JP2015038173A - Photocurable resin composition, laminate sheet, laminate molded article, and method for manufacturing laminate molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate sheet having excellent appearance, designing property, chemical resistance, wear resistance and weather resistance after cured and having good processability for molding in an uncured state and no surface tackiness, and to provide a laminate molded article using the laminate sheet.SOLUTION: A photocurable resin composition is provided, comprising a thermoplastic resin (A) having a radically polymerizable unsaturated group in a side chain, a (meth)acrylate (B) having 6 or more functional groups, and a photopolymerization initiator (C). The photocurable resin composition preferably further includes inorganic fine particles (D). The laminate sheet has a layer of the photocurable resin composition deposited to 2 to 20 μm thickness on a base sheet. The laminate molded article includes a cured laminate sheet laminated on a molded article, where the cured laminate sheet is the above laminate sheet having a cured layer of the photocurable resin composition and the cured layer is disposed to be an outermost surface.

Description

  The present invention relates to a photocurable resin composition, a laminated sheet, a laminated molded article, and a method for producing a laminated molded article. Specifically, a laminated sheet having excellent appearance after photo-curing, design properties, chemical resistance, abrasion resistance and weather resistance, good workability at the time of molding in an uncured state, and having no surface adhesion, The present invention relates to a laminated molded article using a laminated sheet, a method for producing the laminated molded article, and a photocurable resin composition that provides such performance.

  In the case of imparting designability to a plastic molded product or protecting the surface, conventionally, an ultraviolet curable paint or a thermosetting paint has been used. However, in the case of using a paint, a painting process, a drying process, and a curing process are necessary, and since the process becomes long and the yield of the paint is poor, a three-dimensional decorative film has been used recently. There have been many cases.

  For example, the following methods (1) to (3) are known as a method of decorating a molded product with a three-dimensional decorative film. (1) An in-mold transfer method in which a three-dimensional decorative film having a decorative layer is inserted into a mold, injection molding is performed, the film is peeled off, and only the decorative layer is left in the molded product, (2) tertiary The original decorative film is inserted into a mold for injection molding, injection molding is performed, the in-mold molding method and the insert mold molding method for bonding the entire film to the molded product, and (3) three-dimensional decoration having an adhesive layer A TOM molding method in which a film is placed on a molded product, vacuum-compressed after heating, and the entire film is bonded to the molded product. The laminated molded product obtained by these methods may be provided with a surface protective layer for the purpose of protecting the surface of the laminated molded product. As this surface protective layer, scratch resistance, abrasion resistance, chemical resistance From the viewpoints of the above, many coating films cured by active energy rays are used.

  In such a three-dimensional decorative film, in order to maintain the workability at the time of molding, a method has been proposed in which the surface protective layer is molded in an uncured state, bonded to a molded product, and then cured ( For example, see Patent Documents 1, 2, and 3.) The photocurable resin composition or the photocurable sheet described in Patent Documents 1 to 3 has good processability at the time of molding in an uncured state and has no surface tackiness, and has excellent appearance and design properties after photocuring. Since it has chemical resistance, abrasion resistance and weather resistance, it is suitably used for three-dimensional decorative film applications.

JP 2000-85065 A JP 11-314323 A JP 2002-79621 A JP 2001-205752 A

  However, for example, a plastic molded product having a design in which a slight scratch is likely to cause a defect in appearance, such as a piano black tone or a high brightness product with a plating tone, is not satisfactory in wear resistance. In order to solve these problems, a laminated sheet including a layer of colloidal silica-containing acrylic resin composition including colloidal silica has been proposed (Patent Document 4). In order to drastically improve the wear resistance, it is extremely effective to add colloidal silica, and the laminated sheet described in Patent Document 4 is suitably used for design applications that require wear resistance. Is done.

  However, when the wear resistance is improved by adding colloidal silica to the resin composition, the laminate sheet containing the resin composition layer has excellent elongation when heated, but at room temperature, the resin composition There is a problem that the layer becomes brittle, which causes poor handling and yield. In recent years, plastic products used in places that are often touched by hand are strongly required to protect the surface from sweat containing lactic acid as a main component, but the chemical resistance is satisfactory. It wasn't.

  An object of the present invention is to solve the above-mentioned problems, and the handling property is good even after the addition of inorganic fine particles, and it has excellent appearance, design, chemical resistance, abrasion resistance and weather resistance after curing. And it is providing the laminated sheet which has favorable workability at the time of shaping | molding in an uncured state, and has no surface adhesiveness. Another object of the present invention is to provide a laminated molded article using the laminated sheet, a method for producing the laminated molded article, and a photocurable resin composition that provides such performance.

  As a result of intensive studies in order to solve the above problems, the present inventors have completed the following present inventions [1] to [11].

  [1] A photocurable resin composition containing a thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain, a hexafunctional or higher functional (meth) acrylate (B), and a photopolymerization initiator (C). .

  [2] The photocurable resin composition according to the above [1], wherein the (meth) acrylate (B) having 6 or more functional groups has an integrated molecular weight distribution with a molecular weight of polystyrene equivalent of less than 500 and less than 40%.

  [3] The photocurable resin composition according to the above [1] or [2], wherein the hexafunctional or higher (meth) acrylate (B) is urethane (meth) acrylate.

  [4] The mass ratio of “the thermoplastic resin having a radically polymerizable unsaturated group in the side chain (A) / 6-functional or higher functional (meth) acrylate (B)” is “83/17” to “57/43”. The photocurable resin composition according to any one of [1] to [3].

  [5] The thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain is a thermoplastic resin having a (meth) acryloyl group in the side chain, according to any one of the above [1] to [4]. Photocurable resin composition.

  [6] The above [1], wherein the thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain is a copolymer of (meth) acrylate having an epoxy group and a monomer copolymerizable therewith. [5] The photocurable resin composition according to any one of [5].

  [7] The photocurable resin composition according to any one of [1] to [6], further including inorganic fine particles (D).

  [8] When the total mass part of the thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain and the (meth) acrylate (B) having 6 or more functional groups is 100 parts by mass, inorganic fine particles (D) The photocurable resin composition according to any one of [1] to [7], in which the content of is 5 to 400 parts by mass.

  [9] A laminated sheet in which the layer of the photocurable resin composition according to any one of [1] to [8] is laminated with a thickness of 2 to 20 μm on a base sheet.

  [10] A cured laminated sheet obtained by curing a photocurable resin composition layer of the laminated sheet according to [9] is a laminated molded product laminated on a molded product, and the cured layer is on the outermost surface. Laminated molded product provided.

  [11] A step of molding and laminating the laminated sheet according to [9], and a step of curing the layer of the photocurable resin composition by irradiating active energy rays thereafter. A method for producing a laminated molded product.

  According to the present invention, a laminate having excellent appearance, designability, chemical resistance, abrasion resistance and weather resistance after photocuring, good workability at the time of molding in an uncured state, and no surface tackiness A sheet, a laminated molded article using the laminated sheet, a method for producing the laminated molded article, and a photocurable resin composition that provides such performance can be provided.

  Hereinafter, modes for carrying out the present invention will be described in order. However, the scope of the present invention is not limited to these descriptions, and other than the following examples, the scope of the present invention is not limited. Changes can be made. In the following description, the thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain is changed to the thermoplastic resin (A) or (component A), and the (meth) acrylate (B) having 6 or more functionalities is ( Sometimes referred to as (meth) acrylate (B) or (component B). “(Meth) acrylate”, “(meth) acryl” and “(meth) acryloyl” are “acrylate” or “methacrylate”, “acryl” or “methacryl”, and “acryloyl” or “methacryloyl”, respectively. "Means.

<Photocurable resin composition>
The photocurable resin composition of the present invention comprises a thermoplastic resin (A) having a radical polymerizable unsaturated group in the side chain, a (meth) acrylate (B) having 6 or more functional groups, and a photopolymerization initiator (C). It is an essential ingredient.

[Thermoplastic resin (A)]
Examples of the thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain of the present invention include, for example, a thermoplastic resin in which a radically polymerizable unsaturated group is introduced into a polymer (a) obtained by polymerizing monomers. Is mentioned. Examples of the monomer that is a raw material for the polymer (a) include the following compounds. A single unit having a hydroxyl group such as N-methylolacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. Monomers; monomers having a carboxyl group such as (meth) acrylic acid, acryloyloxyethyl monosuccinate; glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) Monomers having an epoxy group such as acrylate glycidyl ether; Monomers having an aziridinyl group such as 2-aziridinylethyl (meth) acrylate and allyl 2-aziridinylpropionate; (meth) acrylamide, diacetone acrylic Monomers having an amino group such as amide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate; Monomers having a sulfo group such as 2-acrylamido-2-methylpropanesulfonic acid; 2,4- An adduct of a radically polymerizable monomer having an active hydrogen and a diisocyanate such as an equimolar adduct of toluene diisocyanate and 2-hydroxyethyl acrylate; a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate. These may use only 1 type and can also use 2 or more types together.

  Furthermore, a monomer copolymerizable with these monomers for the purpose of adjusting the glass transition temperature (Tg) of these polymers (a) or for the purpose of adjusting the physical properties of the laminated sheet. Can be further copolymerized. Examples of the copolymerizable monomer include the following compounds. (Meth) acrylates such as methyl (meth) acrylate, tricyclodecanyl (meth) acrylate and isobornyl (meth) acrylate; imide derivatives such as N-phenylmaleimide, cyclohexylmaleimide and N-butylmaleimide; olefins such as butadiene Monomer; aromatic vinyl compounds such as styrene and α-methylstyrene. These may use only 1 type and can also use 2 or more types together.

  Next, the thermoplastic resin (A) can be produced by introducing a radical polymerizable unsaturated group into the polymer, for example, by the following method.

  When the monomer having the hydroxyl group is used as a raw material of the polymer (a), the polymer (a) is subjected to a condensation reaction with the monomer having the carboxyl group or the sulfo group, or the epoxy group. Further, an equimolar adduct of a monomer or diisocyanate compound having an aziridinyl group or an isocyanate group and a hydroxyl group-containing acrylate monomer can be subjected to an addition reaction. When the monomer having the sulfo group is used as the raw material of the polymer (a), the polymer (a) can be subjected to a condensation reaction with the monomer having the hydroxyl group. When the monomer having the epoxy group, isocyanate group or aziridinyl group is used as the raw material of the polymer (a), the monomer having the hydroxyl group or carboxyl group is added to the polymer (a). Can be made. When the monomer having the carboxyl group is used as the raw material of the polymer (a), the monomer having the hydroxyl group is subjected to a condensation reaction, or the monomer having the epoxy group, aziridinyl group, isocyanate group, or An equimolar adduct of a diisocyanate compound and a hydroxyl group-containing acrylate monomer can be subjected to an addition reaction. These reactions are preferably performed while adding a small amount of a polymerization inhibitor such as hydroquinone and sending dry air. As the thermoplastic resin (A), a resin obtained by subjecting a monomer-containing polymer containing a monomer having an epoxy group to an addition reaction of a monomer having a carboxyl group is preferable. The ratio of the monomer having an epoxy group in the monomer mixture is preferably 5 to 30% by mass.

  Examples of the polymerization method for obtaining the polymer (a) include a solution polymerization method, an emulsion polymerization method and a suspension polymerization method. Moreover, when introducing a radically polymerizable unsaturated group into the polymer (a), for example, by performing the condensation reaction or addition reaction using a solution in which the polymer (a) is dissolved in an organic solvent, A thermoplastic resin (A) can be obtained.

  The amount of radically polymerizable unsaturated groups in the side chain of the thermoplastic resin (A) is such that the double bond equivalent (the amount of resin per 1 mol of unsaturated groups) is 1 to 3000 g / mol in terms of resistance. It is preferable from the viewpoint of improving scratch resistance and wear resistance. The double bond equivalent is more preferably 1 to 1200 g / mol, and still more preferably 1 to 800 g / mol. Thus, by introducing a plurality of radically polymerizable unsaturated groups involved in crosslinking into the thermoplastic resin, the cured physical properties of the thermoplastic resin (A) can be improved efficiently. In addition, the calculation method of a double bond equivalent is mentioned later.

  The number average molecular weight (Mn) of the thermoplastic resin (A) is preferably 5,000 to 2,500,000, and more preferably 10,000 to 1,000,000. When Mn is 5,000 or more, the laminate sheet containing the layer of the photocurable resin composition of the present invention is used to laminate the molding die during molding when performing in-mold molding and insert molding. The sheet becomes difficult to stick. Moreover, the surface hardness of the laminated molded product to be manufactured is appropriate. On the other hand, when Mn is 2,500,000 or less, synthesis is easy, and the cured layer obtained from the layer of the photocurable resin composition has a good appearance and also has good adhesion to the base sheet. . A method for measuring Mn will be described later.

  The glass transition temperature (Tg) of the thermoplastic resin (A) is preferably 25 to 175 ° C, and more preferably 30 to 150 ° C. When Tg is 25 ° C. or higher, the mold release property of the laminated sheet during in-mold molding and insert mold molding is good, and the surface hardness of the laminated molded product is appropriate. On the other hand, when Tg is 175 ° C. or lower, the handleability of the laminated sheet is improved. In consideration of the Tg of the thermoplastic resin (A), it is preferable to use a vinyl polymerizable monomer having a high Tg when a homopolymer is used as the monomer. Further, from the viewpoint of improving the weather resistance of the cured layer obtained from the layer of the photocurable resin composition, it is more preferable to use (meth) acrylates as the main component as the vinyl polymerizable monomer. A method for measuring Tg will be described later.

  Further, when the inorganic fine particles (D) are added to the photocurable resin composition of the present invention, the functional groups capable of reacting with the surface functional groups (hydroxyl group, carboxyl group, silanol group, etc.) of the inorganic fine particles (D). By using a vinyl polymerizable monomer having a group in the molecule as a monomer, the physical properties such as rigidity, toughness and heat resistance of the cured layer obtained from the layer of the photocurable resin composition can be further improved. it can.

  Examples of the functional group capable of reacting with the functional group on the surface of the inorganic fine particle (D) include at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated silyl group, and an alkoxysilyl group. Examples of such vinyl polymerizable monomers include the following compounds. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, vinyltrichlorosilane, vinyltrimethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, and γ- (meta ) Acrylyloxypropyldimethoxymethylsilane and the like. These may use only 1 type and can also use 2 or more types together.

  As the thermoplastic resin (A), a compound having a carboxyl group and a (meth) acryloyl group on an epoxy group of a copolymer produced from a (meth) acrylate having an epoxy group and a monomer copolymerizable therewith A thermoplastic resin having a (meth) acryloyl group in the side chain is preferred because it is easy to balance the physical properties of the uncured photocurable resin composition and the cured product after photocuring. .

[(Meth) acrylate (B)]
The hexafunctional or higher (meth) acrylate (B) of the present invention is a compound having 6 or more radically polymerizable unsaturated groups in the chemical structure. If it is not more than 6 functional groups, chemical resistance after photocuring is insufficient.

  As (meth) acrylate (B), known polyester (meth) acrylate having 6 or more (meth) acryloyl groups, polyether (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, silicone (meta ) Acrylate and the like. Urethane (meth) acrylate is more preferable in terms of good processability during molding of the photocurable resin composition in an uncured state.

  Urethane (meth) acrylates include a reaction product obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyisocyanate having an isocyanate group at the end, and a reaction product having a hydroxyl group-terminated polyol with an isocyanate group-containing (meth) acrylate. Compounds.

  Examples of the polyisocyanate include the following compounds. Hexamethylene diisocyanate, hexamethylene diisocyanate derivative (trade name: Tolonate HDB, Tolonate HDT, manufactured by Perstorp), isophorone diisocyanate, isophorone diisocyanate derivative (Tolonate IDT, manufactured by Perstorp), 4,4′-dicyclohexylmethane diisocyanate, 2,4-tri Range isocyanate, 4,4'-diphenylmethane diisocyanate, etc.

  Examples of the hydroxyl group-containing (meth) acrylate include the following compounds. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-meta (Meth) acrylates having one (meth) acryloyl group such as chloroxyethyl acid phosphate; two (2) such as 2-hydroxy-3-acryloyloxypropyl methacrylate, glycerin dimethacrylate, 2-methacryloxyethyl acid phosphate (Meth) acrylate having a (meth) acryloyl group; (meth) acrylate having three (meth) acryloyl groups such as pentaerythritol triacrylate.

  Examples of the polyol include known low molecular weight polyols, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols. Preferably, a polyol having three or more hydroxyl groups such as glycerin, trimetrol propane, triethanolamine, pentaerythritol, sorbitol, sucrose and the like can be mentioned.

  Examples of the isocyanate group-containing (meth) acrylate include 2-isocyanatoethyl (meth) acrylate and 1,1- (bisacryloyloxymethyl) ethyl isocyanate.

  As the (meth) acrylate (B), for example, the following commercially available products can be used. Pentaerythritol triacrylate hexamethylene diisocyanate (trade name: UA-306H, manufactured by Kyoeisha Chemical Co., Ltd.), pentaerythritol triacrylate toluene diisocyanate (trade name: UA-306T, manufactured by Kyoeisha Chemical Co., Ltd.), pentaerythritol triacrylate isophorone Diisocyanate (trade name: UA-306I, manufactured by Kyoeisha Chemical Co., Ltd.) (trade names: CN9025, CN9006NS, manufactured by Sartomer Japan Co., Ltd.), dipentaerythritol pentaacrylate hexamethylene diisocyanate (trade name: UA-510H, Kyoeisha) Chemical Co., Ltd.), dipentaerythritol hexaacrylate (trade name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. These may use only 1 type and can also use 2 or more types together.

  The number of radically polymerizable unsaturated groups of (meth) acrylate (B) is preferably 15 or less from the viewpoint of easy material acquisition.

  The mass ratio of the thermoplastic resin (A) and the (meth) acrylate (B) in the photocurable resin composition of the present invention, that is, the mass ratio of “(Component A) / (Component B)” is “83 / 17 ”to“ 57/43 ”is preferable,“ 80/20 ”to“ 60/40 ”is more preferable, and“ 80/20 ”to“ 64/36 ”is still more preferable. When the mass% of (Component B) is 17 mass% or more in the total 100 mass% of these two components, the flexibility of the photocurable resin composition at room temperature is good. On the other hand, when this mass% is 43 mass% or less, when performing in-mold molding and insert mold molding using a laminated sheet including a layer of the photocurable resin composition, a molding die for molding is used. A laminated sheet becomes difficult to stick. In addition, the surface appearance of the manufactured laminated molded article is improved.

  The integral molecular weight distribution of molecular weight in terms of polystyrene of (meth) acrylate (B) is preferably less than 40% when the molecular weight is less than 500. When the molecular weight of less than 500 is less than 40%, when performing in-mold molding and insert molding using a laminated sheet containing a layer of a photo-curable resin composition, it is laminated on a molding die at the time of molding. The sheet becomes difficult to stick. In addition, the surface appearance of the manufactured laminated molded article is improved. A method for measuring the integrated molecular weight distribution will be described later.

[Photopolymerization initiator (C)]
As a photoinitiator (C) of this invention, the photoradical polymerization initiator which generate | occur | produces a radical by irradiating active energy rays, such as an electron beam, an ultraviolet-ray, or visible light, is mentioned, for example. As the radical photopolymerization initiator, known compounds can be used and are not particularly limited. In consideration of yellowing during photocuring and deterioration during weathering, compounds such as acetophenone, benzophenone, and acylphosphine oxides that do not contain an amino group in the molecule are preferred.

  Examples of the radical photopolymerization initiator include the following compounds. 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 4,4-trimethyl-pentylphosphine oxide and the like. These may use only 1 type and can also use 2 or more types together.

  Among these compounds, depending on the temperature conditions of the method for producing a laminated molded product of the present invention, the temperature may be temporarily higher than the boiling point of the compound, so the boiling point is higher than the temperature at the time of producing the laminated molded product. It is preferable to use a compound having a high value.

  As content of the photoinitiator (C) in the photocurable resin composition of this invention, since the residual amount after hardening affects a weather resistance, it is 0 with respect to 100 mass parts of thermoplastic resins (A). .1 to 5 parts by mass is preferable. Moreover, when using the amino-type radical photopolymerization initiator in connection with yellowing at the time of hardening as a photoinitiator (C), 1 mass part or less is preferable.

  The method for adding the photopolymerization initiator (C) to the thermoplastic resin (A) is not particularly limited. For example, after polymerizing the thermoplastic resin (A) in advance, the photopolymerization initiator (C) can be mixed. Further, the monomer can be polymerized under a condition in which the monomer constituting the thermoplastic resin (A) and the photopolymerization initiator (C) are mixed in the side chain.

[Other ingredients]
The photocurable resin composition of the present invention can further contain the following various additives as necessary within the scope of the inorganic fine particles (D) described later and the purpose of the present invention. Sensitizers, ultraviolet absorbers, hindered amine light stabilizers, resins for modification, dyes, pigments, leveling agents, repellency inhibitors, oxidation stabilizers, oxygen inhibition inhibitors, and the like. The total content of these additives is preferably 0 to 15 parts by mass, more preferably 0 to 10 parts by mass, and still more preferably 0 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A).

  By mix | blending a sensitizer, the hardening reaction of a photocurable resin composition can be accelerated | stimulated. Examples of the sensitizer include benzophenone, benzoin isopropyl ether, and thioxanthone. These may use only 1 type and can also use 2 or more types together.

  By blending an ultraviolet absorber, it absorbs ultraviolet rays and converts them into thermal energy, so that the photocurable resin composition layer, the base sheet, the decorative layer, the adhesive layer, or the resin layer constituting the molded product By suppressing photoexcitation and photochemical reaction of the chromophore, it is possible to suppress deterioration such as discoloration, discoloration, and deterioration of physical properties of the obtained laminated molded product.

  As the ultraviolet absorber, both an organic ultraviolet absorber and an inorganic ultraviolet absorber can be used. Examples of organic ultraviolet absorbers include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, benzoate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and triazine ultraviolet absorbers. Examples of the inorganic ultraviolet absorber include inorganic compounds such as fine particle zinc oxide, cerium oxide, and titanium oxide having a particle diameter of 0.2 μm or less. These may use only 1 type and can also use 2 or more types together.

  In addition, when using a ultraviolet absorber, the absorption wavelength region of a ultraviolet absorber may overlap with the absorption wavelength region of a photoinitiator (C). In that case, since the curability of the photocurable resin composition, the weather resistance and abrasion resistance of the cured product obtained from the photocurable resin composition may be reduced, the absorption wavelength region of the ultraviolet absorber and It is preferable that the absorption wavelength regions of the photopolymerization initiator (C) do not overlap. Among the above ultraviolet absorbers, organic ultraviolet absorbers are preferable from the viewpoint of the transparency of the cured product of the photocurable resin composition.

  Examples of the hindered amine light stabilizer include a compound having a piperidine ring in which a plurality of substituents having a steric hindrance action are bonded to two carbon atoms adjacent to each other in the chemical structure. Examples of the substituent having such steric hindrance include a methyl group. A known compound can be used as the hindered amine light stabilizer, and is not particularly limited. Examples thereof include a compound having a 2,2,6,6-tetramethyl-4-piperidyl group, a compound having a 1,2,2,6,6-pentamethyl-4-piperidyl group, and the like. As a commercial item, the following are mentioned, for example. For example, the following products are manufactured by BASF Japan. Uvinul (TM) 5050 H, Uvinul (TM) 4050 FF, Tinuvin (TM) 622 LD, Tinuvin (TM) 622 SF, Tinuvin (TM) 144, Tinuvin (TM) PA144, Tinuvin (TM) 765, Tinuvin (TM) 770 DF, Tinuvin (TM) 123, Tinuvin (TM) 292, Sanol (TM) LS-2626, Tinuvin (TM) 152, Chimassorb (TM) 119 FL, Tinuvin (TM) 111 FDL, Chimassorb (TM) 2020 FDL, Chimassorb ™ 944 FDL, Tinuvin ™ 783 FDL, Tinuvin ™ 791 FB, Flamestab ™ NOR 116 F F. Further, for example, the following products manufactured by ADEKA Corporation. ADK STAB (trademark) LA-52, LA-57, LA-63P, LA-68, LA-81, LA-82, LA-87, LA-94G. These may use only 1 type and can also use 2 or more types together.

  In addition, when using the said hindered amine light stabilizer, when improving the weather resistance of hardened | cured material by increasing content, there exists a tendency for the abrasion resistance of hardened | cured material to fall with the content. Therefore, the content is preferably within a range not impairing the wear resistance.

  In addition, when a hindered amine light stabilizer having a radically polymerizable unsaturated group in the side chain and a hindered amine light stabilizer having a triazine skeleton are used, a decrease in wear resistance of the cured product accompanying the addition amount can be suppressed. There is a tendency.

  When the layer of the photocurable resin composition becomes high temperature during the production of the laminated molded product of the present invention described later, in order to improve the surface hardness of the cured layer obtained from the layer of the photocurable resin composition, An oxygen inhibition inhibitor such as n-methyldiethanolamine can be added.

  Moreover, when photocuring a photocurable resin composition, the heat at the time of manufacture of a laminated molded product and the thermosetting using a thermal-polymerization initiator can be used together. As content of a thermal-polymerization initiator, since the residual amount after hardening affects a weather resistance, 0.1-5 mass parts is preferable with respect to 100 mass parts of thermoplastic resins (A). Examples of the thermal polymerization initiator include various peroxides. When thermosetting with a thermal polymerization initiator is used in combination, it is preferably cured at 150 ° C. for about 30 seconds. Accordingly, peroxides having low critical temperatures such as lauroyl peroxide, t-butylperoxy-2-ethylhexanoate and 1,1-bis (t-butylperoxy) -3,3 , 5-trimethylcyclohexane is preferred. These may use only 1 type and can also use 2 or more types together.

  Examples of the method of blending the various additives with the thermoplastic resin (A) include the same methods as those for the inorganic fine particles (D) described later. In addition, the method of mix | blending the said various additives after manufacturing a thermoplastic resin (A) is preferable at the point which does not inhibit the polymerization reaction at the time of manufacture of a thermoplastic resin (A).

  The photocurable resin composition of the present invention can contain a crosslinkable organic compound having a radical polymerizable unsaturated group without departing from the object of the present invention. Such a crosslinkable organic compound should be selected from the viewpoints of storage stability of the photocurable resin composition, adhesiveness during production to obtain a laminated molded product, printing process passability, and mold contamination resistance. is important. A crosslinkable monomer or oligomer having a molecular weight of 2,000 or more is preferred. Moreover, a solid crosslinkable monomer or oligomer is mentioned at 60 degrees C or less, More preferably at 50 degrees C or less, Most preferably at 40 degrees C or less.

  Specific examples of the crosslinkable monomer include the following. Bifunctional (meth) acrylic acid esters such as tripropylene glycol di (meth) acrylate, 1,6-hexanediol diacrylate, tetraethylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri Trifunctional (meth) acrylic acid esters such as (meth) acrylate; tetrafunctional (meth) acrylic acid esters such as tetramethylolmethane tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate.

  Examples of the crosslinkable oligomer include polyester (meth) acrylate, polyether (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, and silicone (meth) acrylate. Specific examples include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A type epoxy acrylate, polyurethane diacrylate, cresol novolac type epoxy (meth) acrylate, and the like. These may use only 1 type and can also use 2 or more types together.

[Inorganic fine particles (D)]
It is preferable that the photocurable resin composition of the present invention further contains inorganic fine particles (D) from the viewpoint of improving the scratch resistance and wear resistance of the cured product of the photocurable resin composition. If the transparency of the hardened | cured material of a photocurable resin composition is ensured as an inorganic fine particle (D), the kind, particle diameter, and form will not be restrict | limited in particular.

  Examples of the inorganic fine particles (D) include colloidal silica, alumina, titanium oxide, tin oxide, foreign element doped tin oxide (ATO, etc.), indium oxide, foreign element doped indium oxide (ITO, etc.), cadmium oxide, antimony oxide, and the like. Is mentioned. These may use only 1 type and can also use 2 or more types together. Among these, colloidal silica is preferable from the viewpoints of availability, price, transparency of the cured product of the photocurable resin composition and expression of wear resistance.

  Colloidal silica can be used in the form of a normal aqueous dispersion and in a form dispersed in an organic solvent. However, in order to disperse uniformly and stably in the photocurable resin composition, it is preferable to use colloidal silica dispersed in an organic solvent.

  Examples of the organic solvent include methanol, isopropyl alcohol, n-butanol, ethylene glycol, xylene / butanol, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, and toluene. These may use only 1 type and can also use 2 or more types together. Among these, it is preferable to select an organic solvent capable of dissolving the thermoplastic resin (A) from the viewpoint that it can be more uniformly dispersed in the photocurable resin composition.

  Examples of colloidal silica in a form dispersed in an organic solvent include those commercially available under the following trade names from Nissan Chemical Industries, Ltd. Methanol silica sol, isopropyl alcohol silica sol IPA-ST, n-butanol silica sol NBA-ST, ethylene glycol silica sol EG-ST, xylene / butanol silica sol XBA-ST, ethyl cellosolve silica sol ETC-ST, butyl cellosolve silica sol BTC-ST, dimethylformamide silica sol DBF -ST, dimethylacetamide silica sol DMAC-ST, methyl ethyl ketone silica sol MEK-ST, methyl isobutyl ketone silica sol MIBK-ST, and the like. These may use only 1 type and can also use 2 or more types together.

  The particle diameter of the inorganic fine particles (D) is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less, from the viewpoint of transparency of the cured product of the photocurable resin composition. The lower limit of the particle diameter of the inorganic fine particles (D) is preferably 1 nm or more. In addition, the particle diameter of the inorganic fine particles (D) is an average value obtained by observing a cross section of a cured product of the photocurable resin composition containing the inorganic fine particles (D) with a TEM photograph.

  The content of the inorganic fine particles (D) in the photocurable resin composition is solid inorganic fine particles when the total mass part of the thermoplastic resin (A) and (meth) acrylate (B) is 100 parts by mass. 5 to 400 parts by mass is preferable, and 10 to 200 parts by mass is more preferable. When the content of the inorganic fine particles (D) is 5 parts by mass or more, an effect of improving the wear resistance of the cured product is recognized. On the other hand, when the content of the inorganic fine particles (D) is 400 parts by mass or less, the storage stability of the photocurable resin composition is high, and the moldability of the laminated sheet is also high.

  In addition, as the inorganic fine particles (D), inorganic fine particles whose surface is previously treated with a silane compound represented by the following formula (I) may be used. This is because when the surface-treated inorganic fine particles are used, the storage stability of the photocurable resin composition is further improved, and the surface hardness and weather resistance of the cured product of the laminated sheet are also improved.

In said formula (I), R < ⁴ > and R < ⁵ > represents the C1-C10 hydrocarbon group which may have an ether bond, an ester bond, an epoxy bond, or a carbon-carbon double bond, respectively. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have an ether bond, an ester bond, an epoxy bond or a carbon-carbon double bond. a and b are each independently an integer of 0 to 3, and c is an integer of 1 to 4 that satisfies “4-ab”.

  Among the silane compounds represented by the formula (I), silane compounds represented by the following formulas (II) to (VII) are more preferable.

In the formulas (II) to (VII), R ⁷ and R ⁸ each represents a hydrocarbon group having 1 to 10 carbon atoms which may have an ether bond, an ester bond or an epoxy bond. R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R ¹⁰ represents a hydrogen atom or a methyl group. R ¹¹ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group. a and b are each independently an integer of 0 to 3, and c is an integer of 1 to 4 that satisfies “4-ab”. n is an integer of 0-2. p is an integer of 1-6.

  Examples of the silane compound represented by the formula (II) include the following. Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, Diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, trimethylethoxysilane, methoxyethyltriethoxysilane, acetoxyethyltriethoxysilane, diethoxyethyldimethoxysilane, tetraacetoxysilane, methyltriacetoxysilane, tetrakis (2- Methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldie Toxisilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

  Examples of the silane compound represented by the formula (III) include the following. Tetrakis (acryloyloxyethoxy) silane, tetrakis (methacryloyloxyethoxy) silane, methyltris (acryloyloxyethoxy) silane, methyltris (methacryloyloxyethoxy) silane, and the like.

  Examples of the silane compound represented by the formula (IV) include the following. β-acryloyloxyethyldimethoxymethylsilane, γ-acryloyloxypropylmethoxydimethylsilane, γ-acryloyloxypropyltrimethoxysilane, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and the like.

  Examples of the silane compound represented by the formula (V) include vinylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Examples of the silane compound represented by the formula (VI) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, and the like. Examples of the silane compound represented by the formula (VII) include p-vinylphenylmethyldimethoxysilane and p-vinylphenyltrimethoxysilane.

  These silane compounds may be used alone or in combination of two or more.

  The method for adding the inorganic fine particles (D) to the thermoplastic resin (A) is not particularly limited. For example, after polymerizing the thermoplastic resin (A) in advance, the inorganic fine particles (D) can be mixed. Moreover, arbitrary methods, such as the method of superposing | polymerizing this monomer on the conditions which mixed the monomer used as the raw material of a thermoplastic resin (A), and inorganic fine particle (D), can be selected.

<Laminated sheet>
The laminated sheet of the present invention is a laminated sheet in which a layer of the photocurable resin composition of the present invention is laminated on a base sheet with a thickness of 2 to 20 μm. A decorative layer and / or an adhesive layer can be further laminated on the layer side of the photocurable resin composition or the base sheet side of the laminated sheet as necessary.

[Base material sheet]
As a base material sheet which comprises the laminated sheet of this invention, the sheet | seat using the at least 1 sort (s) of resin chosen from the following thermoplastic resins, and the laminated body of this sheet | seat are mentioned, for example. ABS (acrylonitrile / butadiene / styrene copolymer) resin, AS (acrylonitrile / styrene copolymer) resin, vinyl chloride resin, polystyrene resin, polyolefin resin such as polypropylene, fluorine resin, cellophane resin, Cellulosic resins, polyurethane resins, polyamide resins such as nylon, polyester resins, polycarbonate resins, polyvinyl alcohol resins, ethylene vinyl alcohol resins, soft acrylic resins, and the like. Among these, a sheet of a thermoplastic resin having an elongation of 100% or more when heated at 100 ° C. is preferable from the viewpoint of following the mold shape during insert molding.

  In addition, in terms of adhesion between the photocurable resin composition and the base sheet, weather resistance of the base sheet, transparency, and the like, the base sheet is a transparent thermoplastic acrylic resin sheet having a crosslinked rubber component. More preferred. As a sheet of a transparent thermoplastic acrylic resin having a crosslinked rubber component, for example, a sheet of a transparent thermoplastic acrylic resin obtained by extruding an acrylic resin having a multilayer structure disclosed in JP-A-9-263614 Is mentioned.

  In the base sheet, various additives such as lubricants such as polyethylene wax and paraffin wax, lubricants such as silica, spherical alumina, and flaky alumina, plasticizers, stabilizers, and coloring agents are blended as necessary. can do.

  Further, for example, when the laminated molded product is used outdoors, an ultraviolet absorber or a light stabilizer can be blended in the base sheet. As said ultraviolet absorber and light stabilizer, the thing similar to what is mix | blended in the photocurable resin composition mentioned above is mentioned.

[Layer of photocurable resin composition]
The thickness of the layer of the photocurable resin composition constituting the laminated sheet of the present invention is preferably in the range of 2 to 20 μm, and more preferably in the range of 3 to 8 μm. When this thickness is 2 μm or more, the cured layer obtained by photocuring the layer of the photocurable resin composition has good characteristics such as scratch resistance, abrasion resistance, and chemical resistance. On the other hand, when this thickness is 20 μm or less, when performing in-mold molding and insert mold molding using a laminated sheet containing a layer of a photocurable resin composition, even if preheating is performed during molding, The laminated sheet is difficult to stick to the mold. Further, the surface appearance of the manufactured laminated molded article is good.

  The layer of the photocurable resin composition constituting the laminated sheet of the present invention has a mass ratio of the thermoplastic resin (A) and the (meth) acrylate (B) in the photocurable resin composition, that is, “(Component A ) / (Component B) ”is a mass ratio of“ 83/17 ”to“ 57/43 ”so that the surface does not have adhesiveness and the change in adhesive with time can be suppressed. Good storage stability when stored in a roll state. Moreover, since the trouble at the time of forming a decoration layer and / or a contact bonding layer can be suppressed, a yield becomes favorable.

  As a method of laminating the layer of the photocurable resin composition on the base sheet, for example, a solution obtained by sufficiently stirring and dissolving the photocurable resin composition in an organic solvent was applied on the base sheet. Then, the method of drying an organic solvent and obtaining a lamination sheet is mentioned.

  When the resin material used for the base sheet is a polyolefin resin such as polyethylene and polypropylene having low adhesion to the photocurable resin composition, the base sheet and the photocurable resin composition In order to improve adhesion, pretreatment is preferably performed. Examples of such pretreatment include a method in which a primer composed of a low molecular weight polyolefin or the like is previously applied on a base sheet, or a method in which the surface of the base sheet is activated in advance by corona discharge or the like. It is done. Furthermore, in order to prevent the photocurable resin composition from shrinking in volume during photocuring and reducing the adhesion between the cured layer of the photocurable resin composition and the base sheet, the base sheet and the photocurable A primer layer can be formed between the resin composition layers. In addition, when performing said corona discharge, a layer of a photocurable resin composition is laminated | stacked on a base material sheet from a viewpoint of improving the adhesiveness of the layer of a photocurable resin composition and a base material sheet. It is preferable to perform a corona discharge treatment immediately before.

  Examples of the method for forming the layer of the photocurable resin composition include a known coating method such as a knife coating method, a comma coating method, a reverse coating method, a dip coating method, or a method similar to the printing layer forming method described later. It is done.

[Protective sheet]
The laminated sheet of the present invention can have a protective sheet on the layer side and / or the base sheet side of the photocurable resin composition of the laminated sheet as necessary. The protective sheet is effective for preventing dust on the surface of the laminated sheet and also for preventing damage to the surface of the layer of the photocurable resin composition before curing.

  The protective sheet is in close contact with the surface of the laminated sheet, and is processed while being peeled or bonded before processing the laminated molded product, and then peeled off. It is preferable to have moldability. Any protective sheet satisfying such conditions can be selected and used, and examples thereof include a polyethylene film, a polypropylene film, and a polyester film.

[Decoration layer]
The laminated sheet of the present invention can have a decorative layer composed of at least one selected from a printing layer and a vapor deposition layer as necessary. The printing layer and the vapor deposition layer are laminated on the base sheet side of the laminated sheet. A decoration layer is a layer for giving a pattern, a character, etc. decoration on the surface of the lamination molded product which uses a lamination sheet. Any kind of decoration can be selected, and examples thereof include wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, and solid pattern. The thickness of the decorative layer can be arbitrarily selected according to, for example, the degree of expansion during insert molding so that a desired surface appearance can be obtained in the laminated molded product.

[Print layer]
As a material used for a printing layer, the coloring ink containing a resin binder and a coloring agent is mentioned, for example.

  Examples of the resin binder include the following. Polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose ester resins, alkyd resins, and the like Chlorinated polyolefin resin.

  Examples of the colorant include at least one selected from known dyes and pigments. Examples of the pigment include the following. Azo pigments such as polyazo, organic pigments such as isoindolinone, yellow pigments such as inorganic pigments such as chrome lead; azo pigments such as polyazo; organic pigments such as quinacridone; red pigments such as inorganic pigments such as petals; Organic pigments such as phthalocyanine blue; blue pigments such as inorganic pigments such as cobalt blue; black pigments such as aniline black; and white pigments such as titanium dioxide.

  Examples of the method for forming the printing layer include a printing method such as an offset printing method, a gravure rotary printing method and a screen printing method, and a coating method such as a roll coating method and a spray coating method.

[Deposition layer]
Examples of the material used for the vapor deposition layer include at least one metal selected from aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead and zinc, or an alloy or metal thereof. Compounds. Examples of the method for forming the vapor deposition layer include a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method.

(Adhesive layer)
The laminated sheet of the present invention is necessary to improve the adhesion between the laminated sheet and the decorative layer, the adhesion between the laminated sheet and a primer sheet described later, or the adhesion between the laminated sheet and a molded product described later. Accordingly, an adhesive layer can be provided. The material used for the adhesive layer may be any material that improves these adhesion properties, and includes any synthetic resin material.

  Examples of the material used for the adhesive layer include a polyacrylic resin when the resin used for the primer sheet or the molded product is a polyacrylic resin. In addition, when the resin used for the primer sheet or the molded product is a polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin or polystyrene blend resin, a polyacrylic resin having an affinity for these resins , Polystyrene resin or polyamide resin. Furthermore, when the resin used for the primer sheet or the molded product is a polyolefin resin such as polypropylene resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, coumarone indene And thermosetting urethane resin using block resin or blocked isocyanate. As the resin used for these adhesive layers, only one kind may be used according to the purpose, or two or more kinds may be used in combination.

  In addition, hydrophobic silica, an epoxy resin, a petroleum resin, etc. can be mix | blended with a contact bonding layer as needed for the purpose of the adhesiveness reduction of a contact bonding layer, or heat resistance improvement.

  Examples of the method for forming the adhesive layer include the same method as the method for forming the layer of the photocurable resin composition and the method for forming the printed layer.

[Primer sheet]
The laminated sheet of the present invention suppresses the propagation of surface defects of the molded product to the cured product layer of the photocurable resin composition on the laminated sheet in order to improve the adhesion between the adhesive layer and the molded product. Therefore, a primer sheet can be provided on the surface of the adhesive layer. The primer sheet is preferably a sheet that uses a resin that is highly compatible with the material constituting the molded article in terms of enhancing the adhesion to the molded article, and more preferably a sheet that uses the same resin material as the molded article.

  The thickness of the primer sheet is preferably 30 to 750 μm. When the thickness of the primer sheet is 30 μm or more, deep drawing can be performed without significantly reducing the sheet thickness on the curved surface. Moreover, when the thickness of a primer sheet is 750 micrometers or less, it can shape | mold, without reducing the shape followable | trackability to a metal mold | die.

<Laminated molded product>
The laminated molded article of the present invention is a laminated molded article obtained by laminating a laminated sheet obtained by curing the photocurable resin composition layer of the laminated sheet of the present invention on the molded article, and the cured layer is provided on the outermost surface. Is a laminated molded product. For example, a laminated molded product laminated so that the base sheet side of the laminated sheet is in contact with the molded product, a laminated molded product laminated so that the decorative layer side of the laminated sheet is in contact with the molded product, and the adhesive layer side of the laminated sheet is molded A laminated molded product laminated so as to be in contact with the product may be mentioned. Moreover, the laminated molded product by which the surface fine uneven structure was provided to the layer of the photocurable resin composition after the hardening provided in the outermost surface of the laminated molded product as needed is mentioned.

  In the case of having the primer sheet, it can be a laminated molded product laminated so that the primer sheet side of the laminated sheet is in contact with the molded product.

  In addition, when the laminated molded product has a large shape such as an automobile body panel or spoiler and the molded product is thin, a gas permeable layer can be provided between the molded product and the laminated sheet. . The gas permeable layer causes a problem that a gas generated from a resin described later at the time of molding the molded product remains in the molded product, a problem that air in the mold is interposed between the molded product and the laminated sheet, and The problem that the adhesiveness of the laminated sheet with respect to a molded article falls can be solved.

  Examples of the gas permeable layer include a woven or non-woven fabric layer composed of spandex, acrylic fiber, polyethylene fiber, polyamide fiber, or the like. Moreover, you may use the layer which has a foaming layer instead of a woven fabric or a nonwoven fabric. Examples of the method for forming the foamed layer include a method in which a resin solution containing a known foaming agent is applied and then foamed by heating or the like to form continuous pores.

  Examples of the use of the laminated molded product include the following. Instrument panel, console box, meter cover, door lock pezel, steering wheel, power window switch base, center cluster, dashboard and other automotive interior parts; weatherstrip, bumper, bumper guard, side mudguard, body panel, spoiler, front grill , Strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts, etc .; various front panels for AV equipment, etc .; buttons Surface decoration materials such as emblems; Various parts such as housings for mobile phones, display windows, buttons, etc .; Exterior materials for furniture; Interior materials for buildings such as walls, ceilings, floors; Architectural exterior materials such as exterior walls such as idings, fences, roofs, gates, and windbreak boards; surface decorative materials for furniture such as window frames, doors, handrails, sills, and duck; various displays, lenses, mirrors, goggles, and window glass Optical members such as: Interior and exterior members of various vehicles other than automobiles such as trains, airplanes, ships, etc .; and various other uses such as bottles, cosmetic containers, various packaging containers such as small items, packaging materials, gifts, miscellaneous goods, etc. .

〔Molding〕
Examples of the molded product constituting the laminated molded product of the present invention include a sheet-like product and a molded product having a three-dimensional shape. Specific examples of the molded product include various members and parts described as “use of laminated molded product”.

  As a manufacturing method of a sheet-like thing, an extrusion molding method or a casting method is mentioned, for example. In addition, examples of a method for producing a molded article having a three-dimensional shape include an injection molding method, a blow molding method, a vacuum molding method, a pressure air molding method, a pressure molding method in which heated rubber is pressed, or a press molding method.

  Examples of the material constituting the molded product include all resins that can be variously molded such as injection molding. For example, the following resins are mentioned. Polyolefin resin, polypropylene resin, polybutene resin, polymethylpentene resin, ethylene-propylene copolymer resin, ethylene-propylene-butene copolymer resin, olefin resin such as olefin thermoplastic elastomer, polystyrene resin , ABS (acrylonitrile / butadiene / styrene copolymer) resin, AS (acrylonitrile / styrene copolymer) resin, acrylic resin, urethane resin, unsaturated polyester resin, epoxy resin, etc. General-purpose engineering such as thermoplastic resins or thermosetting resins; polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, polycarbonate-modified polyphenylene ether resins, polyethylene terephthalate resins, etc. And super engineering resins such as polysulfone resins, polyphenylene sulfide resins, polyphenylene oxide resins, polyetherimide resins, polyimide resins, liquid crystal polyester resins, polyallyl heat resistant resins; PAN carbon fibers, pitch carbon Carbon fiber composite material combining fibers and matrix resin.

  In the resin constituting the molded product, reinforcing materials such as inorganic fillers such as glass fiber, talc, calcium carbonate, silica and mica can be blended according to the purpose, and modifiers such as rubber components can be added. The added composite resin, various modified resins, and the like can be blended.

  Moreover, it is preferable to eliminate problems such as warpage of the laminated molded product and peeling of the laminated sheet by approximating the shrinkage rate after molding of the resin constituting the molded product to the shrinkage rate of the laminated sheet.

[Production method of laminated molded product]
The method for producing a laminated molded product of the present invention includes a step of molding and laminating a laminated sheet to a molded product, and a step of curing a layer of the photocurable resin composition by irradiating active energy rays thereafter. It is a manufacturing method containing. A method of decorating a molded product with a three-dimensional decorative film can be suitably used.

Examples of a method for decorating a molded product with a three-dimensional decorative film include the following methods [I] to [III].
[I] An in-mold transfer method in which a three-dimensional decorative film having a decorative layer is inserted into a mold, injection molding is performed, the film is peeled off, and only the decorative layer is left in the molded product.
[II] An in-mold molding method and an insert mold molding method in which a three-dimensional decorative film is inserted into an injection mold, injection molding is performed, and the entire film is bonded to a molded product.
[III] A TOM molding method in which a three-dimensional decorative film having an adhesive layer is placed on a molded product, vacuum-pressure forming is performed after heating, and the entire film is bonded to the molded product.

  Specifically, as the in-mold transfer method of the method [I], first, in the sheet inserting step (1), the base sheet side of the laminated sheet is inserted and disposed so as to face the inner wall surface of the mold. Next, in the preforming step (2), the laminated sheet is preformed and the laminated sheet follows the mold shape. Thereafter, in the molded product forming step (3), the mold in which the laminated sheet was inserted and closed was closed, the molten resin was injected into the mold, and the resin was solidified to arrange the laminated sheet on the surface. A laminated molded product is formed. Further, in the photocuring step (4), before or after the substrate sheet is peeled off, the layer of the photocurable resin composition on the surface of the laminated molded product is photocured by irradiating active energy rays, and the present invention. A laminated molded product is obtained.

  Specifically, as the in-mold molding method of method [II], first, in the sheet insertion step (1), the layer of the photocurable resin composition on the laminated sheet is inserted so as to face the inner wall surface of the mold. Deploy. Next, in the preforming step (2), the laminated sheet is preformed and the laminated sheet follows the mold shape. Thereafter, in the molded product forming step (3), the mold in which the laminated sheet was inserted and closed was closed, the molten resin was injected into the mold, and the resin was solidified to arrange the laminated sheet on the surface. A laminated molded product is formed. Furthermore, in the photocuring step (4), the layer of the photocurable resin composition on the surface of the laminated molded product is photocured by irradiating with active energy rays to obtain the laminated molded product of the present invention.

  Specifically, as the insert mold forming method of method [II], first, in the sheet insertion step (1), the layer of the photocurable resin composition on the laminated sheet is inserted so as to face the inner wall surface of the mold. Deploy. Next, in the molded product forming step (3), the mold in which the laminated sheet is inserted and closed is closed, the molten resin is injected into the mold, and the laminated sheet is arranged on the surface by solidifying the resin. Form a molded product. Then, in a photocuring process (4), the layer of the photocurable resin composition on the surface of a laminated molded product is photocured by irradiating an active energy ray, and the laminated molded product of this invention is obtained.

  Specifically, as the TOM molding method of method [III], first, in the sheet insertion step (1), the laminated sheet and the molded product are placed so that the base sheet side of the laminated sheet faces the molded product before decorating. Insert it into the chamber box. Next, in the molded product forming step (3), the chamber box is closed, the laminated sheet is preheated, and vacuum / pressure forming is performed to cause the sheet to follow the shape of the molded product. Then, in a photocuring process (4), the layer of the photocurable resin composition on the surface of a laminated molded product is photocured by irradiating an active energy ray, and the laminated molded product of this invention is obtained.

  In the manufacturing method of the laminated molded product of this invention, when the protective sheet is provided on the surface of the laminated sheet, it is preferable to peel and use the protective sheet from the laminated sheet. The protective sheet may be peeled off at any time before the sheet insertion step (1), but immediately before the sheet insertion step (1) in terms of preventing dust and scratches on the surface of the photocurable resin composition layer. It is preferable to peel off.

  As a method of inserting a laminated sheet in the sheet inserting step (1), there are a method of intermittently feeding necessary portions in the state of a long sheet while unwinding from a roll, and a method of feeding a laminated sheet into single sheets and feeding them one by one Either method is acceptable. Moreover, when using the long sheet-like thing with which the decoration layer was laminated | stacked as a lamination sheet, the register of a decoration layer and a metal mold | die should correspond using a feeder which has a positioning mechanism. Is preferable. In addition, when the laminated sheet is intermittently fed, if the laminated sheet is fixed after detecting the position of the laminated sheet with a sensor, the sheet can always be fixed at the same position, and the decorative layer is displaced. This is convenient because it does not occur.

  As a pre-forming method in the pre-forming step (2), for example, the laminated sheet is softened at a temperature equal to or higher than its softening point by a heating means such as a hot pack, and vacuum suction is performed through a suction hole provided in the mold. The method of making a sheet | seat follow a mold shape is mentioned. If the laminated sheet is preheated to a temperature lower than the thermal deformation temperature of the laminated sheet before the laminated sheet is inserted into the mold, the heating time after the laminated sheet is inserted into the mold is shortened. This is preferable in terms of improving productivity. Further, in the pre-molding step (2), a blow molding method, a vacuum molding method, a pressure molding is performed using a three-dimensional processing molding die different from the injection molding die used in the molded product forming step (3). The laminated sheet may be preformed into a desired shape in advance by a known molding method such as a method, a pressure molding method for pressing heated rubber, or a press molding method. Moreover, when forming this molded product in the molded product formation step (3) without going through the preliminary molding step (2), the laminated sheet can be preheated and softened in advance.

  Examples of the method for forming a molded product in the molded product forming step (3) include the same molding method as the above-described preforming.

In the method for producing a laminated molded product of the present invention, the photocurable resin composition on the surface of the laminated molded product is irradiated with an active energy ray on the layer of the photocurable resin composition in the photocuring step (4). Light cure the layer. The time for irradiating the layer of the photocurable resin composition with the active energy rays is a method of irradiating the molded product obtained in the molded product forming step (3) after peeling from the mold, and the molded product forming step. Any of the methods of irradiating the molded product obtained in (3) while remaining in the mold may be used. The active energy ray is not particularly limited as long as the photopolymerization initiator (C) according to the embodiment of the present invention generates radicals when irradiated with the active energy ray. Irradiation conditions can be arbitrarily set, but are usually about 100 to 10,000 mJ / cm ^{2 in} terms of irradiation energy.

  In the method for producing a laminated molded product of the present invention, an unnecessary portion of the laminated sheet formed on the end portion of the obtained laminated molded product or a cured product thereof can be appropriately trimmed and removed. The trimming time may be any time after the laminated sheet is inserted and arranged in the mold, or before or after irradiation of the active energy ray to the laminated molded product. Examples of the trimming method include a method of burning a sheet by irradiating a laser beam or the like, a method of producing a trimming punching die and punching the sheet by pressing, and a method of tearing and removing the sheet manually.

  According to the method for producing a laminated molded article of the present invention, a laminated molded article having a color or a design simultaneously with molding can be obtained, and a laminated molded article having a surface excellent in wear resistance can be obtained by irradiation for a short time. Can be obtained. Furthermore, by the method of the present invention, the process can be shortened, the yield can be improved, and the influence on the environment can be reduced as compared with conventional spray coating after molding.

  Below, the aspect of this invention is demonstrated concretely based on an Example. In the examples, “parts” means “parts by mass”. In addition, various measurements and evaluations in this example were performed by the following methods.

(1) Polymerization rate of thermoplastic resin (A) Monomer remaining in the solution of thermoplastic resin (A) obtained by polymerization was analyzed by gas chromatography (manufactured by Agilent Technologies, model: HP6890). From the amount of the remaining monomer, the polymerization rate (%) of the monomer at the time of producing the thermoplastic resin (A) was calculated.

(2) Solid content of thermoplastic resin (A) The solid content of the thermoplastic resin (A) was measured by the following method. About 0.5 g of the thermoplastic resin (A) solution or dispersion was sampled on an aluminum pan, and the accurate mass was measured. Next, after volatilizing the solvent or dispersion medium at room temperature, the mixture was heated at 80 ° C. for 4 hours, the mass of the obtained transparent solid was measured, and the solid content (% by mass) was calculated.

(3) Number average molecular weight (Mn) of thermoplastic resin (A)
Mn of the thermoplastic resin (A) was measured using a high-speed GPC device (manufactured by Tosoh Corporation, model: HLC-8220 GPC). In addition, about the numerical value, the value converted into polystyrene was used.

(4) The double bond equivalent of the thermoplastic resin (A) The double bond equivalent of the thermoplastic resin (A) is calculated from the polymerization rate of the monomer calculated by the synthesis recipe and the method described above. And the double bond equivalent (g / mol) was calculated.

(5) Glass transition temperature (Tg) and melting point (mp)
The Tg of the thermoplastic resin (A), the (meth) acrylate (B), and the mp of the bifunctional (meth) acrylate were measured using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., model: DSC6200) in an aluminum container. 10 mg was weighed and measured from −100 ° C. to 150 ° C. under the conditions of a heating rate of 10 ° C./min and an N ₂ flow rate of 50 mL / min.

(6) Integrated molecular weight distribution The integrated molecular weight distribution of (meth) acrylate (B) and bifunctional (meth) acrylate was analyzed using a high-speed GPC apparatus (manufactured by Tosoh Corporation, model: HLC-8320GPC) Measurement was carried out under the conditions of a temperature of 40 ° C., a flow rate of 0.600 ml / min, and an eluent of THF under a TSKgel SuperH2000 and TSKgel SuperH2000 series connection) and guard column (TSKgel guardcolumn SuperH-L). The molecular weight was calculated by polystyrene conversion using TSK standard polystyrene, and the integrated molecular weight distribution was calculated from the obtained molecular weight.

(7) Total light transmittance and haze The total light transmittance and haze are based on JIS K 7361-1 and JIS K 7136 using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model: NDH4000). It was measured.

(8) Surface tackiness of uncured state The surface tack was evaluated about the layer of the photocurable resin composition of an uncured state. In this evaluation, the presence or absence of tackiness on the coating film surface was determined by touch.
Rank A: There is no tackiness on the surface of the coating film.
Rank C: There is a tack feeling on the surface of the coating film.

(9) Stretchability at room temperature The laminate sheet was cut into 15 mm × 150 mm test pieces to obtain samples for evaluating stretchability at room temperature. After setting the sample so that the distance between chucks becomes 100 mm using a tensile tester (made by Toyo Seiki Seisakusho Co., Ltd., Strograph T), the tensile speed is 20 mm / min under a temperature condition of 25 ° C. The sample was pulled and stretched 10%. About the layer of the photocurable resin composition of the sample after extending | stretching, the presence or absence of the crack of a coating-film surface was determined visually.
Rank A: There is no crack on the coating film surface.
Rank C: There is a crack on the coating film surface.

(10) Molding appearance Appearance evaluation of the laminated molded product was performed when in-mold molding was performed under conditions where the molding die temperature was heated to 50 ° C and 70 ° C. In the laminated molded product in which the layer of the photocurable resin composition was provided on the outermost layer, it was visually determined whether or not the uneven shape not existing in the molding die was confirmed on the outermost layer of the laminated molded product.
Rank A: Concave and convex shapes are not confirmed on the entire surface of the outermost layer.
Rank B: Concave and convex shapes are confirmed in part on the outermost layer.
Rank C: Concave and convex shapes are confirmed on the entire surface of the outermost layer.

(11) Scratch resistance A laminated molded product after photocuring was cut into 50 mm × 100 mm test pieces to obtain a scratch resistance evaluation sample. Using a steel wool scratch tester, steel wool No. 1 was loaded with a load of 13.7 kPa. After 0000 was set on the sample, the surface of the sample was scratched under conditions of a reciprocation distance of 45 mm, a reciprocation speed of 100 mm / sec, and a reciprocation number of 11 times. The haze of the sample after the abrasion test was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model: NDH4000) in accordance with JIS K7136. Haze is shown as scratch resistance (%).

(12) Abrasion resistance The laminated molded article after photocuring was cut into 100 mm × 100 mm test pieces to obtain samples for wear resistance evaluation. Using a Taber abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: rotary abrasion tester, model: TS), wear wheel (made by Taber, trade name: CS-10F (Type IV)) with a load of 500 g on one side Was set on the sample, and the surface of the sample was worn under the conditions of a suction port height of 1.5 mm, a rotation speed of 70 rpm, and the number of tests of 100. The haze of the sample after the wear test was measured according to JIS K. In accordance with No. 7105, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model: NDH4000) was measured with a luminous flux of 7φ, and expressed as “(cloudiness value after test) − (cloudiness value before test)”. The numerical value obtained is shown as wear resistance (%).

(13) Lactic acid resistance About 0.2 ml of an aqueous solution having a lactic acid concentration of 10% by mass was dropped onto the laminated molded article after photocuring, and the laminated molded article was evaluated for appearance after being left at 80 ° C. for 24 hours. In the laminated molded product in which the cured product layer of the photocurable resin composition layer is provided on the outermost layer, whether unevenness and whitening that do not exist before the lactic acid resistance test are confirmed on the outermost layer of the laminated molded product It was judged visually.
Rank A: Concavity and convexity and whitening are not confirmed on the outermost layer.
Rank B: Whitening is confirmed on the outermost layer.
Rank C: Concavity and convexity and whitening are confirmed on the outermost layer.

[Synthesis Example 1] Synthesis of thermoplastic resin (A-1) 80 parts of methyl ethyl ketone as a solvent was placed in a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the temperature was raised to 80 ° C. did. The flask was then placed under a nitrogen atmosphere and a monomer mixture (1) of 27.5 parts of methyl ethyl ketone, 86 parts of methyl methacrylate, 21.5 parts of glycidyl methacrylate and 0.376 parts of azobisisobutyronitrile was taken over 4 hours. And dripped.

  Thereafter, a mixture of 32.3 parts of methyl ethyl ketone and 0.2 part of azobisisobutyronitrile was dropped over 30 minutes to carry out polymerization. After 11 hours and 30 minutes from the start of polymerization, a monomer mixture (2) of 72.5 parts of methyl ethyl ketone, 0.538 parts of hydroquinone monomethyl ether, 2.69 parts of triphenylphosphine, and 10.9 parts of acrylic acid was added for 30 minutes. The mixture was added dropwise and stirred at 80 ° C. for 34 hours and 30 minutes while blowing air.

  Subsequently, after cooling the inside of the flask, the reaction product was taken out from the flask to obtain a solution of the thermoplastic resin (A-1) having a radically polymerizable unsaturated group in the side chain. The polymerization rate of the monomer in the thermoplastic resin (A-1) is 99.5% or more, the solid content is about 37% by mass, the Mn is about 25,000, the double bond equivalent is about 782 g / mol, and Tg was about 96 ° C.

[Synthesis Example 2] Synthesis of inorganic fine particles (D-1) In a 4-liter flask having a volume of 3 L equipped with a stirrer, a thermometer and a condenser, methanol silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MT-ST, dispersant: methanol, SiO ₂ concentration: 30 wt%, primary particle diameter:: 10 to 20 nm) 1200 parts of, as the organic silane compound γ- methacryloxypropyl trimethoxysilane (Shin-Etsu silicone Co., Ltd., trade name: KBM- 503, molecular weight: 248) 230 parts were added and heated with stirring.

  After reflux of volatile components began, 33 parts of deionized water was added and hydrolysis was performed with stirring for 2 hours under reflux to distill off volatile components such as alcohol and water, resulting in a solid content concentration of 60% by mass. It was adjusted to become.

  Thereafter, 700 parts of toluene was added, and alcohol, water and the like were azeotropically distilled together with toluene while stirring for 3 hours. Furthermore, in order to perform solvent substitution completely, reaction was implemented at 110 degreeC for 4 hours, distilling alcohol and toluene. The solid content was 61.8%.

[Example 1]
A 300-μm thick transparent soft acrylic resin sheet (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBS010) containing a crosslinked rubber component was used as the base material sheet. A solution of a photocurable resin composition having the composition shown in Table 1 was prepared. The symbols in Table 1 (B-1), (C-1) and (E-1) are the products shown in Table 2. The obtained photocurable resin composition solution was applied on a substrate sheet with a coating width of 300 mm, and then dried using a hot air dryer, and the photocurable resin composition layer having a thickness of 5 μm was formed on the substrate. A laminated sheet laminated on the sheet was obtained. The total light transmittance, haze, uncured surface tackiness, and stretchability at room temperature of this laminated sheet were evaluated. The evaluation results are shown in Table 1.

  The laminated sheet is inserted into a mold for injection molding, injection molding is performed, in-mold molding is performed in which the entire laminated sheet is bonded to a molded product, and a cured product layer of a layer of the photocurable resin composition of the laminated sheet Was obtained as a laminated molded product provided on the outermost layer.

  Specifically, using a mold having an evacuation function shown in Table 3 and an in-mold molding apparatus, vacuum molding is performed in a direction in contact with the cavity side of the mold under the in-mold molding conditions shown in Table 3. Resin constituting the product (trade name: Bulksum ™ TM-25B, manufactured by UMG ABS Co., Ltd.) was injected. The molded appearance of the obtained laminated molded product was evaluated. The evaluation results are shown in Table 1.

The obtained laminated molded product was irradiated with ultraviolet rays of about 560 mJ / cm ² using an ultraviolet irradiation device (trade name: Igrantage (trademark) (4 kw) ECS-401GX, manufactured by Eye Graphics Co., Ltd.). The layer of the photocurable resin composition was cured to obtain a laminated molded product in which the cured product layer of the photocurable resin composition was laminated on the base sheet. The laminated molded product after photocuring was evaluated for scratch resistance, abrasion resistance, and lactic acid resistance. The evaluation results are shown in Table 1.

[Examples 2-6 and Comparative Examples 1-6]
Except having changed the photocurable resin composition into the composition shown in Table 1, a laminated sheet, a laminated molded article, and a laminated molded article after photocuring were obtained in the same manner as in Example 1, and various evaluations were performed. The evaluation results are shown in Table 1. The symbols (B-2) to (B-6), (b-7) to (b-11), (C-1) and (E-1) in Table 1 are the products shown in Table 2. .

[Summary of evaluation results]
Examples 1 to 7 contain (meth) acrylate (B) and the content of (meth) acrylate (B) is in a preferred range, so both stretchability and lactic acid resistance at room temperature are achieved. The performance was good. Moreover, in Examples 1-4 whose molecular weight distribution of molecular weight of polystyrene conversion molecular weight in (meth) acrylate (B) is less than 40% is less than 40%, the surface appearance after in-mold molding was also good.

  Since Comparative Example 1 did not contain (meth) acrylate (B), both room temperature stretchability and lactic acid resistance were poor. Since Comparative Examples 2 to 6 contain a bifunctional (meth) acrylate instead of a hexafunctional or higher (meth) acrylate (B), the stretchability at room temperature is good, but the lactic acid resistance is high. It was bad. In addition, the wear resistance tended to deteriorate.

  Laminated molded products obtained by using a laminated sheet containing a layer of the photocurable resin composition of the present invention include automotive interior members, automotive exterior members such as automotive exterior members, architectural interior materials, and architectural exterior materials. It can be used for many applications such as building materials such as various surface decorative materials and optical members.

Claims (11)

  The photocurable resin composition containing the thermoplastic resin (A) which has a radically polymerizable unsaturated group in a side chain, (meth) acrylate (B) of 6 or more functionalities, and a photoinitiator (C).   The photocurable resin composition according to claim 1, wherein the hexafunctional (meth) acrylate (B) has a molecular weight of less than 500 in an integrated molecular weight distribution with a molecular weight in terms of polystyrene of less than 40%.   The photocurable resin composition according to claim 1, wherein the hexafunctional or higher (meth) acrylate (B) is urethane (meth) acrylate.   The mass ratio of “the thermoplastic resin having a radically polymerizable unsaturated group in the side chain (A) / 6-functional or higher functional (meth) acrylate (B)” is “83/17” to “57/43”. The photocurable resin composition as described in any one of 1-3.   The photocurable property according to any one of claims 1 to 4, wherein the thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain is a thermoplastic resin having a (meth) acryloyl group in the side chain. Resin composition.   The thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain is a copolymer of a (meth) acrylate having an epoxy group and a monomer copolymerizable therewith. The photocurable resin composition according to claim 1.   Furthermore, the photocurable resin composition as described in any one of Claims 1-6 containing an inorganic fine particle (D).   Content of inorganic fine particles (D) when the total mass part of the thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain and the hexafunctional or higher (meth) acrylate (B) is 100 parts by mass Is 5 to 400 parts by mass, The photocurable resin composition according to any one of claims 1 to 7.   The laminated sheet by which the layer of the photocurable resin composition as described in any one of Claims 1-8 was laminated | stacked by thickness 2-20 micrometers on the base material sheet.   A laminated molded product in which a cured laminated sheet obtained by curing a layer of the photocurable resin composition of the laminated sheet according to claim 9 is laminated on a molded product, wherein the cured layer is provided on the outermost surface. Goods.   A laminated molded article comprising: a step of molding and laminating the laminated sheet according to claim 9 to a molded article; and a step of curing the layer of the photocurable resin composition by irradiating an active energy ray thereafter. Manufacturing method.