cured, and the hardness that can be used in outdoor applications cannot be secured. On the other hand, when the molar equivalent of the hydroxyl group or carboxyl group of the binder resin is less than the molar equivalent of the isocyanate group, the base material adhesion force becomes larger than necessary, and the base material peeling after transfer becomes difficult.

  When the molar equivalent of the isocyanate group of the aliphatic isocyanate is larger than the molar equivalent of the isocyanate group of the alicyclic isocyanate, the base material adhesion force becomes unnecessarily large, and the base material peeling after transfer becomes difficult. In addition, when the molar equivalent of the isocyanate group of the alicyclic isocyanate is more than 3 times the molar equivalent of the isocyanate group of the aliphatic isocyanate, the adhesion of the substrate is unnecessarily reduced, and the transfer sheet is easy to handle. Decreases.

  In these protective layers, other additives can be added to achieve further functions. For example, in the field of cosmetic materials, addition of antibacterial properties, deodorizing properties, antifouling properties, and antifogging functions using a photocatalytic function is desired. In order to express these functions, these function-expressing materials must be on the protective surface of the transfer layer transferred to the transfer medium. In order to realize a transparent protective layer having a photocatalytic function and having a hard coat suitability, titanium oxide and zinc oxide fine particles having a particle diameter of 0.1 μm or less, which are known in this field, are dispersed in a hard coat material. It is preferable to use a protective layer. In addition, in these protective layers, metal-doped fine particles of indium oxide, tin oxide, fine particles of graphite fibrils, etc. are dispersed and added to provide an antistatic function, or an ultraviolet absorber is added to provide an ultraviolet cut function. It is also possible to do.

  In general, the protective layer is preferably applied using a bar coater, a micro coater, a gravure coater or the like so as to have a thickness of 1 to 15 μm. Thereafter, a cured resin film is formed by heating or the like.

  A pattern layer is provided on the protective layer. Conventionally known printing ink can be used as the printing ink used for the pattern layer, but it is desirable to select a binder resin and a pigment component in consideration of use in outdoor applications.

  As binder resins for use in outdoor applications, acrylic resins such as polymethyl methacrylate, styrene acrylic, acrylic polyol, silicone resins such as silicone acrylic copolymers and silicone urethane copolymers, fluoroethylene alkyl vinyl ether copolymers, Examples thereof include fluororesins such as fluoroethylene alkyl vinyl ester copolymers. Using these inks, a picture printing layer is formed by a desired publicly known printing method such as gravure printing, offset printing, screen printing, and the like.

  An adhesive layer is provided on the pattern layer. The adhesive layer may be appropriately selected according to the type of transfer target, and its composition and formation method can be known, but it is further possible to select components taking into account use in outdoor applications. desirable.

  In addition, when transferring the transfer sheet to the transfer target, a conventionally known heat-resistant layer made of silicon resin or the like is provided on the back surface of the support of the transfer sheet having the transfer layer in order to prevent the transfer roll from fusing due to heat. It may be provided.

  The surface of the adhesive layer of the transfer sheet prepared by the above method is superposed on the transfer target, and after transferring the pattern layer and the adhesive layer by hot pressure, the support is peeled off to form a transfer film on the surface of the adherend.

  As a transfer method, a transfer machine capable of softening the binder resin used for the adhesive layer and applying a sufficient pressure, such as a known laminator, a heat press, a printer having a thermal head, a handy iron, or the like is used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this.

On a polyester film having a thickness of 12 μm, 6.49 parts by weight of hexamethylene diisocyanate (NCO%: 10%) and isophorone diisocyanate (hydroxyl value: 52 mg KOH / g) are added to 100 parts by weight of a fluoroethylene / alkyl vinyl ether copolymer (hydroxyl value: 52 mgKOH / g). NCO%: 8%) was prepared so as to have a ratio of 8.11 parts by weight, and diluted with toluene to a solid content ratio of 30% to obtain a protective layer ink. This protective layer ink is applied to a thickness of 5 μm using a micro coater or a gravure coater. After coating, this was heat-dried under a temperature condition of 100 ° C. for 5 minutes to form a protective layer of a cured film. (Mole ratio of hydroxyl group / isocyanate group = 3/1, molar ratio of each isocyanate group of aliphatic isocyanate / alicyclic isocyanate = 1/1)
Next, on the protective layer, black pigment (PBk-7), indigo pigment (PB-15: 3), red pigment (PR-122), yellow with respect to 100 parts by weight of ink having the same composition as the protective layer ink. Using black, indigo, red, and yellow printing inks each containing 133.8 parts by weight of a pigment (PY-173), a desired pattern is printed on a gravure printing machine, and then dried at 100 ° C. for 5 minutes. A pattern layer consisting of a cured and cured film was formed.

  Furthermore, 53.5 parts by weight of a blocked isocyanate (hexamethylene diisocyanate, NCO%: 10.5) with respect to 100 parts by weight of a fluoroethylene / alkyl vinyl ether copolymer (hydroxyl value: 50 mgKOH / g) on the printed layer, A transfer sheet was obtained by applying an adhesive layer ink consisting of 100 parts by weight of titanium oxide and 253.5 parts by weight of toluene to a thickness of 15 μm using a microcoater or gravure coater.

  On a polyester film having a thickness of 25 μm, the composition of the protective layer ink is 3.24 parts of hexamethylene diisocyanate (NCO%: 10%) with respect to 100 parts by weight of a fluoroethylene / alkyl vinyl ether copolymer (hydroxyl value: 52 mg KOH / g). A transfer sheet was obtained in the same manner as in Example 1, except that the weight part and isophorone diisocyanate (NCO%: 8%) were changed to 12.15 parts by weight. (Molar ratio of hydroxyl group / isocyanate group = 3/1, molar ratio of each isocyanate group of aliphatic isocyanate / alicyclic isocyanate = 1/3)

On the polyester film having a thickness of 12 μm, the composition of the protective layer ink is 2.81 parts by weight of hexamethylene diisocyanate (NCO%: 12%), 100 parts by weight of acrylic polyol (hydroxyl value: 45 mg KOH / g), isophorone diisocyanate ( A transfer sheet was obtained in the same manner as in Example 1 except that NCO%: 15%) was 2.25 parts by weight.
(Molar ratio of hydroxyl group / isocyanate group = 5/1, molar ratio of each isocyanate group of aliphatic isocyanate / alicyclic isocyanate = 1/1)

  10.42 parts by weight of hexamethylene diisocyanate (NCO%: 6%) on 100 parts by weight of polyester (acid value (carboxyl group value): 25 mgKOH / g) on the polyester film having a thickness of 25 μm. A transfer sheet was obtained in the same manner as in Example 1 except that 31.25 parts by weight of isophorone diisocyanate (NCO%: 4%) was used. (Mole ratio of hydroxyl group / isocyanate group = 1/1, molar ratio of each isocyanate group of aliphatic isocyanate / alicyclic isocyanate = 1/2)

[Comparative Example 1] On a polyester film having a thickness of 25 µm, the composition of the protective layer ink was hexamethylene diisocyanate (NCO%: 10%) with respect to 100 parts by weight of a fluoroethylene / alkyl vinyl ether copolymer (hydroxyl value: 52 mgKOH / g). ) And 2.99 parts by weight of isophorone diisocyanate (NCO%: 8%), and a transfer sheet was obtained in the same manner as in Example 1.
(Molar ratio of hydroxyl group / isocyanate group = 3/1, molar ratio of each isocyanate group of aliphatic isocyanate / alicyclic isocyanate = 1/4)

[Comparative Example 2] On a polyester film having a thickness of 25 µm, the composition of the protective layer ink was hexamethylene diisocyanate (NCO%: 10%) with respect to 100 parts by weight of a fluoroethylene / alkyl vinyl ether copolymer (hydroxyl value: 52 mgKOH / g). ) And 8.41 parts by weight of isophorone diisocyanate (NCO%: 8%), and a transfer sheet was obtained in the same manner as in Example 1. (Mole ratio of hydroxyl group / isocyanate group = 3/1, molar ratio of each isocyanate group of aliphatic isocyanate / alicyclic isocyanate = 2/1)

[Comparative Example 3] On a polyester film having a thickness of 25 µm, the composition of the protective layer ink was hexamethylene diisocyanate (NCO%: 10%) with respect to 100 parts by weight of a fluoroethylene / alkyl vinyl ether copolymer (hydroxyl value: 52 mgKOH / g). ) And 3.05 parts by weight of isophorone diisocyanate (NCO%: 8%), and a transfer sheet was obtained in the same manner as in Example 1. (Mole ratio of hydroxyl group / isocyanate group = 6/1, molar ratio of each isocyanate group of aliphatic isocyanate / alicyclic isocyanate = 1/1)

[Comparative Example 4] On a polyester film having a thickness of 25 µm, the composition of the protective layer ink was hexamethylene diisocyanate (NCO%: 10%) with respect to 100 parts by weight of a fluoroethylene / alkyl vinyl ether copolymer (hydroxyl value: 52 mgKOH / g). ) And 24.34 parts by weight, and isophorone diisocyanate (NCO%: 8%) was 30.45 parts by weight. A transfer sheet was obtained in the same manner as in Example 1. (Molar ratio of hydroxyl group / isocyanate group = 0.8 / 1, molar ratio of each isocyanate group of aliphatic isocyanate / alicyclic isocyanate = 1/1)

[Comparative Example 5] On a polyester film having a thickness of 25 µm, the composition of the protective layer ink was hexamethylene diisocyanate (NCO%: 10%) with respect to 100 parts by weight of a fluoroethylene / alkyl vinyl ether copolymer (hydroxyl value: 52 mgKOH / g). ) Was changed to 12.97 parts by weight, and a transfer sheet was obtained in the same manner as in Example 1. (Mole ratio of hydroxyl group / isocyanate group = 3/1, molar ratio of each isocyanate group of aliphatic isocyanate / alicyclic isocyanate = 1/0)

[Comparative Example 6] On a polyester film having a thickness of 25 µm, the composition of the protective layer ink is isophorone diisocyanate (NCO%: 8%) with respect to 100 parts by weight of a fluoroethylene / alkyl vinyl ether copolymer (hydroxyl value: 52 mgKOH / g). A transfer sheet was obtained in the same manner as in Example 1 except that the amount was 16.2 parts by weight. (Mole ratio of hydroxyl group / isocyanate group = 3/1, molar ratio of each isocyanate group of aliphatic isocyanate / alicyclic isocyanate = 0/1)

With the transfer sheet obtained by the above method, a commercially available 0.5 mm thick aluminum plate (surface acrylic coating, acid value: 15.0 mg KOH / g), with the adhesive layer side superimposed on the aluminum plate, rubber Using a laminator machine having rubber rolls consisting of two pairs of rolls with a hardness of 80 °, the upper roll temperature is 150 ° C., the lower roll temperature is 130 ° C., the roll pressure is 4.0 kg / cm ² , and the line speed is 5 m / min. Transcribed. After the transferred aluminum plate was cooled to room temperature, the substrate was peeled off and baked at 150 ° C. for 30 minutes using a gear oven to obtain a transfer sample.

(Comparison results) About the transfer sheets and transfer samples obtained in Examples 1 to 4 and Comparative Examples 1 to 6, the sheet handling properties (base material adhesion), the base material peelability, the pencil hardness, and the resistance to resistance. When the boiling water was evaluated, Examples 1 to 4 clearly showed better performance than Comparative Examples 1 to 6. Table 1 shows the evaluation results.

It is explanatory drawing which shows one Example of the transfer sheet of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base film 2 ... Protective layer 3 ... Picture layer 4 ... Adhesive layer

Claims (2)

In a transfer sheet formed by laminating at least a protective layer, a pattern layer, and an adhesive layer on a support, the protective layer is a curing mainly composed of a binder resin having a hydroxyl group or a carboxyl group, and at least an aliphatic isocyanate and an alicyclic isocyanate. consisting agent, Ri cured film der by reactive resins, and the molar equivalents of hydroxyl groups or carboxyl groups of the binder resin, the ratio of the molar amount of isocyanate groups of the curing agent is 5: 1 to 1: 1 The molar ratio of the respective isocyanate groups of the aliphatic isocyanate and the alicyclic isocyanate is in the range of 1: 1 to 1: 3, and the pattern layer ink is applied to the protective layer. The ink composition has the same composition as the ink to be used, and a colorant such as a pigment is added. Ane - transfer sheet characterized by containing the door. A surface of the transfer sheet according to claim 1, which is superposed on the surface to be transferred, the protective layer, the pattern layer, and the adhesive layer are transferred by hot pressure, and then the support is peeled off. Production method.

Images