JP2009196152A - Laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin film having excellent chemical resistance and excellent flexibility. <P>SOLUTION: A layer B of a styrene monomer-(meth)acrylic acid copolymer is laminated on at least one face of a layer A comprising a thermoplastic resin and rubber particles. A thickness of the layer A is not less than 0.5 times the whole thickness. Preferably, the thickness of the whole laminated film is 20-500 μm, and preferably, a thickness of the layer B is 1 μm or above. Preferably, a methacrylic resin is used as the thermoplastic resin, and preferably, an acrylic rubber particle is used as the rubber particle. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminated film. The present invention also relates to a decorative film or a decorative sheet using the laminated film, and further to a decorative molded product.

  Thermoplastic resin (plastic) films are applied to various uses by taking advantage of their respective characteristics. For example, acrylic films are used for exterior members of automobiles and automobiles by taking advantage of their excellent transparency and weather resistance. It is preferably used as a surface decorating film such as an interior member. Polypropylene film is preferably used as a product packaging film, taking advantage of its excellent tensile strength and rigidity, and polyester film is used for PET bottles, etc., taking advantage of its excellent heat resistance and thin film formability. It is preferably used as a shrink film for labels.

JP-A-9-12741 JP-A-10-279766 JP 2000-86853 A JP 2003-183471 A

  The thermoplastic resin film as described above may come into contact with chemicals during the manufacturing process or secondary processing process, and the surface may be eroded and the appearance may be deteriorated, or cracks and cracks may occur. There is. Also, in the usage environment after commercialization, it may be touched by humans or may come into contact with chemicals. Especially when the frequency or degree is high, as an effect when touched by humans, for example, in sweat Liquid traces may remain or cracks may occur due to the action of lactic acid. Also, as an influence when contacting with chemicals, for example, due to the action of organic solvents contained in fragrances and cleaning agents, May remain or cracks may occur. Accordingly, an object of the present invention is to provide a thermoplastic resin film having excellent chemical resistance and excellent flexibility. And it is in providing the decorative film or the sheet | seat for decoration which is excellent in chemical resistance, and also the decorative molded product using this thermoplastic resin film.

  As a result of intensive studies, the present inventor has found that a laminated film having a predetermined composition and a layer thickness ratio is suitable for the above purpose, and has completed the present invention. That is, in the present invention, a layer (B) made of a copolymer of a styrene monomer and (meth) acrylic acid is laminated on at least one surface of the layer (A) made of a thermoplastic resin and rubber particles. Thus, the present invention provides a laminated film characterized in that the thickness of the layer (A) is 0.5 times or more of the total thickness.

  This laminated film can be used as a decorative film, for example, by printing on one surface thereof. Moreover, it can also be set as a decorating sheet | seat by laminating | stacking a thermoplastic resin sheet on the surface to which the printing was given. Then, by laminating a thermoplastic resin molded product on the surface on which the decorative film is printed or the surface on which the thermoplastic resin sheet of the decorative sheet is laminated, the chemical resistance is excellent. A decorative molded product can be obtained.

  The laminated film of the present invention is excellent in chemical resistance and flexibility, and by using this, a decorative film or decorative sheet excellent in chemical resistance, and a decorative molded product are obtained. be able to.

  Hereinafter, the present invention will be described in detail. In the laminated film of the present invention, a layer (B) made of a copolymer of a styrene monomer and (meth) acrylic acid is laminated on at least one surface of the layer (A) made of a thermoplastic resin and rubber particles. It has been made.

  Examples of the thermoplastic resin constituting the layer (A) include methacrylic resin, polyester resin, polycarbonate resin, polycyclic olefin resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), and polyvinylidene fluoride resin (PVDF resin). Etc. Although the kind is suitably selected by the use of the laminated body obtained, for example, if it is a surface decoration use, a highly transparent thing, especially a methacryl resin are used preferably.

  The methacrylic resin is a polymer mainly composed of a methacrylic acid ester, and may be a homopolymer of a methacrylic acid ester, or a methacrylic acid ester of 50% by weight or more and other monomers of 50% by weight or less. A copolymer may also be used. Here, as the methacrylic acid ester, an alkyl ester of methacrylic acid is usually used.

  The preferred monomer composition of the methacrylic resin is 50 to 100% by weight of alkyl methacrylate, 0 to 50% by weight of alkyl acrylate, and 0 to 49% by weight of other monomers based on all monomers. More preferably, the alkyl methacrylate is 50 to 99.9% by weight, the alkyl acrylate is 0.1 to 50% by weight, and other monomers are 0 to 49% by weight.

  Here, examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. The alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. It is. Of these, methyl methacrylate is preferably used.

  Examples of alkyl acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. The alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. is there.

  The monomer other than alkyl methacrylate and alkyl acrylate may be a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule, or a polyfunctional monofunctional monomer. Although it may be a monomer, that is, a compound having at least two polymerizable carbon-carbon double bonds in the molecule, a monofunctional monomer is preferably used. Examples of the monofunctional monomer include styrene monomers such as styrene, α-methylstyrene and vinyltoluene, alkenyl cyanide such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid and maleic anhydride. , N-substituted maleimide and the like. Examples of polyfunctional monomers include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, allyl acrylate, allyl methacrylate, and cinnamon. Alkenyl esters of unsaturated carboxylic acids such as allyl acids, polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, aromatic polyalkenyl compounds such as divinylbenzene, etc. Can be mentioned.

  In addition, as for said alkyl methacrylate, alkyl acrylate, and monomers other than these, respectively, you may use those 2 or more types as needed.

  The methacrylic resin preferably has a glass transition temperature of 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of heat resistance of the layer (A). This glass transition temperature can be appropriately set by adjusting the type of monomer and the ratio thereof.

  The methacrylic resin can be prepared by polymerizing the monomer component by a method such as suspension polymerization, emulsion polymerization or bulk polymerization. At that time, in order to obtain a suitable glass transition temperature or to obtain a viscosity showing a moldability to a suitable laminated film, it is preferable to use a chain transfer agent during the polymerization. The amount of the chain transfer agent may be appropriately determined according to the type of monomer and the ratio thereof.

  By blending rubber particles into a thermoplastic resin, particularly a methacrylic resin, and forming the layer (A) with the composition, the flexibility of the resulting laminated film can be improved. Here, as the rubber particles, for example, acrylic, butadiene, styrene-butadiene, and the like can be used. Among these, acrylic rubber particles are preferably used from the viewpoint of weather resistance.

  The acrylic rubber particle is a particle containing an elastic polymer mainly composed of an acrylate ester as a rubber component, and may be a particle having a single layer structure made of only this elastic polymer, or a layer of this elastic polymer. However, in view of the surface hardness of the layer (A), particles having a multilayer structure are preferable. The elastic polymer may be a homopolymer of an acrylate ester or a copolymer of 50% by weight or more of an acrylate ester and 50% by weight or less of other monomers. . Here, as the acrylic ester, an alkyl ester of acrylic acid is usually used.

  A preferable monomer composition of the elastic polymer mainly composed of an acrylate ester is 50 to 99.9% by weight of alkyl acrylate, 0 to 49.9% by weight of alkyl methacrylate, based on all monomers, The monofunctional monomer other than these is 0 to 49.9% by weight, and the polyfunctional monomer is 0.1 to 10% by weight.

  Here, the example of alkyl acrylate is the same as the example of alkyl acrylate mentioned above as a monomer component of methacrylic resin, The carbon number of the alkyl group is 1-8 normally, Preferably it is 4-8. is there. Moreover, the example of alkyl methacrylate is the same as the example of alkyl methallylate previously mentioned as a monomer component of a methacryl resin, The carbon number of the alkyl group is 1-8 normally, Preferably it is 1-4.

  The monofunctional monomers other than these are the same as the examples of the monofunctional monomers other than the alkyl methacrylate and alkyl acrylate mentioned above as the monomer component of the methacrylic resin. Of these, styrene monomers such as styrene, α-methylstyrene and vinyltoluene are preferably used.

  Examples of the polyfunctional monomer are the same as the examples of the polyfunctional monomer previously mentioned as the monomer component of the methacrylic resin, and among them, alkenyl esters of unsaturated carboxylic acids and polybasic acids. Polyalkenyl esters are preferably used.

  In addition, as for said alkyl acrylate, the other monofunctional monomer, and a polyfunctional monomer, you may use those 2 or more types as needed, respectively.

  When the acrylic rubber particles having a multilayer structure are used, a preferable example is one having a polymer layer mainly composed of methacrylic acid ester outside the elastic polymer layer mainly composed of acrylate ester. That is, an at least two-layer structure in which an elastic polymer mainly composed of an acrylate ester is used as an inner layer and a polymer mainly composed of a methacrylic acid ester is used as an outer layer. Here, as the methacrylic acid ester which is a monomer component of the polymer in the outer layer, alkyl methacrylate is usually used. The outer layer polymer is usually formed at a ratio of 10 to 400 parts by weight, preferably 20 to 200 parts by weight with respect to 100 parts by weight of the inner layer elastic polymer. By setting the polymer of the outer layer to 10 parts by weight or more with respect to 100 parts by weight of the elastic polymer of the inner layer, the elastic polymer is less likely to aggregate and the transparency of the layer (A) is improved.

  The preferred monomer composition of the polymer of the outer layer is based on all monomers, the alkyl methacrylate is 50 to 100% by weight, the alkyl acrylate is 0 to 50% by weight, and other monomers are 0 to 0% by weight. 50% by weight, and 0 to 10% by weight of the polyfunctional monomer.

  Here, the example of alkyl methacrylate is the same as the example of alkyl methacrylate previously mentioned as a monomer component of a methacryl resin, The carbon number of the alkyl group is 1-8 normally, Preferably it is 1-4. is there. Of these, methyl methacrylate is preferably used.

  Moreover, the example of alkyl acrylate is the same as that of the alkyl acrylate previously mentioned as a monomer component of a methacryl resin, The carbon number of the alkyl group is 1-8 normally, Preferably it is 1-4. .

  In addition, examples of monomers other than alkyl methacrylate and alkyl acrylate are the same as those of monofunctional monomers other than alkyl methacrylate and alkyl acrylate mentioned above as the monomer component of methacrylic resin. Moreover, the example of a polyfunctional monomer is the same as the example of the polyfunctional monomer previously mentioned as a monomer component of a methacryl resin.

  In addition, as for said alkyl methacrylate, alkyl acrylate, monomers other than these, and a polyfunctional monomer, you may use those 2 or more types as needed, respectively.

  Further, as a preferred example of the acrylic rubber particles having a multilayer structure, a polymer layer mainly composed of a methacrylic acid ester is further provided inside the elastic polymer layer mainly composed of an acrylate ester which is the inner layer of the two-layer structure. In other words, the polymer mainly composed of methacrylic acid ester is used as the inner layer, the elastic polymer mainly composed of acrylate ester is used as the intermediate layer, and the polymer mainly composed of the methacrylic acid ester is used as the outer layer. There can also be mentioned at least a three-layer structure. Here, as a methacrylic acid ester which is a monomer component of the polymer of the inner layer, alkyl methacrylate is usually used. The polymer of the inner layer is usually formed at a ratio of 10 to 400 parts by weight, preferably 20 to 200 parts by weight, with respect to 100 parts by weight of the elastic polymer of the intermediate layer.

  A preferable monomer composition of the polymer of the inner layer is 70 to 100% by weight of alkyl methacrylate, 0 to 30% by weight of alkyl acrylate, and 0 to 30% of other monomers based on all monomers. 30% by weight, and 0 to 10% by weight of the polyfunctional monomer.

  Here, the example of alkyl methacrylate is the same as the example of alkyl methacrylate previously mentioned as a monomer component of a methacryl resin, The carbon number of the alkyl group is 1-8 normally, Preferably it is 1-4. is there. Of these, methyl methacrylate is preferably used. Moreover, the example of alkyl acrylate is the same as that of the alkyl acrylate previously mentioned as a monomer component of a methacryl resin, The carbon number of the alkyl group is 1-8 normally, Preferably it is 1-4. .

  In addition, examples of monomers other than alkyl methacrylate and alkyl acrylate are the same as those of monofunctional monomers other than alkyl methacrylate and alkyl acrylate mentioned above as the monomer component of methacrylic resin. Moreover, the example of a polyfunctional monomer is the same as the example of the polyfunctional monomer previously mentioned as a monomer component of a methacrylic acid resin.

  In addition, as for said alkyl methacrylate and monomers other than these, respectively, you may use those 2 or more types as needed.

  Acrylic rubber particles can be prepared by polymerizing the monomer component of the above-mentioned elastic polymer mainly composed of an acrylate ester by at least one stage reaction by an emulsion polymerization method or the like. At this time, as described above, when a polymer layer mainly composed of methacrylic acid ester is formed outside the elastic polymer layer, the monomer component of the outer layer polymer is added to the elastic polymer layer. What is necessary is just to graft to the said elastic polymer by making it superpose | polymerize by reaction of at least 1 step | paragraph by emulsion polymerization method etc. in presence of a polymer. Further, as described above, when a polymer layer mainly composed of methacrylic acid ester is formed inside the elastic polymer layer, first, the monomer component of the polymer in the inner layer is Polymerization is carried out by at least one stage reaction by emulsion polymerization or the like, and then the monomer component of the elastic polymer is polymerized by at least one stage reaction by emulsion polymerization or the like in the presence of the resulting polymer. In the presence of the resulting elastic polymer, the monomer component of the outer layer polymer is polymerized in an at least one-stage reaction by an emulsion polymerization method or the like. To be grafted to the elastic polymer. When the polymerization of each layer is performed in two or more stages, it is sufficient that the monomer composition as a whole is within a predetermined range, not the monomer composition of each stage.

  Regarding the particle diameter of the acrylic rubber particles, the average particle diameter of the elastic polymer layer mainly composed of acrylic acid ester in the rubber particles is preferably 0.01 to 0.4 μm, and more preferably 0. It is 05-0.3 micrometer, More preferably, it is 0.07-0.25 micrometer. If the average particle size is too large, the transparency of the layer (A) is lowered, which is not preferable. On the other hand, if the average particle size is too small, the surface hardness of the layer (A) is lowered and easily scratched, or the flexibility of the layer (A) is lowered and easily broken, which is not preferable.

  The average particle diameter was determined by mixing acrylic rubber particles with a methacrylic resin to form a film, dyeing the elastic polymer layer with ruthenium oxide in the cross section, and observing with an electron microscope. It can be determined from the diameter. That is, when acrylic rubber particles are mixed with methacrylic resin and the cross section thereof is dyed with ruthenium oxide, the methacrylic resin of the parent phase is not dyed, and the polymer mainly composed of methacrylic acid ester is outside the elastic polymer layer. If there is a layer, the polymer of this outer layer is not dyed, only the elastic polymer layer is dyed. The diameter can be determined. When a polymer layer mainly composed of methacrylic acid ester is present inside the elastic polymer layer, the polymer of the inner layer is not dyed and the outer elastic polymer layer is dyed 2 In this case, the outer diameter of the two-layer structure, that is, the outer diameter of the elastic polymer layer may be considered.

  The blending ratio of the thermoplastic resin and the rubber particles is 20 to 95 parts by weight for the thermoplastic resin and 5 to 80 parts by weight for the rubber particles based on the total of 100 parts by weight of both. When the ratio of the thermoplastic resin is too small and the ratio of the rubber particles is too large, the surface hardness of the layer (A) is lowered and easily damaged. On the other hand, when the proportion of the thermoplastic resin is too large and the proportion of the rubber particles is too small, the flexibility of the layer (A) is lowered and it becomes easy to crack.

  When acrylic rubber is used as the rubber particles, the amount of the elastic polymer mainly composed of acrylic acid ester in the acrylic rubber particles is 5 to 5 parts on the basis of a total of 100 parts by weight of the thermoplastic resin and the acrylic rubber particles. The amount is preferably 50 parts by weight, more preferably 7 to 40 parts by weight. If the amount of the elastic polymer is 5 parts by weight or more per 100 parts by weight of the total of the thermoplastic resin and the acrylic rubber particles, the film forming property can be improved without the layer (A) itself becoming brittle. it can. On the other hand, if the amount of the elastic polymer is 50 parts by weight or less per 100 parts by weight of the total of the thermoplastic resin and the acrylic rubber particles, the transparency and surface hardness of the layer (A) can be improved.

  The thermoplastic resin constituting the layer (A) includes rubber particles and other components as necessary, for example, ultraviolet absorbers, organic dyes, inorganic dyes, pigments, antioxidants, antistatic agents. You may mix | blend an agent, surfactant, etc.

  The layer (B) laminated on at least one surface of the layer (A) is composed of a copolymer of a styrene monomer and (meth) acrylic acid (hereinafter, this copolymer is referred to as “copolymer”). May be referred to as “union (B)”

  Examples of the styrenic monomer include, in addition to styrene, α-methylstyrene, 2-methylstyrene, methylstyrene such as 4-methylstyrene, dimethylstyrene such as 2,4-dimethylstyrene, ethylstyrene, 4-tert -Butyl styrene, methoxy styrene, bromo styrene, fluoro styrene, nitro styrene, chloromethyl styrene, acetoxy styrene, 4- (dimethylaminomethyl) styrene, etc. may be mentioned, and two or more of them may be used as necessary. .

  (Meth) acrylic acid means acrylic acid or methacrylic acid, and if necessary, acrylic acid and methacrylic acid may be used in combination.

  The proportion of the styrene monomer and (meth) acrylic acid is determined from the viewpoint of the chemical resistance and mechanical strength of the resulting laminated film, and the adhesion between the layer (A) and the layer (B). Based on the total monomers constituting B), the styrene monomer is usually 50 to 97% by weight, the (meth) acrylic acid is 3 to 50% by weight, and preferably the styrene monomer is 70 to 95% by weight, (meth) acrylic acid is 5 to 30% by weight, and more preferably, the styrene monomer is 80 to 93% by weight and (meth) acrylic acid is 7 to 20% by weight. In addition, as monomers constituting the copolymer (B), monomers other than styrene monomers and (meth) acrylic acid may be included, but the amount is usually up to 10% by weight. is there.

  The copolymer (B) can be used by mixing with other resin, for example, a methacrylic resin, if necessary. As this methacrylic resin, the same methacrylic resin as mentioned as an example as a thermoplastic resin previously can be used. The ratio of the copolymer (B) and the other resin is usually 25 to 100% by weight of the copolymer (B) and 0 to 0% of the other resin from the viewpoint of chemical resistance, based on the total of both. It is 75 weight%, Preferably, a copolymer (B) is 40 to 100 weight%, and another resin is 0 to 60 weight%. The copolymer (B) and other resin may be mixed by melt-mixing them using an extruder or mixer to form a mixed resin composition, and then forming a film by the method described later, or mixing the two as they are. The film may be formed while melt extrusion.

  The copolymer (B) contains other components as necessary, for example, an ultraviolet absorber, an organic dye, an inorganic dye, a pigment, an antioxidant, an antistatic agent, an interface, as in the thermoplastic resin. You may mix | blend an active agent etc.

  In order to develop a mat-like design, the composition comprising the thermoplastic resin and rubber particles constituting the layer (A), the copolymer (B) constituting the layer (B), or both It is effective to mix organic or inorganic fine particles to make the layer (A) and / or the layer (B) a light-diffusible mat layer. Examples of the organic fine particles include cross-linked acrylic polymer particles and cross-linked styrene polymer particles, and examples of the inorganic fine particles include silica and alumina. The amount of these fine particles used is appropriately adjusted depending on the desired surface gloss and design, but is usually about 0.1 to 50% by weight based on the total material constituting the layer to be added.

  By forming the composition composed of the thermoplastic resin and rubber particles as the constituent material of the layer (A) described above and the copolymer (B) as the constituent material of the layer (B) into a laminated film, The laminated film of the present invention can be obtained by forming the layer (B) made of the copolymer (B) on at least one surface of the layer (A) made of the plastic resin and the rubber particles. The method for forming the laminated film is appropriately selected. For example, a coextrusion molding method in which each constituent material is melted by an extruder and laminated using a feed block method or a multi-manifold method, a thermoplastic resin, and a rubber are used. A method of forming a composition comprising particles into a film by an extrusion method or the like, and coating the surface of this film by dissolving the copolymer (B) in a solvent as required is advantageously employed. A molding method is preferably used.

  The thickness of the laminated film thus obtained is usually 20 to 500 μm, preferably 50 to 250 μm, more preferably 50 to 150 μm. When the laminated film is too thick, for example, when it is molded as an automobile interior material, it takes time for the molding process, and the effect of improving physical properties and design properties is small, and the cost is high. On the other hand, when the laminated film is too thin, the film formation itself by extrusion becomes difficult due to mechanical restrictions, and the breaking strength is reduced, and the probability of production failure is increased. The thickness of the laminated film can be adjusted by adjusting the film forming speed, the thickness of the outlet of the T-shaped die, the gap between the rolls, and the like.

  The layer (A) made of thermoplastic resin and rubber particles has a thickness of 0.5 times or more of the total thickness of the laminated film. When the layer (A) is thin, the laminated film is inferior in flexibility, fragile and easily broken. Further, the layer (B) made of the copolymer (B) has a thickness of usually 1 μm or more, preferably 3 μm or more, more preferably 10 μm or more. When the layer (B) is too thin, the chemical resistance becomes insufficient. In addition, when arrange | positioning a layer (B) on both surfaces of a layer (A), the thickness of each layer (B) should just be 1 micrometer or more, Preferably it is 3 micrometers or more, More preferably, it is 10 micrometers or more.

  The laminated film of the present invention is preferably used as a decorative film, and in this case, a film with printing on one surface is preferably used. Examples of the printing method include a method of printing directly on the surface of the resin film by continuous gravure printing or silk printing, a method of laminating another resin film on which printing has been performed, and the like.

  If the laminated film is formed by laminating the layer (B) on one surface of the layer (A), printing is performed on the surface opposite to the surface on which the layer (B) is laminated, that is, the layer (A). By applying, it can be used as a decorative film having excellent chemical resistance with the layer (B) as a surface layer. On the other hand, when the layer (A) is easily affected by chemicals contained in the printing ink during printing, the layer (A) is printed by printing on the layer (B) having excellent chemical resistance. Can be prevented from being attacked by chemicals contained in the printing ink. Furthermore, if the laminated film is formed by laminating the layer (B) on both sides of the layer (A), it is excellent in chemical resistance with the layer (B) as a surface layer by printing on one side. It can be used as a decorative film, and even when the layer (A) is easily affected by chemicals contained in the printing ink, it can be prevented.

  Moreover, the said film for decorating can also laminate | stack a thermoplastic resin sheet as a backing material on the surface to which the printing was given, and can also make it a sheet for decorating. Here, examples of the resin constituting the thermoplastic resin sheet include ABS resin, methacrylic resin, polyvinyl chloride resin, polyurethane resin, polyester resin, and polyolefin resin. Further, the thickness of the thermoplastic resin sheet includes the thickness of the so-called film region, and is usually about 0.2 to 2 mm.

  Then, the decorative film or decorative sheet thus obtained is laminated on the thermoplastic resin molded product so that the laminated film surface not printed is arranged on the front side, that is, for decorative use. In the case of a film, a thermoplastic resin molded product is laminated on the surface on which printing is performed. In the case of a decorative sheet, the thermoplastic resin molded product is laminated on the surface on which the thermoplastic resin sheet is laminated. By laminating, a decorative molded product can be obtained. Here, examples of the resin constituting the thermoplastic resin molded article include ABS resin, methacrylic resin, polyvinyl chloride resin, polyurethane resin, polyester resin, and polyolefin resin.

  As a method for obtaining a decorative molded product, an injection molding simultaneous bonding method is advantageously employed. The injection molding simultaneous laminating method is, for example, inserting the above film or sheet into an injection mold without pre-molding, and injecting a molten resin therein to form an injection molded product, and at the same time, add the above to the molded product. A method of pasting the film or sheet (sometimes referred to as narrow-injection simultaneous molding method), the above film or sheet is preformed by vacuum molding or pressure molding, and then inserted into an injection mold. A method of injecting a molten resin there to form an injection-molded product and simultaneously bonding the film or sheet to the molded product (sometimes called an insert molding method), injection-molding the film or sheet After preforming in a mold by vacuum molding or pressure molding, etc., a molten resin is injected there to form an injection-molded product, and at the same time, the above film or sheet is applied to the molded product. Preparative (sometimes referred to as in-mold molding method) methods of bonding may be performed by such. More detailed explanation of the simultaneous injection molding method is described in, for example, Japanese Patent Publication No. 63-6339, Japanese Patent Publication No. 4-9647, Japanese Patent Application Laid-Open No. 7-9484, and the like.

  Examples of the present invention will be described below, but the present invention is not limited thereto. In the examples, “%” and “part” representing the content or amount used are based on weight unless otherwise specified.

  As the methacrylic resin, pellets of a thermoplastic polymer (glass transition temperature 104 ° C.) obtained by bulk polymerization of a monomer composed of 97.8% methyl methacrylate and 2.2% methyl acrylate were used. This glass transition temperature is an extrapolated glass transition start temperature obtained at a heating rate of 10 ° C./min by differential scanning calorimetry according to JIS K7121: 1987.

  As the acrylic rubber particles (A), the innermost layer is a hard polymer obtained by polymerization of a monomer composed of 93.8% methyl methacrylate, 6% methyl acrylate, and 0.2% allyl methacrylate, The intermediate layer is an elastic polymer obtained by polymerization of a monomer composed of 81% butyl acrylate, 17% styrene and 2% allyl methacrylate, and the outermost layer is 94% methyl methacrylate and 6% methyl acrylate. The weight ratio of the innermost layer / intermediate layer / outermost layer is 35/45/20, and the average particle diameter of the elastic polymer layer of the intermediate layer A rubber particle having a spherical three-layer structure by an emulsion polymerization method having a diameter of 0.22 μm was used.

  The acrylic rubber particles (B) have basically the same composition as the acrylic rubber particles (A), but by changing the polymerization conditions, the average particle diameter of the elastic polymer layer of the intermediate layer becomes 0.14 μm. Rubber particles having a spherical three-layer structure were used.

  As the acrylic rubber particles (C), the innermost layer is an elastic polymer obtained by polymerization of a monomer composed of 81% butyl acrylate, 17% styrene and 2% allyl methacrylate, and the outermost layer is methyl methacrylate. It is a hard polymer obtained by polymerization of a monomer consisting of 94% and methyl acrylate 6%, the innermost layer / outermost layer weight ratio is 80/20, and the innermost elastic polymer layer Spherical two-layer rubber particles by an emulsion polymerization method having an average particle size of 0.08 μm were used.

The average particle size of the elastic polymer layer of the intermediate layer in the acrylic rubber particles (A), (B) and (C) was measured by the following method.
(Measurement of average particle diameter of elastic polymer layer)
Acrylic rubber particles are mixed with a methacrylic resin to form a film, and the resulting film is cut into an appropriate size, and the slice is immersed in a 0.5% aqueous ruthenium tetroxide solution at room temperature for 15 hours. The polymer layer was dyed. Further, the sample was cut to a thickness of about 80 nm using a microtome, and then photographed with a transmission electron microscope. After randomly selecting 100 dyed elastic copolymer layers from this photograph and calculating the particle diameter of each, the number average value was taken as the average particle diameter.

  As the styrene resin (a), a styrene-methacrylic acid copolymer [T080 manufactured by Toyo Styrene Co., Ltd .; methacrylic acid unit 8% by weight] was used.

  As the styrene resin (b), a styrene-methacrylic acid copolymer [Lurex A-14 manufactured by Dainippon Ink & Chemicals, Inc .; methacrylic acid unit 14% by weight] was used.

  Polystyrene resin [GPPS HF77 manufactured by PS Japan Co., Ltd.] was used as the styrene resin (c).

Examples 1-9, Comparative Examples 1-3
The methacrylic resin pellets were mixed with the acrylic rubber particles (A), (B) or (C) at a ratio shown in Table 1 by a super mixer, and melt-kneaded with a twin screw extruder to obtain a methacrylic resin composition pellets. (Examples 1 to 9, Comparative Examples 2 and 3). Further, the styrene resin (b) is mixed with a mat material [organic fine particles; XX-24K manufactured by Sekisui Plastics Co., Ltd.] at a ratio shown in Table 1 (Example 5), or a styrene resin. Resin (b) was mixed with a methacrylic resin at a ratio shown in Table 1 (Examples 7 to 9), and melt-kneaded with a twin screw extruder to obtain pellets of a styrenic resin composition. Next, the methacrylic resin or a pellet of the composition thereof was transferred to a 65 mmφ single screw extruder manufactured by Toshiba Machine Co., Ltd., and the styrene resin (a), (b) or (c), or the pellet of the styrene resin composition was transferred to Toshiba Machine. In a 45 mmφ single-screw extruder manufactured by Co., Ltd., melted and integrated by a feed block method, extruded through a T-shaped die with a set temperature of 275 ° C., and the resulting film-like product has a pair of surfaces Molded by sandwiching between smooth metal rolls. Thus, a laminated film having a two-layer structure shown in Table 1 was produced, the following evaluation was performed, and the results are shown in Table 1.

[Flexibility test]
According to JIS K5600-5-1: 1999, the bending resistance of the film was evaluated. The test piece did not break and the flexibility was good. The test piece did not break but delamination was observed between the layers. A sample was evaluated as Δ, and a test piece was broken and the sample was not flexible.

[Lactic acid resistance test]
A 10% aqueous solution of lactic acid was prepared, and after dropping one drop on the film surface [styrene resin layer (layer (B)) side], the lactic acid was allowed to stand in an oven at 40 ° C. for 24 hours, and the state was visually confirmed. Those in which droplet traces were clearly confirmed, those in which the film surface was dissolved, or those in which cracks occurred in the film were evaluated as x, those in which the droplet traces were slightly confirmed were evaluated as △, and those without change were evaluated as ◯. .

[Methanol resistance test]
5 ml of methanol was dropped on the film surface [the styrene-based resin layer (layer (B)) side], sealed with a polyethylene wrap, allowed to stand at room temperature for 24 hours, and then visually confirmed. Those in which droplet traces were clearly confirmed, those in which the film surface was dissolved, or those in which cracks occurred in the film were evaluated as x, those in which the droplet traces were slightly confirmed were evaluated as △, and those without change were evaluated as ◯. .

Comparative Example 4
The methacrylic resin pellets were mixed with the acrylic rubber particles (A) at a ratio shown in Table 1 with a super mixer, and melt-kneaded with a twin screw extruder to obtain methacrylic resin composition pellets. Next, the methacrylic resin composition pellets were melted with a 65 mmφ single screw extruder manufactured by Toshiba Machine Co., Ltd. and extruded through a T-shaped die with a set temperature of 275 ° C., and the resulting film-like product was smoothed on a pair of surfaces. The metal roll was sandwiched and molded. Thus, the single-layer acrylic film shown in Table 1 was produced, and the same evaluation as described above was performed. The results are shown in Table 1.

Claims (14)

  A layer (B) made of a copolymer of a styrene monomer and (meth) acrylic acid is laminated on at least one surface of the layer (A) made of a thermoplastic resin and rubber particles. A laminated film, wherein the thickness of A) is 0.5 times or more of the total thickness.   The laminated film according to claim 1, wherein the thermoplastic resin is a methacrylic resin.   The methacrylic resin is a polymer obtained by polymerizing 50 to 100% by weight of alkyl methacrylate, 0 to 50% by weight of alkyl acrylate, and 0 to 49% by weight of other monomers. The laminated film according to claim 1 or 2.   The laminated film according to any one of claims 1 to 3, wherein the rubber particles are acrylic rubber particles.   Acrylic rubber particles comprise 50-99.9 wt% of alkyl acrylate, 0-49.9 wt% of alkyl methacrylate, 0-49.9 wt% of other monofunctional monomers, and polyfunctional mono The laminated film according to claim 4, which is a particle containing an elastic polymer obtained by polymerizing a monomer at a ratio of 0.1 to 10% by weight.   Acrylic rubber particles are placed on the outer side of the elastic polymer layer with 50 to 100% by weight of alkyl methacrylate, 0 to 50% by weight of alkyl acrylate, 0 to 50% by weight of other monomers, and many more. The laminated film according to claim 5, which is a multilayer structure particle having a polymer layer obtained by polymerizing a functional monomer at a ratio of 0 to 10% by weight.   Acrylic rubber particles have 70 to 100% by weight of alkyl methacrylate, 0 to 30% by weight of alkyl acrylate, 0 to 30% by weight of other monomers, and many more inside the elastic polymer layer. The laminated film according to claim 5 or 6, which is a particle having a multilayer structure having a polymer layer obtained by polymerizing a functional monomer at a ratio of 0 to 10% by weight.   The laminated film according to any one of claims 1 to 7, wherein the whole thickness is 20 to 500 µm, and the thickness of the layer (B) is 1 µm or more.   The laminated film according to any one of claims 1 to 8, wherein the layer (A) and / or the layer (B) is a layer containing organic or inorganic fine particles.   The laminated film according to any one of claims 1 to 9, wherein a composition comprising a thermoplastic resin and rubber particles and the copolymer are coextruded.   Printing is given to one surface of the laminated | multilayer film in any one of Claims 1-10, The film for decorating characterized by the above-mentioned.   A thermoplastic resin sheet is laminated on the surface on which the decorative film according to claim 11 is printed.   A decorative molded product, wherein a thermoplastic resin molded product is laminated on a surface on which the decorative film according to claim 11 is printed.   A decorative molded product, wherein a thermoplastic resin molded product is laminated on a surface of the decorative sheet according to claim 12 on which the thermoplastic resin sheet is laminated.