WO2014203507A1 - 転写フィルム及びこれを用いた転写成形品 - Google Patents

転写フィルム及びこれを用いた転写成形品 Download PDF

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Publication number
WO2014203507A1
WO2014203507A1 PCT/JP2014/003148 JP2014003148W WO2014203507A1 WO 2014203507 A1 WO2014203507 A1 WO 2014203507A1 JP 2014003148 W JP2014003148 W JP 2014003148W WO 2014203507 A1 WO2014203507 A1 WO 2014203507A1
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Prior art keywords
layer
transfer
mat
film
release layer
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PCT/JP2014/003148
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English (en)
French (fr)
Japanese (ja)
Inventor
恵 渡邊
渡邉　学
友美 樋爪
啓佑 松田
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凸版印刷株式会社
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Application filed by 凸版印刷株式会社 filed Critical 凸版印刷株式会社
Priority to CN201480034260.9A priority Critical patent/CN105307858B/zh
Priority to JP2015522552A priority patent/JP6597305B2/ja
Publication of WO2014203507A1 publication Critical patent/WO2014203507A1/ja

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    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent

Definitions

  • the present invention relates to a transfer film that imparts a matte appearance to the surface of a molded product and a transfer molded product using the same, and in particular, a mat layer that does not peel from a base film, and a release layer formed on the surface of the mat layer, And a transfer molded product using the same.
  • a transfer film for decorating the surface of the transfer object is often provided with a surface protective layer such as a hard coat layer.
  • the transfer film has a release film in which a release layer is formed on one surface of a base film, and a hard coat layer / decorative layer / adhesive layer in this order on the surface of the release layer.
  • the formed transfer layer is sequentially laminated.
  • the said transfer film is produced as follows, for example. First, a release layer is formed on one surface of the base film to produce a release film. Next, a transfer film capable of desired decoration is produced by sequentially laminating a transfer layer such as a hard coat layer, a decorative layer, and an adhesive layer on the surface of the release layer.
  • the release layer has a good releasability for peeling the transfer layer (particularly the hard coat layer) from the release film and transferring it to the transfer body during thermal transfer to a transfer object such as a plastic molding. It is required to have. Further, the hard coat layer is required to have surface performance such as scratch resistance and chemical resistance. Moreover, it is calculated
  • top coatability No repellency of the coating liquid for hard coat layer at the time of coating liquid coating (top coatability), heat resistance that can withstand the heat at the time of transfer, strong adhesion to the base film or substrate, Is required to have the performance of being able to follow the three-dimensional shape of the transfer target (stretchability).
  • organic particles and inorganic particles are used as a matting agent in the release layer. May be added.
  • the transfer layer is transferred while the release layer itself to which the matting agent is added remains integral with the release film, and the fine uneven pattern on the release layer surface is transferred to the outermost surface of the transfer layer. Is transcribed. As a result, a matte appearance can be imparted to the transfer object.
  • the mat layer formed on the surface of the above-mentioned base film is mainly composed of a thermosetting resin such as an amino alkyd resin, a urea melamine resin, or a mixture thereof.
  • a baking process is needed in the manufacturing process of a transfer film. Specifically, in this baking step, for example, heating in an oven at 180 to 200 ° C. for about 30 seconds to 1 minute is required. Therefore, the base film needs to be able to withstand the heating conditions, and a thin base material or a heat-sensitive base material is often not suitable for the base film.
  • a uniform hard coat layer can be formed while exhibiting releasability and suppressing the repellency phenomenon of the coating liquid for hard coat layer applied on the release layer. Furthermore, adhesion between the mat layer and the release layer can also be obtained. Further, since the release layer is formed on the surface of the mat layer, the surface glossiness of the transfer target can be easily controlled by adjusting the film thickness of the release layer. Moreover, since the transfer film which concerns on 1 aspect of this invention does not contain the melamine resin, it can also reduce an environmental load (human load).
  • the matte appearance can also be further provided to the surface of a to-be-transferred body by further including a 2nd mat agent in a mold release layer.
  • the release layer is formed on the surface of the mat layer, the surface glossiness of the transfer target can be easily controlled by adjusting the mat agent content and film thickness of the release layer. Can do.
  • the influence on the surface glossiness of the transfer object due to the change in the thickness of the release layer can be suppressed, a transfer film with less glossiness variation can be produced.
  • it can suppress that the manufacturing cost of a transfer film rises by making a 1st mat agent and a 2nd mat agent into the same mat agent.
  • a transfer film 11A includes a base film 1, a mat layer 2, a release layer 3A, a hard coat layer 4, a primer layer 5, a decorative (printing) layer 6, and an adhesive layer. 7 is a laminated body provided with this order.
  • the decoration (printing) layer 6 (hereinafter, also simply referred to as “decoration layer 6”) is usually a plurality of layers, and is a decoration material having an optical effect such as embossing or pearl pigment. Can also be included.
  • each layer provided in the transfer film 11A according to the present embodiment will be described.
  • the substrate film 1 for example, a substrate such as a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a triacetyl cellulose film, a polycarbonate film, a nylon film, a cellophane film, an acrylic film, or a vinyl chloride film can be used. is there.
  • the usable film thickness is preferably in the range of 25 ⁇ m or more and 250 ⁇ m or less, and more preferably in the range of 38 ⁇ m or more and 150 ⁇ m or less because it is advantageous in terms of the balance of cost and film formability.
  • the mat layer 2 is a layer having fine irregularities formed on the surface, and is a layer to which a mat agent (first mat agent) is added.
  • a mat agent first mat agent
  • various inorganic particles and organic particles can be used, and the material and the like are not particularly limited.
  • the average particle size of the particles used for the matting agent is preferably in the range of 0.01 ⁇ m to 50 ⁇ m, and more preferably in the range of 1 ⁇ m to 30 ⁇ m. If the average particle size of the particles used in the matting agent is less than 0.01 ⁇ m, the surface of the transfer molded article may not be sufficiently imparted with a matte appearance, and if it exceeds 50 ⁇ m, pinholes may be generated in each printing step. May be a factor.
  • the average thickness of the mat layer 2 is preferably in the range of 2 ⁇ m or more and 15 ⁇ m or less in consideration of the average particle diameter of the matting agent used, since it can be expected to show a matte effect.
  • the mat layer 2 may contain a cellulose derivative containing a hydroxyl group in order to improve heat resistance.
  • the reason for improving the heat resistance in this way is that heat may be extremely applied when the transfer layer is transferred to the transfer target.
  • the cellulose derivative containing a hydroxyl group include nitrocellulose, cellulose acetate butyrate, cellulose acetate propionate, and the like.
  • the blending amount of the cellulose derivative is preferably in the range of 20 wt% or more and 100 wt% or less with respect to the resin material (for example, acrylic polyol resin) which is the main component of the coating film constituting the mat layer 2. . If it is in this range, sufficient heat resistance can be imparted to the mat layer 2.
  • the mat layer 2 may contain an acrylic resin having a long chain alkyl group having 10 to 30 carbon atoms and a hydroxyl group, or an acrylic silicone resin containing a hydroxyl group as a release agent.
  • the release layer 3A is a layer mainly composed of an acrylic urethane resin containing a long-chain alkyl group having 10 to 30 carbon atoms.
  • the acrylic urethane resin includes at least an acrylic polyol resin, a hydroxyl group, and 10 carbon atoms. It is a resin produced from a crosslinking reaction between an acrylic resin containing a long-chain alkyl group of 30 or less and an isocyanate compound.
  • an acrylic urethane resin having a long-chain alkyl group in such a carbon number range, it exhibits excellent releasability at the time of thermal transfer and is applied on the release layer 3A.
  • a uniform hard coat layer 4 can be formed without causing repellency of the liquid.
  • the number of carbon atoms When the number of carbon atoms is less than 10, the releasability at the time of thermal transfer is insufficient, and transfer unevenness may occur on the surface of the transfer object, resulting in a quality defect. On the other hand, when the number of carbon atoms exceeds 30, repelling occurs when the hard coat layer coating solution is applied, and the uniform hard coat layer 4 may not be formed.
  • the ink composition can be adjusted by blending an acrylic polyol resin or an acrylic urethane resin into the ink composition containing the acrylic resin having a long-chain alkyl group and a hydroxyl group and an isocyanate compound, and the release layer. 3A may be formed.
  • the performance of the release layer 3A such as releasability, stretchability, and heat resistance can be adjusted.
  • the blending amount of the acrylic resin having a long chain alkyl group and a hydroxyl group is preferably in the range of 2% by weight to 30% by weight with respect to the acrylic polyol resin, but is not particularly limited.
  • the release layer 3A in the present embodiment is a cured product of an ink composition containing at least an acrylic polyol resin, an acrylic resin having a hydroxyl group and a long-chain alkyl group having 10 to 30 carbon atoms, and an isocyanate compound, that is, The main component is acrylic urethane resin.
  • the main component is acrylic urethane resin.
  • the release layer 3A can be formed by low temperature curing.
  • the said acrylic polyol resin is an acrylic resin which has a some hydroxyl group, and is obtained by (co) polymerizing the (meth) acryl monomer which has a hydroxyl group.
  • a (meth) acrylic acid ester monomer having no hydroxyl group, a styrene monomer, a vinyl acetate monomer or the like may be copolymerized.
  • Examples of (meth) acrylic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. There is.
  • the acrylic resin having a long chain alkyl group and a hydroxyl group can be obtained by copolymerization of an acrylic monomer having a long chain alkyl group and a (meth) acryl monomer having a hydroxyl group.
  • the release layer 3A may be blended with a cellulose derivative containing a hydroxyl group in the same manner as the mat layer 2 for the purpose of improving heat resistance when the transfer film 11A is used for in-mold molding.
  • the cellulose derivative containing a hydroxyl group include nitrocellulose, cellulose acetate butyrate, cellulose acetate propionate, and the like.
  • the blending amount of the cellulose derivative is within the range of 20% by weight or more and 100% by weight or less with respect to the resin material (for example, acrylic polyol resin) which is the main component of the coating film constituting the release layer 3A. Is preferred. Within this range, sufficient heat resistance can be imparted to the release layer 3A.
  • the release layer 3A when laminating the hard coat layer 4 containing a functional group having a high polarity such as a urethane bond in the molecule, or when increasing the speed at the time of peeling, the release layer 3A is required to be lighter.
  • the amount of the acrylic silicone resin containing a hydroxyl group is 0.5% by weight or more based on the resin material (for example, acrylic polyol resin) which is the main component of the coating film constituting the release layer 3A. If it is in the range of 15% by weight or less, it is appropriate, and thereby the release property of the release layer 3A can be improved.
  • the thickness of the release layer 3A is not particularly limited, but is optimally in the range of 0.1 ⁇ m to 5 ⁇ m. By changing the thickness of the release layer 3A, the glossiness of the transfer layer 10 covering the outermost surface of the transfer molded product (transfer object) can be adjusted. Increasing the thickness of the release layer 3A increases the glossiness of the surface of the transfer molded product, and decreasing the thickness of the release layer 3A decreases the glossiness.
  • the hard coat layer 4 is in a tack-free state (a state in which the stickiness is eliminated simply by evaporating the solvent component) in the transfer film before being used for transfer, and after being transferred to the transfer target, ultraviolet rays, electron beams, etc. It is preferable to form with resin which can be bridge
  • the reason for crosslinking by irradiating active energy rays after transfer is that if the transfer film is provided with a hard coat layer 4 that has been previously crosslinked, the transfer film tends to follow the surface of the transfer object. This is because cracks are likely to occur in the hard coat layer 4 during stretching, resulting in poor appearance.
  • the first method is a method of using a polymer acrylate or methacrylate as the resin constituting the hard coat layer 4.
  • a crosslinking reaction product such as an isocyanate / polyol resin or an epoxy resin / amine is contained. It is a method of hardening moderately.
  • the third method uses an active energy ray-curable resin as the resin constituting the hard coat layer 4 and irradiates an appropriate amount of active energy rays within a range that does not impair the shape followability to the transferred body.
  • This is a method of making a linear curable resin into a semi-cured state. In this embodiment, any method may be used.
  • nanosilica particles can be added to the acrylic resin for the purpose of supplementing the surface hardness.
  • the addition amount of the nano silica particles is optimally in the range of 10 wt% or more and less than 40 wt% with respect to the acrylic resin. If the amount added is less than 10% by weight, the effect of improving the surface hardness may be poor. On the other hand, when the added amount is 40% by weight or more, the cured coating film becomes too brittle and the wear resistance may be deteriorated.
  • the nanosilica particles added to the hard coat layer 4 have a particle diameter in the range of 10 nm or more and less than 100 nm.
  • the nanosilica particles are desirably nanosilica particles surface-treated with an acryloyl / methacryloyl group-containing silane coupling agent or the like, but may be simply untreated nanosilica particles.
  • the thickness of the hard coat layer 4 is not particularly limited, but is preferably in the range of 2 ⁇ m or more and 10 ⁇ m or less in consideration of the balance between the expression of surface hardness, curing shrinkage, cost, and the like.
  • the primer layer 5 is a layer for maintaining adhesion between the hard coat layer 4 and the decorative layer 6, and is a hydroxyl group such as a polyol resin such as a polyester polyol resin or an acrylic polyol resin and / or a hydroxyl group-containing vinyl acetate resin.
  • a resin composed of a resin and an isocyanate compound can be used.
  • the thickness of the primer layer 5 is not particularly limited, but is optimal within the range of 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the decorative layer 6 is a layer for imparting design properties to the transfer target.
  • a printing layer such as an offset printing method, a gravure printing method, a screen printing method, or an ink jet method is used using a coloring ink containing a pigment or dye of an appropriate color as a colorant. It can be formed by the method.
  • Adhesive layer 7 As the adhesive layer 7, a known heat-sealable adhesive or pressure-sensitive adhesive can be used. Examples of the adhesive layer 7 include vinyl acetate resin, ethylene vinyl acetate copolymer resin, vinyl acetate resin, acrylic resin, butyral resin, epoxy resin, polyester resin, polyurethane resin, acrylic adhesive, rubber adhesive, and silicone. Type adhesive, urethane type adhesive and the like. The thickness of the adhesive layer 7 is not particularly limited, but is optimal within the range of 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the mat layer 2 is formed of a two-component curable urethane resin, so that the printability during gravure printing can be improved and the curing reaction can be performed at a low temperature of about room temperature to 50 ° C. Is completed, and the mat layer 2 with less heat load on the base film 1 can be produced. Furthermore, since the mat layer 2 contains the first mat agent, a matte appearance can be imparted to the surface of the transfer molded product.
  • the release layer 3A is formed of an acrylic urethane resin having a long-chain alkyl group having 10 to 30 carbon atoms, the printability during gravure printing can be enhanced, and the release layer 3A can be used during thermal transfer.
  • the uniform hard coat layer 4 can be formed while exhibiting excellent releasability and suppressing the repellency phenomenon of the coating liquid for hard coat layer applied on the release layer 3A. Furthermore, adhesion between the mat layer 2 and the release layer 3A can be obtained.
  • the transfer film 11A according to the present embodiment does not include a melamine resin, it is possible to reduce the environmental load (human load).
  • the transfer film 11A according to the present embodiment includes a cellulose derivative containing a hydroxyl group in at least one of the mat layer 2 and the release layer 3A. For this reason, since the heat resistance is improved with the transfer film 11A, even in the case of in-mold transfer that transfers simultaneously with injection molding, that is, in-mold transfer that requires heat resistance at high temperatures, Problems such as a blocking phenomenon can be suppressed.
  • the release layer 3A includes an acrylic silicone resin containing a hydroxyl group. For this reason, if it is 11A of transfer films, the outstanding mold release property which can fully respond also to the high-speed of thermal transfer can be exhibited.
  • Example 1 A biaxially stretched polyester film (Mitsubishi Resin Co., Ltd .: G440E50) having a thickness of 50 ⁇ m was used as a base film, and a mat layer coating solution having the following composition was applied to one surface at 120 ° C. using a gravure printing method. The mat layer was formed by coating so that the film thickness after drying for 2 seconds was 4.3 ⁇ m.
  • composition of mat layer coating solution Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560): 100 parts by weight, silica filler (Evonik Degussa, particle size: 6 ⁇ m): 5 parts by weight, polyacrylonitrile filler (Toyobo, particle size: 7 ⁇ m): 5 parts by weight, isocyanate compound (manufactured by Nippon Polyurethane, Coronate HL) : 10 parts by weight
  • a release layer coating solution having the following composition is applied using a microgravure printing method so that the film thickness after drying is 5.2 ⁇ m to form a release layer. Thereafter, the mat was aged at 50 ° C. for 5 days to produce a mat release film.
  • composition of release layer coating solution Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560): 100 parts by weight / acrylic resin: 5 parts by weight (having hydroxyl group and long-chain alkyl group (18 carbon atoms) which is a copolymer of 6-hydroxyhexyl acrylate and stearyl methacrylate) ⁇ Isocyanate compound (manufactured by Nippon Polyurethane Co., Ltd .: Coronate L): 20 parts by weight
  • a hard coat layer coating solution having the following composition was applied using a microgravure printing method so that the thickness after drying was 5.0 ⁇ m. Thus, a hard coat layer was formed.
  • UV curable resin 100 parts by weight (manufactured by DIC: RC29-117, with UV polymerization initiator, solid content 30%)
  • Silica 20 parts by weight (manufactured by Nissan Chemical Co., Ltd .: particle size 10-20 nm, MEK dispersion, solid content 30%)
  • an acrylic polyol / isocyanate-based ink (manufactured by Toyo Ink Co., Ltd .: V425 anchor) is applied as a primer layer coating solution on the hard coat layer so that the film thickness after drying becomes 1 ⁇ m using a gravure printing method.
  • black ink (V428UR92 black ink, manufactured by Toyo Ink Co., Ltd.) is applied as a decorative layer coating solution so that the film thickness after drying is 3 ⁇ m using a gravure printing method, and a decorative layer is formed. did.
  • an adhesive layer coating liquid (manufactured by Toyo Ink Co., Ltd .: K539HP adhesive varnish) was applied thereon so as to have a film thickness after drying of 1 ⁇ m using a gravure printing method to form an adhesive layer.
  • a transfer film according to Example 1-1 was produced.
  • the transfer film produced as described above was set in a mold of an injection molding machine, and a polycarbonate ABS alloy resin (manufactured by Nippon A & L Co., Ltd .: Techno Ace T-105) was injection molded.
  • the mold for injection molding is opened, the mat release film constituting the transfer film is peeled off from the transfer molded product, and then the accumulated light quantity is 1000 mJ / cm 2 with respect to the surface of the transfer molded product using a high-pressure mercury lamp.
  • the hard coat layer was crosslinked and cured. Thereby, a transfer molded product having a high surface strength was obtained.
  • Example 1-2 A mat release film was produced in the same manner as in Example 1-1 except that the release layer coating solution having the following composition was used.
  • (Composition of release layer coating solution) Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560): 100 parts by weight-Nitrocellulose (H1 / 4): 10 parts by weight-Acrylic resin: 5 parts by weight (A hydroxyl group and a long-chain alkyl group (carbon number 18), which is a copolymer of 6-hydroxyhexyl acrylate and stearyl methacrylate) Have) ⁇ Isocyanate compound (manufactured by Nippon Polyurethane Co., Ltd .: Coronate L): 20 parts by weight Next, a hard coat layer, a primer layer, a decorative layer, and an adhesive layer were laminated on the release layer of the mat release film in the same manner as in Example 1-1, and Example 1-2 was obtained.
  • Acrylic polyol resin Toei Kas
  • Such a transfer film was prepared. This transfer film was set inside a mold of an injection molding machine, and injection molding and ultraviolet irradiation of the surface of the transfer molded product were performed in the same manner as in Example 1-1 to obtain a transfer molded product having high surface strength.
  • Example 1-3 A mat release film was produced in the same manner as in Example 1-1 except that the release layer coating solution having the following composition was used.
  • (Composition of release layer coating solution) Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560): 100 parts by weight-Nitrocellulose (H1 / 4): 10 parts by weight-Acrylic resin: 5 parts by weight (A hydroxyl group and a long-chain alkyl group (carbon number 18), which is a copolymer of 6-hydroxyhexyl acrylate and stearyl methacrylate) Have) Silicone-modified acrylic resin (manufactured by NOF Corporation: FS730): 5 parts by weight Isocyanate compound (manufactured by Nippon Polyurethane Co., Ltd .: Coronate L): 20 parts by weight Next, on the release layer of the mat release film, a hard coat layer, a primer layer, a decorative layer, and an adhesive layer were laminate
  • Such a transfer film was prepared. This transfer film was set inside a mold of an injection molding machine, and injection molding and ultraviolet irradiation of the surface of the transfer molded product were performed in the same manner as in Example 1-1 to obtain a transfer molded product having high surface strength.
  • Example 1-4 Using the same base film as in Example 1-1, a mat layer was formed on one surface in the same manner as in Example 1-1. Thereafter, a release layer coating liquid having the same composition as in Example 1-3 was applied using a microgravure printing method so that the film thickness after drying was 2.2 ⁇ m, and then a release layer was formed. A mat release film was produced by aging at 50 ° C. for 5 days. Next, a hard coat layer, a primer layer, a decorative layer, and an adhesive layer are laminated on the release layer of the mat release film in the same manner as in Example 1-1, and the transfer film according to Example 1-4. Was made. This transfer film was set inside the mold of an injection molding machine, and injection molding and ultraviolet irradiation were performed on the surface of the transfer molded product in the same manner as in Example 1-1 to obtain an injection molded product having high surface strength.
  • Example 1-5 Using the same base film as in Example 1-1, a mat layer was formed on one surface in the same manner as in Example 1-1. Thereafter, a release layer coating liquid having the same composition as in Example 1-2 was applied using a micro gravure printing method so that the film thickness after drying was 0.8 ⁇ m, and then a release layer was formed. A mat release film was produced by aging at 50 ° C. for 5 days. Next, a hard coat layer, a primer layer, a decorative layer, and an adhesive layer are laminated on the release layer of the mat release film in the same manner as in Example 1-1, and the transfer film according to Example 1-5 Was made. This transfer film was set inside the mold of an injection molding machine, and injection molding and ultraviolet irradiation were performed on the surface of the transfer molded product in the same manner as in Example 1-1 to obtain an injection molded product having high surface strength.
  • Example 1-2 Using the same base film as in Example 1-1, a mat layer was formed on one surface in the same manner as in Example 1-1. Thereafter, acrylic / melamine-based ink (manufactured by Toyo Ink Co., Ltd .: HP200 gloss coat N varnish) was applied as a release layer coating solution using a bar coater so that the film thickness after drying was 0.5 ⁇ m. Then, it baked at 180 degreeC and formed the release layer, and produced the mat
  • acrylic / melamine-based ink manufactured by Toyo Ink Co., Ltd .: HP200 gloss coat N varnish
  • a case where uniform application is impossible means a case where the application itself was attempted to form a film but the application could not be performed uniformly.
  • “when the layer is not formed” means that the layer to be laminated on the underlying layer could not be formed due to a defect (such as wrinkles) that occurred in the underlying layer. To do.
  • FIG. 3 is a schematic cross-sectional view of a transfer film according to the second embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view of a transfer molded product manufactured using the transfer film according to the second embodiment.
  • the transfer film 11B according to the present embodiment includes a base film 1, a mat layer 2, a release layer 3B, a hard coat layer 4, a primer layer 5, a decorative layer 6, and an adhesive layer 7. It is the laminated body prepared in order.
  • the transfer film 11B according to the second embodiment is different from the transfer film 11A according to the first embodiment only in the release layer 3B, and other layers (that is, the base film 1 and the mat).
  • Layer 2, hard coat layer 4, primer layer 5, decorative layer 6 and adhesive layer 7) are the same. More specifically, the release layer 3B provided in the transfer film 11B is different from the release layer 3A provided in the transfer film 11A in that it includes a matting agent (second matting agent). Therefore, in this embodiment, the description of the base film 1, the mat layer 2, the hard coat layer 4, the primer layer 5, the decorative layer 6, and the adhesive layer 7 described in the first embodiment is omitted, and the release layer is omitted. Only 3B will be described.
  • the release layer 3B is a layer having fine unevenness on the surface and having release properties.
  • the release layer 3B includes a matting agent (second matting agent), and the matting agent is not particularly limited as in the case of the matting layer 2, and various inorganic particles and organic particles are used. Can do.
  • the release layer 3B containing the matting agent is also referred to as “matt release layer 3B” for convenience. That is, this mat release layer 3B is the same as the release layer 3A described in the first embodiment except that it contains a matting agent.
  • the average particle size of the matting agent contained in the mat release layer 3B is preferably in the range of 0.01 ⁇ m to 50 ⁇ m, and more preferably in the range of 1 ⁇ m to 30 ⁇ m. If the average particle size of the matting agent is less than 0.01 ⁇ m, the matte appearance of the surface of the transfer molded product may be insufficient, and if it exceeds 50 ⁇ m, it may cause pinholes in each printing process. There is.
  • the thickness of the mat release layer 3B is not particularly limited, but can be determined in consideration of the average particle diameter of the matting agent used and the surface glossiness of the transfer target after transfer. By changing the thickness of the mat release layer 3B, the surface glossiness of the transfer target can be adjusted.
  • the surface glossiness of the transferred body can be adjusted to be high. Conversely, when the thickness of the mat release layer 3B is decreased, the surface of the transferred body is increased. The glossiness can be adjusted low.
  • the addition amount of the matting agent is not particularly limited, but the mat is included in a coating solution for forming the mat release layer 3B (hereinafter, also simply referred to as “mat release layer coating solution”). It is preferably in the range of more than 0.0% by weight and 5.0% by weight or less with respect to the resin material that is the main component of the coating film constituting the release layer 3B, and is 0.2% by weight to 2.0% by weight The following range is more preferable. If the addition amount is within such a range, it is possible to adjust the surface glossiness in a slightly higher region than the surface glossiness of only the mat layer 2 and easily increase the glossiness variation of the matte appearance. be able to.
  • the non-image property of the surface of the transfer molded product obtained by injection molding tends to deteriorate.
  • the number of irregularities on the surface of the mat release film 9 is reduced in order to reduce the mat agent ratio of the mat layer 2 when adjusting the glossiness.
  • the glossiness can be adjusted without reducing the number of irregularities on the surface of the mat layer 2. .
  • the surface of the transfer molded product can be imparted to the surface of the transfer molded product, and good results can be obtained even in non-image characteristics.
  • the surface glossiness of a slightly higher region can be imparted with a uniform matte appearance.
  • materials other than the matting agent that is, resin materials forming the mat release layer 3B, the resin forming the release layer 3A described in the first embodiment. Since it is the same as material etc., the description is abbreviate
  • the matting agent (second matting agent) contained in the mat release layer 3B and the matting agent (first matting agent) contained in the mat layer 2 may be the same matting agent or different. A matting agent may be used.
  • the mat layer 2 is formed of a two-component curable urethane resin, so that the printability during gravure printing can be improved and the curing reaction can be performed at a low temperature of about room temperature to 50 ° C. Is completed, and the mat layer 2 with less heat load on the base film 1 can be produced. Furthermore, since the mat layer 2 contains the first mat agent, a matte appearance can be imparted to the surface of the transfer molded product.
  • the mat release layer 3B is formed of an acrylic urethane resin having a long-chain alkyl group having 10 to 30 carbon atoms, the printability during gravure printing can be improved, and the mat release layer 3B A uniform hard coat layer 4 can be formed while exhibiting excellent releasability at the time of thermal transfer and suppressing the repellency phenomenon of the hard coat layer coating solution applied onto the mat release layer 3B. Furthermore, adhesion between the mat layer 2 and the mat release layer 3B can be obtained.
  • the surface of the transfer target (transfer molded product) can be adjusted by adjusting the mat agent content and film thickness of the mat release layer 3B. Glossiness can be easily controlled. Furthermore, since the influence on the surface glossiness of the transfer target due to the film thickness variation of the mat release layer 3B can be suppressed, the transfer film 11B with less glossiness variation can be produced. Moreover, since the transfer film 11B which concerns on this embodiment does not contain a melamine resin, it can also reduce an environmental load (human load).
  • the transfer film 11B according to the present embodiment includes a cellulose derivative containing a hydroxyl group in at least one of the mat layer 2 and the mat release layer 3B. For this reason, since the heat resistance of the transfer film 11B is improved, even in the case of in-mold transfer that transfers simultaneously with injection molding, that is, in-mold transfer that requires heat resistance at high temperature, Problems such as a blocking phenomenon can be suppressed.
  • the release layer 3B includes an acrylic silicone resin containing a hydroxyl group. For this reason, if it is the transfer film 11B, the outstanding mold release property which can fully respond also to the high-speed of thermal transfer can be exhibited.
  • Example 2 The invention according to the second embodiment will be described in detail below based on each example. In addition, this invention is not limited only to a following example.
  • a mat layer coating liquid having the following composition is applied to one surface at 100 ° C. using a gravure printing method. The mat layer was formed by coating so that the film thickness after drying for 2 seconds was 4.5 ⁇ m.
  • composition of mat layer coating solution Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560): 100 parts by weight, silica filler (Evonik Degussa, particle size: 6 ⁇ m): 5 parts by weight, polyacrylonitrile filler (Toyobo, particle size: 7 ⁇ m): 5 parts by weight, isocyanate compound (manufactured by Nippon Polyurethane, Coronate HL) : 10 parts by weight
  • a mat release layer coating solution having the following composition was applied using a microgravure printing method so that the film thickness after drying was 2.5 ⁇ m. And then aged at 50 ° C. for 5 days to produce a mat release film.
  • composition of coating liquid for mat release layer Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560): 100 parts by weight, silica filler (Evonik Degussa, particle size: 6 ⁇ m): 1 part by weight, acrylic resin: 5 parts by weight (hydroxyl group and long chain alkyl group, which is a copolymer of 6-hydroxyhexyl acrylate and stearyl methacrylate) Having 18 carbon atoms) ⁇ Isocyanate compound (manufactured by Nippon Polyurethane Co., Ltd .: Coronate L): 20 parts by weight
  • a coating liquid for hard coat layer having the following composition is dried by microgravure printing so that the film thickness after drying becomes 5.0 ⁇ m.
  • the hard coat layer was formed by coating.
  • composition of coating solution for hard coat layer -UV curable resin: 100 parts by weight (manufactured by DIC: RC29-117, with UV polymerization initiator, solid content 30%)
  • Silica 20 parts by weight (manufactured by Nissan Chemical Co., Ltd .: particle size 10-20 nm, MEK dispersion, solid content 30%)
  • an acrylic polyol / isocyanate-based ink (manufactured by Toyo Ink Co., Ltd .: V425 anchor) is applied as a primer layer coating solution on the hard coat layer so that the film thickness after drying becomes 1 ⁇ m using a gravure printing method.
  • a black ink (manufactured by Toyo Ink Co., Ltd .: V428UR92 black) is applied as a decorative layer coating liquid on the top of the coating layer using a gravure printing method so that the film thickness after drying is 3 ⁇ m. Formed.
  • an adhesive layer coating liquid (manufactured by Toyo Ink Co., Ltd .: K539HP adhesive varnish) was applied thereon so as to have a film thickness after drying of 1 ⁇ m using a gravure printing method to form an adhesive layer.
  • a transfer film according to Example 2-1 was produced.
  • the transfer film produced as described above was set inside a mold of an injection molding machine, and injection molded using a polycarbonate ABS alloy resin (manufactured by Nippon A & L Co., Ltd .: Techno Ace T-105).
  • the mold for injection molding is opened, the mat release film constituting the transfer film is peeled off from the molded product, and then the surface of the transfer molded product has an integrated light quantity of 1000 mJ / cm 2 using a high-pressure mercury lamp.
  • the hard coat layer was crosslinked and cured by irradiation with ultraviolet rays. Thereby, a transfer molded product having a high surface strength was obtained.
  • (Composition of coating liquid for mat release layer) Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560): 100 parts by weight, silica filler (Evonik Degussa, particle size: 6 ⁇ m): 1 part by weight, nitrocellulose (H1 / 4): 20 parts by weight, acrylic resin: 5 parts by weight (composition of 6-hydroxyhexyl acrylate and stearyl methacrylate (It has a hydroxyl group and a long-chain alkyl group (carbon number 18) as a copolymer) ⁇ Isocyanate compound (manufactured by Nippon Polyurethane Co., Ltd .: Coronate L): 20 parts by weight Next, on the mat release layer of the mat release film, a hard coat layer, a primer layer, a decorative layer,
  • the transfer film which concerns on was produced.
  • This transfer film was set inside a mold of an injection molding machine, and injection molding and ultraviolet irradiation of the surface of the transfer molded product were performed in the same manner as in Example 2-1, thereby obtaining a transfer molded product having high surface strength.
  • (Composition of coating liquid for mat release layer) Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560): 100 parts by weight, silica filler (Evonik Degussa, particle size: 6 ⁇ m): 1 part by weight, nitrocellulose (H1 / 4): 20 parts by weight, acrylic resin: 5 parts by weight (composition of 6-hydroxyhexyl acrylate and stearyl methacrylate (It has a hydroxyl group and a long-chain alkyl group (carbon number 18) as a copolymer) Silicone-modified acrylic resin (manufactured by NOF Corporation: FS730): 5 parts by weight Isocyanate compound (manufactured by Nippon Polyurethane Co., Ltd .: Coronate L): 20 parts by weight Next,
  • the transfer film which concerns on was produced.
  • This transfer film was set inside a mold of an injection molding machine, and injection molding and ultraviolet irradiation of the surface of the transfer molded product were performed in the same manner as in Example 2-1, thereby obtaining a transfer molded product having high surface strength.
  • Example 2-4 Using the same base film as in Example 2-1, a mat layer was formed on one surface in the same manner as in Example 2-1. Thereafter, a mat release layer coating solution having the same composition as that of Example 2-1 was applied using a micro gravure printing method so that the film thickness after drying was 1.9 ⁇ m. Thereafter, aging was performed at 50 ° C. for 5 days to prepare a mat release film. Next, a hard coat layer, a primer layer, a decorative layer, and an adhesive layer are laminated on the mat release layer of the mat release film in the same manner as in Example 2-1, and the transfer according to Example 2-4 is performed. A film was prepared. This transfer film was set inside a mold of an injection molding machine, and injection molding and ultraviolet irradiation of the surface of the transfer molded product were performed in the same manner as in Example 2-1, thereby obtaining a transfer molded product having high surface strength.
  • Example 2-5> Using the same base film as in Example 2-1, a mat layer was formed on one surface in the same manner as in Example 2-1. Thereafter, a mat release layer coating solution having the following composition was applied using a micro gravure printing method so that the film thickness after drying was 2.5 ⁇ m to form a mat release layer, and then 5 ° C. at 5 ° C. A mat release film was prepared by aging for a day.
  • Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560): 100 parts by weight, silica filler (Evonik Degussa, particle size: 6 ⁇ m): 3 parts by weight, acrylic resin: 5 parts by weight (hydroxyl group and long chain alkyl group (copolymer of 6-hydroxyhexyl acrylate and stearyl methacrylate) Having 18 carbon atoms) ⁇
  • Isocyanate compound manufactured by Nippon Polyurethane Co., Ltd .: Coronate L
  • a hard coat layer, a primer layer, a decorative layer, and an adhesive layer are laminated in the same manner as in Example 2-1, and Example 2-5.
  • the transfer film which concerns on was produced.
  • This transfer film was set inside a mold of an injection molding machine, and injection molding and ultraviolet irradiation of the surface of the transfer molded product were performed in the same manner as in Example 2-1, thereby obtaining a transfer molded product having high surface strength.
  • Example 2-1 Using the same base film as in Example 2-1, on one surface, acrylic / melamine-based ink (manufactured by Toyo Ink Co., Ltd .: HP216 mat coat N varnish) was used as a coating liquid for the mat layer, and a bar coater was used. The film thickness after drying was applied to 4.3 ⁇ m. Thereafter, baking was performed at 180 ° C. to form a mat layer. Next, an attempt was made to form a mat release layer on the surface of the mat layer in the same manner as in Example 2-1. However, the baking at 180 ° C. performed at the time of forming the mat layer caused problems such as wrinkles and heat shrinkage on the base film, and the mat release layer could not be applied uniformly. Therefore, the subsequent hard coat layer, primer layer, decorative layer, and adhesive layer could not be formed, and the transfer film was not produced.
  • Example 2-2 Using the same base film as in Example 2-1, a mat layer was formed on one surface in the same manner as in Example 2-1. Thereafter, acrylic / melamine-based ink (manufactured by Toyo Ink Co., Ltd .: mixed ink of HP200 gloss coat N varnish and HP216 mat coat N varnish) as a coating liquid for the mat release layer, the film thickness after drying using a bar coater is 0. It was applied so as to be 5 ⁇ m. Then, it baked at 180 degreeC and formed the mat
  • the baking at 180 ° C. performed at the time of forming the mat release layer caused problems such as wrinkles and heat shrinkage on the base film, and the hard coat layer could not be applied uniformly. Therefore, the subsequent primer layer, decorative layer, and adhesive layer could not be formed, and the transfer film was not produced.
  • Example 2-3 Using the same base film as in Example 2-1, the coating thickness of the mat layer coating liquid having the following composition on one surface thereof was dried at 100 ° C. for 10 seconds using the gravure printing method. A mat layer was formed by coating to a thickness of 6.5 ⁇ m, and then aged at 50 ° C. for 5 days to prepare a mat release film.
  • a transfer film was prepared. This transfer film was set inside a mold of an injection molding machine, and injection molding and ultraviolet irradiation of the surface of the transfer molded product were performed in the same manner as in Example 2-1, thereby obtaining a transfer molded product having high surface strength.
  • Example 2-4 Using the same base film as in Example 2-1, a mat layer was formed on one surface in the same manner as in Example 2-1. Then, a gloss release layer coating solution having the following composition was applied using a micro gravure printing method so that the film thickness after drying was 2.2 ⁇ m to form a gloss release layer. A gloss release film was prepared by aging for a day.
  • Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560): 100 parts by weight / acrylic resin: 5 parts by weight (having hydroxyl group and long-chain alkyl group (18 carbon atoms) which is a copolymer of 6-hydroxyhexyl acrylate and stearyl methacrylate) ⁇ Isocyanate compound (manufactured by Nippon Polyurethane Co., Ltd .: Coronate L): 20 parts by weight Next, a hard coat layer, a primer layer, a decorative layer, and an adhesive layer were laminated on the gloss release layer of the above gloss release film in the same manner as in Example 2-1, and Comparative Example 2-4.
  • the transfer film which concerns on was produced.
  • This transfer film was set inside a mold of an injection molding machine, and injection molding and ultraviolet irradiation of the surface of the transfer molded product were performed in the same manner as in Example 2-1, thereby obtaining a transfer molded product having high surface strength.
  • Example 2-5 Using the same base film as in Example 2-1, a mat layer was formed on one surface in the same manner as in Example 2-1. Thereafter, a gloss release layer coating liquid having the same composition as Comparative Example 2-4 was applied using a microgravure printing method so that the film thickness after drying was 1.9 ⁇ m. Thereafter, the film was aged at 50 ° C. for 5 days to prepare a gloss release film. Next, a hard coat layer, a primer layer, a decorative layer, and an adhesive layer are laminated on the gloss release layer of the gloss release film in the same manner as in Comparative Example 2-4, and the transfer according to Comparative Example 2-5 is performed. A film was prepared. This transfer film was set inside a mold of an injection molding machine, and injection molding and ultraviolet irradiation of the surface of the transfer molded product were performed in the same manner as in Example 2-1, thereby obtaining a transfer molded product having high surface strength.
  • Comparative Example 2-2 it was possible to form a mat layer and a mat release layer on the base film, but wrinkles and heat shrinkage were caused by baking at 180 ° C. performed at the time of forming the mat release layer. Such a problem occurred in the base film, and the hard coat layer could not be applied uniformly. Therefore, the subsequent decorative layer and adhesive layer could not be formed, and the transfer film was not produced.
  • the glossiness (60 °) of the transfer molded product obtained by injection molding is the thickness of the mat release layer and the mat. It was confirmed that there was a correlation between the amount of silica filler contained in the release layer. This is because the uneven state of the surface of the mat release layer laminated on the mat layer changes according to the thickness of the mat release layer to be laminated and the amount of silica filler contained in the mat release layer. Conceivable. Also, good results were obtained with respect to the non-image property of the surface of the transfer molded product.
  • the transfer film obtained according to one embodiment of the present invention can be used for surface protection and decoration of panel members used for home appliances, housing equipment, office equipment, automobile parts, and the like.

Landscapes

  • Laminated Bodies (AREA)
  • Decoration By Transfer Pictures (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
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JP7260474B2 (ja) 2018-08-09 2023-04-18 東レフィルム加工株式会社 離型フィルム
WO2020059255A1 (ja) * 2018-09-21 2020-03-26 尾池工業株式会社 加飾フィルム成形体、加飾フィルム成形体の製造方法、サテンめっき調製品、容器、筐体、車両用内外装部材
JPWO2020059255A1 (ja) * 2018-09-21 2020-12-17 尾池工業株式会社 加飾フィルム成形体、加飾フィルム成形体の製造方法、サテンめっき調製品、容器、筐体、車両用内外装部材
JP2021054002A (ja) * 2019-09-30 2021-04-08 大日本印刷株式会社 熱転写シート
JP7375435B2 (ja) 2019-09-30 2023-11-08 大日本印刷株式会社 熱転写シート
JP2021130291A (ja) * 2020-02-21 2021-09-09 大槻工業株式会社 熱転写シート用基材および熱転写シート
JP7385266B2 (ja) 2020-02-21 2023-11-22 大槻工業株式会社 熱転写シート用基材および熱転写シート
JP2021084433A (ja) * 2020-03-03 2021-06-03 尾池工業株式会社 加飾フィルム成形体の製造方法
JP2021152121A (ja) * 2020-03-24 2021-09-30 日本化工塗料株式会社 熱硬化性離型コーティング剤及び積層体

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