JP4307242B2 - Acrylic resin film, acrylic resin laminated film, photocurable acrylic resin film or sheet, laminated film or sheet, and laminated molded product obtained by laminating them - Google Patents

Description

  The present invention relates to an acrylic resin film-like material, an acrylic resin laminated film, a photocurable acrylic resin film or sheet, a laminated film or sheet, and a laminated molded product obtained by laminating these.

  As a method for imparting design properties to a molded product at low cost, there are an insert molding method and an in-mold molding method. In the insert molding method, a polyester resin, polycarbonate resin, acrylic resin sheet or film that has been decorated such as printing is molded into a three-dimensional shape in advance by vacuum molding or the like, and unnecessary film or sheet portions are removed. Thereafter, the molded product is transferred into an injection molding die, and an integrated molded product is obtained by injection molding a resin as a base material. On the other hand, the in-mold molding method is a method in which a sheet or film of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated for printing or the like is placed in an injection mold, vacuum molded, and then placed in the same mold. In this way, an integrated molded product is obtained by injection molding a resin as a base material.

  As an acrylic resin film-like material having excellent surface hardness and heat resistance that can be used for insert molding or in-mold molding, a rubber-containing polymer having a specific composition and a thermoplastic polymer having a specific composition are specified. An acrylic resin film-like product formed by mixing at a ratio is disclosed (for example, see Patent Documents 1 to 4). Such an acrylic resin film-like product not only imparts a decorative property to a molded product, but also has a function as an alternative material for clear coating.

  In addition, an acrylic resin film-like material containing a rubber-containing polymer having a specific composition and a thermoplastic polymer having a specific composition in a specific ratio, or a rubber-containing polymer having a specific composition and a specific composition An acrylic resin film-like material containing a thermoplastic polymer and a matting agent in a specific ratio is disclosed (for example, see Patent Documents 5 and 6). Such an acrylic resin film-like product not only imparts decorativeness to a molded product, but also has a function as an alternative material for matte coating.

  Further, in order to obtain an acrylic resin film having excellent surface hardness and scratch resistance that can be used for in-mold molding or insert molding, at least one side of the acrylic resin layer containing rubber particles is substantially free of rubber particles. An acrylic resin laminated film obtained by laminating an acrylic resin layer has been proposed (see, for example, Patent Documents 14 and 15).

  Similarly, the inclusion of rubber particles causes problems such as deterioration in weather resistance and chemical resistance. For this reason, at least one surface of the acrylic resin layer containing rubber particles is a resin having excellent weather resistance and chemical resistance, and a fluorine resin such as a vinylidene fluoride polymer having good adhesion to the acrylic resin. A laminated film formed by laminating has also been proposed (see, for example, Patent Document 16).

  In addition, it can be used advantageously in the production of molded products with good design that can be used for in-mold molding or insert molding. It has excellent wear resistance, weather resistance and chemical resistance, and has no adhesiveness. A photocurable film or sheet having a photocurable resin excellent in processability and storage stability on its surface is disclosed (Patent Documents 17 and 18). Such a photocurable film or sheet not only imparts a decorative property to a molded product, but also has a function as an alternative material for coating.

  Furthermore, a laminated film or sheet that can be suitably used in an insert molding method or an in-mold molding method and in which an acrylic resin film or sheet is laminated as an acrylic resin layer has been disclosed (for example, see Patent Documents 19 to 22).

  Further, an acrylic resin film-like material having a high workability and flexibility made of a multilayered polymer containing a rubber component, which can be used for in-mold molding, is disclosed (for example, see Patent Document 7).

  On the other hand, acrylic resin film-like materials made of rubber-containing acrylic resin are used on the surface of various resin molded products, woodwork products, and metal molded products, taking advantage of excellent properties in transparency, weather resistance, flexibility, and workability. It is laminated and used as a covering material, marking film, and high-intensity reflector coating film for interior and exterior of vehicles, furniture, door materials, window frames, baseboards, bathroom interiors, and other building materials.

  Conventionally, various resin compositions have been proposed and put into practical use as raw materials for acrylic resin film-like materials used in the above applications. Of these, alkyl acrylates, methacrylic acid alkyl esters, and graft crossing agents are particularly used as raw materials to provide acrylic resin film-like materials having excellent weather resistance, transparency, and resistance to whitening such as bending whitening. A multilayer structure polymer having a specific structure in which is a constituent component of a polymer is known (for example, see Patent Documents 8 and 9). Moreover, the multilayer structure polymer as a raw material of the acrylic resin film-like thing which has the same characteristic is disclosed (for example, refer patent documents 10-12). Further, as a thermoplastic resin composition that gives an acrylic resin film having excellent matting properties, a thermoplastic resin comprising a multilayer structure polymer having a specific structure and a linear polymer having a hydroxyl group having a specific composition The composition is disclosed (for example, refer patent document 13).

  In recent years, a member having an acrylic resin film-like layer as a surface layer, which has been formed by an insert molding method or an in-mold molding method, has been used as a component for vehicles.

  By containing a specific amount of a rubber-containing polymer having a specific average particle diameter, an acrylic resin film-like product having excellent surface hardness, heat resistance, and moldability can be obtained (for example, see Patent Document 1). By using a rubber-containing polymer having an average particle diameter of less than 0.2 μm, an acrylic resin film-like material for coating substitution having excellent transparency can be obtained (for example, see Patent Document 3). By using a rubber-containing polymer having a specific structure, it is possible to obtain an acrylic resin film-like material for paint replacement that is compatible with plasticizer whitening resistance and moldability without impairing surface hardness and heat resistance (for example, (See Patent Document 4). An acrylic resin film-like material using a rubber-containing polymer having a hard core structure with a Tg of about 105 ° C. has been proposed, and an acrylic resin film-like material having excellent surface hardness can be obtained (for example, see Patent Document 2). . By containing a specific amount of a matting agent and a rubber-containing polymer having a specific average particle size, an acrylic resin film-like material having excellent matting properties, surface hardness, heat resistance, and moldability can be obtained (for example, patent document) 5). An acrylic resin film-like material having a specific film surface glossiness, good printing suitability, and excellent matteness, surface hardness, heat resistance, and moldability can be obtained (see, for example, Patent Document 6). An acrylic resin film-like product has a concern about the resistance to molding whitening.

  Specifically, (1) In insert molding, an acrylic resin film or a laminated sheet laminated with an acrylic resin film after vacuum forming is removed, and in in-mold molding, an acrylic resin film protruding from the base resin. When punching is performed to remove the object, whitening occurs at the end of the molded product, which deteriorates the design of the molded product. (2) Whitening occurs when removing a molded product with an undercut design from the mold. (3) When a mold having a concave or convex shape is used to obtain a molded article having a convex or concave design such as a character, an acrylic resin film-like material remains in the concave or convex portion even after vacuum or pressure forming. Since the base resin must be injection-molded without following the mold and the acrylic resin film temperature is Tg or less, the resin pressure More When the film is stretched whitening occurs, it cracked in some cases.

  Due to the above-mentioned problem of whitening resistance of acrylic resin film-like products, there is a design limitation that removes the protruding film by hand instead of punching, and there are restrictions on the design. Industrial use value was low, such as a work process to remove

  Moreover, for example, an acrylic resin film-like material excellent in weather resistance, solvent resistance, stress whitening resistance, water whitening resistance, and transparency or matting properties can be obtained (see, for example, Patent Documents 8 to 12 and 13). . However, the publication does not describe insert molding or in-mold molding of the obtained acrylic resin film, and further does not describe surface hardness and heat resistance. Moreover, neither the surface hardness nor the heat resistance of the acrylic resin film-like material having the composition described in the examples has reached the level required for vehicle use. Although there is what is described in in-mold molding of the acrylic resin film-like material, which is rich in workability and flexibility (see, for example, Patent Document 7), the surface hardness, Heat resistance has not reached the required level for vehicle applications.

  Moreover, by laminating a resin layer having a Rockwell hardness of 90 or more on an M scale, the main component of which is an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, on at least one surface of an acrylic resin layer containing rubber particles, An acrylic resin laminated film having excellent scratch resistance can be obtained (for example, see Patent Document 14).

  However, since the surface hardness of the acrylic resin layer containing the rubber particles described in the publication is low, the surface hardness (scratch resistance) of the finally obtained acrylic resin laminated film cannot be improved for use in vehicles. There was room. Moreover, in the acrylic resin laminated film described in the examples, the processing conditions for obtaining a good molded product are narrow, and depending on the processing conditions, the acrylic resin layer may crack, break, peel off at the laminated portion, etc. was there. That is, the processing temperature of the acrylic resin laminated film, the injection speed of the base resin, and the like are limited, and the industrial utility value is low.

  Furthermore, bending is performed by laminating a hard layer made of an acrylic resin having a bending elastic modulus of 1600 MPa or more on at least one side of a soft layer made of an acrylic resin containing rubber particles and having a bending elastic modulus of 1500 MPa or less. Alternatively, an acrylic resin laminated film that has an appropriate surface hardness and flexibility and can be made into a molded product with little molding whitening when applied to a molding process including tension is obtained (for example, Patent Document 15).

  In this publication, there is a description regarding the resistance to molding whitening, and as its evaluation method, a tensile test is performed according to JIS K7113-1995 “Plastic tensile test method”, and the haze of the fractured part before and after that is measured. is doing. In the evaluation of molding whitening resistance by the tensile test, the haze value after the test varies depending on the test conditions such as the tensile speed, temperature condition, distance between chucks, and distance between chucks at the end point. However, in this publication, there is no description regarding these test conditions, and it is unclear as an evaluation of molding whitening resistance.

  In addition, the composition of the two-layer structure acrylic rubber used in the acrylic resin laminated film described in the examples is not clearly described.

  For this reason, the two-layer structure acrylic rubber (for example, refer to Patent Document 3) that has already been known, and that is prepared with an average particle diameter of about 75 nm when mixed with an acrylic resin, is used in the examples. When the acrylic resin laminated film described is produced and subjected to insert molding or in-mold molding, the acrylic resin laminated film of Example 1 using the acrylic resin containing rubber particles as the hard layer is cracked, Although no breakage or peeling at the laminated portion occurred, molding whitening was observed.

  Moreover, in the acrylic resin laminated films of Examples 2 to 4 using the acrylic resin containing no rubber particles as the hard layer, the acrylic resin layer was cracked, broken, peeled off at the laminated portion, etc. depending on the processing conditions. That is, there were severe restrictions on the processing temperature of the acrylic resin laminated film, the injection speed of the base resin, etc., and the industrial utility value was low.

  In this publication, a hard layer made of an acrylic resin having a flexural modulus of 1600 MPa or more is effectively prevented from containing rubber particles, thereby improving the molding whitening resistance. However, the molding whitening phenomenon when the above-mentioned insert molding or in-mold molding is performed occurs in the soft layer that occupies most of the acrylic resin laminated film, and the relatively whitened portion of the molding is relatively inconspicuous. The whitening of the printed pattern could be confirmed, and the industrial utility value was low.

  If the rubber particles used in the acrylic resin film are not used, for example, rubber particles having a specific taper structure and graft structure and excellent in stress whitening resistance (see, for example, Patent Documents 5 and 6), they are practically used. This is because it does not reach a level satisfying the molding whitening resistance.

  However, when rubber particles having a specific taper structure and graft structure that are currently known and excellent in stress whitening resistance can be obtained, a good molded product in which molding whitening resistance is not noticeable can be obtained. In addition, it has been difficult to obtain a molded product having a surface hardness that can be used for vehicles.

  In the acrylic resin laminated film of Example 5 of the publication, the surface hardness (scratch resistance) and heat resistance do not reach the levels required for vehicle use.

  In addition, by laminating a vinylidene fluoride polymer layer having excellent weather resistance and solvent resistance and good adhesion to the acrylic resin layer and an acrylic resin layer made of a specific multilayer structure polymer, transparency, A laminated film having excellent stress whitening resistance and water whitening resistance and excellent adhesion between the layers can be obtained (for example, Patent Document 16). However, in this publication, there is no description regarding insert molding or in-mold molding of the obtained laminated film. Furthermore, there is no description regarding surface hardness (abrasion resistance) and heat resistance.

  Moreover, in the laminated film described in the Examples, there was room for improvement in use of the surface hardness (scratch resistance) and heat resistance for vehicle applications.

  In addition, a photocurable film or sheet having a photocurable resin on the surface which is excellent in wear resistance, weather resistance and chemical resistance, has no tackiness, and has excellent workability and storage stability can be obtained ( Patent Documents 17 and 18).

  For example, when an acrylic resin film excellent in surface hardness, heat resistance, and moldability (for example, see Patent Document 1) is used as a base film or sheet in order to obtain a photocurable film or sheet, these acrylics are used. Since the resin film has a concern about the molding whitening resistance, the photocurable film or sheet to be obtained is similarly concerned with the molding whitening resistance.

  Furthermore, when an acrylic resin film (see, for example, Patent Documents 8 and 9) excellent in weather resistance, solvent resistance, stress whitening resistance, water whitening resistance, and transparency is used as the base film or sheet. Since these acrylic resin films are inferior in heat resistance, the photocurable resin composition and the acrylic resin film are stretched in the drying process for removing the solvent after the photocurable resin composition is applied to the film. There was a problem that the scratch resistance after curing and the surface hardness were lowered. In addition, when these acrylic resin films are used, it is possible to minimize the degree of stretching of the acrylic resin film by optimizing the drying conditions, but the drying process equipment has only been lengthened. However, the industrial utilization value was low because the production efficiency decreased. Furthermore, since the drying temperature cannot be increased, the amount of the remaining organic solvent in the photocurable resin layer cannot be reduced as described later, and various problems due to the remaining solvent are likely to occur. In addition, the surface hardness of the photocurable film or sheet after photocuring is strongly influenced by the surface hardness of the film or sheet serving as the base material. Therefore, photocuring when these acrylic resin films are used as the base material. Only a low surface hardness of the later photocurable film or sheet was obtained.

  Moreover, it can use suitably by the insert molding method or the in-mold molding method, and the laminated | multilayer film or sheet | seat which laminated | stacked the acrylic resin film-like thing or sheet | seat as an acrylic resin layer is obtained (for example, refer patent documents 19-22). However, in the laminated film and sheet having these acrylic resin layers, no mention is made regarding the importance and solution of the resistance to molding whitening.

  Next, as a laminated film or sheet (hereinafter referred to as “a laminated film or sheet for building materials”) used for surface decoration of an exterior sash such as an opening sash such as a window, an entrance sliding door, or an entrance door, poly is used. The mainstream is a structure in which a surface protective layer made of an acrylic resin having excellent weather resistance is provided on the surface of a base material sheet made of a thermoplastic resin such as vinyl chloride resin. This laminated film or sheet for building materials has the property that the acrylic resin of the surface protective layer is less susceptible to deterioration such as oxidation and decomposition due to ultraviolet rays, and for example, an ultraviolet absorber such as benzotriazole or benzophenone. Therefore, the substrate sheet and the pattern layer usually provided on the surface thereof are protected from ultraviolet rays contained in sunlight, and weather resistance sufficient for exterior use can be obtained.

  A laminated film or sheet for building materials in which an acrylic resin film or sheet is laminated on a surface protective layer, which is laminated by a conventionally known lamination method, is disclosed (for example, see Patent Documents 23 to 25).

  The laminated film or sheet for the above uses is required to have the following functions.

(1) Anti-glare property A laminated film or sheet for building materials has a problem in that it tends to cause a change in surface gloss during the manufacturing and processing steps and in use. In other words, the surface of the laminated film or sheet for building materials is adjusted to a predetermined gloss state by means of drawing processing, addition of a gloss adjusting agent, formation of a gloss adjusting layer, or the like so that a desired moderate gloss state is obtained. It is common. However, in the case of the laminated film or sheet for building materials, even if the surface is adjusted to a predetermined moderate gloss during the manufacturing process of the laminated film or sheet for building materials, such as an aluminum sash substrate or a steel plate door substrate. During the process of attaching to the surface of various base materials by lapping, etc., or while using the various members processed in this way on a building such as a house, the surface gloss rises and becomes shiny. This is because there is a tendency to easily become a design defect state such as gloss unevenness. This design defect causes the surface temperature of the laminated film or sheet to be in a high temperature state due to heat or the like during the processing step or in the state of being used as a building material member, and the thermoplastic resin layer of the surface protective layer is softened by this high temperature. It is due to that. That is, the anti-glare property required for the laminated film or sheet corresponds to the heat resistance of the thermoplastic resin layer of the surface protective layer.

(2) Secondary processing suitability Laminating films or sheets for building materials are generally made of woody base materials such as plywood, particle board, medium density fiber board (MDF), calcium silicate board, slate board, wood wool cement board, etc. It is used by sticking to the surface of various base materials such as inorganic base materials, synthetic resin base materials such as fiber reinforced plastics (FRP), etc., but only sticking to flat base materials In some cases, it may be used after being subjected to a bending process such as a V-cut process, or three-dimensionally formed on a surface of a substrate having an uneven shape by a method such as a lapping method or a vacuum forming method. In recent years, in particular, due to the diversification of consumer preferences, demand for various special three-dimensional decorative members has increased, and accordingly, the laminate film or sheet for building materials also has a bending workability, three-dimensional formability, etc. This is because there is an increasing demand for suitability for secondary processing.
For example, when bending a base material on which a laminated film or sheet is laminated in a cold region or the like, when forming a V-shaped groove in the base material and performing a bending process (V-cut process), or unevenness on the surface When the stress relaxation of the acrylic resin layer of the surface layer is insufficient when performing a process (wrapping process) to be bonded to a long substrate having a shape while bending it along the surface of the concavo-convex shape, bending is performed. Part may be whitened, cracked, broken or the like.

(3) Scratch resistance In the process of obtaining a laminated molded product, there is no appearance defect due to scratches. Furthermore, there is a high possibility of scratches such as window sashes, entrance sliding doors, entrance doors, etc. There is a strong demand for a laminated film or sheet for building materials having excellent scratch resistance from the viewpoint of expanding applications. As an index of scratch resistance, it is required that the acrylic hardness of the acrylic resin layer located on the surface layer of the laminated molded product is 2B or more. In the case of an acrylic resin layer having a pencil hardness of 2B or more, the laminated molded product obtained by using the building material laminated film or sheet has practical scratch resistance and is further in the process until becoming a laminated molded product. This is because there are few problems that cause appearance defects due to scratches, and it can be used for various exterior building members such as the above-described window sashes, entrance sliding doors, entrance doors, and the like.

  In the laminated film or sheet for building materials having an acrylic resin film as a surface protective layer described in Patent Documents 23 to 25, the importance of having these scratch resistance, anti-glare resistance, and molding whitening resistance together And no mention of solutions. For example, in Patent Documents 23 and 24, although mention is made regarding the resistance to molding whitening, the anti-gloss resistance is not described.

  Patent Document 25 mentions anti-glare resistance but does not describe scratch resistance and molding whitening resistance.

  Specifically, by using an acrylic resin film having a glass transition temperature of 90 ° C. or higher for the surface protective layer, even if the surface temperature of the laminated film or sheet may be exposed to a high temperature of 60 ° C. or higher, glossing, etc. It is described that a laminated film or sheet that is less prone to change in gloss is obtained. However, the publication does not clearly describe the composition relating to the acrylic resin film or the method for measuring the glass transition temperature. Furthermore, it is clear that there is a basis for “the surface temperature of the laminated film or sheet is 60 ° C. or higher”, which is assumed to be for each processing step to obtain a laminated molded product, or an actual use after construction on a building. Not listed. Further, there is no detailed description regarding processing for obtaining a laminated molded product.

  Among the fields of use of laminated molded products for building materials that include laminated films or sheets, for example, surface protection of acrylic resin films on parts with the highest heat resistance requirements such as outer walls such as siding, fences, roofs, roof decks, balconies, etc. In order to use a laminated film or sheet having a layer, it is desirable that there is no gloss change such as gloss return even when the surface temperature of the laminated film or sheet is kept for 24 hours in an environment of 90 ° C.

  However, the acrylic resin film (HBS006 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.) described in the examples of the publication cannot satisfy the required performance of heat resistance in the above applications, and the laminated film or sheet When the surface temperature is kept at 90 ° C. for 24 hours, gloss change such as gloss return is observed. For this reason, the usage was limited.

  Further, a laminated film or sheet obtained by using the acrylic resin film (HBS006 and HBS027 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.) described in the examples of the publication is a polyester resin having a shape with a radius of curvature of 0.5. When a laminated molded product having a three-dimensional shape is produced by three-dimensionally laminating a three-dimensional shaped substrate on a laminated film or sheet at a temperature of 80 ° C., the laminated film or sheet using HBS006 is slightly whitened. And whitening was observed in the laminated film or sheet using HBS027. For this reason, there have been limitations on the molding processing temperature, processing conditions, and the like.

  From these examples, the laminated film or sheet for building materials having the acrylic resin film described in Patent Document 25 as a surface protective layer has room for improvement with respect to molding whitening resistance and anti-glare resistance.

  Further, by using a specific resin composition, an acrylic resin film having improved workability that can be used for a bending process with a small radius of curvature and a high bending speed with improved flexibility is disclosed. (For example, Patent Document 26). An acrylic resin film having excellent low-temperature processability by using a specific resin composition is also disclosed (for example, Patent Documents 27 and 28). However, the acrylic resin films described in Patent Documents 26 to 28 are not described with respect to anti-gloss resistance, and the acrylic resin films using the resin compositions described in Examples as raw materials are expected. All of the anti-glare properties did not reach the level required for building materials, and were unsuitable for use as a laminated film or sheet for building materials.

On the other hand, when an acrylic resin film excellent in heat resistance (for example, Patent Documents 1 to 4) is used, it is excellent in anti-glare property, but is not suitable for use as a laminated film or sheet for building materials due to poor molding whitening resistance. Met.
JP-A-8-323934 Japanese Patent Laid-Open No. 11-147237 JP 2002-80678 A JP 2002-80679 A Japanese Patent Laid-Open No. 10-237261 JP 2002-361712 A JP-A-8-267500 Japanese Examined Patent Publication No. 62-19309 Japanese Patent Publication No. 63-8983 Japanese Patent Laid-Open No. 11-60876 JP 11-335511 A JP 2001-81266 A JP-A-7-238202 JP-A-4-166334 JP 2002-292808 A JP-A-3-288640 JP 2002-80550 A JP 2002-79621 A JP 2000-86853 A JP 2001-232660 A JP 2001-334609 A JP 2002-3620 A JP 2000-225672 A JP 2001-1465 A JP 2002-347185 A Japanese Patent Laid-Open No. 11-80487 JP 2002-241445 A JP 2003-128734 A Japanese Patent No. 2808251 WO 97/28950 Polymer HandBook (J. Brandrup, Interscience, 1989)

  The present invention relates to an acrylic resin film-like product having a surface hardness, heat resistance, and transparency or matte property that does not whiten the molded product when subjected to insert molding or in-mold molding. It aims at providing an acrylic resin laminated film. Further, when insert molding or in-mold molding is performed, the molded product is not whitened, and can be used for vehicle applications. Photocurable acrylic resin film or sheet or laminated film having heat resistance, scratch resistance, and surface hardness. The purpose is to provide a sheet. Further, it is an object of the present invention to provide a laminated film or sheet for building materials in which a molded product is not whitened in a step of processing such as V-cut processing or lapping processing in a cold region, and satisfies scratch resistance and anti-glare resistance. Objective. Furthermore, an object of this invention is to provide the laminated molded product which laminated | stacked these on the base material.

The above object of the present invention can be solved by the following present invention.
[1] A test piece after performing a tensile test on a test piece having a width of 20 mm under an initial chuck distance of 25 mm, a speed of 50 mm / min, and a temperature of 23 ° C. so that the end-chuck distance is 33 mm is JIS K7136. The difference between the value measured by the (method of measuring the haze) and the value measured by the test method of JIS K7136 (method for measuring the haze) of the test piece before the test is 30% or less, And pencil hardness (measurement based on JIS K5400) is 2B or more,
Containing an innermost layer polymer layer composed of two layers of an inner layer and an outer layer, an intermediate layer polymer layer, and a multilayer structure polymer having an outermost layer polymer layer;
The inner layer and the outer layer are both obtained by polymerizing a monomer component containing an alkyl acrylate ester and a graft crossing agent,
The intermediate layer polymer layer is obtained by polymerizing a monomer component containing an alkyl acrylate ester, an alkyl methacrylate ester and a graft crossing agent,
The outermost polymer layer is obtained by polymerizing a monomer component containing an alkyl methacrylate.
The acrylic resin film-like product (A) in which the Tg of the inner layer is less than −30 ° C. and the Tg of the outer layer is −15 ° C. to 10 ° C.
[2] The acrylic resin film-like product (A) according to [1], wherein at least one surface has a 60 ° surface glossiness of 100% or less.
[3] The acrylic resin film-like product (A) according to [1] or [2], wherein the heat distortion temperature (measured based on ASTM D648) is 80 ° C. or higher.
[4] The acrylic resin film-like product (A) according to any one of [1] to [3], further including a decorative layer on at least one side.
[5] An acrylic resin laminated film having the acrylic resin film-like product (A) according to any one of the above [1] to [3], and further another acrylic resin film-like product (A ′) or a fluororesin An acrylic resin laminated film having a film-like material (A ″).
[6] The acrylic resin laminated film according to [5], further including a decorative layer on at least one side.
[7] The acrylic resin film-like product (A) according to any one of [1] to [3] or the acrylic resin laminated film according to [5], and heat having a radical polymerizable unsaturated group in a side chain. A photocurable acrylic resin film or sheet having a photocurable resin composition (Z) layer containing a plastic resin (z-1) and a photopolymerization initiator (z-2).
[8] The photocurable acrylic resin film or sheet according to [7], further having a decorative layer on at least one side.
[9] The acrylic resin film (A) according to any one of [1] to [3], the acrylic resin laminated film according to [5], and the photocurable acrylic resin according to [7]. A laminated film or sheet having one selected from the group consisting of a film or a sheet and a thermoplastic resin layer (C).
[10] The laminated film or sheet according to [9], further including a decorative layer.
[11] A laminated film or sheet for building materials comprising the laminated film or sheet according to [9] or [10].
[12] The acrylic resin film-like product (A) according to any one of [1] to [4], the acrylic resin laminated film according to [5] or [6], and the above [7] or [8] 1 selected from the group consisting of the photocurable acrylic resin film or sheet of [9] or [10], and the building film laminate film or sheet of [11]. A laminated molded product characterized by being laminated on a material (E).
[13] The acrylic resin film-like product (A) according to any one of [1] to [4], the acrylic resin laminated film according to [5] or [6], and the above [7] or [8] Injecting into one selected from the group consisting of the photocurable acrylic resin film or sheet of [9] or [10], and the building film laminate film or sheet of [11] The laminate according to [12], which is obtained by performing vacuum forming or pressure forming in a molding die, and then injection-molding and integrating the resin to be the base material (E) in the injection molding die. Molding.
[14] The acrylic resin film-like product (A) according to any one of [1] to [4], the acrylic resin laminated film according to [5] or [6], and the above [7] or [8] One selected from the group consisting of the photocurable acrylic resin film or sheet of [9] or [10], and the building film laminate sheet or sheet of [11] above, Lamination molding according to [12], which is obtained by performing molding or pressure molding, and then inserting into an injection mold and injection molding the resin to be the base material (F) in the injection mold. Goods.

  As in the present invention, a test piece after performing a tensile test on a test piece having a width of 20 mm under the conditions of a distance between chucks of 25 mm, a speed of 50 mm / min, and a temperature of 23 ° C. so that the distance between chucks of the end point is 33 mm. The difference between the value measured by the test method of K7136 (cloudiness value measurement method) and the value measured by the test method of JIS K7136 (cloudiness value measurement method) of the test piece before the test is 30% or less. In addition, when an acrylic resin film (A) having a pencil hardness (measured based on JIS K5400) of 2B or more is employed, the molded product will not be whitened when subjected to insert molding or in-mold molding, and for use in vehicles. Acrylic resin film (A) and an acrylic resin laminated film satisfying the surface hardness, heat resistance, and transparency or mattness that can be used are provided. It can be. Further, when insert molding or in-mold molding is performed, the molded product is not whitened, and can be used for vehicle applications. Photocurable acrylic resin film or sheet and laminated film having heat resistance, scratch resistance, and surface hardness Sheets can be provided. In addition, it is possible to provide a laminated film or sheet for building materials that does not whiten a molded product and satisfies scratch resistance and anti-glare property in a process of performing processing such as V-cut processing or lapping processing in a cold region. Furthermore, a laminated molded product in which these are laminated on a base material can be provided.

  In particular, the acrylic resin film-like product of the present invention (A), an acrylic resin laminated film, a photocurable acrylic resin film or sheet, which is excellent in resistance to molding whitening when subjected to insert molding or in-mold molding, and Using one selected from the group consisting of laminated films or sheets, removes the film that protrudes by hand instead of punching, re-heats the whitened parts with design restrictions, and removes whiteness The work process is no longer necessary. The acrylic resin film-like product (A), acrylic resin laminated film, photocurable acrylic resin film or sheet, and laminated film or sheet of the present invention have extremely high industrial utility value, and have a conventional use application. It can be expanded dramatically.

<Acrylic resin film (A)>
The acrylic resin film-like product (A) of the present invention is a tensile test so that a test piece having a width of 20 mm has an initial chuck-to-chuck distance of 25 mm, a speed of 50 mm / min, and a temperature of 23 ° C. Measured by the test method of JIS K7136 (measuring method of haze value) of the test piece after the test and the test method of JIS K7136 (measuring method of haze value) of the test piece before the tensile test The difference from the measured value is 30% or less. The difference is more preferably 10% or less, and particularly preferably 5% or less. Acrylic resin film-like product (A), and an acrylic resin laminated film, a photocurable acrylic resin film or sheet containing the same, and molding whitening that occurs in the step of performing insert molding or in-mold molding on the laminated film or sheet, It corresponds to the difference. Moreover, the whitening that occurs in the process of performing processing such as V-cut processing and lapping processing in a cold region when used as a building material also corresponds to the above difference.

  When the acrylic resin film (A) having the above difference of 30% or less is used, the whitening that occurs in the step of insert molding or in-mold molding becomes inconspicuous, so the printed pattern does not disappear, and the design A laminated molded product can be obtained without lowering the properties. In addition, when a laminated film or sheet having an acrylic resin film (A) is used as a building material, the whitening that occurs in the process of processing such as V-cut processing or lapping processing in a cold region is inconspicuous. A molded product can be obtained without disappearing and without deteriorating the design.

  In addition, a tensile test of a test piece after performing a tensile test on a test piece having a width of 20 mm at an initial chuck distance of 25 mm, a tensile speed of 300 mm / min, and a temperature of 15 ° C. so that the end-chuck distance is 33 mm. The difference between the values obtained by measuring the test piece before and after the test piece by the test method of JIS K7136 (fogging value measurement method) is preferably 10% or less. When the difference under this condition is 10% or less, the whitening portion becomes less noticeable even in a printed pattern such as jet black tone where the whitened portion is more conspicuous than the normal wood grain / metallic pattern, and the industrial utility value is extremely high. The difference in values measured by the above test method under these conditions is more preferably 5% or less, and most preferably 1% or less.

  Furthermore, the acrylic resin film-like product (A) of the present invention has a pencil hardness (measurement based on JIS K5400) of 2B or more. Furthermore, HB or more is more preferable, and F or more is most preferable.

  When an acrylic resin film (A) having a pencil hardness of 2B or more is used, the acrylic resin film (A), an acrylic resin laminated film including the acrylic resin film, and light are used in the process of insert molding or in-mold molding. The curable acrylic resin film or sheet and the laminated film or sheet are hardly damaged, and the molded article has good scratch resistance.

  When used for vehicle applications, the pencil hardness of the acrylic resin film (A) of the present invention is preferably HB or higher. An acrylic resin film (A) having a pencil hardness of HB or higher, and an acrylic resin laminated film, a photocurable acrylic resin film or sheet containing the acrylic resin film, and a laminated molded product using the laminated film or sheet are a door waist garnish, It can be suitably used for various vehicle members such as a front control panel, a power window switch panel, and an airbag cover. It is very useful industrially from the viewpoint of expanding applications.

  Further, when the pencil hardness is F or more, the scratches are not noticeable even when scratched with a cloth having a rough surface such as gauze, and practically equivalent to a molded product using an acrylic resin film (A) having a pencil hardness of 2H. Therefore, the industrial utility value is very high.

  Using the acrylic resin film material (A) having a pencil hardness of 2B or more according to the present invention, an acrylic resin laminated film can be obtained. Such an acrylic resin laminated film of the present invention will be described later. Of course, when the acrylic resin film-like material (A) is located in the outermost layer of the acrylic resin laminated film, an acrylic resin layer having a pencil hardness of 2H or more ( Even when A′-a) is located in the outermost layer of the acrylic resin laminated film (that is, the upper layer of the acrylic resin film-like product (A)), it is difficult to reduce the surface hardness. Using this acrylic resin laminated film, it is difficult to be damaged during the process of insert molding or in-mold molding, and the scratch resistance of the molded product is also good. HB or more is preferable, and F or more is more preferable.

  The acrylic resin film-like material (A) having a pencil hardness of 2B or more according to the present invention can be used as a photocurable acrylic resin film or sheet. Although such a photocurable acrylic resin film or sheet of the present invention will be described later, the photocurable acrylic resin film or sheet is hardly damaged during the process of insert molding or in-mold molding. In addition, since the pencil hardness of the photocurable acrylic resin film or sheet after photocuring is also strongly influenced by the pencil hardness of the acrylic resin film (A) as a substrate, the acrylic resin film (A) The hardness needs to be 2B or more. HB or more is preferable, and F or more is more preferable.

  Using the acrylic resin film material (A) having a pencil hardness of 2B or more according to the present invention, for example, a laminated film or sheet for building materials can be obtained. Such a laminated film or sheet for building material of the present invention will be described later. However, the laminated film or sheet for building material is less likely to be damaged during the process of processing such as V-cut processing and wrapping processing, and the molded product is resistant to damage. Abrasion is also good.

  When used for building materials, the acrylic hardness of the acrylic resin film (A) of the present invention is preferably HB or higher. If the pencil hardness of the acrylic resin film (A) is HB or more, the molded product using the laminated film or sheet for building materials having the acrylic resin film (A) is used for an opening sash such as a window or the entrance. It can be suitably used for various building materials such as sliding doors and entrance doors. It is very useful industrially from the viewpoint of expanding applications.

  When the acrylic resin film material (A) of the present invention is used as an alternative to clear coating, the haze value of the acrylic resin film material (A) measured by the test method of JIS K7136 is preferably 2% or less. . Such an acrylic resin film-like product (A) is preferable because the design layer looks clear and faithful without being affected by the acrylic resin film-like product (A) even if a blackish design layer such as jet black is provided. Such an acrylic resin film-like product (A) has an appearance equivalent to that of clear coating. More preferably, it is 1% or less, More preferably, it is 0.5% or less, Most preferably, it is 0.4% or less.

  Further, when the acrylic resin film-like product (A) of the present invention is combined with a pattern layer such as a metallic tone, it is preferable that the 60 ° surface glossiness of at least one surface is 100% or less. The surface glossiness is more preferably 50% or less, and particularly preferably 20% or less. The acrylic resin film-like product (A) having a 60 ° surface glossiness of 100% or less on at least one side has excellent design properties and a matte appearance.

  The acrylic resin film-like product (A) of the present invention preferably has a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher. When the heat distortion temperature is 80 ° C. or higher, since the surface of the acrylic resin film (A) is not whitened or clouded when exposed at a high temperature for a long time, the industrial utility value is high. Moreover, in the vehicle use, when the thermal deformation temperature of the acrylic resin film (A) is 80 ° C. or higher, the acrylic resin film (A), an acrylic resin laminated film containing the acrylic resin film (A), and a photocurable acrylic A laminated molded product using a resin film or sheet and a laminated film or sheet can also be used for a part that receives direct sunlight in a vehicle, such as a front control panel. From the viewpoint of further expanding the application, the thermal deformation temperature is more preferably 90 ° C. or higher. The above-mentioned measurement of the heat distortion temperature is carried out by using a heat distortion temperature measurement specimen obtained by forming the raw material pellet of the acrylic resin film (A) by injection molding and annealing at 60 ° C. for 4 hours. The heat deformation temperature is usually the same as the heat deformation temperature of the acrylic resin film (A).

  In the case of an acrylic resin film (A) having a 60 ° surface glossiness of 100% or less on at least one side, if the thermal deformation temperature is 80 ° C. or higher, the acrylic resin film is exposed when exposed to high temperatures for a long time. The change in the matte property of the surface of the object (A) is small. Therefore, the acrylic resin film-like product (A) having a heat distortion temperature of 80 ° C. or higher has a higher industrial utility value. If the heat distortion temperature is 90 ° C. or higher, it can be suitably used for a part that receives direct sunlight in the vehicle, such as a front control panel. For this reason, the thermal deformation temperature is more preferably 90 ° C. or more from the viewpoint of further expanding the application.

  When used as a photocurable acrylic resin film or sheet, the acrylic resin film-like product (A) of the present invention preferably has a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher. When the heat distortion temperature is 80 ° C. or higher, the photocurable resin composition and the acrylic resin film are not easily stretched in the drying process for removing the solvent after the photocurable resin composition is applied to the film, and after the curing In addition to minimizing the deterioration of the scratch resistance and surface hardness, the drying temperature can be increased, so that the drying can be performed efficiently with the minimum drying equipment. Furthermore, if the drying temperature can be increased, the amount of the remaining organic solvent in the photocurable resin (Z) layer can be reduced as described later, so that various problems caused by the remaining solvent are less likely to occur. The thermal deformation temperature of the acrylic resin film is more preferably 85 ° C. or higher, and most preferably 90 ° C. or higher.

  When a laminated film or sheet having an acrylic resin film (A) is used for building materials, the acrylic resin film (A) has a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher. Is preferred. When the heat distortion temperature is 80 ° C or higher, glossy return, etc., when pasting to the surface of various base materials by lapping, etc., or when various processed parts are actually used for a long time after construction on a building such as a house Since a laminated film or sheet that is less susceptible to gloss change is obtained, the industrial utility value is high. Also, in building material applications, especially in actual applications, the surface of laminated films or sheets may become hot, door materials, window frame materials, outer wall materials, fences, roofs, roof decks, balconies, shutters, etc. From the viewpoint of further expanding applications such as semi-exterior applications, it is more preferable that the heat distortion temperature is 90 ° C. or higher.

  Although not specifically limited, the acrylic resin film-like product (A) satisfying the above-described molding whitening resistance, surface hardness, heat resistance and transparency is a multilayer structure polymer (I) shown below. Selected from the group consisting of a resin composition (III) containing this and a thermoplastic resin (II) mainly composed of an alkyl methacrylate and a resin composition (IV) containing these and a matting agent. Can be obtained from one.

[Multilayer structure polymer (I)]
The multilayer structure polymer (I) is composed of the following monomer components, the innermost layer polymer (IA), and the intermediate layer polymer (I) having a composition different from that of the innermost layer polymer (IA). -B) and each polymer layer of outermost layer polymer (IC).

Monomer component for constituting innermost layer polymer (IA) (I-A1) Acrylic acid alkyl ester 50-99.9% by mass
(I-A2) Methacrylic acid alkyl ester 0 to 49.9% by mass
(I-A3) having a copolymerizable double bond
Monomers other than (I-A1) and (I-A2) 0 to 20% by mass
(I-A4) Polyfunctional monomer 0 to 10% by mass
(I-A5) Graft crossing agent 0.1 to 10% by mass
Monomer component for constituting the intermediate layer polymer (IB) (I-B1) Acrylic acid alkyl ester 9.9 to 90% by mass
(I-B2) Methacrylic acid alkyl ester 9.9 to 90% by mass
(I-B3) having a double bond capable of copolymerization
Monomers other than (I-B1) and (I-B2) 0 to 20% by mass
(I-B4) Polyfunctional monomer 0 to 10% by mass
(I-B5) Graft crossing agent 0.1 to 10% by mass
Monomer component for constituting outermost layer polymer (IC) (I-C1) 80-100% by mass of methacrylic acid alkyl ester
(I-C2) Acrylic acid alkyl ester 0 to 20% by mass
(I-C3) having a copolymerizable double bond
Monomers other than (I-C1) and (I-C2) 0 to 20% by mass.

  Here, “different composition” means that the kind and / or amount of at least one monomer component constituting each polymer is different.

  It is preferable that Tg of the intermediate layer polymer (IB) alone is 25 to 100 ° C. with the above as constituent components.

  The acrylic acid alkyl ester of the component (IA-1) contained in the monomer component for constituting the innermost layer polymer (IA) may be either linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used alone or in admixture of two or more. As the acrylic acid alkyl ester of the component (I-A1), n-butyl acrylate is particularly preferable.

  The methacrylic acid alkyl ester of the component (I-A2) contained as necessary in the monomer component for constituting the innermost layer polymer (IA) may be either linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used alone or in admixture of two or more. As the alkyl methacrylate of component (I-A2), methyl methacrylate is particularly preferable.

  (I-A1) having a copolymerizable double bond of the component (I-A3) included as necessary in the monomer component for constituting the innermost layer polymer (IA), (I Examples of the monomer other than -A2) include acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, and methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, and methacrylonitrile. These can be used alone or in admixture of two or more.

  The polyfunctional monomer of the component (I-A4) contained as necessary in the monomer component for constituting the innermost layer polymer (IA) is the same copolymerizable duplex. A monomer having two or more bonds in one molecule is defined. Specific examples thereof include alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate. In addition, polyvinylbenzene such as divinylbenzene and trivinylbenzene can be used. These can be used alone or in admixture of two or more. As a polyfunctional monomer of the component (I-A4), 1,3-butylene glycol dimethacrylate is particularly preferable. Even when the polyfunctional monomer (I-A4) does not act at all, as long as the graft crossing agent (I-A5) is present, a fairly stable multilayer structure polymer (I) is obtained. For example, when the hot strength or the like is strictly required, it may be arbitrarily performed depending on the purpose of addition.

  The graft crossing agent (IA5) contained in the monomer component for constituting the innermost layer polymer (IA) is a single copolymer having two or more different copolymerizable double bonds in one molecule. Defined as a mer. Specific examples thereof include allyl, methallyl, or crotyl ester of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid, or fumaric acid. Of these, allyl methacrylate is preferable because of its excellent effect. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. These can be used alone or in admixture of two or more. Graft-crossing agent (I-A5) reacts and chemically bonds mainly with the conjugated unsaturated bond of its ester much faster than allyl, methallyl or crotyl groups. During this time, a substantial portion of the allyl, methallyl, or crotyl group works effectively during the polymerization of the next layer polymer to provide a graft bond between adjacent two layers.

  In addition, you may superpose | polymerize in presence of a chain transfer agent.

  The content of the acrylic acid alkyl ester (I-A1) in the monomer component for constituting the innermost layer polymer (I-A) is 50 to 99.9% by mass. From the viewpoint of molding whitening resistance of the resulting acrylic resin film-like product (A), it is preferably 55% by mass or more, more preferably 60% by mass or more. Further, from the viewpoint of the surface hardness and heat resistance of the acrylic resin film-like product (A) obtained (in the case of building materials, anti-gloss return property), more preferably 79.9% by mass or less, most preferably 69.9% by mass. % Or less.

  The content of the methacrylic acid alkyl ester (I-A2) in the monomer component for constituting the innermost layer polymer (IA) is 0 to 49.9% by mass. Preferably it is 20 mass% or more, More preferably, it is 30 mass% or more. Moreover, Preferably it is 44.9 mass% or less, More preferably, it is 39.9 mass% or less.

  Monomers (I-A3) other than (I-A1) and (I-A2) having a copolymerizable double bond in the monomer component for constituting the innermost layer polymer (IA) Is 0-20 mass%. Preferably it is 15 mass% or less.

  Content of the polyfunctional monomer (IA-4) in the monomer component for constituting the innermost layer polymer (IA) is 0 to 10% by mass. From the viewpoint of molding whitening resistance of the obtained acrylic resin film-like product (A), it is preferably 0.1% by mass or more, more preferably 3% by mass or more. From the viewpoint of imparting sufficient flexibility and toughness, it is preferably 6% by mass or less, more preferably 5% by mass or less.

  The content of the graft crossing agent (IA5) in the monomer component for constituting the innermost layer polymer (IA) is 0.1 to 10% by mass. When the content is 0.1% by mass or more, the resulting acrylic resin film-like product (A) has good whitening resistance and can be molded without deteriorating optical properties such as transparency. Preferably it is 0.5 mass% or more. Moreover, in content of 10 mass% or less, sufficient softness | flexibility and toughness can be provided to the acrylic resin film-like thing (A) obtained. Preferably it is 5 mass% or less, More preferably, it is 2 mass% or less.

  Although not particularly limited, the Tg of the innermost layer polymer (IA) alone is preferably 10 ° C. or less. More preferably, it is 0 ° C. or lower. When Tg is 10 ° C. or lower, the resulting multilayer structure polymer (I) is preferable because it exhibits favorable impact resistance. Tg can be calculated from the FOX equation using the values described in the Polymer Handbook [Polymer HandBook (J. Brandrup, Interscience, 1989) (Non-patent Document 1)].

  The content of the innermost layer polymer (IA) in the multilayer structure polymer (I) is preferably 15 to 50% by mass. When the content is 15% by mass or more, the resulting acrylic resin film (A) can be imparted with molding whitening resistance, and both film-forming properties and toughness capable of insert molding and in-mold molding can be achieved. Moreover, when it is 50 mass% or less, since the film which has the surface hardness and heat resistance (in the case of a building material use) required for a vehicle use is obtained, it is preferable. More preferably, it is 35 mass% or less.

  The innermost layer polymer (IA) may be a single layer or multiple layers, but more preferably is two layers. Although not particularly limited, it is preferable that the monomer composition ratios of the two layers in the innermost layer polymer (IA) are different.

When the innermost layer polymer (IA) consists of two layers, the resulting acrylic resin film-like product (A) has whitening resistance, impact resistance, heat resistance (in the case of building materials, anti-gloss return) and from the viewpoint of surface hardness, Tg of the inner layer (I-a ₁₎ is more lower than the Tg of the outer layer (I-a ₂₎ is preferred. Specifically, the Tg of the inner layer (I-A _1), is preferably less than -30 ° C. in view of耐成type whitening resistance and impact resistance, the Tg of the outer layer (I-A _2), surface hardness, From the viewpoint of heat resistance (anti-glare resistance in the case of building materials), −15 ° C. to 10 ° C. is preferable. In addition, from the viewpoint of surface hardness and heat resistance (anti-glare resistance in the case of building materials), the content of the inner layer (IA- ₁ ) in the innermost layer polymer (IA) is 1 to 20% by mass. preferably, the content of the outer layer (I-a ₂₎ is preferably 80 to 99 wt%.

  The acrylic acid alkyl ester of the component (IB1) contained in the monomer component for constituting the intermediate layer polymer (IB) may be either linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used alone or in admixture of two or more. Of these, preferred are methyl acrylate and n-butyl acrylate.

  The alkyl methacrylate of component (IB2) contained in the monomer component for constituting the intermediate layer polymer (IB) may be either linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used alone or in admixture of two or more. Of these, methyl methacrylate is preferred.

  (I-B1) having a copolymerizable double bond of the component (I-B3) included as necessary in the monomer component for constituting the intermediate layer polymer (IB), (I-B1) Examples of the monomer other than -B2) include acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, and methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, and the like. These can be used alone or in admixture of two or more.

  The polyfunctional monomer of the component (I-B4) contained as necessary in the monomer component for constituting the intermediate layer polymer (IB) is ethylene glycol dimethacrylate, 1,3-butylene. It is preferable to use alkylene glycol dimethacrylates such as glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate. In addition, polyvinylbenzene such as divinylbenzene and trivinylbenzene can be used. Of these, 1,3-butylene glycol dimethacrylate is preferred. These can be used alone or in admixture of two or more. Further, even when the polyfunctional monomer (I-B4) does not act at all, as long as the graft crossing agent (I-B5) is present, a considerably stable multilayer structure polymer (I) is obtained. For example, when the hot strength or the like is strictly required, it may be arbitrarily performed depending on the purpose of addition.

  As the graft crossing agent (I-B5) contained in the monomer component for constituting the intermediate layer polymer (IB), allyl of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid, Examples include methallyl or crotyl ester. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid, or fumaric acid. Of these, allyl methacrylate is preferable because of its excellent effect. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. These can be used alone or in admixture of two or more. Graft-crossing agent (I-B5) is chemically bonded, mainly because the conjugated unsaturated bond of its ester reacts much faster than allyl group, methallyl group, or crotyl group. During this time, a substantial portion of the allyl, methallyl, or crotyl group works effectively during the polymerization of the next layer polymer to provide a graft bond between adjacent two layers.

  In addition, you may superpose | polymerize in presence of a chain transfer agent.

  Content of the acrylic acid alkyl ester (I-B1) in the monomer component for constituting the intermediate layer polymer (IB) is 9.9 to 90% by mass. From the viewpoint of molding whitening resistance, surface hardness and heat resistance (anti-delustration in the case of building materials) of the obtained acrylic resin film-like product (A), it is preferably 19.9% by mass or more, more preferably 29. It is 9 mass% or more. Moreover, Preferably it is 60 mass% or less, More preferably, it is 50 mass% or less.

  The content of the methacrylic acid alkyl ester (I-B2) in the monomer component for constituting the intermediate layer polymer (IB) is 9.9 to 90% by mass. From the viewpoint of molding whitening resistance, surface hardness and heat resistance (anti-delustration in the case of building materials) of the obtained acrylic resin film-like product (A), it is preferably 39.9% by mass or more, more preferably 49. It is 9 mass% or more. Moreover, Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less.

  Monomers (I-B3) other than (I-B1) and (I-B2) having a copolymerizable double bond in the monomer component for constituting the intermediate layer polymer (IB) The content of is 0 to 20% by mass. Preferably it is 15 mass% or less.

  Content of the polyfunctional monomer (IB4) in the monomer component for constituting the intermediate layer polymer (IB) is 0 to 10% by mass. From the viewpoint of imparting sufficient flexibility and toughness to the resulting acrylic resin film-like product (A), it is preferably 6% by mass or less, more preferably 3% by mass or less.

  The content of the graft crossing agent (IB5) in the monomer component for constituting the intermediate layer polymer (IB) is 0.1 to 10% by mass. If the content is 0.1% by mass or more, the resulting acrylic resin film-like product (A) has good whitening resistance and can be molded without deteriorating optical properties such as transparency. Preferably it is 0.5 mass% or more. Moreover, in content of 10 mass% or less, sufficient softness | flexibility and toughness can be provided to the acrylic resin film-like thing (A) obtained. Preferably it is 5 mass% or less, More preferably, it is 2 mass% or less.

  The Tg of the intermediate layer polymer (IB) alone is preferably in the range of 25 to 100 ° C. When the Tg is 25 ° C. or higher, the surface hardness and heat resistance (anti-gloss return resistance in the case of building materials) of the resulting acrylic resin film (A) are at a level necessary for vehicle use or building material use, which is preferable. . More preferably, it is 40 degreeC or more, Most preferably, it is 50 degreeC or more. Moreover, when Tg is 100 degrees C or less, since the acrylic resin film-form thing (A) with favorable shaping | molding whitening resistance and film forming property is obtained, it is preferable. More preferably, it is 80 degrees C or less, Most preferably, it is 70 degrees C or less.

  Thus, by providing the intermediate layer polymer (IB) having a specific composition and Tg, molding whitening resistance, surface hardness, and heat resistance (in the case of building materials) An acrylic resin film-like product (A) that can achieve both gloss return properties can be obtained.

  Although not particularly limited, the content of the intermediate layer polymer (IB) in the preferred multilayer structure polymer (I) is preferably 5 to 35% by mass. If it is within this range, the function of the intermediate layer polymer (IB), which is important for achieving both the above-described molding whitening resistance, surface hardness and heat resistance (in the case of building materials, resistance to delustering), is achieved. While being able to express, the other physical property of the acrylic resin film-like material (A) obtained, for example, film forming property, insert molding, and toughness which can be in-mold-molded, are preferable. More preferably, it is 20 mass% or less.

  The intermediate layer polymer (IB) is usually a single layer, but it may be composed of two or more layers.

  The alkyl methacrylate of the component (I-C1) contained in the monomer component for constituting the outermost layer polymer (IC) may be either linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used alone or in admixture of two or more. Of these, methyl methacrylate is preferred.

  The acrylic acid alkyl ester of the component (I-C2) contained as necessary in the monomer component for constituting the outermost layer polymer (IC) may be either linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used alone or in admixture of two or more. Of these, preferred are methyl acrylate and n-butyl acrylate.

  (I-C1) having a copolymerizable double bond of the component (I-C3), which is included as necessary in the monomer component for constituting the outermost layer polymer (IC), Monomers other than -C2) are acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, maleic anhydride, itaconic anhydride Examples thereof include unsaturated dicarboxylic acid anhydrides such as acids, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These can be used alone or in admixture of two or more.

  The content of the methacrylic acid alkyl ester (I-C1) in the monomer component for constituting the outermost layer polymer (IC) is 80 to 100% by mass. From the viewpoint of the surface hardness and heat resistance of the resulting acrylic resin film-like product (A) (in the case of building materials), it is preferably 90% by mass or more, more preferably 93% by mass or more. Moreover, Preferably it is 99 mass% or less.

  Content of the acrylic acid alkyl ester (I-C2) in the monomer component for constituting the outermost layer polymer (IC) is 0 to 20% by mass. Preferably it is 1 mass% or more. Moreover, Preferably it is 10 mass% or less, More preferably, it is 7 mass% or less.

  Monomers (I-C3) other than (I-C1) and (I-C2) having a copolymerizable double bond in the monomer component for constituting the outermost layer polymer (IC) The content of is 0 to 20% by mass. Preferably it is 15 mass% or less.

  Although it does not specifically limit, a chain transfer agent is used at the time of superposition | polymerization of outermost layer polymer (IC), and the molecular weight of outermost layer polymer (IC) can be adjusted. This chain transfer agent is preferably selected from those usually used for radical polymerization, and specific examples thereof include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol, carbon tetrachloride, and the like. These can be used alone or in admixture of two or more. As for content of a chain transfer agent, 0.01-5 mass parts is preferable with respect to 100 mass parts of monomers ((I-C1)-(I-C3)) of a polymer (IC). More preferably, it is 0.2 mass part or more, Most preferably, it is 0.4 mass part or more.

  Although not particularly limited, the Tg of the outermost layer polymer (IC) alone is preferably 60 ° C. or higher. A Tg of 60 ° C. or higher is preferable because an acrylic resin film (A) having surface hardness suitable for vehicle use and heat resistance (anti-delustration in the case of building materials use) can be obtained. More preferably, it is 80 degreeC or more, Most preferably, it is 90 degreeC or more.

  Although it does not specifically limit, 15-80 mass% of content of outermost layer polymer (IC) in multilayer structure polymer (I) is preferable. When the content is 15% by mass or more, it is preferable from the viewpoints of surface hardness and heat resistance (in the case of building materials, resistance to gloss return). More preferably, it is 45 mass% or more. Moreover, when content is 80 mass% or less, since the toughness which can be formed whitening-proof, insert molding, and in-mold molding can be provided to the obtained film, it is preferable.

  The outermost layer polymer (I-C) is usually a single layer, but may be two or more layers.

  The multilayer structure polymer (I) preferably used for the acrylic resin film-like product (A) of the present invention includes the innermost layer polymer (IA), the intermediate layer polymer (IB), and the like as described above. It is comprised from the polymer layer of outermost layer polymer (IC).

The gel content of the multilayer structure polymer (I) is preferably 50% or more, more preferably 60% or more, from the viewpoint of obtaining more excellent molding whitening resistance. The gel content in this case is a predetermined amount (mass before extraction) of the multilayer structure polymer (I) extracted under reflux in an acetone solvent, the treated solution is separated by centrifugation, and the acetone insoluble matter is dried, The mass is measured (mass after extraction) and is calculated by the following method:
Gel content rate (%) = mass after extraction (g) / mass before extraction (g) × 100.

  From the viewpoint of molding whitening resistance, the larger the gel content, the more advantageous. However, from the viewpoint of easy moldability, the gel content is 80% because a certain amount of free polymer must be present. The following is preferred.

  The weight average particle diameter of the multilayer structure polymer (I) is preferably in the range of 0.03 μm to 0.3 μm. From the viewpoint of the mechanical properties of the resulting acrylic resin film (A), it is more preferably 0.07 μm or more, and most preferably 0.09 μm or more. Moreover, from a viewpoint of shaping | molding whitening-proof property and transparency, More preferably, it is 0.15 micrometer or less, Most preferably, it is 0.13 micrometer or less. The weight average particle diameter can be measured by a dynamic light scattering method using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd.

  As the method for producing the multilayer structure polymer (I), the sequential multi-stage polymerization method by the emulsion polymerization method is the most suitable polymerization method, but is not particularly limited to this, for example, after the emulsion polymerization, It can also be carried out by an emulsion suspension polymerization method in which the polymer (IC) is converted to a suspension polymerization system at the time of polymerization.

  In addition, although not particularly limited, when the multilayer structure polymer (I) is produced by emulsion polymerization, the monomer that gives the innermost layer polymer (IA) in the multilayer structure polymer (I) An emulsion prepared by mixing the components with water and a surfactant in advance is supplied to the reactor for polymerization, and then the intermediate layer polymer (IB) and the outermost layer polymer (IC) are obtained. A method in which a monomer or a monomer component is sequentially supplied to the reactor and polymerized is preferable.

  The monomer component that gives the innermost layer polymer (IA) was mixed with water and a surfactant in advance and supplied to the reactor to be polymerized and dispersed, particularly in acetone. In this case, the multilayer structure polymer (I) in which the number of particles having a diameter of 55 μm or more present in the dispersion is 0 to 50 per 100 g of the multilayer structure polymer (I) can be easily obtained. The acrylic resin film-like product (A) using the multilayer structure polymer (I) thus obtained as a raw material has a characteristic that the number of fish eyes in the film is small, and in particular, has a printing pressure that tends to cause printing omission. Even when solid gravure printing such as a low-light wood pattern, metallic tone, jet black tone, etc. is performed, it is preferable because there is little printing loss and high level printability.

  As the surfactant used for preparing the emulsion, anionic, cationic, and nonionic surfactants can be used, and anionic surfactants are particularly preferable. Examples of anionic surfactants include rosin soap, potassium oleate, sodium stearate, sodium myristate, sodium N-lauroylsarcosate, alkenyl succinate dipotassium, sulfate esters such as sodium lauryl sulfate , Sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sulfonates such as sodium alkyldiphenyl ether disulfonate, phosphate esters such as sodium polyoxyethylene alkylphenyl ether phosphate, sodium polyoxyethylene alkyl ether phosphate And phosphoric acid ester salts. Of these, sodium phosphate esters such as sodium polyoxyethylene alkyl ether phosphates are preferred. Preferable specific examples of the surfactant include NC-718 manufactured by Sanyo Chemical Industries, Phosphanol LS-529, Phosphanol RS-610NA, Phosphanol RS-620NA, Phosphorol manufactured by Toho Chemical Industry Co., Ltd. Nors RS-630NA, Phosphanol RS-640NA, Phosphanol RS-650NA, Phosphanol RS-660NA, Latemu P-0404, Latemulu P-0405, Latemulu P-0406, Latemulu P-0407 (Kao Corporation) All of the above are trade names).

  Moreover, as a method for preparing an emulsion, a method in which a monomer component is charged in water and then a surfactant is added, a method in which a surfactant is charged in water and then a monomer component is charged, monomer Examples thereof include a method in which a surfactant is charged into a component and then water is added. Among them, the method of charging the surfactant after charging the monomer component into water and the method of charging the monomer component after charging the surfactant into water yield the multilayer structure polymer (I). It is preferable as a method.

  Further, as a mixing device for preparing an emulsion prepared by mixing the monomer component giving the innermost layer polymer (IA) with water and a surfactant, a stirrer and a homogenizer equipped with a stirring blade And various types of forced emulsification devices such as homomixers, membrane emulsification devices, and the like.

  As the emulsion to be prepared, either a W / O type in which water droplets are dispersed in the monomer component oil or an O / W type dispersion structure in which oil droplets of the monomer component are dispersed in water is used. However, it is particularly preferable that the diameter of the oil droplets in the dispersed phase is 100 μm or less in the O / W type in which the oil droplets of the monomer component are dispersed in water.

  On the other hand, the polymerization used when forming the innermost layer polymer (IA), the intermediate layer polymer (IB), and the outermost layer polymer (IC) constituting the multilayer structure polymer (I). As the initiator, a known one can be used, and as a method for adding the initiator, a method of adding to one or both of the aqueous phase and the monomer phase can be used. As a particularly preferred initiator, a peroxide, an azo initiator, or a redox initiator combined with an oxidizing agent / reducing agent is used. A redox initiator is preferable, and a sulfoxylate initiator combined with ferrous sulfate, disodium ethylenediaminetetraacetate, longalite, and hydroperoxide is particularly preferable.

  As a method for adding the polymerization initiator, a method of adding to one or both of an aqueous phase and a monomer phase (oil phase) can be used.

  In addition, what is necessary is just to determine the addition amount of a polymerization initiator suitably according to superposition | polymerization conditions.

  As the method for obtaining the multilayer structure polymer (I), in particular, after heating the aqueous solution containing ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and Rongalite charged in the reactor to the polymerization temperature, the innermost layer polymer An emulsion prepared by mixing a monomer component containing a polymerization initiator such as peroxide to give (IA) with water and a surfactant is supplied to the reactor for polymerization. A monomer component containing a polymerization initiator such as a peroxide that gives the coalescence (I-B) is supplied to the reactor for polymerization, and then a peroxide that gives the outermost layer polymer (I-C) A method in which a monomer component containing a polymerization initiator and the like is supplied to the reactor for polymerization is preferred.

  In addition, although superposition | polymerization temperature changes with kinds and quantity of the polymerization initiator to be used, normally 40 degreeC or more is preferable, 60 degreeC or more is more preferable, 120 degreeC or less is preferable, and 95 degreeC or less is more preferable.

  The polymer latex containing the preferred multilayer structure polymer (I) obtained by the above method can be treated using a filtration device provided with a filter medium as necessary. This filtration treatment is for removing scales generated during the polymerization from the latex, or for removing impurities mixed in from the polymerization raw material and from the outside during the polymerization, and the multilayer structure polymer (I) is obtained. Therefore, it is a more preferable method.

  In addition, as a filtering device in which the filter medium used at that time is arranged, a GAF filter system of ISP Filters PTE Ltd. using a bag-shaped mesh filter or a cylindrical filter medium on the inner surface of a cylindrical filter chamber is used. It is preferable to use a centrifugal type filtration device in which a stirring blade is arranged in the filter medium, or a vibration type filter device in which the filter medium performs horizontal circular motion and vertical amplitude motion with respect to the filter medium surface.

  The multilayer structure polymer (I) can be produced by recovering the multilayer structure polymer (I) from the polymer latex produced by the above-described method. The method of recovering the multilayer structure polymer (I) from the polymer latex is not particularly limited, and examples thereof include salting out or acid precipitation coagulation, spray drying, freeze drying, and the like, and the powder is recovered in a powder form. .

  Among these, when salting out using a metal salt, the residual metal content in the finally obtained multilayer structure polymer (I) is preferably 800 ppm or less. In particular, when a metal salt having strong affinity with water such as magnesium or sodium is used as a salting-out agent, the final multilayer structure polymer (I) must be obtained unless the residual metal content is reduced as much as possible. When the acrylic resin film material (A) made from the raw material is immersed in boiling water, a whitening phenomenon occurs, which is a serious problem in practical use. In addition, when calcium-based and sulfuric acid-based coagulation is performed, a relatively good tendency is shown. In any case, in order to give excellent water whitening resistance, it is necessary to make the residual metal amount 800 ppm or less, The smaller the amount, the better.

  In the present invention, the multilayer structure polymer (I) can be used alone, but the resin composition (III) in combination with the thermoplastic polymer (II) shown below can also be used.

[Thermoplastic polymer (II)]
The thermoplastic polymer (II) preferably contains a methacrylic acid alkyl ester (II-A) unit as a main component. Specifically, it contains 50 to 100% by mass of a C 1-4 methacrylic acid alkyl ester (II-A) and, if necessary, 0 to 50% by mass of an acrylic acid alkyl ester (II-B), and if necessary, a copolymer. It is obtained by polymerizing a monomer component containing at least one monomer (II-C) other than (II-A) and (II-B) having a possible double bond, and 0 to 50% by mass. A polymer having a reduced viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) of 0.15 L / g or less is preferable. By using such a thermoplastic polymer (II) in combination, the surface hardness and heat resistance (in the case of a building material application, anti-delustration property) can be improved. Therefore, it is preferable that the glass transition temperature is 80 ° C. or higher, preferably 90 ° C. or higher.

  Examples of the alkyl methacrylate (II-A) contained in the monomer component for constituting the thermoplastic polymer (II) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. Among them, methyl methacrylate is preferable. These can be used alone or in admixture of two or more.

  The acrylic acid alkyl ester (II-B) contained in the monomer component for constituting the thermoplastic polymer (II) as necessary includes methyl acrylate, ethyl acrylate, propyl acrylate, and acrylic acid n. -Butyl etc. are mentioned, but methyl acrylate is preferred among these. These can be used alone or in admixture of two or more.

  Monomers other than (II-A) and (II-B) having a copolymerizable double bond, which are included in the monomer component for constituting the thermoplastic polymer (II) as necessary. As II-C), known monomers can be used as required. For example, aromatic vinyl compounds such as styrene, vinyl cyanide monomers such as acrylonitrile, unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, N-cyclohexylmaleimide and the like can be mentioned. . These can be used alone or in admixture of two or more.

  The content of the alkyl methacrylate (II-A) contained in the monomer component for constituting the thermoplastic polymer (II) depends on the surface hardness and heat resistance of the resulting acrylic resin film (A) ( In the case of building materials, 50 to 100% by mass is preferable from the viewpoint of anti-glare property. More preferably, it is 80 mass% or more, and is 99.9 mass% or less.

  The content of the acrylic acid alkyl ester (II-B) contained in the monomer component for constituting the thermoplastic polymer (II) is the film forming property of the resulting acrylic resin film (A), insert molding And 0-50 mass% is preferable from a viewpoint of providing the toughness which can be shape | molded in-mold. Preferably it is 0.1 mass% or more and 20 mass% or less.

  Monomers (II-C) other than (II-A) and (II-B) having a copolymerizable double bond contained in the monomer component for constituting the thermoplastic polymer (II) The content of is preferably 0 to 50 mass.

  The reduced viscosity of the thermoplastic polymer (II) (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) is the insert moldability and in-mold moldability of the resulting acrylic resin film (A). And from a viewpoint of film forming property, 0.15 L / g or less is preferable. More preferably, it is 0.1 L / g or less. Moreover, 0.01 L / g or more is preferable from a viewpoint of film forming property, and 0.03 L / g or more is more preferable.

  The method for producing the thermoplastic polymer (II) is not particularly limited, and the polymerization can be performed by a usual method such as suspension polymerization, emulsion polymerization, or bulk polymerization.

[Resin composition (III)]
The resin composition (III) suitably used for the acrylic resin film-like product (A) of the present invention comprises a multilayer structure polymer (I) and a thermoplastic polymer (II). Preferably, it consists of 1 to 99% by mass of the multilayer structure polymer (I) and 1 to 99% by mass of the thermoplastic polymer (II). From the viewpoint of molding whitening resistance of the resulting acrylic resin film (A), the content of the multilayer structure polymer (I) in the resin composition (III) is more preferably 50% by mass or more, most preferably. 70% by mass or more. The content of the thermoplastic polymer (II) in the resin composition (III) is more preferably 50% by mass or less, and most preferably 30% by mass or less.

  The gel content of the resin composition (III) is preferably 10 to 80% from the viewpoints of resistance to molding whitening and film forming. More preferably, it is 20% or more, and most preferably 40% or more. Further, it is more preferably 75% or less, and most preferably 70% or less.

[Resin composition (IV)]
In the present invention, the acrylic resin film-like product (A) having a matte property can be obtained from the multilayer structure polymer (I) or the resin composition (III), but the multilayer structure polymer (I) or It is preferable to obtain from resin composition (IV) containing 0.1-40 mass parts of matting agents with respect to 100 mass parts of resin composition (III). By using the matting agent, it is possible to further reduce the matte return of the acrylic resin film-like product (A) due to heat during the secondary molding process.

  Examples of the matting agent include various conventionally known matting agents regardless of whether they are organic or inorganic. Matting agents can be used alone or in admixture of two or more. As the matting agent, for example, spherical fine particles having a weight average particle diameter of about 2 to 15 μm made of a crosslinked resin mainly composed of PMMA are preferable from the viewpoint of transparency. Further, from the viewpoints of transparency, matting property, film-forming property and moldability, the following polymer (V) containing a hydroxyl group and / or polymer (VI) containing a hydroxyl group are preferred.

  When the polymer (V) containing a hydroxyl group and / or the polymer (VI) containing a hydroxyl group are used as the matting agent, physical properties such as elongation of the acrylic resin film-like product (A) are hardly lowered. Therefore, the acrylic resin film-like product (A) using the polymer (V) containing a hydroxyl group and / or the polymer (VI) containing a hydroxyl group as a matting agent requires a vacuum forming of the film in advance. Even in-mold molding or the like, film breakage does not occur, and it can be used more favorably.

[Polymer containing hydroxyl group (V)]
Polymer (V) containing a hydroxyl group is a methacrylic acid alkyl ester 10 having 1 to 80 parts by weight of a (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms and an alkyl group having 1 to 13 carbon atoms. It is obtained by copolymerizing a monomer component consisting of a total of 100 parts by mass of ˜99 parts by mass and 0 to 79 parts by mass of an alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms.

  Examples of the (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, and 2-hydroxyethyl acrylate. And 4-hydroxybutyl acrylate. These can be used alone or in admixture of two or more. As the (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 2-hydroxyethyl methacrylate is particularly preferable.

  Content of the (meth) acrylic-acid hydroxyalkyl ester which has a C1-C8 alkyl group in the monomer component which gives the polymer (V) containing a hydroxyl group is the range of 1-80 mass%. By setting the content of the hydroxyalkyl ester of (meth) acrylic acid having an alkyl group having 1 to 8 carbon atoms to 1% by mass or more, the matte effect is further enhanced. Moreover, the dispersibility of particle | grains becomes more favorable by making content of the (meth) acrylic-acid hydroxyalkyl ester which has a C1-C8 alkyl group into 80 mass% or less, and the film forming property of a film is more favorable. It becomes. The content of the (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms in the monomer component giving the polymer (V) containing a hydroxyl group is 5% by mass from the viewpoint of matteness. The above is preferable, and 20% by mass or more is more preferable. Moreover, content of the (meth) acrylic-acid hydroxyalkyl ester which has a C1-C8 alkyl group in the monomer component which gives the polymer (V) containing a hydroxyl group is 50 from a film forming viewpoint. The mass% or less is preferable.

  On the other hand, in a vehicle interior use, since a fragrance | flavor, a hair-styling agent, etc. may adhere to interior components, generally chemical resistance is calculated | required by the interior member. From the viewpoint of sufficiently developing resistance to these chemicals by the acrylic resin film (A), an alkyl group having 1 to 8 carbon atoms in the monomer component that gives a polymer (V) containing a hydroxyl group is used. The content of the (meth) acrylic acid hydroxyalkyl ester is preferably 5% by mass or more, and more preferably 25% by mass or less. (Meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms in the monomer component giving polymer (V) containing a hydroxyl group from the viewpoint of compatibility between matte properties and chemical resistance The content of is preferably 10% by mass or more, and more preferably 20% by mass or less.

  As the alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms, lower methacrylate esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like are preferable, and methyl methacrylate is particularly preferable. These can be used alone or in admixture of two or more.

  The content of the methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms in the monomer component giving the polymer (V) containing a hydroxyl group is in the range of 10 to 99% by mass. The content of the methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms in the monomer component giving the polymer (V) containing a hydroxyl group is preferably 30% by mass or more. Moreover, 90 mass% or less is preferable for content of the methacrylic acid alkylester which has a C1-C13 alkyl group in the monomer component which gives the polymer (V) containing a hydroxyl group.

  As the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, lower acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate are preferable. These can be used alone or in admixture of two or more.

  Content of the acrylic acid alkylester which has a C1-C8 alkyl group in the monomer component which gives the polymer (V) containing a hydroxyl group is the range of 0-79 mass%. The content of the alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms in the monomer component giving the polymer (V) containing a hydroxyl group is preferably 0.5% by mass or more, and more preferably 5% by mass or more. More preferred. In addition, the content of the alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms in the monomer component giving the polymer (V) containing a hydroxyl group is preferably 40% by mass or less, and 25% by mass or less. More preferred.

  On the other hand, the glass transition temperature of the polymer (V) containing a hydroxyl group is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of chemical resistance. In this case, the content of the alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms in the monomer component giving the polymer (V) containing a hydroxyl group is more than 0% by mass and 5% by mass or less. The range is preferable, and the range of more than 0% by mass and 2% by mass or less is more preferable.

  The intrinsic viscosity of the polymer (V) containing a hydroxyl group is preferably in the range of 0.05 to 0.3 L / g from the viewpoint of matte appearance and appearance. The intrinsic viscosity of the polymer (V) containing a hydroxyl group is more preferably 0.06 L / g or more. The intrinsic viscosity of the polymer (V) containing a hydroxyl group is more preferably 0.15 L / g or less.

  Further, in order to adjust the molecular weight within the above range, it is preferable to use a polymerization regulator such as mercaptan. Examples of mercaptans include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and the like. However, the mercaptan is not particularly limited, and various conventionally known mercaptans can be used.

[Polymer containing hydroxyl group (VI)]
Polymer (VI) containing a hydroxyl group is (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, and methacrylic acid alkyl ester 10 having an alkyl group having 1 to 13 carbon atoms. It is obtained by copolymerizing monomer components consisting of a total of 100 parts by mass of 94 parts by mass and 1 to 80 parts by mass of an aromatic vinyl monomer.

  Examples of the (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms include those similar to the case of the polymer (V) containing a hydroxyl group, and preferred ones are also the same. The (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms can be used alone or in admixture of two or more.

  Content of the (meth) acrylic-acid hydroxyalkyl ester which has a C1-C8 alkyl group in the monomer component which gives the polymer (VI) containing a hydroxyl group is the range of 5-80 mass%. By setting the content of the hydroxyalkyl ester of (meth) acrylic acid having an alkyl group having 1 to 8 carbon atoms to 5% by mass or more, the matte effect is further enhanced. Moreover, the dispersibility of particle | grains becomes more favorable by making content of the (meth) acrylic-acid hydroxyalkyl ester which has a C1-C8 alkyl group into 80 mass% or less, and the film forming property of a film is more favorable. It becomes. The content of the (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms in the monomer component giving the polymer (VI) containing a hydroxyl group is 5% by mass from the viewpoint of matteness. The above is preferable, and 10 mass% or more is more preferable. The content of the (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms in the monomer component giving the polymer (VI) containing a hydroxyl group is film-forming and chemical-resistant. From a viewpoint, 50 mass% or less is preferable, and 20 mass% or less is more preferable.

  Examples of the methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms include those similar to the case of the polymer (V) containing a hydroxyl group, and preferred ones are also the same. The methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms can be used alone or in admixture of two or more.

  The content of the alkyl methacrylate having a C1-C13 alkyl group in the monomer component giving the polymer (VI) containing a hydroxyl group is in the range of 10 to 94% by mass. The content of the alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms in the monomer component giving the polymer (VI) containing a hydroxyl group is preferably 50% by mass or more. Moreover, 90 mass% or less of content of the alkyl methacrylate which has a C1-C13 alkyl group in the monomer component which gives the polymer (VI) containing a hydroxyl group is preferable.

  Any known aromatic vinyl monomer can be used. Specific examples thereof include styrene and α-methylstyrene. These can be used alone or in admixture of two or more. Of these, styrene is preferred as the aromatic vinyl monomer. By using an aromatic vinyl monomer, the chemical resistance of the film-like product can be further improved.

  Content of the aromatic vinyl monomer in the monomer component which gives the polymer (VI) containing a hydroxyl group is in the range of 1 to 80% by mass. The content of the aromatic vinyl monomer in the monomer component giving the polymer (VI) containing a hydroxyl group is preferably 5% by mass or more. In addition, the content of the aromatic vinyl monomer in the monomer component giving the polymer (VI) containing a hydroxyl group is preferably 40% by mass or less, and more preferably 20% by mass or less.

  The glass transition temperature of the polymer (VI) containing a hydroxyl group is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of chemical resistance.

  The intrinsic viscosity of the polymer (VI) containing a hydroxyl group is preferably in the range of 0.05 to 0.3 L / g from the viewpoint of matte appearance and appearance. The intrinsic viscosity of the polymer (VI) containing a hydroxyl group is more preferably 0.06 L / g or more. Further, the intrinsic viscosity of the polymer (VI) containing a hydroxyl group is more preferably 0.15 L / g or less.

  Further, in order to adjust the molecular weight within the above range, it is preferable to use a polymerization regulator such as mercaptan. Examples of mercaptans include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and the like. However, the mercaptan is not particularly limited, and various conventionally known mercaptans can be used.

  The production method of the polymer (V) containing a hydroxyl group and the polymer (VI) containing a hydroxyl group is not particularly limited, but suspension polymerization, emulsion polymerization and the like are preferable.

  As the initiator for suspension polymerization, various conventionally known initiators can be used. Specific examples thereof include organic peroxides and azo compounds. These can be used alone or in admixture of two or more.

  The addition amount of the initiator may be appropriately determined according to the polymerization conditions and the like.

  As the suspension stabilizer, conventionally known various suspension stabilizers can be used. Specific examples thereof include organic colloidal polymer materials, inorganic colloidal polymer materials, inorganic fine particles, and combinations of these with surfactants. These can be used alone or in admixture of two or more.

  In addition, what is necessary is just to determine the addition amount of a suspension stabilizer suitably according to superposition | polymerization conditions.

  Suspension polymerization is usually carried out by suspending an aqueous monomer together with a polymerization initiator in the presence of a suspension stabilizer. In addition, suspension polymerization can be performed by using a polymer soluble in the monomer dissolved in the monomer.

  The resin composition (IV) is a polymer (V) containing a hydroxyl group or a polymer (VI) containing a hydroxyl group based on 100 parts by mass of the multilayer structure polymer (I) or the resin composition (III). What contains 0.1-40 mass parts of matting agents, such as these, is preferable.

  By making the content of the matting agent in the resin composition (IV) 0.1 parts by mass or more with respect to 100 parts by mass of the multilayer structure polymer (I) or the resin composition (III), a more excellent gloss Erasing effect appears. The content of the matting agent in the resin composition (IV) is 2 masses per 100 parts by mass of the multilayer structure polymer (I) or the resin composition (III) from the viewpoint of obtaining better matting properties. Part or more is more preferable, and 5 parts by mass or more is most preferable. Preferably it is 40 mass parts or less, More preferably, it is 20 mass parts or less, Most preferably, it is set as 15 mass parts, and it becomes favorable film forming property.

  It is preferable that the gel content rate of the resin composition (IV) of this invention is 10 to 80% from a viewpoint of shaping | molding whitening-proof property and film forming property. More preferably, it is 20% or more, and most preferably 40% or more. Further, it is more preferably 75% or less, and most preferably 70% or less.

  In the present invention, apart from the above-mentioned thermoplastic polymer (II), a thermoplastic polymer having a reduced viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) exceeding 0.15 L / g. (VII) can also be used. Specifically, the thermoplastic polymer (VII) is obtained by polymerizing 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another monomer having a double bond copolymerizable therewith. Is obtained. Other monomers having a double bond copolymerizable therewith can be used alone or in admixture of two or more. The thermoplastic polymer (VII) is a component that further improves the matting property when the film-forming property and the polymer (V) or (VI) containing a hydroxyl group are used.

  The thermoplastic polymer (VII) is in a range of more than 0 parts by mass and 20 parts by mass or less with respect to 100 parts by mass of the multilayer structure polymer (I), the resin composition (III) or the resin composition (IV). It is preferable to use it. More preferably, it is the range of 1-10 mass parts from a film film forming viewpoint.

  The acrylic resin film-like product (A) of the present invention may be a general compounding agent such as a stabilizer, a lubricant, a processing aid, a plasticizer, an impact resistance agent, a foaming agent, a filler, an antibacterial agent, if necessary. Anti-mold agents, mold release agents, antistatic agents, colorants, ultraviolet absorbers, light stabilizers, and the like can be included.

  From the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber in order to impart weather resistance. A well-known thing can be used as a ultraviolet absorber, A copolymer type thing can also be used. The molecular weight of the ultraviolet absorber used is preferably 300 or more, more preferably 400 or more. When an ultraviolet absorbent having a molecular weight of 300 or more is used, mold contamination due to volatilization of the ultraviolet absorbent when performing vacuum molding or pressure molding in an injection mold can be prevented. In general, a UV absorber having a higher molecular weight is less prone to long-term bleed-out after being processed into a film state, and its UV absorption performance lasts longer than that having a lower molecular weight. Furthermore, when the molecular weight of the ultraviolet absorber is 300 or more, the amount of the ultraviolet absorber that volatilizes before the acrylic resin film-like product (A) is extruded from the T die and cooled by the cooling roll is small. Therefore, since the amount of the remaining ultraviolet absorber is sufficient, good performance is exhibited. In addition, the volatilized UV absorber recrystallizes on the chain that suspends the T die at the top of the T die and the exhaust hood and grows over time. This eventually falls on the film and becomes a defect in appearance. This also reduces the problem.

  Although the kind of ultraviolet absorber is not particularly limited, a benzotriazole type having a molecular weight of 400 or more or a triazine type having a molecular weight of 400 or more can be particularly preferably used. Specific examples of the former include a trade name of Ciba Specialty Chemicals: Tinuvin 234, a trade name of Asahi Denka Kogyo Co., Ltd .: ADK STAB LA-31, and a specific example of the latter includes a trade name of Ciba Specialty Chemicals, Inc. 1577 etc. are mentioned.

  When the acrylic resin film-like product (A) of the present invention is used for vehicle applications, the hair-styling resistance property and the fragrance resistance property which are in the vehicle standards of various automobile manufacturers are required. Considering these characteristics, it is preferable to use an ultraviolet absorber having a melting point of 180 ° C. or lower. Such ultraviolet absorbers are commercially available from Ciba Specialty Chemicals, Inc., such as hair styling agents and fragrances when applied to the acrylic resin film (A). Tinuvin 1577 is particularly preferred. By using such an ultraviolet absorber, since the appearance change hardly occurs when the hair styling agent and the fragrance are attached, the industrial utility value is very high.

  The addition amount of the ultraviolet absorber is preferably in the range of 0.1 to 10 parts by mass. From the viewpoint of improving weather resistance, the addition amount is more preferably 0.5 parts by mass, and most preferably 1 part by mass or more. From the viewpoint of roll stain during film formation, chemical resistance, and transparency, the addition amount is preferably 5 parts by mass or less, and most preferably 3 parts by mass or less.

  Moreover, although a well-known thing can be used as a light stabilizer, in order to improve not only the light resistance of an acrylic resin film-like thing (A) but chemical resistance more, radicals, such as a hindered amine light stabilizer, are used. It is preferable to use a scavenger. For example, the appearance change when the hairdressing material is attached can be remarkably improved, and the industrial utility value is high.

  The amount of hindered amine light stabilizer added is preferably in the range of 0.01 to 5 parts by mass. From the viewpoint of improving light resistance and chemical resistance, the addition amount is more preferably 0.1 parts by mass, and most preferably 0.2 parts by mass or more. From the viewpoint of roll contamination during film formation, the addition amount is preferably 2 parts by mass or less, and most preferably 1 part by mass or less.

  By using these specific ultraviolet absorbers and hindered amine light stabilizers in combination, an acrylic resin film-like product (A) particularly suitable for vehicle use can be obtained.

  In particular, when the polymer (V) containing a hydroxyl group and / or the polymer (VI) containing a hydroxyl group is used as a matting agent in the resin composition (IV), the resin composition (IV) is used in an amount of 100 parts by mass. It is preferable to contain 0.01 to 3 parts by mass of a phosphorus compound as a compounding agent. By making the content of the phosphorus compound 0.01 parts by mass or more with respect to 100 parts by mass of the resin composition (IV), the matte property is further improved. Moreover, it is preferable from a roll stain | pollution | contamination at the time of film forming, and an economical viewpoint that content of a phosphorus compound shall be 3 mass parts or less with respect to 100 mass parts of resin composition (IV). As for content of a phosphorus compound, 0.1 mass part or more is more preferable with respect to 100 mass parts of resin compositions (IV). Moreover, as for content of a phosphorus compound, 1 mass part or less is more preferable with respect to 100 mass parts of resin compositions (IV).

  Phosphorus compounds include trialkyl phosphites, alkylaryl phosphites, aryl phosphites, nonylphenyl phosphites, alkylnonylphenyl phosphites, etc .; trialkyl phosphates, tripolyoxyethylene alkyl ether phosphates, dialkyl phosphates And its metal salts, phosphate compounds such as dipolyoxyethylene alkyl ether phosphate and its metal salt, alkyl phosphate and its metal salt, polyoxyethylene alkyl ether phosphate and its metal salt; dialkyl alkyl phosphonate, alkyl alkyl phosphonate and its metal Phosphonate compounds such as salts; and the like. Among these, phosphite compounds are preferable from the viewpoint of matte expression. Furthermore, among the phosphite compounds, those having no bulky substituent around the phosphite group are more preferable from the viewpoint of matte expression. Moreover, a trialkyl phosphite is preferable from the viewpoint of hydrolysis resistance (roll dirt during film formation).

  As a method for adding the compounding agent as described above, a multilayer structure polymer (I), a resin composition (III) or a resin composition (IV) is added to an extruder for forming an acrylic resin film (A). A method of supplying a compounding agent together with a component containing a mixture, and a mixture obtained by adding a compounding agent in advance to a component containing a multilayer structure polymer (I) or a resin composition (III) or a resin composition (IV) in various kneaders And kneading and mixing. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.

  Examples of the method for producing the acrylic resin film (A) used in the present invention include known methods such as a melt casting method, a melt extrusion method such as a T-die method and an inflation method, and a calendar method. From the viewpoint of properties, the T-die method is preferable.

  In addition, when the acrylic resin film-like product (A) is formed by the T-die method, it can be obtained by using a method of forming a film by sandwiching it between a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts. The surface smoothness of the acrylic resin film-like product (A) to be produced can be improved, and printing omission when the acrylic resin film-like product (A) is subjected to printing treatment can be suppressed. In addition, as a metal roll, a metal mirror surface touch roll; a metal sleeve (metal thin-film pipe) and a molding roll described in Japanese Patent No. 2808251 (Patent Document 29) or WO 97/28950 (Patent Document 30) The roll etc. which are used by the sleeve touch system which consists of can be illustrated. Moreover, as a nonmetallic roll, touch rolls, such as silicone rubber property, etc. can be illustrated. Furthermore, examples of the metal belt include a metal endless belt. A plurality of these metal rolls, non-metal rolls and metal belts can be used in combination.

  In the above-described method for forming a film by sandwiching a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts, the multilayer structure polymer (I) or resin composition (III) after melt extrusion ) Or a component containing the resin composition (IV) (hereinafter may be referred to as an “acrylic resin composition”) in a state where there is substantially no bank (resin pool) and is substantially rolled. It is preferable to form the film by surface transfer without any problem. When the film is formed without forming a bank (resin pool), the acrylic resin composition in the cooling process is surface-transferred without being rolled, so the acrylic resin film-like material (A) formed by this method It is also possible to reduce the heat shrinkage rate.

  In addition, when performing melt extrusion by the T-die method or the like, it is also preferable to extrude while filtering the acrylic resin in a molten state with a screen mesh of 200 mesh or more.

  When the acrylic resin film (A) is in a matte state, it is sandwiched between a mirror roll and a rubber roll or a wrinkled roll immediately after the acrylic resin composition T is formed into a film by a melt extrusion method such as a T-die method. Thus, a method of forming a film is preferred. In particular, the method of forming a film by sandwiching it between a mirror surface roll and a rubber roll produces a film having a relatively thin film thickness of about 50 μm as compared with the method of forming a film by sandwiching it between a mirror surface roll and a textured roll. It is more preferable in that it becomes possible.

  In the calendar method, one side of the two mirror rolls between which the film is finally sandwiched can be replaced with a rubber roll or a textured roll to form a film. Or after forming into a film shape once by a well-known method, an acrylic resin film-form thing (A) is heated again more than a glass transition point temperature, and a film is manufactured by inserting | pinching with a mirror surface roll, a rubber roll, or a wrinkled roll. You can also.

  Various conventionally known rolls can be used as the mirror roll. As the mirror roll, a roll having a surface roughness of 0.5 S or less subjected to chrome plating is preferable.

  During film production, if the temperature of the mirror roll is high, the followability to the rubber roll or the wrinkled roll becomes better, and a good matte property is exhibited by the film surface in contact with the rubber roll or wrinkled roll. The mirror surface transfer property to the acrylic resin film (A) of the roll becomes better, the smoothness of the surface in contact with the mirror surface roll is increased, and printing omission tends to be further reduced. However, if the temperature of the mirror surface roll is too high, the peelability of the acrylic resin film material (A) from the mirror surface roll may be reduced, or the acrylic resin film material (A) may be wound. Also, if the temperature of the mirror surface roll is too low, the mirror surface transfer property of the mirror surface roll to the acrylic resin film (A) will be reduced, and it will be difficult to obtain the effect of reducing printing loss or the film will be wrinkled. It becomes easy. Although it depends on the glass transition temperature of the acrylic resin, the temperature of the cooling roll is preferably controlled within a range of 20 to 140 ° C. The temperature of the cooling roll is more preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher. Further, the temperature of the cooling roll is more preferably 120 ° C. or less, and particularly preferably 100 ° C. or less.

  As the rubber roll, various conventionally known ones can be used. Among these, silicone rubber is preferable from the viewpoint of heat resistance. From the viewpoint of obtaining good matting properties, silicone rubber containing alumina is preferable. In the acrylic resin film-like product (A), the preferred matte appearance varies depending on the use. Therefore, the particle size and amount of alumina added to the silicone rubber may be appropriately determined according to the use. Specifically, for example, a silicone rubber roll to which 50% by mass of alumina having an average particle size of 40 μm is added can be used.

  In addition, a textured roll can be used instead of the rubber roll. As the embossed roll, various conventionally known rolls can be used.

  Moreover, when performing melt extrusion, it is also preferable to extrude while filtering the acrylic resin in a molten state with a screen mesh of 200 mesh or more.

  Difference in surface glossiness of acrylic resin film (A) obtained by the above method [(60 ° surface glossiness of film surface in contact with mirror surface roll side) − (not in contact with mirror surface roll side) The absolute value of the 60 ° surface glossiness of the film surface] can be controlled by the film forming conditions and the type of non-specular rolls such as rubber rolls and embossed rolls. The difference in surface glossiness is preferably 5% or more from the viewpoints of print omission and matteness. Furthermore, the difference in surface glossiness is more preferably 10% or more, and particularly preferably 15% or more.

  Since the mirror surface is transferred to the film surface that has been in contact with the mirror surface roll, surface protrusions due to foreign matters that cause printing omission can be significantly reduced. Therefore, when printing is performed on the surface that is in contact with the mirror surface roll, the printing omission can be remarkably reduced.

  On the other hand, the 60 ° surface glossiness of the film surface not in contact with the mirror roll side can be controlled by the type of non-specular roll such as a rubber roll or a textured roll. The 60 ° surface glossiness of the film surface not in contact with the mirror surface roll side is preferably 100% or less from the viewpoint of design and matte appearance. Furthermore, the 60 ° surface glossiness of the film surface not in contact with the mirror roll side is more preferably 50% or less.

  Moreover, compared with the film which has comparable surface glossiness, the glossiness at the time of insert molding or in-mold shaping | molding reduces, so that the heat deformation temperature of an acrylic resin film-like thing (A) is high. Therefore, from the viewpoint of glossiness at the time of insert molding or in-mold molding, it is preferable that the thermal deformation temperature of the acrylic resin film (A) is higher. From the viewpoints of peelability from the aforementioned mirror roll, followability to rubber rolls or wrinkled rolls, and gloss return at the time of molding, the thermal deformation temperature of the acrylic resin film (A) is in the range of 85 ° C to 105 ° C. It is preferable that it is in 90 degreeC or more, and 100 degreeC or less is more preferable.

  The thickness of the acrylic resin film-like product (A) of the present invention is preferably 10 to 500 μm. By setting the thickness of the acrylic resin film (A) to 500 μm or less, rigidity suitable for insert molding and in-mold molding can be obtained, and a film can be manufactured more stably. Moreover, by making the thickness of the acrylic resin film-like product (A) 10 μm or more, a sense of depth can be more sufficiently imparted to the obtained molded product together with the protection of the base material. The thickness of the acrylic resin film (A) is more preferably 30 μm or more, and most preferably 50 μm or more. Further, the thickness of the acrylic resin film (A) is more preferably 300 μm or less, and most preferably 200 μm or less.

  In order to form a coating film having a sufficient thickness on a molded product by coating, it may be necessary to apply ten or more times of recoating. In this case, the cost is high and the productivity is not so good. On the other hand, since the acrylic resin film-like product (A) itself becomes a coating film, the laminated molded product of the present invention can easily form a very thick coating film and has high industrial utility value.

<Acrylic resin laminated film>
The acrylic resin laminated film of the present invention has the acrylic resin film-like product (A) of the present invention, and further has another acrylic resin film-like product (A ′) or fluororesin film-like product (A ″). It is what has.

  When the acrylic resin film-like product (A) is used as a substrate and the other acrylic resin film-like product (A ′) is used as a surface layer as the acrylic resin laminated film of the present invention, the acrylic resin film-like product (A It is preferable to use an acrylic resin film-like product (A′-a) having a higher surface hardness than (A). Specifically, it is preferable to use an acrylic resin film (A′-a) having a pencil hardness (measured based on JIS K5400) of 2H or more. As the base material, the acrylic resin film material (A) of the present invention is used as the base material, and the acrylic resin film material (A′-a) having a pencil hardness of 2H or more is used as the surface layer. Compared with the acrylic resin laminated film, an acrylic resin laminated film having both molding whitening resistance, surface hardness (abrasion resistance) and heat resistance can be obtained, which is preferable.

  At this time, the acrylic resin film-like product (A′-a) may be formed of a thermoplastic resin mainly composed of alkyl methacrylate, and the rubber-containing polymer is added to the thermoplastic resin. It may be formed from the resin composition formed by mixing and is not particularly limited. When insert molding or in-mold molding is applied to an acrylic resin laminated film, stress relaxation of the acrylic resin film (A'-a) becomes insufficient, causing cracks, breakage, peeling at the laminated portion, etc. From the viewpoint of avoiding the occurrence, it is preferably formed from a resin composition obtained by mixing a small amount of a rubber-containing polymer with a thermoplastic resin mainly composed of alkyl methacrylate.

  When the pencil hardness is 2H or more, it is particularly preferable to use an acrylic resin film (A′-a) having a different content of the multilayer polymer (I) from the acrylic resin film (A). .

  Other examples include preferable resin compositions containing the following (i) and (ii).

(I) Thermoplastic resin mainly composed of alkyl methacrylate.
A thermoplastic resin comprising 50 to 100% by mass of methacrylic acid alkyl ester, 0 to 50% by mass of acrylic acid alkyl ester, and 0 to 49% by mass of other vinyl monomers copolymerizable therewith.

(Ii) Rubber-containing polymer:
(Ii-a) An average particle diameter of less than 0.2 μm having a two-layer structure in which a hard polymer is formed by graft polymerization of an alkyl methacrylate ester monomer in the presence of an acrylic acid alkyl ester elastomer. Rubber-containing polymer.

  (Ii-b) Innermost layer polymer obtained by polymerizing monomers of methacrylic acid alkyl ester and acrylic acid alkyl ester having a Tg of 0 ° C. or higher and lower than 25 ° C., single amount of acrylic acid alkyl ester having a Tg of less than 0 ° C. A rubber-containing polymer having an average particle size of 0.2 to 0.4 μm having a three-layer structure comprising an intermediate layer elastic polymer obtained by polymerizing a polymer and an outermost layer polymer comprising a monomer of an alkyl methacrylate.

More specifically, the following resin composition is mentioned, for example.
○ Resin composition for acrylic resin film described in JP-A-2002-80678:
The alkyl acrylate in the rubber-containing polymer (ii-a) comprising 20 to 94.5 parts by weight of the thermoplastic resin (i) and 5.5 to 80 parts by weight of the rubber-containing polymer (ii-a). A resin composition comprising an ester-based elastic polymer in an amount of 5 to 72 parts by mass [total 100 parts by mass of component (i) and component (ii)].
○ Acrylic resin film resin composition described in JP-A-2002-80679:
The innermost layer weight in the rubber-containing polymer (ii-b) comprising 75 to 94.5 parts by weight of the thermoplastic resin (i) and 5.5 to 25 parts by weight of the rubber-containing polymer (ii-b). The resin composition which the quantity of the elastic polymer which consists of a coalescence and an intermediate | middle layer elastic polymer consists of 5-18 mass parts [100 mass parts in total of a component (i) and a component (ii)].

  The acrylic resin film-like product (A′-a) used in the present invention is a general compounding agent such as a stabilizer, a lubricant, a processing aid, a plasticizer, an impact resistance agent, a foaming agent, if necessary. Fillers, antibacterial agents, antifungal agents, mold release agents, antistatic agents, colorants, matting agents, ultraviolet absorbers, light stabilizers, and the like can be included.

  In particular, it is preferable to add an ultraviolet absorber in order to provide weather resistance in terms of protecting the base material, color pattern such as printing, and coloring agent. The molecular weight of the ultraviolet absorber used is preferably 300 or more, more preferably 400 or more. When an ultraviolet absorbent having a molecular weight of 300 or more is used, mold contamination due to volatilization of the ultraviolet absorbent when performing vacuum molding or pressure molding in an injection mold can be prevented. In general, a UV absorber having a higher molecular weight is less prone to long-term bleed out after being processed into an acrylic resin laminated film state, and its UV absorption performance lasts longer than that having a lower molecular weight.

  As a method for adding the above compounding agent, a method of supplying to an extruder together with a raw material for an acrylic resin film (A′-a) for forming the acrylic resin film (A′-a) of the present invention, There is a method in which a mixture in which a compounding agent is added to a raw material for an acrylic resin film (A′-a) in advance is kneaded and mixed with various kneaders. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.

  Furthermore, the gloss of the acrylic resin film-like product (A′-a) of the present invention can be reduced by a known method as necessary. Specifically, a method of kneading inorganic fillers or crosslinkable polymer particles, a method of copolymerizing an epoxy group-containing monomer, a method of using a linear polymer having a hydroxyl group, a method of embossing, etc. Can be implemented. In addition, the acrylic resin film-like product (A′-a) according to the present invention may be colored.

  At this time, the thickness of the acrylic resin film (A) in the acrylic resin laminated film of the present invention is preferably 10 to 500 μm, more preferably 30 μm or more and 200 μm or less. In the case of 500 μm or less, the finally obtained acrylic resin laminated film has rigidity suitable for insert molding and in-mold molding, and when the acrylic resin film (A) is molded into a film, the film is stably formed. It is preferable because it can be manufactured. When the thickness is 10 μm or more, the protective property of the base material and a sense of depth can be imparted to the obtained laminated molded product, which is preferable.

  In addition, the thickness of the acrylic resin film (A′-a) in the acrylic resin laminated film of the present invention is preferably 1 to 30 μm, more preferably 3 μm or more and 20 μm or less. In the case of 30 μm or less, the surface hardness (abrasion resistance) and heat resistance of the acrylic resin laminated film of the present invention are improved, and when the laminated film is subjected to insert molding or in-mold molding, an acrylic resin film-like material ( A′-a) is preferable because a laminated molded product can be obtained without conspicuous cracking, breakage, peeling at the laminated portion, whitening, and the like, and without impairing the design. When the thickness is 1 μm or more, the acrylic resin film-like product (A′-a) has a uniform thickness while maintaining the effect of improving the surface hardness (scratch resistance) and heat resistance of the acrylic resin laminated film of the present invention. Is preferable. Moreover, in order to make a coating film having a sufficient thickness by painting on a molded product, it is necessary to perform recoating ten times or more, which is costly and extremely deteriorated in productivity. In the case of a molded article, the acrylic resin laminated film itself becomes a coating film, so that a very thick coating film can be easily formed, and the industrial utility value is high.

  On the surface layer side or back surface side of the acrylic resin laminated film using the acrylic resin film material (A) of the present invention as a base material and the acrylic resin film material (A′-a) having a pencil hardness of 2H or more as the surface layer. From the viewpoint of surface hardness (abrasion resistance) and heat resistance, an acrylic resin film (A′-a) having a pencil hardness of 2H or more may be laminated. Further, from the viewpoint of weather resistance and solvent resistance, a fluororesin film (A ″) may be laminated.

  Moreover, you may laminate | stack the acrylic resin film-like thing (A'-b) whose pencil hardness is F or less from a viewpoint of workability provision further to the base-material side of an acrylic resin laminated film. Thereby, since a three-dimensional shaped molded product can be obtained not only by vacuum molding such as insert molding or in-mold molding but also by other processing methods such as lapping processing, the industrial utility value is increased.

  Moreover, as an acrylic resin laminated film of the present invention, when another acrylic resin film (A ′) is used as a substrate and the acrylic resin film (A) is used as a surface layer, the acrylic resin film It is preferable to use an acrylic resin film (A′-b) having a lower surface hardness than (A), and specifically, an acrylic resin film having a pencil hardness (measured based on JIS K5400) of F or less ( A′-b) is preferably used. More preferably, it is HB or less, More preferably, it is 3B or less.

  Acrylic resin film (A'-b) having a pencil hardness of F or less as a base material and the acrylic resin film material (A) of the present invention as a surface layer is used as a base material. Compared to a resin (laminated) film, an acrylic resin laminated film having excellent surface whitening resistance and excellent surface hardness (abrasion resistance) and heat resistance can be obtained, which is preferable.

  Further, at this time, the acrylic resin film (A′-b) is formed by mixing a multilayer structure polymer having a specific structure alone or, if necessary, a thermoplastic resin containing a methacrylic acid alkyl ester as a main component. It is preferably formed from a resin composition.

  Specifically, the resin composition containing the following (iii) and (iv) is mentioned.

(Iii) Thermoplastic resin mainly composed of alkyl methacrylate ester:
(Iii-a) the general formula CH ₂ = CHX or a homopolymer of a vinyl monomer or vinylidene monomer having a CH ₂ = CXY, or thermoplastic resins comprising two or more of these monomers. In the general formula, X and Y may be the same or different, and are each H, Cl, F, Br, CH ₃ , COOH, COOCH ₃ , CN, OCOCH ₃ , C ₆ H ₅ , An O-lower alkyl group, COCH ₃ , SO ₃ H;

  (Iii-b) 50 to 100% by mass of a C 1-4 methacrylic acid alkyl ester, 0 to 50% by mass of an acrylic acid alkyl ester, and at least one of other copolymerizable vinyl monomers A thermoplastic resin comprising 50% by mass, having a glass transition temperature of less than 70 ° C. and a weight average molecular weight of 100,000 to 300,000.

(Iv) Multilayer structure polymer (rubber-containing polymer) having a specific structure:
(Iv-a) 80-100 mass% C1-C8 alkyl acrylate and / or C1-C4 methacrylic acid alkyl ester (iv-aa1), 0-20 mass% (iv-aa1) ) Monomer having another double bond copolymerizable with component (iv-aa2), 0 to 10% by mass of polyfunctional monomer (iv-aa3), (iv-aa1) to (iv-) The innermost layer polymer (iv-aa) comprising a composition of 0.1 to 5 parts by mass of a graft crossing agent with respect to 100 parts by mass of the total amount of aa3), 80 to 100% by mass of an acrylic having 1 to 8 carbon atoms Monomer having an acid alkyl ester and / or a C 1-4 methacrylic acid alkyl ester (iv-ab1) and another double bond copolymerizable with 0 to 20% by mass of (iv-ab1) component ( iv-ab2), 0-10 mass Cross-linking comprising a composition of 0.1 to 5 parts by mass of the grafting agent with respect to 100 parts by mass of the total amount of the polyfunctional monomers (iv-ab3) and (iv-ab1) to (iv-ab3) Elastic polymer (iv-ab), 51 to 100% by mass of C1-C4 methacrylic acid alkyl ester (iv-ac1), 0 to 49% by mass of a monomer having a copolymerizable double bond ( The outermost layer polymer (iv-ac) having a glass transition temperature of at least 60 ° C. having a composition of iv-ac2) is a basic structural unit, and the polymer (iv-ab) layer and the polymer (iv-ac) layer As an intermediate layer (iv-ad), 10 to 90% by mass of a C 1-8 alkyl acrylate ester (iv-ad1), 90 to 10% by mass of a C 1-4 alkyl methacrylate (iv) -Ad2), 0-20 mass Other monomer (iv-ad3) having a double bond copolymerizable with the components (iv-ad1) and (iv-ad2), 0 to 10% by mass of a polyfunctional monomer (iv-ad4) ) And (iv-ad1) to (iv-ad4), a multilayer polymer comprising a composition of 0.1 to 5 parts by mass of the grafting agent with respect to 100 parts by mass.

  (Iv-b) 50 to 99.9% by mass of alkyl acrylate ester, 0 to 49.9% by mass of other copolymerizable vinyl monomers, and 0.1 to 0.1% of copolymerizable crosslinkable monomer In the presence of 100 parts by mass of an elastic copolymer consisting of 10% by mass, a monomer comprising 40-100% by mass of a methacrylic acid alkyl ester and 0-60% by mass of a vinyl monomer copolymerizable therewith, Alternatively, a multilayer structure polymer obtained by polymerizing 10 to 400 parts by mass of the mixture.

Specifically, the following resin composition is mentioned, for example.
○ Resin composition for acrylic resin film described in JP-B-63-8983:
A resin composition comprising 1 to 99 parts by mass of a thermoplastic resin (iii-a) and 1 to 99 parts by mass of a rubber-containing polymer (iv-a).
O Resin composition for acrylic resin film described in JP-A-11-80487:
A resin composition comprising 5 to 30 parts by mass of a thermoplastic resin (iii-b) and 75 to 95 parts by mass of a rubber-containing polymer (iv-b).

More specifically, the following resin composition is mentioned, for example.
○ Resin composition for acrylic resin film described in JP-B-63-8983:
A resin composition comprising 1 to 99 parts by mass of a thermoplastic resin (iii-a) and 1 to 99 parts by mass of a rubber-containing polymer (iv-a).
O Resin composition for acrylic resin film described in JP-A-11-80487:
A resin composition comprising 5 to 30 parts by mass of a thermoplastic resin (iii-b) and 75 to 95 parts by mass of a rubber-containing polymer (iv-b).

  The acrylic resin film-like product (A′-b) used in the present invention, if necessary, is a general compounding agent such as a stabilizer, a lubricant, a processing aid, a plasticizer, an impact resistance agent, a foaming agent, Fillers, antibacterial agents, antifungal agents, mold release agents, antistatic agents, colorants, matting agents, ultraviolet absorbers, light stabilizers, and the like can be included.

  As a method of adding the compounding agent, a method of supplying the raw material for the acrylic resin film (A′-b) together with the raw material for the acrylic resin film (A′-b) to the extruder for forming the acrylic resin film (A′-b) of the present invention, There is a method in which a mixture in which a compounding agent is added to a raw material for an acrylic resin film (A′-b) in advance is kneaded and mixed with various kneaders. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.

  Furthermore, the gloss of the acrylic resin film-like product (A′-b) of the present invention can be reduced by a known method as necessary. Specifically, a method of kneading inorganic fillers or crosslinkable polymer particles, a method of copolymerizing an epoxy group-containing monomer, a method of using a linear polymer having a hydroxyl group, a method of embossing, etc. Can be implemented. In addition, the acrylic resin film-like product (A′-b) according to the present invention may be colored.

  At this time, the thickness of the acrylic resin film (A′-b) in the acrylic resin laminated film of the present invention is preferably 10 to 500 μm, more preferably 30 μm or more and 200 μm or less. When the thickness is 500 μm or less, the finally obtained acrylic resin laminated film has rigidity suitable for insert molding and in-mold molding, and the film is stably formed when the acrylic resin film (A) is previously formed into a film shape. Is preferable because it can be manufactured. When the thickness is 10 μm or more, the protective property of the base material and a sense of depth can be imparted to the obtained laminated molded product, which is preferable.

  Moreover, 1-30 micrometers is preferable, as for the thickness of the acrylic resin film-like material (A) in the acrylic resin laminated film of this invention, More preferably, it is 3 micrometers or more and 20 micrometers or less. When the thickness is 30 μm or less, the surface hardness (scratch resistance) and heat resistance of the acrylic resin laminated film of the present invention are improved, and when the laminated film is subjected to insert molding or in-mold molding, molding whitening does not occur. Since a molded product can be obtained, it is preferable. Moreover, in the case of 1 micrometer or more, while maintaining the effect of improving the surface hardness (abrasion resistance) and heat resistance of the acrylic resin laminated film of the present invention, an acrylic resin film (A) is obtained with a uniform film thickness. Is preferable. In order to make a coating film of sufficient thickness by painting on a molded product, it is necessary to apply several times over, which is costly and extremely deteriorated in productivity, whereas the laminated molded product of the present invention Then, since the acrylic resin laminated film itself becomes a coating film, a very thick coating film can be easily formed, and industrial utility value is high.

  Surface hardness (scratch resistance) on the surface layer side of the acrylic resin laminated film using the acrylic resin film material (A′-b) as a base material and the acrylic resin film material (A) of the present invention as a surface layer, From the viewpoint of heat resistance, an acrylic resin film (A′-a) layer having a pencil hardness of 2H or more may be laminated. Further, from the viewpoint of weather resistance and solvent resistance, a fluororesin film (A ″) may be laminated.

  Further, as the acrylic resin laminated film of the present invention, the acrylic resin film material (A) can be used as a base material and the fluororesin film material (A ″) can be used as a skin material.

  The kind of the fluororesin constituting the fluororesin film (A ″) is not particularly limited, and a known fluororesin can be used. Specifically, a vinylidene fluoride polymer, a copolymer of vinylidene fluoride and a fluorine compound such as vinyl fluoride or tetrafluoroethylene, or an acrylic monomer such as an alkyl acrylate ester or an alkyl methacrylate ester, Or the resin composition which has a vinylidene fluoride polymer as a main component is mentioned.

  At this time, the position where the fluororesin film-like product (A ″) is provided is not particularly limited, but from the viewpoint of the weather resistance and solvent resistance of the acrylic resin laminated film, the fluororesin film-like product (A ″) is It is preferable to provide the acrylic resin film-like product (A) in the upper layer (that is, the fluororesin film-like product (A ″) as the outermost layer).

  The fluororesin film-like product (A ″) used in the present invention may be prepared by adding a general compounding agent such as a stabilizer, a lubricant, a processing aid, a plasticizer, an impact resistance agent, a foaming agent, and a filler as necessary. Agents, antibacterial agents, antifungal agents, mold release agents, antistatic agents, colorants, matting agents, ultraviolet absorbers, light stabilizers and the like.

  In particular, it is preferable to add an ultraviolet absorber in order to provide weather resistance in terms of protecting the base material, color pattern such as printing, and coloring agent. The molecular weight of the ultraviolet absorber used is preferably 300 or more, more preferably 400 or more. When an ultraviolet absorbent having a molecular weight of 300 or more is used, mold contamination due to volatilization of the ultraviolet absorbent when performing vacuum molding or pressure molding in an injection mold can be prevented. In general, a UV absorber having a higher molecular weight is less prone to long-term bleed out after being processed into an acrylic resin laminated film state, and its UV absorption performance lasts longer than that having a lower molecular weight.

  Furthermore, when the molecular weight of the ultraviolet absorber is 300 or more, when the fluororesin film (A ″) is formed into a film, the film is extruded from the T-die and cooled by the cooling roll. The amount of volatilization of the UV absorber is small. Therefore, since the amount of the remaining ultraviolet absorber is sufficient, good performance is exhibited. In addition, the volatilized UV absorber recrystallizes on the chain that suspends the T die at the top of the T die and the exhaust hood and grows over time. This eventually falls on the film and becomes a defect in appearance. This also reduces the problem.

  Although the kind of ultraviolet absorber is not particularly limited, a benzotriazole type having a molecular weight of 400 or more or a triazine type having a molecular weight of 400 or more can be particularly preferably used. Specific examples of the former include a trade name of Ciba Specialty Chemicals Co., Ltd .: Tinuvin 234, a trade name of Asahi Denka Kogyo Co., Ltd .: Adeka Stub LA-31, and a specific example of the latter includes a trade name of Ciba Specialty Chemicals Co., Ltd. 1577 etc. are mentioned.

  As a method for adding the compounding agent, there are a method of supplying the raw material together with the raw material for the fluororesin film (A ″) to the extruder for forming the fluororesin film (A ″) of the present invention, There is a method in which a mixture obtained by adding a compounding agent to a raw material for a resin film (A ″) is kneaded and mixed with various kneaders. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.

  Furthermore, the gloss of the fluororesin film-like product (A ″) of the present invention can be reduced by a known method as necessary. Specifically, a method of kneading inorganic fillers or crosslinkable polymer particles, a method of copolymerizing an epoxy group-containing monomer, a method of using a linear polymer having a hydroxyl group, a method of embossing, etc. Can be implemented. In addition, the fluororesin film-like product (A ″) according to the present invention may be colored.

  At this time, the thickness of the acrylic resin film (A) in the acrylic resin laminated film of the present invention is preferably 10 to 500 μm, more preferably 30 μm or more and 200 μm or less. When the thickness is 500 μm or less, the finally obtained acrylic resin laminated film has rigidity suitable for insert molding and in-mold molding, and stably manufactures a film when the acrylic resin film material (A) is previously formed into a film shape. This is preferable. When the thickness is 10 μm or more, the protective property of the base material and a sense of depth can be imparted to the obtained laminated molded product, which is preferable.

  The thickness of the fluororesin film (A ″) in the acrylic resin laminated film of the present invention is preferably 1 to 30 μm, more preferably 3 μm or more and 20 μm or less. In the case of 30 μm or less, the weather resistance does not increase significantly when the acrylic resin laminated film of the present invention is produced, and the surface hardness and scratch resistance of the resulting acrylic resin laminated film are not lowered. , And solvent resistance can be imparted. Moreover, when it is 1 μm or more, the fluororesin film-like product (A ″) can be obtained with a uniform film thickness while maintaining the effect of improving the weather resistance and solvent resistance of the acrylic resin laminated film of the present invention. Therefore, it is preferable. In order to make a coating film of sufficient thickness by painting on a molded product, it is necessary to apply several times over, which is costly and extremely deteriorated in productivity, whereas the laminated molded product of the present invention Then, since the acrylic resin laminated film itself becomes a coating film, a very thick coating film can be easily formed, and industrial utility value is high.

  In general, the surface hardness of the fluororesin film (A ″) is equal to or lower than that of the acrylic resin film (A). However, since the slidability is good, the scratch resistance of the acrylic resin laminated film having the fluororesin film (A ″) on the surface is relatively good.

  As a method for forming the acrylic resin laminated film of the present invention, (1) acrylic resin film (A) and other acrylic resin film (A ′) or fluororesin film (A ″) in advance. (2) Acrylic resin film (A) that has been previously molded with another acrylic resin film (A ′) or fluororesin film (A ″). (3) Another acrylic resin film (A ′) or fluororesin film (A ′) that has been previously molded with the acrylic resin film (A). (4) Acrylic resin film (A) and other acrylic resin film (A ') or fluororesin film Lum-like material (A ''), a method of laminating city melt extruded while simultaneously, and the like.

  As a manufacturing method when the acrylic resin film material (A), the other acrylic resin film material (A ′), and the fluororesin film material (A ″) are previously formed into a film shape, a melt casting method is used. And known molding methods such as a melt extrusion method such as a T-die method and an inflation method, and a calendar method. In addition, when forming into a film, the T-die method is preferable from the point of economical efficiency.

  As a method of laminating the acrylic resin film (A) and the other acrylic resin film (A ′) or the fluororesin film (A ″) in advance, the above-mentioned (1) acrylic resin film (A) is laminated with acrylic. Lamination such as a method of laminating resin film (A) and other acrylic resin film (A ') or fluororesin film (A' ') by dry lamination, wet lamination, hot melt lamination, etc. There are methods. If heat fusion is possible, lamination can be performed by a hot press laminating method.

  In addition, when an acrylic resin film material (A), another acrylic resin film material (A ′), or a fluororesin film material (A ″) is formed in advance, a metal roll, a non-metal roll, and a metal belt It is preferable to form a film by sandwiching it between a plurality of rolls or belts selected from the following.

  While the above-mentioned (2) other acrylic resin film (A ′) or fluororesin film (A ″) has been previously molded, the acrylic resin film (A) is melt extruded. As a method of laminating at the same time, the acrylic resin film material (A) is placed on another acrylic resin film material (A ′) or fluororesin film material (A ″) that has been molded in advance using a T-die or the like. Examples thereof include extrusion laminating and the like which are laminated while being melt extruded into a film.

  In addition, when other acrylic resin film material (A ′) or fluororesin film material (A ″) is formed in advance, a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts are used. It is preferable to form a film by sandwiching it.

  While the above-mentioned (3) Acrylic resin film (A) has been previously molded, other acrylic resin film (A ′) or fluororesin film (A ″) is melt extruded. As a method of laminating at the same time, another acrylic resin film (A ′) or fluororesin film (A ″) is added to a previously molded acrylic resin film (A) with a T-die or the like. Examples thereof include extrusion laminating and the like which are laminated while being melt extruded into a film.

  In addition, when shape | molding an acrylic resin film-form thing (A) previously, it is preferable to form into a film by pinching | interposing to the some roll or belt chosen from a metal roll, a nonmetallic roll, and a metal belt.

  As a method of simultaneously laminating the above-mentioned (4) acrylic resin film material (A) and other acrylic resin film material (A ′) or fluororesin film material (A ″) while melt extrusion. And a lamination method by coextrusion molding such as a method of adhering before a die such as a feed block method, a method of adhering inside a die such as a multi-manifold method, and a method of adhering outside the die such as a multi-slot method.

  Among these, although not particularly limited, from the viewpoint that the production process of the acrylic resin laminated film can be reduced, the above-mentioned (4) acrylic resin film (A) and other acrylic resin film (A The method of laminating | stacking ') or a fluororesin film-like thing (A' ') simultaneously with melt extrusion is preferable.

  In addition, when laminating an acrylic resin laminated film by the T-die method, an acrylic resin laminated film obtained by using a method in which a film is formed by being sandwiched between a plurality of rolls or belts selected from metal rolls, non-metal rolls, and metal belts. The surface smoothness of the film can be improved, and printing omission when printing processing is performed on the acrylic resin laminated film can be suppressed.

  In addition, as a metal roll, it is a metal mirror surface touch roll; a roll used in a sleeve touch system comprising a metal sleeve (metal thin-film pipe) and a molding roll described in Japanese Patent No. 2808251 or WO97 / 28950. Etc. can be illustrated. Moreover, as a nonmetallic roll, touch rolls, such as silicone rubber property, etc. can be illustrated. Furthermore, examples of the metal belt include a metal endless belt. A plurality of these metal rolls, non-metal rolls and metal belts can be used in combination.

  In the above-described method for forming a film by sandwiching a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts, the acrylic resin composition after melt extrusion is substantially made into a bank (resin reservoir). It is preferable to form a film by holding the film in a state where there is no) and transferring the surface without substantially rolling. When the film is formed without forming a bank (resin pool), the acrylic resin composition in the cooling process is surface-transferred without rolling, so the heat shrinkage rate of the acrylic resin laminated film formed by this method Can also be reduced.

<Photocurable acrylic resin film or sheet>
The photocurable acrylic resin film or sheet of the present invention comprises an acrylic resin film-like product (A) of the present invention or an acrylic resin laminated film of the present invention, and a thermoplastic resin (z -1) and a photocurable resin composition (Z) layer containing a photopolymerization initiator (z-2).

  Said photocurable resin composition (Z) contains the thermoplastic resin (z-1) which has a radically polymerizable unsaturated group in a side chain, and a photoinitiator (z-2), thermoplastic resin (z It is preferable that it is substantially free of crosslinkable compounds other than -1). In this invention, a photocurable acrylic resin film or sheet can be obtained by laminating the layer of this photocurable resin composition (Z) on the acrylic resin film (A) or the acrylic resin laminated film. it can. The photocurable resin composition (Z) in the present invention is remarkably good because a cross-linking reaction proceeds between polymer side chains by introducing a structure having a radically polymerizable unsaturated group in the polymer side chain in this way. Photo-curing acrylic resin film that has excellent wear resistance and scratch resistance, and that does not need to contain a low molecular weight crosslinkable compound having a reactive vinyl group, and therefore has no surface tackiness and excellent storage stability. Or it has the advantage that a sheet is obtained.

  Examples of the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain include a radically polymerizable unsaturated group in the polymer having a glass transition temperature of 25 to 175 ° C., preferably 30 to 150 ° C. The thing which has is mentioned. Specifically, a polymer obtained by polymerizing or copolymerizing the following compounds (1) to (7) as a polymer and introducing a radical polymerizable unsaturated group by the methods (a) to (f) described later. Can be used. “(Meth) acrylate” represents acrylate or methacrylate, “(meth) acrylic acid” represents acrylic acid or methacrylic acid, “(meth) acrylamide” represents acrylamide or methacrylamide, and “( “(Meth) acryloyloxy” represents acryloyloxy or methacryloyloxy.

(1) Monomer having a hydroxyl group: N-methylolacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (2) Monomers having a carboxyl group: (meth) acrylic acid, acryloyloxyethyl monosuccinate, etc. (3) Monomers having an epoxy group: glycidyl (meth) acrylate, 3,4- Epoxycyclohexylmethyl (meth) acrylate, etc. (4) Monomers having an aziridinyl group: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate, etc. (5) Monomers having an amino group: (Meth) acrylamide, diacetone acrylamide Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. (6) Monomer having a sulfone group: 2-acrylamido-2-methylpropanesulfonic acid, etc. (7) Monomer having an isocyanate group: 2, Adducts of radically polymerizable monomers having diisocyanate and active hydrogen, such as equimolar adducts of 4-toluene diisocyanate and 2-hydroxyethyl acrylate, 2-isocyanate ethyl (meth) acrylate, and the like.

  Furthermore, in order to adjust the glass transition temperature of the polymer or copolymer of the above compound or to harmonize the physical properties of the photocurable film or sheet, it is possible to co-polymerize with a monomer copolymerizable with the above compound. It can also be polymerized. Examples of such copolymerizable monomers include (meth) acrylates such as methyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and isobornyl (meth) acrylate, N-phenylmaleimide, and cyclohexylmaleimide. And imide derivatives such as N-butylmaleimide, olefinic monomers such as butadiene, and aromatic vinyl compounds such as styrene and α-methylstyrene.

  A radically polymerizable unsaturated group can be introduced into the above-described polymer or copolymer by the methods (i) to (d) described below.

  (A) In the case of the polymer or copolymer of the monomer (1) having a hydroxyl group, the monomer (2) having a carboxyl group such as (meth) acrylic acid is subjected to a condensation reaction.

  (B) In the case of a polymer or copolymer of the monomer (2) having a carboxyl group and the monomer (6) having a sulfone group, the monomer (1) having a hydroxyl group described above is condensed. React.

  (C) In the case of the polymer or copolymer of the monomer (3) having an epoxy group, the monomer (7) having an isocyanate group, or the monomer (4) having an aziridinyl group, The monomer (1) having a hydroxyl group or the monomer (2) having a carboxyl group is subjected to an addition reaction.

  (D) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, the monomer (3) having an epoxy group, the monomer (4) having an aziridinyl group, or an isocyanate group Addition monomer (7), or an equimolar adduct of a diisocyanate compound and a hydroxyl group-containing acrylate monomer is subjected to an addition reaction.

  (E) In the case of the polymer or copolymer of the monomer (5) having an amino group, the monomer (2) having the carboxyl group described above is subjected to a condensation reaction.

  (F) In the case of a polymer or copolymer of the monomer (5) having an amino group, the above-mentioned monomer (3) having an epoxy group or a monomer having an acetoacetoxy group is subjected to an addition reaction. Let

  The above reaction is preferably carried out while adding a small amount of a polymerization inhibitor such as hydroquinone and sending dry air.

  The amount of the radically polymerizable unsaturated group in the side chain of the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain is the double bond equivalent (per one side chain radically polymerizable unsaturated group). The average molecular weight) is preferably an average of 3000 g / mol or less as calculated from the charged value from the viewpoint of improving scratch resistance and wear resistance. A more preferable range of double bond equivalent is an average of 1200 g / mol or less, and a more preferable range is an average of 800 g / mol or less.

  In this way, by introducing a plurality of radically polymerizable unsaturated groups involved in crosslinking into the thermoplastic resin, it is not necessary to use a low molecular weight crosslinking compound, and at the time of long-term storage and thermoforming described later. Moreover, it becomes possible to improve hardened | cured material property efficiently, without having surface adhesiveness.

  The number average molecular weight of the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain is preferably in the range of 5,000 to 2,500,000, and in the range of 10,000 to 1,000,000. Is more preferable. Insert or in-mold molding a photocurable acrylic resin film or sheet formed using a photocurable resin composition (Z) containing a thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain. At this time, the number average molecular weight is preferably 5,000 or more from the viewpoint of improving mold releasability and improving the surface hardness of the insert or in-mold molded product after photocuring. On the other hand, the number average molecular weight is preferably 2,500,000 or less from the viewpoint of ease of synthesis and appearance, and from the viewpoint of developing adhesiveness with the acrylic resin film-like product (A).

  The thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain preferably has a glass transition temperature adjusted to 25 to 175 ° C, and preferably adjusted to 30 to 150 ° C. Further preferred. From the point that the mold releasability of the photocurable acrylic resin film or sheet at the time of insert or in-mold molding is improved and the surface hardness of the insert or in-mold molded product after photo-curing is improved, the glass transition temperature is It is preferable that it is 25 degreeC or more. On the other hand, it is preferable that a glass transition temperature is 175 degrees C or less from a viewpoint of the handleability of a photocurable acrylic resin film or sheet.

  Further, in consideration of the glass transition temperature of the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the obtained side chain, a vinyl polymerizable monomer that has a high glass transition temperature as a homopolymer is used. It is preferable to use it. Furthermore, from the viewpoint of improving the weather resistance of the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain, an acrylic resin using (meth) acrylates as a main component as a vinyl polymerizable monomer. It is preferable to use a resin. As will be described later, when the inorganic fine particles (a-3) are added to the photocurable resin composition (Z) of the present invention, the functional groups (hydroxyl groups, carboxyls) on the surface of the inorganic fine particles (a-3) Group, silanol group, etc.), a vinyl polymerizable monomer having in its molecule at least one functional group selected from the group consisting of hydroxyl group, carboxyl group, halogenated silyl group and alkoxysilyl group. The monomer acts to further improve the physical properties such as rigidity, toughness, heat resistance, etc. of the resulting photocurable resin composition, so that such a functional group can be used as a part of a vinyl polymerizable monomer component capable of radical polymerization. It may be contained.

  Examples of vinyl polymerizable monomers containing such reactive groups in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, vinyltrichlorosilane, Examples include vinyltrimethoxysilane and γ- (meth) acryloyloxypropyltrimethoxysilane.

  As a photoinitiator (z-2) used by this invention, the photoradical polymerization initiator which generates a radical by light irradiation is mentioned.

  As the radical photopolymerization initiator, known compounds can be used, and are not particularly limited, but considering yellowing during curing and deterioration during weathering, such as acetophenone-based, benzophenone-based, acylphosphine oxide-based An initiator containing no amino group in the molecule is preferable. For example, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Phosphine oxide is preferred. Among these, depending on the molding method, the temperature may be temporarily higher than the boiling point of the compound, and therefore may be appropriately selected according to the molding method. In order to increase the surface hardness of the molded product, an additive such as n-methyldiethanolamine that suppresses polymerization hardening inhibition by oxygen may be added. In addition to these photopolymerization initiators, various peroxides may be added in consideration of curing using heat during molding. When a peroxide is contained in a photocurable acrylic resin film or sheet, it is necessary to cure at 150 ° C. for about 30 seconds. Therefore, a peroxide having a low critical temperature, such as lauroyl peroxide, t-butyl, etc. Peroxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like are preferably used.

  The amount of the radical photopolymerization initiator added is preferably 5% by mass or less based on the compound having a radically polymerizable unsaturated group in the side chain, since the residual amount after curing affects the weather resistance. The amount of amino radical photoinitiator related to alteration is preferably 1% by mass or less.

  Inorganic fine particles (a-3) can be added to the photocurable resin composition (Z) of the present invention for the purpose of further improving scratch resistance and abrasion resistance. In the inorganic fine particles (a-3) used in the present invention, the type, particle diameter, and form are not particularly limited as long as the obtained photocurable resin composition becomes transparent. Examples of the inorganic fine particles include colloidal silica, alumina, titanium oxide, and the like. These may be used alone or in combination of two or more. Of these, colloidal silica is particularly preferable from the viewpoints of availability, price, transparency of the resulting photocurable resin composition layer, and expression of wear resistance.

  Colloidal silica can be used in the form of a normal aqueous dispersion or in a form dispersed in an organic solvent, but with a thermoplastic resin having a radically polymerizable unsaturated group in the side chain as component (z-1). In order to disperse uniformly and stably, it is preferable to use colloidal silica dispersed in an organic solvent.

  Examples of such organic solvents include methanol, isopropyl alcohol, n-butanol, ethylene glycol, xylene / butanol, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, toluene and the like. Especially, in order to disperse | distribute uniformly with a thermoplastic resin, it is preferable to select the organic solvent which can melt | dissolve the thermoplastic resin (z-1) which has a radically polymerizable unsaturated group in a side chain. Further, as will be described later, when producing the photocurable acrylic resin film or sheet of the present invention, these organic solvents are dried by heating and volatilized, and thus are the main constituents of the acrylic resin film (A). An organic solvent having a boiling point not higher than the glass transition temperature of the resin component by 80 ° C. or more, preferably not higher by 30 ° C. or less is preferable because it hardly remains in the photocurable acrylic resin film or sheet.

  Colloidal silica in a form dispersed in an organic solvent includes commercially available products dispersed in a dispersion medium, such as methanol silica sol MA-ST, isopropyl alcohol silica sol IPA-ST, n-butanol silica sol NBA-ST, ethylene glycol silica sol EG. -ST, xylene / butanol silica sol XBA-ST, ethyl cellosolve silica sol ETC-ST, butyl cellosolve silica sol BTC-ST, dimethylformamide silica sol DBF-ST, dimethylacetamide silica sol DMAC-ST, methyl ethyl ketone silica sol MEK-ST, methyl isobutyl ketone silica sol MIBK- ST (trade name, manufactured by Nissan Chemical Co., Ltd.) or the like can be used.

  The particle diameter of the inorganic fine particles (a-3) is usually 200 nm or less from the viewpoint of the transparency of the resulting photocurable resin composition layer. More preferably, it is 100 nm or less, More preferably, it is 50 nm or less.

  The added amount of the inorganic fine particles (a-3) is 5 to 400 mass in terms of solid content of the inorganic fine particles with respect to 100 mass parts of the solid content of the thermoplastic resin (z-1) having a radical polymerizable unsaturated group in the side chain. The range of parts is preferable, and the range of 10 to 200 parts by weight is particularly preferable. When the addition amount of the inorganic fine particles is less than 5 parts by mass, the effect of improving the abrasion resistance may not be recognized. When the addition amount exceeds 400 parts by mass, the photocurable resin composition (Z ), The moldability of the resulting photocurable acrylic resin film or sheet may be reduced.

  Moreover, as an inorganic fine particle (a-3) used by this invention, you may use what the surface was previously processed with the silane compound represented by the following structural formula (a3-1). Use of the surface-treated inorganic fine particles further improves the storage stability of the photocurable resin composition (Z), and also improves the surface hardness and weather resistance of the resulting photocurable acrylic resin film or sheet. preferable.

SiR ¹ _a R ² _b (OR ³ ) _c (a3-1)
(In the above formula, R ¹ and R ² each represent a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond, an ester bond, an epoxy bond or a carbon-carbon double bond; ³ represents a hydrogen atom or an ether bond, an ester bond, an epoxy bond or a carbon residue having 1 to 10 carbon atoms which may have a carbon-carbon double bond, and a and b are 0 to 3 respectively. And c is an integer of 1 to 4 that satisfies 4-ab.
Among the silane compounds represented by the structural formula (a3-1), silane compounds represented by the following structural formulas (a3-2) to (a3-7) can be given as preferable examples.

SiR ⁴ _a R ⁵ _b (OR ⁶ ) _c (a3-2)
SiR ⁴ _n (OCH ₂ CH ₂ OCO (R ⁷ ) C═CH ₂ ) _4-n (a3-3)
^{_{CH 2 = C (R 7)}} COO (CH 2) p SiR 8 n (OR 6) 3-n (a3-4)
CH ₂ = CHSiR ⁸ _n (OR ⁶ ) _3-n (a3-5)
HS (CH ₂ ) _p SiR ⁸ _n (OR ⁶ ) _3-n (a3-6)

(In the above formula, R ⁴ and R ⁵ each represent a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond, an ester bond or an epoxy bond, and R ⁶ represents a hydrogen atom or a carbon number. Represents a hydrocarbon residue having 1 to 10, R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and a and b each represent 0 to 3 C is an integer of 1 to 4 satisfying 4-ab, n is an integer of 0 to 2, and p is an integer of 1 to 6)
Examples of the silane compound represented by the structural formula (a3-2) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, trimethylethoxysilane, methoxyethyltriethoxysilane, acetoxyethyltriethoxysilane, Diethoxyethyldimethoxysilane, tetraacetoxysilane, methyltriacetoxysilane, tetrakis (2-methoxyethoxy) silane, γ-glycidoxy Trimethoxysilane, .gamma.-glycidoxypropylmethyldiethoxysilane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  Examples of the silane compound represented by the structural formula (a3-3) include tetrakis (acryloyloxyethoxy) silane, tetrakis (methacryloyloxyethoxy) silane, methyltris (acryloyloxyethoxy) silane, and methyltris (methacryloyloxyethoxy) silane. Etc.

  Examples of the silane compound represented by the structural formula (a3-4) include β-acryloyloxyethyldimethoxymethylsilane, γ-acryloyloxypropylmethoxydimethylsilane, γ-acryloyloxypropyltrimethoxysilane, and β-methacryloyloxy. Examples include ethyldimethoxymethylsilane and γ-methacryloyloxypropyltrimethoxysilane.

  Examples of the silane compound represented by the structural formula (a3-5) include vinylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

  Examples of the silane compound represented by the structural formula (a3-6) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, and the like.

  Examples of the silane compound represented by the structural formula (a3-7) include p-vinylphenylmethyldimethoxysilane and p-vinylphenyltrimethoxysilane.

Such a silane compound is preferably used in a proportion of 0 to 3 mole parts relative to 1 mole part of the solid content of the inorganic fine particles (a-3). When the usage-amount of a silane compound exceeds 3 mol part, the abrasion resistance of the photocurable acrylic resin film or sheet obtained may fall. Here, the molar part is a value obtained by dividing the mass part of the inorganic fine particles or the silane compound by the molecular weight. For example, 100 parts by mass of solid content of colloidal silica (SiO ₂ ), which is an inorganic fine particle, corresponds to 100 ÷ 60 = 1.666 mol part.

  The inorganic fine particles surface-treated with the silane compound can be obtained by using a commercially available product or by surface-treating the inorganic fine particles by a known method. As a known surface treatment method, for example, the treatment can be performed by heating and stirring the silane compound and the inorganic fine particles in the presence of a small amount of water.

  As a method of adding the inorganic fine particles (a-3) to the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain, a thermoplastic resin having a radically polymerizable unsaturated group in the side chain in advance. After synthesizing (z-1), inorganic fine particles may be mixed, and the vinyl polymerizable monomer and inorganic constituting the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain. Any method such as a method of polymerizing under a condition in which fine particles are mixed can be selected.

  In the photocurable resin composition (Z) used in the present invention, a thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain of essential components and a photopolymerization initiator (z-2), Furthermore, in addition to the above-mentioned inorganic fine particles (a-3) that can be used as necessary, sensitizers, modifying resins, dyes, pigments, leveling agents, anti-repelling agents, and ultraviolet absorbers as necessary. Additives such as light stabilizers and oxidation stabilizers can be blended.

  The above sensitizer accelerates the photocuring reaction, and examples thereof include benzophenone, benzoin isopropyl ether, and thioxanthone.

  However, the photocurable resin composition (Z) should not contain substantially any crosslinkable compound other than the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain. In particular, liquid crosslinkable monomers and oligomers at 40 ° C. and low molecular weight crosslinkable monomers and oligomers having a molecular weight of 2000 or less should not be substantially contained. In particular, when it contains a liquid crosslinkable monomer / oligomer at 40 ° C. or a low molecular weight crosslinkable monomer / oligomer having a molecular weight of 2000 or less, it will have surface tackiness during long-term storage or thermoforming, and printing. In some cases, problems may occur in the process, or the mold may be contaminated during insert molding or in-mold molding. More preferably, it should substantially not contain a liquid crosslinkable monomer or oligomer at 50 ° C., and more preferably it should substantially not contain a liquid crosslinkable monomer or oligomer at 60 ° C.

  In the present invention, since the photocurable resin composition (Z) as described above is used, the photocurable resin composition is laminated on the acrylic resin film (A) or the acrylic resin laminated film and photocured. Even when the acrylic resin film or sheet is formed, the surface of the photocurable acrylic resin film or sheet is not tacky, and the phenomenon that the tackiness of the surface changes with time does not occur. Storage stability is improved.

  Since the photocurable acrylic resin film or sheet of the present invention has the above-described configuration, it has excellent moldability and storage stability before photocuring, and excellent surface properties (hardness, weather resistance, etc.) after photocuring. ) Is a photocurable acrylic resin film or sheet that is compatible with high dimensions. As will be described later, the photocurable acrylic resin film or sheet of the present invention is usually an acrylic resin prepared by mixing and dissolving a photocurable resin composition (Z) in a solvent such as an organic solvent by various coating methods. After coating on the film-like product (A) or acrylic resin laminated film, it is manufactured by heating and drying for removing the solvent. At this time, if a large amount of the solvent remains in the photocurable acrylic resin film or sheet, the surface of the photocurable resin composition (Z) layer before light irradiation comes to have adhesiveness in the printing process. Problems such as a decrease in yield, a decrease in storage stability in a roll state, and a decrease in mold contamination during insert molding or in-mold molding occur. In addition, even if an insert molded product or an in-mold molded product obtained by insert molding or in-mold molding a photocurable acrylic resin film or sheet is photocured, the scratch resistance, chemical resistance, weather resistance, etc. Surface properties may be inferior. In order to solve such a problem, it is preferable to reduce the amount of the solvent in the photocurable acrylic resin film or sheet as much as possible.

  As a manufacturing method of the photocurable acrylic resin film or sheet of the present invention having an acrylic resin film-like product (A) or an acrylic resin laminated film and a photocurable resin composition (Z) layer, for example, side chains of essential components A photocurable resin composition (Z) containing a thermoplastic resin (z-1) having a radically polymerizable unsaturated group, a photopolymerization initiator (z-2), and inorganic fine particles (a-3) as necessary. Is sufficiently stirred and dissolved in a solvent such as an organic solvent, and known printing methods such as a gravure printing method, a screen printing method, an offset printing method, a flow coating method, a spray coating method, a bar coating method, a gravure coating method, and a roll coating. Method, blade coating method, rod coating method, roll doctor coating method, air knife coating method, comma roll coating method, reverse roll coating method, transfer roll coating method Coating on the acrylic resin film (A) by a known coating method such as a coating method, kiss roll coating method, curtain coating method, dipping coating method, etc., and heat drying for solvent removal to form a laminated film or sheet. There is a way. An organic solvent having a boiling point that is not higher than the glass transition temperature by 80 ° C. or more, preferably not higher than 30 ° C. is preferably not likely to remain in the photocurable acrylic resin film or sheet.

  As a solvent for stirring and dissolving the photocurable resin composition (Z), each component of the photocurable resin composition (Z) is dissolved or uniformly dispersed, and the acrylic resin film (A) or the acrylic resin laminate The physical properties (mechanical strength, transparency, etc.) of the film are not adversely affected in practice, and the glass transition temperature of the resin component that is the main constituent of the acrylic resin film (A) or acrylic resin laminated film A volatile solvent having a boiling point not higher than 80 ° C., preferably not higher than 30 ° C. is preferable. Examples of such solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and ethylene glycol; aromatic solvents such as xylene, toluene and benzene; aliphatic hydrocarbon solvents such as hexane and pentane; Halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride; phenol solvents such as phenol and cresol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and acetone; diethyl ether, methoxytoluene, 1,2-dimethoxyethane, 1 Ether solvents such as 1,2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane, THF; fatty acid solvents such as formic acid, acetic acid, propionic acid; acetic anhydride, etc. Acid anhydride solvents; ethyl acetate, butyl acetate, Ester solvents such as butyl acid; nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide and dimethylacetamide; sulfur-containing solvents such as thiophene and dimethyl sulfoxide; diacetone alcohol, 2-methoxyethanol (methylcellosolve), 2-ethoxy Solvents having two or more functional groups such as ethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, morpholine; or various known solvents such as water are used. be able to.

  A photocurable acrylic resin film or sheet is produced in a shorter time for the purpose of eliminating the above-described problems caused by the residual solvent in the photocurable acrylic resin film or sheet and improving production efficiency at a low cost. In order to achieve this, it is necessary to enhance the heat drying conditions for removing the solvent and perform the drying sufficiently. However, at this time, if the photocurable acrylic resin film or sheet is continuously heated and dried for 20 seconds or more at a temperature equal to or higher than the thermal deformation temperature of the acrylic resin film (A) or the acrylic resin laminated film, photocurability is obtained. The acrylic resin film or sheet is stretched even with a slight tension, and not only the photocurable resin composition (Z) layer, the acrylic resin film-like material (A) or the acrylic resin laminated film becomes thin, but also after photocuring. The photo-curing resin composition (Z) may have a scratch resistance, a decrease in surface hardness, and the like.

  The heat-drying conditions of the photocurable acrylic resin film or sheet may be heat-dried at a temperature not exceeding the thermal deformation temperature of the acrylic resin film (A) or the acrylic resin laminated film, or the acrylic resin film ( When drying at a temperature higher than the thermal deformation temperature of A) or the acrylic resin laminated film, the thermal deformation temperature of the acrylic resin film (A) or acrylic resin laminated film is not higher than + 15 ° C., preferably not higher than + 10 ° C., and The heat drying time at that temperature is 20 seconds or less, preferably 10 seconds or less, more preferably 5 seconds or less.

  When using a flammable organic solvent as a solvent, use a device equipped with an air heating type heat source by steam from the point of safety, and use a method and nozzle that counteracts hot air in the dryer. A method of spraying on a photocurable acrylic resin film or sheet can be used. As the shape of the dryer, a known one such as an arch type or a flat type can be selected and used according to the purpose.

<Acrylic resin film (A), acrylic resin laminated film, photocurable acrylic resin film or sheet having a decorative layer (B)>
The acrylic resin film-like product (A), acrylic resin laminated film, and photocurable acrylic resin film or sheet of the present invention are provided with a decorative layer (B) in order to impart design properties to various substrates. be able to. For example, what was printed by the appropriate printing method as needed can be used. In this case, a single-side printing process is applied to one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet, and a decorative layer (B It is preferable to use it as a film having Moreover, it is preferable from the point of protection of a decorating surface or provision of a high-class feeling to arrange | position a decorating layer (B) at the time of shaping | molding on an adhesive surface with base-material resin. Although a decoration layer (B) can be formed by a well-known method, it is preferable to form as a printing layer by a printing method, and a vapor deposition layer by a vapor deposition method.

  The printed layer as the decorative layer (B) becomes a pattern or a character on the surface of the insert or in-mold molded product. The printed pattern is arbitrary, but examples thereof include a pattern composed of wood grain, stone grain, cloth grain, grain pattern, geometric pattern, character, full-color solid, and the like. As the binder material for the printing layer, polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, Examples thereof include cellulose ester resins, alkyd resins, and chlorinated polyolefin resins. As the polyacrylic resin, for example, a multilayer structure polymer (I), a resin composition (III), or a resin composition (IV) can be used as a binder material. For the printing layer, it is preferable to use a colored ink containing a pigment or dye of an appropriate color as a colorant.

  As the ink pigments used in the printing layer, for example, the following can be used. Usually, as pigments, yellow pigments as azo pigments such as polyazo, isoindolinone and other organic pigments and inorganic pigments such as yellow lead, red pigments as azo pigments such as polyazo, quinacridone and other organic pigments and petals An inorganic pigment such as phthalocyanine blue or an inorganic pigment such as cobalt blue, an organic pigment such as aniline black as a black pigment, and an inorganic pigment such as titanium dioxide as a white pigment can be used.

  Various known dyes can be used as the dye of the ink used in the printing layer as long as the effects of the present invention are not impaired.

  Further, as a method for forming the printing layer, a known printing method such as an offset printing method, a gravure rotary printing method, a screen printing method, a known coating method such as a roll coating method or a spray coating method, or a flexographic printing method is used. Is good. The thickness of the printing layer may be appropriately determined as necessary, but is usually about 0.5 to 30 μm. In addition, in the photocurable acrylic resin film or sheet of the present invention, since a photocurable resin composition having a structure in which polymers are crosslinked instead of using a low molecular weight crosslinkable compound is used, there is no adhesiveness on the surface. There are few troubles at the time of printing, and the yield is good.

  Moreover, you may provide a vapor deposition layer as a decoration layer (B) in one chosen from the group which consists of an acrylic resin film-form thing (A), an acrylic resin laminated film, and a photocurable acrylic resin film or a sheet | seat. And you may provide both a printing layer and a vapor deposition layer. The vapor deposition layer is formed of at least one metal selected from the group of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, or an alloy or compound thereof. . Examples of the method for forming the vapor deposition layer include a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method. The thickness of the decorative printing layer or vapor deposition layer may be appropriately selected according to the degree of extension during the insert or in-mold molding so that the desired surface appearance of the insert or in-mold molding can be obtained. .

  When printing on an acrylic resin film (A) having a 60 ° surface glossiness of 100% or less on at least one side, the surface with the higher 60 ° surface glossiness of the film is particularly desirable from the viewpoint of reducing printing omissions. It is preferable to perform a printing process.

The number of missing prints on the surface printed on one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet is a design property and a decoration. From the viewpoint of property, 10 pieces / m ² or less is preferable. By setting the number of printing omissions to 10 pieces / m ² or less, the appearance of the laminated product of this film becomes better. The number of missing prints on the printed surface is more preferably 5 pieces / m ² or less, and particularly preferably 1 piece / m ² or less.

  In addition, when the color tone of the plastic used as the base material is utilized as an alternative to transparent coating, it can be used as it is transparent. In particular, for applications utilizing the color tone of such a substrate, one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet is chlorinated. Compared to vinyl and polyester resin films, it excels in transparency, depth and luxury.

  A colored product can be used as one selected from the group consisting of the acrylic resin film (A), the acrylic resin laminated film, and the photocurable acrylic resin film or sheet of the present invention.

  An adhesive layer (D) is provided as necessary to one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet of the present invention. be able to.

  The adhesive layer (D) increases the adhesion between the decorative layer (B) and the thermoplastic resin layer (C) described later, or the adhesion between the decorative layer (B) and the substrate (E) described later. Any synthetic resinous material can be selected and used as long as it has properties. For example, when the thermoplastic resin layer (C) is a polyacrylic resin, a polyacrylic resin may be used. In addition, the thermoplastic resin layer (C) is made of ABS resin (acrylonitrile-butadiene-styrene resin), AS resin (acrylonitrile-styrene resin), vinyl chloride resin, polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer system. In the case of a resin or a polystyrene blend resin, a polyacrylic resin, a polystyrene resin, a polyamide resin, an ABS resin, a vinyl chloride resin or the like having an affinity for these resins may be used. Further, when the thermoplastic resin layer (C) is a polyolefin resin such as polypropylene resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, coumarone indene resin, block A thermosetting urethane resin using isocyanate can be used. In addition, hydrophobic silica, an epoxy resin, a petroleum resin, or the like can be further included for the purpose of reducing the tackiness of the adhesive layer or improving the heat resistance.

  Moreover, a cover film can also be provided on one selected from the group consisting of the acrylic resin film-like material (A), the acrylic resin laminated film, and the photocurable acrylic resin film or sheet of the present invention. This cover film is effective for preventing dust on one surface selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet, and is also irradiated with active energy rays. It is also effective in preventing scratches on the surface of the previous photocurable resin composition (Z) layer.

  When the above cover film is used for a photocurable acrylic resin film or sheet, it adheres to the photocurable resin composition (Z) layer until insert molding, and immediately peels when insert molding. It is necessary to have appropriate adhesion and good releasability to the composition (Z) layer. Any film can be selected and used as long as it satisfies such conditions. Examples of such a film include a polyethylene film, a polypropylene film, and a polyester film.

<Laminated film or sheet and laminated molded product>
In the present invention, one selected from the group consisting of the acrylic resin film-like product (A), the acrylic resin laminated film, and the photocurable acrylic resin film or sheet of the present invention is laminated on the base material (E). A laminated molded product can be obtained. Or the lamination which has one selected from the group which consists of an acrylic resin film-form thing (A) of this invention, an acrylic resin laminated film, and a photocurable acrylic resin film or a sheet | seat, and a thermoplastic resin layer (C). It is also possible to make a laminated molded product in which a film or a sheet is laminated on the substrate (E). For example, in the case of an insert molding method in which a preform such as vacuum molding or pressure forming is applied, and the preform is inserted into another mold, a resin as a base material is injection molded to obtain an acrylic laminate molded product. It is preferable to use a laminated film or sheet.

  The laminated film or sheet of the present invention is a thermoplastic resin layer selected from the group consisting of the acrylic resin film (A), the acrylic resin laminated film, and the photocurable acrylic resin film or sheet of the present invention. (C). A laminated film or sheet for building materials is preferable. Sufficient strength for handling against external forces such as impact and deformation. For example, even if the film is vacuum-molded by insert molding or the like and removed from the mold, or when the vacuum-molded product is mounted on an injection mold, cracks or the like hardly occur, Handleability is improved. Alternatively, the thermoplastic resin layer (C) can also be used for the purpose of increasing the adhesion to the substrate (E). Furthermore, by using the thermoplastic resin layer (C), for example, the surface defect of the injection-molded product is from the group consisting of the acrylic resin film (A), the acrylic resin laminated film, and the photocurable acrylic resin film or sheet. Propagation to the selected one is minimized, or when the base material (E) is injection-molded, the decorative layer (B) is hardly lost.

  The thermoplastic resin layer (C) is preferably made of a material compatible with the substrate (E) for the purpose of improving the adhesion with the substrate (E). Actually, the thermoplastic resin layer (C) is preferably made of the same polymer material as that of the base material (E), and a known thermoplastic resin film or sheet can be used. For example, acrylic resin, ABS resin (acrylonitrile-butadiene-styrene resin), AS resin (acrylonitrile-styrene resin), vinyl chloride resin, polyolefin resin such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer A polymer or a saponified product thereof, a polyolefin copolymer such as an ethylene- (meth) acrylic acid ester copolymer, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, and polycarbonate, 6-nylon, Polyamide resins such as 6,6-nylon, 6,10-nylon and 12-nylon, polystyrene resins, cellulose derivatives such as cellulose acetate, nitrocellulose, polyvinyl fluoride, polyester Fluorine resins such as vinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, etc., or two or more copolymers or mixtures selected from these, mixtures, composites, laminates, etc. Can be mentioned. As the thermoplastic resin layer (C), among these, from the viewpoint of the formability of the decorative layer (B) on the thermoplastic resin layer (C) and the secondary moldability of the laminated film or sheet, an acrylic resin, an ABS resin, Vinyl chloride resin, polyolefin and polycarbonate are preferred.

  However, when used for building materials, it is preferable to use a resin not containing a halogen element such as chlorine or fluorine, that is, a non-halogen resin. Above all, including market price, distribution volume and ease of procurement, moderate balance of flexibility and strength, processability such as bending, cutting and cutting, surface properties such as wear resistance and solvent resistance, In view of various aspects such as weather resistance, it is preferable to use a thermoplastic resin selected from polyolefin resins, acrylic resins, and polyester resins.

  For the thermoplastic resin layer (C), if necessary, general compounding agents such as stabilizers, antioxidants, lubricants, processing aids, plasticizers, impact agents, foaming agents, fillers, antibacterial agents , Mold inhibitors, mold release agents, antistatic agents, colorants, ultraviolet absorbers, light stabilizers, heat stabilizers, flame retardants, and the like.

  Examples of the antioxidant include phenol-based, sulfur-based, and phosphorus-based materials, and examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, formamidine-based, oxanilide-based, triazine-based, and the like. As the light stabilizer, for example, hindered amine series, nickel complex series, etc., as the thermal stabilizer, for example, hindered phenol series, sulfur series, hydrazine series, etc., the plasticizer depends on the type of resin, For example, phthalate ester-based, phosphate ester-based, fatty acid ester-based, aliphatic dibasic acid ester-based, oxybenzoic acid ester-based, epoxy-based, polyester-based, etc., as lubricants, for example, fatty acid ester-based, fatty acid-based, Metal soap, fatty acid amide, higher alcohol, paraffin, etc. Examples of the flame retardant include, for example, cationic, anionic, nonionic, amphoteric, and the like. Examples of the flame retardant include bromine, phosphorus, chlorine, nitrogen, aluminum, antimony, magnesium, boron, and zirconium. As the system and the like, the filler is used in one or a mixture of two or more selected from, for example, calcium carbonate, barium sulfate, talc, wax, kaolin and the like.

  As a method for adding the compounding agent, a method of supplying the compounding agent to the extruder for forming the thermoplastic resin layer (C) together with the thermoplastic resin, and a mixture obtained by adding the compounding agent to the thermoplastic resin in advance in various kneaders. There is a method of kneading and mixing. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.

  In general, the laminated film or sheet as in the present invention often requires a concealability against the color and defects of the surface of the substrate to be adhered. Therefore, in order to give the desired laminated film or sheet sufficient concealability, the thermoplastic resin layer (C) is added by adding a concealing pigment to the thermoplastic resin constituting the thermoplastic resin layer (C). It can also be concealed. Further, instead of making the thermoplastic resin layer (C) concealable, a concealed solid print layer made of a printing ink composition containing a concealable pigment may be provided on the front or back surface of the thermoplastic resin layer (C). However, both can be used in combination.

  As the concealing pigment, it is desirable to use an inorganic pigment having a high refractive index and excellent concealing property. Specifically, for example, yellow lead, yellow iron oxide, cadmium yellow, titanium yellow, barium yellow, quinacridone, aureolin, molybdate orange, cadmium red, petal, red lead, cinnabar, mars violet, manganese violet, cobalt blue, Organic pigments such as cerulean blue, ultramarine blue, bitumen, emerald green, chrome vermilion, chromium oxide, viridian, iron black, carbon black, etc., for example, titanium oxide (titanium white, titanium white), zinc oxide (zinc white), basic White pigments such as lead carbonate, zinc sulfide, lithopone, and titanox can be used.

  The thermoplastic resin layer (C) of the present invention may be constituted by a laminate of a plurality of layers made of the same kind or different kinds of thermoplastic resins.

  As a manufacturing method when using the thermoplastic resin layer (C) as a film or a sheet in advance, a melt extrusion method or a calendering method through a polishing roll is preferable. In addition, at the time of melt extrusion, it is preferable to extrude the resin in a molten state while removing foreign matters with a screen mesh of 200 mesh or more. At this time, the surface smoothness of the film or sheet which is the thermoplastic resin layer (C) to be obtained can be obtained by using a method in which a film is formed by being sandwiched between a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts. It is possible to improve the properties. By doing in this way, when giving a decorating layer (B) to a thermoplastic resin layer (C), the fish eye which causes external appearance defects, such as printing omission, can be reduced more.

  The thickness of the thermoplastic resin layer (C) may be appropriately determined as necessary, but is usually preferably about 20 to 500 μm. The thickness of the thermoplastic resin layer (C) is such that the appearance of one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet is completely smooth. It is necessary to have such a thickness that the surface defect of the substrate (E) is absorbed or the decorative layer (B) is not lost during injection molding.

  In order to obtain a laminated film or sheet, (1) one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet, and a thermoplastic resin layer The film or sheet which is (C) can be performed by a known method such as thermal lamination, dry lamination, wet lamination, hot melt lamination or the like.

  Moreover, it can also laminate | stack by extrusion lamination. Specifically, (2) Lamination while melt-extruding an acrylic resin film (A) or an acrylic resin laminated film into a film or sheet with a T-die or the like on the film or sheet as the thermoplastic resin layer (C). (3) A thermoplastic resin layer (C) is formed on one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet. A method of laminating while being melt extruded into a film or sheet with a die or the like can be used.

  Further, (4) there is a method of laminating the acrylic resin film (A) and the thermoplastic resin layer (C) simultaneously while melt extrusion. Specifically, a laminating method by co-extrusion molding such as a method of adhering inside a die by a feed block method or a multi-manifold method, or a method of adhering a plurality of die lips to one die and adhering outside the die can be mentioned.

  Moreover, as a method of obtaining a laminated film or sheet having an acrylic resin laminated film and a thermoplastic resin layer (C), an acrylic resin film (A) and another acrylic resin film (A ′) or fluorine There is a method of simultaneously laminating a resin-based resin film (A ″) and a thermoplastic resin layer (C) while melt extrusion. Specifically, a laminating method by co-extrusion molding such as a method of adhering inside a die by a feed block method or a multi-manifold method, or a method of adhering a plurality of die lips to one die and adhering outside the die can be mentioned.

  Between the one selected from the group consisting of the acrylic resin film (A), the acrylic resin laminated film, and the photocurable acrylic resin film or sheet, and the thermoplastic resin layer (C), the above-mentioned decoration A layer (B) and / or a colored layer (F) can be provided.

  Of the above-mentioned (1) one selected from the group consisting of the acrylic resin film (A), the acrylic resin laminated film, and the photocurable acrylic resin film or sheet, and the thermoplastic resin layer (C) in advance. When each is formed as a film or sheet, the decorative layer (B) can be formed on either film or sheet. In this case, it is preferable to use what formed the decoration layer (B) in the one side of a film or a sheet | seat, and arranging a decoration layer (B) surface in a non-surface at the time of forming into a laminated film and a sheet | seat is a decoration layer It is preferable from the viewpoint of protection of (B) and imparting a high-class feeling.

  In the above-described method of (2) forming the thermoplastic resin layer (C) into a film or sheet in advance and laminating it, after the decorative layer (B) is formed on the thermoplastic resin layer (C), The decorative layer (B) side is laminated so as to face one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet.

  In the method of laminating after molding one selected from the group consisting of the acrylic resin film (A), the acrylic resin laminated film, and the photocurable acrylic resin film or sheet in advance, The decorative layer (B) is formed on one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet, and then the decorative layer. (B) Laminate with the side facing the thermoplastic resin layer (C).

  If necessary, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, anchor, primer treatment, etc. on one side of the acrylic resin film (A), thermoplastic resin layer (C), etc. The surface treatment can be performed. Adhesiveness such as between the thermoplastic resin layer (C) and the decorative layer (B), between the acrylic resin film (A) and the thermoplastic resin layer (C) can also be improved.

  The position at which the colored layer (F) is provided is not particularly limited, but may be one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet. It is preferable to provide in the position which touches a decoration layer (B), such as between a decoration layer (B).

  The transparent colored layer (F) is one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet, and a decorative layer (B). By providing in between, it can be set as the external appearance which has a various color tone with the same decorating layer (B).

  For example, when a decorative layer (B) is provided by a printing method, a laminated film or sheet having a design with different color tones can be easily obtained without changing the plate or ink on the printing process. In particular, when a metallic print layer or metal layer is used as the decorative layer (B), by providing a transparent colored layer (F), a metallic appearance having various hues such as silver metallic, gold metallic, and blue metallic This is preferable.

  By providing the colored layer (F) between the decorative layer (B) and the thermoplastic resin layer (C), the same decorative layer (B) can have an appearance having various background colors. it can.

  For example, when a decorative layer (B) is provided by a printing method, the background color uses the color of the colored layer (F), and only the pattern other than the background color is printed, so that the plate is printed on the printing process. A laminated film or sheet having a design with a different color tone can be easily obtained without changing the ink or the ink. In particular, when a transparent metallic decorative layer is used as the decorative layer (B), a metallic appearance having various hues such as silver metallic, gold metallic, and blue metallic is provided by providing a colored layer (F). Is preferable.

  Moreover, an adhesive layer (D) can be provided as needed. For example, it can be provided between the colored layer (F) or the decorative layer (B) and the thermoplastic resin layer (C), on the surface of the thermoplastic resin layer (C) on the side in contact with the substrate (E).

  The laminated molded product of the present invention comprises one selected from the group consisting of the acrylic resin film (A), the acrylic resin laminated film, the photocurable acrylic resin film or sheet, and the laminated film or sheet of the present invention. It is characterized by being laminated on the base material (E) by melt bonding or the like.

  Regardless of the type of resin used as the base material (E), all known resins can be used. Examples of such resins include polyethylene resins, polypropylene resins, polybutene resins, polymethylpentene resins, ethylene-propylene copolymer resins, ethylene-propylene-butene copolymer resins, and olefin thermoplastic elastomers. Such as olefin resin, polystyrene resin, ABS (acrylonitrile / butadiene / styrene copolymer) resin, AS (acrylonitrile / styrene copolymer) resin, acrylic resin, urethane resin, unsaturated polyester Examples include general-purpose thermoplastic or thermosetting resins such as resins and epoxy resins. Also, general engineering resins such as polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, polycarbonate-modified polyphenylene ether resins, polyethylene terephthalate resins, polysulfone resins, polyphenylene sulfide resins, polyphenylene oxide resins, polyethers Super engineering resins such as imide resins, polyimide resins, liquid crystal polyester resins, and polyallyl heat resistant resins can also be used. Further, reinforcing materials such as glass fibers and inorganic fillers (talc, calcium carbonate, silica, mica, etc.), composite resins added with modifiers such as rubber components, and various modified resins can be used.

  Among these, one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, and a photocurable acrylic resin film or sheet, or a thermoplastic resin layer in the case of a laminated film or sheet It is preferable that it can be melt-bonded to (C). For example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or resin containing these as main components can be given. In terms of adhesiveness, an ABS resin, an AS resin, a polycarbonate resin, a vinyl chloride resin, or a resin containing these as a main component is preferable, and an ABS resin, a polycarbonate resin, or a resin containing these as a main component is more preferable.

  However, by using an adhesive layer (D) even with a base resin that is not heat-sealed, such as polyolefin resin, an acrylic resin film (A), an acrylic resin laminated film, a photocurable acrylic resin film or sheet, and a laminate It is possible to adhere one selected from the group consisting of a film or a sheet and the substrate (E) at the time of molding.

  When the laminated molded product of the present invention is molded into a two-dimensional laminate, a known method such as thermal lamination can be used for a base material that can be heat-sealed. For example, for wood boards such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), water quality boards such as wood fiber board, and base materials (E) that are not thermally fused to metal such as iron and aluminum Can be bonded via an adhesive layer (D).

  When forming into a three-dimensionally shaped laminate, a known method such as an insert molding method or an in-mold molding method can be used, and the in-mold molding method is preferred from the viewpoint of productivity.

  The in-mold molding method involves heating one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, a photocurable acrylic resin film or sheet, and a laminated film or sheet, and then vacuuming. Vacuum forming is performed in a functional mold. This method is preferable from the viewpoints of workability and economy because the film can be molded and injection molded in one step.

  In addition, when performing in-mold molding using a known acrylic resin film having a decorative layer (B), the decorative layer near the gate may disappear depending on the shape of the mold and the injection molding conditions. There is. Gates are roughly divided into a non-restricted gate in which the resin flow path is not narrowed at the gate portion and a restricted gate in which the flow path is narrowed. Typical examples of the latter include pinpoint gates, side gates, and submarine gates. Although these gate shapes reduce the residual stress in the vicinity of the gate, they increase the temperature of the resin passing through the gate and increase the injection resin pressure per unit area on the surface of the acrylic resin film near the gate. Layer (B) tends to disappear. However, when the acrylic resin film material (A) of the present invention is used, the disappearance of the decorative layer (B) can be reduced as compared with the case where a conventionally known acrylic resin film material is used. it can.

  In addition, when performing in-mold molding or insert molding using a laminated film or sheet having a thermoplastic resin layer (C), the decoration layer (B) disappears due to the presence of the thermoplastic resin layer (C). This is preferable because it can be further reduced.

  The heating temperature at the time of in-mold molding is equal to or higher than the temperature at which one selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, a photocurable acrylic resin film or sheet, and a laminated film or sheet is softened. Is desirable. Specifically, although it depends on the thermal properties of the film or the shape of the molded product, it is usually 70 ° C. or higher. On the other hand, if the temperature is too high, the surface appearance tends to deteriorate or the releasability tends to deteriorate. Although this also depends on the thermal properties of the film or the shape of the molded product, it is usually preferably 170 ° C or lower. Furthermore, from the viewpoint of energy efficiency, it is preferable that the preheating temperature during vacuum forming is low. Specifically, 135 ° C. or lower is preferable. In addition, a film that can be molded even if the preheating temperature is low can shorten the preheating time instead of lowering the preheating temperature. In this case, it is possible to increase the cycle of vacuum forming, and the industrial utility value is high.

  Thus, when giving a three-dimensional shape to a film by vacuum forming, from the group which consists of an acrylic resin film-like thing (A), an acrylic resin laminated film, a photocurable acrylic resin film or sheet, and a laminated film or sheet One of the choices is very advantageous because of its high elongation at high temperatures.

  In addition, a decorative layer having a high brightness such as a metallic tone using an acrylic resin film (A) formed by being sandwiched between a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts (A) When vacuum forming is performed using the acrylic resin film-like product (A) having B), appearance defects may occur due to fish eyes in the acrylic resin film-like product (A). The appearance defect referred to here is a defect that appears as if the surface of the vacuum molded product is recessed, unlike printing failure. In this case, it is preferable to use a laminated film or sheet having the thermoplastic resin layer (C) because the occurrence of such appearance defects can be reduced.

  As the base material (E) to be injection-molded, any resin that can be injection-molded can be used regardless of the type. It is preferable to approximate the shrinkage rate after molding of the molding resin to the shrinkage rate of the film or sheet because problems such as warpage of the insert molded product and peeling of the film or sheet can be solved.

  When the laminated film or sheet of the present invention is used for building materials, a method of laminating the laminated film or sheet other than the insert molding method or the in-mold method includes lapping and V-cut.

  In lapping processing, a columnar body is constituted by a number of different rollers while supplying a laminated film or sheet via an adhesive layer (D) in the longitudinal direction of a columnar substrate such as a cylinder or polygonal column. In this method, a laminated molded product is obtained by sequentially pressure-bonding a laminated film or sheet to a plurality of side surfaces.

  In the V-cut process, a laminated film or sheet is first laminated on a plate-like substrate via an adhesive layer (D), and then the laminated film or sheet is placed on the surface of the plate-like substrate opposite to the laminated film or sheet. A V-shaped or U-shaped groove is cut so as to reach the interface with the plate-like substrate, and then an adhesive is applied in the groove, and then the groove is bent to form a box or a columnar body. This is a method for obtaining a laminated molded product.

  When the laminated film or sheet containing the acrylic resin film-like product (A) of the present invention is used, the phenomenon of whitening of the acrylic film during lapping or V-cutting can be reduced.

In the case of a laminated molded product obtained using the photocurable acrylic resin film or sheet of the present invention, the photocurable resin composition on the surface of the laminated molded product is photocured by light irradiation. Examples of light to be irradiated include electron beams, ultraviolet rays, and γ rays. Although irradiation conditions are determined according to the photocuring property of a photocurable resin composition (Z) layer, irradiation amount is about 500-10,000mJ / cm < ² > normally. Thereby, the laminated molded product in which the photocurable resin composition (Z) is cured and a hard film is formed on the surface can be obtained.

  Necessary for one surface selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, a photocurable acrylic resin film or sheet, a laminated film or sheet, and a laminated molded product of the present invention. Accordingly, surface treatment for imparting various functions can be performed on the surface. Surface treatments for imparting functions include printing processes such as silk printing and inkjet printing, metal tone imparting, metal deposition for antireflection, sputtering, wet plating treatment, surface hardening treatment for improving surface hardness, dirt Examples thereof include water repellency treatment for prevention, photocatalyst layer formation treatment, dust adhesion prevention, antistatic treatment for the purpose of cutting electromagnetic waves, antireflection layer formation, and antiglare treatment.

  One selected from the group consisting of the acrylic resin film (A), acrylic resin film (A), acrylic resin laminated film, photocurable acrylic resin film or sheet, and laminated film or sheet of the present invention. The laminated product is particularly suitable for vehicle use and building material use. Specific examples include instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior applications, weather strips, bumpers, bumper guards, side mud guards, body panels, Spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts, and other automotive exterior applications, AV equipment and furniture products Applications such as front panels, buttons, emblems, surface cosmetics, housings for mobile phones, display windows, buttons, etc. Building interior materials such as surfaces, ceilings, floors, exterior walls such as siding, exterior materials for buildings such as fences, roofs, gates, and windbreak boards, surfaces of furniture such as window frames, doors, handrails, sills, and duck Cosmetic materials, various displays, lenses, mirrors, goggles, window glass and other optical components, trains, airplanes, ships and other vehicles other than automobiles, interior and exterior applications, bottles, cosmetic containers, various packaging such as accessories It can be suitably used for various other uses such as containers and materials, miscellaneous goods such as prizes and accessories.

  One selected from the group consisting of an acrylic resin film (A), an acrylic resin laminated film, a photocurable acrylic resin film or sheet, and a laminated film or sheet according to the present invention is molding whitening resistance, surface hardness. In addition, it satisfies the performances of heat resistance, transparency or matte, and can dramatically expand the conventional usage. In particular, it has excellent molding whitening resistance when subjected to insert molding and in-mold molding, and by using the acrylic resin film-like material (A) of the present invention, a film that protrudes manually instead of punching is used. The industrial use value is extremely high because there is no need for a work process to remove, there is a design restriction, and the whitened portion is reheated to remove the whiteness.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by an Example. In the examples, “part” represents “part by mass”, and “%” represents “% by mass”. Abbreviations in the examples are as follows.

Methyl methacrylate MMA,
Methyl acrylate MA,
n-butyl acrylate n-BA,
Styrene St,
1,3-butylene glycol dimethacrylate 1,3-BD,
Allyl methacrylate AMA,
Cumene hydroperoxide CHP,
t-butyl hydroperoxide t-BH,
t-hexyl hydroperoxide t-HH,
n-octyl mercaptan n-OM,
Ethylenediaminetetraacetic acid disodium EDTA,
2-hydroxyethyl methacrylate HEMA,
Lauroyl peroxide LPO.

[Measurement and evaluation method of physical properties]
Physical properties of the obtained multilayer structure polymer (I), thermoplastic polymer (II), hydroxyl group-containing polymer (V-1) and thermoplastic polymer (VII-1), resin composition (III) and The gel content of the resin composition (IV), and the physical properties of the acrylic resin film-like product (A) and laminated molded product obtained in Examples 1 to 40 and Comparative Examples 1 to 20 were measured as follows. ,evaluated.

  In addition, evaluation of the laminated molded product was performed by the laminated molded product produced for evaluation of molding whitening resistance. However, the evaluations in Examples 24 to 27 and Comparative Examples 13 and 14 were carried out with laminated molded products produced by the method described in the text.

(1) Weight average particle diameter of the multilayer structure polymer (I) The polymer latex of the multilayer structure polymer (I) obtained by emulsion polymerization was converted into a light scattering photometer DLS-700 (product of Otsuka Electronics Co., Ltd.) Name) and measured by the dynamic light scattering method.

(2) Gel content of multilayer structure polymer (I), resin composition (III) and resin composition (IV) Predetermined amount (mass before extraction) of multilayer structure polymer (I) (obtained after polymerization) (Coagulated powder), resin composition (III) (pellet obtained after extrusion) or resin composition (IV) (pellet obtained after extrusion) was extracted in an acetone solvent under reflux. Then, this treatment solution was separated by centrifugation, and the acetone-insoluble matter was dried, then the mass was measured (mass after extraction), and calculated by the following formula:
Gel content rate (%) = mass after extraction (g) / mass before extraction (g) × 100.

(3) Glass transition temperature (Tg) of multilayer structure polymer (I) and polymer (V) containing a hydroxyl group
It calculated from the formula of FOX using the value described in the polymer handbook [Polymer HandBook (J. Brandrup, Interscience, 1989)].

(4) Reduced viscosity of thermoplastic polymer (II), intrinsic viscosity of polymer (V) containing hydroxyl group and reduced viscosity of thermoplastic polymer (VII) 0.1 g of polymer was dissolved in 100 mL of chloroform, 25 Measured at ° C.

(5) The haze value before and after the tensile test of the acrylic resin film-like product (A) and the haze value of the insert laminate molded product The tensile test of the acrylic resin film-like product (A) is 20 mm wide and 125 μm thick. Using a test piece of Toyo Seiki Seisakusho Co., Ltd., and using a strograph T (trade name), the initial chuck distance 25 mm, the speed 50 mm / min, the temperature 23 ° C., and the end point chuck distance 33 mm ( The test was carried out according to the test method of JIS K7127 under a) or under conditions (b) in which the distance between the chucks was 25 mm, the speed was 300 mm / min, the temperature was 15 ° C., and the distance between the chucks was 33 mm.

  The haze value was measured according to the test method of JIS K7136 for the test piece before the tensile test and the test piece after the tensile test. The acrylic resin film (A) having a haze value exceeding 40% was also subjected to the same test method.

  Further, the insert molded articles described in Examples 24-27 and Comparative Examples 13 and 14 were also measured according to the test method of JIS K7136.

(6) Surface gloss of acrylic resin film (A) Using a gloss meter (Murakami Color Research Laboratory, GM-26D type (trade name)), the surface of the surface not in contact with the mirror roll during film formation The surface gloss at 60 ° was measured.

(7) Acrylic resin film (A) HDT (thermal deformation temperature)
The resin composition pellets were molded into a heat distortion temperature measurement test piece based on ASTM D648 by injection molding and annealed at 60 ° C. for 4 hours. And this test piece was used and measured according to ASTM D648 with a low load (0.45 MPa).

(8) Acrylic resin film-like product (A), acrylic resin laminated film, and light-curing acrylic resin film molding whitening resistance, near-gate printed state during in-mold molding obtained acrylic resin film-like product (A) Alternatively, a woodgrain and jet black decorative layer (B) was formed by gravure printing on an acrylic resin laminated film or a photocurable acrylic resin film.

J85ELII type injection molding machine using a mold that has a vacuuming function and has a 1cm ² square 1cm deep recess (position 3cm laterally from the center gate) on the bottom of the mold on the cavity side. In-mold molding was performed with an in-mold molding apparatus that combines Nippon Steel Works Co., Ltd. (trade name) and hot pack system (Nissha Printing Co., Ltd., trade name).

  The detailed shape of the molded product is a box shape with a length of 150 mm x width of 120 mm x thickness of 2 mm and a depth of 10 mm. There are a total of three locations, one each at a position of 40 mm, and the gate shape is a pinpoint gate with a diameter of 1 mm.

  In addition, the vacuum forming of the film having the decorative layer (B) is performed by heating at a heater temperature of 260 ° C., a heating time of 15 seconds, and a distance between the heater and the film of 15 mm, and the non-decorative layer is in contact with the mold. The vacuum forming was carried out.

  In addition, in the injection molding performed continuously in the same mold, the base resin was injected from the decorative layer side under the conditions of a cylinder temperature of 250 ° C., an injection speed of 30%, an injection pressure of 43%, and a mold temperature of 60 ° C. A heat-resistant ABS resin (manufactured by UMGABS, trade name “Bulksum TM25B”) was used as the base resin.

The state of the 1 cm ² square convex portion of the obtained laminated molded product was observed and evaluated as follows. Moreover, the printing state which is the decoration layer (B) near the gate was also observed and evaluated as follows.

(About whitening)
○: No film whitening
Δ: Film has weak whitening,
×: The film has strong whitening,
* When a matte film (Examples 7 to 16, Comparative Examples 4 and 5) is used ○: No film whitening,
×: Film whitening
(About cracking)
○: No film breakage,
X: There is a film crack,
(Regarding the print status near the gate)
○: No loss of printing
×: Printing disappeared.

(9) Molding whitening resistance of laminated film The obtained laminated film was placed in a mold having a vacuuming function so that the acrylic resin film (A) side became the cavity side, After heating for a minute, vacuum forming was performed, and unnecessary portions were trimmed. Acrylic resin film-like laminated film is vacuum-molded on a mold that has a 1 cm ² square recess at the bottom of the mold on the cavity side and a depth of 1 mm (position is 3 cm laterally from the center gate). It was placed at the bottom of the mold so that the side was the cavity side. Next, an ABS resin (trade name “Diapet ABS Bulk Sum TM25” manufactured by UMG ABS Co., Ltd.) serving as a base material was injection-molded on the thermoplastic resin film side of the laminated film, and a laminated molded product was obtained by insert molding.

  The detailed shape of the molded product is a box shape with a length of 150 mm x width of 120 mm x thickness of 2 mm and a depth of 10 mm. There are a total of three locations, one each at a position of 40 mm, and the gate shape is a pinpoint gate with a diameter of 1 mm.

  The injection molding was performed using a J85 ELII type injection molding machine (trade name) manufactured by Nippon Steel Works under the conditions of a cylinder temperature of 250 ° C., an injection speed of 30%, an injection pressure of 43%, and a mold temperature of 60 ° C.

The state of the 1 cm ² square convex portion of the obtained laminated molded product was observed and evaluated according to the same criteria as (8).

(10) Heat aging resistance test of laminated molded product The appearance of the molded product when heated at 80 ° C. for 400 hours was evaluated as follows.

○: No change
X: Whitening and cloudy.

  Moreover, about the molded article using the matte film (Examples 7-16, Comparative Examples 4 and 5), the external appearance of the molded article when heated at 100 degreeC for 400 hours was evaluated as follows.

○: no gloss return
X: There is gloss return.

(11) Pencil hardness of acrylic resin film-like product (A) and laminated molded product Measured according to JIS K5400.

(12) Scratch resistance of laminated molded products and laminated films for building materials Laminated molding when a load of 0.049 MPa is applied on a 5-layer gauze and 200 strokes are scratched at a rate of 30 strokes / min. The appearance of the product and the laminated film was evaluated as follows.

○: No damage,
Δ: scratched, no whitening is seen in the scratched part,
X: Scratched and whitened in the scratched part.

  Moreover, about the lamination | stacking molded product using a matte film (Examples 7-16, Comparative Examples 4 and 5), the external appearance of the molded product when 100 reciprocating abrasions was evaluated as follows.

○: No damage,
Δ: weak scratched,
X: There is a strong scratch.

(13) Fragrance resistance of laminated molded product A polyethylene cylinder having an inner diameter of 38 mm and a height of 15 mm is placed on the surface of the molded product, and it is brought into close contact with the test piece with a crimping machine. 5 mL of the product name “Grace Mate Poppy Citrus” manufactured by the company was injected. Then, the opening was covered with a glass plate, and then placed in a thermostatic bath maintained at 55 ° C. and left for 4 hours. Then, after removing the crimping device and washing the test piece with water, it was air-dried, and the surface state of the test part was observed and evaluated as follows.

○: No change
X: Crystalline substance precipitated.

(14) Appearance of Laminated Molded Product The appearance of the wood grain pattern printing or jet black pattern printing on the molded product was visually evaluated as follows.

○: The print looks clear.
Δ: The print appears to be slightly white.
X: The print looks white.

(15) Film thickness of photocurable acrylic resin film Using a transmission electron microscope JEM100S (manufactured by JEOL Ltd., trade name), cross-sectional observation of the photocurable acrylic resin film is performed, and a photocurable resin composition ( The film thickness of the Z) layer and the acrylic resin film-like material (A) layer was measured.

(16) Abrasion resistance of laminated molded product obtained from photocurable acrylic resin film Taber abrasion test (500 g load on one side, CS-10F (trade name) wear wheel, rotation speed 60 rpm, number of tests 100 times and 500 The haze value was measured after the test was carried out once. And the numerical value represented by (the haze value after the test) − (the haze value before the test) was shown as wear resistance (%).

(17) Adhesiveness of insert-molded product The cross-molded tape method was evaluated according to JIS K5400.

(18) Flexural modulus of resin composition (III) Using a strograph T manufactured by Toyo Seiki Seisakusho Co., Ltd., the test was performed according to ASTM D790 under the conditions of 100 mm between fulcrums and a bending speed of 3 mm / min.

  Each resin composition (III) pellet was molded into a heat distortion temperature measurement specimen based on ASTM D648 by injection molding and measured using the specimen.

(19) Molding whitening resistance of laminated film for building materials The appearance of the surface of a laminated molded product at the time of lapping performed to obtain a laminated molded product is shown. The display is as follows.

(About whitening)
○: No film whitening
Δ: Film has weak whitening,
×: The film has strong whitening,
(About cracking)
○: No film breakage,
X: There is a film crack.

(20) Anti-glare property of laminated film for building materials The appearance of the laminated film after being kept for 24 hours in a state where the surface temperature of the laminated film is 90 ° C. is shown. The display is as follows.

○: no gloss return
X: There is gloss return.

<1. Production of Multilayer Structure Polymer (I-1)>
After charging 10.8 parts of deionized water in a container equipped with a stirrer, it consists of MMA 0.3 part, n-BA 4.5 part, 1,3-BD 0.2 part, AMA 0.05 part and CHP 0.025 part. Monomer components were added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Industry Co., Ltd., trade name “phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

Next, 139.2 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 75 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was added dropwise to the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization of the innermost polymer inner layer (I-1-A ₁ ). . Subsequently, a monomer component consisting of 9.6 parts of MMA, 14.4 parts of n-BA, 1.0 part of 1,3-BD and 0.25 part of AMA was dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP. Thereafter, the reaction was continued for 60 minutes to obtain an innermost layer polymer (I-1-A) including an innermost layer polymer outer layer (I-1-A ₂ ). The Tg of the innermost polymer inner layer (I-1-A ₁ ) alone was −48 ° C., and the Tg of the innermost polymer outer layer (I-1-A ₂ ) alone was −10 ° C.

  Subsequently, a monomer component consisting of 6 parts of MMA, 4 parts of MA and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes to obtain an intermediate layer polymer (I -1-B) was formed. The Tg of the intermediate layer polymer (I-1-B) alone was 60 ° C.

  Subsequently, a monomer component consisting of 57 parts of MMA, 3 parts of MA, 0.264 part of n-OM and 0.075 part of t-BH was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes to obtain the outermost layer polymer. (I-1-C) was formed to obtain a polymer latex of the multilayer structure polymer (I-1). The Tg of the outermost layer polymer (I-1-C) alone was 99 ° C.

  The weight average particle diameter of the multilayer structure polymer (I-1) measured after the polymerization was 0.11 μm.

  The polymer latex of the obtained multilayer structure polymer (I-1) was filtered using a vibration type filtration device in which a SUS mesh (average opening: 62 μm) was attached to the filter medium, and then calcium acetate 3.5 The solution was salted out in an aqueous solution containing parts, washed with water, collected, and dried to obtain a powdery multilayer structure polymer (I-1). The gel content of the multilayer structure polymer (I-1) was 70%.

  Further, 214.3 g of the obtained multilayer structure polymer (I-1) was added to 1500 ml of acetone filtered through a nylon mesh having an opening of 25 μm, and stirred for 3 hours to obtain acetone of the multilayer structure polymer (I-1). A dispersion was prepared. Next, this dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and then the nylon mesh was washed in chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. Next, the captured substance after ultrasonic cleaning is put into 150 ml of acetone filtered through a nylon mesh having a mesh size of 25 μm together with the nylon mesh, and this liquid is subjected to ultrasonic treatment for 15 minutes. 150 ml of an acetone dispersion of the trapped material was prepared. Next, 70 ml of this dispersion was measured at 25 ° C. with an automatic liquid particle counter (model: KL-01) manufactured by Rion Co., Ltd., and the number of particles having a diameter of 55 μm or more was determined. there were.

<2. Production of multilayer structure polymer (I-2)>
Innermost layer polymer (I-1-) including innermost layer polymer inner layer (I-1-A ₁ ) and innermost layer polymer outer layer (I-1-A ₂ ) of multilayer structure polymer (I-1) In the same manner as in A), an innermost layer polymer (I-2-A) including an innermost layer polymer inner layer (I-2-A ₁ ) and an innermost layer polymer outer layer (I-2-A ₂ ) Obtained. The Tg of the innermost polymer inner layer (I-2-A ₁ ) alone was −48 ° C., and the Tg of the innermost polymer outer layer (I-2-A ₂ ) alone was −10 ° C.

  Subsequently, an intermediate layer polymer (I-2-B) was formed in the same manner as the intermediate layer polymer (I-1-B) of the multilayer structure polymer (I-1). The Tg of the intermediate layer polymer (I-2-B) alone was 60 ° C.

  Subsequently, after dropping a monomer component consisting of 59.4 parts of MMA, 0.6 part of MA, 0.264 part of n-OM and 0.075 part of t-BH to the polymerization vessel over 140 minutes, the reaction is continued for 60 minutes, The outermost layer polymer (I-2-C) was formed to obtain a polymer latex of the multilayer structure polymer (I-2). The Tg of the outermost layer polymer (I-2-C) alone was 104 ° C.

  The weight average particle diameter of the multilayer structure polymer (I-2) measured after the polymerization was 0.11 μm.

  The polymer latex of the obtained multilayer structure polymer (I-2) was filtered using a vibration type filtration device in which a SUS mesh (average opening: 62 μm) was attached to the filter medium, and then calcium acetate 3.5 It was salted out in an aqueous solution containing parts, washed with water, recovered, and dried to obtain a powdery multilayer structure polymer (I-2). The gel content of the multilayer structure polymer (I-2) was 70%.

  Moreover, when the number of particles having a diameter of 55 μm or more of the obtained multilayer structure polymer (I-2) was determined in the same manner as in the multilayer structure polymer (I-1), it was 11.

<3. Production of multilayer structure polymer (I-3)>
After charging 8.5 parts of deionized water into a vessel equipped with a stirrer, it consists of 0.3 part of MMA, 4.5 parts of n-BA, 0.2 part of 1,3-BD, 0.05 part of AMA and 0.025 part of CHP. Monomer components were added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Industry Co., Ltd., trade name “phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

Next, 186.5 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 70 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was added dropwise to the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization of the innermost polymer inner layer (I-3-A ₁ ). . Subsequently, a monomer component consisting of 1.5 parts of MMA, 22.5 parts of n-BA, 1.0 part of 1,3-BD and 0.25 part of AMA was dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP. Thereafter, the reaction was continued for 60 minutes to obtain an innermost layer polymer (I-3-A) including an innermost layer polymer outer layer (I-3-A ₂ ). The Tg of the innermost polymer inner layer (I-3-A ₁ ) alone was −48 ° C., and the Tg of the innermost polymer outer layer (I-3-A ₂ ) alone was −48 ° C.

  Subsequently, a monomer component consisting of 6 parts of MMA, 4 parts of n-BA and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes to obtain an intermediate layer polymer. (I-3-B) was formed. The Tg of the intermediate layer polymer (I-3-B) alone was 20 ° C.

  Subsequently, a monomer component consisting of 55.2 parts of MMA, 4.8 parts of n-BA, 0.19 part of n-OM and 0.08 part of t-BH was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes. The outermost layer polymer (I-3-C) was formed to obtain a polymer latex of the multilayer structure polymer (I-3). The Tg of the outermost layer polymer (I-3-C) alone was 84 ° C.

  The weight average particle diameter of the multilayer structure polymer (I-3) measured after the polymerization was 0.12 μm.

  The polymer latex of the obtained multilayer structure polymer (I-3) was filtered using a vibration type filtration device in which a SUS mesh (average opening: 62 μm) was attached to the filter medium, and then 3 parts of calcium acetate was added. Salting out was carried out in an aqueous solution containing, recovered by washing with water, and then dried to obtain a powdery multilayer structure polymer (I-3).

  The gel content of the multilayer structure polymer (I-3) was 60%.

<4. Production of multilayer structure polymer (I-4)>
Under a nitrogen atmosphere, 310 parts of deionized water was placed in a reaction vessel equipped with a reflux condenser, and the temperature was raised to 80 ° C. Then, the following raw material (b) for the innermost layer polymer (I-4-A) shown below is added continuously while adding (i) shown below and stirring, followed by further polymerization for 120 minutes. The latex of the innermost layer polymer (I-4-A) was obtained. The Tg of the innermost layer polymer (I-4-A) alone was -35 ° C.

  Subsequently, 10 parts of deionized water and 0.15 part of sodium formaldehyde sulfoxylate were added to the latex and held for 15 minutes. Then, while stirring at 80 ° C. in a nitrogen atmosphere, the raw material (C) for the outermost layer polymer (I-4-C) shown below was continuously added over 100 minutes, and then at 80 ° C. for 60 minutes. The outermost layer polymer (I-4-C) was formed by holding and polymerizing to obtain a polymer latex of the multilayer structure polymer (I-4). The Tg of the outermost layer polymer (I-4-C) alone was 99 ° C.

  The weight average particle diameter of the obtained multilayer structure polymer (I-4) was 0.12 μm.

  The polymer latex of the obtained multilayer structure polymer (I-4) is coagulated, agglomerated and solidified using calcium acetate, filtered, washed with water, and dried to obtain a multilayer structure polymer (I-4). )

(I) Mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40%
Di (polyoxyethylene nonylphenyl ether) phosphoric acid 60%
0.5 parts of a partially neutralized mixture of sodium hydroxide,
0.1 part sodium carbonate,
0.5 parts of sodium formaldehyde sulfoxylate,
0.00024 parts of ferrous sulfate,
EDTA 0.00072 part,
(B) 81.0 parts of n-BA,
19.0 parts of St,
1.0 part AMA,
0.25 part t-BH,
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
Di (polyoxyethylene nonylphenyl ether) phosphoric acid 60%
1.1 parts of a partially neutralized mixture of sodium hydroxide,
(C) MMA 57.0 parts,
3.0 parts of MA,
n-OM 0.2 part,
t-BH 0.1 part.

<5. Production of multilayer structure polymer (I-5)>
Under a nitrogen atmosphere, 244 parts of deionized water was placed in a reaction vessel equipped with a reflux condenser, and the temperature was raised to 80 ° C. Then, (15) shown below was added, and while stirring, 1/15 of the raw material (e) for the innermost polymer inner layer (I-5-A ₁ ) shown below was charged and held for 15 minutes. . Next, the remaining raw material (e) was continuously added at an increase rate of 8% / hour of the monomer component [raw material (e)] with respect to water, and then held for 60 minutes, and the innermost polymer inner layer ( to obtain a I-5-a ₁₎ latex. The Tg of the innermost polymer inner layer (I-5-A ₁ ) alone was 24 ° C.

Subsequently, 0.6 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. Then, while stirring at 80 ° C. in a nitrogen atmosphere, the raw material (he) for the innermost polymer outer layer (I-5-A ₂ ) shown below was converted into a monomer component [raw material (he)] for water. After the continuous addition at an increase rate of 4% / hour, the mixture was held for 120 minutes, and the innermost polymer outer layer (I-5-A ₂ ) was polymerized to produce the innermost polymer (I-5-5). A latex of A) was obtained. The Tg of the innermost polymer outer layer (I-5-A ₂ ) alone was -38 ° C.

  Subsequently, 0.4 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. Then, while stirring at 80 ° C. under a nitrogen atmosphere, the raw material (g) for the outermost layer polymer (I-5-C) shown below is increased by the monomer component [raw material (g)] with respect to water. After continuously adding at 10% / hour, holding for 60 minutes, the outermost layer polymer (I-5-C) is polymerized to obtain a polymer latex of the multilayer structure polymer (I-5). It was. The Tg of the outermost layer polymer (I-5-C) alone was 99 ° C.

  The weight average particle diameter of the obtained multilayer structure polymer (I-5) was 0.28 μm.

  The polymer latex of the obtained multilayer structure polymer (I-5) is subjected to coagulation, aggregation, and solidification reaction using calcium acetate, filtered, washed with water, and dried to obtain a multilayer structure polymer (I-5). )

(D) 0.6 parts of sodium formaldehyde sulfoxylate,
0.00012 parts of ferrous sulfate,
0.0003 parts EDTA,
(E) MMA 22.0 parts,
n-BA 15.0 parts,
3.0 parts of St,
0.4 part AMA,
1,3-BD 0.14 parts,
0.18 parts t-BH,
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
Di (polyoxyethylene nonylphenyl ether) phosphoric acid 60%
1.0 part of a partially neutralized mixture of sodium hydroxide,
(F) 50.0 parts of n-BA,
10.0 parts of St,
0.4 part AMA,
1,3-BD 0.14 parts,
0.2 part of t-HH,
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
Di (polyoxyethylene nonylphenyl ether) phosphoric acid 60%
1.0 part of a partially neutralized mixture of sodium hydroxide,
(G) MMA 57.0 parts,
3.0 parts of MA,
n-OM 0.3 part,
0.06 parts t-BH.

<6. Production of Polymer (V-1) Containing Hydroxyl Group>
The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.

MA 1 part,
79 parts of MMA,
20 parts of HEMA,
n-OM 0.14 parts,
0.5 parts LPO,
0.05 parts of a copolymer of methyl methacrylate / methacrylate / ethyl methacrylate sulfonate,
Sodium sulfate 0.5 part,
250 parts of ion exchange water.

  After sufficiently replacing the inside of the container with nitrogen gas, the mixture was heated to 75 ° C. with stirring and polymerized in a nitrogen gas stream. After 2 hours, the temperature was raised to 90 ° C. and maintained for an additional 45 minutes to complete the polymerization. Then, the obtained polymer beads were dehydrated and dried to obtain a polymer (V-1) containing a hydroxyl group.

  The obtained polymer (V-1) containing a hydroxyl group had an intrinsic viscosity of 0.076 L / g and a glass transition temperature of 93 ° C.

<7. Production of thermoplastic polymer (VII-1)>
The reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, and as an emulsifier, 1 part of a trade name “Latemul ASK” and 0.15 part of potassium persulfate were charged.

  Next, 40 parts of MMA, 2 parts of n-BA and 0.004 part of n-OM were charged and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization.

  Subsequently, a monomer component consisting of 44 parts of MMA and 14 parts of n-BA was added dropwise over 2 hours and then held for 2 hours to complete the polymerization.

  The polymer latex of the obtained thermoplastic polymer (VII-1) is added to a 0.25% aqueous sulfuric acid solution, and the polymer is acidified, then dehydrated, washed with water, and dried to give a powdery thermoplastic heavy. Combined (VII-1) was recovered.

  The reduced viscosity of the obtained thermoplastic polymer (VII-1) was 0.38 L / g.

<8. Production of multilayer structure polymer (I-6)>
The following (C) and (R) were charged into a reaction vessel, and added at 75 ° C. under a nitrogen atmosphere over 8 minutes with stirring. Thereafter, this was held for 60 minutes to obtain a latex of the innermost polymer inner layer (I-6-A ₁ ). The Tg of the innermost polymer inner layer (I-6-A ₁ ) was -37 ° C. Subsequently, the following (nu) was added dropwise at 75 ° C. under a nitrogen atmosphere over 120 minutes while stirring, and then held for 60 minutes to complete the polymerization, and the innermost polymer outer layer (I-6-A ₂ ) Formed. The innermost polymer outer layer (I-6-A ₂ ) had a Tg of −49 ° C.

  Subsequently, the following (l) was added dropwise at 75 ° C. under a nitrogen atmosphere over 45 minutes while stirring, and then held for 60 minutes to complete the polymerization, thereby forming an intermediate layer (I-6-B). The Tg of the intermediate layer (I-6-B) alone was -10 ° C.

  Finally, the following (v) was added dropwise over 90 minutes while stirring at 75 ° C. under a nitrogen atmosphere. After completion of the addition, the mixture was stirred at 75 ° C. for 60 minutes to react the outermost polymer layer (I-6-C). Completed. The Tg of the outermost polymer layer (I-6-C) alone was 68 ° C.

  The average particle size of the obtained multilayer structure polymer (I-6) was 0.11 μm.

  The polymer latex of the obtained multilayer structure polymer (I-6) was filtered using a vibration type filtration device in which a SUS mesh (average opening 62 μm) was attached to a filter medium, and then 3.5 parts of calcium acetate was contained. Salting out was performed in an aqueous solution, and after washing with water and drying, a powdery multilayer structure polymer (I-6) was obtained. The gel content of the multilayer structure polymer (I-6) was 75%.

(H) 200 parts of deionized water,
Sodium formaldehyde sulfoxylate 0.2 part,
0.0001 part ferrous sulfate,
0.0003 parts EDTA,
(Li) 1.6 parts of MMA,
n-BA 8.0 parts,
0.4 parts of 1,3-BD,
0.1 part AMA,
CHP 0.05 parts,
Toho Chemical Industries, Ltd .: Phosphanol RS610NA 0.9 part,
(Product name)
(Nu) 2 parts of MMA,
37 parts of n-BA,
1,3-BD 1 part,
0.5 parts AMA,
0.5 part of CHP,
(Le) MMA 4 parts,
6 parts of n-BA,
0.1 part AMA,
CHP 0.05 parts,
(Wo) 34 parts of MMA,
6 parts of n-BA,
0.5 parts t-BH,
n-OM 0.13 parts.

<9. Production of thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain>
50 parts of methyl ethyl ketone was placed in a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the temperature was raised to 80 ° C. Under a nitrogen atmosphere, a mixture of 79.9 parts of methyl methacrylate, 20.1 parts of glycidyl methacrylate and 0.5 parts of azobisisobutyronitrile was added dropwise over 3 hours. Thereafter, a mixture of 80 parts of methyl ethyl ketone (boiling point 79.6 ° C.) and 0.2 part of azobisisobutyronitrile was added and polymerized. After 4 hours, 74.4 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine and 10.1 parts of acrylic acid were added and stirred at 80 ° C. for 30 hours while blowing air. Then, after cooling, the reaction product was taken out from the flask, and a solution of a thermoplastic resin (z-1) having a radical polymerizable unsaturated group in the side chain was obtained.

  The polymerization rate of the monomer in the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain is 99.5% or more, the polymer solid content is about 35% by mass, and the number average molecular weight is about 3%. The glass transition temperature was about 105 ° C., and the double bond equivalent was an average of 788 g / mol.

<10. Production of colloidal silica (inorganic fine particles (a-3))>
In a flask equipped with a stirrer, a condenser, and a thermometer, IPA-ST (isopropanol-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd.), silica particle size = 15 nm) 1 part, KBM503 (γ- Add 0.1 part of methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight = 248) and 0.3 part of water, raise the temperature of the hot water bath to 75 ° C. with stirring, and increase the temperature to 2 at that temperature. By reacting for a period of time, colloidal silica dispersed in isopropanol and having a surface treated with a silane compound was obtained. Subsequently, isopropanol was distilled off and toluene (boiling point 110.6 ° C.) was repeatedly added. By completely replacing isopropanol with toluene, the colloidal was dispersed in toluene and the surface was treated with a silane compound. Silica was obtained.

<11. Production of photocurable resin solution>
100 parts by weight of thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain, 3 parts of 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator (z-2)) A photocurable resin solution composed of 66 parts of colloidal silica (inorganic fine particles (a-3)) was prepared by stirring with a propeller mixer.

[Example 1]
In 100 parts of the multilayer structure polymer (I-1), 2.7 parts of a trade name “Tinuvin 234” manufactured by Ciba Specialty Chemicals Co., Ltd. And 0.3 parts of “Adeka Stub LA-57” (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) were added, and then mixed using a Henschel mixer. This mixture [resin composition (III-1)] was supplied to a degassing extruder (PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.) heated to 230 ° C. and kneaded to obtain pellets.

  The pellets produced by the above method were dried overnight at 80 ° C., and using a 40 mmφ non-vent screw type extruder (L / D = 26) fitted with a 300 mm wide T die, the cylinder temperature was 180-240 ° C., T An acrylic resin film (A) having a thickness of 125 μm was formed under the condition of a die temperature of 240 ° C. In addition, in formation of a decoration layer (B), there were few printing omissions and it was favorable.

[Example 2]
Instead of 100 parts of multilayer structure polymer (I-1), 90 parts of multilayer structure polymer (I-1) and thermoplastic polymer (II-1) [MMA / MA copolymer (MMA / MA = 99 / 1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g)] was used in the same manner as in Example 1 except that 10 parts were used to obtain a mixture [resin composition (III-2)]. A film-like material (A) was formed. In addition, in formation of a decoration layer (B), there were few printing omissions and it was favorable.

Example 3
In the same manner as in Example 1, except that 75 parts of the multilayer polymer (I-1) and 25 parts of the thermoplastic polymer (II-1) were used instead of 100 parts of the multilayer polymer (I-1). Thus, a mixture [resin composition (III-3)] was obtained, and an acrylic resin film (A) was formed. In addition, in formation of a decoration layer (B), there were few printing omissions and it was favorable.

Example 4
The same procedure as in Example 1 was conducted except that 90 parts of the multilayer structure polymer (I-2) and 10 parts of the thermoplastic polymer (II-1) were used instead of 100 parts of the multilayer structure polymer (I-1). Thus, a mixture [resin composition (III-4)] was obtained, and an acrylic resin film (A) was formed into a film. In addition, in formation of a decoration layer (B), there were few printing omissions and it was favorable.

Example 5
Instead of 2.7 parts of the product name “Tinubin 234” manufactured by Ciba Specialty Chemicals, which was used as one of the compounding agents, 2.1 parts of the product name “Adeka Stub LA-31” manufactured by Asahi Denka Kogyo Co., Ltd. was added. A mixture [resin composition (III-5)] was obtained in the same manner as in Example 3, and an acrylic resin film (A) was formed. In addition, in formation of a decoration layer (B), there were few printing omissions and it was favorable.

Example 6
As a compounding agent, 75 parts of the multilayer structure polymer (I-1) and 25 parts of the thermoplastic polymer (II-1), 1.4 parts of the product name “Tinubin 234” manufactured by Ciba Specialty Chemicals, and the product of Asahi Denka Kogyo Co., Ltd. In the same manner as in Example 3, except that 0.1 part of the name “Adeka Stub AO-50” and 0.3 part of the product name “Adeka Stub LA-67” manufactured by Asahi Denka Kogyo Co., Ltd. were added [Resin Composition (III −6)] pellets were obtained. And using the pellet of this mixture [resin composition (III-6)], in the case of film forming, two acrylic resin film-like materials in the melted state were extruded under the condition that the slit width of the T die was 0.5 mm. A 125 μm acrylic resin film is formed by passing between the metal cooling rolls and holding the resin without any bank (resin pool), transferring the surface without rolling, and winding it around a paper roll with a winder. A film was produced in the same manner as in Example 3 except that the product (A) was produced. In addition, in formation of a decoration layer (B), there was no printing omission and it was favorable.

[Comparative Example 1]
As a compounding agent, 100 parts of the multilayer structure polymer (I-3), 2.1 parts of a product name “ADK STAB LA-31” manufactured by Asahi Denka Kogyo Co., Ltd., 0.1 parts of a product name “ADK STAB AO-50” manufactured by Asahi Denka Kogyo Co., Ltd. And 0.3 part of “Adeka Stub LA-57” manufactured by Asahi Denka Kogyo Co., Ltd. were added, followed by mixing using a Henschel mixer. This mixture [resin composition (III-7)] was supplied to a degassing extruder (PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.) heated to 230 ° C. and kneaded to obtain pellets. Then, an acrylic resin film (A) was formed in the same manner as in Example 1 except that the pellet of the mixture [resin composition (III-7)] was used.

[Comparative Example 2]
In the same manner as in Comparative Example 1, except that 32 parts of the multilayer structure polymer (I-4) and 68 parts of the thermoplastic polymer (II-1) were used instead of 100 parts of the multilayer structure polymer (I-3). Thus, a mixture [resin composition (III-8)] was obtained, and an acrylic resin film (A) was formed.

[Comparative Example 3]
In the same manner as in Comparative Example 1, except that 16 parts of the multilayer structure polymer (I-5) and 84 parts of the thermoplastic polymer (II-1) were used instead of 100 parts of the multilayer structure polymer (I-3). Thus, a mixture [resin composition (III-9)] was obtained, and an acrylic resin film (A) was formed.

Example 7
100 parts of a multilayer structure polymer (I-1), 10 parts of a polymer (V-1) containing a hydroxyl group, 2.7 parts of a trade name “Tinuvin 234” manufactured by Ciba Specialty Chemicals as a compounding agent, manufactured by Asahi Denka Kogyo Co., Ltd. The product name “Adeka Stub AO-50” 0.1 part and the product name “Adeka Stub LA-57” 0.3 part by Asahi Denka Kogyo Co., Ltd. were mixed using a Henschel mixer. This mixture [resin composition (IV-1)] was supplied to a degassing extruder (PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.) heated to 230 ° C. and kneaded to obtain pellets.

  The obtained pellets were dried overnight at 80 ° C., and using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm wide T die, the cylinder temperature was 180 to 240 ° C., the T die temperature was 240 An acrylic resin film (A) having a thickness of 125 μm was formed under the condition of ° C.

Example 8
Instead of using 100 parts of the multilayer structure polymer (I-1), 90 parts of the multilayer structure polymer (I-1) and 10 parts of the thermoplastic polymer (II-1) used in Example 2 were used. A mixture [resin composition (IV-2)] was obtained in the same manner as in Example 7, and an acrylic resin film (A) was formed.

Example 9
Instead of using 100 parts of the multilayer structure polymer (I-1), 75 parts of the multilayer structure polymer (I-1) and 25 parts of the thermoplastic polymer (II-1) used in Example 2 were used. A mixture [resin composition (IV-3)] was obtained in the same manner as in Example 7, and an acrylic resin film (A) was formed.

Example 10
As a compounding agent, 2.7 parts of a trade name “Tinubin 234” manufactured by Ciba Specialty Chemicals, 0.1 part of a trade name “Adeka Stub AO-50” manufactured by Asahi Denka Kogyo Co., Ltd., a trade name “Adeka Stub LA-57” manufactured by Asahi Denka Kogyo Co., Ltd. A mixture [resin composition (IV-4)] was obtained in the same manner as in Example 8, except that 0.3 part and 0.4 part of Asahi Denka Kogyo's trade name “ADK STAB 260” were used, and an acrylic resin was obtained. A film-like material (A) was formed.

Example 11
Pellets were obtained in the same manner as in Example 8.

  The obtained pellets were dried overnight at 80 ° C., and using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm wide T die, the cylinder temperature was 180 to 240 ° C., the T die temperature was 240 Melt extrusion was performed through a T die under the condition of ° C. The extruded resin is sandwiched between a mirror mirror roll for cooling adjusted to 75 ° C. (a chrome-plated roll having a surface roughness of 0.2S) and a silicone rubber roll containing 50 parts of alumina having an average particle size of 40 μm. A 125 μm thick acrylic resin film (A) was formed. In addition, when the film of Example 11 was used, printing omission did not occur.

Example 12
Asahi Denka Kogyo Co., Ltd. trade name “Adeka Stub LA-31” 2.1 parts, Asahi Denka Kogyo Co., Ltd. trade name “Adeka Stub AO-50”, and Asahi Denka Kogyo Co., Ltd. trade name “Adeka Stub LA” A mixture [resin composition (IV-5)] was obtained in the same manner as in Example 9 except that 0.3 part of -57 "was used, and an acrylic resin film (A) was formed into a film.

Example 13
70 parts of multilayer polymer (I-1), thermoplastic polymer (II-2) [MMA / MA copolymer (MMA / MA = 90/10 (mass ratio), reduced viscosity ηsp / c = 0.56 L) / G)] 20 parts, 10 parts of a polymer (V-1) containing a hydroxyl group, 3 parts of a thermoplastic polymer (VII-1) as a compounding agent, trade name “Tinuvin 234” 1.4 manufactured by Ciba Specialty Chemicals Part, Asahi Denka Kogyo Co., Ltd. product name “Adeka Stub AO-60” 0.1 part, Asahi Denka Kogyo Co., Ltd. product name “Adeka Stub LA-67”, and Johoku Chemical Industry Co., Ltd. product name “JP333E” 0 3 parts were mixed using a Henschel mixer. This mixture [resin composition (IV-6)] was supplied to a degassing extruder (PCM-30 (trade name) manufactured by Ikegai Iron Works Co., Ltd.) heated to 230 ° C. and kneaded to obtain pellets. Then, an acrylic resin film (A) was formed in the same manner as in Example 11 except that pellets of this mixture [resin composition (IV-6)] were used. In addition, when the film of Example 13 was used, printing omission did not occur.

Example 14
The compounding ratio of the multilayer structure polymer (I-1) and the thermoplastic polymer (II-2) was 65 parts multilayer polymer (I-1) and 25 parts thermoplastic polymer (II-2). In the same manner as in Example 13, a mixture [resin composition (IV-7)] was obtained, and an acrylic resin film (A) was formed. In addition, when the film of Example 14 was used, printing omission did not occur.

Example 15
Non-vented 40mmφ with 400 mesh screen mesh, using ABS resin (trade name “Diapet ABS SW7” manufactured by UMG ABS Co., Ltd.) as the thermoplastic resin layer (C), with a 300mm wide T die attached. Using a screw type extruder (L / D = 26), melt extrusion was performed through a T die under conditions of a cylinder temperature of 180 ° C. to 220 ° C. and a T die temperature of 230 ° C. The extruded resin was formed into a 125 μm-thick thermoplastic resin film through three polishing rolls adjusted to 75 ° C.

  Next, the surface of the acrylic resin film product (A) produced in Example 13 that was in contact with the mirror roll was subjected to silver metallic printing to form a decorative layer (B). The printed acrylic resin film (A) was heat-laminated through an embossing roll so that the thermoplastic resin film layer and the decorative layer were in contact with the thermoplastic resin film to obtain a laminated film. .

Example 16
A laminated film was obtained in the same manner as in Example 15 except that the acrylic resin film (A) produced in Example 8 was used.

[Comparative Example 4]
Multilayer structure polymer (I-3) 100 parts, hydroxyl group-containing polymer (V-1) 10 parts, Asahi Denka Kogyo Co., Ltd. trade name “ADK STAB LA-31” 2.1 parts, Asahi Denka Using a mixture [resin composition (IV-8)] in which 0.1 part of the trade name “Adeka Stub AO-50” manufactured by Kogyo Co., Ltd. and 0.3 part of the trade name “Adeka Stub LA-57” manufactured by Asahi Denka Kogyo Co., Ltd. Acrylic resin film (A) was formed in the same manner as in Example 7 except that.

[Comparative Example 5]
16 parts of the multilayer structure polymer (I-5), 84 parts of the thermoplastic polymer (II-1), 10 parts of the polymer (V-1) containing a hydroxyl group, Asahi Denka Kogyo's trade name “ 2.1 parts of ADK STAB LA-31, 0.1 part of “ADK STAB AO-50” manufactured by Asahi Denka Kogyo Co., Ltd., 0.3 part of trade name “ADK STAB LA-57” manufactured by Asahi Denka Kogyo Co., Ltd., and Asahi Denka Kogyo An acrylic resin film (A) was formed in the same manner as in Example 7 except that a mixture [resin composition (IV-9)] in which 0.4 part of a trade name “ADK STAB 260” manufactured by the company was mixed was used. did.

Example 17
Pellets (resin composition (III-1)) obtained in Example 1 as an acrylic resin film (A) and pellets obtained in Comparative Example 3 as an acrylic resin film (A′-a) ( Resin composition (III-9), except that 2.7 parts of Ciba Specialty Chemicals trade name “Tinuvin 234” was used instead of 2.1 parts of trade name “ADK STAB LA31” manufactured by Asahi Denka Kogyo Co., Ltd.) Then, an acrylic resin laminated film was formed.

  Specifically, the pellets were dried at 80 ° C. for a whole day and night, using a 65 mmφ non-vent screw single screw extruder, a 40 mmφ non vent screw single screw extruder, and a 300 mm wide multi-manifold die, respectively, Co-extrusion molding is performed at a die temperature of 240 ° C., and the thickness of the acrylic resin film (A′-a) located on the surface layer is 10 μm, and the thickness of the acrylic resin film (A) located on the lower layer is 115 μm. A 125 μm thick acrylic resin laminated film was obtained. The acrylic resin film (A) was extruded with 65 mmφ, and the acrylic resin film (A′-a) was extruded with a 40 mmφ extruder.

[Examples 18 to 20]
Acrylic resin laminated film as in Example 17, except that the pellets (resin compositions (III-2) to (III-4)) obtained in Examples 2 to 4 were used as the acrylic resin film (A). Was formed.

Example 21
Pellet (resin composition) obtained by carrying out similarly to Example 1 except mixing a multilayer structure polymer (I-1) and a thermoplastic polymer (II-1) in the ratio shown in Table 6, respectively. An acrylic resin laminated film was formed in the same manner as in Example 18 except that (II-A′-1)) was used as the acrylic resin film material (A′-a).

[Example 22]
An acrylic resin laminated film was formed in the same manner as in Example 18 except that an acrylic resin “Acrypet MD” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. was used as the acrylic resin film (A′-a). In addition, the pencil hardness at the time of making this acrylic resin film-form thing (A'-a) into a 125 micrometers film independently was 3H.

Example 23
Except for using a vinylidene fluoride polymer “HYLAR460” (trade name) manufactured by Solvay Solexis, which is a fluororesin film material (A ″), instead of the acrylic resin film material (A′-a), Examples In the same manner as in Example 17, an acrylic resin laminated film was formed.

[Comparative Example 6]
Pellet (resin composition (III-9) obtained in Comparative Example 3 as an acrylic resin film (A′-a), but instead of 2.1 parts of trade name “ADK STAB LA31” manufactured by Asahi Denka Kogyo Co., Ltd. Ciba Specialty Chemicals' product name "Tinubin 234" (2.7 parts was used) and an acrylic resin film (A'-b) obtained in Comparative Example 1 (resin composition (III-7)) This was carried out in the same manner as in Example 17 except that the thickness of each layer was set to the value shown in Table 7. The acrylic resin film (A′-b) was extruded with 65 mmφ, and the acrylic resin film (A′-a) was extruded with a 40 mmφ extruder.

[Comparative Example 7]
Multilayer structure polymer (I-6) and thermoplastic polymer (II-3) [MMA / n-BA copolymer (MMA / n-BA = 77/23 (mass ratio), reduced viscosity ηsp / c = 0.08 L / g)] are mixed in the proportions shown in Table 6, and 1.5 parts by trade name “ADK STAB LA-31” manufactured by Asahi Denka Kogyo Co., Ltd. as a compounding agent, “ADK STAB AO by trade name manufactured by Asahi Denka Kogyo Co., Ltd. -50 "0.1 part, Asahi Denka Kogyo brand name" Adeka Stub LA-57 "0.3 part, Sanyo Kasei Kogyo brand name" polyethylene glycol PEG 20000 "2 parts was added, then using a Henschel mixer Except that they were mixed in the same manner as in Example 1, pellets for the acrylic resin film (A′-b) (resin composition (II-A′-2)) were obtained. It implemented like the comparative example 6 except using this pellet.

[Comparative Example 8]
It implemented similarly to the comparative example 6 except using the pellet (resin composition (III-8)) obtained by the comparative example 2 as an acrylic resin film-form (A'-b).

[Comparative Example 9]
Except mixing the multilayer structure polymer (I-4) and the thermoplastic polymer (II-3) in the ratio shown in Table 6, the same procedure as in Example 1 was carried out, and an acrylic resin film (A′- The pellet (resin composition (II-A'-3)) for b) was obtained.

  The same procedure as in Comparative Example 6 was performed except that the pellet was used as an acrylic resin film (A′-b).

[Comparative Example 10]
Pellets obtained in Comparative Example 3 (resin composition (III-9), except that 2.1 parts by trade name “Adeka Stub LA31” manufactured by Asahi Denka Kogyo Co., Ltd., trade name “Tinuvin 234” 2 manufactured by Ciba Specialty Chemicals Was used in the same manner as in Comparative Example 3 except that a 125 μm acrylic resin film was formed.

[Comparative Example 11]
An acrylic resin laminated film was formed in the same manner as in Comparative Example 6 except that an acrylic resin “Acrypet MD” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. was used as the acrylic resin film (A′-a).

[Comparative Example 12]
A comparative example, except that a vinylidene fluoride polymer “HYLAR460” (trade name) manufactured by Solvay Solexis, which is a fluororesin film material (A ″), is used instead of the acrylic resin film material (A′-a). In the same manner as in 6, an acrylic resin laminated film was formed.

Example 24
The photocurable resin solution was coated on the acrylic resin film (A) obtained in Example 1 with a comma roll coater with a coating width of 250 mm. Subsequently, the tunnel-type drying furnace (width 800 mm, height 100 mm, length 8 m, divided into four drying zones (one zone length 2 m)) set to the temperature conditions shown in Table 1 below is suitable for sheet movement. The solvent was volatilized by passing it through a method in which hot air was fed so as to form a flow) at a speed of 10 m / min to form a photocurable resin (Z) layer. The residence time in each drying zone at this time is shown in Table 1 below.

  Subsequently, it was slit into a width of 200 mm and wound into a roll shape around an ABS core to a length of 20 m.

  This photocurable acrylic resin film is placed in the mold so that the photocurable resin composition faces the inner wall surface of the mold, and then the photocurable acrylic resin film is preliminarily prepared at a temperature of 350 ° C. for 10 seconds by an infrared heater. After heating, the photocurable acrylic resin film was made to follow the mold shape by vacuum suction while further heating. The shape of the mold is a truncated pyramid shape, the size of the truncated surface is 100 mm × 100 mm, the size of the bottom surface is 108 mm × 117 mm, the depth is 10 mm, and the radius of curvature of the edge of the truncated surface is Were 3, 5, 7, and 10 mm, respectively. When the mold following property at that time was visually evaluated, each end portion followed well.

  Next, under the conditions of a molding temperature of 280 to 300 ° C. and a mold temperature of 40 to 60 ° C., a laminate molded product in which a polycarbonate resin is used as a molding resin and insert molding is performed, and a photocurable acrylic resin film is in close contact with the molded product surface. Got.

Next, using an ultraviolet irradiation device, ultraviolet rays of about 700 mJ / cm ² were irradiated to cure the photocurable resin composition, and the surface physical properties of the laminated molded product were evaluated.

Example 25
The same operation as in Example 24 was performed except that the acrylic resin film-like product (A) obtained in Example 2 was used.

Example 26
The same operation as in Example 24 was performed except that the acrylic resin film-like product (A) obtained in Example 3 was used.

Example 27
The same operation as in Example 24 was performed except that the acrylic resin film-like product (A) obtained in Example 4 was used.

Example 28
40mmφ non-vent screw type extrusion with 400 mesh screen mesh attached with 300mmT die using ABS resin (trade name “Diapet ABS SW7”, manufactured by UMG ABS) as the thermoplastic resin layer (C) Three polishing rolls using a machine (L / D = 26) with a cylinder temperature of 180 ° C. to 220 ° C. and a T die temperature of 230 ° C., and the temperature of the resin melt-extruded through the T die adjusted to 75 ° C. Was formed into a 200 μm-thick thermoplastic resin film.

  Next, on the acrylic resin film-like material (A) side of the photocurable acrylic resin film obtained in Example 26, a silver metallic-tone decorative layer (B) was formed by gravure printing.

  On the decorative layer (B) side of the photocurable acrylic resin film, the thermoplastic resin film obtained above was thermally laminated to obtain a photocurable laminated film.

  Using this photo-curable laminated film, insert molding was performed by the method described in (9) of [Measurement of physical properties and evaluation method] to produce a laminated molded product.

Next, using an ultraviolet irradiation device, ultraviolet rays of about 700 mJ / cm ² were irradiated to cure the photocurable resin composition, thereby obtaining a laminated molded product.

  The obtained laminated molded article was a molded article having a printed pattern and having excellent design properties.

[Comparative Example 13]
The same operation as in Example 24 was performed except that the acrylic resin film material (A) obtained in Comparative Example 2 was used.

[Comparative Example 14]
The same operation as in Example 24 was performed except that the acrylic resin film material (A) obtained in Comparative Example 3 was used.

Example 29
The acrylic resin film-like product (A) obtained in Example 1 was subjected to gravure printing with a wood grain pattern and jet black pattern as a decorative layer (B). Next, it arranged so that a decoration layer (B) might contact the thermoplastic resin film (C) obtained in Example 15 via the heating roll, and it heat-laminated, and obtained the laminated | multilayer film.

[Examples 30 to 33]
It implemented similarly to Example 29 except using the acrylic resin film-like material (A) obtained in Examples 2-5.

Example 34
The thermoplastic resin film (C) obtained in Example 15 is subjected to a wood grain pattern and jet black pattern by gravure printing as a decoration layer (B), and finally the decoration layer (B) is carried out via a heating roll. A laminated film was obtained by placing in contact with the acrylic resin film-like material (A) obtained in Example 3 and thermal lamination.

Example 35
It was carried out in the same manner as in Example 31 except that a laminate molded product by in-mold molding was obtained by the method described in column [8] of [Measurement of physical properties and evaluation].

Example 36
The same operation as in Example 29 was carried out except that the acrylic resin film (A) obtained in Example 6 was used.

  In addition, in the decoration layer (B) formation, there was no printing omission and it was favorable.

[Comparative Examples 15-17]
The same operation as in Example 29 was performed except that the acrylic resin film (A) obtained in Comparative Examples 1 to 3 was used.

Example 37
Two-component curable urethane formed by blending 3% by mass of an isocyanate curing agent with a polyester polyol-based vehicle on the surface of a colored random polypropylene resin film (manufactured by Riken Vinyl Industry Co., Ltd.) having a thickness of 90 μm as the thermoplastic resin layer (C). The decorative layer (B) (wood grain pattern and jet black pattern) is printed by the gravure printing method using resin-based ink "Lamistor" (manufactured by Toyo Ink Co., Ltd .; trade name), and acrylic-polyester- is printed on the printed surface. A vinyl chloride-based heat-adhesive resin was applied by a gravure coating method to a coating amount after drying of 1.5 g / m ² to form an adhesive layer (D). Thereafter, a 50 μm acrylic resin film (A) obtained by the same method as in Example 1 as a surface protective layer was thermally laminated on the adhesive layer surface under the condition of a film surface temperature of 120 ° C., and the surface temperature of 180 ° C. The pipe pattern was embossed with a metal embossing roll to obtain a laminated film for building materials. Next, an aqueous two-component urethane adhesive is applied as an adhesive layer (D) to this building material laminated film by spray coating to a coating amount of 10 g / m ² after drying, and is a polyester resin tertiary having a radius of curvature of 0.5R. The original shape base material was three-dimensionally laminated under the condition of a laminated film temperature for building materials of 80 ° C. to obtain a laminated molded product having a three-dimensional shape.

[Examples 38 to 40]
The same procedure as in Example 37 was performed except that a 50 μm acrylic resin film (A) obtained by the same method as in Examples 2 to 4 was used.

[Comparative Examples 18-20]
It implemented like Example 37 except using the 50-micrometer acrylic resin film-form (A) obtained by the method similar to Comparative Examples 1-3.

  Table 2 shows the resin component compositions and gel contents of the resin compositions (III) [resin compositions (III-1 to 9)] used in Examples 1 to 6 and Comparative Examples 1 to 3. Table 3 shows the evaluation results of the obtained acrylic resin film (A) and laminated molded product.

  Table 4 shows the resin component compositions and gel contents of the resin compositions (IV) [resin compositions (IV-1 to 9)] used in Examples 7 to 16 and Comparative Examples 4 and 5. Table 5 shows the evaluation results of the obtained acrylic resin film (A) and laminated molded product.

  Resin composition (III-1 to 4) and (III-7 to 9) and resin composition of resin composition (III-A'-1 to 3), gel content, flexural modulus and the like Table 6 shows the evaluation results of the produced acrylic resin film (A). Table 7 shows the types of film-like materials used for the acrylic resin laminated film and the evaluation results of the obtained laminated molded product.

  Table 8 shows the evaluation results of the acrylic resin film products (A), photocurable acrylic resin films, and laminated molded products obtained in Examples 24-28 and Comparative Examples 13 and 14.

  Table 9 shows the evaluation results of the acrylic resin film products (A), laminated films and laminated molded products obtained in Examples 29 to 36 and Comparative Examples 15 to 17.

  Table 10 shows the evaluation results of the acrylic resin film (A) and the laminated film for building materials obtained in Examples 37 to 40 and Comparative Examples 18 to 20.

  The acrylic resin film materials (A) of Examples 1 to 16 having a pencil hardness of 2B or more were excellent in scratch resistance. The acrylic resin film-like materials (A) of Examples 2 to 6 and 8 to 16 having a pencil hardness of F or more showed particularly excellent scratch resistance, and no damage was observed. Further, a test piece after performing a tensile test on a test piece having a width of 20 mm under a condition of a chuck distance of 25 mm, a speed of 50 mm / min, and a temperature of 23 ° C. so that the end-chuck distance is 33 mm is JIS K7136 (cloudy Example 1 in which the difference between the value measured by the test method of the titer) and the value measured by the test method of JIS K7136 (the haze value measuring method) of the test piece before the test is 30% or less In the acrylic resin film-like material (A) to -16, no problem occurred in both the grain and jet black in terms of molding whitening resistance. Moreover, the acrylic resin film material (A) of Examples 1-16 did not have a problem in the printed state near the gate.

  On the other hand, the acrylic resin film-like materials (A) of Comparative Examples 1 and 4 having a pencil hardness of less than 2B lack in scratch resistance, and further have a heat deformation temperature of 79 ° C., so that they satisfy heat aging resistance. It is not a thing, and industrial utility value will become low. The acrylic resin film-like material (A) of Comparative Examples 2, 3 and 5 in which the difference in the haze value of each test piece exceeds 30% before and after the tensile test is sufficiently satisfying the molding whitening resistance. However, the value is low when considering industrial use, such as molding whitening is noticeable in both wood grain and jet black, and the printed pattern disappears.

  Moreover, the laminated molded products of Examples 17 to 40 each having the acrylic resin film-like product (A) of Examples 1 to 16 all had good characteristics.

  In Examples 17 to 23, an acrylic resin multilayer film excellent in molding whitening resistance, scratch resistance, and heat aging resistance during wood grain printing, which could not be obtained with a conventionally known acrylic resin multilayer film, was obtained. It was.

  The laminated molded article having the acrylic resin film-like product (A) of the present invention is particularly suitable for vehicle use and building material use. Specific examples include instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior applications, weather strips, bumpers, bumper guards, side mud guards, body panels, Spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts, and other automotive exterior applications, AV equipment and furniture products Applications such as front panels, buttons, emblems, surface cosmetics, housings for mobile phones, display windows, buttons, etc. Building interior materials such as surfaces, ceilings, floors, exterior walls such as siding, exterior materials for buildings such as fences, roofs, gates, and windbreak boards, surfaces of furniture such as window frames, doors, handrails, sills, and duck Cosmetic materials, various displays, lenses, mirrors, goggles, window glass and other optical components, trains, airplanes, ships and other vehicles other than automobiles, interior and exterior applications, bottles, cosmetic containers, various packaging such as accessories It can be suitably used for various other uses such as containers and materials, miscellaneous goods such as prizes and accessories.

Claims (14)

A test piece having a width of 20 mm was subjected to a tensile test with an initial chuck distance of 25 mm, a speed of 50 mm / min, and a temperature of 23 ° C. so that the end-chuck distance was 33 mm. The test piece was JIS K7136 (cloudiness value). The difference between the value measured by the test method of) and the value measured by the test method of JIS K7136 (cloudiness value measurement method) of the test piece before the test is 30% or less, and a pencil Hardness (measurement based on JIS K5400) is 2B or more,
Containing an innermost layer polymer layer composed of two layers of an inner layer and an outer layer, an intermediate layer polymer layer, and a multilayer structure polymer having an outermost layer polymer layer;
The inner layer and the outer layer are both obtained by polymerizing a monomer component containing an alkyl acrylate ester and a graft crossing agent,
The intermediate layer polymer layer is obtained by polymerizing a monomer component containing an alkyl acrylate ester, an alkyl methacrylate ester and a graft crossing agent,
The outermost polymer layer is obtained by polymerizing a monomer component containing an alkyl methacrylate.
The acrylic resin film-like product (A) in which the Tg of the inner layer is less than −30 ° C. and the Tg of the outer layer is −15 ° C. to 10 ° C.   The acrylic resin film-like product (A) according to claim 1, wherein at least one surface has a 60 ° surface glossiness of 100% or less.   The acrylic resin film-like product (A) according to claim 1 or 2, wherein the heat distortion temperature (measured based on ASTM D648) is 80 ° C or higher.   Furthermore, the acrylic resin film material (A) in any one of Claims 1-3 which has a decorating layer at least on one side.   It is an acrylic resin laminated film which has an acrylic resin film-like material (A) in any one of Claims 1-3, Comprising: Another acrylic resin film-like material (A ') or a fluororesin film-like material (A' ') Acrylic resin laminated film having.   Furthermore, the acrylic resin laminated film of Claim 5 which has a decorating layer at least on one side.   The acrylic resin film (A) according to any one of claims 1 to 3 or the acrylic resin laminated film according to claim 5, and a thermoplastic resin (z-1) having a radically polymerizable unsaturated group in a side chain. And a photocurable resin composition (Z) layer containing a photopolymerization initiator (z-2).   Furthermore, the photocurable acrylic resin film or sheet | seat of Claim 7 which has a decorating layer at least on one side.   The acrylic resin film-like product (A) according to any one of claims 1 to 3, the acrylic resin laminated film according to claim 5, and the photocurable acrylic resin film or sheet according to claim 7 selected from the group. And a laminated film or sheet having a thermoplastic resin layer (C).   The laminated film or sheet according to claim 9, further comprising a decorative layer (B).   A laminated film or sheet for building materials comprising the laminated film or sheet according to claim 9 or 10.   The acrylic resin film-like product (A) according to any one of claims 1 to 4, the acrylic resin laminated film according to claim 5 or 6, the photocurable acrylic resin film or sheet according to claim 7 or 8, and A laminated molded product, wherein one of the laminated film or sheet according to claim 9 or 10 and one selected from the group consisting of the laminated film or sheet for building materials according to claim 11 are laminated on a substrate (E).   The acrylic resin film-like product (A) according to any one of claims 1 to 4, the acrylic resin laminated film according to claim 5 or 6, the photocurable acrylic resin film or sheet according to claim 7 or 8, and One selected from the group consisting of the laminated film or sheet according to 9 or 10 and the laminated film or sheet for building material according to claim 11 is subjected to vacuum forming or pressure forming in an injection mold, and thereafter The laminated molded product according to claim 12, which is obtained by injection molding and integrating the resin to be the base material (E) in an injection mold.   The acrylic resin film-like product (A) according to any one of claims 1 to 4, the acrylic resin laminated film according to claim 5 or 6, the photocurable acrylic resin film or sheet according to claim 7 or 8, and One selected from the group consisting of the laminated film or sheet according to claim 9 or 10 and the laminated film or sheet for building material according to claim 11 is subjected to vacuum forming or pressure forming, and then inserted into an injection mold. The laminated molded product according to claim 12, which is obtained by injection molding a resin to be the base material (E) in the injection mold.