JP2017177607A - Method for producing hard coat layer laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat layer laminate excellent in all of scratch resistance, weather resistance, transparency and combustion resistance, specifically, a resin molded article with a hard coat layer.SOLUTION: A method for producing a hard coat layer laminate 1 which is obtained by laminating a hard coat film 10 for transfer on a surface of a resin substrate 20 formed from a thermoplastic amorphous resin includes: a transfer step of heating and pressing an adhesive layer 14 of the hard coat film 10 for transfer onto a surface of the resin substrate 20 in a state where the adhesive layer faces the surface thereof, and thereby transferring a transfer layer 15 onto the surface of the resin substrate 20; and a post-transfer laminate re-pressing step of heating and pressing a post-transfer laminate obtained by laminating the transfer layer 15 onto the resin substrate 20 at a heating temperature at which the resin substrate 20 exceeds a glass transition temperature of the resin substrate 20 and is lower than a melting point of the resin substrate 20, after the transfer step.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for producing a resin molded product with a hard coat layer formed by transferring a hard coat layer to the surface of a resin substrate by thermal transfer.

  A resin molded product in which a hard coat layer for imparting scratch resistance is formed on the surface of a resin substrate is widely used. Such a resin-molded product with a hard coat layer is required to have weather resistance and transparency in addition to scratch resistance when used for, for example, a vehicle window.

  Such a resin molded product with a hard coat layer is a laminate using a transfer film for three-dimensional molding in which a hard coat layer, a primer layer, and an adhesive layer are laminated in this order on a resin substrate, A hard coat layer laminate is disclosed in which a coat layer is formed of a cured product of an ionizing radiation curable resin composition containing a polycarbonate (meth) acrylate and an isocyanate compound (see Patent Document 1).

Japanese Patent Laying-Open No. 2015-193248

  By the way, when using the hard coat layer laminate as described above as a vehicle window, in addition to scratch resistance, weather resistance, and transparency, extremely high combustion resistance is required. In particular, for railway vehicle windows, the Japan Railway Vehicle Machinery Technology Association has strict standards for combustion resistance. However, the hard coat layer has lower combustion resistance than the resin base, the adhesive layer, and the primer layer, and the laminate described in Patent Document 1 has room for improvement in terms of combustion resistance.

  In order to improve the combustion resistance, it is conceivable to add a flame retardant to the material constituting the hard coat layer. However, when a large amount of a flame retardant is added to the hard coat layer, there is a concern that the hard coat layer has poor scratch resistance.

  Further, when the hard coat layer is transferred onto the resin substrate by thermal transfer, the resin substrate is softened by heat. Since the temperature applied to the hard coat film for transfer by thermal transfer exceeds the glass transition temperature of the adhesive layer and the primer layer, the adhesive layer and the primer layer can follow the resin substrate softened by heat. On the other hand, since the hard coat layer is not as flexible as the adhesive layer and the primer layer, if the resin substrate is softened by heat, the hard coat layer cannot follow the resin substrate softened by heat, and the resin substrate There is a possibility of peeling from. In addition, it has been found by the inventors' research that even such slight separation causes a decrease in combustion resistance.

  The present invention has been made in view of the above situation, and the object thereof is a hard coat layer laminate excellent in all of scratch resistance, weather resistance, transparency, and flame resistance, that is, with a hard coat layer. It is to provide a resin molded product.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have conducted heat transfer of a transfer hard coat film to a resin substrate in the production of a hard coat layer laminate, and then transferred the transfer hard coat film to the resin substrate. The present invention has been developed by finding that the above-mentioned problems can be solved by further hot-pressing the laminate in a state where the selenium has been transferred under predetermined conditions. More specifically, the present invention provides the following.

  (1) A method for producing a hard coat layer laminate in which a transfer hard coat film is laminated on the surface of a resin substrate made of a thermoplastic amorphous resin, wherein the transfer hard coat film is cured. A multilayer film comprising a transfer layer in which a primer layer and an adhesive layer are arranged in this order on the surface of a hard coat layer made of a cured product of a functional resin composition, wherein the transfer film is applied to the surface of the resin substrate. A transfer step of transferring the transfer layer to the surface of the resin substrate by thermocompression bonding with the adhesive layer of the hard coat film facing, and after the transfer step, the transfer layer is laminated on the resin substrate. The post-transfer laminate is heated and pressed at a heating temperature at which the resin substrate exceeds the glass transition temperature of the resin substrate and less than the melting temperature of the resin substrate. Method for producing a hard coat layer laminated body that performs the scan step.

  (2) The resin substrate is polycarbonate, and in the post-transfer laminate repressing step, the post-transfer laminate is heated at a heating temperature at which the temperature of the resin substrate is 160 ° C. or higher and 190 ° C. or lower ( The manufacturing method of the hard-coat layer laminated body as described in 1).

  (3) The hard coat layer is a layer made of a cured product of a curable resin composition containing a curable resin and a flame retardant, and the content of the flame retardant in the cured product is 30 mass. % Of the hard coat layer laminate according to (1) or (2).

  (4) The manufacturing method of the hard-coat layer laminated body as described in (1) or (2) whose said hard-coat layer is a resin layer which consists of hardened | cured material of a curable resin composition, and does not contain a flame retardant.

  (5) From the above (1) to (4), the hard coat layer laminate is classified as non-combustible or extremely incombustible, based on the combustion standard for railway vehicle materials specified by the Japan Railway Vehicle Machinery Association. ). The manufacturing method of the hard-coat layer laminated body in any one of.

  According to the present invention, a hard coat layer laminate excellent in all of scratch resistance, weather resistance, transparency and combustion resistance, that is, a resin molded product with a hard coat layer can be produced.

It is a cross-sectional schematic diagram showing the layer structure about an example of the hard-coat film for transfer used for the manufacturing method of the hard-coat layer laminated body of this invention. It is one Embodiment of the hard-coat layer laminated body which can be manufactured with the manufacturing method of the hard-coat layer laminated body of this invention, Comprising: (a) The form of the state before peeling a base film, and (b) It is a cross-sectional schematic diagram showing the form of the state which peeled the base film, respectively. It is a schematic diagram which shows the combustion test method of the material for railway vehicles which Japan Association of Railway Vehicle Machine Technology establishes.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. The present invention can be implemented with appropriate modifications within the scope of the object.

<Hard coat layer laminate>
A hard coat layer laminate 1 that can be produced by the method for producing a hard coat layer laminate of the present invention is a laminate portion including a hard coat layer 12 in a transfer hard coat film 10 as shown in FIG. A transfer layer 15 (see FIG. 1) is a laminate in which the transfer substrate 15 is laminated on the resin substrate 20. The transfer layer 15 is a laminate in which the primer layer 13 and the adhesive layer 14 are laminated in this order on the hard coat layer 12. In addition, the transfer layer in the present specification refers to a laminate portion including all layers from a hard coat layer to an adhesive layer serving as an adhesive surface with a resin substrate in a transfer hard coat film including a hard coat layer. Means. It is not necessarily limited to the structure consisting of only the hard coat layer 12, the primer layer 13, and the adhesive layer 14 shown in FIG.

  The hard coat layer 12 is a layer made of a cured product of the curable resin composition. By laminating the hard coat layer 12 on the resin substrate 20, the hard coat layer laminate 1 can be provided with excellent scratch resistance. The “lamination on the resin substrate” means that the portion of the transfer hard coat film 10 including the hard coat layer 12 is directly laminated on the resin substrate 20 as well as via a printing layer or the like. The thing of the form laminated | stacked indirectly is also included. Further, the lamination of the hard coat layer is not limited to the form performed on one surface of the resin substrate 20, and the hard coat layer may be laminated on both surfaces of the resin substrate. By setting it as the hard-coat layer laminated body of such a layer structure, favorable scratch resistance can be provided to both surfaces of the resin base | substrate 20. FIG.

  As shown in FIG. 1, the transfer hard coat film 10 is a multilayer film in which a transfer layer 15 and, if necessary, a base film 11 are laminated on a hard coat layer 12. The hard coat layer laminate 1 uses this transfer hard coat film 10 to press the transfer layer 15 to the resin substrate 20 via the primer layer 13 and the adhesive layer 14, and at least a portion including the transfer layer 15 is made of resin. It can obtain by peeling on the transfer layer 15 in the arbitrary steps in a use process about the base film 11, after transferring on the base | substrate 20 (refer FIG. 2). The details of the transfer hard coat film 10 and the details of the method for producing a hard coat layer laminate using the same will be described later.

[Resin substrate]
The thermoplastic resin used for the resin substrate 20 constituting the hard coat layer laminate 1 is an organic glass made of an amorphous resin having excellent transparency, and from the viewpoint of heat resistance, the glass transition temperature Tg exceeds 80 ° C., and As long as the melting point exceeds 150 ° C., the glass transition temperature Tg exceeds 120 ° C., and the melting point preferably exceeds 200 ° C. Specific examples of preferable resins include acrylic resins such as polycarbonate resin and ABS resin as the resin constituting the resin base 20 that requires heat resistance and transparency. Among these, a polycarbonate resin excellent in transparency and impact resistance is particularly preferable as the resin constituting the resin substrate 20. The resin substrate 20 can be obtained by performing extrusion molding or injection molding using the resin as a material. The polycarbonate resin has a glass transition temperature Tg of about 150 ° C. and a melting point of about 250 ° C., and the ABS resin has a glass transition temperature Tg of about 100 ° C. and a melting point of about 160 ° C.

  The thickness of the resin substrate 20 is usually preferably 1 mm or more and 20 mm or less, and more preferably 2 mm or more and 10 mm or less. If the resin base 20 is too thin, practical strength such as surface rigidity becomes insufficient, and if the resin base 20 is too thick, the processability of the resin base 20 is affected. The shape of the resin substrate 20 may be appropriately selected according to the use of the organic glass, and is not limited to a plate shape.

[Hard coat film for transfer]
The transfer hard coat film 10 is a multilayer film in which the transfer layer 15 is laminated on the base film 11 as described above. The transfer layer 15 in which the hard coat layer 12, the primer layer 13, and the adhesive layer 14 are laminated in this order is a mode in which the surface on the hard coat layer 12 side faces the surface of the base film 11. Are stacked. The transfer hard coat film 10 may be laminated with other layers in addition to the base film 11 and the transfer layer 15 as long as the effects of the present invention are not hindered. Examples of the other layers include an example in which a release layer or a colored layer (decorative layer) is disposed in the intermediate layer portion between the base film 11 and the hard coat layer 12.

(Base film)
The base film 11 constituting the transfer hard coat film 10 is preferably composed of a polyester resin film or a polyolefin resin film. Moreover, it is more preferable that it is a stretched film among the said films. By constituting the base film 11 with these stretched films, shrinkage caused by heat treatment or cross-linking treatment by irradiation of ionizing radiation when producing the transfer hard coat film 10 is suppressed, and the transfer hard coat The stability of the shape and dimensions of the film 10 and the hard coat layer laminate 1 can be enhanced.

  Preferred examples of the polyester resin film include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyarylate, polycarbonate, and ethylene terephthalate-isophthalate copolymer. Can be listed. Among these, PET and PBT are preferable, and PET is particularly preferable in consideration of heat shrinkage at the time of manufacturing the transfer hard coat film 10 and shrinkage due to irradiation of ionizing radiation.

  As the polyolefin resin film, in consideration of heat shrinkage at the time of producing the transfer hard coat film 10 and shrinkage due to irradiation of ionizing radiation, for example, polyethylene resin, polypropylene resin, polybutene resin, ethylene-propylene Preferred is a stretched resin film made of a polyolefin resin such as a copolymer resin, an ethylene-propylene-butene copolymer resin, and an olefin thermoplastic elastomer. Among these, a stretched polypropylene resin film is preferable.

  The stretched polyolefin resin may be either uniaxially stretched or biaxially stretched, but in consideration of the fact that heat shrinkage during production of a transfer hard coat film and shrinkage due to irradiation of ionizing radiation are less likely to occur. Biaxially stretched is preferable. The biaxially stretched polyolefin resin sheet is usually heated to a glass transition temperature (Tg) or higher by using a longitudinal stretching machine, and preferably stretched by about 5 to 30 times, and then using a widthwise stretching machine. And heated to a glass transition temperature (Tg) or higher and stretched in the width direction, preferably 5 to 30 times. Moreover, when the draw ratio is within the above range, thermal shrinkage during production of the transfer hard coat film 10 and shrinkage due to irradiation with ionizing radiation are less likely to occur.

  Although the thickness of the base film 11 is not specifically limited, What is necessary is just 4 micrometers or more and 200 micrometers or less. If it is 4 μm or more, curls and wrinkles are difficult to enter, and if it is 200 μm or less, the cost can be kept low, the heat conduction efficiency does not decrease, and each layer is taken when the base film 11 is peeled after transfer. Therefore, excellent transferability can be obtained. The base film 11 may have a multilayer structure. In that case, it is preferable that it exists in the range of the said thickness with the whole multilayer structure.

  In addition, in order to ensure the mold release property between the base film 11 and the hard coat layer 12 at the time of transfer, a known mold release treatment is performed on the surface of the base film 11 as necessary, or A release layer such as a silicone resin may be provided. On the contrary, in order to improve the adhesion with the hard coat layer 12, corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment, and easy adhesion coating agent are added as necessary. A surface treatment such as coating may be performed.

(Hard coat layer)
The hard coat layer 12 is a layer made of a cured product of the curable resin composition, and is a layer that imparts scratch resistance to the resin substrate 20. The curable resin composition is mainly composed of a curable resin, and if necessary, the content of the flame retardant in the cured product, that is, a mass ratio of 35% by mass or less in the resin solid content of the curable resin composition. Contains flame retardant in proportions. The content of the flame retardant is preferably 10% by mass or more and 30% by mass or less in the mass ratio. When the content of the flame retardant exceeds 35% by mass of the curable resin, the scratch resistance is lowered, which is not preferable.

  On the other hand, according to the production method of the present invention, even if the content of the flame retardant in the cured product constituting the hard coat layer 12 is 0% by mass (even if it does not contain the flame retardant), the Japan Railway Vehicle It is possible to obtain a non-combustible determination in the classification determination based on the combustion standard for railway vehicle materials established by the Japan Society for Mechanical Technology. According to the fact that the addition of the flame retardant becomes unnecessary, it can be first desired to improve the economy by reducing the material cost and simplifying the manufacturing process. Furthermore, for example, when the hard coat layer 12 is made of a cured product obtained by crosslinking treatment, such as a cured product of an ionizing radiation curable resin, there is a risk that the addition of a flame retardant reduces the crosslinking density of the hard coat layer 12. is there. Even if a flame retardant is not added, if sufficient nonflammability can be ensured, the risk of lowering the high mechanical strength and long-term weather resistance due to such a decrease in the crosslinking density can be avoided. Such a “hard flame retardant-free” hard coat layer 12 exhibits a particularly advantageous effect in applications that require special long-term weather resistance, for example.

  In addition, the curable resin composition forming the hard coat layer 12 has a weathering agent, scratch resistant particles, a non-reactive silicone compound, and other lubricants as necessary to improve the weather resistance and scratch resistance of the hard coat layer laminate 1. It may be included within a range that does not impair.

  The hard coat layer 12 is preferably a layer made of a cured material such as a polyester resin, an epoxy resin, a polyurethane resin, an amino alkyd resin, a melamine resin, a guanamine resin, a urea resin, a thermosetting acrylic resin, or an ionizing radiation curable resin. Can be mentioned. Moreover, it is preferable that the hard-coat layer 12 is a layer which consists of hardened | cured material of ionizing-radiation-hardening resin from a weather resistance or a scratch resistant viewpoint.

  An ionizing radiation curable resin is a curable resin that cures when irradiated with ionizing radiation. As ionizing radiation, electromagnetic waves or charged particle beams having an energy quantum capable of polymerizing or crosslinking molecules, for example, ultraviolet rays (UV) or electron beams (EB) are used, and X-rays, γ-rays, etc. Charged particle beams such as electromagnetic waves, α rays and ion beams are also used.

  The ionizing radiation curable resin that can be used for the hard coat layer 12 is appropriately selected from polymerizable oligomers (prepolymers) and polymerizable polymers conventionally used as resins having ionizing radiation curable properties. It can be used. From the viewpoint of obtaining good curing characteristics, it is difficult to bleed out, and has a coating property even if it is about 95% or more and 100% or less as a solid content standard, and cure shrinkage when cured to form the hard coat layer 12 Those that do not easily occur are preferred.

  As the polymerizable oligomer, an oligomer having a radically polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate type, urethane (meth) acrylate type, polyether type urethane (meth) acrylate, and caprolactone type urethane (meth) Preferred examples include acrylate, polyester (meth) acrylate and polyether (meth) acrylate oligomers, and urethane (meth) acrylate is more preferred. The (meth) acrylate means acrylate or methacrylate.

  Among these oligomers, polyfunctional polymerizable oligomers are preferred, and the number of functional groups is preferably 2 or more and 15 or less from the viewpoint of imparting scratch resistance due to high crosslink density, and 2 or less and 8 or less from the viewpoint that curing shrinkage hardly occurs. More preferably, it is 2 or more and 6 or less. Examples of the monofunctional polymerizable oligomer include caprolactone urethane (meth) acrylate obtained by reaction of caprolactone polyol, organic isocyanate and hydroxy (meth) acrylate, and (meth) acrylate on the side chain of polybutadiene oligomer. Examples thereof include high molecular urethane (meth) acrylates such as polybutadiene (meth) acrylate having high hydrophobicity having a group.

  Examples of the polymerizable polymer include polymers having radically polymerizable unsaturated groups in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, polyether urethane (meth) acrylate, and polycaprolactone urethane (meta ) Acrylate, polyester (meth) acrylate-based, polyether (meth) acrylate-based polymers, and the like are preferable, and polycaprolactone-based urethane (meth) acrylate or urethane (meth) acrylate-based is more preferable. The (meth) acrylate means acrylate or methacrylate. These polymers may be used alone or in combination.

  The weight average molecular weight (Mw) of the resin contained in the hard coat layer 12 varies depending on the type and cannot be defined uniformly, but is, for example, 200 to 100,000, preferably 500 to 50,000, Preferably 1,000-30,000 are mentioned. If the weight average molecular weight (Mw) is too small, the hardness of the hard coat layer 12 may be insufficient, so that sufficient scratch resistance and solvent resistance may not be obtained. On the other hand, if the weight average molecular weight (Mw) is excessive, depending on the type, the crosslinking density cannot be sufficiently increased, and the hardness of the hard coat layer 12 is insufficient, and the viscosity of the ink before curing is low. There is a possibility that the coating suitability will be lowered. If the weight average molecular weight (Mw) is too small or too large, sufficient flame resistance cannot be obtained even if the content of the flame retardant contained in the hard coat layer 12 is appropriate. This is presumably because the flame retardant bleeds out or is unevenly distributed in the layer. The weight average molecular weight of the resin in the present specification is a value measured by GPC method and converted to standard polystyrene.

  When a flame retardant is contained in the curable resin composition, the type thereof is not particularly limited. Examples of the flame retardant include halogen compounds, phosphorus compounds, inorganic hydroxides, and silicone compounds.

  The halogen-based compound has a radical trap effect, and has a function of stabilizing the active radical of the thermal decomposition product (gas phase) of the cured product of the curable resin composition and blocking the reaction with oxygen. Examples of halogen compounds include chlorine compounds and bromine compounds. Examples of the chlorine compound include ammonium chloride and dechlorane. Examples of the bromine-based compound include tetrabromobisphenol A, hexabromocyclododecane, pentabromodiphenyl ether, tetrabromoethane, ammonium bromide and the like.

  The phosphorus compound has a radical trap effect by phosphoric acid and a function of forming a barrier layer on the surface of the hard coat layer 12 by dehydration and carbonization. Thereby, while a barrier layer functions as a heat insulation layer, while suppressing the thermal decomposition of hardened | cured material, it can prevent that the thermal decomposition product of the hardened | cured material of a curable resin composition diffuses out of the layer of the hard-coat layer 12. . Examples of phosphorus compounds include diammonium hydrogen phosphate, phosphate esters, ammonium dihydrogen phosphate, sodium metaphosphate, and guanidine phosphate.

  The inorganic hydroxide has a function of preventing thermal decomposition of the cured product of the curable resin composition by an endothermic reaction. When heat is applied to the inorganic hydroxide, the inorganic hydroxide is dehydrated and decomposed, accompanied by a large endotherm. Therefore, it can suppress that a heat | fever is added to the hardened | cured material of curable resin composition, As a result, the thermal decomposition of the hardened | cured material of curable resin composition can be prevented. Examples of inorganic hydroxides include aluminum hydroxide and magnesium hydroxide.

  The silicone-based compound has a function of forming a silicon-based surface barrier layer on the surface of the hard coat layer 12. Thereby, while a barrier layer functions as a heat insulation layer, while suppressing the thermal decomposition of hardened | cured material, it can prevent that the thermal decomposition product of the hardened | cured material of a curable resin composition diffuses out of the layer of the hard-coat layer 12. .

  Among them, the halogen-based phosphate ester has a flame-retardant function of both the halogen-based compound and the phosphorus-based compound, and thus tends to have a high flame-retardant effect per the same addition amount. The location where the flame retardant is added to the hard coat layer 12 is not particularly limited, and the amount of the flame retardant added is also relatively small, so that the physical properties of the cured layer are reduced due to the addition of the flame retardant and the environment caused by the volatile products of the flame retardant. From the viewpoint of suppressing the load, the flame retardant is preferably a halogen phosphate.

  Examples of halogen phosphates include tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, 2,2-bis (chloromethyl) -1 , 3-propanebis (chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (tribromoneopentyl) phosphate, 2,2-bis (chloromethyl) trimethylenebis (bis (2-chloroethyl) phosphate ), Polyoxyalkylene bisdichloroalkyl phosphate and the like.

  Further, the curable resin composition forming the hard coat layer 12 may contain scratch-resistant particles. Scratch-resistant particles include inorganic and organic particles. Examples of inorganic particles include particles of alumina, silica, kaolinite, iron oxide, diamond, silicon carbide, and the like. Examples of the shape of the inorganic particles include a spherical shape, an ellipsoid shape, a polyhedron shape, a scale shape, and the like. Although there is no particular limitation, the hardness of the hard coat layer 12 becomes higher and excellent scratch resistance can be obtained. Spherical shape is preferred. The particle diameter of the scratch-resistant particles is not particularly limited, but is preferably 0.1 μm or more and 4 μm or less, more preferably 0.5 μm or more and 3 μm or less from the viewpoint of the hardness and smoothness of the hard coat layer 12. . The average particle diameter of the particles is a volume average particle diameter. The volume average particle size can be measured by laser diffraction type or laser scattering type particle size distribution measurement.

  The thickness of the hard coat layer 12 is not particularly limited, but is preferably about 1 μm or more and 20 μm or less. From the viewpoint of obtaining excellent weather resistance and durability, and further transparency, it is more preferably 2 μm or more and 20 μm or less, further preferably 2 μm or more and 10 μm or less, and most preferably 2 μm or more and 6 μm or less. In addition, by making the thickness of the hard coat layer 12 thinner, the occurrence of curing shrinkage can be reduced, and the production stability and production efficiency can be improved, so that the thickness is particularly 2 μm or more and 4 μm or less. Is preferred.

(Primer layer)
The primer layer 13 is composed of a resin composition for forming a primer layer containing a binder resin and an antiblocking agent, and functions as a stress relaxation layer for the hard coat layer 12 and improves the adhesion of the hard coat layer 12. Is a layer.

  The binder resin constituting the primer layer 13 preferably contains a two-component curable resin composed of a main agent and a curing agent.

  The main component of the binder resin constituting the primer layer 13 is not particularly limited, and examples thereof include polyurethane resin, (meth) acrylic resin, vinyl chloride / vinyl acetate copolymer, polyester resin, petital resin, chlorinated polypropylene, and chlorinated polyethylene. Etc. These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type. Among these binder resins, polyurethane resins are preferable from the viewpoints of adhesion and weather resistance.

  The polyurethane resin is more preferably a polyurethane resin having an acrylic skeleton in the polymer chain of the polyurethane resin from the viewpoint of weather resistance and durability. Examples of the polyurethane resin having an acrylic skeleton in the polymer chain include, for example, a urethane acrylic copolymer which is a copolymer of a urethane component and an acrylic component, a hydroxyl group or an isocyanate group as a polyol component or a polyisocyanate component constituting the polyurethane. Among them, urethane acrylic copolymers are preferable. Urethane acrylic copolymers are, for example, a method in which a polyol compound and an isocyanate compound are reacted with an acrylic resin having at least two hydroxyl groups in one molecule (see JP-A-6-1000065, etc.), It can be obtained by a method in which an acrylic monomer is reacted with a urethane prepolymer having bonds at both ends (see JP-A-10-1524).

  Among the polyurethane resins having an acrylic skeleton in the polymer chain, those having a polycarbonate skeleton or a polyester skeleton in the polymer chain are preferable from the viewpoint of adhesion to the hard coat layer. Polyurethane having an acrylic skeleton in the polymer chain, and further having a polycarbonate skeleton or a polyester skeleton, a polycarbonate urethane acryl copolymer, which is a copolymer of a polycarbonate urethane component and an acrylic component, or a polyester urethane component A polyester urethane acrylic copolymer, which is a copolymer of an acrylic component, is more preferred, and a polycarbonate urethane acrylic copolymer is particularly preferred from the viewpoint of providing even better weather resistance. These polyurethanes may be used alone or in combination of two or more.

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

Specific examples of the diisocyanate include aliphatic isocyanates such as hexamethylene diisocyanate; and alicyclic isocyanates such as isophorone diisocyanate and hydrogen-converted xylylene diisocyanate. Further, as the carbonate diol, specifically, a compound represented by the following general formula (1) (wherein R ¹ may be the same or different and may have a substituent having 1 to 12 carbon atoms). The following alkylene groups, divalent heterocyclic groups having 1 to 12 carbon atoms that may have a substituent, or divalent fats having 1 to 12 carbon atoms that may have a substituent A cyclic group, and m ₁ is an integer of 1 or more and 10 or less.
HO— [R ¹ —O— (C═O) —O] m ₁ —R ¹ —OH (1)

  The polycarbonate urethane acrylic copolymer can also be obtained by radical polymerization of a polycarbonate polyurethane prepolymer having a radical polymerizing group introduced therein with an acrylic monomer. Specific examples of the acrylic monomer include (meth) acrylic acid and alkyl (meth) acrylic esters having an alkyl group with 1 to 6 carbon atoms.

The polyester urethane acrylic copolymer can be obtained, for example, by copolymerizing a polyester urethane obtained by reacting an ester diol and a diisocyanate with a diol having an acrylic skeleton. Alternatively, it can also be obtained by reacting an ester diol and a diisocyanate with a diol having an acrylic skeleton. Here, the diol and diisocyanate having an acrylic skeleton are the same as those used in the production of the polycarbonate urethane acrylic copolymer. In addition, as the ester diol, specifically, a compound represented by the following general formula (2) (wherein R ² is the same or different and may have a substituent having 1 to 12 carbon atoms) An alkylene group, a divalent heterocyclic group having 1 to 12 carbon atoms that may have a substituent, or a divalent alicyclic group having 1 to 12 carbon atoms that may have a substituent. And m ₂ is an integer of 1 or more and 10 or less.
_{^{HO- [R 2 -O- (C =}} O)] m 2 -R 2 -OH (2)

  The polyester-based urethane acrylic copolymer can also be obtained by radical polymerization of a polyester-based polyurethane prepolymer into which a radical-polymerizing group is introduced with an acrylic monomer. The acrylic monomer is the same as that used for the production of the polycarbonate urethane acrylic copolymer.

  The polyurethane used for the primer layer preferably has an acrylic component content of 1 to 30% by mass in order to provide excellent weather resistance. Here, the content of the acrylic component in the polyurethane is a ratio (mass%) occupied by monomers constituting the acrylic skeleton per the total mass of the polyurethane. From the viewpoint of providing even better weather resistance, the content of the acrylic component in the polyurethane is preferably 5% by mass or more and 20% by mass or less. The acrylic component content in the polyurethane is calculated by measuring the NMR spectrum of the polyurethane and determining the ratio of the peak area attributed to the acrylic component to the total peak area.

  In the primer layer, when the polyurethane and other binder resin are used in combination, the mixing ratio is not particularly limited. For example, the polyurethane is 50 parts by mass or more per 100 parts by mass of the binder resin. What is necessary is just to set so that it may become 70 mass parts or more preferably, More preferably, it will be 85 mass parts or more.

  From the viewpoint of accelerating the curing of the main agent, there may be mentioned isocyanate curing agents such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, cyclohexanephenylene diisocyanate, 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 more preferably 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. Further preferred.

  The primer layer 13 may contain various additives other than those described above as long as the effects of the present invention are not impaired. Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, infrared absorbers, light stabilizers, antistatic agents, adhesion improvers, leveling agents, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a colorant. These additives can be appropriately selected from those commonly used.

  The thickness of the primer layer 13 relating to the present embodiment is not particularly limited, and examples thereof include 0.1 μm to 10 μm, preferably 0.1 μm to 5 μm, and more preferably 1 μm to 4 μm.

(Adhesive layer)
The adhesive layer 14 relating to the present embodiment is a layer provided for adhering the hard coat layer 12 to the resin substrate 20, and has a function of adhering such a hard coat layer 12 to the resin substrate 20. In addition, when the primer layer 13 contains particles and protrudes to the surface of the primer layer 13, so-called cueing occurs, the surface flatness is improved, the decrease in transparency is suppressed, and excellent It also has a function of ensuring optical performance.

  The adhesive resin that can be used for the adhesive layer 14 is determined according to the material of the resin substrate 20 and the transfer temperature and pressure at the time of transfer. Generally, acrylic resin, vinyl chloride-vinyl acetate copolymer are used. , Polyamide resin, polyester resin, chlorinated polypropylene, chlorinated rubber, urethane resin, epoxy resin, styrenic resin and the like are preferable, and depending on the material of the resin substrate 20 and the use of the transfer product, 1 type or 2 or more types of resin is selected from. From the standpoint of a small difference in refractive index from the particles contained in the primer layer 13, excellent transparency, and improvement in transparency and weather resistance, it is particularly preferable to use an acrylic resin alone as the above heat-sealing resin.

  The thickness of the adhesive layer 14 is preferably thicker than the primer layer 13, but the function of adhering the transfer layer including the hard coat layer 12 to the resin substrate 20 and the viewpoint of ensuring excellent transparency. Therefore, it is preferably 1 μm or more and 7 μm or less, and more preferably 1 μm or more and 6 μm or less.

  In addition, the transfer hard coat film 10 of the present embodiment can be protected by attaching a cover film (protective film) made of a resin such as polyethylene resin on the adhesive layer 14. In the case of providing a cover film, the transfer hard coat film 10 of the present embodiment is peeled off to expose the adhesive layer 14 and transferred to the resin substrate 20 through the surface of the adhesive layer 14.

(Colored layer)
In order to improve the design of the hard coat layer laminate 1, a colored layer (decorative layer) may be further provided on a part or the entire surface of the transfer hard coat film as necessary. Although the pattern of the colored layer is arbitrary, for example, a pattern or a pattern made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, character or the like can be provided.

  The colored layer is laminated, for example, between the primer layer and the adhesive layer, but is not limited thereto, and may be formed on the adhesive layer in the case of an adhesive material. The colored layer can be formed by, for example, using a primer such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, or a cellulose resin as a binder, and a pigment or dye of an appropriate color. Can be formed by printing with a printing ink containing a colorant. Examples of the printing method include known printing methods such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and ink jet printing. The thickness of the colored layer is preferably 5 μm or more and 40 μm or less, and more preferably 5 μm or more and 30 μm or less from the viewpoint of design.

<Method for producing hard coat film for transfer>
The transfer hard coat film 10 according to this embodiment can be manufactured by a transfer hard coat film manufacturing method in which the following steps (a) to (d) are sequentially performed.
(A) The process of forming the hard-coat layer 12 on the base film 11 (b) The process of forming the primer layer 13 on the hard-coat layer 12 using the composition for primer layer formation (c) On the primer layer 13 The process of forming the contact bonding layer 14 using the composition for contact bonding layer formation (d) The process of hardening a primer layer

[(A) Step of forming a hard coat layer on a substrate film]
As a method for forming a transfer layer including the hard coat layer 12 on the base film 11, the resin composition for forming the hard coat layer is usually gravure coated so that the thickness after curing is usually about 1 μm to 20 μm. There are methods such as bar coating, roll coating, reverse roll coating, comma coating, etc., preferably by gravure coating and curing. In the case where the resin composition contains a solvent, it is preferable that after coating, the coating layer is preliminarily heated and dried with a hot air dryer or the like, and then further subjected to heat treatment or ionizing radiation.

  Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer. Usually, the acceleration voltage is not lower than 70 kV and not higher than 300 kV and the irradiation dose is not lower than 5 Mrad and not higher than 10 Mrad. It is preferable to cure the cured resin layer.

[(B) Step of forming primer layer using primer layer forming composition]
Next, the primer layer 13 is formed using the primer layer forming composition on the hard coat layer 12. The primer layer 13 can be formed by a coating method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, or a transfer coating method. Here, the transfer coating method is a method in which a coating film of the primer layer 13 is formed on a thin sheet (film substrate) and then the surface of the hard coat layer 12 is coated. The gravure coating is preferable.

  Further, when forming the primer layer 13 according to the present embodiment, in order to improve the adhesion between the hard coat layer 12 and the primer layer 13, the hardening of the hard coat layer 12 is left in a semi-cured state, and thereafter The adhesion between the hard coat layer 12 and the primer layer 13 can be enhanced by completely curing the hard coat layer 12 after applying the resin composition for forming the primer layer 13.

The primer layer 13 may dry the cured product surface within a range where the uncured state can be maintained. Here, the uncured state is a state in which an unreacted curing agent remains in the primer layer, and the higher the residual rate, the more preferable from the viewpoint of preventing the transparency of the primer layer 13 from being lowered. A state in which the peak intensity of the infrared spectrum 2260 cm ⁻¹ corresponding to the isocyanate part of the curing agent is 50% or more based on the peak intensity immediately after application of the primer layer is preferable.

[(C) Step of forming an adhesive layer using the adhesive layer forming composition]
Next, the adhesive layer 14 is formed on the primer layer 13 using the adhesive layer forming composition. The method for forming the adhesive layer 14 can be the same method as in the above (b), and is not particularly limited.

[(D) Step of curing primer layer]
Although this step is optional, the primer layer 13 may be cured as necessary. Curing here is a step in which the curing agent remaining in the primer layer 13 is completely reacted with the main agent. Specifically, the curing reaction may be promoted by a conventionally known method. Typically, the curing reaction is performed at a temperature of 40 ° C. or more and 60 ° C. or less for 24 hours or more and 72 hours or less, depending on the type of the curing agent. Good.

  The hard coat layer laminate 1 is formed by disposing the transfer hard coat film 10 on the surface of the resin substrate 20 so that the adhesive layer 14 faces the substrate, and heat-pressing with a nip roll or the like (thermal transfer method). A hard coat layer laminate with a material film can be produced.

<Method for producing hard coat layer laminate>
The method for producing a hard coat layer laminate of the present invention includes, for example, the following (A) using the transfer hard coat film 10 and the resin substrate 20 that can be obtained by the transfer hard coat film production method described above. And it is a manufacturing method of the hard-coat layer laminated body which can manufacture the hard-coat layer laminated body 1 which is extremely excellent in combustion resistance by performing the process of (B) in order. The manufacturing method of the present invention is a method of heating at a temperature such that the temperature of the resin substrate 20 reaches a predetermined temperature in each step (A) and (B). The surface temperature of the resin substrate 20 in each step is measured with a non-contact type thermometer such as an infrared radiation thermometer, and this temperature information is fed back to the heating means.
(A) Transfer process (B) Post-transfer laminate re-press process

[(A) Transfer process]
The transfer layer 15 is transferred by heat-pressing the transfer hard coat film 10 (see FIG. 1) on which the base film 11 is laminated to the surface of the resin substrate 20 with a transfer roll such as a nip roll. This thermocompression bonding is performed with the adhesive layer 14 of the transfer hard coat film 10 facing the surface of the resin substrate 20 (see FIG. 2). The heating temperature for this transfer needs to be a heating temperature at which the temperature of the resin substrate 20 is equal to or higher than the glass transition temperature Tg of the resin substrate. Therefore, the temperature of the transfer roll needs to be preheated to an appropriate temperature equal to or higher than the glass transition temperature Tg of the resin substrate 20.

  Prior to the above-described thermocompression bonding, it is desirable to perform a preheating treatment in which the surface temperature of the resin substrate is preliminarily heated to a temperature close to the thermocompression bonding temperature with a heater or the like. For example, when the above-described thermocompression bonding is performed at 160 ° C., the preheating treatment is preferably a heat treatment such that the surface temperature of the resin substrate is about 150 ° C.

  The transfer hard coat film is not limited to the transfer hard coat film 10 described in detail above, and a primer layer and an adhesive layer are arranged in this order on the surface of the hard coat layer made of a curable resin. A multilayer film comprising a transfer layer can be widely used. As described above, the resin base is made of a non-crystalline resin having a predetermined thermophysical property and excellent transparency, such as a polycarbonate resin, which can be obtained by extrusion molding or injection molding. Can do.

[(B) Post-transfer laminate re-pressing step]
After performing the above transfer step (A), the post-transfer laminate in which the transfer layer 15 is laminated on the resin substrate 20 is transferred to the resin substrate 20 exceeding the glass transition temperature Tg of the resin substrate. A post-transfer laminated body re-pressing step is performed in which heating and pressing are performed at a heating temperature that is lower than the melting point temperature. Thereby, the fine peeling of the hard coat layer from the resin substrate softened by the heat that can occur in the transfer step can be prevented. For example, when the base resin of the resin substrate 20 is a polycarbonate resin, the microbubbles in the transfer layer grow at a stage where the temperature of the resin exceeds 100 ° C. due to reheating. This is because the fine bubbles are removed by pressurizing the resin in a softened state at a temperature in the vicinity of 0 ° C. Thereby, even if it uses a flame retardant at all, the hard-coat layer laminated body which is extremely excellent in flame resistance can be manufactured by using a small amount of flame retardant of the predetermined range.

  In addition, the glass transition temperature (Tg) of polycarbonate resin is about 150 degreeC, The melting | fusing point is about 250 degreeC. For example, when the base resin of the resin substrate 20 is a polycarbonate resin, the heating temperature in the post-transfer laminated body re-pressing step may be 150 ° C. or higher and lower than 250 ° C., but the effect of the present invention can be sufficiently exhibited. On the other hand, from the viewpoint of efficiently producing a hard coat layer laminate having high quality stability by avoiding the occurrence of defective deformation of the laminate due to excessive heating, the above heating temperature is 160 ° C. or higher and 190 ° C. or lower. Is preferred.

<Flammability standard>
The hard coat layer laminate has extremely high combustion resistance. Specifically, the flammability standard based on the classification determination based on the combustion standard of the railway vehicle material established by the Japan Railway Vehicle Machinery Technology Association is more than extremely flame retardant.

[Combustion test method]
FIG. 3 is a schematic diagram showing a combustion test method for railway vehicle materials defined by the Japan Railway Vehicle Machinery Technology Association.

  A B5-size sample material (182 mm x 257 mm) is held at an angle of 45 °, and the center of the bottom of the fuel container is 25.4 mm (1 inch) vertically below the center of the bottom surface (combustion surface) of the sample material. As shown, place it on a base of low thermal conductivity such as cork, put 0.5 cc of pure ethyl alcohol, ignite, and let it stand until the fuel is burned out (burning time about 90 seconds).

  Combustion judgment is divided into alcohol combustion and after combustion. During combustion, the specimen is observed for ignition, ignition, smoke generation, flame condition, etc. After combustion, afterflame, residual dust, Investigate carbonization and deformation state. The evaluation criteria are as shown in Table 1 below.

  In order to further confirm the combustion resistance, it is preferable to carry out an additional test in which the amount of pure ethyl alcohol is increased to 0.7 cc, the same test is performed, and the situation up to a combustion time of 120 seconds is observed.

  In the examples described below, as demonstrated, according to the hard coat layer laminate manufacturing method of the present invention, the classification determination based on the combustion standards for railcar materials set by the Japan Railway Vehicle Machinery Association is nonflammable. A hard coat layer laminate can be produced.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. it can.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

<Manufacture of transfer hard coat film>
The transfer hard coat film used for the production of the hard coat layer laminates of Examples and Comparative Examples was produced as follows.

(Formation of hard coat layer)
A film made of polyethylene terephthalate resin (PET) having a thickness of 50 μm (“E5101 (trade name)” manufactured by Toyobo Co., Ltd.) is used as a base film, and the following hard coat layer is formed on one surface of the base film. The curable resin composition is applied to form an uncured resin layer, and irradiated with an electron beam under the conditions of 90 kV and 7 Mrad (70 kGy) to crosslink and cure the uncured resin layer, thereby forming a hard coat layer ( Layer thickness: 3 μm).

A resin composition comprising the following curable resin (A), a flame retardant (B), and the following additives (C) to (F) is used as a curable resin for a hard coat film for transfer in Examples and Comparative Examples. Used as. The content of the flame retardant was adjusted so that the mass ratio in the solid content of the curable resin composition was the content ratio shown in Table 2. The addition amount of (C)-(F) was prepared so that it might become the following content ratio similarly in all the Examples and the comparative examples.
(A) Curable resin Hexafunctional ionizing radiation curable resin: 60 parts by mass of hexafunctional urethane acrylate (molecular weight of about 1,000) and 40 parts by mass of bifunctional lower prolactone-modified urethane acrylate (molecular weight of about several thousand) Mixture (B) Flame retardant Halogen phosphate flame retardant (Product name: CR-570, manufactured by Daihachi Chemical Co., Ltd.)
(C) Ultraviolet absorber Hydroxyphenyl triazine type ultraviolet absorber (product name: Tinuvin479, manufactured by BASF Japan Ltd.). In each Example and Comparative Example, 0.7 mass% is contained in a mass ratio in the solid content of the curable resin composition.
(D) Light stabilizer A light stabilizer having a reactive functional group (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, product name: Sanol LS-3410, manufactured by Nippon Emulsifier Co., Ltd.). In each Example and Comparative Example, 4.2 mass% is contained by mass ratio in the solid content of the curable resin composition.
(E) Silicone compound Non-reactive silicone compound (polyether-modified silicone oil). In each Example and Comparative Example, 0.3 mass% is contained by mass ratio in the solid content of the curable resin composition.
(F) Particles Scratch resistant filler (silica particles, average particle size: 2 μm). In each Example and Comparative Example, 0.8 mass% is contained by mass ratio in the solid content of the curable resin composition.

(Formation of primer layer)
Next, after applying a corona discharge treatment to the surface of the hard coat layer, a primer layer forming resin composition having the following composition is applied, and the surface is dried to the extent that it does not block, thereby providing a primer layer (thickness: 3 μm) Formed.
Polycarbonate urethane acrylic copolymer ^{* 1} : 100 parts by weight Hydroxyphenyltriazine type UV absorber ^{* 2} : 17 parts by weight Hydroxyphenyltriazine type UV absorber ^{* 3} : 13 parts by weight Hindered amine light stabilizer ^{* 4} : 8 parts by weight Anti-blocking agent ^{* 5} : 9 parts by mass Curing agent (hexane methylene diisocyanate): 25 parts by mass * 1, The mass ratio of the urethane component to the acrylic component in the polycarbonate urethane acrylic copolymer is 70/30.
* 2, Tinuvin 400 (trade name), 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, manufactured by BASF Japan Ltd. * 3, Tinuvin 479 (trade name), 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4 -Phenylphenyl) -1,3,5-triazine, manufactured by BASF Japan Ltd. * 4, Tinuvin 123 (trade name), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate Manufactured by BASF Japan Ltd. * 5, silica particles, average particle diameter: 3 μm

(Formation of adhesive layer)
Thereafter, an adhesive layer (thickness: 5 μm) is laminated on the primer layer using an acrylic resin (weight average molecular weight (Mw): 7.6 × 10 ⁴ ), thereby transferring the examples and comparative examples. A hard coat film was obtained.

<Manufacture of hard coat layer laminate>
Using the above-mentioned transfer hard coat film, a hard coat layer laminate according to each of Examples and Comparative Examples was produced by the following method.

(Preheating)
A polycarbonate plate having a thickness of 5 mm (glass transition temperature Tg: 150 ° C., melting point: 250 ° C.) was used as a resin substrate, and this was heated using a hot plate. In each example and comparative example, the heating temperature was set such that the resin substrate temperature at the time of transfer of the transfer hard coat film was the resin substrate temperature at the transfer step shown in Table 2, respectively.
(Transcription)
The transfer hard coat film described above was placed on one side of the heated resin substrate (polycarbonate plate) so that the adhesive layer was on the polycarbonate plate side, and then a transfer step was carried out by heat-pressing with a hot lami roll.
(Re-press)
Immediately after the transfer step, a post-transfer laminate re-pressing step was performed in which the laminate in which the transfer hard coat film was laminated on the resin substrate was heated and pressed again. In each example and comparative example, the heating temperature during the same step was set such that each resin substrate temperature during re-pressing was the resin substrate temperature during the post-transfer laminate re-pressing step shown in Table 2, respectively. . However, for the hard coat layer laminate of Comparative Example 1, the post-transfer laminate re-pressing step after the transfer step was not performed.

[Flame resistance]
About each hard-coat layer laminated body manufactured with each manufacturing method of an Example and a comparative example, the combustion resistance was evaluated according to the combustion test method of the material for rolling stock defined by Japan Railway Vehicle Machinery Technology Association (burning time) : About 90 seconds). “A” indicates that it is nonflammable, “B” indicates that it is ignited when 60 seconds or more and less than 90 seconds have elapsed since the start of the test (when it is extremely flame retardant), and less than 60 seconds after the start of the test. When ignited (when it is flame retardant), it was designated as “C”. The results are shown in Table 2. In Comparative Examples 5 and 6, since the resin substrate was deformed to a level that could not be recovered by re-pressing or the like during heating at 190 ° C., this test was not performed.

[Scratch resistance]
Using a Gakushin type wear tester, the surface of the hard coat layer is steel wool (product name: Bonstar # 0000 (trade name), manufactured by Nippon Steel Wool Co., Ltd.) with a load of 1000 g and 1000 round trips of Gakushin wear. A test was conducted. And the increase amount of the haze value (haze value) after the test with respect to the test before was measured. A case where the increase in haze (haze value) was less than 5% was defined as “A”. The case where the increase amount of the haze value (haze value) was 5% or more and less than 10% was designated as “B”, and the case where the increase amount of the haze value (haze value) was 10% or more was designated as “C”. The results are shown in Table 2.

  From Table 2, according to the production method of the present invention in which re-pressing is performed at a predetermined heating temperature after transfer, it is extremely excellent without using a flame retardant or by adding a flame retardant having a content of 30% by mass or less. It can be seen that a hard coat layer laminate having flame resistance and excellent scratch resistance can be obtained.

DESCRIPTION OF SYMBOLS 1 Hard coat layer laminated body 10 Hard coat film for transfer 11 Base film 12 Hard coat layer 13 Primer layer 14 Adhesive layer 15 Transfer layer 20 Resin substrate

Claims (5)

A method for producing a hard coat layer laminate, wherein the transfer hard coat film is laminated on the surface of a resin substrate made of a thermoplastic amorphous resin,
The transfer hard coat film is a multilayer film comprising a transfer layer in which a primer layer and an adhesive layer are arranged in this order on the surface of a hard coat layer made of a cured product of a curable resin composition,
A transfer step of transferring the transfer layer to the surface of the resin substrate by thermocompression bonding with the adhesive layer of the transfer hard coat film facing the surface of the resin substrate; and after the transfer step, the resin After the transfer, the post-transfer laminate in which the transfer layer is laminated on the base is heated and pressed at a heating temperature at which the resin base exceeds the glass transition temperature of the resin base and is lower than the melting temperature of the resin base. And a laminate re-pressing step.   2. The post-transfer laminate is heated at a heating temperature at which the temperature of the resin substrate is 160 ° C. or higher and 190 ° C. or lower in the post-transfer laminate re-pressing step. The manufacturing method of the hard-coat layer laminated body of description. The hard coat layer is a layer made of a cured product of a curable resin composition comprising a curable resin and a flame retardant,
The manufacturing method of the hard-coat layer laminated body of Claim 1 or 2 whose content of the said flame retardant in the said hardened | cured material is 30 mass% or less.   The method for producing a hard coat layer laminate according to claim 1, wherein the hard coat layer is a resin layer made of a cured product of a curable resin composition and containing no flame retardant.   The hard coat layer laminate according to any one of claims 1 to 4, wherein the classification determination based on a combustion standard for a railcar material specified by the Japan Railway Vehicle Machinery Association is nonflammable or extremely incombustible. The manufacturing method of the hard-coat layer laminated body of description.

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