Matte acrylic resin film

Abstract

The present invention provides a matte acrylic resin film that has a good matte appearance, high thermal stability during molding, allows for stable production, and further has excellent appearance design, high mechanical strength, easy handling, and is applicable to a variety of applications. Specifically, the present invention provides a matte acrylic resin film made of an acrylic resin composition (a) having a surface with a 60° surface gloss (Gs60°) of less than 100% on at least one side of the film, the arithmetic mean roughness (Ra) of the surface having the surface gloss satisfies the following formula (1), and the surface satisfying the formula (1) has a gel content of 40 mass% or more: 2.2×NGs60° (-0.97) ≦ Ra ≦ 4.4 × NGs60° (-0.97) ...Equation (1) (In the formula, NGs60° represents a percentage of Gs60°, which is less than 100%).)

Description

[Technical Field]

[0001] The present invention relates to a matte acrylic resin film containing an acrylic resin composition capable of exhibiting matte properties. [Background technology]

[0002] Acrylic resin molded articles have excellent transparency, beautiful appearance, and weather resistance, and are therefore widely used in applications such as electrical parts, vehicle parts, optical parts, ornaments, signs, etc. In particular, acrylic resin molded articles made from acrylic resin compositions containing rubber-containing polymers are widely used.

[0003] Such rubber-containing polymers are produced, for example, by emulsion polymerization, etc. That is, polybutadiene latex, styrene-butadiene copolymer latex, acrylonitrile-butadiene-styrene copolymer latex, rubber-containing acrylic graft copolymer latex, etc. are produced by emulsion polymerization, etc., and these latexes are subjected to treatments such as salting out, acid precipitation coagulation, spray drying, or freeze drying, to separate and recover powdery polymers.

[0004] This powdery polymer is usually mixed with appropriate compounding agents in a compounding step, melt-kneaded in a single-screw extruder, a twin-screw extruder, or the like, extruded as strands, and cut into pellets by a cold-cut method, a hot-cut method, or the like. The pellets are then fed to a T-die extruder, a molding machine, or the like, and processed into an acrylic resin molded article.

[0005] Film-like acrylic resin moldings (hereinafter referred to as "acrylic resin films") are laminated onto the surfaces of various resin moldings, wood products, and metal moldings, taking advantage of their excellent transparency, weather resistance, flexibility, and processability.

[0006] Widely used methods for decorating the surface of resin molded products include the transfer method, in which a film decorated by printing or other methods instead of painting is inserted into an injection molding mold, and after injection molding, only the decorative layer is transferred to the surface of the molded product and the film is then peeled off; the insert molding method, in which the decorated film remains on the molded product as the outermost surface; the in-mold molding method, in which decoration is applied simultaneously with injection molding; and the method of laminating a film onto the surface of an injection molded product.

[0007] Acrylic resin films are used as decorative films for these applications, but when used as interior and exterior materials for automobiles, optical materials, construction materials, computer components, and protective films for home appliances, the presence of impurities (flakes) of 100 μm or larger in the film has been a problem, significantly limiting the conditions under which the decorative films can be used.

[0008] In recent years, there has been a demand for matte surfaces of printed acrylic resin films to add design and decorative properties such as a sense of luxury and depth, etc. Such demands can be met by printing on matte acrylic resin films (see Patent Documents 1 and 2).

[0009] When the hydroxyl group-containing polymers described in Patent Documents 1 and 2 are used as a matting agent, an acrylic matte resin film with a better matte appearance can be obtained compared to organic crosslinked particles or inorganic particles that are generally used as matting agents. However, when the present inventors further tested the acrylic matte resin films described in the examples of Patent Documents 1 and 2, they found that the matte appearance had a glare, and that there was still room for improvement in terms of satisfying customer demands.

[0010] Furthermore, when a polymer containing a hydroxyl group is used as a matting agent, if the resulting molded product is a film, problems such as an increase in defects called fish eyes caused by thermal degradation over time are likely to occur, making it difficult to carry out melt extrusion such as film molding over a long period of time. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-342389 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-255555 Summary of the Invention [Problem to be solved by the invention]

[0012] Therefore, an object of the present invention is to provide an acrylic matte resin film that has a good matte appearance, high thermal stability during molding, allows for stable production, and further has excellent appearance design, high mechanical strength, is easy to handle, and is applicable to a variety of uses. [Means for solving the problem]

[0013] The above issues can be addressed by the following measures [1]-[ 10 The present invention provides the following means [1] to [ 10 ] is provided.

[0014] [1] 60 ° Surface gloss (Gs60 ° ) is less than 100% on at least one side of the film, and the arithmetic mean roughness (Ra) of the surface having the surface gloss is [μm] satisfies the following formula (1), and the surface that satisfies the following formula (1) is made of an acrylic resin composition (a) having a gel content of 40 mass% or more, The acrylic matte resin film, wherein the acrylic resin composition (a) contains a phosphorus-based antioxidant (a-3), and the phosphorus-based antioxidant (a-3) is at least one selected from the group of compounds represented by the following general formula (2): 2.2×NGs60° (-0.97) ≦Ra≦4.4×NGs60° (-0.97) ...Equation (1) (In the formula, NGs represents a percentage of Gs60°, which is less than 100%). [ka] (In the formula, R 1 , R 2 and R 3 are each independently an alkyl group having 8 to 18 carbon atoms.

[0015] [2] At least one surface of the film has a 60° surface gloss (Gs60°) of less than 100%, and the arithmetic mean roughness (Ra) of the surface having the surface gloss [μm] is between 0.05 and 0.47, and the average length of the profile curve element (Rsm [μm] ) is 30.00 or more and 80.00 or less, and the gel content of the surface having the surface gloss is 40 mass% or more, The acrylic matte resin film, wherein the acrylic resin composition (a) contains a phosphorus-based antioxidant (a-3), and the phosphorus-based antioxidant (a-3) is at least one selected from the group of compounds represented by the following general formula (2): [ka] (In the formula, R 1 , R 2 and R 3 are each independently an alkyl group having 8 to 18 carbon atoms. ).

[0016] [3] Matte acrylic Made of resin film Matte acrylic It has a laminated structure of a resin layer and a transparent acrylic resin layer. [1] or [2] Matte acrylic resin film.

[0017] [4] The acrylic matte resin film according to any one of [1] to [3], wherein the acrylic resin composition (a) has an MFR retention (M2 / M1), which is the ratio of the melt flow rate (M1) measured in accordance with JIS K7210 at a temperature of 240°C and a load of 49 N for a holding time of 4 minutes to the melt flow rate (M2) measured in accordance with JIS K7210 at a temperature of 240°C and a load of 49 N for a holding time of 20 minutes, from 0.7 to 1.3.

[0018] [5] The acrylic resin composition (a) comprises an acrylic rubber-containing polymer (a-1), and Polymer containing hydroxyl groups (a-2 )of [4] The acrylic matte resin film according to [4].

[0019] [6] The acrylic matte resin film according to [5], wherein the amount of the hydroxyl group-containing polymer (a-2) added is 0.9 to 40 parts by mass per 100 parts by mass of the resins constituting the acrylic resin composition (a) (the total parts by mass of the acrylic rubber-containing polymer (a-1), the optionally present thermoplastic polymer (D), and the hydroxyl group-containing polymer (a-2)).

[0020] [7] The matte acrylic resin film according to any one of [1] to [6], wherein the content of the phosphorus-based antioxidant (a-3) in the acrylic resin composition (a) is 0.45 to 2.00 mass %. [8] The matte acrylic resin film according to any one of [1] to [7], wherein the matte acrylic resin film has a total light transmittance of 90% or more. [9] The matte acrylic resin film according to any one of [1] to [8], wherein the acrylic resin composition (a) has a gel content of 80 mass % or less.

[10] R in the general formula (2) 1 , R 2 and R 3 is an alkyl group having 10 or more carbon atoms. [Effects of the Invention]

[0021] According to the present invention, it is possible to provide an acrylic matte resin film that has a good matte appearance, high thermal stability during molding, allows for stable production, and further has excellent appearance design, high mechanical strength, is easy to handle, and is applicable to a variety of uses. [Brief explanation of the drawings]

[0022] [Figure 1] 1 is a conceptual diagram showing the scattering frequency and scattering state of incident light on the surface of the acrylic matte resin film of the present invention. Incident light has a high scattering frequency. [Figure 2] 1 is a conceptual diagram showing the scattering frequency and scattering state of incident light on the surface of a matte acrylic resin film shown in Comparative Example 1. In some cases, the incident light is not scattered but is reflected, resulting in a low scattering frequency. [Figure 3] FIG. 1 is a diagram showing the relationship between formula (1) and examples and comparative examples. DETAILED DESCRIPTION OF THE INVENTION

[0023] The following describes in detail aspects of the present invention, but the scope of the present invention is not limited to these descriptions, and modifications other than those exemplified below can be made as appropriate within the scope that does not detract from the spirit of the present invention.

[0024] <Matte acrylic resin film> The acrylic matte resin film according to the present invention contains an acrylic resin, and at least one side has a 60° surface gloss (Gs60°) of less than 100%. In the present invention, a side with a Gs60° of less than 100% is referred to as a "side with matte properties." Furthermore, a side with a Gs60° of 100% or more is referred to as a "side without matte properties." In the case of a single-layer film, the matte acrylic resin film has a single-layer structure of a matte acrylic resin layer made of a matte acrylic resin film having at least one surface with a matte finish.In the case of a multi-layer film, the matte acrylic resin film has a matte acrylic resin layer made of a matte acrylic resin film having a matte finish on the non-laminated surface, and a transparent acrylic resin layer having a non-laminated surface that does not have a matte finish laminated thereon. The matte surface can be formed using an acrylic resin composition (a) that can exhibit matte properties, as described below, and the transparent acrylic resin layer can be formed using an acrylic resin composition (b) that does not exhibit matte properties, as described below.

[0025] The acrylic matte resin film according to the present invention has a relationship between the 60° surface gloss (Gs60°) of the matte surface (NGs) as a percentage and the arithmetic mean roughness (Ra), where Ra is 2.2×NGs60°. (-0.97) Over 4.4×NGs60° (-0.97) Ra is 2.3×NGs60° (-0.97) Over 4.1×NGs60° (-0.97) Preferably, it is less than 2.4 × NGs60° (-0.97) Over 3.8×NGs60° (-0.97) More preferably, it is:

[0026] Ra is 2.2 × NGs60° (-0.97)If the values ​​are above this, the values ​​of Ra and the average length (Rsm) [μm] of the contour curve elements are not too small, the scattering frequency is not too low, and since the incident light is not scattered and is not reflected, the intensity of the reflected light does not become too high, the glare of the matte appearance is reduced, and the design and decorative properties such as a sense of luxury and depth are excellent, which is preferable.

[0027] Ra is 4.4 × NGs60° (-0.97) If the values ​​are below this, the values ​​of Ra and the average length of the contour curve element (Rsm) [μm] are not too large, the scattering frequency is not too low, and incident light is unlikely to be reflected without being scattered, so the intensity of the reflected light does not become too high, the matte texture becomes fine, the glare in the appearance is extremely reduced, and the design and decorative properties such as a sense of luxury and depth are excellent, which is preferable.

[0028] In the present invention, Ra is 2.2 × NGs60° (-0.97) Over 4.4×NGs60° (-0.97) The method for achieving this is not particularly limited, but examples include a method using a resin composition that can exhibit matte properties, and a method of imparting a matte shape by post-processing after film formation, in order to achieve an optimal arithmetic mean roughness (Ra) for the 60° surface gloss (Gs60°). The 60° surface gloss (Gs60°) is a value measured in accordance with JIS Z8741, and the arithmetic mean roughness (Ra) is a value measured in accordance with JIS B0601-2001, as described in detail in the Examples.

[0029] Gs60° is less than 100%. On the other hand, the lower limit of Gs60° is preferably 1%. Gs60° is preferably 5% or more and less than 70%, more preferably 6% or more and less than 32%, and particularly preferably 7% or more and less than 20%. When the Gs60° of the matte surface is 1% or more and less than 100%, the resulting matte acrylic resin film has matte properties and is excellent in design and decorative properties such as a luxurious feel and a deep impression. Furthermore, if Gs60° is less than 70%, the film is less affected by processing conditions and film-forming conditions, resulting in excellent stability of the matte appearance. On the other hand, if Gs60° is 5% or more, it is not necessary to add a large amount of matting agent, reducing film appearance defects such as fisheyes. This is also preferable from an economical standpoint.

[0030] In the acrylic matte resin film according to the present invention, the arithmetic mean roughness (Ra) and the mean length of the profile curve element (Rsm) are such that Ra is 0.05 to 0.47 and Rsm is 30.00 to 80.00, respectively. This results in moderate scattering of incident light, preventing direct reflection of incident light, a fine matte finish, and reduced glare, providing excellent design and decorative properties such as a luxurious feel and a sense of depth. Ra is more preferably 0.14 to 0.45 and Rsm is 43.00 to 78.00, resulting in a Gs60° of less than 32%. Ra is particularly preferably 0.18 to 0.43 and Rsm is 46.00 to 76.00, resulting in a Gs60° of less than 20%. The average length (Rsm) of the profile curve elements is a value measured in accordance with JIS B0601-2001, and details are as described in the Examples.

[0031] The 60° surface gloss (Gs60°) of the non-matt surface is 100% or more, preferably 120% or more, and more preferably 140% or more. If the 60° surface gloss (Gs60°) of the non-matte side is 100% or higher, printability and lamination suitability are improved. That is, in the case of a multilayer film, the non-laminated side of the transparent acrylic resin layer has excellent smoothness, so printing defects can be greatly reduced. Furthermore, when the matte acrylic resin film after printing is laminated onto a substrate, the smooth side of the transparent acrylic resin layer can be laminated so that it contacts the substrate, resulting in excellent lamination suitability.

[0032] The layer thickness ratio of the matte acrylic resin layer and the transparent acrylic resin layer in the matte acrylic resin film is not particularly limited, but is preferably 1 / 99 to 99 / 1, more preferably 50 / 50 to 10 / 90, from the viewpoints of the transparency, matte appearance, and printability of the matte acrylic resin film.

[0033] The matte acrylic resin film can be produced by known methods such as melt casting, T-die method, inflation method, etc., but the T-die method is preferred from the viewpoint of economy. In the case of a multilayer film, a matte acrylic resin layer made of a matte acrylic resin film using the acrylic resin composition (a) described below and a transparent acrylic resin layer made of the acrylic resin composition (b) described below can be co-extruded by the T-die multilayer method or the like to form a laminated matte acrylic resin film.

[0034] When forming a film using the T-die method, using a method in which the film is sandwiched between multiple rolls or belts selected from metal rolls, non-metal rolls, and metal belts can improve the surface smoothness of the resulting film and prevent missing prints when the film is printed. Examples of metal rolls include the metal mirror-finish touch roll described in Japanese Patent No. 2808251, and the roll used in the sleeve touch method consisting of a metal sleeve (metal thin film pipe) and a forming roll described in WO97 / 28950. Examples of non-metal rolls include touch rolls made of silicone rubber, etc. Examples of metal belts include endless metal belts, etc. It is also possible to use a combination of these metal rolls, non-metal rolls, and metal belts.

[0035] In the above-mentioned film-forming method in which the acrylic resin composition (a) capable of exhibiting a matte finish after melt extrusion is sandwiched between a plurality of rolls or belts selected from metal rolls, non-metal rolls, and metal belts, it is preferable to sandwich the acrylic resin composition (a) capable of exhibiting a matte finish after melt extrusion in a state in which there is substantially no bank (resin pool), and to form a film by surface transfer without substantially rolling. When a film is formed without forming a bank (resin pool), the acrylic resin composition (a) capable of exhibiting a matte finish during the cooling process is surface transferred without rolling, and the heat shrinkage rate of the film formed by this method can also be reduced.

[0036] When melt extrusion is performed by a T-die method or the like, a screen for removing foreign matter mixed in the extrusion raw materials may be installed in a zone before the T-die of the extruder, and the foreign matter may be removed from the acrylic resin composition (a) capable of exhibiting a matte finish. Examples of such a screen include filter packs, screen changers, leaf disk-type and pleated-type polymer filters using wire mesh or sintered metal nonwoven fabric.

[0037] The thickness of the acrylic matte resin film is preferably 300 μm or less. When used in a laminate molded product, the thickness is preferably 50 μm to 300 μm. A thickness of 50 μm or more is preferred because it provides sufficient depth in the appearance of the molded product. In particular, when molding into a complex shape, sufficient thickness can be obtained by stretching. On the other hand, a thickness of 300 μm or less is preferred because it provides appropriate rigidity, which tends to improve lamination properties, secondary processability, etc. Furthermore, it is economically advantageous in terms of mass per unit area. Furthermore, film formability is stable, making film production easy.

[0038] The total light transmittance of the matte acrylic resin film is preferably 90% or more. If the total light transmittance is 90% or more, the matte acrylic resin film will have excellent design properties when laminated onto the surface of various three-dimensional resin molded products, wood products, or metal molded products, either directly or after being laminated onto a resin sheet.

[0039] The acrylic matte resin film may be subjected to a surface treatment to impart various functions, as required. Examples of the surface treatment include printing treatment such as silk printing or inkjet printing, metal vapor deposition treatment for imparting a metallic tone or preventing reflection, sputtering, wet plating treatment, surface hardening treatment for improving surface hardness, water repellent treatment or photocatalytic layer formation treatment for preventing staining, antistatic treatment for preventing dust adhesion or blocking electromagnetic waves, antireflection layer formation, antiglare treatment, etc. Among the above-mentioned treatments, when a printing treatment is applied, it is preferable to perform a one-side printing treatment on the film, and among these, a reverse side printing treatment in which the printed surface is placed on the adhesive surface with the base resin is particularly preferable from the viewpoint of protecting the printed surface and imparting a luxurious feel.

[0040] <Acrylic resin composition (a) capable of exhibiting matte finish> The acrylic resin composition (a) capable of exhibiting matte properties and used to produce the matte acrylic resin film of the present invention is a resin composition that constitutes the matte acrylic resin film in the case of a single-layer film. Furthermore, in the case of a multilayer film, it is a resin composition that constitutes the matte acrylic resin layer of the matte acrylic resin film. The acrylic resin composition (a) capable of exhibiting matte properties is not particularly limited, and any composition that exhibits matte properties when formed into a film and contains an acrylic resin as a main component may be used.

[0041] Examples of methods for imparting matte properties include blending organic crosslinked particles, inorganic particles, and resin compositions that have low compatibility with the acrylic resin composition. Examples of the organic crosslinked particles include styrene-based resin crosslinked particles, acrylic-based resin crosslinked particles, fluorine-based resin crosslinked particles, and silicone-based resin crosslinked particles. Examples of inorganic particles include particles of silica, alumina, calcium carbonate, titanium oxide, mica, and talc. An example of a resin composition having low compatibility with an acrylic resin composition is a polymer (a-2) containing a hydroxyl group. Among the methods for imparting matte properties, the hydroxyl group-containing polymer (a-2) described below can be preferably used, from the viewpoints of extremely low glare in the matte appearance of the resulting acrylic matte resin film and excellent design and decorative properties such as a luxurious feel and a deep impression.

[0042] The acrylic resin composition (a) has a gel content of 40% by mass or more, more preferably 40% by mass or more and 80% by mass or less, even more preferably 42% by mass or more and 70% by mass or less, and even more preferably 45% by mass or more and 60% by mass or less. When the gel content of the acrylic resin composition (a) is 40% by mass or more, the resulting molded article has high mechanical strength and is easy to handle. In particular, when the molded article is a film, it can be easily laminated onto the surface of various three-dimensional resin molded products, wood products, or metal molded products, either directly or after lamination onto a resin sheet, and the design properties are excellent. If the gel content of the acrylic resin composition (a) is 80% by mass or less, the fluidity and thermal stability during molding will not be too low, the melt viscosity can be kept low, and retention in the molding machine can be reduced, thereby suppressing thermal degradation of the resin, which is preferable. When the resulting molded product is a film, problems such as an increase over time in defects called fisheyes due to thermal degradation products are less likely to occur, and melt extrusion such as film molding can be performed for a relatively long period of time.

[0043] The gel content of the acrylic resin composition (a) can be calculated using the following formula. G = (m / M) × 100 In the formula, G (%) represents the gel content of the acrylic resin composition (a), M represents the mass of a predetermined amount of the acrylic resin composition (a) (also referred to as the mass before extraction), and m represents the mass of the acetone-insoluble matter of the predetermined amount of the acrylic resin composition (a) (also referred to as the mass after extraction). More specifically, m was obtained by dissolving the acrylic resin composition (a) in acetone at a concentration of 1 g / 100 mL, refluxing the solution at 65°C for 4 hours, centrifuging the solution, refluxing the solution, centrifuging the solution, and decanting the resulting solid again, and drying the resulting solid at 50°C for 24 hours.

[0044] The MFR retention (M2 / M1) of the acrylic resin composition (a) is calculated as the ratio of the melt flow rate (M2) measured in accordance with JIS K7210 (Method A) at a temperature of 240°C and a load of 49 N for a holding time of 20 minutes to the melt flow rate (M1) measured in accordance with JIS K7210 (Method A) at a temperature of 240°C and a load of 49 N for a holding time of 4 minutes. The MFR retention (M2 / M1) is preferably in the range of 0.7 to 1.3, more preferably in the range of 0.85 to 1.15, and even more preferably in the range of 0.9 to 1.1. An MFR retention rate (M2 / M1) of 0.7 or higher is preferable because it can improve thermal stability during molding, suppress the increase in melt viscosity due to thermal degradation of the resin, reduce retention in the molding machine, and suppress thermal degradation of the resin. When the obtained molded product is a film, problems such as an increase over time in defects called fisheyes caused by thermal degradation are unlikely to occur, and melt extrusion such as film molding can be performed over a long period of time. An MFR retention rate (M2 / M1) of 1.3 or less is preferable because it increases the thermal stability during molding, suppresses thermal decomposition of the resin, and suppresses thermal degradation of the resin due to side reactions. When the resulting molded product is a film, defects such as fisheyes caused by thermal degradation are less likely to increase over time, making it possible to perform melt extrusion such as film molding over a long period of time.

[0045] The acrylic resin composition (a) can be produced by a known method such as a single-screw kneading method using an extruder, which is a general compounding method, a co-rotating twin-screw kneading method, or a counter-rotating twin-screw kneading method, but a method with a large kneading effect, such as a twin-screw kneading method, is preferred. Preferred examples of twin-screw extruders include the TEM series manufactured by Toshiba Machine Co., Ltd. Examples of the screw configuration include a screw configuration having a conveying section for conveying the acrylic resin composition (a) and a kneading section for kneading the acrylic resin composition (a), such as a kneading zone or a screw segment in which the melt is fed in the opposite direction (screw segment in which the spiral winding direction is opposite).

[0046] Furthermore, the extruder preferably has a vent capable of degassing the water content in the raw material acrylic resin composition (a) and the volatile gases generated from the melt-kneaded molten material. A pressure-reducing pump such as a vacuum pump is preferably installed in the vent. This installation allows the generated water and volatile gases to be efficiently discharged to the outside of the extruder. It is also possible to install a screen in the zone before the die of the extruder to remove foreign matter mixed in the extrusion raw material, thereby removing the foreign matter from the acrylic resin composition (a). Examples of such screens include filter packs, screen changers, and leaf disk-type and pleated-type polymer filters using wire mesh or sintered metal nonwoven fabric.

[0047] Furthermore, a method for increasing the kneading effect includes increasing the screw rotation speed as much as possible and reducing the amount of acrylic resin composition (a) supplied, but the acrylic resin composition (a) melt-extruded in this manner is prone to shear heat generation and the temperature at the head tends to rise. The molten material melt-kneaded in the extruder is extruded as a strand from a die having a nozzle with a diameter of about 3 to 5 mm installed at the head, and is cut by a cold cut method, a hot cut method, or the like, and then pelletized.

[0048] The acrylic resin composition (a) preferably contains an acrylic rubber-containing polymer (a-1), a hydroxyl group-containing polymer (a-2), and a phosphorus-based antioxidant (a-3) having an alkyl group having 8 or more carbon atoms.

[0049] <Acrylic rubber-containing polymer (a-1)> In this specification, a polymer containing crosslinked rubber or vulcanized rubber, which has a molecular structure with crosslinking points within the molecule and forms a three-dimensional network structure, is referred to as a "rubber-containing polymer." The "rubber" referred to here is defined as a polymer corresponding to the acetone-insoluble portion of the acrylic rubber-containing polymer (a-1).

[0050] The acrylic resin composition (a) according to the present invention preferably contains an acrylic rubber-containing polymer (a-1). The acrylic rubber-containing polymer (a-1) is not particularly limited, and may be a rubber-containing polymer whose main component is acrylic. However, the acrylic rubber-containing polymer (a-1) preferably imparts thermoplasticity to the acrylic resin composition (a) according to the present invention, and more preferably is a rubber-containing polymer having thermoplasticity.

[0051] The acrylic rubber-containing polymer (a-1) in the present invention is preferably a rubber-containing acrylic graft copolymer contained in various conventionally known acrylic resin compositions. In particular, when flexibility is required for building materials, etc., the rubber-containing acrylic graft copolymers described in JP-B-62-19309 (particularly the multilayer structure polymer described in claim 1) and JP-B-63-8983 (particularly the multilayer structure polymer [I] described in claim 1) are preferred. In particular, when scratch resistance, pencil hardness, heat resistance, and chemical resistance sufficient for use in vehicle applications are required, the rubber-containing acrylic graft copolymers described in JP-A-8-323934 (particularly the rubber-containing copolymer (II) described in claim 1), JP-A-11-147237 (particularly the three-layer structure acrylic polymer described in claim 1), JP-A-2002-80678 (particularly the rubber-containing polymer (II) described in claim 1), JP-A-2002-80679 (particularly the rubber-containing polymer (II) described in claim 1), JP-A-2005-97351 (particularly the multilayer structure polymer (II) described in claim 2) and the like are preferred. Furthermore, when resistance to molding whitening is required particularly when insert molding or in-mold molding is performed, rubber-containing acrylic graft copolymers described in JP 2004-137298 A (particularly the acrylic graft copolymer containing the acrylic ester-based rubber-like polymer (A) described in claim 1), JP 2005-163003 A (particularly the multilayer structure polymer (I) described in claim 1), JP 2005-139416 A (particularly the acrylic resin film material (A) described in claim 1), JP 2008-106252 A (particularly the rubber-containing polymer (I) and rubber-containing polymer (II) described in claim 1) are preferred. The rubber-containing acrylic graft copolymer may be used alone or in combination of two or more kinds.

[0052] The gel content of the acrylic rubber-containing polymer (a-1) is preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 95% by mass or less, and even more preferably 55% by mass or more and 90% by mass or less. When the gel content of the acrylic rubber-containing polymer (a-1) is 40% by mass or more, the mechanical strength of the obtained molded article can be increased, making it easier to handle. In particular, when the molded article is a film, it can be easily laminated on the surface of various three-dimensional resin molded articles, wood products, or metal molded articles, either directly or after being laminated on a resin sheet, and the design properties are excellent. If the gel content of the acrylic rubber-containing polymer (a-1) is 99% by mass or less, the fluidity and thermal stability during molding will not be too low, the melt viscosity can be kept low, and retention in the molding machine can be reduced, thereby suppressing thermal degradation of the resin, which is preferable. When the resulting molded product is a film, problems such as an increase over time in defects called fisheyes caused by thermal degradation products are less likely to occur, and melt extrusion such as film molding can be performed for a relatively long period of time.

[0053] Here, the gel content of the acrylic rubber-containing polymer (a-1) can be calculated by the following formula. G' = (m' / M') x 100 In the formula, G' (%) represents the gel content of the acrylic rubber-containing polymer (a-1), M' represents the mass of a predetermined amount of the acrylic rubber-containing polymer (a-1) (also referred to as the mass before extraction), and m' represents the mass of the acetone-insoluble portion of the predetermined amount of the acrylic rubber-containing polymer (a-1) (also referred to as the mass after extraction).

[0054] Since the gel content of the acrylic resin composition (a) is preferably 80% by mass or less, when the gel content of the acrylic rubber-containing polymer (a-1) described below is 80% by mass or more, the gel content of the acrylic resin composition (a) can be adjusted by further adding a thermoplastic polymer (D). The ratio of the acrylic rubber-containing polymer (a-1) to the thermoplastic polymer (D) in the acrylic resin composition (a) is preferably 100:0 to 40:60 (parts by mass), and more preferably 95:5 to 70:30 (parts by mass).

[0055] <Hydroxyl Group-Containing Polymer (a-2)> The acrylic resin composition (a) used in the present invention preferably contains a polymer (a-2) containing hydroxyl groups. The polymer (a-2) containing hydroxyl groups is not particularly limited, and may be any polymer having a chemical structure containing hydroxyl groups.

[0056] The hydroxyl group-containing polymer (a-2) used in the present invention is preferably a hydroxyl group-containing polymer contained in various conventional acrylic resin compositions. Examples include a hydroxyl group-containing polymer having a glass transition temperature of 80 to 120°C obtained by polymerizing a monomer composition comprising 1 to 30% by mass of a (meth)acrylic acid hydroxyalkyl ester having an alkyl group of 1 to 8 carbon atoms, 10 to 99% by mass of a methacrylic acid alkyl ester having an alkyl group of 1 to 13 carbon atoms, 0 to 10% by mass of an acrylic acid alkyl ester having an alkyl group of 1 to 8 carbon atoms, and 0 to 50% by mass of at least one other copolymerizable vinyl monomer.

[0057] Examples of (meth)acrylic acid hydroxyalkyl esters having an alkyl group having 1 to 8 carbon atoms used in the hydroxyl group-containing polymer (a-2) include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. Of these, 2-hydroxyethyl methacrylate is preferred. The amount of this (meth)acrylic acid hydroxyalkyl ester used is preferably in the range of 1 to 30% by mass. A use amount of 1% by mass or more provides a sufficient matting effect, while a use amount of 30% by mass or less improves the film's water whitening resistance. From the viewpoints of matting and water whitening resistance, the use amount is more preferably 5 to 25% by mass, and even more preferably 10 to 20% by mass.

[0058] The alkyl methacrylate ester having an alkyl group of 1 to 13 carbon atoms used in the hydroxyl group-containing polymer (a-2) is preferably an alkyl methacrylate ester having a lower alkyl group of 1 to 4 carbon atoms, such as methyl methacrylate, ethyl methacrylate, or butyl methacrylate, with methyl methacrylate being the most suitable. The amount of the alkyl methacrylate used is preferably 10 to 99% by mass, and more preferably 50 to 95% by mass from the viewpoint of water whitening resistance.

[0059] For the hydroxyl group-containing polymer (a-2), an alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms can be used. Specifically, lower alkyl acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are suitable. Although the matte finish and water whitening resistance of the film are excellent without using an alkyl acrylate ester, the use of an alkyl acrylate ester is preferable from the viewpoint of thermal decomposition. Furthermore, in order to improve the water whitening resistance of the film, it is preferable to use an alkyl acrylate ester in an amount of 10% by mass or less. The amount of alkyl acrylate used is more preferably 0 to 10% by mass, and from the viewpoint of thermal decomposition and water whitening resistance, it is even more preferably 0.1 to 5% by mass, and even more preferably 0.1 to 2% by mass.

[0060] The hydroxyl group-containing polymer (a-2) can contain at least one other copolymerizable vinyl monomer. Specific examples of the copolymerizable vinyl monomer include aromatic vinyl compounds such as styrene, cyanide vinyl monomers such as acrylonitrile, unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, and N-cyclohexylmaleimide. In particular, the use of unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, and N-cyclohexylmaleimide can increase the glass transition temperature of the hydroxyl group-containing polymer (a-2), thereby further improving the water whitening resistance of the film. The amount of the copolymerizable vinyl monomer used is preferably 0 to 50% by mass.

[0061] The glass transition temperature of the hydroxyl group-containing polymer (a-2) is preferably 80 to 120° C. From the viewpoint of water whitening resistance, the glass transition temperature is preferably 80° C. or higher, and more preferably higher than 90° C. Furthermore, from the viewpoint of dispersibility during melt-kneading in the compounding step, the glass transition temperature is preferably 120° C. or lower, and more preferably 110° C. or lower.

[0062] The intrinsic viscosity of the hydroxyl group-containing polymer (a-2) is preferably adjusted to the range of 0.05 to 0.3 L / g from the viewpoint of matte development and the appearance of the matte surface, and more preferably to the range of 0.06 to 0.15 L / g.

[0063] In addition, during polymerization, it is preferable to use a polymerization regulator such as mercaptan to adjust the molecular weight. Examples of mercaptans that can be used here include n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan. However, the mercaptan is not limited to these, and various conventionally known mercaptans can also be used.

[0064] The method for producing the hydroxyl group-containing polymer (a-2) is not particularly limited, but suspension polymerization, emulsion polymerization, etc. are preferred. As the initiator for suspension polymerization, various conventionally known substances can be used, specifically organic peroxides, azo compounds, etc. As the suspension stabilizer, various conventionally known substances can be used, specifically organic colloidal polymeric substances, inorganic colloidal polymeric substances, inorganic fine particles, and combinations of these with surfactants, etc. Suspension polymerization is usually carried out by suspending monomers together with a polymerization initiator in an aqueous solution in the presence of a suspension stabilizer. Alternatively, suspension polymerization can be carried out by dissolving a polymer soluble in the monomer in the monomer and using it.

[0065] The amount of the hydroxyl group-containing polymer (a-2) added is preferably 0.9 to 40 parts by mass, more preferably 1.4 to 20 parts by mass, and even more preferably 1.9 to 15 parts by mass, relative to 100 parts by mass of the resins constituting the acrylic resin composition (a) (the total parts by mass of the acrylic rubber-containing polymer (a-1), any thermoplastic polymer (D) present, and the hydroxyl group-containing polymer (a-2)). When the amount of hydroxyl group-containing polymer (a-2) added is 0.9 parts by mass or more, a sufficient matte appearance is achieved. When the amount of hydroxyl group-containing polymer (a-2) added is 40 parts by mass or less, the fluidity and thermal stability during molding are not too low, the melt viscosity can be kept low, and retention in the molding machine can be reduced, thereby suppressing thermal degradation of the resin, which is preferable. The resulting film is less likely to suffer from defects such as an increase in fisheyes caused by thermal degradation over time, and melt extrusion such as film molding can be performed for a relatively long period of time.

[0066] <Phosphorus-based antioxidants (a-3) having alkyl groups with 8 or more carbon atoms> The acrylic resin composition (a) preferably contains a phosphorus-based antioxidant (a-3) having an alkyl group having 8 or more carbon atoms. The phosphorus-based antioxidant (a-3) having an alkyl group having 8 or more carbon atoms is not particularly limited, and may be a known phosphorus-based antioxidant that is a phosphite ester compound having an alkyl group having 8 or more carbon atoms. By having an alkyl group having 8 or more carbon atoms, the matte appearance of a matte surface formed using the acrylic resin composition (a) can be improved.

[0067] For example, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (commercially available, for example, Adeka STAB PEP-8, manufactured by ADEKA CORPORATION), 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite (commercially available, for example, Adeka STAB HP-10, manufactured by ADEKA CORPORATION), trisnonylphenyl phosphite (commercially available, for example, Adeka STAB 1178, manufactured by ADEKA CORPORATION), tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene)bis(phosphite) [commercially available products include, for example, ADEKA Corporation under the trade name Adeka STAB 1500, 2-ethylhexyl diphenyl phosphite [commercially available products include, for example, ADEKA Corporation under the trade name Adeka STAB C, isodecyl diphenyl phosphite [commercially available products include, for example, ADEKA Corporation under the trade name Adeka STAB 135A], triisodecyl phosphite [commercially available products include, for example, ADEKA Corporation under the trade name Adeka STAB 135A], : Adekastab 3010), trisnonylphenyl phosphite [commercially available products, for example, trade name: JP-351 manufactured by Johoku Chemical Industry Co., Ltd.], tris(2-ethylhexyl) phosphite [commercially available products, for example, trade name: JP-308E manufactured by Johoku Chemical Industry Co., Ltd.], tridecyl phosphite [commercially available products, for example, trade name: JP-310 manufactured by Johoku Chemical Industry Co., Ltd.], trilauryl phosphite [commercially available products, for example, trade name: JP-310 manufactured by Johoku Chemical Industry Co., Ltd.], ), trade name: JP-312L, tris(tridecyl)phosphite (a commercially available product, for example, trade name: JP-333E, manufactured by Johoku Chemical Industry Co., Ltd.), trioleyl phosphite (a commercially available product, for example, trade name: JP-318-O, manufactured by Johoku Chemical Industry Co., Ltd.), diphenylmono(2-ethylhexyl)phosphite (a commercially available product, for example, trade name: JPM-308, manufactured by Johoku Chemical Industry Co., Ltd.), diphenylmonodecyl phosphite (a commercially available product, for example, trade name: JPM-308, manufactured by Johoku Chemical Industry Co., Ltd.), Examples of such compounds include diphenyl mono(tridecyl) phosphite (a commercially available product, for example, JPM-311 manufactured by Johoku Chemical Industry Co., Ltd.), diphenyl mono(tridecyl) phosphite (a commercially available product, for example, JPM-313 manufactured by Johoku Chemical Industry Co., Ltd.), a mixture of tetraphenyl (tetratridecyl) pentaerythritol tetraphosphite and bis(2-ethylhexyl) phthalate (a commercially available product, for example, JPP-613M manufactured by Johoku Chemical Industry Co., Ltd.), tetra(C12-C15 alkyl)-4,Examples of such a product include 4'-isopropylidenediphenyl diphosphite (a commercially available product, for example, JA-805, manufactured by Johoku Chemical Industry Co., Ltd.), a mixture of bis(tridecyl)pentaerythritol diphosphite and bis(nonylphenyl)pentaerythritol diphosphite (a commercially available product, for example, JPP-88, manufactured by Johoku Chemical Industry Co., Ltd.), bis(decyl)pentaerythritol diphosphite (a commercially available product, for example, JPE-10, manufactured by Johoku Chemical Industry Co., Ltd.), bis(tridecyl)pentaerythritol diphosphite (a commercially available product, for example, JPE-13R, manufactured by Johoku Chemical Industry Co., Ltd.), tristearyl phosphite (a commercially available product, for example, JP-318E, manufactured by Johoku Chemical Industry Co., Ltd.), and distearyl pentaerythritol diphosphite (a commercially available product, for example, JPP-2000PT, manufactured by Johoku Chemical Industry Co., Ltd.). The phosphorus-based antioxidant (a-3) having an alkyl group having 8 or more carbon atoms may be used alone or in combination of two or more. From the viewpoint of weather resistance of a film using the acrylic resin composition (a), it is preferable that the phosphorus-based antioxidant (a-3) having an alkyl group with 8 or more carbon atoms does not have an aromatic ring structure.

[0068] Examples of the phosphorus-based antioxidant (a-3) not having an aromatic ring structure include the aforementioned products manufactured by ADEKA CORPORATION under the trade names of ADK STAB PEP-8 and ADK STAB 3010, and products manufactured by Johoku Chemical Industry Co., Ltd. under the trade names of JP-308E, JP-310, JP-312L, JP-333E, JP-318-O, JPE-10, JPE-13R, JP-318E, and JPP-2000PT.

[0069] In addition, from the viewpoint of the matte appearance of the matte surface formed using the acrylic resin composition (a), at least one member of the group of compounds represented by the following general formula (2) can be suitably used as the phosphorus-based antioxidant (a-3).

[0070] [ka] (In the formula, R 1 , R 2 and R 3 each independently represents an alkyl group having 8 to 18 carbon atoms.

[0071] Examples of the alkyl group having 8 to 18 carbon atoms include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl.

[0072] Examples of the compound represented by general formula (2) include the aforementioned Adeka STAB 3010 manufactured by ADEKA CORPORATION, and JP-308E, JP-310, JP-312L, JP-333E, JP-318-O, and JP-318E manufactured by Johoku Chemical Industry Co., Ltd. One type of compound represented by general formula (2) may be used alone, or two or more types may be used in combination.

[0073] The compound represented by general formula (2) is R 1 , R 2 and R 3 The alkyl group represented by the formula (I) has 8 or more carbon atoms, which can improve the matte appearance of the surface having a matte finish using the acrylic resin composition (a), and the alkyl group represented by the formula (I) has 18 or less carbon atoms, which is preferable because it has good solubility in the acrylic resin composition (a). 1 , R 2 and R 3 In view of the matte appearance of the surface having a matte finish using the acrylic resin composition (a) and the effect of suppressing volatilization during film formation, it is more preferable that the alkyl group have 10 or more carbon atoms.

[0074] The amount of the phosphorus-based antioxidant (a-3) having an alkyl group with 8 or more carbon atoms added is preferably 0.45 to 2.00 mass %, more preferably 0.50 to 1.50 mass %, and even more preferably 0.60 to 1.00 mass %, in the acrylic resin composition (a).

[0075] When the amount of the phosphorus-based antioxidant (a-3) having an alkyl group containing 8 or more carbon atoms is 0.45% by mass or more, the matte appearance and MFR retention (M2 / M1) of the acrylic resin composition (a) can be improved. More specifically, in the compounding step for producing the acrylic resin composition (a), the phosphorus-based antioxidant (a-3) having an alkyl group containing 8 or more carbon atoms promotes the crosslinking reaction of the hydroxyl-containing polymer (a-2), thereby improving the matte appearance of the matte surface produced using the acrylic resin composition (a). Furthermore, the completion of the crosslinking reaction of the hydroxyl-containing polymer (a-2) during the compounding step improves the MFR retention (M2 / M1) of the acrylic resin composition (a) and suppresses a decrease in fluidity due to the progression of the crosslinking reaction in subsequent steps. When the amount of the phosphorus-based antioxidant (a-3) having an alkyl group with 8 or more carbon atoms added is 2.00 mass% or less, the matte appearance of a matte surface formed using the acrylic resin composition (a) can be improved. More specifically, in the compounding step for producing the acrylic resin composition (a), the viscosity of the molten resin falls within an appropriate range, resulting in a good degree of dispersion of the hydroxyl group-containing polymer (a-2), and thus an improved matte appearance of a matte surface formed using the acrylic resin composition (a).

[0076] <Thermoplastic polymer (D)> A polymer that does not have a crosslinking point in its molecular structure and has thermoplastic properties is referred to as a "thermoplastic polymer (D)" in this specification. The acrylic resin composition (a) may contain this thermoplastic polymer (D). The thermoplastic polymer (D) is not particularly limited and may be any known thermoplastic polymer, except for the polymer (a-2) containing a hydroxyl group.

[0077] Examples of the thermoplastic polymer (D) include polyethylene resins, polypropylene resins, vinyl chloride resins, polystyrene resins, AS resins, PET resins, acrylic resins, EVA resins, vinylidene chloride resins, polycarbonate resins, polyamide resins, polyacetal resins, PBT resins, fluorine-containing resins, thermoplastic elastomers, etc. The thermoplastic polymer (D) may be used alone or in combination of two or more. The thermoplastic polymer (D) that can be used in the present invention is preferably an acrylic polymer that meets quality requirements such as transparency, weather resistance, etc. In particular, acrylic resin films that require transparency, weather resistance, flexibility, processability, etc. are particularly suitable for use because they contain a rubber-containing polymer that is prone to burning.

[0078] <Acrylic polymer> In the following description, "(meth)acrylic" means acrylic and / or methacrylic. "Alkyl (meth)acrylate" means alkyl acrylate and / or alkyl methacrylate. Furthermore, "alkyl acrylate" and "alkyl methacrylate" mean alkyl esters of acrylic acid and alkyl esters of methacrylic acid, respectively.

[0079] The acrylic polymer that can be used as the thermoplastic polymer (D) in the present invention is not particularly limited, as long as it contains alkyl (meth)acrylate as the main component. The acrylic polymer is preferably an alkyl methacrylate-alkyl acrylate copolymer. Specific examples of such acrylic polymers include those containing 50 to 100% by mass of alkyl (meth)acrylate units having an alkyl group containing 1 to 4 carbon atoms and 0 to 50% by mass of at least one monomer unit of another vinyl monomer copolymerizable therewith, and having a reduced viscosity of 0.1 L / g or less. This reduced viscosity is measured by dissolving 0.1 g of the polymer in 100 ml of chloroform at 25°C. The content of alkyl (meth)acrylate units is preferably 70 to 100% by mass. Furthermore, the acrylic polymer preferably has a glass transition temperature of 80 to 110°C. Examples of acrylic polymers satisfying these physical properties include trade names such as ACRYPET VH, ACRYPET MD, and ACRYPET MF, manufactured by Mitsubishi Chemical Corporation.

[0080] Furthermore, from the viewpoint of improving the physical properties and productivity of the acrylic matte resin film, the film may contain an acrylic resin modifier such as high molecular weight acrylic polymers manufactured by Mitsubishi Chemical Corporation under the trade names of Metablen P-531A, Metablen P-530A, Metablen P-551A, Metablen P-550A, Metablen P-501A, Metablen P-570A, Metablen P-700, and Metablen P-710, or an acrylic polymer external lubricant manufactured by Mitsubishi Chemical Corporation under the trade name of Metablen L-1000.

[0081] <Additives> The acrylic resin composition (a) may contain additives such as stabilizers, lubricants, processing aids, plasticizers, impact resistance aids, foaming agents, fillers, antibacterial agents, antifungal agents, mold release agents, antistatic agents, colorants, ultraviolet absorbers, light stabilizers, and antioxidants, as needed. In particular, when the acrylic matte resin film of the present invention is used as a protective layer for a substrate, it is preferable that the acrylic resin composition (a) contains an ultraviolet absorber and / or a light stabilizer to impart weather resistance, and further preferably contains an antioxidant to suppress thermal decomposition of the ultraviolet absorber and / or the light stabilizer.

[0082] <UV absorber> Known UV absorbers can be used, and copolymer types can also be used. The molecular weight of the UV absorber used is preferably 300 or more, more preferably 400 or more. The use of a UV absorber with a molecular weight of 300 or more can prevent mold contamination due to volatilization of the UV absorber during vacuum molding or pressure molding in an injection molding die. In addition, UV absorbers with higher molecular weights are generally less likely to bleed out over the long term after processing into a film, and their UV absorption performance lasts longer than those with lower molecular weights.

[0083] Furthermore, when the molecular weight of the UV absorber is 300 or more, the amount of UV absorber that volatilizes during the time the matte acrylic resin film is extruded from the T-die and cooled by the cooling roll is small. Therefore, a sufficient amount of UV absorber remains, resulting in good performance. This also reduces the problem of the volatilized UV absorber recrystallizing and growing over time on the chains suspending the T-die or the exhaust hood above the T-die, eventually dropping onto the film and causing defects in appearance.

[0084] The type of ultraviolet absorber is not particularly limited, but particularly preferred are benzotriazole-based ones having a molecular weight of 400 or more and triazine-based ones having a molecular weight of 400 or more. Specific examples of the former include those manufactured by ADEKA CORPORATION under the trade names of ADK STAB LA-24 and ADK STAB LA-31RG, and those manufactured by BASF Japan Ltd. under the trade names of Tinuvin 234 and Tinuvin 360, while specific examples of the latter include those manufactured by ADEKA CORPORATION under the trade names of ADK STAB LA-46 and ADK STAB LA-F70, and those manufactured by BASF Japan Ltd. under the trade names of Tinuvin 1577ED and Tinuvin 1600. From the viewpoint of the long-term thermal stability of the ultraviolet absorber itself, ADK STAB LA-31RG can be preferably used.

[0085] The amount of the ultraviolet absorber added is preferably in the range of 0.1 to 10 parts by mass relative to 100 parts by mass of the resin constituting the acrylic resin composition (a). From the viewpoint of improving weather resistance, it is more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more. On the other hand, from the viewpoint of preventing process contamination during film formation and from the viewpoint of transparency of the molded product, it is more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.

[0086] <Light stabilizer> Any known light stabilizer can be used, and radical scavengers such as hindered amine light stabilizers are particularly preferred. Examples include trade names of ADEKA CORPORATION: ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-57G, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-81, and ADK STAB LA-94G; and trade names of BASF Japan Ltd.: Chimassorb 2020FDL and Chimassorb 944FDL.

[0087] From the viewpoint of the long-term thermal stability of the acrylic resin composition (a), Chimassorb 2020FDL can be suitably used. The amount of light stabilizer added is preferably in the range of 0.1 to 2 parts by mass relative to 100 parts by mass of the resin constituting the acrylic resin composition (a). From the viewpoint of the weather resistance of the acrylic resin composition (a), 0.2 parts by mass or more is more preferable. On the other hand, from the viewpoint of the MFR retention (M2 / M1) of the acrylic resin composition (a), 1 part by mass or less is more preferable, and 0.5 parts by mass or less is even more preferable. When the amount of light stabilizer added is 0.1 parts by mass or more, the weather resistance of the matte acrylic resin film can be improved. When the amount of light stabilizer added is 2 parts by mass or less, the thermal stability during molding can be improved, the increase in melt viscosity due to thermal degradation of the resin can be suppressed, and retention in the molding machine can be reduced, thereby suppressing thermal degradation of the resin. The resulting film is less susceptible to defects such as an increase in defects called fisheyes caused by thermal degradation over time, and can be subjected to melt extrusion such as film molding over long periods of time.

[0088] <Antioxidants> As the antioxidant, known ones can be used, and phenolic antioxidants, particularly hindered phenolic antioxidants, are preferred. The phenolic antioxidant is not particularly limited, and may be any known phenolic antioxidant that is a compound containing a phenolic hydroxyl group. Examples of phenolic antioxidants include those manufactured by ADEKA CORPORATION under the trade names: Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-60, Adeka Stab AO-80, and Adeka Stab AO-330, and those manufactured by BASF Japan Ltd. under the trade names: Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 259, Irganox 3114, and Irganox 565. One type of phenolic antioxidant may be used alone, or two or more types may be used in combination. From the viewpoint of the long-term thermal stability of the acrylic resin composition (a), ADK STAB AO-60 or Irganox 1010 can be suitably used.

[0089] The amount of the phenolic antioxidant added is preferably in the range of 0.2 to 10 parts by mass relative to 100 parts by mass of the resin constituting the acrylic resin composition (a). From the viewpoints of thermal stability and weather resistance during molding, it is more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more. On the other hand, from the viewpoints of preventing process contamination during film formation and transparency of the molded product, it is more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.

[0090] <Acrylic resin composition (b) that does not exhibit matte finish> The acrylic resin composition (b) used in the present invention, which does not exhibit matte properties, is a resin composition that constitutes a transparent acrylic resin layer when the matte acrylic resin film is a multilayer film. The acrylic resin composition (b) is not particularly limited, and may be any composition that does not exhibit matte properties and contains an acrylic resin as a main component.

[0091] Examples of the acrylic resin composition (b) include acrylic resin compositions that do not contain any of the components exemplified as matting components (matting agents) in the acrylic resin composition (a). Preferred examples include acrylic resin compositions that contain, other than the hydroxyl group-containing polymer (a-2), which is a component (matting agent) that exhibits matting properties, the acrylic rubber-containing polymer (a-1) that can be used in the acrylic resin composition (a), a phosphorus-based antioxidant (a-3) having an alkyl group having 8 or more carbon atoms, a thermoplastic polymer (D), an ultraviolet absorber, a light stabilizer, an antioxidant, and various additives.

[0092] <Laminate> The matte acrylic resin film of the present invention, or a laminated film or sheet obtained by laminating the matte acrylic resin film of the present invention with another thermoplastic resin layer, is useful for applications in which it is laminated on a substrate to form a laminate. In the case of a multilayer film, it is preferred that the matte acrylic resin film is laminated on a substrate so that the non-laminated surface of the transparent acrylic resin layer, which has excellent film surface smoothness, of the matte acrylic resin film is in contact with the substrate.

[0093] Examples of materials for the substrate include resin, wooden veneer, wooden plywood, particle board, wooden board such as medium density fiberboard (MDF), water-resistant board such as wood fiberboard, and metal such as iron or aluminum. Examples of the resin include polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, and olefin-based thermoplastic elastomers; general-purpose thermoplastic or thermosetting resins such as polystyrene resin, ABS resin, AS resin, acrylic resin, urethane resin, unsaturated polyester resin, and epoxy resin; general-purpose engineering resins such as polyphenylene oxide-polystyrene resin, polycarbonate resin, polyacetal, polycarbonate-modified polyphenylene ether, and polyethylene terephthalate; super engineering resins such as polysulfone, polyphenylene sulfide, polyphenylene oxide, polyetherimide, polyimide, liquid crystal polyester, and polyallyl-based heat-resistant resins; and composite resins or various modified resins containing reinforcing materials such as glass fiber or inorganic fillers (talc, calcium carbonate, silica, mica, and the like), or modifiers such as rubber components. Among these, melt-bondable resins are preferred, such as ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or resins containing these as their main components. In terms of adhesiveness, ABS resin, AS resin, polycarbonate resin, vinyl chloride resin, or resins containing these as their main components are preferred, and ABS resin, polycarbonate resin, or resins containing these as their main components are particularly preferred. Furthermore, even resins that do not heat-bond, such as polyolefin-based resins, can be bonded during molding by providing an adhesive layer.

[0094] As a method for producing a laminate, if the laminate has a two-dimensional shape and the substrate is one that can be thermally bonded, known methods such as thermal lamination can be used. For example, it can be attached via an adhesive layer to substrates that cannot be thermally bonded, such as wooden boards such as wood veneers, wooden plywood, particle boards, and medium-density fiberboards (MDF), water-based boards such as wood fiberboards, and metals such as iron and aluminum. In the case of a three-dimensional laminate, known methods such as insert molding and in-mold molding can be used. Insert molding is a method in which a film or sheet that has been decorated with printing or other decorations is first formed into a three-dimensional shape using vacuum forming or other methods, unnecessary parts of the film or sheet are removed, and then the film or sheet is transferred into an injection molding mold, where the base resin is injection molded to integrate it into a molded product (laminate). In-mold molding is a method in which a film or sheet that has been decorated with printing or other additives is placed in an injection molding mold, vacuum formed, and then the base resin is injection molded into the same mold to integrate it and obtain a molded product (laminate).

[0095] The acrylic matte resin film of the present invention, or a laminated film or sheet obtained by laminating the acrylic matte resin film of the present invention with another thermoplastic resin layer, has excellent elongation at high temperatures, and is therefore very advantageous when a three-dimensional shape is imparted by vacuum forming. The substrate resin used in injection molding is preferably a resin whose shrinkage after injection molding is similar to that of the acrylic matte resin film of the present invention or a laminate film or sheet obtained by laminating the acrylic matte resin film of the present invention with another thermoplastic resin layer. When the shrinkage rates of both are similar, problems such as warping of the laminate obtained by in-mold molding or insert molding or peeling of the film or sheet are less likely to occur. [Example]

[0096] The present invention will be further described below with reference to examples and comparative examples. In the following description, "parts" and "%" relating to quantitative ratios mean "parts by mass" and "% by mass", respectively, and abbreviations / abbreviations refer to the names of compounds listed in Table 1. First, the evaluation method, and preparation examples of the acrylic rubber-containing polymer (a-1) and the hydroxyl group-containing polymer (a-2) will be described.

[0097] <Evaluation method> (60° surface gloss (Gs60°)) The surface gloss at 60° was measured using a gloss meter (manufactured by Konica Minolta, Inc., trade name: GM-268Plus) in accordance with JIS Z8741.

[0098] (Arithmetic mean roughness (Ra) and mean length of profile curve elements (Rsm)) Using a surface roughness measuring instrument (manufactured by Tokyo Seimitsu Co., Ltd., product name: SURFCOM 1400D), the arithmetic mean roughness (Ra) and the mean length of the profile curve element (Rsm) were measured in accordance with JIS B0601-2001 under the conditions of a measurement length of 4.0 mm, an evaluation length of 4.0 mm, a cutoff wavelength of 0.8 mm, and a measurement speed of 0.3 mm / s. When measuring a long sample such as a film, measurements can be made in either the cross direction (TD) or the machine direction (MD), but evaluation must be performed in either the TD or MD only. The arithmetic mean roughness (Ra) is the value expressed in micrometers (μm) calculated by the following formula when a reference length is extracted from a roughness curve in the direction of the mean line, the X axis is taken in the direction of the mean line of this extracted portion, and the Y axis is taken in the direction of the longitudinal magnification, and the roughness curve is expressed as y = f(χ).

[0099]

number

[0100] The average length of a profile element (Rsm) is the average of the lengths Xs of the profile elements over the reference length, and is expressed in micrometers (μm) using the following formula: Xsi is the length corresponding to one profile element.

[0101]

number

[0102] (Gel content of acrylic resin composition (a)) An acetone solution prepared by dissolving 0.5 g of acrylic resin composition (a) (pre-extraction mass M) in 50 mL of acetone is refluxed at 65°C for 4 hours. The resulting extract is centrifuged at 14,000 rpm for 30 minutes at 4°C using a high-speed refrigerated centrifuge (manufactured by Hitachi Koki Co., Ltd., product name: CR21G). The solution is removed by decantation to obtain the remaining solid. This solid is subjected to reflux, centrifugation, and decantation again, and the resulting solid is dried at 50°C for 24 hours. The mass of the acetone-insoluble matter obtained is measured as the post-extraction mass m. The gel content G (%) of the acrylic resin composition (a) is calculated from the pre-extraction mass M and the post-extraction mass m using the following formula: G = (m / M) × 100 In the formula, G (%) represents the gel content of the acrylic resin composition (a), M represents a predetermined amount (also referred to as the mass before extraction) of the acrylic resin composition (a), and m represents the mass of the acetone-insoluble matter of the predetermined amount of the acrylic resin composition (a) (also referred to as the mass after extraction).

[0103] (Gel content of acrylic rubber-containing polymer (a-1)) An acetone solution prepared by dissolving 0.5 g of acrylic rubber-containing polymer (a-1) in 50 mL of acetone (pre-extraction mass M') is refluxed at 65°C for 4 hours. The resulting extract is centrifuged at 14,000 rpm for 30 minutes at 4°C using a high-speed refrigerated centrifuge (Hitachi Koki Co., Ltd., product name: CR21G). The solution is removed by decantation to obtain the remaining solid. This solid is subjected to reflux, centrifugation, and decantation again, and the resulting solid is dried at 50°C for 24 hours. The mass of the acetone-insoluble matter obtained is measured as the post-extraction mass m'. The gel content G' (%) of the acrylic rubber-containing polymer (a-1) is calculated from the pre-extraction mass M' and the post-extraction mass m' using the following formula: G' = (m' / M') x 100 In the formula, G' (%) represents the gel content of the acrylic rubber-containing polymer (a-1), M' represents a predetermined amount (also referred to as the mass before extraction) of the acrylic rubber-containing polymer (a-1), and m' represents the mass of the acetone-insoluble portion of the predetermined amount of the acrylic rubber-containing polymer (a-1) (also referred to as the mass after extraction).

[0104] (Melt flow rate (M1)) Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: S-111), the melt flow rate (M1) was measured for a holding time of 4 minutes, measuring a 4 g sample at a temperature of 240°C and a load of 49 N, according to JIS K7210 (Method A). The sample cutting interval was set to 30 to 120 seconds depending on the melt flow rate (M1) of the sample, and the extrusion volume per unit time was measured, and the melt flow rate (M1) in g / 10 min was calculated.

[0105] (Melt flow rate (M2)) Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: S-111), the melt flow rate (M2) was measured for a 20-minute holding time, measuring a 4-g sample at a temperature of 240°C and a load of 49 N, according to JIS K7210 (Method A). The sample cutting interval was set to 30 to 120 seconds depending on the melt flow rate (M2) of the sample, and the extrusion volume per unit time was measured, and the melt flow rate (M2) in g / 10 min was calculated.

[0106] (MFR retention rate (M2 / M1)) The MFR retention rate (M2 / M1) was calculated as the ratio of the melt flow rate (M2) after a holding time of 20 minutes to the melt flow rate (M1) after a holding time of 4 minutes.

[0107] (Transparency (total light transmittance, haze)) Using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: Haze Meter NDH4000), the total light transmittance was measured in accordance with JIS K7361-1, and the haze was measured in accordance with JIS K7136.

[0108] <Preparation Example 1> Production of rubber-containing multistage polymer (I) A vessel equipped with a stirrer was charged with 10.8 parts of deionized water, and then a monomer component (ia-1) consisting of 0.3 parts of MMA, 4.5 parts of n-BA, 0.2 parts of BDMA, 0.05 parts of AMA, and 0.025 parts of CHP was added and mixed with stirring at room temperature. Next, 1.3 parts of emulsifier S was added to the vessel while stirring, and stirring was continued for 20 minutes to prepare "emulsion 1."

[0109] Next, 156.0 parts of deionized water was added to a polymerization vessel equipped with a reflux condenser and heated to 74°C. Furthermore, a mixture was prepared by adding 0.20 parts of sodium formaldehyde sulfoxylate, 0.0001 parts of ferrous sulfate, and 0.0003 parts of EDTA to 4.5 parts of deionized water, and this mixture was added to the polymerization vessel. Next, while stirring under a nitrogen atmosphere, the emulsion 1 was added dropwise to the polymerization vessel over 9 minutes, and the reaction was continued for 15 minutes to complete the polymerization of polymer (I-a1).

[0110] Subsequently, a monomer component (ia-2) consisting of 9.6 parts of MMA, 14.4 parts of n-BA, 1 part of BDMA, 0.25 parts of AMA, and 0.016 parts of CHP was added dropwise to the polymerization vessel over 90 minutes, and the reaction was continued for 60 minutes to produce a polymer (I-a2). In this way, a polymer (IA) containing a polymer (I-a1) and a polymer (I-a2) was obtained. When the monomer components for the polymer (I-a1) and the polymer (I-a2) were polymerized separately under the same conditions as above, the Tg of the polymer (I-a1) was -48 ° C, and the Tg of the polymer (I-a2) was -10 ° C.

[0111] Subsequently, a monomer component (ic) consisting of 6 parts of MMA, 4 parts of MA, 0.075 parts of AMA, and 0.013 parts of CHP was added dropwise to the polymerization vessel over 45 minutes, and the reaction was continued for 60 minutes to form a polymer (IC). When the monomer components for the polymer (IC) were polymerized separately under the same conditions as above, the Tg of the polymer (IC) was 60°C.

[0112] Subsequently, a monomer component (ib) consisting of 57 parts of MMA, 3 parts of MA, 0.075 parts of t-BHP, and 0.248 parts of n-OM was added dropwise to the polymerization vessel over 140 minutes, and the reaction was continued for 60 minutes to form a polymer (IB), thereby obtaining a polymer latex of a rubber-containing multistage polymer (I).

[0113] The resulting polymer latex of the rubber-containing multistage polymer (I) was filtered using a vibration filter equipped with a SUS mesh (average mesh size: 54 μm) as the filter material, and then salted out in an aqueous solution containing 3.5 parts of calcium acetate. The polymer was washed with water, recovered, and then dried to obtain a powder of the rubber-containing multistage polymer (I). Table 2 shows a list of each monomer component. The gel content of the rubber-containing multistage polymer (I) was 70%.

[0114] <Preparation Example 2> Preparation of rubber-containing multistage polymer (II) A vessel equipped with a stirrer was charged with 10.8 parts of deionized water, and then a monomer component (ii-a-1) consisting of 0.3 parts of MMA, 4.5 parts of n-BA, 0.2 parts of BDMA, 0.05 parts of AMA, and 0.025 parts of CHP was added and mixed with stirring at room temperature. Next, 1.1 parts of emulsifier S was added to the vessel while stirring, and stirring was continued for 20 minutes to prepare "emulsion 2."

[0115] Next, 155.8 parts of deionized water was added to a polymerization vessel equipped with a reflux condenser and heated to 74°C. Furthermore, a mixture was prepared by adding 0.20 parts of sodium formaldehyde sulfoxylate, 0.0001 parts of ferrous sulfate, and 0.0003 parts of EDTA to 4.5 parts of deionized water, and this mixture was added to the polymerization vessel. Next, while stirring under a nitrogen atmosphere, the emulsion 2 was added dropwise to the polymerization vessel over 9 minutes, and the reaction was continued for 15 minutes to complete the polymerization of polymer (II-a1).

[0116] Subsequently, the monomer component (ii-a-2) consisting of 1.5 parts of MMA, 22.5 parts of n-BA, 1 part of BDMA, 0.25 parts of AMA, and 0.016 parts of CHP was added dropwise to the polymerization vessel over 90 minutes, and the reaction was continued for 60 minutes to produce polymer (II-a2). In this way, polymer (II-a1) and polymer (II-a2) containing polymer (II-A) were obtained.

[0117] Subsequently, a monomer component (ii-c) consisting of 6 parts of MMA, 4 parts of n-BA, 0.075 parts of AMA, and 0.013 parts of CHP was added dropwise to the polymerization vessel over 45 minutes, and the reaction was continued for 60 minutes to form a polymer (II-C).

[0118] Subsequently, a monomer component (ii-b) consisting of 55.2 parts of MMA, 4.8 parts of n-BA, 0.075 parts of t-BHP, and 0.189 parts of n-OM was added dropwise to the polymerization vessel over 140 minutes, and the reaction was continued for 30 minutes to form a polymer (II-B), thereby obtaining a polymer latex of a rubber-containing multistage polymer (II).

[0119] The resulting polymer latex of rubber-containing multi-stage polymer (II) was filtered using a vibration filter equipped with a SUS mesh (average mesh size: 54 μm) as the filter material, and then salted out in an aqueous solution containing 3 parts of calcium acetate. The polymer was washed with water, recovered, and then dried to obtain powdery rubber-containing multi-stage polymer (II). Table 2 shows a list of each monomer component. The gel content of the rubber-containing multi-stage polymer (II) was 60%.

[0120] <Preparation Example 3> Preparation of rubber-containing multistage polymer (III) 186.3 parts of deionized water was placed in a polymerization vessel equipped with a reflux condenser, and the temperature was raised to 79° C. Furthermore, a mixture was prepared by adding 0.25 parts of sodium formaldehyde sulfoxylate, 0.000025 parts of ferrous sulfate, and 0.000075 parts of EDTA to 3.4 parts of deionized water, and this mixture was placed in the polymerization vessel.

[0121] Next, while stirring under a nitrogen atmosphere, 1 / 10 of a mixture of monomer component (iii-a-1) consisting of 11.25 parts of MMA, 12.5 parts of n-BA, 1.25 parts of St, 0.74 parts of BDMA, 0.09 parts of AMA, and 0.044 parts of t-BHP and 0.75 parts of emulsifier S was added dropwise to the polymerization vessel over 4 minutes, and the reaction was continued for 15 minutes. Thereafter, the remaining 9 / 10 of the mixture was added dropwise to the polymerization vessel over 108 minutes, and at the 40-minute reaction time point, 0.125 parts of sodium formaldehyde sulfoxylate was added, and the reaction was continued for 55 minutes to complete the polymerization of polymer (III-a1).

[0122] Subsequently, the monomer component (iii-a-2) consisting of n-BA30.94 parts, St6.56 parts, BDMA0.10 parts, AMA0.65 parts and CHP0.106 parts was added dropwise to the polymerization vessel over 180 minutes, and then 0.125 parts of sodium formaldehyde sulfoxylate was added at the 105 minute reaction time point, and the reaction was continued for 120 minutes to produce polymer (III-a2). In this way, polymer (III-A) containing polymer (III-a1) and polymer (III-a2) was obtained.

[0123] Subsequently, a monomer component (iii-b) consisting of 35.63 parts of MMA, 1.88 parts of MA, 0.064 parts of t-BHP, and 0.103 parts of n-OM was added dropwise to the polymerization vessel over 120 minutes to form a polymer (III-B), thereby obtaining a polymer latex of a rubber-containing multistage polymer (III).

[0124] The resulting polymer latex of the rubber-containing multi-stage polymer (III) was filtered using a vibration filter equipped with a SUS mesh (average mesh size: 54 μm) as the filter material, and then salted out in an aqueous solution containing 5.0 parts of calcium acetate. The polymer was washed with water, recovered, and then dried to obtain a powder of the rubber-containing multi-stage polymer (III). Table 2 shows a list of each monomer component. The gel content of the rubber-containing multi-stage polymer (III) was 90%.

[0125] Preparation Example 4: Preparation of Hydroxyl-Containing Polymer (I) A monomer mixture consisting of 319 parts deionized water, 0.28 parts sodium sulfate, 1.11 parts sodium chloride, 79.0 parts MMA, 1.0 parts MA, 20.0 parts 2-hydroxyethyl methacrylate, 0.22 parts n-dodecyl mercaptan, and 0.53 parts lauroyl peroxide was added to a polymerization vessel equipped with a reflux condenser, and the atmosphere inside the polymerization vessel was thoroughly purged with nitrogen gas. Next, the monomer mixture was heated to 78°C while stirring and reacted for 2 hours under a nitrogen atmosphere. The liquid temperature inside the polymerization vessel was then raised to 90°C, and after 45 minutes, 0.030 parts potassium persulfate was added. The mixture was then maintained for an additional 90 minutes to obtain polymer beads. The obtained polymer beads were sieved through a 150 mesh (100 μm opening) sieve, and the beads that passed through the mesh were dehydrated and dried to obtain beads of hydroxyl-containing polymer (I). The resulting hydroxyl-containing polymer (I) had a glass transition temperature of 93° C. and an intrinsic viscosity of 0.076 L / g.

[0126] Preparation Example 5: Preparation of Hydroxyl-Containing Polymer (II) A monomer mixture consisting of 262 parts of deionized water, 12.3 parts of a 10% calcium phosphate slurry, 60.0 parts of MMA, 10.0 parts of MA, 30.0 parts of 2-hydroxyethyl methacrylate, 0.25 parts of n-dodecyl mercaptan, and 0.52 parts of lauroyl peroxide was added to a polymerization vessel equipped with a reflux condenser, and the atmosphere inside the polymerization vessel was thoroughly purged with nitrogen gas. The monomer mixture was then heated to 78°C with stirring and reacted for 2 hours under a nitrogen atmosphere. The liquid temperature inside the polymerization vessel was then raised to 85°C, after which 0.022 parts of potassium persulfate was added. The mixture was then maintained for an additional 90 minutes to obtain polymer beads. The resulting polymer beads were sieved through a 150 mesh (100 μm opening) sieve, and the beads that passed through the mesh were dehydrated and dried to obtain beads of hydroxyl-containing polymer (II). The resulting hydroxyl-containing polymer (I) had a glass transition temperature of 77° C. and an intrinsic viscosity of 0.069 L / g.

[0127] Preparation Example 6: Production of acrylic resin composition (b) that does not exhibit matte finish The acrylic rubber-containing polymer (a-1) was 80 parts of the rubber-containing multistage polymer (I) obtained in Preparation Example 1, and 10 parts of the rubber-containing multistage polymer (III) obtained in Preparation Example 3. The thermoplastic polymer (D) was 10 parts of an alkyl methacrylate-alkyl acrylate copolymer (manufactured by Mitsubishi Chemical Corporation; trade name: ACRYPET MD). 1.4 parts of a benzotriazole-based ultraviolet absorber (manufactured by BASF Japan Ltd.; trade name: Tinuvin 234) and 1.4 parts of a hindered amine-based light stabilizer (manufactured by ADEKA Corporation; trade name: Adekastab LA) were used as additives. After adding 0.3 parts of PEG-57G and 0.1 parts of a hindered phenolic antioxidant (BASF Japan Ltd.; trade name: Irganox 1076), the mixture was mixed using a Henschel mixer. The mixture was extruded into strands using a twin-screw extruder (Toshiba Machine Co., Ltd.; trade name: TEM-35B) at a cylinder temperature of 180-240°C and a die head temperature of 240°C while removing impurities using a breaker mesh (Nippon Seisen Co., Ltd.; trade name: NF-12T, nominal filtration diameter: 40 μm). The extrusion was passed through a water bath, cooled, and then cut into pellets. The resin temperature at the die outlet was 273°C at a screw rotation speed of 150 rpm and a discharge rate of 6.8 kg / h. The gel content of the resulting pellets was 66%.

[0128] Example 1 The acrylic resin composition (a) exhibiting the matte properties shown in Table 3 contained 50 parts of the rubber-containing multistage polymer (I) obtained in Preparation Example 1, which is the acrylic rubber-containing polymer (a-1), and 25 parts of the rubber-containing multistage polymer (II) obtained in Preparation Example 2, 23 parts of an alkyl methacrylate-alkyl acrylate copolymer (manufactured by Mitsubishi Chemical Corporation; trade name: ACRYPET VH) as the thermoplastic polymer (D), 0.4 parts of an acrylic polymer external lubricant (manufactured by Mitsubishi Chemical Corporation; trade name: METABLEN L-1000), 2 parts of the hydroxyl group-containing polymer (a-2) obtained in Preparation Example 4, and a phosphite ester compound (manufactured by Johoku Chemical Industry Co., Ltd.; trade name: J The mixture was mixed using a Henschel mixer with 0.7 parts of benzotriazole-based UV absorber (ADEKA Corporation; trade name: ADK STAB LA-31RG), 0.2 parts of hindered amine-based light stabilizer (BASF Japan Ltd.; trade name: Chimassorb 2020FDL), and 0.7 parts of hindered phenol-based antioxidant (ADEKA Corporation; trade name: ADK STAB AO-60). The mixture was extruded into strands using a twin-screw extruder (Toshiba Machine Co., Ltd.; trade name: TEM-35B) at a cylinder temperature of 170-240°C and a die head temperature of 240°C while removing impurities through a 200-mesh screen. The extrusion was then passed through a water bath, cooled, and cut into pellets. The resin temperature at the die outlet was 288°C at a screw rotation speed of 280 rpm and a throughput of 18.5 kg / h. The gel content of the obtained pellets was 46%, the melt flow rate (M1) was 3.6 g / 10 min, the melt flow rate (M2) was 3.4 g / 10 min, and the MFR retention rate (M2 / M1) was 1.0. The evaluation results are shown in Table 3.

[0129] The pellets were dehumidified and dried overnight at 85°C, and then extruded into a 40mmφ non-vented screw extruder (L / D=26) equipped with a 300mm wide T-die and a 200-mesh screen mesh at a cylinder temperature of 200-240°C and a T-die temperature of 245°C to produce a 40μm thick acrylic matte resin film. The arithmetic mean roughness (Ra) [μm] of the resulting acrylic matte resin film was 0.07 in MD and 0.07 in TD, and the 60° surface gloss (Gs60°) was 48.2% in MD and 52.1% in TD.

[0130] <Examples 2 to 11 and Comparative Examples 1 to 4> The same operations as in Example 1 were carried out, except that the acrylic resin composition (a) had the composition shown in Table 3. Table 3 shows the evaluation results of the obtained pellets and acrylic matte resin film.

[0131] Example 12 Pellets of the acrylic resin composition (a) obtained in Example 10 as a resin composition constituting the matte acrylic resin layer made of a matte acrylic resin film, and the acrylic resin composition (b) obtained in Preparation Example 6 as a resin composition constituting the transparent acrylic resin layer were dehumidified and dried at 85 ° C. overnight, and a 30 mm φ non-vented screw extruder equipped with a 200 mesh screen mesh was used to plasticize the acrylic resin composition (a) under conditions of a cylinder temperature of 200 to 240 ° C., and on the other hand, a 40 mm φ non-vented screw extruder equipped with a 500 mesh screen mesh was used to plasticize the acrylic resin composition (b) under conditions of a cylinder temperature of 220 to 240 ° C., and then a 500 mm wide two-type two-layer multi-manifold T-die set at 245 ° C. was used to produce a 75 μm thick acrylic matte resin film so that the transparent acrylic resin layer side was in contact with the mirror-cooled roll.

[0132] When the cross section of the matte acrylic resin film was observed, the matte acrylic resin layer made of the matte acrylic resin film had a thickness of 7.5 μm, and the transparent acrylic resin layer had a thickness of 67.5 μm. The arithmetic mean roughness (Ra) of the matte acrylic resin layer made of the matte acrylic resin film on the side where the transparent acrylic resin layer was not laminated was 0.32 in MD and 0.31 in TD, the 60° surface gloss (Gs60°) of the matte acrylic resin layer made of the matte acrylic resin film on the side where the transparent acrylic resin layer was not laminated was 12.6% in MD and 12.9% in TD, and the 60° surface gloss (Gs60°) of the transparent acrylic resin layer on the side where the matte acrylic resin layer made of the matte acrylic resin film was not laminated was 145% in MD and 146% in TD.

[0133] [Table 1]

[0134] [Table 2]

[0135] [Table 3]

[0136] [Table 4]

[0137] The above examples and comparative examples revealed the following: In the relationship between the numerical portion NGs60° of the 60° surface gloss (Gs60°) of a matte film surface and the arithmetic mean roughness (Ra), Ra is 2.2×NGs60° (-0.97) Over 4.4×NGs60° (-0.97)When the glossiness of the matte appearance was extremely low, and the design and decorative properties such as a sense of luxury and depth were good (Examples 1 to 12). On the other hand, in particular, in the relationship between the 60° surface gloss (Gs60°) of the film surface and the arithmetic mean roughness (Ra), when Ra was 4.4×NGs60° (-0.97) When the amount of the phosphorus-based antioxidant (a-3) having an alkyl group with 8 or more carbon atoms added was less than 0.45 mass%, the MFR retention rate (M2 / M1) was poor (Comparative Examples 2 to 4).

[0138] Furthermore, in the relationship between the arithmetic mean roughness (Ra) and the average length of the contour curve elements (Rsm) of the matte film surface, when the arithmetic mean roughness (Ra) of the surface having a surface gloss was 0.05 to 0.47 and the average length of the contour curve elements (Rsm) was 30.00 to 80.00, the glare of the matte appearance was extremely low, and the design and decorative properties, such as a sense of luxury and depth, were good (Examples 1 to 12). On the other hand, when the arithmetic mean roughness (Ra) of the surface having a surface gloss was 0.05 or less or 0.47 or more and the average length of the contour curve elements (Rsm) was 30.00 or less or 80.00 or more, the glare of the matte appearance was extremely high, and the design and decorative properties, such as a sense of luxury and depth, were poor. Furthermore, when the amount of the phosphorus-based antioxidant (a-3) having an alkyl group with 8 or more carbon atoms added was less than 0.45 mass %, the MFR retention rate (M2 / M1) was poor (Comparative Examples 2 to 4). [Industrial Applicability]

[0139] According to the present invention, it is possible to provide an acrylic matte resin film that has a good matte appearance, high thermal stability during molding, a matte finish that allows for stable production, and further has excellent appearance design, high mechanical strength, easy handling, and is applicable to a variety of uses.

Claims

1. At least one side of the film has a surface having a 60° surface gloss (Gs60°) of less than 100%, and the surface having the surface gloss has an arithmetic mean roughness (Ra) [μm] that satisfies the following formula (1), and the surface that satisfies the following formula (1) is made of an acrylic resin composition (a) having a gel content of 40 mass% or more, The acrylic resin composition (a) contains a phosphorus-based antioxidant (a-3), and the phosphorus-based antioxidant (a-3) is at least one selected from the group of compounds represented by the following general formula (2): 2.2×NGs60° （－０．９７） ≦Ra≦4.4×NGs60° （－０．９７） Formula (1) (In the formula, NGs represents a percentage of Gs60°, which is less than 100%). 【Chemical 1】 (In the formula, R １ , R ２ and R ３ each independently represents an alkyl group having 8 to 18 carbon atoms.

2. a film having a surface on at least one side thereof having a 60° surface gloss (Gs60°) of less than 100%, the surface having said surface gloss having an arithmetic mean roughness (Ra) [μm] of 0.05 or more and 0.47 or less, and an average length of a profile curve element (Rsm) [μm] of 30.00 or more and 80.00 or less, and the surface having said surface gloss having a gel content of 40 mass% or more; The acrylic resin composition (a) contains a phosphorus-based antioxidant (a-3), and the phosphorus-based antioxidant (a-3) is at least one selected from the group of compounds represented by the following general formula (2): 【Chemistry 2】 (In the formula, R １ , R ２ and R ３ each independently represents an alkyl group having 8 to 18 carbon atoms.

3. An acrylic matte resin film as described in claim 1 or 2, having a laminated structure of a matte acrylic resin layer made of a matte acrylic resin film and a transparent acrylic resin layer.

4. 4. The acrylic matte resin film according to any one of claims 1 to 3, wherein the acrylic resin composition (a) has an MFR retention (M2 / M1) of 0.7 to 1.3, which is the ratio of the melt flow rate (M1) measured in accordance with JIS K7210 at a temperature of 240°C and a load of 49N for a holding time of 4 minutes to the melt flow rate (M2) measured in accordance with JIS K7210 at a temperature of 240°C and a load of 49N for a holding time of 20 minutes.

5. The acrylic matte resin film according to claim 4, wherein the acrylic resin composition (a) contains an acrylic rubber-containing polymer (a-1) and a polymer (a-2) containing a hydroxyl group.

6. The amount of the hydroxyl group-containing polymer (a-2) added is 0.9 to 40 parts by mass relative to 100 parts by mass of the resins constituting the acrylic resin composition (a) (the total parts by mass of the acrylic rubber-containing polymer (a-1), the optionally present thermoplastic polymer (D), and the hydroxyl group-containing polymer (a-2)). The acrylic matte resin film according to claim 5.

7. An acrylic matte resin film described in any one of claims 1 to 6, wherein the content of the phosphorus-based antioxidant (a-3) in the acrylic resin composition (a) is 0.45 to 2.00 mass%.

8. The acrylic matte resin film according to any one of claims 1 to 7, wherein the total light transmittance of the acrylic matte resin film is 90% or more.

9. The acrylic matte resin film according to any one of claims 1 to 8, wherein the acrylic resin composition (a) has a gel content of 80 mass% or less.

10. R in the general formula (2) １ , R ２ and R ３ The acrylic matte resin film according to any one of claims 1 to 9, wherein is an alkyl group having 10 or more carbon atoms.

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