JP5910272B2 - Decorative film - Google Patents

Description

  The present invention relates to a decorative film. Moreover, this invention relates to the sheet | seat for decorating which uses this film for decorating, and also the decorative molded product.

As one of methods for decorating the surfaces of members such as vehicle interior / exterior parts, home appliances, notebook PCs, mobile phones, and furniture, there is a method in which a decorative film is bonded to a substrate. A method using this decorative film is superior in design and durability as compared with conventional methods such as painting, and has been increasingly used.
As a method for attaching the decorative film to the substrate, for example, the decorative film is preformed by thermoforming (vacuum forming, pressure forming, vacuum pressure forming, etc.) outside the injection mold or inside the injection mold. After or without pre-molding, place in an injection mold and inject molten resin into it to form an injection-molded product and simultaneously attach a decorative film to the molded product (injection molding) The simultaneous bonding method) is known. In addition, as a method of bonding a decorative film to a molded product after injection molding, or a method of bonding a decorative film to a substrate other than a plastic such as metal, a decorative film is interposed through an adhesive layer. A method (three-dimensional surface decoration molding method) for vacuuming and pressing the substrate surface is known.
A PET film is widely known as a decorating film used in the decorating method as described above. However, the PET film has poor thermoformability and may not be applicable to complicated shapes with a high degree of deep drawing.
On the other hand, an acrylic resin film can be used for a complicated shape having a high deep drawability, but has low toughness and is easily broken during processing such as bending and trimming. In order to improve the mechanical strength, there is an acrylic resin film in which rubber particles are blended. However, the surface hardness and the shape stability under a high temperature and high humidity environment may be problematic. Further, it may be whitened under conditions where stress such as tension or bending is applied or under a high temperature and high humidity environment, and transparency may be impaired.
A multilayer film in which an acrylic resin layer is laminated on a polycarbonate resin layer (for example, Patent Document 1) has a large water absorption characteristic between an acrylic resin and a polycarbonate resin, and a difference in heat resistance typified by a glass transition temperature. May cause warping. If the decorative film is warped, there may be a problem that mechanical conveyance and accurate positioning during molding cannot be performed smoothly or the decorative film is peeled off from the base material. There is a multilayer film (for example, Patent Document 2) in which an acrylic resin layer is laminated on both sides of a polycarbonate resin layer as a method for suppressing warpage. However, when surface impact is applied to one side of the laminate, the acrylic on the opposite side is applied. Cracks are likely to occur in the resin layer, which may be a problem depending on the method of use.

JP 2011-201039 A JP 2010-125645 A

The present invention, from the above situation, a decorative film excellent in surface hardness, trimming properties, thermoformability, and shape stability in a high-temperature and high-humidity environment, and a decorative sheet using the decorative film And it aims at providing a decorative molded product.

  As a result of intensive studies, the inventors have found that a decorative film made of a multilayer film in which a vinyl copolymer resin having a specific structure is laminated on one side of a polycarbonate resin layer has surface hardness, trimming properties, thermoformability, and high temperature. The present inventors have found that it is excellent in shape stability under a high humidity environment, and reached the present invention.

This invention consists of 1-13 invention shown below.
1. A multilayer film in which a layer made of a vinyl copolymer resin (A) is laminated on one side of a layer made of a polycarbonate resin (B),
The resin (A) includes a (meth) acrylic ester structural unit (a) represented by the following formula (1) and a vinyl structural unit (b) represented by the following formula (2), and the structural unit It is a vinyl copolymer resin in which the ratio of the structural unit (a) to the total of (a) and (b) is 60 to 85 mol%.
The total thickness of the multilayer film is 30 to 600 μm, the thickness of the layer made of the resin (A) is 10 to 100 μm, and the thickness of the layer made of the resin (B) is 40 to 90% of the total thickness of the multilayer film. A decorative film using a multilayer film.

(In Formula (1), R1 is a hydrogen atom or a methyl group, R2 is a C1-C16 group which has a hydrocarbon group, and may have a hydroxyl group and an alkoxy group.)

(In Formula (2), R3 is a hydrogen atom or a methyl group, and R4 is a phenyl group that may have a substituent selected from a hydrocarbon group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group, and a halogen atom. Or a part or all of the aromatic double bond of the phenyl group is a hydrogenated group.)

2. 2. The decorative film as described in 1 above, wherein R1 and R2 are methyl groups.
3. 3. The decorative film as described in 1 or 2 above, wherein R4 is a phenyl group or a group in which part or all of the aromatic double bond of the phenyl group is hydrogenated.
4). The total number of aromatic double bonds in all R4s in the resin (A) is 30% or less of the total number of aromatic double bonds when all of R4s are phenyl groups. The film for decorating of description.
5. The above-mentioned 1 to 3, wherein the resin (A) is obtained by polymerizing at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer and then hydrogenating an aromatic double bond. 4. The decorative film according to any one of 4 above.
6). The film for decorating in any one of said 1-5 whose glass transition temperature of the said resin (A) is the range of 110-140 degreeC.
7). The film for decorating in any one of said 1-6 which contains a ultraviolet absorber in at least one of the said resin (A) and resin (B).
8). The decorative film according to any one of 1 to 7 above, wherein a hard coat treatment is performed on the resin (A) layer.
9. The film for decorating in any one of said 1-8 which performed the hard-coat process on the said resin (B) layer.
10. 10. The decorative film according to any one of the above 1 to 9, wherein at least one treatment selected from an antireflection treatment, an antifouling treatment, an antistatic treatment, a weather resistance treatment and an antiglare treatment is performed on one side or both sides.
11. A decorative molded product comprising the decorative film according to any one of 1 to 10 above.
12 A decorative sheet in which a thermoplastic resin sheet is laminated on the decorative film according to any one of 1 to 10 above.
13. A decorative molded product comprising the decorative sheet as described in 12 above.

ADVANTAGE OF THE INVENTION According to this invention, the film for decorating which is excellent in surface hardness, trimming property, thermoformability, and shape stability in a high-temperature, high-humidity environment is provided. It is suitably used for decorating the surface of members such as PCs and mobile phones.

  The multilayer film used for the decorative film of the present invention is a layer made of a vinyl copolymer resin (A) having a specific structure only on one side of a layer made of a polycarbonate resin (B) (hereinafter referred to as “X layer”). (Hereinafter referred to as “Y layer”) are laminated. The decorative film in which the Y layer is laminated only on one side of the X layer, when receiving external force from the Y layer side which is a hard structure, the opposite surface is an X layer with a soft structure, so that cracks and cracks occur. Hard to occur. On the other hand, the multilayer film in which the Y layer is laminated on both sides of the X layer is not preferable because when the external force is applied to one surface thereof, the opposite surface is a Y layer having a hard structure, so that cracks and cracks are likely to occur.

The vinyl copolymer resin (A) includes a (meth) acrylic ester structural unit (a) represented by the following formula (1) and a vinyl structural unit (b) represented by the following formula (2).
Here, “(meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.

(In Formula (1), R1 is a hydrogen atom or a methyl group, R2 is a C1-C16 group which has a hydrocarbon group, and may have a hydroxyl group and an alkoxy group.)

(In Formula (2), R3 is a hydrogen atom or a methyl group, and R4 is a phenyl group that may have a substituent selected from a hydrocarbon group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group, and a halogen atom. Or a part or all of the aromatic double bond of the phenyl group is a hydrogenated group.)

The structural unit (a) is a structural unit derived from a (meth) acrylic acid ester monomer described later, and R1 is a hydrogen atom or a methyl group. Moreover, R2 is a C1-C16 group which has a hydrocarbon group, and may have a hydroxyl group and an alkoxy group. Specifically, alkyl groups such as methyl group, ethyl group, butyl group, lauryl group, stearyl group, cyclohexyl group, isobornyl group; 2-hydroxyethyl group, 2-hydroxypropyl group, 2-hydroxy-2-methylpropyl group Hydroxyalkyl groups such as 2-alkoxyalkyl groups such as 2-methoxyethyl group and 2-ethoxyethyl group; aryl groups such as benzyl group and phenyl group. A plurality of R1 and R2 in the vinyl copolymer resin (A) may be the same or different.
The structural unit (a) is preferably a (meth) acrylic acid ester structural unit in which R2 is a methyl group and / or ethyl group, and more preferably a methyl methacrylate structural unit in which R1 is a methyl group and R2 is a methyl group. is there.

The structural unit (b) is a structural unit derived from an aromatic vinyl monomer or an aliphatic vinyl monomer described later, and R3 is a hydrogen atom or a methyl group. R4 includes a phenyl group, a group in which some of the aromatic double bonds of the phenyl group are hydrogenated, a group in which all of the aromatic double bonds of the phenyl group are hydrogenated (cyclohexyl group), and these And a group in which the hydrogen atom is substituted with a group selected from a hydrocarbon group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group and a halogen atom. Here, R4 is preferably one in which 70% or more of the aromatic double bond of the phenyl group is hydrogenated, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 98% or more. .
A plurality of R3 and R4 in the vinyl copolymer resin (A) may be the same or different.

The vinyl copolymer resin (A) mainly comprises the structural unit (a) and the structural unit (b).
The ratio of the structural unit (a) to the total of the structural units (a) and (b) in the present invention is in the range of 60 to 85 mol%.
If this ratio is less than 60%, the surface hardness of the vinyl copolymer resin (A) may be lowered, or the adhesion to the polycarbonate resin (B) or the hard coat paint may be lowered, which may not be practical. Also, if it exceeds 85%, shape stability in high temperature and high humidity environment decreases, and mechanical conveyance and accurate positioning during molding cannot be performed smoothly, and the decorative film peels off from the substrate. In some cases, it is not practical. More preferably, it is the range of 60-80%, More preferably, it is the range of 70-80%.

The vinyl copolymer resin (A) is not particularly limited, and was obtained by copolymerizing a (meth) acrylic acid ester monomer and an aromatic vinyl monomer and then hydrogenating an aromatic double bond derived from the aromatic vinyl monomer. And those obtained by copolymerizing (meth) acrylic acid ester monomers and aliphatic vinyl monomers are preferred, and the former is particularly preferred.

The (meth) acrylic acid ester monomer used at this time is preferably one having 4 to 20 carbon atoms. The (meth) acrylic acid ester monomer having 4 to 20 carbon atoms is not particularly limited, but methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, (meth ) Stearyl acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid (2-hydroxyethyl), (meth) acrylic acid (2-hydroxypropyl), (meth) acrylic acid (2 -Hydroxy-2-methylpropyl), (meth) acrylic acid (2-methoxyethyl), (meth) acrylic acid (2-ethoxyethyl), benzyl (meth) acrylate, phenyl (meth) acrylate, 2- ( And (meth) acryloyloxyethyl phosphorylcholine. Of these, methyl methacrylate is preferred.
Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene and α-methylstyrene are preferred.
Specific examples of the aliphatic vinyl monomer include vinylcyclohexane, isopropenylcyclohexane, 1-isopropenyl-2-methylcyclohexane, and the like. Of these, vinylcyclohexane is preferred.

A known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer. For example, the vinyl copolymer resin (A) is obtained by a bulk polymerization method, a suspension polymerization method, or a solution polymerization method. Can be manufactured.
In the solution polymerization method, a monomer composition containing a monomer, a chain transfer agent, and a polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ° C.

Examples of the solvent used in this case include hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane; ester solvents such as ethyl acetate and methyl isobutyrate; ketone solvents such as acetone and methyl ethyl ketone; tetrahydrofuran and dioxane And ether solvents such as methanol and alcohols such as isopropanol.

  The hydrogenation reaction of the aromatic double bond after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer is preferably performed in a solvent. The solvent used for the hydrogenation reaction may be the same as or different from the polymerization solvent. For example, hydrocarbon solvents such as cyclohexane and methylcyclohexane; ester solvents such as ethyl acetate and methyl isobutyrate; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as methanol and isopropanol A solvent etc. are mentioned.

  The method for hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out in a batch system or a continuous flow system at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. By setting the temperature to 60 ° C. or higher, the reaction time does not take too long, and by setting the temperature to 250 ° C. or lower, molecular chain scission and ester site hydrogenation are less likely to occur.

  Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium and rhodium or oxides, salts or complex compounds of these metals, carbon, alumina, silica, silica / alumina, zirconia. And a solid catalyst supported on a porous carrier such as diatomaceous earth.

  The vinyl copolymer resin (A) is preferably one in which 70% or more of the aromatic double bonds in the aromatic vinyl monomer are hydrogenated. That is, the proportion of the unhydrogenated portion of the aromatic ring in the structural unit derived from the aromatic vinyl monomer is preferably 30% or less, and if it exceeds 30%, the transparency of the vinyl copolymer resin (A) is high. May decrease. More preferably, it is 10% or less, More preferably, it is 5% or less.

  The polymerization of the (meth) acrylic acid ester monomer and the aliphatic vinyl monomer can be carried out by a known method, for example, the method described in JP-A-63-3011 or JP-A-63-170475.

  In addition to the vinyl copolymer resin (A), the Y layer may be blended with other resins as long as the transparency is not impaired. Examples of the resin that can be blended include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, and polycarbonate.

  The glass transition temperature of the vinyl copolymer resin (A) is preferably in the range of 110 to 140 ° C. When the glass transition temperature is 110 ° C. or higher, the shape stability of the decorative film provided in the present invention under high temperature and high humidity is improved, and appearance defects such as wrinkles and yuzu skin during thermoforming are reduced. Moreover, by being 140 degrees C or less, it is excellent in workability, such as the continuous heat forming by a mirror surface roll and a shaping roll, or the batch type heat forming by a mirror surface mold or a shaping die. In addition, the glass transition temperature in this invention is a temperature when using a differential scanning calorimetry apparatus and measuring by 10 mg of samples and the temperature increase rate of 10 degree-C / min, and calculating by the midpoint method.

  The polycarbonate resin (B) used by this invention is not specifically limited, The polymer manufactured by the well-known method from the bisphenol compound can be used. For example, a carbonate polymer obtained by a transesterification method from 2,2-bis (4-hydroxyphenyl) propane and a carbonic acid diester is exemplified.

  The vinyl copolymer resin (A) and / or the polycarbonate resin (B) in the present invention can be used by mixing with an ultraviolet absorber. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2-hydroxy. -4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, etc. Benzophenone ultraviolet absorbers; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3) -T-butyl-5-methylphenyl) benzotriazo Benzotriazole-based UV absorbers such as (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol; phenyl salicylate, 2,4-di-t-butyl Benzoate UV absorbers such as phenyl-3,5-di-t-butyl-4-hydroxybenzoate; hindered amine UV absorbers such as bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1, 3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphe Ru- (2-hydroxy-4-butoxyphenyl) 1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4 -Diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5 -Triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) Examples include triazine ultraviolet absorbers such as -1,3,5-triazine. The method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.

  Moreover, other various additives can be mixed and used for the vinyl copolymer resin (A) and polycarbonate resin (B) in this invention. Examples of the additive include an antioxidant, an anticolorant, an antistatic agent, a release agent, a lubricant, a dye, and a pigment. The method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.

As a manufacturing method of the multilayer film used for the decorative film of the present invention, a method by co-extrusion, a method of bonding through an adhesive layer, or the like can be used.
The method of coextrusion is not particularly limited. For example, in the feed block method, a Y block made of a vinyl copolymer resin (A) is laminated on one side of an X layer made of a polycarbonate resin (B) in a feed block, and a T die is used. After extruding into a film, it is cooled while passing through a forming roll to form a desired multilayer film. In the multi-manifold system, a Y layer is laminated on one side of the X layer in a multi-manifold die, extruded into a film, and then cooled while passing through a forming roll to form a desired multilayer film.
Moreover, the method of bonding through an adhesive layer is not particularly limited, and a known method can be used. For example, an adhesive is applied to one plate-like molded body using a spray, a brush, a gravure roll, an ink jet, etc., and the other plate-shaped molded body is stacked thereon and pressure-bonded until the adhesive is cured. A multilayer film is formed. In addition, an arbitrary adhesive resin layer can be laminated between the Y layer and the X layer during coextrusion.

  The total thickness of the multilayer film is preferably in the range of 30 to 600 μm. A thin multilayer film having a thickness of less than 30 μm is difficult to manufacture by extrusion due to mechanical constraints, and has a low mechanical strength and a high production failure probability. In addition, a thick multilayer film exceeding 600 μm requires time for thermoforming, has a small effect of improving physical properties and design properties, and increases costs. The total thickness of the multilayer film is more preferably in the range of 40 to 300 μm, still more preferably in the range of 50 to 200 μm.

The thickness of the Y layer of the multilayer film is preferably in the range of 10 to 100 μm. If it is less than 10 μm, the surface hardness, scratch resistance and weather resistance may be insufficient. If it exceeds 100 μm, the trimming property may be insufficient. Preferably it is the range of 30-60 micrometers.
The thickness of the X layer is preferably 40 to 90% of the total thickness of the multilayer film. If it is less than 40%, trimming properties may be insufficient. If it exceeds 90%, the surface hardness, scratch resistance and weather resistance may be insufficient. Preferably it is 50 to 85%.

A hard coat treatment may be applied to each surface of the multilayer film. For example, the X layer or the Y layer may be subjected to a hard coat treatment, or the X layer and the Y layer may be subjected to a hard coat treatment.
In the hard coat treatment in the present invention, a hard coat layer is formed by using a hard coat paint that is cured using heat energy and / or light energy. Examples of the hard coat paint to be cured using thermal energy include a resin composition containing a thermosetting resin such as a polyorganosiloxane type or a cross-linked acrylic type. In addition, as a hard coat paint to be cured using light energy, for example, a photocurable resin in which a photopolymerization initiator is added to a resin composition composed of a monofunctional and / or polyfunctional acrylate monomer and / or oligomer. Examples thereof include a composition.

  Examples of the hard coat paint to be cured using thermal energy applied on the Y layer in the present invention include, for example, 100 parts by mass of organotrialkoxysilane and 10 to 50% by mass of colloidal silica having a particle size of 4 to 20 nm. Examples thereof include a thermosetting resin composition in which 1 to 5 parts by mass of an amine carboxylate and / or a quaternary ammonium carboxylate is added to 100 parts by mass of a resin composition comprising 50 to 200 parts by mass of a silica solution.

  Examples of the hard coat paint to be cured using light energy applied on the Y layer in the present invention include, for example, 40 to 80% by mass of tris (acryloxyethyl) isocyanurate, and a bifunctional and / or trifunctional copolymerizable therewith. And a photocurable resin composition in which 1 to 10 parts by mass of a photopolymerization initiator is added to 100 parts by mass of a resin composition comprising 20 to 40% by mass of the (meth) acrylate compound.

  Examples of the hard coat paint to be cured by using the light energy applied on the X layer in the present invention include 20 to 60% by mass of 1,9-nonanediol diacrylate and a polyfunctional compound having two or more functions copolymerizable therewith ( A compound comprising a (meth) acrylate monomer and a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer and / or a bifunctional or higher polyfunctional polyester (meth) acrylate oligomer and / or a bifunctional or higher polyfunctional epoxy (meth) acrylate oligomer Examples thereof include a photocurable resin composition in which 1 to 10 parts by mass of a photopolymerization initiator is added to 100 parts by mass of a resin composition comprising 40 to 80% by mass.

  The method for applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. Examples thereof include brush, gravure roll, dipping, flow coating, spray, ink jet, and the method described in Japanese Patent No. 4161182.

Any one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment can be applied to one or both sides of the multilayer film. The methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be mentioned.

As the decorative film in the present invention, the multilayer film may be used as it is, or a design layer may be formed on the X layer of the multilayer film to form a decorative film. The design layer is a layer that represents a pattern or the like by printing or the like, and examples thereof include woodgrain, metal, stone, grain, texture, geometric pattern, characters, and symbols. The design layer may have a function such as conductivity in addition to the purpose of decoration. The material constituting the design layer may be any material that can be laminated with good adhesion to adjacent layers such as the X layer and the base material.

The method for forming the design layer in the present invention is not particularly limited, and a known method can be used. The design layer may be directly laminated on the X layer, or may be laminated via a primer layer to improve adhesion. For example, there are methods such as continuous gravure printing and silk printing, etc. that directly prints the wood grain and various designs on the surface, metal plating-like decoration by vapor deposition and sputtering, etc., and decoration such as printing and vapor deposition The method of laminating other applied resin films is mentioned. The decorative film obtained as described above is excellent in transparency, surface hardness, trimming properties, thermoformability and shape stability under high-temperature and high-humidity environment. It is useful as a decorative film to be constructed.

The decorative film of the present invention can be laminated on a thermoplastic resin sheet so that the Y layer side is disposed as the outermost layer to obtain a decorative sheet. As a resin constituting the thermoplastic resin sheet, for example, ABS resin, polycarbonate resin, polystyrene resin, polypropylene resin, acrylic resin, polyvinyl chloride resin, polyurethane resin, polyester resin, or any of them The mixture of 2 or more types is mentioned.

The method for laminating the decorative film on the thermoplastic resin sheet in the present invention is not particularly limited, and a known method can be used. The thermoplastic resin sheet may be directly laminated on the X layer or the design layer, or may be laminated via an adhesive layer. The decorative sheet obtained as described above is excellent in transparency, surface hardness, trimming properties, thermoformability, and shape stability in a high temperature and high humidity environment, and is integrated with a base material to produce a decorative molded product. It is useful as a decorative sheet to constitute.

A decorative molded product can be obtained by laminating the decorative film or decorative sheet obtained as described above on a thermoplastic resin molded product so that the Y layer side is disposed as the outermost layer. Examples of the resin constituting the thermoplastic resin molded article include ABS resin, polycarbonate resin, polystyrene resin, polypropylene resin, acrylic resin, polyvinyl chloride resin, polyurethane resin, and polyester resin. Or a mixture of two or more thereof.

The method for obtaining the decorative molded product in the present invention is not particularly limited, and a known method can be used. For example, an injection molding simultaneous bonding method or a three-dimensional surface decoration molding method can be used. The injection molding simultaneous bonding method is a method in which a decorative film or a decorative sheet is preformed by thermoforming (vacuum molding, pressure molding, vacuum pressure molding, etc.) outside the injection mold or in the injection mold, or Without pre-molding, it is placed in an injection mold, and by injecting molten resin there, an injection molded product is formed, and at the same time, a decorative film or a decorative sheet is bonded to the molded product. . The three-dimensional surface decoration molding method is suitably used when the decorative film is bonded to a molded product after injection molding, or when the decorative film is bonded to a base material other than plastic such as metal. It is performed by vacuuming and pressing the decorative film or the decorative sheet to the substrate surface through the adhesive layer. The decorative molded product obtained as described above is excellent in transparency, surface hardness, trimming properties, thermoformability and shape stability under high temperature and high humidity environment, vehicle interior / exterior parts, home appliances, notebook PCs, It can be used for various applications such as mobile phones and furniture.

Hereinafter, the present invention will be described specifically by way of examples. However, this invention is not restrict | limited at all by these Examples.
Evaluation of the decorative film obtained in the examples and comparative examples was performed as follows.

<Surface hardness evaluation>
Consistent with JIS K 5600-5-4, the hardness that gradually increased the hardness on the surface of the vinyl copolymer resin (A) layer at an angle of 45 degrees with respect to the surface and a load of 750 g and pressed the pencil, and did not produce any scratches. The pencil hardness was evaluated as the pencil hardness. Pencil hardness of 2H or higher was accepted for the hard-coated untreated specimens, and pencil hardness of 3H or higher was accepted for the hard-coated specimens.

<Trimming evaluation>
When the test piece used for the following shape stability evaluation and thermoformability evaluation was cut out, the state of the end portion was visually observed. Those in which no cracks or cracks occurred were regarded as acceptable.

<Evaluation of shape stability under high temperature and high humidity>
The test piece was cut into a size of 12 cm in the width direction and 6 cm in the extrusion direction, and the condition was adjusted by leaving it in an environment of a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more. The test piece was hung in a constant temperature and humidity chamber set at a temperature of 85 ° C. and a relative humidity of 85%, with the center of the upper end of the test piece as a fulcrum in such a direction that the extrusion direction was parallel to the gravity direction. After 24 hours, the test piece was taken out of the constant temperature and humidity chamber, and hung in an environment with a temperature of 23 ° C. and a relative humidity of 50%. The test piece that was curved before and after the test was placed on a horizontal surface such that the convex portion was on top, and the maximum height from the horizontal surface was measured. When the vinyl copolymer resin (A) layer is convex, the amount of warpage is positive, and when it is concave, it is expressed as a negative amount of warpage. The amount of warpage is subtracted from the amount of warpage after the test before the test. Asked. The amount of warpage change was within ± 3.0 mm as acceptable.

<Evaluation of thermoformability>
Cut out the test piece to a size of 25 cm x 40 cm, set it in the frame of a compressed air vacuum molding machine (manufactured by Asano Laboratories) with the vinyl copolymer resin (A) layer facing up, and heat both sides of the test piece with a heater Heated. When the surface temperature of the test piece reached 190 ° C., the mold was lifted from below and evacuated while being pressed. The corner of the shaped product (20 mm long × 20 mm wide × 12 mm deep, with a corner edge curvature R of 0.8 mm) is sufficiently molded, and no wrinkles, slack, or itchy skin was accepted. .

<Comprehensive judgment>
The above-mentioned surface hardness evaluation, trimming evaluation, shape stability evaluation at high temperature and high humidity, and thermoformability evaluation all passed as a comprehensive judgment, and if even one failed, it was rejected.

Synthesis Example 1 [Production of Vinyl Copolymer Resin (A1)]
Methyl methacrylate / styrene copolymer resin (A1 ′) (Estyrene MS750 made by Nippon Steel Chemical Co., Ltd .: methyl methacrylate / styrene = 75/25) was dissolved in methyl isobutyrate (manufactured by Kanto Chemical Co., Inc.) and 10% by weight methyl isobutyrate The solution was adjusted. A 1000 mL autoclave apparatus was charged with 500 parts by weight of a 10% by weight methyl isobutyrate solution (A1 ′) and 1 part by weight of 10% by weight Pd / C (manufactured by NE Chemcat), and maintained at a hydrogen pressure of 9 MPa and 200 ° C. for 15 hours. The benzene ring site was hydrogenated. The catalyst was removed by a filter and introduced into a solvent removal apparatus to obtain a pellet-like vinyl copolymer resin (A1). As a result of the measurement by ¹ H-NMR, the proportion of the methyl methacrylate structural unit was 75 mol%, and as a result of the absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction rate at the benzene ring site was 99%.

Synthesis Example 2 [Production of vinyl copolymer resin (A2)]
Instead of the methyl methacrylate-styrene copolymer resin (A1 ′) used in Synthesis Example 1, methyl methacrylate / styrene copolymer resin (A2 ′) (Estyrene MS600 manufactured by Nippon Steel Chemical Co., Ltd .: methyl methacrylate / styrene = 63/37) Except for the above, a vinyl copolymer resin (A2) was obtained in the same manner as in Synthesis Example 1. As a result of measurement by ¹ H-NMR, the proportion of the methyl methacrylate structural unit was 63 mol%, and as a result of absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction rate at the benzene ring site was 99%.

Synthesis Example 3 [Production of vinyl copolymer resin (A3)]
In place of the methyl methacrylate-styrene copolymer resin (A1 ′) used in Synthesis Example 1, methyl methacrylate / styrene / α-methylstyrene copolymer resin (A3 ′) (clear pole manufactured by JSP: methyl methacrylate / styrene) Vinyl copolymer resin (A3) was obtained in the same manner as in Synthesis Example 1 except that / α-methylstyrene = 75/18/7). As a result of the measurement by ¹ H-NMR, the proportion of the methyl methacrylate structural unit was 75 mol%, and as a result of the absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction rate at the benzene ring site was 99%.

Synthesis Example 4 [Production of vinyl copolymer resin (A4)]
Instead of the methyl methacrylate-styrene copolymer resin (A1 ′) used in Synthesis Example 1, methyl methacrylate / styrene copolymer resin (A4 ′) (Estyrene MS500 manufactured by Nippon Steel Chemical Co., Ltd .: methyl methacrylate / styrene = 48/52) Except for the above, a vinyl copolymer resin (A4) was obtained in the same manner as in Synthesis Example 1. As a result of measurement by ¹ H-NMR, the proportion of the methyl methacrylate structural unit was 48 mol%, and as a result of the absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction rate at the benzene ring site was 99%.

Synthesis Example 5 [Production of photocurable resin composition (a) to be coated on vinyl copolymer resin (A) layer]
In a mixing vessel equipped with a stirring blade, 60 parts of tris (2-acryloxyethyl) isocyanurate (manufactured by Aldrich), 40 parts of neopentyl glycol oligoacrylate (manufactured by Osaka Organic Chemical Industry, trade name: 215D), 1,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by Ciba Japan, trade name: DAROCUR TPO) 1 part, 1-hydroxycyclohexyl phenyl ketone (manufactured by Aldrich) 0.3 part, 2- (2H -Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (product name: TINUVIN234) manufactured by Ciba Japan Co., Ltd. It stirred for 1 hour, hold | maintaining, and the photocurable resin composition (a) was obtained.

Synthesis Example 6 [Production of photocurable resin composition (b) coated on polycarbonate resin (B) layer]
In a mixing tank equipped with a stirring blade, 40 parts of 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Viscoat # 260) and hexafunctional urethane acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., commercial product) Name: U-6HA) 40 parts, succinic acid / trimethylolethane / acrylic acid molar ratio 1/2/4 condensate 20 parts, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Ciba Japan) Product, product name: DAROCUR TPO) 2.8 parts, benzophenone (manufactured by Aldrich) 1 part, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenyl) A composition consisting of 1 part of ethyl) phenol (Ciba Japan Co., Ltd., trade name: TINUVIN234) was introduced and stirred for 1 hour while maintaining at 40 ° C. The mixture was stirred to obtain a photocurable resin composition (b).

Example 1
A multilayer film using a multilayer extruder having a single-screw extruder having a shaft diameter of 35 mm, a single-screw extruder having a shaft diameter of 65 mm, a feed block connected to the whole extruder, and a T-die connected to the feed block Was molded. The vinyl copolymer resin (A1) obtained in Synthesis Example 1 was continuously introduced into a single screw extruder having a shaft diameter of 35 mm and extruded under the conditions of a cylinder temperature of 225 ° C. and a discharge speed of 12.0 kg / h. In addition, a polycarbonate resin (B) (manufactured by Mitsubishi Engineering Plastics, trade name: Iupilon S-1000R, hereinafter sometimes referred to as “PC”) is continuously introduced into a single screw extruder having a shaft diameter of 65 mm, and the cylinder temperature Extrusion was performed at 265 ° C. and a discharge speed of 42.0 kg / h. The feed block connected to the entire extruder was provided with two types and two layers of distribution pins, and the layers were laminated by introducing (A1) and (B) at a temperature of 270 ° C. It is extruded in the form of a film with a T-die having a temperature of 260 ° C. connected to the tip, and cooled while transferring the mirror surface with two mirror finish rolls having a temperature of 110 ° C. and 130 ° C. from the upstream side, and (A1) and (B ) (D1) was obtained. The thickness of the obtained laminate was 180 μm, and the thickness of the (A1) layer was 40 μm near the center. The surface hardness evaluation passed 2H, the trimming evaluation passed, the shape stability evaluation under high temperature and high humidity passed -1.2 mm, the thermoformability evaluation passed, and the overall judgment passed.

Example 2
A bar coater so that the coating thickness after curing the photocurable resin composition (a) obtained in Synthesis Example 5 on the (A) layer of the laminate (D1) obtained in Example 1 is 1 to 2 μm. , Coated with PET film and pressure-bonded, and cured by irradiating with UV rays at a line speed of 1.5m / min on a conveyor equipped with a high pressure mercury lamp with a light source distance of 12cm and an output of 80W / cm. And the laminated body (E1) provided with the hard coat in the (A) layer was obtained. The surface hardness evaluation passed 3H, the trimming evaluation passed, the shape stability evaluation under high temperature and high humidity passed -1.0 mm, the thermoformability evaluation passed, and the overall judgment passed.

Example 3
A bar coater so that the coating thickness after curing the photocurable resin composition (a) obtained in Synthesis Example 5 on the (A) layer of the laminate (D1) obtained in Example 1 is 1 to 2 μm. So that the coating thickness after curing of the photocurable resin composition (b) obtained in Synthesis Example 6 on the (B) layer is 1 to 2 μm. Apply using a bar coater, cover with PET film, and press-bond. PET film is cured by UV irradiation at a line speed of 1.5 m / min on a conveyor equipped with a high-pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm. Was peeled off to obtain a laminate (E2) having a hard coat on the (A) layer and the (B) layer. The surface hardness evaluation passed 3H, the trimming evaluation passed, the shape stability evaluation under high temperature and high humidity passed -1.0 mm, the thermoformability evaluation passed, and the overall judgment passed.

Example 4
Except that the discharge rate of the vinyl copolymer resin (A1) used in Example 1 was 12.0 kg / h and the discharge rate of the polycarbonate resin (B) was 25.5 kg / h, the same as in Example 1 ( A laminate (D2) of A1) and (B) was obtained. The thickness of the obtained laminate was 125 μm, and the thickness of the (A1) layer was 40 μm near the center. The surface hardness evaluation passed 2H, the trimming evaluation passed, the shape stability evaluation under high temperature and high humidity passed -1.0 mm, the thermoformability evaluation passed, and the overall judgment passed.

Example 5
Lamination of (A2) and (B) in the same manner as in Example 1 except that the vinyl copolymer resin (A2) obtained in Synthesis Example 2 was used instead of the vinyl copolymer resin (A1) used in Example 1. A body (D3) was obtained. The thickness of the obtained laminate was 180 μm, and the thickness of the (A2) layer was 40 μm near the center. The surface hardness evaluation was 2H, the trimming evaluation was pass, the shape stability evaluation under high temperature and high humidity was -0.8mm, the thermoformability evaluation was pass, and the comprehensive judgment was pass.

Example 6
Lamination of (A3) and (B) in the same manner as in Example 1 except that the vinyl copolymer resin (A3) obtained in Synthesis Example 3 was used instead of the vinyl copolymer resin (A1) used in Example 1. A body (D4) was obtained. The thickness of the obtained laminate was 180 μm, and the thickness of the (A3) layer was 40 μm near the center. The surface hardness evaluation was 2H, the trimming evaluation was pass, the shape stability evaluation under high temperature and high humidity was -0.8mm, the thermoformability evaluation was pass, and the comprehensive judgment was pass.

Comparative Example 1
Lamination of (A4) and (B) in the same manner as in Example 1 except that the vinyl copolymer resin (A4) obtained in Synthesis Example 4 was used instead of the vinyl copolymer resin (A1) used in Example 1. A body (D5) was obtained. The thickness of the obtained laminate was 180 μm, and the thickness of the (A4) layer was 40 μm near the center. The surface hardness evaluation failed with H, the trimming evaluation evaluated, the shape stability evaluation under high temperature and high humidity passed with -0.8 mm, the thermoformability evaluation passed, and the overall judgment failed.

Comparative Example 2
Except that the discharge rate of the vinyl copolymer resin (A1) used in Example 1 was 15.0 kg / h and the discharge rate of the polycarbonate resin (B) was 4.3 kg / h, the same as in Example 1 ( A laminate (D6) of A1) and (B) was obtained. The thickness of the obtained laminate was 180 μm, and the thickness of the (A1) layer was 140 μm near the center. The surface hardness evaluation is 2H, the trimming evaluation is cracking failure, the shape stability evaluation under high temperature and high humidity is -1.3mm, the thermoformability evaluation is pass, and the comprehensive judgment is not pass. there were.

Comparative Example 3
Instead of the vinyl copolymer resin (A1) used in Example 1, polymethyl methacrylate resin (A5) (manufactured by ARKEMA, trade name: ALTUGLAS V020) was used, and the cylinder temperature of (A5) was 250 ° C. A laminate (D7) of (A5) and (B) was obtained in the same manner as Example 1 except for the above. The thickness of the obtained laminate was 180 μm, and the thickness of the (A5) layer was 40 μm near the center. The surface hardness evaluation was 2H, the trimming evaluation was acceptable, the shape stability evaluation under high temperature and high humidity was -26.8 mm, and the thermoformability evaluation was unacceptable due to the generation of yuzu skin. Therefore, comprehensive judgment was disqualified.

Comparative Example 4
Instead of the vinyl copolymer resin (A1) used in Example 1, polymethyl methacrylate resin (A5) (manufactured by ARKEMA, trade name: ALTUGLAS V020) was used, and the cylinder temperature of (A5) was 250 ° C. ( A5) The discharge speed was 12.0 kg / h, the discharge speed of the polycarbonate resin (B) was 15.0 kg / h, and the feed block distribution pins were of two types and three layers. A laminate (D8) in which (A5) was laminated on both sides of (B) was obtained. The thickness of the obtained laminate was 180 μm, and the thickness of the (A5) layer was 40 μm near the center. The surface hardness evaluation was 2H, the trimming evaluation was rejected due to the occurrence of cracks, the shape stability evaluation under high temperature and high humidity was +1.0 mm, and the thermoformability evaluation was rejected due to the generation of yuzu skin. Therefore, comprehensive judgment was disqualified.

From Table 1, the decorative film of the present invention is excellent in surface hardness, trimming properties, thermoformability, and shape stability in a high temperature and high humidity environment.

The decorative film of the present invention is characterized by excellent surface hardness, trimming properties, thermoformability, and shape stability under high-temperature and high-humidity environments, such as vehicle interior / exterior parts, home appliances, notebook PCs, mobile phones, etc. It is suitably used for decorating various member surfaces.

Claims (12)

A multilayer film in which a layer made of a vinyl copolymer resin (A) is laminated on one side of a layer made of a polycarbonate resin (B),
The resin (A) includes a (meth) acrylic ester structural unit (a) represented by the following formula (1) and a vinyl structural unit (b) represented by the following formula (2), and the structural unit It is a vinyl copolymer resin in which the ratio of the structural unit (a) to the total of (a) and (b) is 60 to 85 mol%.
The total number of aromatic double bonds in all R4s in the resin (A) is 30% or less of the total number of aromatic double bonds when all R4s are phenyl groups;
The total thickness of the multilayer film is 30 to 600 μm, the thickness of the layer made of the resin (A) is 10 to 100 μm, and the thickness of the layer made of the resin (B) is 40 to 90% of the total thickness of the multilayer film. A decorative film using a multilayer film.

(In Formula (1), R1 is a hydrogen atom or a methyl group, R2 is a C1-C16 group which has a hydrocarbon group, and may have a hydroxyl group and an alkoxy group.)
(In Formula (2), R3 is a hydrogen atom or a methyl group, and R4 is a phenyl group that may have a substituent selected from a hydrocarbon group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group, and a halogen atom. Or a part or all of the aromatic double bond of the phenyl group is a hydrogenated group.)   The film for decorating according to claim 1, wherein the R1 and R2 are methyl groups.   The decorative film according to claim 1 or 2, wherein R4 is a phenyl group or a group in which part or all of the aromatic double bond of the phenyl group is hydrogenated. The resin (A) is, according to claim 1 in which at least one (meth) aromatic double bond of an acrylate ester monomer and at least one obtained from an aromatic vinyl monomer polymer is hydrogenated The film for decorating in any one of -3 . The glass transition temperature of the said resin (A) is the range of 110-140 degreeC, The film for decorating in any one of Claims 1-4 . The film for decorating in any one of Claims 1-5 which contains a ultraviolet absorber in at least one of the said resin (A) and resin (B). The film for decorating in any one of Claims 1-6 which performed the hard-coat process on the said resin (A) layer. Decorative film according to any one of claims 1 to 7 were subjected to hard coat treatment on the resin (B) layer. The decorative film according to any one of claims 1 to 8 , wherein one or more treatments selected from an antireflection treatment, an antifouling treatment, an antistatic treatment, a weather resistance treatment and an antiglare treatment are performed on one side or both sides. A decorative molded product comprising the decorative film according to any one of claims 1 to 9 . Claim 1-9 decorative sheet for the thermoplastic resin sheet is laminated decorative film according to any one of. A decorative molded product comprising the decorative sheet according to claim 11 .