JPWO2014203507A1 - Transfer film and transfer molded product using the same - Google Patents

Abstract

There are provided a transfer film having a printability and low-temperature processability of a mat layer, which can give a matte appearance to a transferred material and has a low environmental load, and a transfer molded article using the transfer film. Furthermore, the present invention provides a transfer film capable of controlling the glossiness of the surface of an injection molded product by adjusting the film thickness of the release layer, and a transfer molded product using the transfer film. The transfer film (11) has at least a mat layer (2), a release layer (3A), a hard coat layer (4), and an adhesive layer (7) in this order on one surface of the base film (1). The mat layer (2) is made of a two-component curable urethane resin and includes a first matting agent, and the release layer (3A) is a layer mainly composed of an acrylic urethane resin. The urethane resin is produced from a crosslinking reaction of at least an acrylic polyol resin, an acrylic resin containing a hydroxyl group and a long-chain alkyl group having 10 to 30 carbon atoms, and an isocyanate compound.

Description

  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.

Conventionally, when decorating mainly a plastic molding, it is sometimes decorated by a thermal transfer method using a transfer film instead of a direct decorating method such as painting. Many of these transfer films are required to have a hard coat function for the purpose of protecting the surface of a plastic molded product. This is because, for example, a soft resin typified by polycarbonate resin is often used as an object to be transferred such as a plastic molded product. As described above, 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.
In general, 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. Moreover, 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.

Here, 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 | required to give the designability according to a request | requirement to a decoration layer. Further, the adhesive layer is required to have strong adhesiveness to the transfer target.
Furthermore, the release layer formed as the first layer with respect to the base film has good releasability from the transfer layer (particularly the hard coat layer), in addition to the formation of the hard coat layer. 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).

Examples of a method for thermally transferring a transfer layer to a transfer medium using a transfer film having each of the above-described layers include, for example, a method of transferring simultaneously with injection molding (in-mold molding method), and a method of transferring with the heat pressure of a hot roll. Alternatively, a method of transferring to a transfer medium using vacuum or pressure or a heating machine (vacuum and pressure forming method) may be used.
Further, the release film described above serves as a support member for the transfer layer and also serves as a member for controlling the appearance of the surface of the transfer target. This is because, after the transfer, the surface of the transfer layer in contact with the release film becomes the outermost surface of the transfer target. Therefore, for example, when it is desired to give a matte appearance to the surface of the transfer object, in order to give fine irregularities to the release layer surface of the release film, organic particles and inorganic particles are used as a matting agent in the release layer. May be added. In this way, at the time of transfer, only 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.

  Patent Document 1 describes a transfer film having a mat release film and a transfer layer as a transfer film capable of imparting a matte appearance to the surface of a transfer target (transfer molded product). The mat | matte release film of patent document 1 has a base film and the mat | matte layer formed on the surface of this base film which does not peel from a base film. The transfer layer has a hard coat layer formed on the mat layer surface of the mat release film and an adhesive layer. By setting it as the transfer film of such a structure, the matte appearance is provided to the surface of the to-be-transferred body. Here, the “mat release film” means a release film including a release layer to which a matting agent is added.

JP 2000-108594 A

  By the way, 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. For this reason, in the manufacturing process of a transfer film, what is called a baking process is needed. 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.

Further, the thermosetting resin has a property that the curing reaction proceeds by absorbing heat generated in the printing process. Therefore, for example, when performing gravure printing using a coating liquid (ink) containing a thermosetting resin, ink tends to remain on the convex part (non-image area) of the plate, resulting in printing defects such as plate fogging. Therefore, there is a problem that uniform coating becomes difficult.
Furthermore, the melamine resin described above has a problem that harmful formaldehyde is generated in the production process, and a large amount of the formaldehyde remains in the melamine cured product and the ink drying apparatus. According to a report from the International Agency for Research on Cancer, this formaldehyde is listed as a group 1 that is recognized as carcinogenic to humans, and it is also a problem that it is a causative substance of sick house syndrome.

The present invention is intended to solve such problems, has matting layer printability and low-temperature processability, and can give a matte appearance to a transfer target (mainly a plastic molded product). Another object of the present invention is to provide a transfer film with a low environmental load (human load) and a transfer molded product using the transfer film.
Furthermore, by forming a release layer on the surface of the mat layer, by adjusting the film thickness of the release layer, a transfer film capable of controlling the surface glossiness of the transfer object and a transfer using the transfer film The object is to provide a molded product.

  One aspect of the present invention is a transfer film having at least a mat layer, a release layer, a hard coat layer, and an adhesive layer in this order on one surface of a base film, and the mat layer is cured in two parts. A layer including a first matting agent, the release layer is a layer mainly composed of an acrylic urethane resin, and the acrylic urethane resin includes at least an acrylic polyol resin and a hydroxyl group. And a transfer film produced from a crosslinking reaction between an acrylic resin containing a long-chain alkyl group having 10 to 30 carbon atoms and an isocyanate compound.

In the transfer film, a cellulose derivative containing a hydroxyl group may be further included in at least one of the mat layer and the release layer.
In the transfer film, the release layer may further include an acrylic silicone resin containing a hydroxyl group.
In the transfer film, a second matting agent may be further included in the release layer.
In the transfer film, the first matting agent and the second matting agent may be the same matting agent.
Another aspect of the present invention is a transfer molded product manufactured using the transfer film.

According to the transfer film of one aspect of the present invention, the mat layer is formed of a two-component curable urethane resin, so that the printability at the time of gravure printing can be improved and at a low temperature of room temperature to about 50 ° C. The curing reaction is completed, and a mat layer with less heat load on the base film can be produced. Furthermore, since the mat layer contains the first mat agent, a matte appearance can be imparted to the surface of the transfer object.
Moreover, since the release layer is formed of an acrylic urethane resin having a long-chain alkyl group having 10 to 30 carbon atoms, printability during gravure printing can be improved, and the release layer is excellent during thermal transfer. 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).

Further, in the above transfer film, since heat resistance can be improved by further including a cellulose derivative containing a hydroxyl group in at least one of the mat layer and the release layer, a method of transferring simultaneously with injection molding Even when (in-mold molding) is used, problems such as heat wrinkles and blocking phenomenon can be suppressed.
Further, in the above transfer film, by further including an acrylic silicone resin containing a hydroxyl group in the release layer, it is possible to impart excellent release properties that can sufficiently cope with high-speed thermal transfer.

Moreover, in the said transfer film, 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. In addition, 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 mat agent content and film thickness of the release layer. Can do. Furthermore, since 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.
Moreover, in the said transfer film, 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.

It is a section schematic diagram of a transfer film concerning a 1st embodiment of the present invention. It is a section schematic diagram of a transfer molding manufactured using a transfer film concerning a 1st embodiment. It is a section schematic diagram of the transfer film concerning a 2nd embodiment of the present invention. It is a section schematic diagram of a transfer molding manufactured using a transfer film concerning a 2nd embodiment.

Hereinafter, a first embodiment and a second embodiment of the present invention will be described in detail with reference to the drawings. In addition, in each figure, the same referential mark is attached | subjected to the component which exhibits the same or similar function, and the overlapping description is abbreviate | omitted. In the embodiment of the present invention, the average particle diameter of each particle to be added is measured by a laser diffraction method.
(First embodiment)
FIG. 1 is a schematic cross-sectional view of a transfer film according to the first embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of a transfer molded product manufactured using the transfer film according to the first embodiment.
As shown in FIG. 1, a transfer film 11A according to this embodiment 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. Here, 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. Hereinafter, each layer provided in the transfer film 11A according to the present embodiment will be described.

(Base film 1)
As 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 μm or more and 250 μm or less, and more preferably in the range of 38 μm or more and 150 μm or less because it is advantageous in terms of the balance of cost and film formability.

(Matte layer 2)
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. As the matting agent added to the mat layer 2, 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 μm to 50 μm, and more preferably in the range of 1 μm to 30 μm. If the average particle size of the particles used in the matting agent is less than 0.01 μm, the surface of the transfer molded article may not be sufficiently imparted with a matte appearance, and if it exceeds 50 μm, pinholes may be generated in each printing step. May be a factor. Further, the average thickness of the mat layer 2 is preferably in the range of 2 μm or more and 15 μm 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 matting agent is used in a coating liquid for forming the mat layer 2 (hereinafter, also simply referred to as “mat layer coating liquid”) with respect to a resin material that is a main component of the coating film constituting the mat layer 2. It is preferably contained within a range of 0.5 wt% or more and 20 wt% or less, and more preferably contained within a range of 1 wt% or more and 10 wt% or less. If the amount of the matting agent exceeds 20% by weight, the matting agent tends to settle and aggregate in the matting layer coating solution, which may adversely affect printability. Moreover, when the amount of the matting agent is less than 0.5% by weight, the matte appearance may be insufficiently provided.
Since the resin material which is the main component of the coating film constituting the mat layer 2 requires adhesion to the base film 1 and heat resistance and adhesion to the release layer 3A described later, a two-component curable type It is desirable to contain an acrylic urethane resin, a two-component curable polyester urethane resin, or a mixture thereof (hereinafter, these resins are also simply referred to as “two-component curable urethane resins”). With such a two-component curable urethane resin, since the curing reaction is completed at a low temperature of about room temperature to 50 ° C., the heat load on the base film 1 when forming the mat layer 2 can be reduced.

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. Examples of 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.
Further, 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.

(Release layer 3A)
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. By using 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. 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 acrylic urethane resin that forms the release layer 3A is, for example, an ink composition (a release layer coating solution) containing an acrylic polyol resin and an alkyl isocyanate having a long chain alkyl group, or a long chain alkyl group and It can be obtained from an ink composition containing an acrylic resin having a hydroxyl group and an isocyanate compound.
Further, as described above, the release layer 3A is required to have performance such as releasability, stretchability, and heat resistance. Depending on the shape of the transfer object and the processing conditions during transfer, the release layer 3A has a slight Adjustment may be required. For example, 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. By adjusting the ink composition in this way, 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 this 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. In order to cure this ink composition, it is not necessary to go through a baking step (180 to 200 ° C.) at a high temperature unlike melamine resin, and the curing reaction is completed by aging at a temperature of about room temperature to 50 ° C. . Thus, according to the present embodiment, the release layer 3A can be formed by low temperature curing. Therefore, uncured PET film, vinyl chloride film, and PET-G film, which could not be used in the past, have problems due to wrinkles, heat shrinkage, crystallization, etc. under the curing conditions when the release layer is formed with melamine resin. However, it is also possible to use a substrate film that is weak against heat but has a high elongation rate and excellent molded article followability.

In addition, 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 the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and the like. There is. Examples of the acrylic monomer having a long-chain alkyl group include decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, and pentadecyl (meth) acrylate. , Hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, heicosyl (meth) acrylate, triacontyl (meth) acrylate and the like. 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 isocyanate compound means toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and prepolymers thereof.

  For the purpose of improving heat resistance when the transfer film 11A is used for in-mold molding, the release layer 3A may be blended with a cellulose derivative containing a hydroxyl group, similarly to the mat layer 2. Examples of 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.

Moreover, 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 At this time, by blending an acrylic silicone resin containing a hydroxyl group, peeling can be lightened without degrading the top coatability. In this case, 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 μm to 5 μm. 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.

(Hard coat layer 4)
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 | crosslinked by irradiating an active energy ray. 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. There are mainly the following three methods for bringing the hard coat layer 4 into a tack-free state in the transfer film before being used for transfer. The first method is a method of using a polymer acrylate or methacrylate as the resin constituting the hard coat layer 4. In the second method, as a resin constituting the hard coat layer 4, in addition to a liquid or semi-liquid active energy ray-curable resin, 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.

In the case of the first method, in addition to the polymer type acrylate (acrylic resin), 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.
In order to maintain the transparency of the hard coat layer 4, it is preferable that 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.

In general, active energy ray-curable resins tend to have poor wear resistance. For this reason, in order to supplement the wear resistance, a small amount of polytetrafluoroethylene powder, polyethylene wax, metal soap or the like may be added to the active energy ray-curable resin as a lubricant.
Further, the thickness of the hard coat layer 4 is not particularly limited, but is preferably in the range of 2 μm or more and 10 μm or less in consideration of the balance between the expression of surface hardness, curing shrinkage, cost, and the like.

(Primer layer 5)
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. Further, the thickness of the primer layer 5 is not particularly limited, but is optimal within the range of 0.5 μm or more and 10 μm or less.

(Decoration layer 6)
The decorative layer 6 is a layer for imparting design properties to the transfer target. When a printing layer is formed as the decorative layer 6, a known printing method 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. Other decorative technologies that can be adopted include special printing such as pearl, fluorescence, mirror, retroreflection, and magnetic printing, embossing that forms uneven structures (various lens effects and holograms) by heat and ultraviolet rays, aluminum and silver It is possible to apply a thin film forming technique in which chromium, titanium oxide, zinc sulfide, or the like is formed by vacuum deposition or sputtering.

(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 μm or more and 10 μm or less.

(effect)
In the transfer film 11A according to the present embodiment, since the mat layer 2 is formed of a two-component curable urethane resin, the printability at the time of 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.
In addition, since 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.

Since the release layer 3A is formed on the surface of the mat layer 2, the surface glossiness of the transfer molded product can be easily controlled by adjusting the film thickness of the release layer 3A.
Moreover, since 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).
In addition, 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.
In addition, in the transfer film 11A according to the present embodiment, 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
Hereinafter, the invention according to the first embodiment will be described in detail based on each example. In addition, this invention is not limited only to a following example.
<Example 1-1>
A biaxially stretched polyester film (Mitsubishi Resin Co., Ltd .: G440E50) having a thickness of 50 μm 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 μm.

(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 μm): 5 parts by weight, polyacrylonitrile filler (Toyobo, particle size: 7 μm): 5 parts by weight, isocyanate compound (manufactured by Nippon Polyurethane, Coronate HL) :
10 parts by weight On the mat layer, 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 μm 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 (carbon number: 18) 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, on the release layer of the mat release film, 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 μm. Thus, a hard coat layer was formed.

(Composition of coating solution for hard coat layer)
UV curing resin: 100 parts by weight (manufactured by DIC: RC29-117, containing 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%)

Next, 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 μm using a gravure printing method. Was applied to form a primer layer. On top of that, 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 μm using a gravure printing method, and a decorative layer is formed. did. Further, 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 μm using a gravure printing method to form an adhesive layer. In this manner, a transfer film according to Example 1-1 was produced.
The transfer film produced as described above was set inside 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. After cooling, 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, on the release layer of the mat release film, a hard coat layer, a primer layer, a decorative layer, and an adhesive layer are laminated in the same manner as in Example 1-1, and Example 1-2 is obtained. 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 are laminated in the same manner as in Example 1-1, and Example 1-3 is obtained. 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 μm, 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 of the surface of the transfer molded product were performed 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 μm, 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 of the surface of the transfer molded product were performed in the same manner as in Example 1-1 to obtain an injection molded product having high surface strength.

<Comparative Example 1-1>
A biaxially stretched polyester film (Mitsubishi Resin Co., Ltd .: G440E50) having a thickness of 50 μm is used as a base film, and acrylic / melamine-based ink (manufactured by Toyo Ink Co., Ltd .: HP216 Matt Coat N) is used as a coating liquid for the mat layer on one surface. Varnish) was applied using a bar coater so that the film thickness after drying was 4.3 μm. Thereafter, baking was performed at 180 degrees to form a mat layer.
Next, a release layer was formed on the surface of the mat layer in the same manner as in Example 1-1.

<Comparative 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 μm. Then, it baked at 180 degreeC and formed the release layer, and produced the mat | matte release film.
Next, a hard coat layer was formed on the release layer of the mat release film in the same manner as in Example 1-1.

<Evaluation and method>
About the transfer film produced in each of Examples 1-1 to 1-5, the film formability of the mat layer, the release layer, and the hard coat layer and the transfer property to the molded product by each transfer film were visually evaluated. The case where there was no abnormality in appearance (a level where there was no problem in practical use) was marked with “◯”, and the case where uniform coating was impossible or there was an abnormality in appearance (practical problem) was marked as “x”. Furthermore, the glossiness (60 °) of the molded product using the transfer film produced in Examples 1-1, 1-4, and 1-5 was also measured. The results are shown in Table 1. In addition, the case where layer formation was not implemented, the case where transfer was not implemented, and the case where glossiness was not measured was set to "-". Here, “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. In addition, “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.

<Comparison result>
In the transfer films obtained in Examples 1-1 to 1-5, the mat layer, the release layer, and the hard coat layer were all excellently formed. Also, good results were obtained for transfer to molded articles using the respective transfer films.
On the other hand, in Comparative Example 1-1, although the mat layer could be formed on the base film, defects such as wrinkles and heat shrinkage occurred due to baking at 180 ° C. performed at the time of forming the mat layer. The layer could not be applied uniformly. Therefore, the subsequent hard coat layer, decorative layer, and adhesive layer could not be formed, and the transfer film was not produced. Similarly, in Comparative Example 1-2, the matte layer and the release layer were formed on the base film, but the defects such as wrinkles and heat shrinkage were caused by baking at 180 ° C. performed when the release layer was formed. As a result, the hard coat layer could not be applied uniformly, the subsequent decorative layer and adhesive layer could not be formed, and the transfer film could not be produced.
The gloss (60 °) of the molded product obtained by injection molding using the transfer films obtained in Examples 1-1, 1-4, and 1-5 is the film thickness of the release layer. It was confirmed that there was a correlation between This is presumably because the degree to which the unevenness on the surface of the mat layer is filled varies depending on the thickness of the release layer to be laminated.

(Second Embodiment)
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.
As shown in FIG. 3, 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.
Here, 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.

(Release layer 3B)
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. Hereinafter, 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 diameter of the matting agent contained in the mat release layer 3B is preferably in the range of 0.01 μm to 50 μm, and more preferably in the range of 1 μm to 30 μm. If the average particle size of the matting agent is less than 0.01 μm, the matte appearance of the surface of the transfer molded product may be insufficient, and if it exceeds 50 μm, 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. Specifically, when the thickness of the mat release layer 3B is increased, 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.

By the way, in the case of the mat layer 2 alone, as the glossiness increases, the non-image property of the surface of the transfer molded product obtained by injection molding tends to deteriorate. This is because 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. Thus, even if a target value is obtained as the glossiness, if the non-image property deteriorates, the matte appearance of the surface of the transfer molded product cannot be uniformly imparted, which is not preferable in practice. On the other hand, when the mat release layer 3B is further laminated on the mat layer 2 as in the present embodiment, the glossiness can be adjusted without reducing the number of irregularities on the surface of the mat layer 2. . Therefore, a uniform matte appearance can be imparted to the surface of the transfer molded product, and good results can be obtained even in non-image characteristics. As described above, when the configuration of the present embodiment in which the height of the unevenness on the surface of the mat layer 2 is adjusted without reducing the mat agent ratio of the mat layer 2, when compared with the case of only the mat layer 2. In addition, the surface glossiness of a slightly higher region can be imparted with a uniform matte appearance.
For the mat release layer 3B, 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 | omitted here.
Further, 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.

(effect)
In the transfer film 11B according to the present embodiment, since the mat layer 2 is formed of a two-component curable urethane resin, the printability at the time of 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.
Moreover, since 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.

Further, since the mat release layer 3B is formed on the surface of the mat layer 2, 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).

Further, 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.
In addition, in the transfer film 11B according to the present embodiment, 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.
<Example 2-1>
Using a biaxially stretched polyester film (Mitsubishi Resin Co., Ltd .: G440E50) having a thickness of 50 μm as a base film, 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 μm.

(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 μm): 5 parts by weight, polyacrylonitrile filler (Toyobo, particle size: 7 μm): 5 parts by weight, isocyanate compound (manufactured by Nippon Polyurethane, Coronate HL) :
10 parts by weight On the mat layer, 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 μm. 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 μm): 1 part 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):
20 parts by weight Next, on the mat release layer of the mat release film, 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 μm. 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, containing 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%)

Next, 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 μm using a gravure printing method. Was applied to form a primer layer. Furthermore, 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 μm. Formed. Further, 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 μm using a gravure printing method to form an adhesive layer. In this manner, 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). After cooling, 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.

<Example 2-2>
A mat release film was prepared in the same manner as in Example 2-1, except that the mat release layer coating solution having the following composition was used.
(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 Co., Ltd .: particle size 6 μm): 1 part by weight-Nitrocellulose (H1 / 4): 20 parts by weightAcrylic resin: 5 parts by weight (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, and an adhesive layer are laminated in the same manner as in Example 2-1, and Example 2-2. 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 2-3>
A mat release film was prepared in the same manner as in Example 2-1, except that the mat release layer coating solution having the following composition was used.
(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 Co., Ltd .: particle size 6 μm): 1 part by weight-Nitrocellulose (H1 / 4): 20 parts by weightAcrylic resin: 5 parts by weight (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, 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 to obtain Example 2-3. 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 μm. 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 μm to form a mat release layer, and then 5 ° C. at 5 ° C. A mat release film was prepared by aging for a day.
(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 μm): 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):
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, 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.

<Comparative 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 μm. 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.

<Comparative 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 μm. Then, it baked at 180 degreeC and formed the mat | matte release layer, and produced the mat | matte release film.
Next, an attempt was made to form a hard coat layer on the mat release layer of the mat release film in the same manner as in Example 2-1. However, 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.

<Comparative 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 μm, and then aged at 50 ° C. for 5 days to prepare a mat release film.
(Composition of mat layer coating solution)
Acrylic polyol resin (Toei Kasei Co., Ltd .: LC # 6560):
100 parts by weight, silica filler (Evonik Degussa Co., Ltd .: particle size 6 μm): 4 parts by weight, nitrocellulose (H1 / 4): 10 parts by weight, acrylic resin: 5 parts by weight (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, a hard coat layer, a primer layer, a decorative layer, and an adhesive layer are laminated on the mat layer of the mat release film in the same manner as in Example 2-1, and according to Comparative Example 2-3. 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.

<Comparative 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 μm to form a gloss release layer. A gloss release film was prepared by aging for a day.
(Composition of coating liquid for gloss release layer)
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 (carbon number: 18) 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.

<Comparative 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 μm. 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.

<Evaluation and method>
With respect to the transfer films produced in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-3, the film formation properties of the mat layer, the release layer, and the hard coat layer and the transfer molded products using the respective transfer films The transferability was visually evaluated. The case where there was no abnormality in appearance (a level where there was no problem in practical use) was marked with “◯”, and the case where uniform coating was impossible or there was an abnormality in appearance (practical problem) was marked as “x”. Further, for transfer molded products using the transfer films prepared in Examples 2-1, 2-4, 2-5 and Comparative Example 2-3, the glossiness (60 °) and non-image properties of the surface of the transferred molded product Was evaluated. When the sample is placed approximately 2m below the fluorescent lamp, the non-imaging property is evaluated visually. If the outline of the fluorescent lamp cannot be confirmed (a level that does not cause any practical problems), it can be confirmed (practical) (There is a problem) The evaluation results are shown in Table 2. In addition, when layer formation was not performed, when transfer was not performed, when glossiness was not measured, and when non-imaging property was not evaluated, “-” was given. Similarly to the case of Example 1 described above, the “case where uniform application is not possible” means a case where the application itself was attempted to form a film but the application could not be performed uniformly. In addition, “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.

  For the transfer films prepared in Examples 2-1 and 2-4 and Comparative Examples 2-4 and 2-5, the glossiness (60 °) of the transfer molded product prepared using each transfer film was measured. The state of glossiness change when the thickness of the mat release layer or gloss release layer was changed was evaluated. Specifically, the change in the release layer thickness between the mat release layers (Examples 2-1 and 2-4) and between the gloss release layers (Comparative Examples 2-4 and 2-5) is Δd, Assuming that the change in glossiness is ΔGr, the magnitude of the influence (ΔGr / Δd) of the change in film thickness of the release layer on the change in glossiness was calculated and compared between the examples and the comparative examples. Table 3 shows the evaluation results.

<Comparison result>
As shown in Table 2, in the transfer films obtained in Examples 2-1 to 2-5 and Comparative Example 2-3, all of the mat layer, the mat release layer, and the hard coat layer were successfully formed. . In addition, the transferability was also good when transferred onto the surface of the transfer molded product using each transfer film.
On the other hand, in Comparative Example 2-1, it was possible to form a mat layer on the base film, but due to baking at 180 ° C. performed at the time of forming the mat layer, problems such as wrinkles and heat shrinkage occurred on the base film. As a result, the mat release layer could not be applied uniformly. Therefore, the subsequent hard coat layer, decorative layer, and adhesive layer could not be formed, and the transfer film was not produced. Further, in 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.

Further, as in the results of Examples 2-1, 2-4, and 2-5, 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.
On the other hand, when the transfer film obtained in Comparative Example 2-3 was used, a transfer molded product could be obtained by injection molding, but good results were obtained in the non-image property of the surface of the transfer molded product. There wasn't. This is because the gloss level is adjusted by adjusting the amount of filler in the mat layer and reducing the number of irregularities on the surface of the mat layer. Actually, although the surface glossiness value was the same as in Example 2-1, the non-image property was poor, and the difference in the number of irregularities on the surface of the mat release film was matt. It is thought that it has influenced the finish of.

  Further, as shown in Table 3, with respect to the transfer molded products obtained in Examples 2-1 and 2-4 and Comparative Examples 2-4 and 2-5, a mat release layer formed on the mat layer In addition, the magnitude of the influence (ΔGr / Δd) of the change in the film thickness of the gloss release layer on the glossiness fluctuation was evaluated. As a result, when the transfer film according to this example having a mat release layer is used, it can be confirmed that the influence on the glossiness due to the film thickness variation is as small as about half, and a more uniform matte appearance can be given. Met.

  The transfer film obtained according to one embodiment of the present invention can be used for surface protection and decoration of panel members and the like used for home appliances, housing equipment, office equipment, automobile parts, and the like.

DESCRIPTION OF SYMBOLS 1 ... Base film, 2 ... Matt layer, 3A ... Release layer, 3B ... (Matte) release layer, 4 ... Hard coat layer, 5 ... Primer layer, 6 ... Decorating (printing) layer, 7 ... Adhesive layer , 8 ... Molding resin, 9 ... (Matte) release film, 10 ... Transfer layer, 11A, 11B ... Transfer film

Claims (6)

A transfer film having at least a mat layer, a release layer, a hard coat layer, and an adhesive layer in this order on one surface of the base film,
The mat layer is formed of a two-component curable urethane resin and includes a first mat agent.
The release layer is a layer mainly composed of acrylic urethane resin,
The transfer film, wherein the acrylic urethane resin is produced from a crosslinking reaction of at least an acrylic polyol resin, an acrylic resin containing a hydroxyl group and a long-chain alkyl group having 10 to 30 carbon atoms, and an isocyanate compound .   The transfer film according to claim 1, further comprising a cellulose derivative containing a hydroxyl group in at least one of the mat layer and the release layer.   The transfer film according to claim 1 or 2, further comprising an acrylic silicone resin containing a hydroxyl group in the release layer.   The transfer film according to claim 1, further comprising a second matting agent in the release layer.   The transfer film according to claim 4, wherein the first mat agent and the second mat agent are the same mat agent.   A transfer molded article produced using the transfer film according to claim 1.

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