WO2017022704A1 - Formable coating film - Google Patents

Abstract

The present invention provides a formable coating film that is superior in formability (extensibility) and chemical resistance. The formable coating film according to the present invention is obtained by forming, on an acrylic film, a coating layer formed of an ionizing radiation curable resin composition containing a polyfunctional acrylate-based resin that has in the structure thereof a hydroxyl group and of which the weight average molecular weight (Mw) is 6.0×10³-1.0×10⁴, wherein the area size of a 3200-3500cm^-1 range in an infrared spectrum of the surface of the coating layer is 0.3-1.0 times the area size of a 1650-1750cm^-1 range.

Description

Coating film for molding

The present invention is a resin whose surface is decorated or protected by printing or uneven shape by an in-mold molding method, a film insert molding method, a three-dimensional laminate molding method, a vacuum molding method, a pressure-air molding method, a thermal lamination method, or the like. The present invention relates to a coating film for molding that is suitably used for manufacturing a molded product.

Resin molded products are often used for portable information terminal devices such as mobile phones, notebook computers, home appliances, and automobile interior and exterior parts. As products become more commoditized, the need for differentiation in these products is increasing. Conventionally, as a method for decorating a resin molded product, a colored paint is applied or screen printed on the surface of a three-dimensional resin molded product by injection molding or the like. Furthermore, a method of applying a clear coating by spraying or dipping has been performed for the purpose of protecting the surface of the product.

However, such conventional methods are difficult to decorate with high design, and there is a concern about the impact on the work environment by chemical substances such as volatile solvents contained in the paint used in spray coating etc. There is. Therefore, as an alternative method, an in-mold molding method, a film insert molding method, or a three-dimensional laminate molding method using a decorative film with high design in which a coating layer is provided on a printed base film has been proposed.

The in-mold molding method is a technique in which a decorative film is laminated on the surface of a resin molding by simultaneously performing vacuum molding and injection in an injection mold. In addition, the film insert molding method is, for example, after a decorative film is preliminarily heated (preliminary heating) and a preform of the decorative film is obtained by a vacuum molding method, a pressure molding method, hot pressing between molds, or the like. In the next process, a decorative film preformed in a mold by injection molding is placed, laminated with a resin molding by injection molding, and integrated.
The three-dimensional laminate molding is a molding method in which a decorative sheet with an adhesive layer softened by heat is attached to a molded body in a vacuum / pressure state. At this time, for the decorative film, a backer sheet made of a thermoplastic resin sheet such as ABS resin, or an adhesive layer in advance, as necessary for preforming, maintaining the shape of the sheet during lamination, preventing cracking, and improving adhesion Etc. can also be laminated.
In addition, the above vacuum forming method heats the decorative film in the mold (preliminary heating), then softens the decorative film, stretches it between the decorative film and closes it to the mold, and molds the mold shape. This is a molding method. The compressed air molding method is a method in which a decorative film is heated (preliminarily heated) and softened in a mold as needed, and then the decorative film is brought into close contact with the mold by pressurization with a heated gas as necessary. This is a molding method for shaping a mold shape. Hot pressing between molds is a molding method in which a film is sandwiched between a male mold and a female mold, and the film is pressed while applying heat or pressure.

Conventionally, various configurations have been proposed as a coating film for molding used in a molding method using a decorative film as described above (see Patent Documents 1 to 4, etc.).

JP 2009-274378 A JP 2012-81628 A JP 2012-193265 A JP 2012-512247 A

As the coating film for molding is used in various fields, it has sufficient extensibility to follow three-dimensional molding (because it does not crack in the base film layer or coating layer even if it is stretched) Since the coating film for molding on the surface of the resin molded product has many opportunities to come into contact with the human body, chemical resistance is also regarded as important. For example, in a coating film for molding applied to resin molded products such as automobile interior parts, it is resistant to lactic acid components contained in human sebum and sweat, sunscreen cream, lotion, etc. in summer and hot areas Since chemical properties are also regarded as important, high chemical resistance is required in addition to high moldability. In particular, coating films used for decoration by in-mold molding, insert molding, or three-dimensional laminate molding methods require a higher level of chemical resistance because the base film layer and coating layer are stretched and thinned. Has been.

However, in the prior art, there has not been obtained a coating film for molding that can achieve both sufficient moldability (extensibility) and chemical resistance in a stretched state after molding.

Therefore, an object of the present invention is to provide a coating film for molding which is excellent in moldability (extension) and chemical resistance (particularly chemical resistance in a stretched state after molding).

As a result of intensive studies to solve the above problems, the present inventor is a cause of chemical marks caused by lactic acid components contained in human sebum, sweat, oil components contained in sunscreen creams, lotions, etc. It was found that a coating layer made of a resin containing many hydroxyl groups in the structure is excellent in chemical resistance. In addition, if the weight average molecular weight (Mw) before UV irradiation of a UV (ultraviolet) curable resin containing a hydroxyl group in the structure is 6.0 × 10 ³ or more, high elongation is maintained while maintaining high chemical resistance. I found out that I can do it. And since chemical resistance can be obtained by controlling the amount of hydroxyl groups in the coating layer resin, it is possible to achieve both moldability and chemical resistance by using a resin with high moldability and high elongation. Has been found to be excellent in chemical resistance after stretching of the coating film.
That is, the present inventor has found that the above problems can be solved by an invention having the following configuration.
The configuration of the present invention is as follows.

The first invention is an ionizing radiation curable resin composition comprising a polyfunctional acrylate resin having a weight average molecular weight (Mw) of 6.0 × 10 ³ or more and 1.0 × 10 ⁴ or less having a hydroxyl group in the structure on an acrylic film. a molding coated film formed a coating layer, an area of 3200 ~ 3500 cm ^-1 region of the infrared spectrum of the coating layer surface, 1650 ~ 1750 cm ^-1 or 0.3 times the area of the region 1 made. It is a coating film for molding characterized by being 0 times or less.

According to a second invention, in the first invention, the polyfunctional acrylate resin is a urethane acrylate resin having a urethane resin composition having a main chain and a (meth) acryloyl group in a side chain. It is a coating film for molding.
A third invention is the coating film for molding according to the first or second invention, wherein the coating layer has a thickness in the range of 1 μm to 3 μm.

According to a fourth invention, in any one of the first to third inventions, after applying the paint containing the ionizing radiation curable resin composition to the acrylic film with a dry coating thickness of 1 to 3 μm, A test piece having a width of 10 mm and a length of 80 mm cured by electron beam irradiation was prepared, and when the test piece was pulled at a temperature of 120 ° C. and a tensile speed of 50 mm / min and a distance between chucks of 40 mm, the ionizing radiation curing was performed. It is a molding coating film characterized by having an elongation of 200% or more (according to a test method specified in JIS K5600-5-4) until a crack occurs in a coating layer made of a mold resin composition.

A fifth invention is the thermoplastic acrylic resin according to any one of the first to fourth inventions, wherein the acrylic film contains 50 to 100% by weight of methyl methacrylate units and 0 to 50% by weight of other units. A molding coating film characterized by molding a resin composition containing 20 to 100 parts by weight.

A sixth invention is a coating film for molding according to any one of the first to fifth inventions, wherein the acrylic film contains a rubber component.
According to a seventh invention, in the sixth invention, the rubber component has a single-layer or multi-layer core layer including one or more elastic layers made of a crosslinked polymer mainly composed of an acrylate ester; A molding coating film characterized by being rubber particles having a core-shell structure comprising a shell layer containing an acid ester as a main component.

An eighth invention is a molding characterized in that in any of the first to seventh inventions, it is a surface decorative film or a surface protective film for in-mold molding, insert molding, or three-dimensional laminate molding. Coating film.

According to a ninth aspect of the present invention, there is provided a printed article for surface protection or decoration, comprising a printing, coloring or decorative layer on at least one surface of the molding coating film of any one of the first to eighth aspects of the invention. It is a film.
A tenth aspect of the present invention is a film for surface protection or decoration of a molded article, characterized in that it has a surface shape having irregularities on at least one surface of the molding coating film of any one of the first to eighth aspects of the invention. .

In an eleventh aspect of the invention, there is provided a decorative sheet or decoration for automobile interior, in which the film of any one of the first to tenth aspects of the invention is laminated on the surface of a sheet or molded body containing a thermoplastic resin or a thermosetting resin. It is a decorative panel.
According to a twelfth aspect of the present invention, there is provided a portable electronic device, an acoustic device or an electric device in which the film of any one of the first to tenth aspects of the invention is laminated on the surface of a sheet or a molded body containing a thermoplastic resin or a thermosetting resin. It is a decorative or protective panel for a product casing or surface.

According to the present invention, an ionizing radiation curable resin composition comprising a polyfunctional acrylate-based resin having a weight average molecular weight (Mw) having a hydroxyl group in the structure of 6.0 × 10 ³ or more and 1.0 × 10 ⁴ or less on an acrylic film. The area of the 3200 to 3500 cm ⁻¹ region of the infrared spectrum of the coating layer surface is 0.3 to 1.0 times the area of the 1650 to 1750 cm ⁻¹ region. Thus, it is possible to provide a molding coating film having excellent moldability (extension) and chemical resistance (particularly chemical resistance in a stretched state after molding). In particular, chemical resistance to the oil and fat components contained in the sunscreen creams and lotions described above can be improved.

The polyfunctional acrylate-based resin is preferably a urethane acrylate-based resin having a urethane resin composition having a main chain and a (meth) acryloyl group in a side chain in order to enhance the effects of the present invention.
In addition, the film thickness of the coating layer is preferably in the range of 1 μm to 3 μm from the viewpoint of enhancing the effects of the present invention.
Moreover, it is suitable when the said elongation rate of the coating film for shaping | molding is 200% or more, when expressing the effect of this invention favorably.

The acrylic film may be formed by molding a resin composition containing 20 to 100 parts by weight of a thermoplastic acrylic resin containing 50 to 100% by weight of methyl methacrylate units and 0 to 50% by weight of other units. This is suitable for enhancing the effect of the present invention.
Moreover, it is suitable for improving the effect of this invention that the said acrylic film contains a rubber component. In this case, the rubber component is composed of a core layer having a single layer or a multilayer structure including one or more elastic layers made of a crosslinked polymer mainly composed of an acrylate ester, and a shell layer mainly composed of a methacrylate ester. It is preferable that the rubber particles have a core-shell structure.

The coating film for molding of the present invention is suitable as a surface decorative film or surface protective film for in-mold molding, insert molding, or three-dimensional laminate molding.
Moreover, the coating film for molding of the present invention is suitable as a film for protecting the surface of a molded product having a printing, coloring or decorative layer on at least one surface thereof.
Further, the molding coating film of the present invention is suitable as a film for protecting the surface of a molded article having a surface shape having irregularities on at least one surface thereof or for decorating.

Moreover, the laminated body which laminated | stacked said each film based on this invention on the surface of the sheet | seat or molded object containing a thermoplastic resin or a thermosetting resin is suitable as a decoration sheet or a decoration panel for motor vehicle interior. .
In addition, a laminate in which each of the films according to the present invention is laminated on the surface of a sheet or a molded body containing a thermoplastic resin or a thermosetting resin is a casing for a portable electronic device, an acoustic device, or an electrical product, Suitable for surface decoration or protective panel.

Hereinafter, although the form for implementing this invention is demonstrated in detail, this invention is not necessarily limited to the following embodiment.
The molding coating film according to one embodiment of the present invention is obtained by forming a coating layer on an acrylic film as a base film, and this coating layer includes a polyfunctional acrylate resin having a hydroxyl group in the structure. It consists of an ionizing radiation curable resin composition.
Hereinafter, the configuration will be described in detail.

[Acrylic film]
First, the acrylic film will be described.
An acrylic film can be preferably used for the base film of the coating film for molding of the present invention. By using an acrylic film as the base film, the coating film for molding of the present invention has excellent transparency, weather resistance, surface hardness, stretchability during thermoforming, and secondary moldability, and polycarbonate. Resins, acrylic resins, ASA resins, ABS resins, AS resins and other styrene resins, saturated or unsaturated polyester resins, vinyl ester resins, epoxy resins, polyamide resins, polyphenylene sulfide resins, polyphenylene oxide resins, polyacetal resins, polylactic acid Decoration made of thermoplastic resin such as resin, cellulose acylate resin, olefin- (meth) acrylic acid derivative copolymer resin or thermosetting resin, and fiber / filler reinforced composite material using these. The adhesion to the substrate is excellent.

As the acrylic resin used in the acrylic film used in the present invention, conventionally known ones can be used. From the viewpoint of hardness and moldability, methyl methacrylate units of 50 to 100% by weight and other structural units of 0 to 50 are used. It is preferable to contain 20 to 100 parts by weight of a thermoplastic acrylic polymer consisting of% by weight. Other structural units include, for example, methyl acrylate, butyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, β-hydroxyethyl acrylate, phenoxyethyl acrylate , Benzyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, acrylic acid derivatives such as acrylic acid, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate , Benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate, adamantyl methacrylate Examples include methacrylic acid derivatives such as methacrylic acid, vinyl cyanides such as acrylonitrile and methacrylonitrile, aromatic vinyl derivatives such as styrene, vinyltoluene, and α-methylstyrene, and vinylidene halides such as vinylidene chloride and vinylidene fluoride. . These may be used alone or in combination of two or more.

The method for producing the acrylic resin is not particularly limited, and known polymerization methods such as a known suspension polymerization method, bulk polymerization method, solution polymerization method, emulsion polymerization method, and dispersion polymerization method are applicable.

Also, in order to improve the heat resistance, rigidity, surface hardness and the like of the acrylic resin, a unit having a specific structure may be introduced by copolymerization, functional group modification or modification. Examples of such a specific structure include a glutarimide structure such as those disclosed in JP-A-62-89705, JP-A-02-178310, WO2005 / 54311, JP-A-2004-168882, and the like. A lactone ring structure as shown in JP-A No. 2006-171464, a (meth) acrylic acid unit as shown in JP-A No. 2004-307835, and a product obtained by thermal condensation cyclization thereof. And a glutaric anhydride structure, a maleic anhydride unit as shown in JP-A-5-119217, and an N-substituted maleimide unit as shown in WO2009 / 84541. For example, by introducing these structures into an acrylic resin, the molecular chain becomes more rigid, improving the heat resistance of the molding coating film of the present invention, improving the surface hardness, reducing heat shrinkage, chemical resistance and stain resistance. It can be expected to improve the effect.

Furthermore, a thermoplastic resin that is at least partially compatible with the acrylic resin may be used in combination with the acrylic resin as long as the object of the present invention is not impaired or reinforced. Examples of such thermoplastic resins include styrene-acrylonitrile resins, styrene- (meth) acrylic resins, styrene-maleic anhydride resins, styrene-N substituted or unsubstituted maleimide resins, styrene-acrylonitrile-butadiene resins, styrene. -Styrenic resins such as acrylonitrile-acrylic ester resin, polyvinyl chloride resin, polycarbonate resin, amorphous saturated polyester resin, polyamide resin, phenoxy resin, polyarylate resin, olefin- (meth) acrylic acid derivative resin, cellulose Examples thereof include cellulose derivatives such as acylate, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polylactic acid resin, and PHBH resin. Among these, styrene-based resins and polycarbonate resins have excellent compatibility with acrylic resins, and may improve the bending crack resistance, solvent resistance, low moisture absorption, etc. of the molding coating film of the present invention. Therefore, it is preferable.

The acrylic resin used in the present invention is more preferably an acrylic resin composition containing a rubber component. Such a rubber component can be obtained, for example, by polymerizing vinyl polymerizable units in the presence of particles of an acrylate ester-based cross-linked elastic body [cross-linked elastic body comprising a polymer mainly composed of an acrylate ester]. It is preferable to use a core-shell type graft copolymer having a hard outer layer portion.

More preferably, as shown in JP-A-2003-73520, an acrylic elastic graft copolymer using acrylic ester-based crosslinked elastic particles having a specific particle diameter and crosslinking density, or a special Acrylic elastic graft copolymer having a hard-soft-hard multilayer structure containing hard crosslinked acrylic particles inside the crosslinked rubber particles, for example, as shown in Japanese Patent Publication No. 55-27576 and Japanese Patent No. 3563166 It is preferable to use an acrylic resin composition containing a coalescence. By using an acrylic resin composition containing such an acrylic elastomeric graft copolymer, the molding coating film of the present invention can be made transparent, heat resistant, surface hardness, bending crack resistance, and bending whitening resistance. And a film having an excellent balance of physical properties such as stretchability and secondary formability during thermoforming.

As the acrylic elastomer graft copolymer preferably used in the present invention, an acrylic ester crosslinked elastomer having a layer structure of one layer or two or more layers containing a layer composed of one or more acrylic ester crosslinked elastomers. Those obtained by copolymerizing a monomer mixture (b) comprising 50 to 100% by weight of a methacrylic acid ester and 0 to 50% by weight of another copolymerizable vinyl monomer in the presence of particles are preferred. . In the acrylic ester-based crosslinked elastic particles having a structure of two or more layers, the acrylic ester-based crosslinked elastic layer may be present in any layer, but the outermost layer is an acrylate-based crosslinked elastic layer. It is more preferable to improve the bending cracking resistance.

The acrylic ester-based crosslinked elastic body has an acrylic ester, other vinyl monomers that can be copolymerized as required, and two or more non-conjugated double bonds per copolymerizable molecule. What polymerized the monomer mixture (a) which consists of a polyfunctional monomer can be used preferably. Monomers and polyfunctional monomers may all be mixed (one-stage polymerization) and used more than once (two-stage polymerization) by changing the composition of the monomer and polyfunctional monomer. The polymerization may be used separately.

As the acrylic ester used in the acrylic ester-based crosslinked elastic body, an alkyl acrylate is preferable, and an alkyl group having 1 to 12 carbon atoms can be particularly preferably used. Specific examples of preferable monomers include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, acrylic acid Examples include cyclohexyl and dodecyl acrylate. These may be used alone or in combination of two or more. The amount of the acrylate ester in the acrylate ester-based crosslinked elastic body is preferably 50 to 99.9 wt%, more preferably 70 to 99.9 wt%, based on 100 wt% of the monomer mixture (a), and 80 to 99 .9% by weight is most preferred. When the amount of acrylic ester is 50 to 99.9% by weight, the crosslinked elastic body has good rubber elasticity, the molding coating film of the present invention has excellent bending crack resistance and impact resistance, and secondary molding. Elongation tends to be good.

Examples of other copolymerizable vinyl monomers in the acrylic ester-based crosslinked elastomer include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-methacrylate -Methacrylic esters such as butyl, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, vinyl halides such as vinyl chloride and vinyl bromide, acrylonitrile, methacrylate. Vinyl cyanides such as ronitrile, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, aromatic vinyl derivatives such as styrene, vinyltoluene and α-methylstyrene, vinylidene chloride, vinylidyl fluoride Vinylidene halides such as acrylic acid, acrylic acid such as acrylic acid, sodium acrylate, calcium acrylate and salts thereof, β-hydroxyethyl acrylate, phenoxyethyl acrylate, benzyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate Acrylic acid derivatives such as acrylamide and N-methylol acrylamide, methacrylic acid and salts thereof such as methacrylic acid, sodium methacrylate, calcium methacrylate, methacrylamide, β-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, methacryl And methacrylic acid derivatives such as glycidyl acid, and maleic acid derivatives such as maleic anhydride, N-alkylmaleimide, and N-phenylmaleimide. These may be used alone or in combination of two or more. Among these, acrylic acid esters, methacrylic acid esters and aromatic vinyl derivatives are particularly preferable from the viewpoint of weather resistance and transparency. The amount of the other copolymerizable vinyl monomer in the acrylic ester-based crosslinked elastic body is preferably 0 to 49.9% by weight, preferably 0 to 30% by weight, based on 100% by weight of the monomer mixture (a). Is more preferable, and 0 to 20% by weight is most preferable. When the amount of the other vinyl monomer exceeds 49.9% by weight, the bending cracking resistance and impact resistance are lowered, the elongation at the time of secondary molding is lowered, and cracks are caused during molding and cutting. May be more likely to occur.

The polyfunctional monomer having two or more non-conjugated double bonds per molecule that can be copolymerized in the acrylic ester-based crosslinked elastic body is one that is usually used as a crosslinking agent and / or a graft crossing agent. Good. For example, allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate , Trimethylolpropane trimethacrylate, tetromethylolmethane tetramethacrylate, dipropylene glycol dimethacrylate, and the like can be used. These polyfunctional monomers may be used alone or in combination of two or more.

The amount of the polyfunctional monomer in the acrylate-based crosslinked elastic body is the average particle diameter of the acrylate-based crosslinked elastic body, the whitening property during bending and tensile deformation (stress whitening), and the amount of elongation in secondary molding. , Greatly affects transparency. The blending amount of the polyfunctional monomer in the acrylate-based crosslinked elastic body is preferably 0.1 to 10% by weight, more preferably 1.0 to 4% by weight in 100% by weight of the monomer mixture (a). preferable. A blending amount of the polyfunctional monomer of 0.1 to 10% by weight is preferable from the viewpoint of bending whitening resistance and resin fluidity during molding. If the blending amount of the polyfunctional monomer is less than 0.1% by weight, the bending whitening resistance and transparency may be deteriorated. If the blending amount of the polyfunctional monomer is 10% by weight or more, the bending crack resistance, impact resistance, transparency and the like may be lowered.

In the presence of the acrylic ester-based crosslinked elastic particles, the acrylic elastomer-grafted copolymer is 50 to 100% by weight of methacrylic acid ester and 0 to 50% by weight of other copolymerizable vinyl monomers. Those obtained by graft copolymerization of a monomer mixture (b) comprising: More preferably, in the presence of 5 to 90 parts by weight of acrylic ester-based crosslinked elastic particles, it consists of 50 to 100% by weight of an alkyl methacrylate and 0 to 50% by weight of another copolymerizable vinyl monomer. The monomer mixture (b) is obtained by graft copolymerization of 95 to 10 parts by weight in at least one stage. However, the total amount of the acrylic ester-based crosslinked elastic particles and the monomer mixture (b) shall satisfy 100 parts by weight.

The blending amount of the methacrylic acid alkyl ester in the monomer mixture (b) is preferably 50% by weight or more, more preferably 60% by weight or more, and further preferably 80% by weight or more in terms of hardness and rigidity. As the methacrylic acid alkyl ester, methyl methacrylate is particularly preferred from the viewpoint of polymerizability and compatibility with acrylic resin. Other vinyl monomers that can be copolymerized include other vinyl monomers that can be copolymerized in the production of the acrylic ester-based crosslinked elastic body, or acrylic monomers having 1 to 12 carbon atoms in the alkyl group. Acid alkyl esters can be used as well. Specific examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, styrene, acrylonitrile, (Meth) acrylic acid, N-substituted maleimides and the like. These monomers may be used independently and may use 2 or more types together.

In the production of the acrylic elastomeric graft copolymer, the grafting of the monomer mixture (b) in the presence of the acrylic ester-based crosslinked elastomeric particles is grafted onto the acrylic ester-based crosslinked elastomeric particles. An unbound polymer component (free polymer) may occur. Such a free polymer can be used as what constitutes a part or all of the acrylic resin constituting the matrix phase of the acrylic resin composition and acrylic film of the present invention.

A chain transfer agent may be added to the monomer mixture (b) for the purpose of controlling the molecular weight of the polymer and the amount of the free polymer produced. The chain transfer agent may be selected from those usually used for radical polymerization, and for example, alkyl mercaptan having 2 to 20 carbon atoms, mercapto acids, thiophenol, carbon tetrachloride or a mixture thereof is preferable. The chain transfer agent is used in an amount of 0 to 2 parts by weight, preferably 0 to 0.5 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture (b).

In the production of the acrylic elastic graft copolymer, the graft ratio of the monomer mixture (b) to the acrylate-based crosslinked elastic particles is preferably 5 to 250%, more preferably 10 to 220%, and more preferably 20 to 200. % Is more preferable. If the graft ratio is less than 5%, the bending whitening resistance, transparency, and elongation at the time of secondary molding are lowered, and cracks tend to occur during molding and cutting. If it exceeds 250%, the melt viscosity at the time of acrylic film molding tends to be high, and the moldability tends to decrease.

The average particle diameter d of the acrylic elastic body graft copolymer is preferably 10 nm to 400 nm, more preferably 30 nm to 350 nm, and further preferably 50 nm to 300 nm. When the average particle diameter of the acrylic elastic graft copolymer is less than 10 nm, the bending crack resistance and impact resistance tend to decrease. If it exceeds 400 nm, the transparency of the film and the bending whitening resistance tend to deteriorate. The average particle diameter of the acrylic elastic graft copolymer here is a value measured using a light scattering method in a latex state using a Nikkiso Co., Ltd. Sakai Microtrac particle size distribution analyzer MT3000.

The average particle diameter d (nm) of the acrylic ester-based crosslinked elastic particles and the amount w (% by weight) of the polyfunctional monomer used in the acrylic ester-based crosslinked elastic body are the same as those of the acrylic film or coating film. In order to greatly affect the bending whitening resistance (stress whitening), the elongation at the time of tensile rupture, or the transparency, it preferably satisfies the relational expression: 0.02d ≦ w ≦ 0.06d, and 0.02d ≦ w More preferably, ≦ 0.05d is satisfied. If the amount of the polyfunctional monomer is within the range of the above relational expression, the elongation at the time of secondary molding of the molding coating film of the present invention is less likely to decrease, and cracks are less likely to occur during molding or cutting, It has an advantage that it is excellent in transparency, and stress whitening hardly occurs during bending or tensile deformation.

When such an advantage is imparted to the acrylic film, the amount of the polyfunctional monomer used in the acrylate-based crosslinked elastic particles satisfies the above relational expression, and the average particle diameter d is 50 to 50%. 250 nm is preferable, 50 to 200 nm is more preferable, 50 to 150 nm is further preferable, and 60 to 120 nm is particularly preferable. If the average particle diameter d of the acrylic ester-based crosslinked elastic particles is 50 nm or more, the elongation during secondary molding of the coating film for molding of the present invention is unlikely to decrease, and cracks are unlikely to occur during molding or cutting. The If it is 250 nm or less, stress whitening hardly occurs, and transparency, particularly transparency after secondary molding such as vacuum molding, pressure molding, insert molding, etc. (maintaining transparency before and after heating) should be excellent. it can.

The method for producing the acrylic elastomer graft copolymer is not particularly limited, and a known emulsion polymerization method, emulsion-suspension polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method or dispersion polymerization method may be used. Although applicable, the emulsion polymerization method is particularly preferred.

As an initiator in the polymerization of the acrylic elastic body graft copolymer, known initiators such as organic peroxides, inorganic peroxides, and azo compounds can be used. Specifically, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, succinic acid peroxide, peroxymaleic acid t-butyl ester, cumene hydroperoxide, Organic peroxides such as benzoyl peroxide and lauroyl peroxide, inorganic peroxides such as potassium persulfate and sodium persulfate, and azo compounds such as azobisisobutyronitrile are also used. These may be used alone or in combination of two or more. These initiators may be used as thermal decomposition type radical polymerization initiators, or alternatively sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxyacetone acid, ferrous sulfate, sulfuric acid It may be used as a normal redox type polymerization initiator in combination with a reducing agent such as a complex of ferrous iron and ethylenediaminetetraacetic acid-2-sodium. Among these, inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate are used from the viewpoint of polymerization stability and particle diameter control, or t-butyl hydroperoxide, cumene hydroperoxide, etc. It is more preferable to use a redox initiator in which an organic transition oxide is combined with an inorganic reducing agent such as a divalent iron salt and / or a water-soluble reducing agent such as sodium formaldehyde sulfoxylate, reducing sugar or ascorbic acid. preferable. The above inorganic peroxide or organic peroxide may be added by a known addition method such as a method of directly adding to a polymerization system, a method of adding by dissolving and mixing in a monomer, a method of adding as an aqueous solution or an emulsified dispersion. Can be added.

The surfactant used for the emulsion polymerization of the acrylic elastic body graft copolymer is not particularly limited, and a known surfactant can be widely used. For example, anionic surface activity such as sodium alkyl sulfonate, sodium alkyl benzene sulfonate, sodium dioctyl sulfosuccinate, sodium alkyl sulfate, fatty acid sodium, sodium alkyl phosphate, sodium alkyl ether phosphate, sodium alkyl phenyl ether phosphate And nonionic surfactants such as reaction products of alkylphenols, aliphatic alcohols with propylene oxide, and ethylene oxide. These surfactants may be used alone or in combination of two or more.

The latex of the acrylic elastic graft copolymer obtained by emulsion polymerization can be separated and recovered as a solid from the acrylic elastic graft copolymer by a known method. For example, after adding a water-soluble electrolyte to the latex and coagulating it, the acrylic elastomer graft copolymer powder is separated by washing and drying the solids, or by treatment such as spray drying or freeze drying of the latex. It can be recovered.

More preferably, for the purpose of reducing the appearance defects and internal foreign matter of the acrylic film, the latex of the acrylic elastic graft copolymer is previously filtered through a filter or mesh prior to the separation and recovery of the acrylic elastic graft copolymer. In order to improve the appearance quality of the acrylic film, it is preferable to remove substances that cause foreign matter defects such as environmental foreign matter and polymerization scale. As such a filter or mesh, for example, it is sufficient that the mesh is 2 times or more larger than the average particle diameter of the acrylic elastic graft copolymer, and known filters used for filtration of liquid media can be used. It is.

The content of the acrylic ester-based crosslinked elastic body in the acrylic resin composition used for the acrylic film is preferably 5 to 70% by weight, more preferably 5 to 45% by weight, and still more preferably 10 to 30% by weight. However, in the acrylic film, the total amount of the acrylic resin composition comprising the acrylic elastic graft copolymer and the acrylic resin is 100% by weight. When the content of the acrylic ester-based crosslinked elastic body is 5% by weight or more, the elongation at the time of secondary molding of the obtained film is difficult to decrease, and cracks tend not to occur during molding or cutting. . On the other hand, if it exceeds 70%, the melt fluidity is lowered and the melt processing becomes difficult.

The production method of the acrylic film used for the molding coating film of the present invention can be a known molding method. For example, an inflation method that is a melt processing method, a T-die extrusion method, a calendar molding method, or an acrylic resin composition used in the present invention is dissolved and dispersed in a solvent, and then cast into a film on a belt-like substrate. It can be produced satisfactorily by using a solvent casting method for forming a film by volatilizing. Among these, it is preferable to use a melt extrusion method that does not use a solvent, particularly a T-die extrusion method. According to the melt extrusion method, a film excellent in surface production can be produced with high productivity, and the burden on the global environment and working environment due to production costs and solvents can be reduced.

More preferably, when the acrylic resin composition is processed by a melt processing method or a solvent casting method, an environment in the acrylic resin composition that causes an appearance defect or internal foreign matter of the acrylic film using a filter or a mesh is used. In order to improve the appearance quality of the acrylic film, it is preferable to filter and remove foreign substances, polymerization scale, deteriorated resin, and the like. Such a filtration step may be performed, for example, at the stage of blending and pelletizing an acrylic resin, an acrylic elastic graft copolymer, and other blends at the time of melt processing. You may perform before the film forming process by die | dye, and you may perform both. When the solvent casting method is used, it may be carried out after the solution mixing of the acrylic resin and the acrylic elastic graft copolymer and before cast film formation. Known filters and meshes can be widely used. In particular, when a high-quality acrylic film is produced by melt processing, it is preferable to use a leaf disk type filter in terms of filtration efficiency and productivity.

In the production of the acrylic film used in the present invention, the glass transition temperature of the acrylic resin composition in particular is obtained by simultaneously contacting (sandwiching) both sides of the molten film with a cooling roll or a metal belt when the film is molded. It is also possible to obtain a film having excellent surface smoothness by simultaneously contacting a roll or metal belt maintained at a temperature within Tg-50 ° C, preferably within Tg-30 ° C. More preferably, as a roll for performing such sandwiching, at least one of the rolls is a metal roll having elasticity as disclosed in, for example, Japanese Patent Laid-Open No. 2000-153547, Japanese Patent Laid-Open No. 11-235747, etc. Can be obtained, and a film with less internal strain can be obtained.

Also, depending on the purpose such as improving the rigidity of the film, it is possible to carry out uniaxial stretching or biaxial stretching subsequent to the film formation. Uniaxial or biaxial stretching can be carried out using a known stretching apparatus. For biaxial stretching, both simultaneous biaxial stretching and sequential stretching can be used.

Furthermore, the coating film for molding of the present invention or the acrylic film used therefor is a surface shape having irregularities on one or both sides of the film, for example, hairline, prism, etc. An arbitrary surface shape such as a wood grain shape, a relief, a geometric pattern, a trademark or a logo, a non-uniform rough surface, or a matte surface may be provided. Such surface shape can be imparted by a known method. For example, a roll on the film surface is obtained by sandwiching both sides of a film in a molten state immediately after melt extrusion or a formed film fed from a feeding device with two rolls or belts having a surface shape on at least one surface. A method of transferring the shape of the surface is mentioned. The surface shape may be imparted to the acrylic film as the base material in advance or after the formation of the coating layer. Moreover, you may perform with respect to any of the coating layer side and the acrylic film layer side.

In the acrylic film used in the present invention, conventionally known additives used in acrylic resins and acrylic films can be added within a range not impairing the effects of the present invention. Examples of such additives include hindered phenol-based, phosphorus-based and sulfur-based antioxidants, benzotriazole-based, benzophenone-based, triazine-based UV absorbers, hindered amine-based light stabilizers, halogen-based, Flame retardants such as antimony, phosphorus, silicone, and metal (hydroxide) oxides, cross-linked resin particles and functional group-containing resins, light diffusion agents such as inorganic fine particles, matting agents or anti-blocking agents, lubricants, pigments, Examples thereof include, but are not limited to, colorants such as dyes, infrared reflectors composed of metals and metal oxides, plasticizers, and antistatic agents. These additives do not interfere with the features of the acrylic film and the coating film for molding of the present invention, in a range that does not impair the adhesion of the acrylic film and the coating layer described later, and contaminate the appearance by bleeding out, Any amount can be used as long as the purpose of the coating film for molding of the present invention such as surface decoration and surface protection is not hindered.

In the present invention, the thickness of the acrylic film is not particularly limited, but is in the range of about 25 μm to 250 μm due to the processing conditions of the coating layer and the economics, mechanical strength, handling properties, etc. of the base film. It is preferable.

Surface treatment such as corona treatment and low-temperature plasma treatment on the surface of acrylic film, addition of lubricant for the purpose of improving film runnability, thermoplastic resin or thermosetting during or after acrylic film formation An easy adhesion treatment using a resin can also be performed. In addition, for the purpose of imparting antistatic properties, antistatic treatment and the like can also be performed.

[Coating layer]
Next, the coating layer will be described.
In the present invention, the resin contained in the coating layer is an ionizing radiation curable resin containing a polyfunctional acrylate resin having a hydroxyl group in the structure and a weight average molecular weight (Mw) of 6.0 × 10 ³ or more and 1.0 × 10 ⁴ or less. .
By using a resin containing a hydroxyl group in the structure, chemical resistance can be obtained, and chemical resistance can be improved due to hydrogen bonding between the hydroxyl groups. In addition, by using a polyfunctional acrylate resin with a high elongation ratio that is excellent in moldability with a weight average molecular weight (Mw) of 6.0 × 10 ³ or more and 1.0 × 10 ⁴ or less, sufficient moldability and chemical resistance (especially after molding) (Chemical resistance in a stretched state) is possible. When a resin having a weight average molecular weight (Mw) of less than 6.0 × 10 ³ is used, the elongation percentage of the coating layer is insufficient. Further, when a resin having a weight average molecular weight (Mw) larger than 1.0 × 10 ⁴ is used, another problem such as poor coating suitability arises.

Also, by using an ionizing radiation curable resin containing a polyfunctional acrylate resin, in particular, the surface of the coating layer is given hardness (pencil hardness, scratch resistance), and the degree of crosslinking is adjusted by the amount of ultraviolet light exposure. It is possible to adjust the stretchability and surface hardness (pencil hardness, scratch resistance) of the coating layer.

The polyfunctional acrylate resin having a hydroxyl group can be obtained by reacting a polyhydric alcohol with an isocyanate monomer or organic polyisocyanate and a polyfunctional acrylate monomer having a hydroxyl group in the absence of a solvent or in an organic solvent. Examples of the polyhydric alcohol include acrylic polyols, polyester polyols, polycarbonate polyols, ethylene glycol, and propylene glycol. Examples of the isocyanate monomer include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and the like. Examples of the organic polyisocyanate include adduct type, isocyanurate type and burette type polyisocyanates synthesized from isocyanate monomers. Examples of the polyfunctional acrylate monomer having a hydroxyl group include 2-hydroxy-3-phenoxypropyl acrylate, isocyanuric acid ethylene oxide-modified diacrylate, pentaerythritol tri- and tetraacrylate, and dipentaerythritol pentaacrylate.

Among the above polyfunctional acrylate resins, urethane acrylate resins having a main chain of urethane resin composition and a side chain having a (meth) acryloyl group are known as resins that form high strength, stretched and tough films. It is preferable because the effects of the present invention can be further enhanced. The urethane acrylate resin preferably has a weight average molecular weight (Mw) of 6.0 × 10 ³ or more and 1.0 × 10 ⁴ or less.

In the present invention, the area of the 3200 to 3500 cm ⁻¹ region of the infrared spectrum on the surface of the coating layer is 0.3 to 1.0 times the area of the 1650 to 1750 cm ⁻¹ region.

The 3200 to 3500 cm ⁻¹ region of the infrared spectrum (hereinafter sometimes abbreviated as “IR spectrum”) is an absorption region due to OH stretching vibration, and the 1650 to 1750 cm ⁻¹ region is C═O. This is an absorption region due to stretching vibration. Thus, 3200 ~ 3500 cm ^-1 region area ratio to the area of 1650 ~ 1750 cm ^-1 region of the infrared spectrum, the hydroxyl group for this case relative to the amount of carbonyl groups contained in the resin constituting the coating layer The ratio of the amount of That is, the larger the area ratio value, the greater the amount of hydroxyl groups contained in the resin constituting the coating layer.

In the present invention, the infrared spectrum of the coating layer can be measured on the surface of the coating layer after coating on the acrylic film. That is, the infrared spectrum of the coating layer in the present invention means the infrared spectrum of the coating layer surface after coating on the acrylic film.

For example, an infrared spectrophotometer is used for the coating layer surface formed by applying a coating layer paint on an acrylic film by a predetermined method and curing the coating layer by UV or EB (electron beam) irradiation. An infrared spectrum (infrared absorption spectrum) is measured by the ATR method (total reflection method). Then, on the spectrum chart in which the obtained horizontal axis is the wave number (cm ⁻¹ ) and the vertical axis is the absorbance, a base line is drawn to the peak range (the above wave number region) derived from the target functional group. The area surrounded by the line and the spectrum curve can be the peak area (the area of the wave number region).

In the present invention, excellent chemical resistance can be obtained by using a polyfunctional acrylate resin having a hydroxyl group in the structure and having a weight average molecular weight (Mw) of 6.0 × 10 ³ or more and 1.0 × 10 ⁴ or less. area of 3200 ~ 3500 cm ^-1 region of the infrared spectrum of the coating layer surface, chemical resistance by such a 1.0-fold 0.3-fold or more the area of 1650 ~ 1750 cm ^-1 region, particularly It is possible to improve the chemical resistance against the oil and fat components contained in the aforementioned sunscreen creams and lotions. If the area ratio is less than 0.3 times, chemical resistance cannot be obtained or is insufficient. Moreover, when said area ratio is larger than 1.0 time, another problem will arise, such as it becomes difficult to prepare a coating material and the adhesiveness of a coating film and an acrylic film becomes insufficient.

The amount of hydroxyl group contained in the polyfunctional acrylate resin constituting the coating layer is adjusted to a predetermined value depending on the type of polyfunctional acrylate monomer having a hydroxyl group and the blending ratio in the case of the urethane acrylate resin, for example. Is possible.

The ionizing radiation curable resin used in the coating layer of the present invention is a phenol resin, a urea resin, an unsaturated polyester, an epoxy, a silicon resin, etc. within a range that does not impair the effects of the present invention, that is, the moldability and chemical resistance. A thermosetting resin, an ionizing radiation curable resin such as a polyfunctional acrylate having two or more (meth) acryloyl groups in the molecule, and a thermoplastic resin such as polyethylene, polypropylene, polystyrene, polycarbonate, and polyester. it can.

Specific examples of the polyfunctional acrylate having two or more (meth) acryloyl groups in the molecule include neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other polyol polyacrylates, bisphenol A diglycidyl ether Epoxy (meth) such as diacrylate, dipentyl glycol diglycidyl ether diacrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate Polyester (meth) acrylate, polyhydric alcohol, polyvalent isocyanate and hydroxyl group-containing (meth) acrylate obtained by esterifying acrylate, polyhydric alcohol and polyhydric carboxylic acid and / or anhydride thereof and acrylic acid The urethane (meth) acrylate obtained by making this react, polysiloxane poly (meth) acrylate, etc. can be mentioned.

In the molding coating film of the present invention, a coating containing the ionizing radiation curable resin composition containing the polyfunctional acrylate resin is applied to the acrylic film with a dry coating thickness of 1 to 3 μm, and then applied with ultraviolet rays or electron beams. A test piece having a width of 10 mm and a length of 80 mm cured by irradiation is prepared, and when the test piece is pulled at a tensile speed of 50 mm / min at a temperature of 120 ° C., the ionizing radiation curable resin composition is used. It is preferable that the elongation rate until cracks occur in the coating layer is 200% or more (based on the test method specified in JIS K5600-5-4).
However, since the required elongation varies depending on the application of the molding coating film of the present invention, it cannot be generally stated. However, as long as the elongation is 200% or more as described above, sufficient moldability is obtained in all applications. Can be provided.

As the photopolymerization initiator for the ionizing radiation curable resin in the coating layer, known ones such as acetophenones and phenones containing benzo can be used.

Further, as other additives added to the coating layer, as long as the effects of the present invention are not impaired, an antifoaming agent, a surface tension adjusting agent (leveling agent), an antifouling agent, an antioxidant, an antistatic agent, an ultraviolet ray You may contain an absorber, a light stabilizer, etc. as needed.

In the present invention, the coating layer comprises a coating material obtained by dissolving and dispersing a photopolymerization initiator and other additives in an appropriate solvent in addition to the ionizing radiation curable resin containing the polyfunctional acrylate resin. It is formed by coating and drying on a film. The solvent can be appropriately selected depending on the solubility of the resin contained therein, and may be any solvent that can uniformly dissolve or disperse at least solids (resin, polymerization initiator, and other additives). Examples of such a solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons ( Cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (methanol, ethanol, isopropanol, Butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides, amides and the like. Moreover, a solvent may be used individually or may be used in mixture of 2 or more types.

In the present invention, the coating thickness of the coating layer is not particularly limited, but is preferably in the range of 1 to 3 μm, for example. If the coating thickness is less than 1 μm, sufficient chemical resistance cannot be obtained, or the required hardness is difficult to obtain. Moreover, when the coating film thickness is thicker than 3 μm, it becomes difficult to obtain good extensibility.

The coating layer coating method is not particularly limited, but it is easy to adjust the coating thickness, such as gravure coating, microgravure coating, fountain bar coating, slide die coating, slot die coating, etc. Coating is possible by the method. In addition, the coating film thickness of the applied coating layer can be measured by actually measuring with a micrometer.

Moreover, in the coating film for molding of the present invention, a decorative layer such as a printing layer or coloring / adhesion is directly or via an appropriate primer layer on the surface opposite to the side on which the coating layer of the base film is provided. A film or the like may be provided. Further, an overcoat layer or the like can be further provided on the coating layer.

The decorative layer is composed of, for example, a picture layer and / or a concealing layer, a metal vapor deposition layer, and the like. Here, the pattern layer is a layer provided to express a pattern such as a pattern or characters, and the concealing layer is a solid layer, and is a layer provided to conceal the coloring of the resin or the like. . Moreover, a metal vapor deposition layer is the layer which vapor-deposited one part or the whole surface, and is provided for the purpose of expressing the layer provided for concealing coloring etc. of resin etc., or a resin layer in a metal tone. Is a layer.

The decorative layer (for example, the pattern layer and / or the concealment layer) can be formed by a known printing method such as gravure printing, offset printing, or screen printing. Moreover, the said metal vapor deposition layer can be formed into a film by methods, such as sputtering.

As described above, in the molding coating film of the present invention, a polyfunctional acrylate resin having a weight average molecular weight (Mw) having a hydroxyl group in the structure of 6.0 × 10 ³ or more and 1.0 × 10 ⁴ or less is formed on the acrylic film. the coating layer formed of an ionizing radiation curable resin composition comprising forming an area of 3200 ~ 3500 cm ^-1 region of the infrared spectrum of the coating layer surface, 1650 ~ 1750 cm ^-1 or 0.3 times the area of the region By being 1.0 times or less, it is possible to provide a coating film for molding which is excellent in both moldability (extensibility) and chemical resistance (especially chemical resistance in a stretched state after molding). In particular, chemical resistance to the oil and fat components contained in the sunscreen creams and lotions described above can be improved.

Moreover, the coating film for molding of the present invention is suitable as a surface decorative film or a surface protective film for in-mold molding, insert molding, or three-dimensional laminate molding.
Moreover, the coating film for molding of the present invention is suitable as a film for protecting the surface of a molded product having a printing, coloring or decorative layer on at least one surface thereof.
Further, the molding coating film of the present invention is suitable as a film for protecting the surface of a molded article having a surface shape having irregularities on at least one surface thereof or for decorating.

Moreover, the laminated body which laminated | stacked said each film based on this invention on the surface of the sheet | seat or molded object containing a thermoplastic resin or a thermosetting resin is suitable as a decoration sheet or a decoration panel for motor vehicle interior. .
In addition, a laminate in which each of the films according to the present invention is laminated on the surface of a sheet or a molded body containing a thermoplastic resin or a thermosetting resin is a casing for a portable electronic device, an acoustic device, or an electrical product, Suitable for surface decoration or protective panel.

The following examples illustrate the invention, but are not intended to limit the invention.
Unless otherwise specified, “parts” and “%” described below represent “parts by weight” and “% by weight”, respectively.

[Example 1]
<Preparation of coating layer paint>
100 parts of a hydroxyl group-containing urethane acrylate UV curable resin having a weight average molecular weight (Mw) of 6.7 × 10 ³ , 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator, and bis as a light stabilizer 0.5 parts of (1,1,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate; 2- [4- [4,6-bis ([1,1′-biphenyl] -4-yl) -1,3,5-triazin-2-yl] -3-hydroxyphenoxy] propane as an ultraviolet absorber 0.5 part of acid isooctyl ester and 0.3 part of fluorosiloxane leveling agent are butyl acetate / n-propyl alcohol = 50/50 (parts by weight) and the solid content concentration in the coating of UV curable resin is 20%. And To prepare a coating layer coating was sufficiently stirred and diluted to.

<Production of acrylic film for molding>
(Production of acrylic elastic graft copolymer (c1-1))
The following substances were charged into an 8 L polymerization apparatus equipped with a stirrer.
・ Deionized water 200 parts ・ Dioctyl sodium sulfosuccinate 0.33 parts ・ Sodium formaldehyde sulfoxylate 0.15 parts ・ Ethylenediaminetetraacetic acid-2-sodium 0.001 parts ・ Ferrous sulfate 0.00025 Part While stirring in the polymerization apparatus and sufficiently replacing with nitrogen gas to make it substantially free of oxygen, the internal temperature was set to 60 ° C., and 30 parts of the following monomer mixture (c1-1a) was added to 10 parts by weight. The polymer was continuously added at a rate of / hour, and after completion of the addition, the polymerization was further continued for 0.5 hour to obtain acrylate ester-based crosslinked elastic particles (average particle diameter d = 80 nm). The polymerization conversion rate was 99.5%.
Monomer mixture (c1-1a):
-Vinyl monomer mixture (butyl acrylate (BA) 90% and methyl methacrylate (MMA) 10%) 100 parts-allyl methacrylate (AlMA) 1 part-cumene hydroperoxide (CHP) 0.2 part then dioctyl After charging 0.05 parts by weight of sodium sulfosuccinate, the internal temperature was adjusted to 60 ° C., 100 parts of a vinyl monomer mixture (BA 10% and MMA 90%), 0.5 parts of tarlead decyl mercaptan (t-DM) And 70 parts of a monomer mixture (c1-1b) consisting of 0.5 parts of CHP was continuously added at a rate of 10 parts / hour, and the polymerization was continued for another hour, whereby an acrylic elastomer graft copolymer (c1 -1) (average particle size = 90 nm) was obtained. The polymerization conversion rate was 98.2%. The obtained latex was salted out with calcium chloride, coagulated, washed with water and dried to obtain a resin powder (c1-1) of an acrylic elastic graft copolymer.

(Making acrylic film)
70 parts of an acrylic elastic graft copolymer (c1-1) and 30 parts of a methacrylic polymer (Sumitex MM, manufactured by Sumitomo Chemical Co., Ltd.) were mixed using a Henschel mixer, and the cylinder temperature was changed from 150 ° C. Using a 90 mmφ L / D = 36 vented single screw extruder adjusted to a temperature of 220 ° C., melt kneading at a screw rotation speed of 90 rpm and a discharge rate of 190 kg / hr, taken into a strand shape, cooled in a water bath, Cutting with a pelletizer gave resin pellets of acrylic resin (C-1).
The obtained acrylic resin resin pellet (C-1) was melted at a cylinder set temperature of 170 to 210 ° C. and a discharge rate of 100 kg / hr using a 90 mmφ L / D = 29 single screw extruder with a T-die. The mixture was kneaded and discharged from a T die at a die temperature of 200 to 215 ° C., and both sides of the discharged resin were simultaneously brought into contact with a metal roll and an elastic metal roll to form an acrylic film having a thickness of 75 μm.

<Production of coating film for molding>
The above-mentioned coating layer paint was applied to one side of the obtained 75 μm thick acrylic film with a bar coater, dried with hot air at 80 ° C. for 1 minute, and then cured with an ultraviolet light amount of 450 mJ / m ² to obtain a film thickness of 1.4 μm. A coating film for molding of this example was produced.

[Example 2]
A molding coating film was produced in the same manner as in Example 1 except that the thickness of the coating layer was changed to 1.8 μm.

[Example 3]
A molding coating film was produced in the same manner as in Example 1 except that the thickness of the coating layer was changed to 3.0 μm.

[Comparative Example 1]
Molded in the same manner as in Example 1 except that the UV curable resin used for the coating layer paint was changed to an acrylic acrylate UV curable resin containing no hydroxyl group with a weight average molecular weight (Mw) of 2.5 × 10 ^6. A coating film was prepared.

[Comparative Example 2]
A molding coating film was produced in the same manner as in Example 1 except that the ultraviolet curable resin used for the coating layer coating material was changed to a hydroxyl group-containing ultraviolet curable resin hydroxybutyl acrylate.

[Comparative Example 3]
The UV curable resin used in the coating layer paint was molded in the same manner as in Example 1 except that the hydroxyl group-containing urethane acrylate UV curable resin having a weight average molecular weight (Mw) of 5.0 × 10 ³ was changed. A coating film was prepared.

[Comparative Example 4]
A molding coating film was produced in the same manner as in Example 1 except that the thickness of the coating layer was changed to 0.8 μm.

Each of the molding coating films of Examples and Comparative Examples produced as described above was evaluated for the following items, and the results are summarized in Table 1 below. The weight average molecular weight (Mw) of the ultraviolet curable resin used for the coating layer paint of each molding coating film and the coating film thickness of the coating layer are also shown in Table 1 below.

(1) IR measurement and peak area ratio With respect to the coating layer surface of each molding coating film, an infrared spectrum (infrared absorption spectrum) was measured by an infrared spectrophotometer by the ATR method. As the infrared spectrophotometer, FT-IR Spectrometer Spectrum 100 (Perkin Elmer Japan Co., Ltd.) was used. On the spectrum chart where the obtained horizontal axis is the wave number (cm ^-1 ) and the vertical axis is the absorbance, the peak ranges derived from the target functional group (the above 3200 to 3500 cm ^-1 region and the above 1650 to 1750 cm ^-1 region) ), A base line was drawn, and an area surrounded by the base line and the spectrum curve was defined as a peak area (area of each of the above wavenumber regions). Then, a 3200 ~ 3500 cm ^-1 region area / 1650 ~ 1750 cm ^-1 region value peak area ratio of the area of the.

(2) Elongation rate Each coating film for molding is made into a test piece having a sample size width of 10 mm × length of 80 mm, and the test piece is pulled at a temperature of 120 ° C. with a pulling speed of 50 mm / min and a distance between chucks of 40 mm to coat the surface. The tensile elongation (%) until the layer cracked was measured.
The evaluation criteria are as follows. “○” was accepted.
○: Elongation rate is 200% or more.
X: Elongation rate is less than 200%.

(3) Chemical resistance (unstretched)
A test piece having a sample size width of 10 mm and a length of 80 mm was collected from each molding coating film obtained in the examples and comparative examples. The test piece was left unstretched, and a commercially available sunscreen cream “COPATONE (registered trademark)” was applied to the surface. Then, the sample was allowed to stand in an 80 ° C. environment for 24 hours, and then the sunscreen cream was wiped off. It was observed visually.
The evaluation criteria are as follows. “○” was accepted.
○: No chemical marks are seen.
Δ: Some chemical marks are seen.
X: A chemical mark is clearly seen.

(4) Chemical resistance (after stretching)
A test piece having a sample size width of 10 mm × length of 80 mm was collected from each of the molding coating films obtained in Examples and Comparative Examples in the same manner as in the case of (3) above. After the test piece was stretched to 200% (three times the original length) by the method (2) above, sunscreen cream was applied by the same method as described above and allowed to stand in an 80 ° C. environment for 24 hours. The sunscreen cream was wiped off and the chemical marks were visually observed.
The evaluation criteria are the same as in (3) above.
In addition, the test was not implemented about the sample from which the elongation rate of 200% is not obtained.

As is apparent from the results of Table 1 above, according to the examples of the present invention, good chemical resistance can be obtained both in the unstretched state and after the stretched state, and when left in a high temperature environment. I have. Therefore, according to the Example of this invention, the coating film for shaping | molding which is excellent in both chemical resistance and moldability (elongation property) is obtained. In particular, a molding coating film having excellent chemical resistance against the oil and fat components contained in the aforementioned sunscreen creams and lotions can be obtained.

On the other hand, although the weight average molecular weight of the ultraviolet curable resin used for the coating layer paint is large, the comparative example 1 in which the peak area ratio is less than 0.3 can obtain a certain degree of elongation, but has poor chemical resistance. In either case of unstretched or stretched, and when left in a high temperature environment, chemical resistance cannot be obtained.
In Comparative Example 2, the peak area ratio is larger than 0.3, but the weight average molecular weight of the ultraviolet curable resin used for the coating layer paint is remarkably small, so that the elongation is small and chemical resistance cannot be obtained. It was. Further, in Comparative Example 3 where the peak area ratio is 0.3 or more, but the weight average molecular weight of the ultraviolet curable resin used for the coating layer paint is smaller than 6.0 × 10 ³ , the chemical resistance when unstretched is Although it is good, the elongation rate is insufficient, and it is impossible to achieve both moldability (stretchability) and chemical resistance (especially chemical resistance in a stretched state after molding).
Furthermore, when the coating layer coating is usually the same, the peak area of the coating layer does not change only by changing the film thickness, but the coating layer is more susceptible to the influence of the base film as the coating layer becomes thinner. In Comparative Example 4, the peak area ratio is less than 0.3 due to the thinning of the coating layer, and the elongation is good, but the chemical resistance is slightly inferior, and in any case after unstretched or stretched. In addition, when left in a high temperature environment, the chemical resistance is insufficient.

Claims (12)

1. On the acrylic film, a coating layer made of an ionizing radiation curable resin composition containing a polyfunctional acrylate resin having a weight average molecular weight (Mw) having a hydroxyl group in the structure of 6.0 × 10 ³ or more and 1.0 × 10 ⁴ or less was formed. a molding coated film, said area of 3200 ~ 3500 cm ^-1 region of the infrared spectrum of the coating layer surface is not more than 1.0 times 0.3 times or more the area of 1650 ~ 1750 cm ^-1 region A coating film for molding characterized by
2. 2. The molding coating film according to claim 1, wherein the polyfunctional acrylate resin is a urethane acrylate resin having a urethane resin composition as a main chain and a (meth) acryloyl group as a side chain.
3. The molding coating film according to claim 1 or 2, wherein the coating layer has a thickness in the range of 1 µm to 3 µm.
4. A coating containing the ionizing radiation curable resin composition was applied to the acrylic film with a dry coating thickness of 1 to 3 μm, and then a test piece having a width of 10 mm and a length of 80 mm was cured by irradiation with ultraviolet rays or electron beams. When the test piece is pulled at a temperature of 120 ° C. at a tensile speed of 50 mm / min and a distance between chucks of 40 mm, the elongation until the coating layer made of the ionizing radiation curable resin composition cracks is 200%. The molding coating film according to any one of claims 1 to 3, which is as described above (based on the test method specified in JIS K5600-5-4).
5. The acrylic film is obtained by molding a resin composition containing 20 to 100 parts by weight of a thermoplastic acrylic resin containing 50 to 100% by weight of methyl methacrylate units and 0 to 50% by weight of other units. The molding coating film according to any one of claims 1 to 4.
6. 6. The molding coating film according to claim 1, wherein the acrylic film contains a rubber component.
7. A core-shell structure in which the rubber component is composed of a single-layer or multi-layer core layer including one or more elastic layers made of a crosslinked polymer mainly composed of an acrylate ester, and a shell layer mainly composed of a methacrylate ester. The molding coating film according to claim 6, wherein the molding film is a rubber particle.
8. The molding coating film according to any one of claims 1 to 7, which is a surface decorative film or a surface protective film for in-mold molding, insert molding, or three-dimensional laminate molding.
9. A film for surface protection or decoration of a molded body, comprising a printed, colored or decorative layer on at least one surface of the coating film for molding according to any one of claims 1 to 8.
10. A film for surface protection or decoration of a molded body, wherein the molding coating film according to any one of claims 1 to 8 has a surface shape having irregularities on at least one surface thereof.
11. A decorative sheet or decorative panel for automobile interior, in which the film according to any one of claims 1 to 10 is laminated on the surface of a sheet or a molded body containing a thermoplastic resin or a thermosetting resin.
12. A casing or a surface for a portable electronic device, an acoustic device, or an electrical product in which the film according to any one of claims 1 to 10 is laminated on a surface of a sheet or a molded body containing a thermoplastic resin or a thermosetting resin. Decorative or protective panel.