JP2010030248A - Matted resin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a matted resin film which hardly cracks a mat layer upon molding and enables a user to see a decoration clearly from the mat surface side when the decoration is provided to the surface of opposite side to the mat surface. <P>SOLUTION: The mat layer including a transparent resin and transparent microparticles is laminated on one side surface of a transparent resin layer according to a co-extrusion molding to make the matted resin film. A 60°mirror surface glossiness Gs of the mat layer surface is set to be in the range of 11 to 70%. The surface glossiness Gs and haze H satisfy the relation: H(%)<1,100/Gs(%). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a multilayer matte resin film having a mat layer. The present invention also relates to a decorative film, a decorative sheet, and a decorative molded product using this matte resin film.

  Conventionally, as a target substrate to be matted, a plastic plate such as an acrylic resin plate or a polycarbonate resin plate is generally used, and a matte shape is formed on the surface by thermoforming or the like, and used as a design molded body. It has been. On the other hand, in recent years, a film bonding method such as an injection molding simultaneous bonding method is often employed as a method for producing such a designable molded body, and the demand for a matte resin film is increasing.

  As the matte resin film, those obtained by transferring a matte shape with a mold at the time of film formation or after film formation, and those obtained by adding a matting agent to a raw material resin to form a film are known (for example, Patent Document 1). 2), the former has a problem that matte return tends to occur at the same time of injection molding, and the latter has decoration such as pattern printing on the surface opposite to the mat surface (matte surface). In such a case, there is a problem that the decorative omission easily occurs and the cost is likely to increase. In order to solve the problems of these single-layer matte resin films, a multi-layer matte resin film having a mat layer (matte layer) has been studied. For example, Japanese Patent Laid-Open No. 2003-212598 (Patent Document 3). Discloses that a mat layer (matte layer) is formed on a resin film substrate with a thermosetting resin or a photocurable resin and inorganic fine particles. JP-A-2002-273835 (Patent Document 4) discloses a laminate in which a resin layer containing a matting agent and a resin layer not containing a matting agent are laminated by coextrusion molding or thermal lamination. .

JP-A-3-237134 Japanese Patent Laid-Open No. 10-237261 JP 2003-111598 A JP 2002-273835 A

  The matte resin film disclosed in Patent Document 3 has a problem that the mat layer is easily broken during molding. Further, the matte resin film disclosed in Patent Document 4 has a problem that when the surface opposite to the mat surface is decorated, the decoration seen from the mat surface side is likely to become cloudy and unclear.

  Accordingly, an object of the present invention is to provide a matte resin film in which the mat layer is difficult to break at the time of molding and the decoration is clearly visible from the mat surface side when the surface opposite to the mat surface is decorated. There is. And it is providing the decorative film, decorative sheet, and also decorative molded product excellent in the designability using this matte film.

  As a result of intensive studies, the inventor is a matte resin film in which a matte layer containing a transparent resin and transparent fine particles is laminated on one surface of a transparent resin layer by coextrusion molding, and has a predetermined glossiness and haze. It has been found that what it has is suitable for the above purpose, and has led to the present invention.

  That is, the present invention is a matte resin film in which a mat layer containing transparent resin and transparent fine particles is laminated on one surface of a transparent resin layer by coextrusion molding, and the surface of the mat layer has a specular gloss of 60 degrees. The matte resin film is characterized in that the degree Gs is 11 to 70%, and the Gs and the haze H satisfy the relationship of the formula: H (%) <1100 / Gs (%).

  Further, according to the present invention, the surface of the matte resin film on the side of the transparent resin layer is decorated, and the surface of the surface of the decorative film is decorated. In addition, a decorative sheet is provided in which a thermoplastic resin sheet is laminated, and further on the surface on the decorative side of the decorative film or the surface on the thermoplastic resin sheet side of the decorative sheet, There is provided a decorative molded product obtained by injection-molding a thermoplastic resin.

  The matte resin film of the present invention uses this film because the mat layer is difficult to break at the time of molding and the decoration is clearly seen from the mat surface when the surface opposite to the mat surface is decorated. As a result, a decorative film, a decorative sheet, and a decorative molded product excellent in design can be obtained.

  The matte resin film of the present invention is formed by laminating a matte layer containing transparent resin and transparent fine particles on one surface of a transparent resin layer by coextrusion molding. And 60 degree specular glossiness Gs of the surface of this mat | matte layer is 11-70%, Preferably it is 13-60%, More preferably, it is 15-50%. If Gs is less than 11%, the matte effect is too strong and it becomes difficult to maintain transparency, and the film becomes dull and easy to see. In this case, the decoration that can be seen from the mat surface side is likely to become cloudy and unclear. When Gs exceeds 70%, the matte effect is not sufficient.

  Further, the matte resin film of the present invention has a haze H satisfying the formula: H (%) <1100 / Gs (%) in relation to the 60-degree specular gloss Gs, preferably the formula : H (%) <1050 / Gs (%) is satisfied, and more preferably, the formula: H (%) <1000 / Gs (%) is satisfied. Thus, when H and Gs satisfy the predetermined formula, a matte resin film with excellent transparency is obtained, and when the surface opposite to the mat surface is decorated, the decoration visible from the mat surface side Becomes clear.

  Further, the matte resin film of the present invention preferably has a 60-degree specular gloss Gs ′ and a haze H ′ on the surface of the mat layer in the stretched film state after being uniaxially stretched twice at 150 ° C. It satisfies the relationship of formula: H ′ (%) <1100 / Gs ′ (%), more preferably satisfies the relationship of formula: H ′ (%) <1050 / Gs ′ (%), and Preferably, the relationship of the formula: H ′ (%) <1000 / Gs ′ (%) is satisfied.

  In addition, the matte resin film of the present invention preferably has a formula in which the 60-degree specular gloss Gs on the surface of the mat layer is related to the 60-degree specular gloss Gs ′ on the surface of the mat layer after stretching. | Gs−Gs ′ | / Gs <0.45 is satisfied, and more preferably the equation: | Gs−Gs ′ | / Gs <0.40 is satisfied.

  In this way, after H ′ and Gs ′ satisfy a predetermined formula, after molding such as thermoforming, after film bonding such as simultaneous injection molding or after preliminary molding such as vacuum molding or pressure molding before that The matte resin film maintains an excellent matting effect and transparency.

  The matte resin film of the present invention having the predetermined optical characteristics as described above comprises a transparent resin layer constituting material essential for transparent resin and a mat layer constituting material essential for transparent resin and transparent fine particles. By forming a multilayer film by extrusion molding, a mat layer in which transparent fine particles are dispersed in a transparent resin is laminated on one surface of the transparent resin layer. At that time, the composition and thickness of each layer, co-extrusion molding conditions It can manufacture by adjusting etc.

  Examples of the transparent resins constituting the transparent resin layer and the mat layer include acrylic resins, styrene resins, vinyl chloride resins, olefin resins, polyurethane resins, polyester resins, and polycarbonate resins. Of these, acrylic resins are preferably used from the viewpoint of transparency and weather resistance, and methacrylic resins are particularly preferably used.

  The methacrylic resin is a polymer obtained by polymerizing a monomer mainly composed of a methacrylic acid ester, and may be a homopolymer of the methacrylic acid ester, or 50% by weight or more of the methacrylic acid ester and other simple units. A copolymer with 50% by weight or less of the monomer may 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 preferably 50 to 100% by weight of alkyl methacrylate and 0 to 50% by weight of alkyl acrylate, based on a total of 100% by weight of all monomers. The monomer is 0 to 49% by weight, more preferably 50 to 99.9% by weight of alkyl methacrylate, 0.1 to 50% by weight of alkyl acrylate, and 0 to 49% by weight of other monomers. More preferably, the alkyl methacrylate is 50 to 99.5% by weight, the alkyl acrylate is 0.5 to 50% by weight, and other monomers are 0 to 49% by weight.

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

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

  Monomers other than alkyl methacrylate and alkyl acrylate may be monofunctional monomers, that is, compounds having one polymerizable carbon-carbon double bond in the molecule, or polyfunctional monomers. That is, it may be a compound having at least two polymerizable carbon-carbon double bonds in the molecule, but a monofunctional monomer is preferably used.

  Examples of the monofunctional monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, alkenyl cyanide compounds such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N -Substituted maleimides.

  Examples of the polyfunctional monomer include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, allyl acrylate, allyl methacrylate, and cinnamic acid. Alkenyl esters of unsaturated carboxylic acids such as allyl, polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, aromatic polyalkenyl compounds such as divinylbenzene Is 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. 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 suspension polymerization, emulsion polymerization, bulk polymerization or the like. At that time, in order to obtain a suitable glass transition temperature or to obtain a viscosity exhibiting a moldability to a suitable multilayer film, it is preferable to use a chain transfer agent during the polymerization. What is necessary is just to adjust the quantity of a chain transfer agent suitably according to the kind of monomer, its ratio, etc.

  Examples of the transparent fine particles constituting the mat layer include crosslinked particles such as acrylic and styrene, talc, glass beads, and silicone particles. Among these, acrylic crosslinked particles are preferably used because the refractive index and size can be easily controlled.

  In the transparent fine particles, the difference (| Nd−Nb |) between the refractive index Nd and the refractive index Nb of the transparent resin constituting the mat layer is preferably 0.01 or less, and more preferably 0.008 or less. Preferably, it is 0.005 or less. If | Nd−Nb | is too large, the haze tends to be high, and it becomes difficult to satisfy the above formula: H (%) <1100 / Gs (%).

  The volume average particle diameter of the transparent fine particles is preferably 3 to 10 μm, more preferably 4 to 9 μm, and further preferably 4.5 to 8 μm. If the volume average particle size is too small, it is necessary to increase the amount of transparent fine particles in the mat layer in order to reduce gloss and obtain a desired matte feeling, which is not preferable because it is not economical and the film becomes brittle and easily broken. . If the volume average particle size is too large, it is difficult to satisfy the above formula: H (%) <1100 / Gs (%), and a rough matte feeling is caused, which is not preferable.

  Matte resin obtained by blending rubber particles with the transparent resin layer and / or the matte layer constituting the transparent resin layer and composing the transparent resin layer and / or the mat layer with the composition The flexibility and strength of the film can be improved.

  Examples of the rubber particles include acrylic, butadiene, styrene-butadiene, and olefin rubber particles. Among these, acrylic rubber particles are preferably used from the viewpoint of weather resistance. When rubber particles are contained in both the transparent resin layer and the mat layer, both rubber particles may be the same or different from each other.

  An acrylic rubber particle is a rubber elastic body obtained by copolymerizing an alkyl acrylate having an alkyl group with 4 to 8 carbon atoms and a polyfunctional monomer together with another monofunctional monomer as required. It is good to contain. In addition to single-layer acrylic rubber particles made of such a rubber elastic body, multi-layer acrylic rubber particles having such a rubber elastic body as one layer can also be used. The polyfunctional monomer used here is a compound having at least two polymerizable carbon-carbon double bonds in one molecule, such as allyl (meth) acrylate and methallyl (meth) acrylate. Examples thereof include alkenyl esters of unsaturated carboxylic acids, dialkenyl esters of dibasic acids such as diallyl maleate, and unsaturated carboxylic acid diesters of glycols such as alkylene glycol di (meth) acrylate. Moreover, as another monofunctional monomer arbitrarily used as a copolymerization component, for example, styrene, nuclear alkyl-substituted styrene, α-methylstyrene, and acrylonitrile are exemplified.

  The acrylic rubber particles having a multilayer structure are obtained by, for example, polymerizing a monomer mainly composed of methyl methacrylate around a rubber elastic body layer obtained by copolymerizing an alkyl acrylate and a polyfunctional monomer. A hard polymer layer can be formed, including two, three or more layers. As the acrylic rubber particles having a two-layer structure, for example, the inner layer is a rubber elastic body obtained by copolymerizing an alkyl acrylate and a polyfunctional monomer, and the outer layer is a monomer mainly composed of methyl methacrylate. What is a hard polymer obtained by polymerizing is mentioned. As the acrylic rubber particles having a three-layer structure, for example, the innermost layer is a hard polymer obtained by polymerizing a monomer mainly composed of methyl methacrylate, and the intermediate layer includes an alkyl acrylate and a polyfunctional monomer. And a rubber elastic body obtained by copolymerizing the above and the outermost layer being a hard polymer obtained by polymerizing a monomer mainly composed of methyl methacrylate. The innermost layer is preferably crosslinked using a small amount of a polyfunctional monomer in addition to methyl methacrylate. Such acrylic rubber particles having a three-layer structure can be produced, for example, by the method described in Japanese Patent Publication No. 55-27576 (US Pat. No. 3,793,402). In the present invention, it is preferable to use rubber particles having a multilayer structure of at least two layers, and it is more preferable to use rubber particles having a three-layer structure from the viewpoint of improving the surface hardness of the film.

  The average particle diameter of the acrylic rubber particles is usually 50 nm or more, preferably 80 nm or more, more preferably 150 nm or more, and usually 500 nm or less, preferably 350 nm or less, expressed as the number average diameter of the rubber elastic layer. More preferably, it is 300 nm or less. If the average particle size is too small, the impact resistance of the resulting film tends to be low, and if it is too large, the transparency tends to be low.

  The acrylic rubber particles in which the outermost layer is a hard polymer obtained by polymerizing a monomer mainly composed of methyl methacrylate, and the rubber elastic body is encapsulated in the hard polymer, is a base acrylic resin. When the rubber particles are mixed, the outermost layer of the rubber particles is mixed with the base acrylic resin, so that the rubber elastic body portion is dyed with ruthenium oxide in the cross section, and when observed with an electron microscope, the rubber particles are It is observed as particles in the state excluding. Specifically, when using acrylic rubber particles having a two-layer structure in which the inner layer is a rubber elastic body and the outer layer is a hard polymer obtained by polymerizing a monomer mainly composed of methyl methacrylate, The rubber elastic body part is dyed and observed as particles of a single layer structure, and the innermost layer is a hard polymer obtained by polymerizing a monomer mainly composed of methyl methacrylate, and the intermediate layer is rubber-like elastic. When the acrylic rubber particles having a three-layer structure that is a hard polymer obtained by polymerizing a monomer mainly composed of methyl methacrylate is used as the outermost layer, the central portion of the particle that is the innermost layer is Without being dyed, only the rubber elastic body portion of the intermediate layer is observed as a dyed particle having a two-layer structure. The number average diameter of the rubber elastic layer is the number average value of the diameter of the portion that is dyed and observed in a substantially circular shape when the rubber particles are mixed with the base resin and the cross section is dyed with ruthenium oxide. It is.

  As described above, by adding rubber particles to the transparent resin layer and / or the mat layer, the matte resin film can be improved in flexibility and strength. Therefore, it is preferable that the mat layer does not contain rubber particles. Therefore, in terms of the balance between the flexibility and strength of the matte resin film and the surface hardness of the mat layer, it is preferable that only the transparent resin layer contains rubber particles and the mat layer does not contain rubber particles. The amount of the rubber particles contained in the transparent resin layer may be 10 to 60% by weight based on the total of 100% by weight of the transparent resin and rubber particles contained in the transparent resin. In addition, when emphasizing the flexibility and strength of the matte resin film, it is preferable to include rubber particles in the mat layer, but even in that case, it is included in the mat layer in consideration of the surface hardness of the mat layer. The amount of the rubber particles is reduced to 15% by weight or less based on the total 100 parts by weight of the transparent resin and rubber particles contained in the mat layer, or the total amount of the transparent resin and rubber particles contained in the mat layer is 100. The amount of rubber particles contained in the mat layer based on% by weight is less than the amount of rubber particles contained in the transparent resin layer based on 100% by weight in total of the transparent resin and rubber particles contained in the transparent resin layer. It is good to do.

In addition, the transparent resin layer and the mat layer may contain other components as necessary, for example, an ultraviolet absorber, an organic dye, an inorganic dye, a pigment, an antioxidant, an antistatic agent, and a surfactant. Also good.

  By constructing the constituent material of the transparent resin layer essential for the transparent resin described above and the constituent material of the mat layer essential for the transparent resin and the transparent fine particles into a multilayer film by coextrusion molding, specifically, By melting both constituent materials in an extruder and laminating them using the feed block method and the multi-manifold method, the resulting multilayer film-like melt is brought into close contact with a roll or belt, cooled, and molded, A matte resin film in which a mat layer is laminated on one surface of the transparent resin layer is obtained.

  The number, arrangement, and material of the rolls and belts at this time are appropriately selected. A method of transferring the surface of the rolls or belts by passing the melt between two metal rolls or between the metal rolls and the metal belt. However, it is preferable for improving the surface accuracy of the film surface and improving the decorating property. In addition, the method of contacting and passing both sides of the melt with a metal rigid roll and a metal elastic roll reduces the distortion during molding and obtains a film with reduced strength and heat shrinkable anisotropy. It is suitable for. As the metal elastic roll, for example, a shaft roll and a cylindrical metal thin film disposed so as to cover the outer peripheral surface of the shaft roll and in contact with the melt are provided. Examples include those in which a temperature-controlled fluid such as water or oil is enclosed, or a metal belt wrapped around the surface of a rubber roll. When the melt is sandwiched between the metal elastic roll and the metal rigid roll, the metal elastic roll is elastically deformed into a concave shape along the outer peripheral surface of the metal rigid roll via the melt. Thereby, since a metal rigid roll and a metal elastic roll are crimped | bonded by surface contact with respect to a molten material, the molten material pinched | interposed between these rolls is shape | molded, uniformly pressing in surface shape. If the mat layer side of the melt is brought into contact with the metal elastic roll and molded, the transparent fine particles can be suppressed from being pushed into the transparent resin, so that the appearance of the matte tone can be suppressed, A matte resin film having desired matting properties can be obtained.

  For example, the melt extruded from the die is sandwiched between a first cooling roll, which is a metal elastic roll, and a second cooling roll, which is a metal rigid roll. It is sandwiched between the cooling roll and the third cooling roll, wound around the third cooling roll and cooled. At that time, the fourth and subsequent cooling rolls may be used. In this cooling process, the mat layer is on the side in contact with the first cooling roll between the first cooling roll and the second cooling roll, and then cooled outside the second cooling roll. Further, it is preferable that the second cooling roll and the third cooling roll that pass thereafter are not brought into close contact with each other unlike ordinary coextrusion molding, and are kept slightly wider than the total thickness of the film. As the mat layer is rapidly cooled outside the second cooling roll, more transparent fine particles protrude from the surface due to the difference in thermal shrinkage between the transparent resin and the transparent fine particles. In addition, since no linear pressure is applied to the film between the second cooling roll and the third cooling roll, the protruding transparent fine particles are not pushed back, resulting in a surface state having moderate unevenness.

  The matte resin film thus obtained has a thickness of usually 20 to 800 μm, preferably 30 to 300 μm, more preferably 50 to 150 μm. When the matte resin film is too thick, for example, when it is molded as an automobile interior material, the molding process takes time, and the effect of improving physical properties and design properties is small, and the cost is high. On the other hand, when the matte resin film is too thin, film formation by extrusion becomes difficult due to mechanical constraints, and the breaking strength is reduced, so that the probability of production failure is increased. The thickness of the matte resin 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 mat layer is preferably 50% or less of the total thickness of the matte resin film. Moreover, the thickness becomes like this. Preferably it is 5-100 micrometers, More preferably, it is 7-50 micrometers, More preferably, it is 8-15 micrometers. If the mat layer is too thin, it becomes smaller than the average particle diameter of the transparent fine particles and it becomes difficult to uniformly disperse the transparent fine particles, resulting in spots, satisfying the above formula: H (%) <1100 / Gs (%) It becomes difficult. On the other hand, if the mat layer is too thick, the necessary amount of transparent fine particles increases, which increases the cost, which is not preferable.

  The matte resin film of the present invention is preferably used as a decorative film, particularly as a decorative film for simultaneous injection molding. The decorative film may be one in which the surface on the transparent resin layer side is decorated.

  As decoration methods, for example, a method of directly printing a wood grain or various designs on the surface by continuous gravure printing or silk printing, a method of decorating a metal plating tone by vapor deposition or sputtering, printing or vapor deposition, etc. The method of laminating the other resin film decorated with is mentioned.

  The decorative film can be made a decorative sheet by laminating a thermoplastic resin sheet as a backing material on the surface on the decorative side. Examples of the resin constituting the thermoplastic resin sheet include ABS (acrylonitrile-butadiene-styrene copolymer) resin, olefin resin, acrylic resin, vinyl chloride resin, polyurethane resin, and polyester resin. The thickness of the thermoplastic resin sheet is usually 0.1 to 2 mm.

  By laminating such a decorative film or decorative sheet on a thermoplastic resin molded product so that the mat layer side is arranged on the front side, that is, if it is a decorative film, the surface of the decorative side is thermoplastic. By laminating the resin molded product, and if it is a decorative sheet, the decorative molded product can be obtained by laminating the thermoplastic resin molded product on the surface of the thermoplastic resin sheet. Examples of the resin constituting the thermoplastic resin molded article include ABS resin, olefin resin, acrylic resin, vinyl chloride resin, polyurethane resin, and polyester resin.

  As a method for obtaining a decorative molded product, an injection molding simultaneous bonding method is advantageously employed. The injection molding simultaneous bonding method is a method in which a decorative film or a decorative sheet is not preformed and inserted into an injection mold, and a molten resin is injected therein to form an injection molded product. A method of pasting a decorative film or decorative sheet on the surface (sometimes referred to as a narrow injection molding simultaneous bonding method), pre-molding the decorative film or decorative sheet by vacuum forming or pressure forming, etc., and then injection molding A method of inserting into a mold and injecting a molten resin therein to form an injection-molded product, and simultaneously bonding a decorative film or decorative sheet to the molded product (sometimes called an insert molding method) After the decorative film or decorative sheet is preformed in the injection mold by vacuum forming or pressure forming, the molten resin is injected into it to form an injection-molded product, and at the same time decorate the molded product. fill Or decorative sheet can be accomplished by laminating the (sometimes referred to as in-mold molding method). 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, and Japanese Patent Application Laid-Open No. 7-9484.

  Examples of the present invention will be described below, but the present invention is not limited thereto. In the examples,% representing the content or amount used is based on weight unless otherwise specified. Moreover, the measuring method of each physical property is as follows.

[Haze (H and H ')]
A 100 mm square test piece was prepared from the film and measured according to JIS K7136 using HR-100 from Murakami Color Research Laboratory, with the transparent resin layer side as the light source side.

[60 degree specular gloss (Gs and Gs ′)]
Using the same specimen as that used for the haze measurement, the 60-degree specular gloss of the surface of the mat layer was measured according to JIS Z8741 using a gloss meter GM-268 manufactured by Minolta Co., Ltd.

〔Pencil hardness〕
The pencil hardness of the surface of the mat layer was measured according to JIS K5600.

  The materials constituting the transparent resin layer (A) and the mat layer (B) used in each example are as follows.

[Methacrylic resin]
As a methacrylic resin, the glass transition temperature obtained by bulk polymerization of a monomer consisting of 97.8% methyl methacrylate and 2.2% methyl acrylate is 104 ° C., and the refractive index (Nb) is 1. A 490 thermoplastic polymer pellet was 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.

[Transparent fine particles]
The following were used as transparent fine particles.
Transparent fine particles (a): MBX-5H (refractive index Nd = 1.495, volume average particle size 5.1 μm) of Sekisui Plastics Co., Ltd.
Transparent fine particles (b): XX-219K (refractive index Nd = 1.505, volume average particle size 4.0 μm) of Sekisui Plastics Co., Ltd.
Transparent fine particles (c): XX-24K (refractive index Nd = 1.515, volume average particle size 5.3 μm) of Sekisui Plastics Co., Ltd.
Transparent fine particles (d): MBX-5 (refractive index Nd = 1.495, volume average particle size 5.0 μm) of Sekisui Plastics Co., Ltd.

[Acrylic rubber particles]
As the acrylic rubber particles, the innermost layer is a hard polymer obtained by polymerization of a monomer consisting of 93.8% methyl methacrylate, 6% methyl acrylate, and 0.2% allyl methacrylate, and the intermediate layer is An elastic polymer obtained by polymerization of a monomer composed of 81% butyl acrylate, 17% styrene, and 2% allyl methacrylate. The outermost layer is composed of 94% methyl methacrylate and 6% methyl acrylate. It is a hard polymer obtained by polymerization of monomers, the weight ratio of innermost layer / intermediate layer / outermost layer is 35/45/20, and the number average diameter of the elastic polymer layer of the intermediate layer is 220 nm. A rubber particle having a spherical three-layer structure by an emulsion polymerization method was used. The number average diameter is a value obtained by the following method.

(Measurement of average diameter)
Acrylic rubber particles are mixed with a methacrylic resin to form a film, the resulting film is cut into a suitable size, and the slice is immersed in an aqueous 0.5% ruthenium tetroxide solution at room temperature for 15 hours. The coalesced layer was stained. Further, the sample was cut to a thickness of about 80 nm using a microtome, and then photographed with a transmission electron microscope. From this photograph, 100 dyed elastic polymer layers were randomly selected, their diameters were calculated, and the number average value was determined.

Examples 1-10, Comparative Examples 1-4
80 parts of methacrylic resin and 20 parts of acrylic rubber particles were mixed with a super mixer and melt-kneaded using a twin screw extruder to obtain a resin composition for a transparent resin layer as pellets. Further, methacrylic resin, acrylic rubber particles and any one of the transparent fine particles (a) to (c) shown in Table 1 are mixed by a super mixer at a ratio shown in Table 1, and melt kneaded using a twin screw extruder. The resin composition for the mat layer was obtained as pellets.

  Next, the resin composition for the transparent resin layer was melted with a 65 mmφ single screw extruder (manufactured by Toshiba Machine Co., Ltd.), and the resin composition for the mat layer was melted with a 45 mmφ single screw extruder (manufactured by Toshiba Machine Co., Ltd.). The melt was laminated and integrated by a feed block method and extruded through a T-shaped die having a set temperature of 265 ° C. The obtained film-like product is formed by passing through a cooling unit composed of three rolls in which the first cooling roll is a metal elastic roll and the second cooling roll and the third cooling roll are each a metal rigid roll. A two-layer matte resin film having an overall thickness of 125 μm was produced. At that time, the mat layer side was set to be in contact with the first cooling roll by adjusting the pins of the feed block. At that time, the first cooling roll and the second cooling roll were in close contact with the film, and the second cooling roll and the third cooling roll were not in close contact with each other, and the film was passed with an interval of 0.5 mm. . The ratio of the layer thickness is calculated from the consumption of the resin composition per time of each extruder, and from this ratio and the total thickness, the thickness of the transparent resin layer and the thickness of the mat layer are calculated, and the total thickness is further calculated. The ratio of the thickness of the mat layer to the thickness was determined, and these values are shown in Table 1. The difference (| Nd−Nb |) between the refractive index (Nd) of the transparent fine particles (a), (b) and (c) and the refractive index (Nb) of the methacrylic resin is 0.005, 0.00, respectively. 015 and 0.025.

  The resulting matte resin film was measured for haze H and 60 ° specular gloss Gs, and further determined 1100 / Gs (%). These values are shown in Table 2. The resulting matte resin film was measured for pencil hardness, and the results are shown in Table 2.

  In addition, a test piece having a width direction of 50 mm × extrusion direction of 150 mm was prepared from the resulting matte resin film, set to 50 mm between chucks using INSTRON 5500R manufactured by Instron, and a speed of 50 mm / min at 150 ° C. Then, it was uniaxially stretched twice in the extrusion direction by pulling to 100 mm between the chucks. For the stretched film, the haze H ′ near the center and the 60 ° specular gloss Gs ′ were measured, and further, 1100 / Gs ′ (%) and | Gs−Gs ′ | / Gs were obtained. It is shown in Table 2.

  The matte films obtained in Examples 1-10 have the formula: H (%) <1100 / Gs (%), formula: H ′ (%) <1100 / Gs ′ (%), and formula: | Gs− Gs ′ | / Gs <0.45 was satisfied, whiteness was not seen before and after stretching, and the appearance was also good. On the other hand, the matte films obtained in Comparative Examples 1 to 4 satisfy the formula: | Gs−Gs ′ | / Gs <0.45, but the formula: H (%) <1100 / Gs (%), and the formula : H ′ (%) <1100 / Gs ′ (%) was not satisfied, and the appearance was good before and after stretching, but whitishness was conspicuous.

Comparative Examples 5 and 6
80 parts of methacrylic resin and 20 parts of acrylic rubber particles were mixed with a tumbler type mixer and melt kneaded using a twin screw extruder to obtain a resin composition as pellets. Next, this resin composition was melted with a 65 mmφ single screw extruder (manufactured by Toshiba Machine Co., Ltd.) and extruded through a T-die. The obtained film-like product was passed through a cooling unit consisting of the same three rolls as above to form each of the cooling rolls so that both surfaces were completely in contact with each other, thereby obtaining an acrylic resin film having a thickness of 125 μm.

  Next, 18 parts of transparent fine particles (d), 55 parts of a paint containing acrylic polyol [Topcoat agent PTC-NT U-605 medium (A1) of Dainichi Seika Kogyo Co., Ltd.] PTC-NT No. 2] 27 parts were mixed to obtain a transparent fine particle dispersion. 15.4 parts (Comparative Example 5) or 23.1 parts (Comparative Example 6) of this transparent fine particle dispersion 61.5 parts (Comparative Example 5) or 53.8 parts (Comparative Example) 6) Isocyanate-based curing agent [Daiichi Seika Kogyo Co., Ltd. 73] 7.7 parts and 15.4 parts of the solvent (same as above) were mixed, and this prepared paint was applied to one side of the acrylic resin film obtained above using a bar coater # 6. It was left to stand in an oven at 2 ° C. for 2 hours for drying and curing. Thereby, a matte resin film having a mat layer on one side was obtained. The refractive index (Nd) of the transparent fine particles (d) and the refractive index (Nb) of the binder resin (other than the transparent fine particles) constituting the mat layer were substantially equal (| Nd−Nb | = 0).

  The resulting matte resin film was measured for haze H and 60 ° specular gloss Gs, and further determined 1100 / Gs (%). These values are shown in Table 2. The resulting matte resin film was measured for pencil hardness, and the results are shown in Table 2.

  Further, when the obtained matte resin film was uniaxially stretched twice in the extrusion direction of the acrylic resin film as before, fine cracks were generated in the entire mat layer. For the stretched film, the haze H ′ near the center and the 60 ° specular gloss Gs ′ were measured, and further, 1100 / Gs ′ (%) and | Gs−Gs ′ | / Gs were obtained. It is shown in Table 2.

  The matte films obtained in Comparative Examples 5 and 6 satisfy the formula: H (%) <1100 / Gs (%), but the formula: H ′ (%) <1100 / Gs ′ (%), and the formula: | Gs−Gs ′ | / Gs <0.45 was not satisfied, whitishness was not seen before stretching, and the appearance was good, but after stretching, due to the above cracks, The whitishness was conspicuous and the appearance was bad.

  A matte black paint [Mr. of GSI Creos Co., Ltd.] is formed on the surface of the matte resin film obtained in Examples 1 to 10 and Comparative Examples 1 to 4 on the side opposite to the mat surface. COLOR33] was applied and visually observed from the mat surface side. When Gs close to each other was compared, in Example 6, a clear black color with less whitishness was observed compared to Comparative Examples 1 and 3. In Examples 3 and 7, a black color with less whitishness was observed compared to Comparative Example 2. Furthermore, although Example 4 and 8 compared with the comparative example 4, although Gs was small, black with few whitish was observed.

  Further, a matte black paint [Mr. of GSI Creos Co., Ltd.] is applied to the surface opposite to the matte surface of the film after stretching the matte resin films obtained in Examples 1 to 10 and Comparative Examples 1 to 4. COLOR33] was applied and visually observed from the mat surface side. As a result of comparing the Gs's close to each other, a clear black color with less whitish was observed in Example 6 than in Comparative Examples 1 and 3. Further, in Example 7, a black color with less whitishness was observed compared to Comparative Example 2. Furthermore, in Example 8, a black color with less whitishness was observed compared to Comparative Example 4.

Claims (23)

  A matte resin film in which a matte layer containing a transparent resin and transparent fine particles is laminated on one surface of the transparent resin layer by coextrusion molding, and the surface of the matte layer has a 60-degree specular gloss Gs of 11 to 70. A matte resin film, wherein the Gs and the haze H satisfy the relationship of the formula: H (%) <1100 / Gs (%).   The 60 degree specular gloss Gs ′ of the surface of the mat layer after uniaxially stretching at 150 ° C. twice and haze H ′ after uniaxially stretching at 150 ° C. twice are expressed by the formula: H ′ (%) < The matte resin film of Claim 1 which satisfy | fills the relationship of 1100 / Gs' (%).   The matte resin film according to claim 2, wherein the Gs and the Gs ′ satisfy the relationship of the formula: | Gs−Gs ′ | / Gs <0.45.   The matte resin film according to any one of claims 1 to 3, wherein the entire thickness is 20 to 800 µm.   The matte resin film according to any one of claims 1 to 4, wherein the mat layer has a thickness of 50% or less of the total thickness.   The matte resin film according to any one of claims 1 to 5, wherein the mat layer has a thickness of 5 to 100 µm.   The difference (| Nd−Nb |) between the refractive index (Nd) of the transparent fine particles contained in the mat layer and the refractive index (Nb) of the transparent resin contained in the mat layer is 0.01 or less. The matte resin film according to any one of the above.   The matte resin film according to any one of claims 1 to 7, wherein the transparent fine particles contained in the mat layer have a volume average particle diameter of 3 to 10 µm.   The matte resin film according to any one of claims 1 to 8, wherein the transparent fine particles contained in the mat layer are acrylic crosslinked particles.   The matte resin film according to any one of claims 1 to 9, wherein the transparent resin contained in the transparent resin layer is a methacrylic resin.   The matte resin film according to any one of claims 1 to 10, wherein the transparent resin contained in the mat layer is a methacrylic resin.   The methacrylic resin is composed of 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 the total 100% by weight of all monomers. The matte resin film according to claim 10 or 11, which is a polymer obtained by polymerization at a ratio.   The matte resin film according to any one of claims 1 to 12, wherein the transparent resin layer is a layer containing rubber particles.   The matte resin film according to any one of claims 1 to 13, wherein the mat layer is a layer containing no rubber particles.   The mat layer is a layer containing rubber particles, and the amount of the rubber particles contained in the mat layer is 15% by weight or less based on a total of 100% by weight of the transparent resin and the rubber particles contained in the mat layer. The matte resin film according to any one of the above.   The mat layer is a layer containing rubber particles, and the amount of rubber particles contained in the mat layer based on a total of 100% by weight of the transparent resin and rubber particles contained in the mat layer is contained in the transparent resin and The matte resin film according to claim 13, wherein the amount of the rubber particles contained in the transparent resin layer based on 100% by weight of the rubber particles as a reference is small.   The matte resin film according to claim 13, 15 or 16, wherein the rubber particles are acrylic rubber particles.   Acrylic rubber particles are composed of a single layer mainly composed of methyl methacrylate around a layer of a rubber elastic body obtained by copolymerizing an alkyl acrylate having an alkyl group with 4 to 8 carbon atoms and a polyfunctional monomer. The matte resin film according to claim 17, wherein the matte resin film is a particle having a multilayer structure in which a layer of a hard polymer obtained by polymerizing a monomer is formed.   The matte resin film according to claim 18, wherein the rubber elastic body has a number average diameter of 50 to 500 nm.   The decoration film by which decoration is given to the surface at the side of the transparent resin layer of the matt resin film in any one of Claims 1-19.   A decorative sheet, wherein a thermoplastic resin sheet is laminated on the surface of the decorative film of the decorative film according to claim 20.   A decorative molded product, wherein a thermoplastic resin is injection-molded on a surface on a decorative side of the decorative film according to claim 20.   A decorative molded product, wherein a thermoplastic resin is injection-molded on the surface of the decorative sheet according to claim 21 on the thermoplastic resin sheet side.