JP2007161735A - Matte acrylic resin film-like matter for thermoforming, manufacturing method of matte acrylic resin film-like matter for thermoforming, and laminated product comprising matte acrylic resin film-like matter for thermoforming - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a matte acrylic resin film for thermoforming that has unprecedented designability, is readily handleable, causes no cracks in a matte layer even when molded into a deep drawn shape by insert molding or in-mold molding and exhibits scratch resistance, surface hardness, chemical resistance, heat resistance, matte properties and thermal yellowing resistance which are required of a decoration film of components for vehicles, and a laminated product comprising a substrate and the film laminated thereon. <P>SOLUTION: The matte acrylic resin film for thermoforming comprises an acrylic resin film substrate, a coating comprising a matte agent and a binder resin coated on the surface thereof, and a matte layer formed as the outermost layer, where the matte layer side has a dynamic friction coefficient of at most 0.23. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a matte acrylic resin film for thermoforming, a method for producing a matte acrylic resin film for thermoforming, and a laminate comprising the matte acrylic resin film for thermoforming.

  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 film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated for printing or the like is previously formed into a three-dimensional shape by vacuum forming 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 film or sheet such as polyester resin, polycarbonate resin, or acrylic resin 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.

  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 Document 1). 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.

  Also disclosed is a matted acrylic resin film comprising a matte layer made of a heat or photocurable resin and inorganic fine particles and an acrylic resin film substrate, which can maintain good matting performance even after molding. (For example, refer to Patent Document 2).

  Further, a matte acrylic insert film is disclosed in which a matte layer is formed on one side of a transparent acrylic film and at least a pattern layer is formed on the other side (see, for example, Patent Document 3).

  Further, a suede-like molding sheet is disclosed in which a specific matte paint film is provided on a base film having good moldability (see, for example, Patent Document 4).

  In recent years, members having a matte acrylic resin film-like layer on the surface layer formed by an insert molding method or an in-mold molding method have been used as parts for vehicle applications.

  An acrylic resin film-like product having a specific film surface glossiness, good printability, and excellent matteness, surface hardness, heat resistance, and moldability can be obtained (for example, see Patent Document 1). However, since these acrylic resin film-like materials knead the matting agent into the base acrylic resin, the matting agent to be used is limited. Specifically, when organic fine particles having a cross-linking structure mainly containing components other than acrylic resin or inorganic fine particles are used, the haze value of the matte acrylic resin film is increased although it is in a matte state. Therefore, when a decorative layer is formed on one side of a matte acrylic resin film and the molded product is obtained with the decorative layer in contact with the base material, the decorative pattern of the molded product appears to be cloudy. The utility value was low. In addition, when organic fine particles having a crosslinked structure or inorganic fine particles are used, the matte acrylic resin film-like material becomes brittle, and depending on the amount added, the handling of the film in the film forming process may be difficult. When the film is used under severe conditions such as deep drawing during in-mold molding or insert molding, the film may be cracked or torn.

  Moreover, the acrylic resin film which can maintain favorable matte property after shaping | molding is obtained (for example, refer patent document 2). In this publication, a heat or photocurable resin containing inorganic fine particles is formed on an acrylic resin film as a matte layer. If a matte film using a thermosetting resin is used for the matte layer, the matte layer may break if the film is stretched during vacuum molding during in-mold molding or insert molding. The thickness and the composition of the curable resin to be used are important, but the matte acrylic resin film disclosed in the examples has limitations on molding conditions because the matte layer is easily broken. In addition, when used for vehicle interior applications, scratch resistance is required, so although these acrylic resin films have reached a certain level, the surface wears over time, so they can be used for a long time. In such a case, the appearance may have a glossy appearance. In order to improve the scratch resistance, a wax is often used, but there is no description about an optimal wax. Further, in the matte acrylic resin film obtained by the printing method or the coating method, the matte appearance may change due to heat during molding. Moreover, when insert molding or in-mold molding is performed using an acrylic resin film with a matte layer made of a thermosetting resin, it may turn yellow depending on the heating conditions of the film. No specific method for obtaining a film is described. Moreover, insert molding may be performed using the lamination sheet which consists of an acrylic resin film-form thing and a base material sheet. At this time, if the heat shrinkage rate of the acrylic resin film material is large, the acrylic resin film material peels off from the base sheet during insert molding. In this publication, the heat shrinkage rate of the acrylic resin film material is specific. There is no proper description. In addition, when producing a matte acrylic resin film by a printing method or a coating method, the physical properties of the acrylic resin film as a base material are reduced by the solvent attack. However, there is no description on the optimum coating conditions in this publication.

  Further, a matte acrylic insert film in which a matte layer is formed on one surface of a transparent acrylic film and at least a pattern layer is formed on the other surface is obtained (see, for example, Patent Document 3). In this publication, a matte acrylic film made of fluororesin-based spherical fine particles and an acrylic resin is disclosed as a matte layer, but means for improving moldability when a curable resin is used for the matte layer is disclosed. Not disclosed. In order to improve the scratch resistance, wax is often used, but there is no specific description about the wax. Although it is considered that the fluororesin-based spherical particles also serve as a wax, there is a possibility that there is a problem in productivity. Furthermore, the curable resin used as the binder resin is not specifically described. In the examples, a thermoplastic resin is used and the chemical resistance is poor. Further, in the matte acrylic resin film obtained by the printing method or the coating method, the matte appearance may change due to heat during molding. Moreover, when insert molding or in-mold molding is performed using an acrylic resin film with a matte layer made of a thermosetting resin, it may turn yellow depending on the heating conditions of the film. No specific method for obtaining a film is described.

In addition, a suede-like sheet is provided in which a coating film made of a bead pigment having a specific particle size and an ionizing radiation curable resin is provided on a base film having good moldability (see, for example, Patent Document 4). In this publication, since ionizing radiation curable resin is used as the binder resin, when forming into a deep-drawn shape molded product at the time of in-mold or insert molding, the moldability of the ionizing radiation curable resin and the base film is different. There is a possibility that molding defects such as cracking and tearing may occur due to insufficient expansion of the curable resin layer, but there is no description regarding the optimum mat layer thickness to solve this. Although it has been disclosed that a thermoplastic resin is mixed in order to improve moldability, this method has a problem that chemical resistance is lowered. Further, in the matte film obtained by the printing method or the coating method, the matte appearance may change due to heat during molding. No means for solving these problems is disclosed. Moreover, there is no description about the acrylic resin film suitable for using for a base material.
JP 2002-361712 A JP 2003-111598 A Japanese Patent Laid-Open No. 10-34703 Japanese Examined Patent Publication No. 7-110531

  The present invention expresses a design that is difficult to realize when a matting agent is added to a conventional acrylic resin film layer, has good handleability, is subjected to insert molding or in-mold molding, and has a deep-drawn shape. Even when molded into a molded product, the matte layer does not crack and can be used for vehicle applications with scratch resistance, surface hardness, heat resistance, chemical resistance, heat yellowing, and matte heat An object is to provide a matte acrylic resin film for molding. It is another object of the present invention to provide an optimum manufacturing method for obtaining a matte acrylic resin film for thermoforming. Furthermore, an object of this invention is to provide the laminated body 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 matte acrylic resin film for thermoforming, in which a paint containing a matting agent and a curable binder resin is applied on the surface of an acrylic resin film substrate, and a matte layer is formed on the outermost layer, A matte acrylic resin film for thermoforming having a coefficient of dynamic friction on the matte layer side of 0.23 or less.

  [2] The matte acrylic resin film for thermoforming of [1], further comprising a pattern layer on the surface of the acrylic resin film substrate opposite to the matte layer.

  [3] The method for producing a matte acrylic resin film for thermoforming according to [1], wherein the matte layer is formed by a printing method or a coating method.

  [4] The method for producing a matte acrylic resin film for thermoforming according to the above [1], having 150 or more lines per inch and at an angle of 40 to 50 ° with respect to a roll axis direction. A method for producing a matte acrylic resin film for thermoforming, wherein a matte layer is formed using an engraved oblique roll.

  [5] A laminate obtained by laminating the matte acrylic resin film for thermoforming described in [1] on a base material so that a surface opposite to the matte layer is in contact.

    The matte acrylic resin film for thermoforming of the present invention exhibits a design that is difficult to realize when a matting agent is added to a conventional acrylic resin film substrate, has good handleability, and is insert molded or in-mold. Even when molded and deep-drawn, the matte layer does not crack, and the scratch resistance, surface hardness, chemical resistance, heat resistance, matteness required for automotive parts, It has heat-resistant yellow discoloration.

    Moreover, according to the manufacturing method of the matte acrylic resin film for thermoforming of this invention, such a matte acrylic resin film can be manufactured stably.

    Furthermore, the laminate of the present invention is excellent in design, has scratch resistance, surface hardness, chemical resistance, heat resistance, matting property, and heat yellowing discoloration, and has a crack in the matte layer on the surface. There are no defects.

<Acrylic resin film substrate>
As the acrylic resin film substrate used in the present invention, a known acrylic resin film can be used, but it has scratch resistance, pencil hardness, heat resistance, and chemical resistance that can be used for vehicles. For example, those disclosed in JP-A-8-323934, JP-A-11-147237, JP-A-2002-80678, JP-A-2002-80679, and JP-A-2005-97351 are preferable. Further, from the viewpoint of resistance to molding whitening when insert molding or in-mold molding is performed, those disclosed in JP-A-2005-163003 and JP-A-2005-139416 are preferable.

(Heat shrinkage)
The acrylic resin film base is preferably one that does not shrink as much as possible during heating. When a matte acrylic resin film for thermoforming is bonded to a base material sheet such as ABS and insert molding is performed, if the acrylic resin film base is greatly contracted, it may be peeled off from the base material sheet.

  As the acrylic resin film substrate, an acrylic resin film substrate having a MD direction heat shrinkage of 50% or less and a TD direction heat shrinkage of −10 to 10% by heat treatment at 130 ° C. for 60 minutes is preferable. Such an acrylic resin film substrate is subjected to insert molding or in-mold molding, resulting in good adhesion between the matte layer and the acrylic resin film substrate when formed into a laminate, and has high industrial utility value. Specifically, in a laminate for use in vehicles, a laminate that does not peel at the interface between the matte layer and the acrylic resin film substrate when the adhesion between the matte acrylic resin film and the laminate substrate is evaluated. Is obtained. In addition, when a laminated sheet obtained by laminating a matte acrylic resin film on a base sheet is used as a decorative film or sheet, the base sheet and the acrylic resin film base are heated during insert molding or in-mold molding. From the viewpoint of suppressing peeling at the interface, it is preferable that the acrylic resin film substrate has a small shrinkage ratio upon heating. The MD direction heat shrinkage of the acrylic resin film substrate is preferably 30% or less, and more preferably 15% or less. Moreover, 0% or more is preferable. The TD-direction heat shrinkage of the acrylic resin film substrate is preferably 0 to 5%.

    The measurement of the heat shrinkage rate is performed as follows. First, three parallel straight lines are drawn at intervals of 5 cm in the MD direction (flow direction during film formation) and the TD direction (direction perpendicular to the MD direction) on the surface of the acrylic resin film substrate cut out to A4 size. Measure the interval accurately with calipers. The interval is measured at two locations, and the measured locations are marked. Thereafter, the sample is left in an atmosphere at 130 ° C. for 60 minutes and taken out, and then the interval between the same positions as previously measured is measured again. The heat shrinkage rate is calculated from the following formula using the average value of the distance between the two locations.

Heat shrinkage rate (%) = ((interval before heating−interval after heating) / interval before heating) × 100
In the acrylic resin film in which the MD direction and the TD direction are unknown, the MD direction and the TD direction are specified as follows, for example. Draw a circle with a specific radius on the film, heat-treat the conditions described above, and determine the direction in which the shrinkage rate is maximized from the shape of the circle (or ellipse if there is anisotropy) on the film. The direction is the MD direction, and the direction perpendicular to the MD direction is the TD direction.

(Pencil hardness)
The pencil hardness (measured based on JIS K5600) of the acrylic resin film substrate is preferably 2B or more, more preferably HB or more, in order to increase the pencil hardness of the matte acrylic resin film of the present invention, F The above is particularly preferable.

(Method for producing acrylic resin film substrate)
Examples of the method for producing the acrylic resin film substrate include known methods such as a melt casting method such as a melt casting method, a T-die method, and an inflation method, and a calendar method. Of these, the T-die method is preferable from the viewpoint of economy.

  When the acrylic resin film substrate is formed by the T-die method, it is preferable to use 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. According to this method, the surface smoothness of the resulting matte acrylic resin film is improved, the coating missing when forming the matte layer on the acrylic resin film substrate, and the printing missing when printing on the matte acrylic resin film. Can be suppressed. As the metal roll, it is used in a sleeve touch method comprising a metal mirror surface touch roll; a metal sleeve (metal thin film pipe) described in Japanese Patent No. 2808251 or International Publication No. 97/28950, and a molding roll. Rolls and the like. Examples of the non-metallic roll include a touch roll made of silicon rubber. Examples of the metal belt include a metal endless belt. A plurality of these metal rolls, non-metal rolls and metal belts may be used in combination.

  In the method of forming a film by sandwiching a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts, the raw material after melt extrusion is sandwiched in a state where there is substantially no bank (resin pool). However, it is preferable to form a film by transferring the surface without substantially rolling. When the film is formed without forming a bank (resin pool), the raw material in the cooling process is surface-transferred without being rolled, so the heat shrinkage rate of the acrylic resin film substrate formed by this method is reduced. be able to.

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

  The thickness of the acrylic resin film substrate is preferably 10 to 500 μm. By setting the thickness of the acrylic resin film substrate to 500 μm or less, rigidity suitable for insert molding and in-mold molding can be obtained, and the film can be manufactured more stably. Moreover, by making the thickness of the acrylic resin film substrate 10 μm or more, the sense of depth can be more sufficiently imparted to the resulting laminate together with the protection of the substrate. The thickness of the acrylic resin film substrate is more preferably 30 μm or more, and particularly preferably 50 μm or more. The thickness of the acrylic resin film substrate is more preferably 300 μm or less, and particularly preferably 200 μm or less.

<Matte layer>
The thickness of the matte layer provided on one surface of the acrylic resin film substrate is preferably 0.1 to 5 μm. If the thickness of the matte layer is 0.1 μm or more, surface properties such as scratch resistance when it becomes a laminate can be exhibited. More preferably, it is 0.5 μm or more, and most preferably 0.8 μm or more. If the thickness of the matte layer is 5 μm or less, the occurrence of cracks in the matte layer can be reduced even when insert molding or in-mold molding is performed to form a deep-drawn shape. The thickness of the matte layer is preferably 3 μm or less, more preferably less than 2 μm. Moreover, since the coating amount per unit area used in the coating is reduced, it is possible to reduce the physical property deterioration of the acrylic resin film substrate due to the solvent. Further, when the thickness of the matte layer is 5 μm or less, good matting properties can be expressed. By reducing the thickness of the matte layer, the matte property can be expressed well, so that the amount of the matte agent per unit volume can be reduced, and the physical property deterioration of the matte layer can be reduced. Further, by reducing the thickness of the matte layer, the effect of adding the wax is enhanced, so that good scratch resistance is exhibited.

  The thickness of the matte layer is determined by observing the cross section of the film with a transmission electron microscope, measuring the thickness at five locations, and averaging them. When the thickness of the matting layer is smaller than the mass average particle diameter of the matting agent, the thickness is measured by observing a portion where the matting agent is not present, that is, a portion consisting only of the binder resin.

(Matting agent)
As the matting agent, it is preferable to use organic or inorganic particles having a mass average particle diameter of 0.5 to 50 μm. From the viewpoint of matteness and appearance, the mass average particle diameter is more preferably 2 μm or more. By making the mass average particle diameter 2 μm or more, not only the matteness will be good, but also the reflection of fluorescent lamps will be reduced. For example, when combined with a metallic pattern, the appearance of scraping aluminum It becomes close to, and it looks like a luxury. The mass average particle diameter is more preferably 30 μm or less, and particularly preferably 10 μm or less, from the viewpoints of moldability when forming the matte layer, appearance, and removal of the matting agent from the binder resin. By making it 10 μm or less, not only the moldability of the matte layer will be improved, but also the reflection of the fluorescent lamp will be slightly visible, so when it is combined with a metallic pattern, for example, it looks close to the appearance of scraping aluminum It has a luxurious appearance and high industrial utility value. For example, when a matte acrylic resin film is obtained by gravure coating or gravure reverse coating, the mass average particle diameter is more preferably 30 μm or less, and particularly preferably 10 μm or less, from the viewpoint of reducing doctor lines. Moreover, it is preferable to use the thing which does not contain the coarse grain of 20 micrometers or more from a viewpoint of coating omission generation | occurrence | production in the case of coating, or a doctor streak generation | occurrence | production.

  Known materials can be used as the organic particles. Examples include silicone resins, styrene resins, styrene / acrylic resins, acrylic resins, fluororesins, benzoguanamine / formaldehyde condensates, benzoguanamine / melamine / formaldehyde condensates, and melamine / formaldehyde condensates.

  As a material for the organic particles, it is preferable to select a material having a refractive index as close as possible to that of the binder resin in order to make the pattern clear from the viewpoint of the design feeling when the pattern layer is formed. For example, when an acrylic resin is used as the binder resin, it is preferable to select beads made of cross-linked polymethyl methacrylate (cross-linked PMMA) as a matting agent. On the contrary, the matting agent can be selected according to the kind of the pattern, such as a matting layer having a whiteness by using a matting agent having a slightly different refractive index.

  Known materials can be used for the inorganic particles. Examples thereof include mica, talc, silica, calcium carbonate, titanium oxide, and iron oxide. In addition, inorganic particles surface-treated with acrylic resin, polyurethane resin, surfactant or the like can be used, but it is necessary to select a material to be surface-treated from the viewpoint of yellowing during heating. The use of non-surface-treated inorganic particles is preferable from the viewpoint of yellowing during heating. Of these, silica is particularly preferred from the viewpoints of the appearance and physical properties of the matte acrylic resin film obtained. As the silica, known ones that are commercially available can be used, and examples thereof include Mizusukasil manufactured by Mizusawa Chemical Co., Ltd., and Sicilia manufactured by Fuji Silysia Chemical Co., Ltd.

  When inorganic particles are used as a matting agent, a unique whiteness can be imparted to the matte acrylic resin film, so that the design can be increased depending on the type of the pattern, and the industrial utility value is high. If an acrylic particle film matting agent is kneaded into the acrylic resin film substrate to obtain a matting film, the film itself becomes quite white, and the design is impaired when the pattern layer is formed.

  The addition amount of the matting agent is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the binder resin. The addition amount of the matting agent is more preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more from the viewpoint of matting properties. The amount of matting agent added is from the viewpoint of in-mold moldability and insert moldability, or when a matte acrylic resin film is obtained by gravure coating, gravure reverse coating, kiss reverse coating, microgravure coating, etc. Is preferably 30 parts by mass or less, particularly preferably 20 parts by mass or less, from the viewpoint of reducing doctor muscles.

(wax)
As the wax, known natural waxes such as carnauba wax, wax, montan wax, paraffin wax, etc., known synthetic waxes such as fatty acid amide, polyethylene, polypropylene, polytetrafluoroethylene, alkyl-modified silicone oil, polyether-modified, etc. Examples thereof include known silicone-based waxes such as silicone oil, and other block copolymers containing silicon-based and fluorine-based components.

  In the present invention, it is preferable to use polyolefin wax such as polyethylene, polypropylene, and a composite of polyethylene and polypropylene.

  From the standpoint of mold contamination during in-mold molding and insert molding, the higher the melting point, the harder it is to bleed due to the heat during molding. Therefore, it is preferable that the melting point is 120 ° C. or higher, and 140 ° C. or higher. Is more preferable. In addition, regarding the block copolymer containing a silicon-type and a fluorine-type component, it is possible to express the outstanding bleed resistance even if melting | fusing point is 100 degrees C or less by selecting another copolymer component.

Examples of the wax having such a melting point include polyethylene, polypropylene, a composite of polyethylene and polypropylene, and polytetrafluoroethylene. From the viewpoint of the melting point, a composite of polyethylene and polypropylene is more preferable, and polytetrafluoroethylene is particularly preferable. From the viewpoint of the effect of preventing scratches, polytetrafluoroethylene is more preferable, and polyethylene, polypropylene, and a composite of polyethylene and polypropylene are particularly preferable. Further, by using these in combination, it is possible to develop more excellent scratch resistance, and a combination of polyethylene and polytetrafluoroethylene is particularly preferable.
On the other hand, it is preferable that specific gravity is small from a viewpoint of the wax sedimentation property at the time of coating. For example, polytetrafluoroethylene having a specific gravity exceeding 2 is likely to settle, although it depends on the viscosity of the liquid at the time of coating. If the wax settles down during coating, the amount of wax contained in the matte layer is reduced, resulting in a decrease in scratch resistance. In addition, white streaks generated by winding up the precipitated wax by the plate roll are matte acrylic resin film Transferred as a defect on top.

  From the above, in the present invention, it is preferable to use polyolefin wax such as polyethylene, polypropylene, and a composite of polyethylene and polypropylene.

  In many cases, wax such as polyethylene, polypropylene, and a composite of polyethylene and polypropylene is used in the form of ultrafine powder obtained by dry pulverization. In the present invention, the mass average particle diameter is larger than the thickness of the matte layer. It is preferable to use a wax having the same. From the viewpoint of scratch resistance, it is more preferable to use a wax having a mass average particle diameter larger than a value obtained by doubling the thickness of the matte layer. Moreover, it is preferable to use the thing which does not contain the coarse grain of 20 micrometers or more from a viewpoint of coating omission generation | occurrence | production in the case of coating, or a doctor streak generation | occurrence | production.

  The addition amount of the wax is not particularly limited as long as the coefficient of dynamic friction on the matte layer side as claimed in the present invention can satisfy 0.23 or less. Specifically, it is preferable to set it as 1-20 mass parts with respect to 100 mass parts of binder resin. From the viewpoint of scratch resistance, 3 parts by mass or more is more preferable, and 5 parts by mass or more is particularly preferable. Moreover, it is preferable that it is 20 mass parts or less.

(Curable binder resin)
As the curable binder resin, a known thermosetting resin or photocurable resin is preferably used from the viewpoint of scratch resistance, chemical resistance, and heat resistance. For example, acrylic resins, urethane acrylate resins, silicone acrylate resins, epoxy resins, and ester resins can be used. Of these, urethane acrylate resins are preferred from the viewpoint of physical properties.

  As the urethane acrylate resin, known resins can be used, and in particular, a hydroxyl group having a methacrylic acid alkyl ester unit as a main component, a hydroxyl value of 20 to 120 mgKOH / g, and a glass transition temperature of 50 to 110 ° C. A urethane acrylate thermosetting resin containing a containing acrylic resin and a polyisocyanate is preferred.

  The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, from the viewpoints of pencil hardness and scratch resistance. The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less, from the viewpoint of chemical resistance, adhesion, and cracking of the matte layer during molding.

  The glass transition temperature of the hydroxyl group-containing acrylic resin is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher, from the viewpoints of heat resistance, film blocking properties, pencil hardness, and scratch resistance.

  As the polyisocyanate (curing agent), known ones can be used. In particular, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine that cause little yellowing during heating. An isocyanurate type polyisocyanate composed of diisocyanate or the like, an adduct type polyisocyanate with trimethylolpropane, or a burette type polyisocyanate is preferred. In addition, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate can be used as they are.

  The polyisocyanate is preferably used so as to have an addition amount corresponding to a range of 0.5 to 1.5 times the molar amount of the isocyanate group with respect to the molar amount of the hydroxyl group in the hydroxyl group-containing acrylic resin. By setting it to 0.5 times or more, since the amount of isocyanate groups is sufficient with respect to the hydroxyl group, the curing is sufficiently advanced and the pencil hardness, scratch resistance, and chemical resistance are improved. Less than 1.5 times the added amount, sufficient pencil hardness, scratch resistance and chemical resistance are exhibited, the matte layer is less likely to crack during molding, and there are problems such as film blocking due to excess polyisocyanate. It becomes difficult to occur.

  In addition, when a thermoplastic resin is used for the binder resin, although the moldability is good, the chemical resistance tends to decrease. When used as a vehicle interior, if a fragrance component adheres, the matte layer melts, so that an appearance defect such as a matte return may occur.

<Matte acrylic resin film>
The matte acrylic resin film of the present invention is obtained by coating a paint containing a matting agent and a curable binder resin on the surface of an acrylic resin film substrate to form a matte layer on the outermost layer.

(Method of forming matte layer)
The matte layer is preferably formed by a printing method or a coating method. In this case, the matte layer is dissolved or dispersed in a solvent to prepare a paint, which is applied to one side of the acrylic resin film substrate, and then heated and dried to remove the solvent, thereby matting. A layer is formed. This method is preferable because the adhesion between the matte layer and the acrylic resin film substrate is improved.

  Examples of the printing method include known printing methods such as gravure printing, screen printing, and offset printing.

  Coating methods include flow coating, spray coating, bar coating, gravure coating, gravure reverse coating, kiss reverse coating, micro gravure coating, roll coating, blade coating, rod coating, and roll doctor. Known coating methods such as a coating method, an air knife coating method, a comma roll coating method, a reverse roll coating method, a transfer roll coating method, a kiss roll coating method, a curtain coating method, and a dipping coating method may be mentioned.

  Among these, the gravure coating method and the gravure reverse coating method which are not easily affected by the winding shape of the acrylic resin film substrate are preferable. According to the gravure coating method and the gravure reverse coating method, coating omission and the like caused by film curling are unlikely to occur.

  As the gravure roll used in the gravure coating method, a known one can be used. In particular, it is preferable to use a diagonal roll having an inch width of 150 lines or more from the viewpoint of reducing the influence of the plate. If a plate is formed on the matte acrylic resin film, the design properties are impaired, and the industrial utility value is lowered. In addition, it is preferable to use the one in which the plate is formed in a slanted line because the plate can be reduced as compared with the case of using a gravure roll having a plate formed in a normal lattice shape.

  Further, when a slanted pattern is used, the matte appearance of the molded product when thermoforming such as in-mold molding or insert molding is performed is close to the original matte film appearance. Specifically, the reflection of the fluorescent lamp in the molded product is close to the reflection of the fluorescent lamp in the matte film, so the design feeling at the stage of the matte acrylic resin film or laminated sheet with the decorative layer applied. Since the molded product can be obtained without impairing the quality, the industrial utility value is high. For example, even if a gravure roll with a grid pattern is used, a roll with a small groove between the molds will give a very good appearance at the matte acrylic resin film stage. Alternatively, a molded product obtained by thermoforming such as insert molding is different from the appearance at the film stage.

  Moreover, it is preferable that it is engraved at an angle of 40 to 50 ° with respect to the roll axis direction. By using such a diagonal roll, it is possible to obtain an acrylic resin film having a uniform matte coating surface free from coating spots.

  As a material of the gravure roll, a known material such as a material obtained by subjecting copper to hard chrome plating or a ceramic material can be used, but a ceramic material is preferable from the viewpoint of durability.

  In addition, as the doctor blade used in the gravure coating method, known blades such as steel, stainless steel, and ceramic can be used. However, it is preferable to use a stainless doctor blade from the viewpoint of doctor muscles. Alternatively, it is also preferable to use a doctor blade in which a material made of ceramic and a lubricant is coated on a stainless doctor blade to improve the slipperiness. Also, a plastic doctor blade can be used.

  When coating a paint on an acrylic resin film substrate, the amount of solvent contained in the coating applied per 1 m @ 2 of the acrylic resin fill substrate is 30 g or less from the viewpoint of reducing the physical properties of the acrylic resin fill substrate due to the solvent. Preferably, 20 g or less is more preferable, and 10 g or less is particularly preferable. Moreover, it is preferable that the amount of coating materials to be applied is such that the thickness of the matte layer after drying is 0.1 to 5 μm. When the coating amount is such that the matte layer has a thickness of 0.1 μm or more, the surface physical properties in the case of a laminate can be expressed. Preferably it is 0.5 micrometer or more, More preferably, it is 0.8 micrometer or more. If the amount of paint is such that the thickness of the matte layer is 5 μm or less, the amount of paint per unit area used for coating is reduced, so that the physical property deterioration of the acrylic resin film substrate due to the solvent is reduced. Can do. The thickness of the matte layer is preferably 3 μm or less, more preferably less than 2 μm.

  As the solvent, a solvent having a boiling point not higher than 80 ° C., preferably not higher than 30 ° C., higher than the glass transition temperature of the binder resin is preferable because the solvent hardly remains in the matte acrylic resin film. In particular, each component of the binder resin and the matting agent can be dissolved or uniformly dispersed, and the physical properties (mechanical strength, transparency, etc.) of the acrylic resin film substrate are not adversely affected in practice. A volatile solvent having a boiling point not higher than 80 ° C., preferably not higher than 30 ° C., higher than the glass transition temperature of the resin component which is the main constituent of the acrylic resin film substrate is preferable.

  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 carbon chloride; phenol solvents such as phenol and cresol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone; diethyl ether, methoxytoluene, 1,2-dimethoxyethane, 1, Ether solvents such as 2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane and tetrahydrofuran (THF); fatty acid solvents such as formic acid, acetic acid and propionic acid; acetic anhydride Acid anhydride system such as Agents: Ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate and butyl formate; Nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide and dimethylacetamide; Sulfur-containing solvents such as thiophene and dimethyl sulfoxide; Diacetone alcohol 2-methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, morpholine, 1-acetoxy-2-ethoxyethane, A solvent having two or more kinds of functional groups such as 2-acetoxy-1-methoxypropane; various known solvents such as water can be used. These can be used alone or in combination of two or more.

  Among these, a solvent mainly composed of ethyl acetate, n-propyl acetate, isopropyl alcohol, methyl ethyl ketone, and methyl isobutyl ketone is preferable because it can reduce deterioration of physical properties of the acrylic resin fill substrate due to the solvent. Moreover, it is preferable to use butyl acetate and methyl isobutyl ketone together from the viewpoint of adhesion between the matte layer and the acrylic resin fill substrate. Also, from the viewpoint of gloss after coating, it is preferable to use a medium boiling solvent such as butyl acetate and methyl isobutyl ketone, and a high boiling solvent such as 2-acetoxy-1-methoxypropane and cyclohexanone.

  When coating a paint on an acrylic resin film substrate, from the viewpoint of the appearance of the matte layer, the viscosity of the paint is Iwata cup viscometer (manufactured by Anest Iwata, NK-2) in the atmosphere during coating. The flow time in the model) is preferably in the range of 10 to 40 seconds. When the viscosity of the coating is 10 seconds or more, the gravure roll pattern is not noticeable when applied by the gravure coating method, and it is preferable because a good matte layer can be formed. In addition, when coating for a long time, paint constituent components such as a binder resin, a matting agent, and an anti-scratch agent do not settle with time, and are preferable because of excellent production stability. On the other hand, when the viscosity of the paint is 40 seconds or less, the transfer amount of the paint to the acrylic resin film substrate does not decrease, and doctor streaks tend not to occur, and a good matte layer can be formed. Therefore, it is preferable.

  The paint used is preferably subjected to filtration for the purpose of removing foreign substances, silica and wax coarse particles from the viewpoint of reducing omission of coating and reducing the generation of doctor streaks. Filtration may be performed after preparation of the coating material, or may be performed immediately before coating or while coating.

  Although it can filter with a well-known filtration apparatus, it is preferable to use CPII-10, 03, 01 made from a Chisso filter, for example.

  For paints, known additives for improving solution properties such as anti-skinning agents, thickeners, anti-settling agents, anti-sagging agents, antifoaming agents, leveling agents, etc .; light stabilizers, UV absorbers, oxidation Known additives for improving the coating film performance such as an inhibitor, an antibacterial agent, an antifungal agent and a flame retardant can be added.

  Usually, in order to form a coating film having a sufficient thickness on a molded product by coating, it may be necessary to apply several tens of times, and in this case, the cost is high and the productivity is not so good. On the other hand, since the matte acrylic resin film itself becomes a coating film, the laminate of the present invention can easily form a very thick coating film and has high industrial utility value.

(Dynamic friction coefficient of matte acrylic resin film)
The matte acrylic resin film of the present invention has a coefficient of dynamic friction between the matte layer side and Broad No. 60 (hereinafter referred to as dynamic friction on the matte layer side) under the test conditions of a test speed of 100 mm / min, a moving distance of 10 mm, and a load of 9.8 N. The coefficient is 0.23 or less.

  In the conventionally known matte acrylic resin film, the pencil hardness is often used as an index of scratch resistance. However, in the matte acrylic resin film in which the matte layer is formed on the acrylic resin film, the pencil hardness is used. In addition to hardness, the coefficient of dynamic friction is an important indicator. That is, the smaller the dynamic friction coefficient, the better the scratch resistance of the matte acrylic resin film. For example, a matte acrylic resin film in which a matte layer is provided on an acrylic resin film does not show good scratch resistance even if the pencil hardness is H unless the dynamic friction coefficient is 0.23 or less.

  A matte acrylic resin film with a coefficient of kinetic friction of 0.23 or less on the matte layer side is less likely to scratch or scratch the surface of the matte acrylic resin film during the process of insert molding or in-mold molding. Property is improved.

  The laminate using the matte acrylic resin film of the present invention can be suitably used for various vehicle members such as a door waist garnish, a front control panel, a power window switch panel, and an airbag cover. It is very useful industrially from the viewpoint of expanding applications.

(Pencil hardness of matte acrylic resin film)
The matte acrylic resin film of the present invention preferably has a pencil hardness (measured based on JIS K5600) of 2B or more.

  By using a matte acrylic resin film with a pencil hardness of 2B or more, the surface of the matte acrylic resin film is not easily scratched during the process of insert molding or in-mold molding, and the laminate has good scratch resistance. Become.

  Considering the case where it is used for a laminate such as a vehicle member, the pencil hardness of the matte acrylic resin film of the present invention is preferably HB or more.

  In order to obtain a matte acrylic resin film having such a pencil hardness, the pencil hardness of the acrylic resin film serving as a base material is important. The acrylic hardness of the acrylic resin film serving as the base material is preferably 2B or higher, more preferably HB or higher, and most preferably F or higher.

(Heat-resistant yellowing of matte acrylic resin film)
The matte acrylic resin film of the present invention is heated from the yellowness (hereinafter referred to as YI ′ (200 ° C.)) after being heated to 200 ° C. at a temperature rising speed of 20 to 25 ° C./second in an air atmosphere. The value obtained by subtracting the yellowness (hereinafter referred to as YI) of the matte acrylic resin film is preferably 1.3 or less. When this value is 1.3 or less, when insert molding or in-mold molding is performed, yellowing of the matte acrylic resin film is not recognized in general patterns such as wood grain, and good design is maintained. The laminated body obtained can be obtained. Preferably, it is 1.0 or less. When the ratio is 1.0 or less, the matte acrylic resin film is not prone to yellowing, and the matte acrylic resin film is not yellowed even in a pattern with a strong whiteness or a metallic pattern. A retained laminate can be obtained. More preferably, it is 0.5 or less, and most preferably 0.3 or less. Similarly, from the viewpoint of maintaining the design before molding when insert molding and in-mold molding are performed, the value obtained by subtracting YI from YI ′ (200 ° C.) is preferably −2.0 or more.

  Although not particularly limited, the yellowness (hereinafter referred to as YI ′ (250 ° C.)) of the matte acrylic resin film after being heated to 250 ° C. at a temperature increase rate of 20 to 25 ° C./second in an air atmosphere The value obtained by subtracting the yellowness (YI) of the matte acrylic resin film is preferably 2.0 or less. More preferably, it is 1.5 or less, More preferably, it is 1.0 or less, Most preferably, it is 0.5 or less. The value obtained by subtracting YI ′ (250 ° C.) and YI is preferably −2.0 or more.

  Moreover, although not specifically limited, from the viewpoint of designability when printing is performed, it is preferable that the matte acrylic resin film before heating has a lower yellowness. Specifically, 6.0 or less is preferable.

  When the film is heated, the yellowness of the matte acrylic resin film is cooled to room temperature, and then the snow white oily colored paper (standard color) with a Munsell symbol of N9.5 is placed on the acrylic resin substrate side of the film. Card 230, manufactured by Nippon Color Research Co., Ltd.), and using the spectroscopic color difference meter SE2000 (manufactured by Nippon Denshoku), the value measured on the matte layer side of the film under standard C light and reflection mode conditions is used. .

  The yellowness difference of the matte acrylic resin film before and after the heating as in the present invention is achieved by constituting the matte layer from a specific component. Specifically, constituent components such as a matting agent and a curing agent need to be selected from the viewpoint of heat-resistant yellowing.

<Pattern layer>
A pattern layer may be formed on the matte acrylic resin film of the present invention in order to impart design properties to various substrates. In this case, it is preferable to form a picture layer on the surface of the acrylic resin film substrate opposite to the surface on which the matte layer is provided. Moreover, at the time of manufacture of a laminated body, it is preferable from the point of protection of a decorating surface and provision of a high-class feeling to distribute a pattern layer to the adhesive surface with a base material.

  The pattern layer can be formed by a known method. As the pattern layer, a printing layer formed by a printing method and / or a vapor deposition layer formed by a vapor deposition method is preferable.

(Print layer)
The printed layer becomes a pattern or characters on the surface of the laminate obtained by insert or in-mold molding. Examples of the print pattern include a pattern made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, full face, and the like.

  As binders 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, cellulose Examples of the resin include ester resins, alkyd resins, and chlorinated polyolefin resins.

  For the formation of the printing layer, a colored ink containing a binder and an appropriate color pigment or dye as a colorant may be used.

  Examples of the pigment include the following. Examples of yellow pigments include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as chrome lead. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals. Examples of the blue pigment include organic pigments such as phthalocyanine blue; inorganic pigments such as cobalt blue. Examples of the black pigment include organic pigments such as aniline black. Examples of the white pigment include inorganic pigments such as titanium dioxide.

  As the dye, various known dyes can be used as long as the effects of the present invention are not impaired.

  Examples of the method for forming the printing layer include known printing methods such as offset printing, gravure rotary printing, and screen printing; known coating methods such as roll coating and spray coating; and flexographic printing.

  The thickness of the printing layer may be appropriately determined as necessary, and is usually about 0.5 to 30 μm.

The number of missing prints in the print layer is preferably 10 pieces / m ² or less from the viewpoints of design properties and decorating properties. By setting the number of printing omissions to 10 pieces / m ² or less, the appearance of the laminate using the matte acrylic resin film becomes better. The number of missing prints in the print layer is more preferably 5 pieces / m ² or less, and particularly preferably 1 piece / m ² or less.

  The thickness of the printed layer may be appropriately selected according to the degree of extension during the insert or in-mold molding so that a desired surface appearance can be obtained in the laminate obtained by the insert or in-mold molding.

(Deposition layer)
The vapor deposition layer is formed of at least one metal selected from the group consisting of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., or an alloy or compound thereof. Is done. Examples of the method for forming the vapor deposition layer include vacuum vapor deposition, sputtering, ion plating, and plating.

  The thickness of the vapor-deposited layer may be appropriately selected according to the degree of expansion during the insert or in-mold molding so that a desired surface appearance can be obtained in the laminate obtained by the insert or in-mold molding.

<Other layers>
(Adhesive layer)
If necessary, the matte acrylic resin film of the present invention may be provided with an adhesive layer. The adhesive layer is preferably formed on the surface opposite to the surface provided with the matte layer.

(Cover film)
Further, the matte acrylic resin film of the present invention may further be provided with a cover film. This cover film is effective for dust-proofing the surface of the matte acrylic resin film. The cover film can be provided on either the surface of the matte layer or the surface opposite to the surface on which the matte layer is provided. It is preferably provided at least on the surface of the matte layer.

  When a cover film is provided on the surface of the matte layer, the cover film adheres to the matte layer before in-mold and insert molding, and immediately peels off when in-mold and insert molding. Therefore, it is necessary to have appropriate adhesion and good releasability. As the cover film, 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.

(Thermoplastic resin layer)
The matte acrylic resin film of the present invention may be further laminated on a thermoplastic resin layer to form a laminated film or sheet. The direction in which the matte acrylic resin film is laminated on the thermoplastic resin layer is preferably such that the surface opposite to the surface on which the matte layer is provided is in contact with the thermoplastic resin layer.

  The thermoplastic resin layer is preferably made of a material having compatibility with the base material for the purpose of improving the adhesion with the base material. More preferably, the thermoplastic resin layer is made of the same material as the base material. As the thermoplastic resin layer, a known thermoplastic resin film or sheet can be used. For example, acrylic resin; ABS resin (acrylonitrile-butadiene-styrene copolymer); AS resin (acrylonitrile-styrene copolymer); A vinyl chloride resin; a polyolefin resin such as polyethylene, polypropylene, polybutene, and polymethylpentene; a polyolefin copolymer such as an ethylene-vinyl acetate copolymer or a saponified product thereof, an ethylene- (meth) acrylate copolymer; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate; polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon; poly Tylene resin; Fibrin derivatives such as cellulose acetate and nitrocellulose; Fluororesin such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer; or two selected from these, Or 3 or more types of copolymers or a mixture, a composite, a laminated body, etc. are mentioned.

  Among these, as the thermoplastic resin layer, the formability of the pattern layer (can be formed on the thermoplastic resin layer instead of being formed on the matte acrylic resin film), the secondary formability of the laminated film or sheet From the viewpoint, acrylic resin, ABS resin, vinyl chloride resin, polyolefin, and polycarbonate are preferable.

  If necessary, the thermoplastic resin layer may contain general compounding agents such as stabilizers, antioxidants, lubricants, processing aids, plasticizers, impact agents, foaming agents, fillers, antibacterial agents, and antifungal agents. An agent, a release agent, an antistatic agent, a colorant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a flame retardant, and the like may be blended.

  The thickness of the thermoplastic resin layer may be appropriately determined as necessary, and is usually preferably about 20 to 500 μm. The thermoplastic resin layer preferably has a thickness such that the appearance of the matte acrylic resin film has a completely smooth upper surface, absorbs surface defects of the base material, or the pattern layer does not disappear during injection molding. .

  Examples of a method for obtaining a laminated film or sheet include known methods such as thermal lamination, dry lamination, wet lamination, and hot melt lamination. Further, a matte acrylic resin film and a thermoplastic resin layer can be laminated by extrusion lamination.

  By using the matte acrylic resin film of the present invention as a laminated film or sheet, strength sufficient for handling against external forces such as impact and deformation is exhibited. For example, cracks and the like are less likely to occur when the film is vacuum-molded by insert molding or the like and then removed from the mold, or when the vacuum-molded product is mounted on an injection mold. , Handling becomes good. Furthermore, for example, the surface defect of the injection-molded base material is minimized from being propagated to the matte acrylic resin film, or when the base material is injection-molded, the pattern layer is less likely to disappear. .

  If necessary, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, anchor, primer treatment, etc. on one surface of a matte acrylic resin film, the surface of a thermoplastic resin layer of a laminated film or sheet The surface treatment may be performed. Adhesion between the matte acrylic resin film and the picture layer, between the thermoplastic resin layer and the picture layer, between the matte acrylic resin film and the thermoplastic resin layer, and the like can be improved.

<Laminated body>
The laminate of the present invention is obtained by laminating the matte acrylic resin film of the present invention, the laminated film or sheet thereof on a substrate. At this time, it is preferable to laminate the matte acrylic resin film on the base material so that the surface opposite to the surface on which the matte layer is provided is in contact with the base material.

  Examples of the material of the base material include: resin; wood board such as wood veneer, wood plywood, particle board, medium density fiber board (MDF); water quality board such as wood fiber board; metal such as iron and aluminum.

  As the resin, any known resin can be used regardless of the type. Examples of the resin include polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefin thermoplastic elastomer; polystyrene resin, ABS resin (acrylonitrile) -Butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), general-purpose thermoplastic or thermosetting resin such as acrylic resin, urethane resin, unsaturated polyester resin, epoxy resin; polyphenylene oxide polystyrene General-purpose engineering resins such as resin, polycarbonate resin, polyacetal, polycarbonate-modified polyphenylene ether, polyethylene terephthalate; polysulfone, polyphenylene sulfide, Super engineering resins such as rephenylene oxide, polyetherimide, polyimide, liquid crystalline polyester, polyallyl heat-resistant resin, etc .; reinforcing materials such as glass fiber or inorganic fillers (talc, calcium carbonate, silica, mica, etc.), modification of rubber components, etc. Examples thereof include a composite resin to which a quality agent is added or various modified resins.

  Of these, the material for the substrate is preferably a matte acrylic resin film, a laminated film or a sheet that can be melt bonded. For example, an ABS resin, an AS resin, a polystyrene resin, a polycarbonate resin, a vinyl chloride resin, an acrylic resin, a polyester resin, or a resin containing these as a main component can be given. From the viewpoint 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.

  Even if it is a resin that is not heat-sealed, such as a polyolefin-based resin, by providing an adhesive layer, one selected from the group consisting of a matte acrylic resin film, a laminated film or a sheet thereof, and a base material are bonded at the time of molding. Is possible.

  As a method for producing the laminate of the present invention, a known method such as thermal lamination can be used in the case of a two-dimensional laminate and when the substrate can be heat-sealed. For example, for wood substrates such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), water quality boards such as wood fiber board, metals such as iron and aluminum, etc. It is possible to bond them through an adhesive layer.

  In the case of a three-dimensional laminate, a known method such as an insert molding method or an in-mold molding method can be used.

  The in-mold molding method involves heating a matte acrylic resin film, or its laminated film or sheet, and then vacuum forming it in a mold having a vacuuming function, and then applying a resin as a base material in the same mold. This is a method of obtaining a laminated body in which a matte acrylic resin film or a laminated film or sheet thereof and a substrate are integrated by injection molding. The in-mold molding method is preferable from the viewpoints of workability and economy because the film molding and injection molding can be performed in one step.

  When in-mold molding is performed using a known acrylic resin film having a pattern layer, the pattern layer near the gate may disappear depending on the shape of the mold and injection molding conditions. The gate is roughly classified into a non-restricted gate in which the resin flow path is not narrowed in the gate portion and a restricted gate in which the flow path is narrowed. Representative examples of the latter include pinpoint gates, side gates, submarine gates, and the like. In the case of a restricted gate, although the residual stress near the gate is reduced, the temperature of the resin passing through the gate increases, and the injection resin pressure per unit area on the acrylic resin film surface near the gate increases. Is easy to disappear.

  A laminated film or sheet having a thermoplastic resin layer is preferred in that the disappearance of the pattern layer can be further reduced because of the presence of the thermoplastic resin layer.

  The heating temperature at the time of in-mold molding is preferably equal to or higher than the temperature at which the matte acrylic resin film or the laminated film or sheet thereof is softened. Specifically, it may be appropriately set depending on the thermal properties of the film or the shape of the laminate, and 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. This may be set as appropriate depending on the thermal properties of the film or the shape of the laminate, and is usually 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 when 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.

  When a three-dimensional shape is imparted to a film by vacuum forming, the matte acrylic resin film of the present invention, or a laminated film or sheet thereof has a high degree of elongation at high temperatures, which is very advantageous.

  As the resin to be injection-molded, any resin that can be injection-molded can be used regardless of the type. It is possible to approximate the shrinkage rate of the resin after injection molding to the shrinkage rate of the matte acrylic resin film, or its laminated film or sheet, warp of the laminate obtained by in-mold molding, insert molding, or film or sheet. It is preferable because problems such as peeling off can be solved.

  The laminate of the present invention is particularly suitable for vehicle members and building materials. Examples include instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior components; weather strips, bumpers, bumper guards, side mud guards, body panels , Spoilers, front grilles, 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 components; AV equipment, Front panels of furniture products, buttons, emblems, surface decorative materials, etc .; housings for mobile phones, display windows, buttons, etc .; furniture exterior materials; walls, ceilings, floors, etc. Architectural interior materials; exterior walls for siding, fences, roofs, gates, windbreaks, etc .; exterior decorative materials for furniture such as window frames, doors, handrails, sills, duck; various displays, lenses, mirrors Optical members such as goggles and window glass; Interior and exterior members of various vehicles other than automobiles such as trains, airplanes and ships; Various packaging containers such as bottles, cosmetic containers and accessory cases; packaging materials; Miscellaneous goods such as prizes and accessories It can be suitably used for various other uses.

  As in the present invention, a matte acrylic resin film having a matte layer containing at least a matting agent and a curable binder resin as an outermost layer on one surface of an acrylic resin film substrate, and the gloss When a matte acrylic resin film with a dynamic friction coefficient on the matting layer side of a specific value or less is used, a design that is difficult to realize when a matting agent is added to the conventional acrylic resin film layer and is easy to handle Even if it is subjected to insert molding or in-mold molding and molded into a deep-drawn molded product, no cracking occurs in the matte layer, and scratch resistance, surface hardness, which can be used for vehicle applications, An acrylic resin film having heat resistance, chemical resistance, heat yellowing resistance, and matting properties, and a laminate in which these are laminated on a base material can be provided. In addition, by adopting the method of the present invention, it is possible to stably produce a matte acrylic resin film. Compared to conventional acrylic resin films, it is possible to dramatically expand the usage.

  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 shown in Table 1.

Abbreviations: Compound MMA: Methyl methacrylate MA: Methyl acrylate n-BA: N-butyl acrylate St: Styrene 1,3-BD: 1,3-butylene glycol dimethacrylate AMA: Allyl methacrylate CHP: Cumene hydroperoxide t-BH: t-butyl hydroperoxide n-OM: n-octyl mercaptan EDTA: disodium ethylenediaminetetraacetate HEMA: 2-hydroxyethyl methacrylate [measurement and evaluation method of physical properties]
Physical properties of rubber-containing polymer (I ′) and rubber-containing multistage polymer (I), thermoplastic polymer (II), and thermoplastic polymer (IV), produced acrylic resin film substrates (A) to (C) The physical properties of the matte acrylic resin films and laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were measured and evaluated as follows.

  Evaluation of the laminated body was performed using the laminated body produced for the moldability evaluation shown in the following (12) or (13).

(1) Mass average particle diameter of rubber-containing polymer (I ′) and rubber-containing multistage polymer (I):
About the polymer latex of rubber-containing polymer (I ′) and rubber-containing multistage polymer (I) obtained by emulsion polymerization, a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd. was used. , Measured by a dynamic light scattering method.

(2) Gel content of rubber-containing polymer (I ′) and rubber-containing multistage polymer (I):
A predetermined amount (mass before extraction) of the rubber-containing polymer (I ′) and the rubber-containing multistage polymer (I) (the coagulated powder obtained after polymerization) were subjected to extraction treatment in an acetone solvent under reflux. Was separated by centrifugation, and after drying, the mass of acetone-insoluble matter was measured (mass after extraction), and calculated by the following formula.

Gel content (%) = mass after extraction (g) / mass before extraction (g) × 100
(3) Glass transition temperature (Tg) of rubber-containing polymer (I ′), rubber-containing multistage polymer (I) and binder resin:
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) and thermoplastic polymer (IV):
0.1 g of the polymer was dissolved in 100 mL of chloroform and measured at 25 ° C.

(5) Hydroxyl value of binder resin:
It measured according to JIS K0070.

(6) Mass average molecular weight of binder resin:
Using Shimadzu LC-6A system (manufactured by Shimadzu Corporation), three GF columns connected with KF-805L (manufactured by Showa Denko KK) and THF as a solvent were measured in terms of polystyrene. .

(7) Heat shrinkage rate of acrylic resin film substrate:
On the surface of the acrylic resin film substrate cut out to A4 size, draw three parallel straight lines at 5 cm intervals in the MD direction (flow direction during film formation) and TD direction (direction perpendicular to the MD direction), The interval was accurately measured with calipers. The interval was measured at two locations, and the measured locations were marked. Then, after leaving for 60 minutes in 130 degreeC atmosphere and taking out, the space | interval of the same location as the location measured previously was measured once again. The heat shrinkage rate was calculated from the following formula using the average value of the distance between the two locations.

Heat shrinkage rate (%) = ((interval before heating−interval after heating) / interval before heating) × 100
(8) Thickness of matte layer of matte acrylic resin film:
A sample obtained by cutting a matte acrylic resin film to a thickness of 70 nm in the cross-sectional direction is observed with a transmission electron microscope (J100S manufactured by JEOL Ltd.), the thickness is measured at five locations, and they are averaged. Was used to determine the thickness of the matte layer. The thickness of the matting layer was measured by observing a portion where no matting agent was present, that is, a portion consisting only of a binder resin.

(9) Pencil hardness of matte acrylic resin film:
It measured according to JIS K5400. The pencil hardness on the surface of the matte layer was measured.

(10) Surface gloss of matte acrylic resin film:
Using a gloss meter (GM-26D type (trade name), manufactured by Murakami Color Research Laboratory Co., Ltd.), the surface gloss at 60 ° of the matte surface was measured.

(11) Matting acrylic resin film yellowing when heated:
A matte acrylic resin film with a thickness of about 75 μm is placed on the clamp frame of a vacuum / pressure forming machine (manufactured by Asano Laboratories) with far-infrared heater panels set at 350 ° C and below; Fixed. In addition, the far-infrared heater panel is installed on both sides of a place of 100 mm above and below the matte acrylic resin film set in the clamp.

  The surface temperature of the matte acrylic resin film before the start of heating was 25 ° C. From here, it heated until the surface temperature of the matt acrylic resin film became predetermined temperature. The time required for the surface temperature of the film to reach 250 ° C. was about 11 seconds, and the temperature raising speed was about 20 ° C./second. The time required for the surface temperature of the film to reach 200 ° C. was about 7 seconds, and the temperature raising speed was about 25 ° C./second. The film surface temperature was measured with a non-contact type thermometer arranged above the clamp.

  Thereafter, the film is cooled to room temperature again, and then a Snow White oil-colored paper having a Munsell symbol of N9.5 (standard color card 230, manufactured by Nihon Kenken Business) is superimposed on the acrylic resin substrate side of the film. Using a color difference meter SE2000 (manufactured by Nippon Denshoku), the yellowness YI ′ was measured using the matte layer side of the film as the measurement surface under the conditions of standard C light and reflection mode.

  On the other hand, the yellowness YI of the matte acrylic resin film before heating was measured in the same manner, and the yellow discoloration was evaluated using a value obtained by subtracting YI from YI ′.

(12) Insert moldability of matte acrylic resin film:
A silver metallic layer as a pattern layer was provided on the acrylic resin film substrate side by gravure printing on a matte acrylic resin film having a thickness of about 75 μm. Further, an ABS sheet having a thickness of 1 mm having an adhesive layer was laminated on the matte acrylic resin film by thermal lamination so that the adhesive layer and the silver metallic layer were in contact with each other to obtain a laminate sheet of the matte acrylic resin film. Molding was performed using this laminated sheet.

  Specifically, the obtained laminated sheet was placed in a mold having a vacuum drawing function so that the matte acrylic resin film side became the cavity side, and heated with a heater until the laminated sheet reached 190 ° C. Thereafter, vacuum forming was performed. Then, unnecessary parts were trimmed. On the bottom of the mold on the cavity side and 3 cm in the lateral direction from the central gate, on the bottom of the mold with a recess of 1 cm 2 and 1 mm in depth, a laminated sheet that has been vacuum-formed is matte acrylic resin film side It arranged so that it might become a 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 ABS sheet side of the laminated sheet, and a laminate was obtained by insert molding.

  The detailed shape of the laminated body is a box shape with a length of 150 mm × width of 120 mm × thickness of 2 mm and a depth of 10 mm. The gate position of the mold is one in the middle of the laminated body, and the upper and lower sides of the central gate 3) 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 corner corner R connecting the bottom surface and the side surface on the cavity side of the mold is about 3. That is, the corner R of the laminate edge portion on the side where the acrylic resin film is laminated is about 3. The corner R was measured with RADIUS GAGE manufactured by FUJI TOOL.

  The injection molding was performed using a J85 ELII type injection molding machine (trade name) manufactured by Nippon Steel Works, Ltd. 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 formed on the obtained laminate, the convex portion having a height of 1 mm, or the vicinity of the corner of the laminate edge was observed and evaluated as follows.

(About cracking of convex part)
○: No crack,
X: Large cracks occur in the matte layer.

(About cracks near corners)
○: No crack,
X: Large cracks occur in the matte layer.

(Regarding whitening of convex parts)
○: No film whitening
X: There is strong whitening of the film.

(About whitening near the corner)
○: No film whitening
X: There is strong whitening of the film.

(13) In-mold formability of matte acrylic resin film:
In-mold molding was performed using a matte acrylic resin film having a thickness of about 75 μm.

  Specifically, using a mold having a vacuum function and having a recess of 1 cm 2 and a depth of 1 mm at a position 3 cm laterally from the bottom of the mold on the cavity side and the center gate, J85 ELII type In-mold molding was performed with an in-mold molding apparatus that combines an injection molding machine (trade name, manufactured by Nippon Steel Works, Ltd.) and a hot pack system (trade name, manufactured by Nissha Printing Co., Ltd.).

  The detailed shape of the laminated body is a box shape with a length of 150 mm × width of 120 mm × thickness of 2 mm and a depth of 10 mm. The gate position of the mold is one in the middle of the laminated body, and the upper and lower sides of the central gate 3) 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 corner corner R connecting the bottom surface and the side surface on the cavity side of the mold is about 3. That is, the corner R of the laminate on which the acrylic resin film is laminated is about 3. The corner R was measured with RADIUS GAGE manufactured by FUJI TOOL.

  The matte acrylic resin film was vacuum-formed under the conditions that the heater set temperature was about 330 ° C., the heating time was 12 seconds, and the distance between the heater and the film was 15 mm, and the matte layer was in a direction in contact with the mold.

  Further, in the injection molding carried out in the same mold, the base resin was injected from the matte layer 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. As the base resin, heat resistant ABS resin (trade name “Bulksum TM25B” manufactured by UMG ABS Co., Ltd.) was used.

  The state of the 1 cm @ 2 formed on the obtained laminate, the convex portion having a height of 1 mm, or the vicinity of the corner of the laminate edge was observed and evaluated as follows.

(About cracking of convex part)
○: No crack,
X: Large cracks occur in the matte layer.

(About cracks near corners)
○: No crack,
X: Large cracks occur in the matte layer.

(Regarding whitening of convex parts)
○: No film whitening
X: There is strong whitening of the film.

(About whitening near the corner)
○: No film whitening
X: There is strong whitening of the film.

(14) Coefficient of dynamic friction of laminate Lamination laminated with matte acrylic resin film when Broad No. 60 is used as the material to be rubbed under test conditions of test speed 100 mm / min, moving distance 10 mm, load 9.8 N The dynamic friction coefficient on the matte layer side of the body was measured. In addition, the sample used what was shape | molded by (13), and the dynamic friction coefficient used the average value of five measurement points.

(15) Scratch resistance of the laminate:
(Condition 1)
The laminated body was pressed while applying a load of 0.01 MPa on the No. 60 broad sheet, and the laminated body was reciprocated 1000 at a stroke width of 100 mm and at a speed of 30 reciprocations / minute. The appearance of the laminate was evaluated as follows.

  A: No change in appearance.

  ○: Slightly damaged.

  (Triangle | delta): There exists weak glossiness return.

  ×: Strong gloss return.

(Condition 2)
The laminate was pressed onto a five-layered case while applying a load of 0.049 MPa, and the laminate was reciprocated 200 times at a stroke of 100 mm and at a speed of 30 reciprocations / minute. The appearance of the laminate was evaluated as follows.

  A: No change in appearance.

  ○: Slightly damaged.

  (Triangle | delta): There exists weak glossiness return.

  ×: Strong gloss return.

(16) Chemical resistance of the laminated body A polyethylene cylinder having an inner diameter of 38 mm and a height of 15 mm is placed on the surface of the laminated molded product, and is firmly attached to the test piece with a crimping machine. Inject 5 ml of Grace Mate Poppy Citrus. After the opening is covered with a glass plate, it is placed in a thermostat kept at 55 ° C. and left for 4 hours. After the test, the crimper is removed, the test piece is washed with water and then air-dried, and the whitening state of the surface of the test part is observed.

○-There is no peeling of the matte layer (no gloss return)
△ -Slightly peeled off matte layer (slightly matte)
×-There is peeling off of the matte layer (there is glossy return)
(17) Appearance of laminate:
The appearance of the picture layer of the laminate under the light of a fluorescent lamp was visually evaluated as follows.

  ○: Reflection of the fluorescent lamp can be confirmed slightly. In the insert molded product, the pattern of the pattern layer is clearly visible and slightly white, so the silver metallic feeling is good.

  X: Reflection of the fluorescent lamp can be confirmed, but since the waviness of the matte surface of the molded product is larger than that of the matte acrylic resin film before molding, the way of reflection is blurred.

(18) Appearance of the laminate (evaluation of yellow discoloration):
The appearance of the pattern layer of the laminate was visually evaluated as follows.

  ○: No change from the pattern layer before molding.

  X: The yellowish color is more conspicuous than the pattern layer before molding, and the design looks different.

[Production Example 1]
(Production of rubber-containing multistage polymer (I))
After charging 10.8 parts of deionized water into a vessel equipped with a stirrer, MMA 0.3 part, n-BA 4.5 part, 1,3-BD 0.2 part, AMA 0.05 part and CHP 0 A monomer component consisting of 0.025 parts was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical 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 charged into a polymerization vessel equipped with a condenser, 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, the prepared emulsion was dropped into the polymerization vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes to complete the first stage polymerization of the elastic polymer (IA-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 is added over 90 minutes together with 0.016 part of CHP. After dropping into the polymerization vessel, the reaction was continued for 60 minutes to complete the polymerization of the second stage polymer of the elastic polymer (IA-2), and the elastic polymer (IA) was obtained. The Tg of the polymer (IA-1) alone was −48 ° C., and the Tg of the polymer (IA-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 added dropwise to the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes. A coalescence (IB) was formed. The Tg of the intermediate polymer (IB) alone was 60 ° C.

  Subsequently, after dropping 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 over 140 minutes, the reaction is continued for 60 minutes, A hard polymer (IC) was formed to obtain a polymer latex of a rubber-containing multistage polymer (I). The Tg of the hard polymer (IC) alone was 99 ° C. Moreover, the mass average particle diameter of the rubber-containing multistage polymer (I) measured after polymerization was 0.11 μm.

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

  Further, 214.3 g of the obtained rubber-containing multistage polymer (I) 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 an acetone dispersion of the rubber-containing multistage polymer (I). Was prepared. Next, the dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and the nylon mesh was washed with chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. Then, the captured substance after ultrasonic cleaning is put into 150 ml of acetone filtered through a nylon mesh having an opening 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. It was a piece.

[Production Example 2]
(Production of rubber-containing polymer (I ′))
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, (i) shown in Table 2 was added and, while stirring, 1/15 of the raw material (b) for the first stage polymer (I′-A-1) of the elastic polymer shown in Table 3 was charged. For 15 minutes. Next, the remaining raw material (b) is continuously added at a rate such that the rate of increase of the monomer component [raw material (b)] with respect to water is 8% / hour, and then held for 60 minutes to obtain an elastic polymer. A latex of the first stage polymer (I′-A-1) was obtained. The Tg of the polymer (I′-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 (c) for the second stage polymer (I′-A-2) of the elastic polymer shown in Table 3 was added to the monomer component [raw material] (C)] is continuously added at a rate of 4% / hour and then held for 120 minutes to form a second stage polymer (I′-A-2) of an elastic polymer, An elastic polymer (I′-A) latex was obtained. The Tg of the polymer (I′-A-2) alone was −38 ° C.

  Subsequently, 0.4 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. And while stirring at 80 degreeC in nitrogen atmosphere, the increase rate of the monomer component [raw material (ni)] with respect to the water for the hard polymer (I'-C) shown in Table 3 is increased. After continuous addition at a rate of 10% / hour, the mixture was held for 60 minutes to form a hard polymer (I′-C) to obtain a polymer latex of a rubber-containing polymer (I ′). The Tg of the hard polymer (I′-C) alone was 99 ° C. The mass average particle diameter of the rubber-containing polymer (I ′) measured after polymerization was 0.28 μm.

  Calcium acetate is added to the polymer latex of the obtained rubber-containing polymer (I ′), and coagulation, aggregation, and solidification reaction are performed, followed by filtration, washing with water, and drying to obtain a powdery rubber-containing polymer ( I ′) was obtained. The gel content of the rubber-containing polymer (I ′) was 90%.

Compound: Amount used (a) Sodium formaldehyde sulfoxylate: 0.6 parts Ferrous sulfate: 0.00012 parts EDTA: 0.0003 parts (b) MMA: 18.0 parts n-BA: 20. 0 parts St: 2.0 parts AMA: 0.4 parts 1,3-BD: 0.14 parts t-BH: 0.18 parts Emulsifiers ^* : 0.75 parts (c) n-BA: 50.0 parts St: 10.0 parts AMA: 0.4 parts 1,3-BD: 0.14 parts t-BH: 0.2 parts Emulsifier ^* : 0.6 parts (d) MMA: 57.0 parts MA: 3. 0 part n-OM: 0.3 part t-BH: 0.06 part *) Toho Chemical Industry Co., Ltd., trade name "phosphanol RS610NA"
[Production Example 3]
(Production of thermoplastic polymer (IV))
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 added.

  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 (IV) was added to a 0.25% aqueous sulfuric acid solution, and the polymer was acidified, and then dehydrated, washed with water, and dried to obtain a powdery thermoplastic polymer ( IV) was recovered. The reduced viscosity of the obtained thermoplastic polymer (IV) was 0.38 L / g.

[Production Example 4]
(Manufacture of acrylic resin film substrate (A))
75 parts of rubber-containing multistage polymer (I) and thermoplastic polymer (II) [MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g) In 25 parts, as a compounding agent, Ciba Specialty Chemicals Co., Ltd., trade name “Tinubin 234” 1.4 parts, Asahi Denka Kogyo Co., Ltd., trade name “Adeka Stub AO-50” 0.1 part, and Asahi Denka Kogyo After adding 0.3 part of product name "ADK STAB LA-67" manufactured by Co., Ltd., the mixture was mixed using a Henschel mixer. This mixture [acrylic resin composition (III-1)] was supplied to a degassing type extruder (Ikegai Iron Works Co., Ltd., PCM-30 (trade name)) heated to 230 ° C., kneaded, and 300 mesh. Extruding while removing foreign matter with a screen mesh of Pellets (A) was obtained.

  The pellets (A) produced by the above method were dried at 80 ° C. all day and night, and a cylinder temperature of 180 to 240 was used using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm wide T die. Extruded while removing foreign matter with a 500 mesh screen mesh under the condition of ℃, the molten acrylic resin film extruded under the conditions of T die temperature of 240 ℃ and slit width of T die of 0.3 mm, two metal cooling rolls An acrylic resin film substrate (A) having a thickness of 75 μm is formed by sandwiching the resin without any bank (resin pool), transferring the surface without rolling, and winding it around a paper roll with a winder. Was formed.

  The acrylic resin film substrate (A) had a pencil hardness of H.

[Production Example 5]
(Manufacture of acrylic resin film substrate (B))
16 parts of rubber-containing polymer (I ′) and thermoplastic polymer (II) [MMA / MA copolymer (MMA / MA = 90/10 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g) ] 84 parts, thermoplastic polymer (IV) 1 part as a compounding agent, Ciba Specialty Chemicals, trade name "Tinubin 234" 1.4 parts, Asahi Denka Kogyo Co., Ltd., trade name "ADK STAB AO-50" “0.1 part” and 0.3 part of “Adeka Stab LA-67” manufactured by Asahi Denka Kogyo Co., Ltd. were added and mixed using a Henschel mixer. This mixture [acrylic resin composition (III-2)] was supplied to a degassing type extruder (Ikegai Iron Works Co., Ltd., PCM-30 (trade name)) heated to 230 ° C., kneaded, and 300 mesh. Extruding while removing foreign matters with a screen mesh of No. 1 to obtain pellets (B).

  An acrylic resin film substrate (B) having a thickness of 75 μm was formed in the same manner as in the formation of the acrylic resin film substrate (A) except that the pellet (B) produced by the above method was used.

  The acrylic hardness of the acrylic resin film substrate (B) was 2H.

[Production Example 6]
(Manufacture of acrylic resin film substrate (C))
In Production Example 5, [MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g)] is used as the thermoplastic polymer (II). Similarly, an acrylic resin film substrate (C) having a thickness of 75 μm was formed.

  The acrylic hardness of the acrylic resin film substrate (C) was 2H.

[Example 1]
27.5 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 80 mg KOH / g, Tg 90 ° C., mass average molecular weight of about 80,000) which is a copolymer of MMA 85%, HEMA 12% and n-BA 3%, and hexamethylene diisocyanate (polyisocyanate) 6.8 parts of an isocyanurate type), 6 parts of amorphous silica having a mass average particle diameter of 5 to 6 μm, 1.5 parts of amorphous silica having a mass average particle diameter of 0.1 μm as a precipitation inhibitor, and a mass average One part of polytetrafluoroethylene wax SST-3 (trade name, manufactured by SHAMROCK, melting point 321 ° C.) having a particle diameter of 5 μm was dispersed in a solvent composed of 22 parts of MEK, 43 parts of MIBK and 40 parts of butyl acetate to obtain a paint. In addition, when this paint was measured with the Iwata cup viscometer immediately before coating, the flow-down time was 18 seconds. After adjusting the viscosity, the coating solution was filtered using CPII-10 manufactured by Chisso Filter Co., Ltd.

Next, an oblique gravure roll having an inch width of 200 lines on one side of an acrylic resin film substrate (A) having a thickness of 75 μm (the oblique line angle with respect to the roll axis direction is about 45 °, the opening width of the plate is 116 μm, the bottom of the plate (Wide 13 μm, plate depth 33 μm, cell capacity 16.9 cm ³ / m ² , diameter 120 mm) Using a ceramic doctor blade, a gravure coater was applied at a coating speed of 20 m / min, and then 90 ° C. The volatile acrylic resin film was obtained by volatilizing the solvent under the atmosphere. The appearance of the resulting matte acrylic resin film was free of faint or noticeable prints due to a decrease in the transfer amount, and a good matte layer could be formed. The matte acrylic resin film was wound around a paper tube and aged at 40 ° C. for 2 days to cure the matte layer.

  The coating was carried out for about 3000 m on the acrylic resin film substrate, but during that time there was an appearance defect (white streaks were intermittently transferred in the flow direction) generated by winding up the wax on which the gravure roll settled. I was able to confirm from time to time. Moreover, although the bottom of the bread | pan which stored the coating liquid was confirmed after completion | finish of coating, the deposit was confirmed.

[Example 2]
In Example 1, instead of polytetrafluoroethylene wax SST-3 (trade name), wax S-363 (trade name, manufactured by SHAMROCK, melting point 142 ° C.) made of polyethylene and polypropylene having a mass average particle diameter of 5 μm is used. In the same manner as in Example 1 to obtain a matte acrylic resin film. Note that. When this paint was measured with an Iwata cup viscometer immediately before coating, the flow-down time was 19 seconds. The appearance of the resulting matte acrylic resin film was free of faint or noticeable prints due to a decrease in the transfer amount, and a good matte layer could be formed.

  In addition, although coating was performed about 3000 m with respect to the acrylic resin film base | substrate, the external appearance defect which generate | occur | produces by winding up the wax which the gravure roll settled did not generate | occur | produce. Further, after the coating was completed, the bottom of the pan where the coating liquid was stored was confirmed, but no precipitate was confirmed.

Example 3
A matte acrylic resin film was obtained in the same manner as in Example 2 except that the wax S-363 (trade name) made of polyethylene and polypropylene was increased to 2 parts. In addition, when this paint was measured with the Iwata cup viscometer immediately before coating, the flow-down time was 19 seconds. The appearance of the resulting matte acrylic resin film was free of faint or noticeable prints due to a decrease in the transfer amount, and a good matte layer could be formed.

Example 4
27.4 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 80 mg KOH / g, Tg glass transition temperature 90 ° C., mass average molecular weight about 80,000), which is a copolymer of MMA 85%, HEMA 12% and n-BA 3%, 6.8 parts of hexamethylene diisocyanate (isocyanurate type) trimer, 7 parts of amorphous silica having a mass average particle diameter of 5 to 6 μm, 1.5 parts of amorphous silica having a mass average particle diameter of 0.1 μm as a suspending agent 1 part of wax S-363 (trade name, manufactured by SHAMROCK, melting point 142 ° C.) made of polyethylene and polypropylene having a mass average particle diameter of 5 μm, from 22.3 parts of MEK, 49.6 parts of MIBK, and 45.8 parts of butyl acetate. A paint was obtained by dispersing in a solvent. In addition, when this paint was measured with an Iwata cup viscometer immediately before coating, the flow-down time was 15 seconds. After adjusting the viscosity, the coating solution was filtered using CPII-10 manufactured by Chisso Filter Co., Ltd.

Next, an oblique gravure roll having an inch width of 200 lines on one side of an acrylic resin film substrate (A) having a thickness of 75 μm (the oblique line angle with respect to the roll axis direction is about 45 °, the opening width of the plate is 116 μm, After applying the paint at a coating speed of 30 m / min with a gravure coater using a ceramic doctor blade, the width of the bottom is 13 μm, the plate depth is 33 μm, the cell capacity is 16.9 cm ³ / m ² , and the diameter is 120 mm. The solvent was volatilized under an atmosphere of ° C to obtain a matte acrylic resin film. The appearance of the resulting matte acrylic resin film was free of faint or noticeable prints due to a decrease in the transfer amount, and a good matte layer could be formed. The matte acrylic resin film was wound around a paper tube and aged at 40 ° C. for 2 days to cure the matte layer.

  The thickness of the matte layer was 1 μm. Further, the obtained matte acrylic resin film had a good appearance with a reflection of a fluorescent lamp and no grain.

Example 5
In Example 4, instead of the 200-line oblique gravure roll with inch width, the 250-inch diagonal gravure roll with an inch width (the oblique line angle with respect to the roll axis direction is about 45 °, the opening width of the plate is 80 μm, the bottom of the plate The width was 11 μm, the plate depth was 35 μm, the cell capacity was 15.6 cm ³ / m ² , the diameter was 120 mm, and the coating speed was 40 m / min.

  The thickness of the matte layer was 1 μm. Further, the obtained matte acrylic resin film had a good appearance with a reflection of a fluorescent lamp and no grain.

Example 6
In Example 4, instead of the 200-line diagonal gravure roll with inch width, a 250-line lottofloat type gravure roll (plate depth 34 μm, cell capacity 13.2 cm ³ / m ² , diameter 120 mm) was used. The same operation as in Example 4 was performed.

  The thickness of the matte layer was 0.8 μm. Further, the obtained matte acrylic resin film had a good appearance with a reflection of a fluorescent lamp and no grain.

[Reference Example 1]
In Example 4, instead of the 200-line diagonal gravure roll with inch width, the 250-inch diagonal gravure roll with inch width (the diagonal angle with respect to the roll axis direction is about 75 °, the opening width of the plate is 90 μm, the bottom of the plate) This was carried out in the same manner as in Example 4 except that a width of 8 μm, a plate depth of 32 μm, a cell capacity of 15.4 cm ³ / m ² , and a diameter of 120 mm were used.

  The resulting matte acrylic resin film has a surface glossiness of 19% and good matteness, but there are places where the coating liquid is not applied in some places, and an acrylic having a uniform matte coating surface. A resin film was not obtained.

[Comparative Example 1]
23 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 80 mg KOH / g, Tg 90 ° C., mass average molecular weight of about 80,000), which is a copolymer of MMA 85%, HEMA 12% and n-BA 3%, and hexamethylene diisocyanate as polyisocyanate (Isocyanurate type) 5.6 parts of trimer and 4 parts of amorphous silica having a mass average particle diameter of 6 to 7 μm are composed of 48 parts of ethyl acetate, 16 parts of npropyl acetate, and 10 parts of butyl acetate. A paint was obtained by dispersing in a solvent. This paint was diluted with ethyl acetate, and the viscosity was adjusted so that the flow time by a Iwata cup viscometer was 14 seconds. After adjusting the viscosity, the coating solution was filtered using CPII-10 manufactured by Chisso Filter Co., Ltd.

Next, an oblique gravure roll having an inch width of 200 lines on one side of an acrylic resin film substrate (A) having a thickness of 75 μm (the oblique line angle with respect to the roll axis direction is about 45 °, the opening width of the plate is 116 μm, the bottom of the plate After applying the viscosity-adjusted paint at a coating speed of 20 m / min with a gravure coater using a steel doctor blade with a width of 13 μm, a plate depth of 33 μm, a cell capacity of 16.9 cm ³ / m ² and a diameter of 120 mm. The solvent was volatilized under an atmosphere of 85 ° C. to obtain a matte acrylic resin film. The appearance of the resulting matte acrylic resin film was free of faint or noticeable prints due to a decrease in the transfer amount, and a good matte layer could be formed. The matte acrylic resin film was wound around a paper tube and aged at 40 ° C. for 2 days to cure the matte layer. The thickness of the matte layer was 1.1 μm.

[Comparative Example 2]
Hydroxyl group-containing acrylic resin (hydroxyl value 60 mgKOH / g, glass transition temperature 65 ° C., mass average molecular weight about 30,000), which is a copolymer of MMA 68%, HEMA 9%, n-BA 9%, and n-butyl methacrylate 14% ) 32 parts, 5.6 parts of hexamethylene diisocyanate (isocyanurate type) trimer as polyisocyanate, and 4.8 parts of amorphous silica having a mass average particle diameter of 6 to 7 μm, 33 parts of ethyl acetate, A paint was obtained by dispersing in a solvent consisting of 15 parts of n-propyl acetate and 15 parts of butyl acetate. This paint was diluted with ethyl acetate, and the viscosity was adjusted so that the flow time by a Iwata cup viscometer was 14 seconds. After adjusting the viscosity, the coating solution was filtered using CPII-10 manufactured by Chisso Filter Co., Ltd. It implemented similarly to the comparative example 1 except apply | coating this dilution coating material to an acrylic resin film base | substrate (B). The appearance of the resulting matte acrylic resin film was free of faint or noticeable prints due to a decrease in the transfer amount, and a good matte layer could be formed. The thickness of the matte layer was 1.3 μm.

[Comparative Example 3]
It implemented similarly to the comparative example 1 except having used the 75-micrometer-thick acrylic resin film base | substrate (C) instead of the acrylic resin film base | substrate (A). The appearance of the resulting matte acrylic resin film was free of faint or noticeable prints due to a decrease in the transfer amount, and a good matte layer could be formed. The thickness of the matte layer was 1.1 μm.

[Comparative Example 4]
A matte acrylic resin film was obtained in the same manner as in Example 1 except that polyethylene wax S-395 (trade name) was not used. In addition, when this paint was measured with the Iwata cup viscometer immediately before coating, the flow-down time was 19 seconds. The appearance of the resulting matte acrylic resin film was free of faint or noticeable prints due to a decrease in the transfer amount, and a good matte layer could be formed. The thickness of the matte layer was 1 μm.

Table 3 summarizes the evaluation results of the acrylic resin film substrate, matte acrylic resin film, and laminate obtained above.

  From Examples 1-6, it turns out that the laminated body which laminated | stacked the matt acrylic resin film and whose dynamic friction coefficient is 0.23 or less shows favorable abrasion resistance.

  Moreover, it turns out that the mat | matte acrylic resin film coated in the range of 0.1-5 micrometers does not generate | occur | produce a crack of a mat | matte layer at the time of shaping | molding, but shows favorable moldability. Moreover, it turns out that favorable chemical resistance is shown by using curable binder resin. Further, a matte acrylic resin film having a difference between the yellowness (YI ′ (200 ° C.)) when heated to 200 ° C. and the yellowness (YI) before heating is 1.3 or less has no change in appearance during molding. I understand that.

  From Examples 4 to 6 and Reference Example 1, by using a diagonal roll having 150 or more lines per inch and engraved at an angle of 40 to 50 ° with respect to the roll axis direction, It can be seen that a film having a good appearance can be obtained, and that a film having a small change in appearance can be obtained even by thermoforming.

  As described above, by adopting a matte acrylic resin film having the configuration of the present invention, it is possible to develop a design that is difficult to realize when a matting agent is added to a conventional acrylic resin film layer, and to be handled. Even if it is subjected to insert molding or in-mold molding and molded into a deep-drawn molded product, the matte layer does not crack and can be used for vehicle applications, scratch resistance, surface hardness, A matte acrylic resin film having heat resistance, chemical resistance, heat yellowing resistance, and matting properties, and a laminate in which these are laminated on a substrate can be provided. Moreover, it becomes possible to manufacture a matte acrylic resin film stably by employ | adopting the manufacturing method of this invention.

  The laminated molded product having the matte acrylic resin film 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, windbreak boards, etc., 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, aircraft, ships and other vehicles other than automobiles, various packaging such as bottles, cosmetic containers, and accessories It can be suitably used for various other uses such as containers and materials, miscellaneous goods such as prizes and accessories.

Claims (5)

A matte acrylic resin film for thermoforming, in which a paint containing a matting agent and a curable binder resin is applied on the surface of an acrylic resin film substrate, and a matte layer is formed on the outermost layer. A matte acrylic resin film for thermoforming having a layer side dynamic friction coefficient of 0.23 or less.   The matte acrylic resin film for thermoforming according to claim 1, further comprising a pattern layer on the surface of the acrylic resin film substrate opposite to the matte layer.   The method for producing a matte acrylic resin film for thermoforming according to claim 1, wherein the matte layer is formed by a printing method or a coating method.   It is a manufacturing method of the matte acrylic resin film for thermoforming of Claim 1, Comprising: It has 150 or more lines per inch, and was engraved at an angle of 40-50 degrees with respect to a roll axial direction A method for producing a matte acrylic resin film for thermoforming, wherein a matte layer is formed using a diagonal roll. A laminate comprising the matte acrylic resin film for thermoforming according to claim 1 laminated on a substrate so that a surface opposite to the matte layer is in contact therewith.