JP7167561B2 - Hard coat film laminate for transfer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a hard coat film laminate for transfer and a method for producing the same. Specifically, the present invention relates to a transfer hard coat film laminate capable of forming a patterned hard coat layer, and a method for producing the same.

In order to impart hard coat properties such as scratch resistance to resin molded products, a hard coat layer is provided on the surface of various molded products such as resin molded products. It is formed by transcription. Conventionally, a thermal transfer film in which an adhesive layer and a surface protective layer (hard coat layer) are laminated has been widely used in order to provide such a hard coat layer on a resin molded product (see Patent Document 1).

Molded products having a hard coat layer provided on the surface in this way are used as exterior and interior materials for building structures of general residences and public facilities, interior and exterior parts for automobiles, solar cell covers or solar cell substrates, and home electric appliances. It can be used as a member of These molded products are often colored in a desired pattern to form a pattern in order to improve the design and other functions in addition to the hard coat properties.

Conventionally, in a molded article having a hard coat layer provided on the surface, a pattern for improving the design property etc. is provided on the surface of any layer constituting the hard coat layer, that is, the surface of the hard coat layer, or , a pattern or the like is printed in advance on the surface of the adhesive layer or the like in a required pattern before these layers are laminated and integrated (see Patent Documents 2 and 3).

In the production of the hard coat film, the additional step of printing a design in a required pattern in advance before laminating and integrating each constituent member becomes a factor that inhibits the productivity improvement of the hard coat film.

JP 2014-208493 A JP-A-2000-62396 WO2016/072450

An object of the present invention is to improve productivity of a hard coat film provided with a pattern for improving designability.

The present inventors added a retrograde colorant having the property of fading by absorbing thermal energy or light energy into the adhesive layer of the hard coat film, and intentionally added only a desired portion of this colorant. The inventors have found that the above-mentioned problems can be solved by a novel method of fading to a high temperature, and have completed the present invention. More specifically, the present invention provides the following.

(1) A hard coat in which a hard coat layer and an adhesive layer are laminated, and the adhesive layer contains a regressive coloring agent having a property of fading by absorbing thermal energy or light energy. the film.

According to the hard coat film of (1), in the production of a hard coat film having a pattern, there is no need for a process for printing a pattern or the like in advance in a necessary pattern before laminating and integrating each constituent member. Productivity can be improved. In addition, when this hard coat film is integrated with a hard coat molded product, it is possible to form various patterns by, for example, simply changing the design of the masking material that limits the portion to be irradiated with energy.

(2) The hardware according to (1), wherein a pattern consisting of a colored portion and a non-colored portion is formed in the adhesive layer, and the colored portion is formed of the regressive coloring agent. coat film.

According to the hard coat film of (2), in the production of a hard coat film having a pattern, there is no need for a process for printing a pattern or the like in advance in a necessary pattern before lamination and integration of each constituent member, Productivity can be improved. In addition, since the pattern of this hard coat film is completed before it is integrated with the hard coat molded product, the process of integration with the hard coated molded product is carried out in exactly the same manner as in the conventional method. A hard-coated molded article with a desired pattern can be obtained.

(3) The adhesive layer comprises a primer layer formed on the surface of the hard coat layer and a heat seal layer formed on the surface of the primer layer, and the retrograde colorant is The hard coat film according to (1) or (2), which is formed in layers.

According to the hard coat film of (3), in the hard coat molded product, the pattern is arranged on the inner side closer to the molded product substrate than the hard coat layer and the primer layer, so that the pattern on the molded product substrate 20 The superiority of the hard coat film (1) or (2) to conventional products can be further enhanced in that the accuracy of the formation position of (1) or (2) can be easily improved and the weather resistance of the pattern after formation can be easily maintained.

(4) A hard coat for transfer, comprising a substrate film further laminated on the surface of the hard coat layer of the hard coat film according to any one of (1) to (3) opposite to the adhesive layer. film laminate.

According to the hard coat film of (4), the hard coat film laminate for transfer is superior to the conventional one by enjoying the above effects of the hard coat film according to any one of (1) to (3). It can be manufactured under high productivity.

(5) A hard-coated molded product in which the hard-coated film according to any one of (1) to (3) is adhered to the surface of a molded product substrate via the adhesive layer.

According to the hard-coated molded product of (5), the hard-coated molded product can be produced more excellently than before by enjoying the above effects of the hard-coated film according to any one of (1) to (3). Can be manufactured under sexual conditions.

(6) The hard-coated molded article according to (5), wherein the surface of the molded article substrate is a curved surface, and the regressive coloring agent is a coloring agent having a property of being decolored by heating.

According to the hard-coated molded product of (6), especially when manufacturing a hard-coated molded product that needs to form a curved surface by heat bending, enjoying the significance of the hard-coated molded product of (5), A hard-coated molding having a curved surface subjected to hard-coating can be manufactured with higher productivity than before.

(7) A method for producing a patterned hard coat film, wherein the hard coat film is formed by laminating a hard coat layer and an adhesive layer, and the adhesive forming the adhesive layer is applied with heat energy or light energy. A step of forming an adhesive layer composed of the adhesive on the surface of the hard coat layer, and heating a part of the adhesive layer, or the adhesion A method for producing a hard coat film, comprising a step of irradiating a part of the layer with light to cause a part of the recessive colorant to fade, thereby forming the pattern in the adhesive layer.

According to the method for producing a hard coat film of (7), in the production of a hard coat film having a pattern, there is a step of printing a pattern or the like in a necessary pattern in advance before lamination and integration of each constituent member. It becomes unnecessary, and productivity can be improved.

(8) A method for producing a patterned hard-coated molded product, comprising the steps of transferring a hard-coated film formed by laminating a hard coat layer and an adhesive layer onto the surface of a molded product substrate, and heating the molded product substrate. and the adhesive forming the adhesive layer contains a regressive coloring agent having a property of fading by absorbing thermal energy, and the molded article substrate is bent and deformed. A method for producing a hard-coated molded product, wherein a portion of the retrogradable colorant is faded by heat heated to a temperature high enough to form the pattern in the adhesive layer.

According to the method for producing a hard-coated molded product of (8), in the case of producing a hard-coated molded product having a pattern, in which a curved surface must be formed by heat bending, the hard-coated molded product By remarkably enhancing productivity, it is possible to manufacture a hard-coated molding in which a curved surface is hard-coated, with higher productivity than in the past.

ADVANTAGE OF THE INVENTION According to this invention, the productivity of the hard-coat film provided with the pattern for the design improvement can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the hard-coat film laminated body for transfer which is one Embodiment of the hard-coat film of this invention. It is a cross-sectional schematic diagram in the middle stage of the manufacturing process of the hard-coat film laminated body for transfer|transfer of this invention with which it uses for description of the manufacturing method of the said laminated body. It is a cross-sectional schematic diagram in the middle stage of the manufacturing process of the hard-coat film laminated body for transfer|transfer of this invention with which it uses for description of the manufacturing method of the said laminated body. FIG. 2 is a plan view of the transfer hard coat film laminate of the present invention when viewed from the adhesive layer side. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a drawing for explaining a manufacturing method for manufacturing a hard-coated molded article having a patterned hard-coated layer using the hard-coated film laminate for transfer of the present invention, (a) transfer before peeling off the base film; FIG. 3B is a schematic cross-sectional view showing the state of a hard coat film laminate for a printer, and (b) the state of the hard coat film after peeling off the base film. FIG. 2 is a drawing for explaining another embodiment of the production method for producing a hard-coated molded product having a patterned hard-coated layer using the transfer hard-coated film laminate of the present invention, and (a) a substrate film; The state of the transfer hard coat film laminate before peeling, (b) the state of applying energy for design formation in the state where the masking material is laminated on the hard coat film after peeling the base film. , and (c) a schematic cross-sectional view showing a hard-coated molding on which a pattern is formed, respectively.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is by no means limited to the following embodiments. The present invention can be implemented with appropriate modifications within the scope of its purpose.

<Hard coat film laminate for transfer>
The configuration of the transfer hard coat film laminate of the present invention will be described below with reference to the drawings as appropriate. As shown in FIG. 1, the transfer hard coat film laminate 10 of the present invention is a resin film obtained by laminating a hard coat film 1 and a base film 11 as a support base for supporting the hard coat film 1. be.

The transfer hard coat film laminate 10 of the present invention contains a coloring agent having a specific property, which has not been conventionally selected for the hard coat film 1, that is, the property of easily fading due to heat or light energy. characterized by containing This coloring agent is transferred from the completion of the hard coat film 1 to the stage of integration as the transfer hard coat film laminate 10 (FIGS. 1 to 3), and is transferred to the surface of the molded product substrate 20 to form the hard coat. At any stage up to the stage of forming the product 100 (FIGS. 5 and 6), the hard-coated molded product 100 is imparted with a pattern that can be visually recognized from the outside by discoloring an arbitrary part of it. That is, the transfer hard coat film laminate 10 of the present invention can be preferably used for producing a patterned hard coat molded product, and can contribute to the improvement of productivity. It is a film laminate material for layer transfer.

In this transfer hard coat film laminate 10, the hard coat film 1 constituting this laminate is transferred to the surface of a molded article substrate 20 made of thermoplastic resin, glass, or the like to form a hard coat layer. This hard coat layer can have any pattern as described above. In the transfer hard coat film laminate 10, the base film 11 is a supporting base material for supporting the hard coat film 1, and is separated from the hard coat film 1 after the transfer (see FIGS. 5 and 6). .

The hard coat film 1 constituting the transfer hard coat film laminate 10 is a multi-layer film in which at least a hard coat layer 12 and an adhesive layer 13 are laminated and integrated.

The adhesive layer 13 constituting the hard coat film 1 is preferably a two-layered adhesive layer in which a primer layer 131 and a heat seal layer 132 are arranged in order from the hard coat layer 12 side. That is, the hard coat film 1 is preferably a multilayer film in which the hard coat layer 12, the primer layer 131, and the heat seal layer 132 are arranged in this order.

The hard coat film 1 contains a coloring agent that forms a pattern visible from the outside of the hard coat film 1 in the layers of the adhesive layer 13 (the primer layer 131 and the heat seal layer 132). This colorant is a retrograde colorant that has the property of fading by absorbing thermal energy or light energy. This regressive colorant is partially decolored by heat energy or light energy, so that an arbitrary pattern consisting of the colored portion 14A and the non-colored portion 14B is formed in the layer of the adhesive layer 13. is formed (see FIGS. 4 and 5).

In the hard coat film 1, when the adhesive layer 13 has a multilayer structure including the primer layer 131 and the heat seal layer 132, the pattern can be formed in the heat seal layer 132. preferable. In the hard coat molded product 100, it is easier to increase the accuracy of the pattern formation position with respect to the molded product substrate 20 by arranging the pattern on the inner side closer to the molded product substrate 20 than the hard coat layer 12 and the primer layer 131. This is because it is easy to keep good weather resistance of the pattern after formation. Further, as will be described later, the primer layer 131 may be configured to add various additives (for example, an ultraviolet absorber, a light stabilizer, etc.) to ensure the weather resistance of the hard coat film 1. In this case, it is preferable to add the coloring agent to the heat seal layer 132 from the viewpoint of further enhancing the weather resistance of the pattern.

Here, the "pattern" in this specification is, for example, a pattern such as that illustrated in FIG. Various patterns, figures, characters, etc. that can be composed of "colored parts" and "non-colored parts" that are not colored or clearly faded, or any visible coloring / It is intended to include aspects of articles comprising non-colored combinations. Such a "pattern" is not limited to a "design" that gives rise to aesthetics. It is formed by combining a colored part and a non-colored part, and includes all aspects of visible articles for the purpose of exhibiting various functions other than aesthetic appearance. In addition, "colored part" refers to a colored part that constitutes a pattern that can be visually recognized from the outside of the product, etc., and "non-colored part" refers to a colorless and transparent part of the entire pattern. Or, even if it is not completely colorless and transparent, it is more transparent than the colored part, which is the main part of the design, and only the color of that part clearly protrudes from the other surrounding parts. It shall refer to the part which is fading.

[Base film]
The base film 11 is preferably a resin film that has a good balance of flexibility and rigidity suitable for the purpose of use as a supporting base material, and is also a resin film that can be peeled off from the hard coat film 1 after transfer. I wish I had. For example, a polyester resin film or a polyolefin resin film can be preferably used as the base film 11 . Moreover, it is more preferable that these resin films are stretched films. By forming the base film 11 from a stretched film, shrinkage caused by heat treatment or cross-linking treatment due to irradiation of ionizing radiation when manufacturing the transfer hard coat film laminate 10 is suppressed, and the transfer hard coat film laminate 10 is suppressed. The shape and dimensional stability of the coat film laminate 10 can be enhanced.

Examples of the polyester resin film used as the base film 11 include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyarylate, polycarbonate, and ethylene terephthalate-isophthalate copolymer. As a specific example, a resin film containing a system resin as a main material can be preferably used. Among these, PET film and PBT film are preferable in consideration of heat shrinkage during production of the transfer hard coat film laminate 10 and shrinkage due to irradiation of ionizing radiation, etc., and among these, the PET film is preferred. Especially preferred.

As the polyolefin resin film used as the base film 11, in consideration of heat shrinkage during production of the transfer hard coat film laminate 10 and shrinkage due to irradiation of ionizing radiation, for example, polyethylene resin, polypropylene, etc. As a specific example, a stretched resin film made of polyolefin resin such as resin, polybutene resin, ethylene/propylene copolymer resin, ethylene/propylene/butene copolymer resin, or olefin thermoplastic elastomer can be preferably used. can be mentioned. Among these, a stretched polypropylene resin film is particularly preferred.

The stretched polyolefin resin may be either uniaxially stretched or biaxially stretched. Considering the fact that it is less likely to occur, it is more preferable to be biaxially stretched. A sheet of biaxially oriented polyolefin resin is usually heated to a glass transition temperature Tg or higher using a longitudinal stretching machine, preferably stretched about 5 times or more and 30 times or less, and then glassed using a width direction stretching machine. It is obtained by heating to a transition temperature Tg or higher and stretching in the width direction, preferably 5 times or more and 30 times or less. Further, when the draw ratio is within the above range, it is preferable in that heat shrinkage during production of the transfer hard coat film laminate 10 and shrinkage due to irradiation with ionizing radiation are less likely to occur.

The thickness of the base film 11 is not particularly limited. For example, it may be 4 μm or more and 200 μm or less. If it is 4 μm or more, unfavorable deformation such as curling or wrinkles is unlikely to occur, and if it is 200 μm or less, the cost can be kept low, the heat conduction efficiency will not decrease, and the base film 11 can be peeled off after transfer. Since each layer is difficult to peel off, excellent transferability can be obtained. The base film 11 may have a multilayer structure. In that case, it is preferable that the thickness of the entire multilayer structure is within the above range.

In addition, the substrate film 11 may be provided on the surface of the substrate film 11 as necessary in order to ensure releasability between the hard coat film 1 and the hard coat film 1 when the hard coat film 1 is transferred to the surface of the molded product substrate 20 . may be subjected to a release treatment, or a release layer such as a silicone resin may be provided. Conversely, in order to improve the adhesion between the base film 11 and the hard coat layer 12, corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone/ultraviolet treatment, and an adhesive coating agent are applied. Surface treatment such as coating may be applied. Moreover, the base film 11 may be a single layer using the above resin film alone, or may be a multilayer structure in which a plurality of types of resin films are laminated.

[Hard coat layer]
The hard coat layer 12 is a layer made of a curable resin composition. It is a layer forming a hard coat layer on the outermost surface of 100 . The hard coat layer 12 is a layer that is cured by each means described in detail below, but this curing can also be performed after the above transfer. Therefore, the transfer hard coat film laminate 10 and the hard coat layer 12 of the hard coat film 1 constituting this are not limited to cured layers. As described above, as long as it is a layer that constitutes the hard coat film and is composed of a curable resin composition, even if it is a layer in an uncured stage, the hard coat layer that constitutes the hard coat film or the like of the present invention. It must be.

As the base resin of the curable resin composition forming the hard coat layer 12, a thermosetting resin or an ionizing radiation-curable resin that is cured by irradiation with ionizing radiation can be preferably used.

When using a thermosetting resin as the base resin of the curable resin composition for forming the hard coat layer 12, polyester resins, epoxy resins, polyurethane resins, aminoalkyd resins, melamine resins, guanamine resins, urea resins, thermosetting resins, etc. A thermosetting resin such as a curable acrylic resin can be used. However, considering weather resistance and hard coat properties, it is more preferable to use an ionizing radiation-curable resin.

When an ionizing radiation-curable resin is used as the base resin of the curable resin composition for forming the hard coat layer 12, polymerizable oligomers and prepolymers conventionally used as ionizing radiation-curable resins are selected. It can be selected and used as appropriate. Examples of such polymerizable oligomers and prepolymers include oligomers and prepolymers having radically polymerizable unsaturated groups in the molecule, such as epoxy (meth)acrylate, urethane (meth)acrylate and polyether urethane (meth)acrylates. ) acrylate, caprolactone-based urethane (meth)acrylate, polyester (meth)acrylate-based, polyether (meth)acrylate-based oligomers and prepolymers, and the like can be preferably used.

When an ionizing radiation curable resin is used as the curable resin for forming the hard coat layer 12, the ionizing radiation irradiated to these resins may be an electromagnetic wave or a charged particle beam, which can polymerize or crosslink molecules. such as ultraviolet (UV) or electron beam (EB). In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be selected.

Moreover, the curable resin composition can contain a non-reactive silicone compound from the viewpoint of improving weather resistance and hard coat properties and obtaining excellent transparency. The non-reactive silicone compound is not particularly limited as long as it is a silicone compound that does not have reactive functional groups such as amino group, epoxy group, mercapto group, carboxy group, hydroxy group, (meth)acryloyl group, and allyl group. , polysiloxane-based silicone oils, polyether-modified silicone oils, aralkyl-modified silicone oils, fluoroalkyl-modified silicone oils, long-chain alkyl-modified silicone oils, higher fatty acid ester-modified silicone oils, higher fatty acid amide-modified silicone oils, phenyl-modified Preferred examples include silicone oil and the like. It is preferable that the curable resin composition should not contain a reactive silicone compound having such a reactive functional group in the molecule, since curing shrinkage tends to occur. The content of the non-reactive silicone compound in the curable resin composition is preferably 0.05 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the curable resin, and 0.05 parts by mass or more and 10 parts by mass. It is more preferably not more than 0.1 part by mass and even more preferably 0.1 part by mass or more and 5 parts by mass or less. When the content of the non-reactive silicone compound is within the above range, excellent weather resistance and hard coat properties are obtained, and curing shrinkage does not occur.

Moreover, the curable resin composition forming the hard coat layer 12 preferably further contains a scratch resistant filler and a weather resistant agent in order to improve hard coat properties and weather resistance. The scratch-resistant filler that can be contained in the hard coat film 1 and the transfer hard coat film laminate 10 includes inorganic and organic fillers. Examples of inorganic substances include alumina, silica, kaolinite, iron oxide, and diamond. , inorganic particles such as silicon carbide. The shape of the particles may be spherical, ellipsoidal, polyhedral, scaly, etc., and is not particularly limited, but is preferably spherical in terms of higher hardness and excellent hard coat properties. Silica particles are one of the preferred inorganic scratch-resistant fillers. This is because the silica particles improve the hard coat properties and do not impair the transparency of the hard coat layer. As the silica particles, it is possible to appropriately select and use from conventionally known silica particles, and colloidal silica particles are also suitable. Colloidal silica particles have little effect on transparency even when the amount added is increased.

Moreover, the curable resin composition used for forming the hard coat layer 12 preferably contains a weather resistance improving agent in order to obtain excellent weather resistance. As the weather resistant agent, there are UV absorbers, light stabilizers, and the like. UV absorbers absorb harmful UV rays and improve the long-term weather resistance and stability of hard-coated moldings. Also, the light stabilizer itself hardly absorbs ultraviolet rays, but it is said that stabilization can be obtained by efficiently trapping harmful free radicals generated by ultraviolet rays. Preferred examples of the UV absorber include inorganic compounds such as titanium dioxide, cerium oxide, and zinc oxide, and organic UV absorbers such as benzotriazole and triazine compounds. Among them, triazine UV absorbers are preferred. As the light stabilizer, for example, a hindered amine light stabilizer (HALS) is preferably used.

Among triazine-based UV absorbers, hydroxyphenyltriazine-based UV absorbers are particularly preferable as the UV-absorber to be contained in the hard coat film 1 and the transfer hard coat film laminate 10 . Examples of hydroxyphenyltriazine-based UV absorbers include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5- triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tri Decyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2 '-Ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and the like are preferred examples.

The content of the triazine-based ultraviolet absorber in the curable resin composition forming the hard coat layer 12 is preferably 0.1 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the curable resin. It is more preferably 0.1 parts by mass or more and 2 parts by mass or less, and more preferably 0.3 parts by mass or more and 1.5 parts by mass or less. If the content of the triazine-based UV absorber is within the above range, the UV absorber does not bleed out and sufficient UV absorbency can be obtained.

The hindered amine light stabilizer is preferably a hindered amine light stabilizer having a reactive functional group. The reactive functional group is not particularly limited as long as it is reactive with the ionizing radiation curable resin. For example, (meth)acryloyl group, vinyl group, functional group having an ethylenic double bond such as allyl group etc. are preferably mentioned, and at least one selected from these is preferable. Among them, a (meth)acryloyl group is preferred. Hindered amine light stabilizers having such reactive functional groups include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(1,2,2,6,6-pentamethyl- 4-piperidyl) sebacate, bis (2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2, 2,6,6-pentamethyl-4-piperidinyl)sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino] -6-(2-Hydroxyethylamine)-1,3,5-triazine and the like are preferred examples.

The content of the hindered amine light stabilizer having a reactive functional group is preferably 1 part by mass or more and 10 parts by mass or less, and is 2 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the curable resin. More preferably, it is 3 parts by mass or more and 6 parts by mass or less. If the content of the hindered amine light stabilizer is within the above range, sufficient light stability can be obtained without bleeding out of the light stabilizer.

In addition, when a regressive colorant having a property of fading by absorbing light energy such as ultraviolet rays is selected as the fading colorant, the hard coat layer 12 may contain a By adding an appropriate ultraviolet absorber or light stabilizer, it is possible to prevent fading during use of the colored portion 14A located on the inner layer side of the hard coat layer 12 .

Further, the curable resin composition forming the hard coat layer 12 may contain various additives as long as the performance thereof is not impaired. Various additives include, for example, polymerization inhibitors, cross-linking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents and the like.

[Adhesion layer]
The adhesive layer 13 is a layer having a function of adhering the hard coat film 1 to the surface of the molded product substrate 20 . Although the adhesive layer 13 may be a single layer, it preferably has a two-layer structure in which the primer layer 131 and the heat seal layer 132 are laminated in this order from the hard coat layer 12 side, as described above. . A case where the adhesive layer 13 has such a two-layer structure will be described below.

[Primer layer]
The primer layer 131 is a layer that functions as a stress relieving layer for the hard coat layer 12 and also has the function of improving the adhesion of the hard coat layer 12 . The primer layer 131 is composed of a primer layer-forming resin composition containing a binder resin and an antiblocking agent.

The binder resin that constitutes the primer layer 131 is preferably a two-liquid curable resin composed of a main agent and a curing agent. The main component of the binder resin that constitutes the primer layer 131 is not particularly limited. Examples of the main component of the binder resin that can be preferably used include polyurethane resin, (meth)acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, chlorinated polyethylene, and the like. . These binder resins can be used singly or in combination of two or more. Among these binder resins, polyurethane resins are particularly preferable from the viewpoint of adhesion and weather resistance.

When a polyurethane resin is used as the main component of the binder resin that constitutes the primer layer 131, the polyurethane resin is more preferably a polyurethane resin having an acrylic skeleton in its polymer chain from the viewpoint of weather resistance and durability. Polyurethane resins having an acrylic skeleton in the polymer chain include, for example, urethane-acrylic copolymers, which are copolymers of urethane components and acrylic components, and hydroxyl groups or isocyanate groups as polyol components or polyisocyanate components constituting polyurethanes. As an example, an acrylic resin having Among them, a urethane-acrylic copolymer can be particularly preferably used as the base material of the binder resin that constitutes the primer layer 131 . The urethane-acrylic copolymer can be produced, for example, by a method of reacting an acrylic resin having at least two hydroxyl groups in one molecule with a polyol compound and an isocyanate compound (see JP-A-6-100653, etc.), or by an unsaturated double It can be obtained by, for example, a method of reacting an acrylic monomer with a urethane prepolymer having bonds at both ends (see JP-A-10-1524, etc.).

The polycarbonate-based urethane acrylic copolymer can be obtained, for example, by copolymerizing a polycarbonate-based urethane obtained by reacting a carbonate diol and a diisocyanate with a diol having an acrylic skeleton. A polycarbonate-based urethane acrylic copolymer can also be obtained by reacting a diol having an acrylic skeleton with a carbonate diol and a diisocyanate. Here, specifically, the diol having an acrylic skeleton includes (meth)acrylic acid, (meth)acrylic acid alkyl ester having an alkyl group having about 1 to 6 carbon atoms, or an oligomer obtained by radical polymerization of these, or Compounds in which two hydroxyl groups are introduced into a prepolymer (with a degree of polymerization of about 2 or more and 10 or less) can be mentioned.

From the viewpoint of accelerating the curing of the main agent, the primer layer may contain a curing agent. Examples of such curing agents include isocyanate curing agents such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, cyclohexanephenylene diisocyanate and naphthalene-1,5-diisocyanate. The amount of the curing agent used is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 10 parts by mass or more and 30 parts by mass or less, and 20 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin as the main agent. More preferred.

Various additives other than those described above may be added to the primer layer 131, if necessary, as long as the effects of the present invention are not impaired. Such additives include, for example, weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, infrared absorbers, light stabilizers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents, colorants and the like. These additives can be appropriately selected and used from commonly used ones.

Although the thickness of the primer layer 131 is not particularly limited, it is preferably 0.1 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less.

[Heat seal layer]
The heat seal layer 132 is a layer having a function of adhering the hard coat film 1 to the surface of the molded article substrate 20 together with the primer layer 131, and can be transferred to the molded article substrate 20 satisfactorily by heating and pressing. It is composed of an adhesive resin such as a heat-sealing resin so as to be able to be made.

The adhesive resin contained in the heat seal layer 132 is determined according to the material of the molded product substrate 20, the transfer temperature and pressure during transfer, the application of the transfer product, etc., and is not particularly limited. In general, heat-sealing resins such as acrylic resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin, chlorinated polypropylene, chlorinated rubber, urethane resin, epoxy resin, and styrene resin are used as adhesive resins. can be used as appropriate. Each of these resins can be used alone, or two or more of them can be used in combination. Among the above resins, the adhesive resin to be contained in the heat seal layer 132 is acrylic resin, which has a small difference in refractive index from the particles contained in the primer layer 131 and is likely to improve the transparency and weather resistance of the sheet. It is particularly preferable to use the resin alone.

The heat seal layer 132 is preferably thicker than the primer layer 131 . From the viewpoint of securing the function of bonding the hard coat film 1 including the hard coat layer 12 to the molded product substrate 20 and excellent transparency, the thickness of the heat seal layer 132 should be 1 μm or more and 7 μm or less. and more preferably 1 μm or more and 6 μm or less.

Moreover, the surface of the transfer hard coat film laminate 10 can be protected by attaching a cover film (protective film) made of resin such as polyethylene resin on the heat seal layer 132 . When a cover film is provided on the transfer hard coat film laminate 10 , the cover film is peeled off to expose the heat seal layer 132 , which is then transferred to the molded article substrate 20 via the surface of the heat seal layer 132 .

[Design]
The hard coat film 1 and the transfer hard coat film laminate 10 formed by using the same have a visible colored pattern. As an example of this pattern, for example, a striped pattern consisting of a colored portion 14A and a non-colored portion 14B as shown in FIG. 4 can be cited. By using the hard coat film 1 or the hard coat film laminate 10 for transfer using the same, it is possible to impart a pattern to the molded product substrate 20 of the molded product and contribute to the improvement of its design. Alternatively, as described above, it is possible to contribute to the enhancement of product functions and efficacy by manifesting various other functions. Examples of functions other than the improvement in design that can be realized by providing the pattern according to the present invention include, for example, coloring the outer periphery of the car window with a dark color to blur the boundary between the body and pillars, or the car window. As a specific example, the display portion of the surface panel of the display is made transparent and the non-display portion is patterned to be opaque.

In the hard coat film 1, the colored portion 14A forming the pattern is formed of a retrograde colorant contained in the adhesive layer 13, or more preferably in the heat seal layer 132. An embodiment in which a pattern is formed within the heat seal layer 132 will be described in detail below.

In the hard coat film 1, the regressive coloring agent that constitutes the colored portion 14A is used in the layer in which the pattern is arranged (preferred example It is added so as to spread over substantially the entirety of the heat seal layer 132), or at least the entire assumed pattern formation range including the portion assumed to be the non-colored portion 14B. At this stage, the pattern such as the stripe pattern shown in FIG. 4 cannot be visually recognized yet (see FIG. 1). However, a coloring agent that easily fades has not been intentionally used as a coloring agent for imparting patterns to hard-coated moldings that normally require a high level of weather resistance. The hard coat film 1 is different from conventional patterned hard coats in that a coloring agent having regressive properties is intentionally selected in the above stage (for example, the stage shown in FIG. 1) before pattern formation. It differs significantly from the film in the composition of the coloring material.

The colorant added in the adhesive layer 13 or the heat seal layer 132 is a retrograde colorant that has the property of fading by absorbing thermal energy or light energy. After the regressive coloring agent is contained in the entire portion forming the pattern, only the coloring agent in an arbitrary portion is faded by a masking method or the like to be described later, thereby forming a pattern consisting of the colored portion 14A and the non-colored portion 14B. can be formed.

(Regressive coloring agent having the property of fading by absorbing thermal energy)
In the adhesive layer 13 or the heat seal layer 132, a "coloring agent that has the property of fading by absorbing thermal energy (hereinafter also referred to as a "thermal regression type coloring agent") is adopted as a regressive coloring agent that forms a pattern. In that case, a known colorant having such properties can be appropriately selected. As a specific example, for example, the “discolorable adhesive composition” disclosed in JP-A-2010-174183 can be used. This "discolorable adhesive composition" contains a binder, an organic solvent, a basic dye or an oil-soluble dye, and a silane coupling agent, and when heated to 150 to 200°C, the color disappears as it cures. , and becomes colorless and transparent.

By using a "thermal regression type coloring agent" having such properties as a design-forming regression coloring agent in the adhesive layer 13 or the heat seal layer 132, any color heated to a predetermined temperature can be used. Only in the portion of , the colorant can be rendered colorless and transparent or sufficiently faded. As a result, an arbitrary pattern consisting of the colored portion 14A and the non-colored portion 14B can be formed in the adhesive layer 13 or the heat seal layer 132 .

As the binder resin of the "discolorable adhesive composition" suitable as the above-mentioned "heat-regressive colorant", any colorless binder resin that is usually used in adhesives can be used without particular limitation. be. For example, epoxy resin, polyester resin, unsaturated polyester resin, phenol resin, phenoxy resin, acrylic resin, silicone resin, urethane resin, fluorine resin, polyimide resin, polyamide resin, ABS resin, polyethylene, polycarbonate, or modification of these resins. Resin etc. can be mentioned as an example.

As the organic solvent used in the above-mentioned "discolorable adhesive composition", any organic solvent that dissolves or disperses the binder resin can be used without particular limitation. For example, hydrocarbon solvents such as toluene, xylene, hexane, and octane; alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, and diacetone alcohol; methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone. Examples include ketone solvents such as ethyl acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, butyl stearate, methyl benzoate, methyl lactate, ethyl lactate, and butyl lactate. can.

Basic dyes used in the above-mentioned "discolorable adhesive composition" include triphenylmethane dyes, trimethylmethane dyes, diphenylmethane dyes, polymethine dyes, xanthene dyes, cyanine dyes, azo dyes, and anthraquinone. dyes, cyanine dyes, and the like. Among these, triphenylmethane-based dyes are particularly preferable in that they are excellent in color erasability.

The silane coupling agent used in the "discolorable adhesive composition" can be used without particular limitation. γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane are preferred, and γ- Glycidoxypropyltrimethoxysilane is preferred over decolorization.

(Regressive colorant having the property of fading by absorbing light energy)
In the adhesive layer 13 or the heat seal layer 132, a coloring agent having a property of fading by absorbing "light energy" (hereinafter also referred to as "light-regressing coloring agent") is adopted as a regressing coloring agent forming a pattern. In that case, a known colorant having such properties can be appropriately selected. As a specific example, for example, a “discolorable dye” disclosed in JP-A-5-132655 can be used. The "light" that gives "light energy" to the above-mentioned "light-regressing colorant" naturally includes light other than visible light, such as ultraviolet rays and infrared rays.

In the adhesive layer 13 or the heat seal layer 132, by using a "photo-regressive colorant" having such properties as a regressive colorant that forms a pattern, specific light can be directed only to any specific part. By irradiating, the colorant can be rendered colorless and transparent only in that portion, or can be sufficiently faded. As a result, an arbitrary pattern consisting of the colored portion 14A and the non-colored portion 14B can be formed in the adhesive layer 13 or the heat seal layer 132 .

Examples of dyes that can be used as the "discolorable dye" suitable for the above-mentioned "light-regressing colorant" include cyanine dyes. It has an absorption maximum in light having an infrared wavelength, typically a wavelength of 780 nm or more and 880 nm or less, and by irradiating an arbitrary part with light having a near-infrared wavelength, light having the wavelength It can be absorbed to accelerate the decoloration of the above-mentioned "discolorable dye" in the arbitrary portion to make it colorless and transparent, or it can be sufficiently discolored.

Further, as the regressive coloring agent, a coloring agent containing a dye having a property of being decolored by being irradiated with ultraviolet rays having a wavelength of 200 nm or more and 400 nm or less as a coloring component can be preferably used. For example, it has been confirmed that food dyes such as tar dyes can be faded to the extent that they become almost transparent by promoting the decomposition of the dyes by ultraviolet irradiation for generally within 100 hours. Moreover, the hard coat film and the hard coat film laminate for transfer according to this embodiment are suitable when it is assumed that the hard coat molded product, which is the final product, will not be exposed to ultraviolet rays.

In addition to the above, a gardenia blue pigment can also be used as the retrograde coloring agent. This gardenia blue dye is a dye that fades by 75% when irradiated with a xenon arc lamp (ultraviolet to infrared rays) for 1 hour.

[Method for producing hard coat film and transfer hard coat film laminate]
The hard coat film laminate for transfer and the method for producing the hard coat film of the present invention will be described.

The hard coat film and the hard coat film laminate for transfer of the present invention are obtained by laminating and integrating a hard coat layer, an adhesive layer (a heat seal layer and a primer layer), and a base film. This can be obtained by going through the same steps as in the conventional method. However, the hard coat film laminate for transfer and the hard coat film of the present invention have a design, and are characterized in that the pattern is formed by a process completely different from conventional processes. .

Specifically, the steps for obtaining the laminate are as follows. For example, the hard coat layer 12 is made of a resin composition containing the curable resin described above, and optionally a non-reactive silicone compound, a scratch-resistant filler, an ultraviolet absorber, and a light stabilizer as weathering agents. It can be formed by coating on 11 . The primer layer 131 can be formed by subjecting the surface of the hard coat layer 12 to corona discharge treatment and applying a composition (primer layer-forming resin composition) containing components constituting the primer layer 131 . The heat seal layer 132 can be formed by applying a composition (resin composition for forming a heat seal layer) containing components constituting the heat seal layer 132 onto the primer layer 131 . Then, the hard coat layer 12 is cured by ionizing radiation during the process of forming the laminate thus obtained, or after the process of forming the laminate. Normally, it is preferable to form the primer layer 131 after the hard coat layer 12 is formed on the base film 11 and then irradiated with ionizing radiation to cure the hard coat layer 12 .

Through the above steps, the laminate formed by integrating the hard coat layer, the adhesive layer (heat seal layer and primer layer), and the base film is subjected to the pattern formation process described below by a unique method. By carrying out, the patterned hard coat film and transfer hard coat film laminate according to the present invention can be obtained.

Formation of this pattern can be performed by the method shown in FIGS. That is, in the laminate obtained by the above steps, the portion where the pattern is to be formed as the colored portion 14A is protected on the surface of the adhesive layer 13 (heat seal layer 132) that contains the "regressive coloring agent" in advance. A masking material 15 formed so that energy E for promoting fading of the "regressive coloring agent", such as light of a specific wavelength, reaches only the portion where fading is desired to be promoted as the non-colored portion 14B is installed, and In this state, the surface of the adhesive layer 13 (heat seal layer 132) is irradiated with energy E (for example, light of a specific wavelength) through the holes 151 of the masking material 15 (see FIG. 2). Then, the masking material 15 is peeled off when the irradiation of the energy E is completed to the extent that the fading progresses sufficiently. Through this process, an arbitrary layer consisting of the colored portion 14A, which is a portion protected from the energy E, and the non-colored portion 14B, whose discoloration is accelerated by the energy E, is formed in the adhesive layer 13 (heat seal layer 132). A pattern can be formed.

When the retrogressive coloring agent previously contained in the layer of the adhesive layer 13 (heat seal layer 132) is a coloring agent having a property of decolorizing when irradiated with ultraviolet rays. , the above energy E may be irradiated with ultraviolet rays. In this case, if the hard coat layer is also an ultraviolet curable resin, as described above, the hard coat film and the hard coat film laminate for transfer can be made more advantageous in terms of productivity. When ultraviolet rays are used as ionizing radiation, radiation containing ultraviolet rays having a wavelength of 190 to 380 nm is emitted. The ultraviolet light source is not particularly limited, and for example, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, carbon arc lamps and the like are used.

It should be noted that the irradiation of the light energy or the like depends on the type and intensity of the energy wave or the like to be used and the type of the fadeable colorant to be selected. Alternatively, irradiation from either side of the substrate film 11 can be used. The energy irradiation step may be performed during the manufacturing process of the hard-coated molded article described below, instead of being performed during the manufacturing process of the hard coat film laminate for transfer.

<Hard coat molding>
As shown in FIGS. 5 and 6, the hard coat molded product 100 of the present invention uses the transfer hard coat film laminate 10 to transfer the hard coat film 1 to the molded product substrate 20 via the heat seal layer 132. obtained by doing Specifically, as shown in FIG. 5(a), the hard-coated molded product 100 has at least an adhesive layer 13, a hard-coated layer 12, and a base film 11 formed on the surface of a molded product substrate 20 in this order. are placed. The arrangement of the base film 11 is arbitrary, and as shown in FIG. 2(b), the base film 11 may be peeled off from the hard coat film 1 at any stage during use.

[Molded product substrate]
The molded article substrate 20 may be appropriately selected according to the desired resin molding. Examples of the resin that constitutes the molded product base body 20 include polycarbonate resin, ABS resin, acrylic resin, and the like. The thickness of the molded product substrate 20 is preferably 1 mm or more and 20 mm or less, and more preferably 2 mm or more and 10 mm or less. If the molded product substrate 20 is too thin, the practical strength such as surface rigidity will be insufficient, and if the molded product substrate 20 is too thick, the workability of the molded product substrate 20 will be affected. The shape of the molded product substrate 20 may be appropriately selected according to the intended use of the resin molded product, and is not limited to a plate shape.

<Method for manufacturing hard-coated molded product>
The hard-coated molded product 100 of the present invention can be processed by the same manufacturing method as a known hard-coated molded product, except for the processing related to the process of forming the above pattern. For example, when using the transfer hard coat film laminate 10 in which the pattern has been formed in advance by the above-described method, this is transferred onto the molded product substrate 20 by a conventional method. , a patterned hard-coated molding 100 can be obtained.

In addition, the hard coat film laminate 10 for transfer is not subjected to energy irradiation or the like for forming the pattern, and the hard coat film laminate for transfer 10 ( The hard coat film 1) can be used to accelerate the fading of any part of the retrograde colorant during the manufacturing process of this hard coat molded product, and any pattern can be completed during this process. .

In particular, when the hard-coated surface of the hard-coated molded article is a curved surface, a coloring agent having the property of being decolored by heating is selected as the regressive coloring agent, and the molded article substrate is subjected to heat bending. A hard-coated molded article can be efficiently produced by a procedure in which the fading of an arbitrary portion of the retrograde colorant is accelerated by heating by irradiation with infrared rays or the like.

In the production of the hard coat molded product 100, first, the transfer hard coat film laminate 10 (hard coat film 1) is transferred onto the molded product substrate 20 via the heat seal layer 132 to form the hard coat layer. A product substrate is obtained (transfer step). For transfer, known roll transfer, in-mold molding, press transfer, or the like can be employed.

In the case of carrying out the above-described heating bending process, after this transfer step, the hard coat layer-attached molding substrate 20 is bent while being heated by irradiation with infrared rays or the like, or the hard coat layer-attached molding substrate 20 is bent. After that, the laminate is heated by the same means to cure the cured product previously added to the laminate (heat bending step). The heating temperature in this case is not particularly limited, but may generally be 100° C. or higher and 180° C. or lower. Also, the heating time is preferably 60 seconds or more and 1000 seconds or less.

If the coloring agent to be added to the adhesive layer is a "heat-regressive coloring agent" when performing such a heat bending process, for example, the heating can be performed so as to enable the formation of a "design" consisting of a desired pattern. By performing heat treatment in the same manner as above while masking with aluminum foil or the like that can block infrared rays, the fading of the "thermal regression type coloring agent" is accelerated only in an arbitrary part, and an arbitrary pattern can be created. can be completed.

The material to be transferred to form the hard-coated molded product is not particularly limited, and it requires hard-coated properties such as weather resistance and scratch resistance. It can be used for exterior and interior materials, automobile interior and exterior parts, solar cell covers or solar cell substrates, home appliance members, etc., especially balcony partitions, roof members for terraces and carports, vehicles and buildings. windows, and other products using transparent plastic such as soundproof walls and windbreak walls. As resin materials for forming such members, acrylic resins, ABS resins, polyolefin resins, polycarbonate resins, and the like are preferably mentioned, and these single resin materials or composite resin materials in which a plurality of types are combined may be used. .

REFERENCE SIGNS LIST 1 hard coat film 10 hard coat film laminate for transfer 11 substrate film 12 hard coat layer 13 adhesive layer 131 primer layer 132 heat seal layer 14 design 14A colored part 14B non-colored part 15 mask 151 hole 20 molded product substrate 100 hard coat molding

Claims (10)

A hard coat layer formed of a curable resin and an adhesive layer are laminated,
The adhesive layer contains a regressive coloring agent having a property of fading by absorbing thermal energy or light energy ,
The adhesive layer comprises a primer layer formed on the surface of the hard coat layer and a heat seal layer formed on the surface of the primer layer,
wherein the retrograde colorant is formed within the heat seal layer;
hard coat film. A pattern consisting of a colored portion and a non-colored portion is formed in the layer of the adhesive layer,
2. The hard coat film according to claim 1, wherein the colored portion is formed from the retrograde colorant. A hard coat layer made of a curable resin and an adhesive layer are laminated, and the adhesive layer contains a regressive coloring agent having a property of fading by absorbing heat energy or light energy. In the hard coat film that is
A substrate film is further laminated on the surface of the hard coat layer opposite to the adhesive layer,
Hard coat film laminate for transfer. A pattern consisting of a colored portion and a non-colored portion is formed in the layer of the adhesive layer,
wherein the colored portion is formed from the regressive coloring agent;
The hard coat film laminate for transfer according to claim 3 . The adhesive layer comprises a primer layer formed on the surface of the hard coat layer and a heat seal layer formed on the surface of the primer layer,
wherein the retrograde colorant is formed within the heat seal layer;
The hard coat film laminate for transfer according to claim 3 or 4. 3. A hard-coated molded article, wherein the hard-coated film according to claim 1 is adhered to the surface of a molded article substrate via the adhesive layer. 7. The hard-coated molded article according to claim 6 , wherein said surface of said molded article substrate is a curved surface, and said retrogressive coloring agent is a coloring agent having a property of being decolored by heating. A hard coat layer made of a curable resin and an adhesive layer are laminated, and the adhesive layer contains a regressive coloring agent having a property of fading by absorbing heat energy or light energy. The hard coat film is in close contact with the surface of the molded product substrate through the adhesive layer,
The surface of the molded article substrate is a curved surface, and the regressive coloring agent is a coloring agent having a property of being decolored by heating.
Hard coat molded product. A method for producing a hard coat film having a pattern,
The hard coat film is formed by laminating a hard coat layer and an adhesive layer,
The adhesive forming the adhesive layer contains a regressive coloring agent having a property of fading by absorbing thermal energy or light energy,
a step of forming an adhesive layer made of the adhesive on the surface of the hard coat layer;
a step of heating a portion of the adhesive layer or irradiating a portion of the adhesive layer with light to fade a portion of the regressive colorant to form the pattern in the adhesive layer; A method for producing a hard coat film, comprising: A method for producing a hard-coated molded article having a pattern,
a step of transferring a hard coat film formed by laminating a hard coat layer and an adhesive layer onto the surface of a molded article substrate;
a step of bending and deforming the molded product substrate while heating;
The adhesive that forms the adhesive layer contains a regressive colorant that has the property of fading by absorbing thermal energy,
The pattern is formed in the adhesive layer by causing a portion of the retrograde colorant to fade due to the heat applied to bend and deform the molded article substrate.
A method for producing a hard-coated molded product.

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