JP2008265029A - Metal decorative sheet and metal molded product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallic tone decorative sheet having durability for a long period of time, excellent design property, or thermal moldability, and a metallic tone molded article using the sheet. <P>SOLUTION: In the metallic tone decorative sheet having at least a thermoplastic acrylic resin sheet and a metallic thin film layer, the metallic tone decorative sheet satisfies the condition that when the thermoplastic acrylic resin sheet is heated at 175°C for 30 sec, newly protruded structure having a depth of 50 nm or more or a recessed structure having a depth of 50 nm or more is not generated on the surface of the thermoplastic acrylic resin sheet. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a metallic decorative sheet having long-term durability, excellent design properties and thermoformability, and a metallic molded article using the sheet. In particular, the present invention can be thermoformed into various three-dimensional shapes, has excellent wear resistance, scratch resistance, chemical resistance, and weather resistance, and is beautiful even after thermoforming. The present invention relates to a metallic decorative sheet in which the metallic appearance does not change, and a metallic molded article using the sheet.

  Applying a metallic appearance to the surface of a resin molded product can replace conventional metal materials without reducing the sense of quality, and at the same time achieve the advantages of lighter weight, lower cost, and increased shape flexibility. This is very useful industrially.

  As a method of obtaining a resin molded product having a metal-like appearance, (1) forming a metal-designed layer directly or after subjecting the surface of a resin molded product obtained in advance to an adhesion improving treatment (metal plating) And metal-like painting). However, this method required environmental measures accompanying wastewater and solvent odor generation. Furthermore, since the surface of the obtained metal design layer is weak against various external stimulating factors, it is necessary to provide a new protective layer for the purpose of protecting the metal film surface. There was a problem of up.

  In addition to the above (1), as a method of giving a metallic appearance to the surface of the resin molded product, (2) a transfer sheet in which a metallic design layer is formed by vapor deposition or painting on a release sheet is sandwiched in a molding die, A method of forming a metal design layer on the surface of the resin molded product by peeling and releasing the release sheet after the transfer sheet is adhered to the surface by injecting resin into the cavity to obtain a resin molded product. Transfer method) and (3) a method in which an insert sheet having a metal design layer or the like formed on a base sheet is inserted into a molding die, and the insert sheet is integrated on the surface of the resin molded product simultaneously with injection molding ( Insert method).

  However, in the method (2), as in the method (1), the metal design layer on the surface of the obtained molded product has low durability, and it is newly added to provide long-term durability. There is a problem that it is necessary to provide a protective layer, the manufacturing process becomes complicated, and the cost increases. In addition, a method is also known in which a cross-linked resin composition layer is provided on a release sheet in order to impart durability, and an outermost layer of the obtained molded product is used as a cross-linked resin composition layer (for example, Japanese Patent Application Laid-Open No. Hei 11- No. 227394, JP-A 2000-43082, and JP-A 2004-142439). However, in this method, in order to ensure the storage stability as the transfer sheet, it is necessary to keep the crosslinked resin composition layer in a completely cured or semi-cured state. There is a problem that it can be applied only to a molded product having a shape with little undulation.

  The method (3) also has a problem with the durability of the metallic design layer of the molded product obtained in the same manner, and as means for solving the problem, 1) a new protective layer is obtained after the molded product is obtained. 2) The base sheet of the insert sheet is a thermoplastic acrylic resin sheet that is relatively excellent in scratch resistance and hardness (for example, Japanese Patent Application Laid-Open No. 2004-1243 (Patent Document 1), JP-A-3703111 (Patent Document 2), JP-A-2003-112399 (Patent Document 3), JP-A-10-735 (Patent Document 4), JP-A-2005-262447 (Patent Document 5), No. 10-180795 (see Patent Document 6)), or 3) a method of previously providing a crosslinked resin composition layer on the outermost layer of the insert sheet (for example, JP-A-10-26420). No. See (Patent Document 7)) was known.

  However, the method 1) has a problem of increasing the number of manufacturing steps as described above. In the method 2), the outermost layer of the molded product is a thermoplastic acrylic resin sheet, but the durability of the molded product is improved as compared with a conventional PET film or the like, but it can withstand long-term use. It has not yet reached the point of developing only the durability.

  On the other hand, also in the method of 3), it is necessary to completely cure or semi-cure the crosslinked resin composition layer in order to ensure the storage stability of the insert sheet and the resistance to mold contamination (Patent Document 7 discloses specifics regarding curing) Therefore, there was a problem that the heat elongation of the insert sheet was lowered, and the molded product having a three-dimensional shape with large undulations could not be handled.

  Furthermore, in the insert method of (3), depending on the type of base sheet used for the insert sheet, a streak pattern is generated after thermoforming, and the insert sheet originally has an excellent metallic tone appearance. The problem of being unable to reproduce has also become apparent, and a solution has been desired.

JP 2004-1243 A Japanese Patent Laid-Open No. 2002-370311 JP 2003-112399 A JP-A-10-735 JP 2005-262447 A Japanese Patent Laid-Open No. 10-180795 JP-A-10-264201

  Therefore, the present invention eliminates the problems of the prior art as described above, has a long-term durability, excellent design and thermoformability, and a metal-like decorative sheet using the sheet The purpose is to provide goods.

That is, the present invention provides a metallic decorative sheet characterized in that, in a metallic decorative sheet having at least a thermoplastic acrylic resin sheet and a metal thin film layer, the thermoplastic acrylic resin sheet satisfies the following conditions: It is.
Condition: When heated at 175 ° C. for 30 seconds, a convex structure having a height of 50 nm or more or a concave structure having a depth of 50 nm or more is not newly generated on the surface of the thermoplastic acrylic resin sheet.

  According to the present invention, by using a metallic decorative sheet having a thermoplastic acrylic resin sheet satisfying at least a specific condition and a metal thin film layer, various three-dimensional shaped articles having an excellent metallic appearance are short. It can be easily obtained in the manufacturing process. Furthermore, by using a metallic decorative sheet with a specific photocurable resin composition layer on the surface of the thermoplastic acrylic resin sheet, not only has an excellent metallic appearance, but also a long-term durability (wear resistance) A molded product having a high degree of productivity, scratch resistance, chemical resistance, weather resistance, etc.).

  Hereinafter, preferred embodiments of the present invention will be described. However, it should be understood that the present invention is not limited to these embodiments, and various modifications can be made within the spirit and scope of implementation.

  The metallic decorative sheet of the present invention has at least a thermoplastic acrylic resin sheet and a metal thin film layer, and when the thermoplastic acrylic resin sheet is heated for 30 seconds at 175 ° C., the thermoplastic acrylic resin sheet A new convex structure with a height of 50 nm or more or a concave structure with a depth of 50 nm or more does not occur on the surface).

  As a base material sheet for a metallic decorative sheet, for example, ABS (acrylonitrile / butadiene / styrene copolymer) resin, AS (acrylonitrile / styrene copolymer) resin, vinyl chloride resin, polystyrene resin, polypropylene, etc. Polyolefin resin, fluorine resin, cellophane resin, cellulose resin, polyurethane resin, polyamide resin such as nylon, polyester resin, polycarbonate resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, etc. Sheets, composites of these sheets, laminates, etc. can be used, but in the metallic decorative sheet of the present invention, the transparency, designability, weather resistance, surface hardness of the molded product obtained In view of the above, the base sheet is a thermoplastic active material having a crosslinked rubber component. Preferably a Le resin sheet.

  Transparent thermoplastic acrylic resin sheets having a crosslinked rubber component are disclosed in JP-A-8-323934, JP-A-9-263614, JP-A-11-147237, JP-A-2001-106742, and the like. There is a transparent thermoplastic acrylic resin sheet. Commercially available transparent thermoplastic acrylic resin sheets include acryloprene HBX-N47, HBS-006, HBD-013 (above, manufactured by Mitsubishi Rayon Co., Ltd.), Technoloy S001, S003, SN101 (above, Sumitomo Chemical Co., Ltd.) )), Sanduren SD007, SD009 (above, manufactured by Kaneka Chemical Co., Ltd.) and the like.

  Furthermore, when the thermoplastic acrylic resin sheet of the metallic decorative sheet of the present invention is heated at 175 ° C. for 30 seconds, a new convex structure having a height of 50 nm or more or a depth of 50 nm is newly formed on the surface of the thermoplastic acrylic resin sheet. The above concave structure does not occur. By using a thermoplastic acrylic resin sheet having such characteristics, it is possible to suppress the generation of streaks in the metal-decorated sheet after thermoforming, which has been a problem in the prior art, It is possible to reproduce the excellent design properties inherent to the sheet in the molded product. Preferably, when the thermoplastic acrylic resin sheet is heated at 175 ° C. for 30 seconds, a convex structure having a height of 30 nm or more or a concave structure having a depth of 30 nm or more is newly generated on the surface of the thermoplastic acrylic resin sheet. Is not to.

  Even if a metallic decorative sheet using a thermoplastic acrylic resin sheet that generates a convex structure with a height of less than 30 nm or a concave structure with a depth of less than 30 nm is formed, the molded product after thermoforming The presence of the streak pattern is almost difficult to confirm visually, and an excellent metallic appearance can be reproduced. On the other hand, when a metallic decorative sheet using a thermoplastic acrylic resin sheet that generates a convex structure having a height of 50 nm or more or a concave structure having a depth of 50 nm or more is attached to the molded product, As a result, the streak pattern can be remarkably visually recognized, and the beautiful metallic appearance is significantly impaired.

  Note that the height or depth of the convex or concave structure newly generated on the surface of the thermoplastic acrylic resin sheet after heating is the maximum peak height (Pp) of the cross-sectional curve defined by JIS B0601 on the surface of the thermoplastic acrylic resin sheet after heating. It can be evaluated by measuring the maximum valley depth (Pv) of the cross section curve.

  The values of Pp and Pv on the surface of the thermoplastic acrylic sheet after heating can be measured using an atomic force microscope (AFM), a laser confocal microscope, etc. It is preferable to use a contact three-dimensional surface shape measuring instrument because it is simpler and can measure a wider range of sheet surfaces. Examples of such a non-contact three-dimensional surface shape measuring instrument include “Micromap MM5000 series” manufactured by Ryoka System Co., Ltd. or “New View 6000 series” manufactured by Zygo. These measuring machines have a high resolution of 1 nm or less in the vertical direction of the sheet, and can measure a cross-sectional shape at an arbitrary position of the sheet. Furthermore, various parameters defined in JIS B0601 can be analyzed from the shape of the obtained sheet cross section, and the required Pp and Pv values can be easily obtained. In addition, the site | part which the convex structure 50 nm or more in height or the concave structure 50 nm or more in depth which becomes a problem in the thermoplastic acrylic resin sheet after a heating generate | occur | produces visually, or the thermoplastic acrylic resin after a heating When a sheet is projected onto a screen by OHP or the like, it can be generally confirmed as a streak-like distortion portion, and thus it is possible to determine whether or not it exists.

  In the thermoplastic acrylic resin sheet, if necessary, lubricants such as polyethylene wax and paraffin wax, lubricants such as silica, spherical alumina and flaky alumina, benzotriazole, benzophenone, triazine, fine particles The effects of the present invention are not impaired by various additives such as UV absorbers such as cerium oxides, light stabilizers such as hindered amine radical scavengers, plasticizers, thermal stabilizers having an antioxidant function, pigments, and dyes. Can be added in a range. In particular, it is useful for some purposes to add pigments or dyes in order to positively adjust the color tone in consideration of the influence of the metallic luster on the color tone.

The thickness of the thermoplastic acrylic resin sheet is preferably 500 μm or less, and more preferably 300 μm or less. Further, this thickness is more preferably 10 μm or more. When the thickness is 10 μm or more, a particularly sufficient depth feeling and surface hardness can be obtained as the appearance of the molded product, and particularly a sufficient thickness can be maintained even when the film is stretched to form a complicated shape. In addition, the upper limit of these ranges is that the rigidity is moderately suppressed to maintain good laminating properties and secondary workability, the mass per unit area is reduced to maintain economy, and the metal condition is more stable. This is significant in terms of manufacturing a decorative sheet.
In addition, the transparency of the thermoplastic acrylic resin sheet can be appropriately selected according to the design of the resulting molded product, but when a light transmittance of 85% or more is used, the metal exhibited by the metal thin film layer described later This is preferable because gloss tends to be sufficiently exhibited.

  The metallic decorative sheet of the present invention has a metal thin film layer. The metal thin film layer may be provided on the entire surface of the thermoplastic acrylic resin sheet, which is a base sheet, or may be provided partially. The metal thin film layer can be directly formed on one surface of a thermoplastic acrylic resin sheet as a base sheet by a wet plating method or a dry thin film forming method such as vacuum deposition, sputtering, ion plating, or plasma CVD. It is desirable to use a dry thin film forming method in that waste liquid treatment is not required when forming a metal thin film layer and that a uniform thin film is obtained.

The metal constituting the metal thin film layer is a simple substance such as aluminum, zinc, gallium, nickel, tin, silver, gold, chromium, titanium, platinum, palladium, indium, etc., depending on the texture of the molded product having the required metallic appearance. Aluminum alloys, alloys such as stainless steel and hastelloy, or metals and alloys that can provide a sufficient metallic luster such as silicon and can be selected and used.
Among these, aluminum, indium, and alloys thereof are advantageous when performing deep drawing three-dimensional forming, and particularly in the case of a metal thin film layer made of high purity indium of 99.9% or more, forming with a very small radius of curvature. It is particularly preferable because it can be applied to molding of products.

  The thickness of the metal thin film layer is not particularly limited as long as it can withstand various processes applied to the metallic decorative sheet, but is usually preferably in the range of 3 to 200 nm, particularly when three-dimensionally forming. The lower limit is more preferably 5 nm, and the upper limit is more preferably 100 nm. If the thickness of the metal thin film layer is less than 3 nm, it may not be possible to impart sufficient metallic luster to the molded product. On the other hand, even if a metal thin film layer having a thickness of more than 200 nm is formed, not only can a useful effect commensurate with the increase in thickness be obtained with respect to the design of the resulting molded product, but also the manufacturing cost increases. In addition, it is disadvantageous because the metal thin film layer is easily broken when the metal-like decorative sheet is formed.

  In the metallic decorative sheet of the present invention, when the adhesion between the thermoplastic acrylic resin sheet as the base material sheet and the metal thin film layer is low, an anchor layer can be provided between them. For the anchor layer, a resin that can withstand various process conditions (particularly the heat and pressure of the molten resin during injection molding) applied to the metallic decorative sheet is preferably used. Such resins include thermosetting urethane resins, melamine resins, cellulose ester resins, chlorine-containing rubber resins, vinyl chloride vinyl acetate copolymer resins, acrylic resins, epoxy resins, polyester resins, polyamide resins. Resin, ethylene butyl alcohol resin, ethylene vinyl acetate copolymer resin, and the like. These resin layers may be used as an anchor layer by a known printing method (offset printing method, gravure printing method, screen printing method, flexographic printing method, etc.). In addition, when selecting the resin used for the anchor layer, adhesion development with the thermoplastic acrylic resin sheet or the metal thin film layer is an important factor, but the metal of the molded product that also provides the transparency of the anchor layer itself. It is necessary to pay careful attention to the fact that it is an important factor that affects the appearance of the tone. In consideration of the influence of the metallic luster on the color tone, a pigment or a dye may be added to the anchor layer in order to positively adjust the color tone.

  Examples of the method for obtaining the metallic decorative sheet of the present invention include a method of forming a metal thin film layer directly on the thermoplastic acrylic resin sheet or on the anchor layer surface provided in advance on the thermoplastic acrylic resin sheet. Can do. In addition, a metal thin film layer is provided on the backing film directly or via an anchor layer, and the backing film with the metal thin film layer and the thermoplastic acrylic resin sheet are bonded together via an adhesive layer. Can also be obtained. Examples of the backing film used at this time include acrylic films, polypropylene films, thermoplastic elastomer films, polycarbonate films, nylon films, ABS films, AS films, polystyrene films, polyurethane films, and polyester films. It is necessary to withstand the temperature at the time of molding the decorative sheet. Further, as a bonding method, there are a dry laminating method, a hot melt laminating method, a thermal laminating method and the like. When the adhesive layer is used for bonding, a resin as described above for the anchor layer can be employed.

  The metallic decorative sheet of the present invention is provided with a hard coat layer or an antistatic layer for the purpose of imparting excellent scratch resistance, chemical resistance, antistatic property, antireflection property and the like to the molded product obtained. Various transparent resin composition layers such as a conductive layer and an antireflection layer are placed on the surface opposite to the surface on which the metal thin film layer exists, that is, on the surface of the thermoplastic acrylic resin sheet corresponding to the outermost layer surface of the obtained molded product. Can be provided. Various commercially available coating compositions can be used for the transparent resin composition layer formed on the surface of the metallic decorative sheet. In this case, the adhesiveness with the thermoplastic acrylic resin sheet is excellent, or the metallic It is necessary to select as appropriate from the viewpoint of not inhibiting the thermoformability of the decorative sheet.

  In particular, by providing a hard coat layer on the surface of the molded product and adding properties such as scratch resistance, abrasion resistance, chemical resistance, and high surface hardness, the beautiful metallic appearance of the molded product can be obtained over a long period of time. It is extremely useful in maintaining. At this time, it is not preferable that the hard coat layer is composed of a crosslinked resin composition having a low heat elongation because such a problem that the transparent resin layer breaks when the metallic decorative sheet is thermoformed. As a hard coat layer capable of imparting excellent durability such as scratch resistance to the obtained molded product without inhibiting the thermoformability of the metallic decorative sheet, heat having a photopolymerizable functional group is used. The layer formed from the photocurable resin composition containing a plastic resin (a-1) and a photoinitiator (a-2) is mentioned.

As the thermoplastic resin (a-1) having a photopolymerizable functional group, a compound having two or more photopolymerizable functional groups in one molecule and being cured by a photopolymerization reaction to form a crosslinked product A composition containing is preferred. Examples of the photopolymerizable functional group of such a compound include radical polymerizable unsaturated groups such as vinyl groups and (meth) acryl groups, and functional groups that react by a photocationic polymerization mechanism such as alicyclic epoxy groups. In particular, when the photopolymerizable functional group is a radically polymerizable unsaturated group, compared with a functional group that reacts by a photocationic polymerization mechanism such as an alicyclic epoxy group, the physical properties after curing include warm water resistance and weather resistance. There is a tendency to be excellent in properties, which is preferable.
From the viewpoint of the weather resistance of the thermoplastic resin (a-1), the thermoplastic resin (a-1) is preferably an acrylic resin having a photopolymerizable functional group in the molecule.

Furthermore, the thermoplastic resin (a-1) is more preferably an acrylic resin having a photopolymerizable functional group in the side chain from the viewpoint of developing durability such as good wear resistance and chemical resistance.
Especially, when a photocurable resin composition contains the thermoplastic resin (a-1) which has a photopolymerizable functional group in a side chain, and does not contain crosslinkable compounds other than (a-1), When the photocurable resin composition is cured, it exhibits extremely good wear resistance and chemical resistance, and in the uncured state, it exhibits excellent thermoformability, storage stability, and tack-free properties. Is particularly preferred.

  In particular, it is preferable not to contain a crosslinkable monomer or oligomer that is liquid at 40 ° C., or a low molecular weight crosslinkable monomer or oligomer having a molecular weight of 2,000 or less. If such a liquid or molecular weight of 2,000 or less crosslinkable monomer or oligomer is contained, it will have surface tackiness during long-term storage or thermoforming, resulting in poor handling or thermoforming. At times, problems such as contamination of the mold may occur. More preferably, it does not contain a liquid crosslinkable monomer or oligomer at 50 ° C., and more preferably does not contain a liquid crosslinkable monomer or oligomer at 60 ° C.

  A thermoplastic resin having a photopolymerizable functional group in the side chain is synthesized by a known method (for example, a monomer having a photopolymerizable functional group described in JP-A No. 2003-34002). ) A method of polymerizing, a polymer having a first functional group such as a hydroxyl group, an epoxy group, or a carboxyl group in a side chain, a second functional group that reacts with the first functional group, and a compound having a photopolymerizable function. And the like.

  The amount of the photopolymerizable functional group in the side chain of the thermoplastic resin (a-1) is a photopolymerizable functional group equivalent (average molecular weight per photopolymerizable functional group) calculated from the charged value. An average of 3,000 g / mol or less is preferable from the viewpoint of improving durability such as scratch resistance, abrasion resistance, and chemical resistance. A more preferable range is 1,200 g / mol or less on average, and a most preferable range is 800 g / mol or less on average.

  By introducing a structure having a photopolymerizable functional group in the side chain in this way, the cross-linking reaction proceeds between the side chains, so that durability such as good wear resistance is obtained without including a low molecular weight cross-linking compound. In addition, since there is no low molecular weight crosslinkable compound, there is no stickiness on the sheet surface, so the sheet storage stability and mold contamination resistance are excellent, and light before the crosslinking reaction Since the curable resin composition is thermoplastic, it does not hinder the thermoformability of the sheet.

  The number average molecular weight of the thermoplastic resin (a-1) is preferably in the range of 5,000 to 2,500,000. The lower limit is more preferably 10,000 or less. The upper limit is more preferably 1,000,000 or less. From the viewpoint of improving mold releasability, surface hardness after photocuring, and the like when molding a laminated sheet formed using a photocurable resin composition containing a thermoplastic resin (a-1). The number average molecular weight is preferably 5,000 or more. On the other hand, it is preferable that the number average molecular weight is 2,500,000 or less from the viewpoint of ease of synthesis and appearance, and from the viewpoint of adhesion with the substrate sheet.

  Moreover, it is preferable that the glass transition temperature of the thermoplastic resin (a-1) is adjusted to 25 to 175 ° C. The lower limit of the glass transition temperature is more preferably 30 ° C. or higher. The upper limit of the glass transition temperature is more preferably 150 ° C. or less. From the viewpoint of mold releasability of the laminated sheet at the time of molding and molded product hardness after photocuring, the glass transition temperature is preferably 25 ° C. or higher. On the other hand, it is preferable that a glass transition temperature is 175 degrees C or less from a viewpoint of the handleability of a lamination sheet.

  The photocurable resin composition may contain a photopolymerization initiator (a-2). Examples of the photopolymerization initiator (a-2) include a photoradical polymerization initiator that generates radicals by light irradiation and a photocationic polymerization initiator that generates acid. Photopolymerization of the thermoplastic resin (a-1). When the functional functional group is a radical polymerizable unsaturated group, a photo radical polymerization initiator is used, and when it is an alicyclic epoxy group, a photo cationic polymerization initiator is used.

  Furthermore, inorganic fine particles (a-3) can be added to the photocurable resin composition for the purpose of improving durability such as scratch resistance, abrasion resistance, and chemical resistance after photocuring. . In the inorganic fine particles (a-3), the type, particle diameter, and form are not particularly limited as long as the obtained photocurable resin composition becomes transparent. Examples of the inorganic fine particles include colloidal silica, alumina, titanium oxide, tin oxide, foreign element doped tin oxide (ATO, etc.), indium oxide, foreign element doped indium oxide (ITO, etc.), cadmium oxide, antimony oxide, and the like. . These may be used alone or in combination of two or more. Of these, colloidal silica is particularly preferable from the viewpoints of availability, price, transparency of the resulting photocurable resin composition layer, and expression of wear resistance.

The particle diameter of the inorganic fine particles (a-3) is usually preferably 200 nm or less from the viewpoint of the transparency of the resulting photocurable resin composition layer. More preferably, it is 100 nm or less, More preferably, it is 50 nm or less.
Moreover, the addition amount of the inorganic fine particles (a-3) is preferably in the range of 5 to 400 parts by mass in terms of solids of the inorganic fine particles with respect to 100 parts by mass of the solids of the thermoplastic resin (a-1). The lower limit of the addition amount is more preferably 10 parts by mass or more. Further, the upper limit of the addition amount is more preferably 200 parts by mass or less. When the addition amount of the inorganic fine particles is less than 5 parts by mass, the effect of addition may not be observed, and when the addition amount exceeds 400 parts by mass, the photocurable resin composition (A) is stored. Not only stability will fall, but the moldability of the metal decoration sheet obtained may fall.

  As the inorganic fine particles (a-3), those whose surfaces are previously treated with various silane compounds may be used. The use of surface-treated inorganic fine particles makes the storage stability of the photocurable resin composition even better, and also the surface hardness, weather resistance, scratch resistance, chemical resistance, etc. of the photocurable resin composition after curing Is also preferable.

  In the photocurable resin composition used in the present invention, in addition to the thermoplastic resin (a-1), the photopolymerization initiator (a-2), and the inorganic fine particles (a-3), sensitization is performed as necessary. Additives such as an agent, a modifying resin, a dye, a pigment, a leveling agent, a repellency inhibitor, an ultraviolet absorber, a light stabilizer, and an oxidation stabilizer can be blended.

  The thickness of the photocurable resin composition layer of the present invention is preferably in the range of 0.3 to 50 μm. Further, the lower limit of the thickness is more preferably 1 μm, and the upper limit is more preferably 30 μm. When the thickness of the photocurable resin composition layer is less than 0.3 μm, the scratch resistance, abrasion resistance, chemical resistance, and the like of the photocurable resin composition after photocuring may decrease. Moreover, when the thickness of a photocurable resin composition layer exceeds 100 micrometers, even if light irradiation is performed, a hardening reaction will not be completed and, for that reason, a weather resistance, chemical-resistance, etc. may fall.

  As a method for forming a transparent resin composition layer such as a photocurable resin composition on a thermoplastic acrylic resin sheet, for example, a transparent resin composition such as a photocurable resin composition is sufficient in a solvent such as an organic solvent. The cast liquid composition stirred and dissolved is heated by a known printing method such as a gravure printing method, a screen printing method, an offset printing method, or a known coating method such as a knife coating method, a comma coating method, or a reverse roll coating method. There is a method of coating on a plastic acrylic resin sheet and heating and drying to remove the solvent to obtain a laminated sheet. At this time, a metal thin film layer may or may not be formed on the thermoplastic acrylic resin sheet.

  In the metallic decorative sheet having the above-described photocurable resin composition layer as a surface layer, when the photocurable resin composition layer is in an uncured state, it has no surface tackiness and is completely thermoplastic. Since it has, it does not inhibit the thermoformability of a metallic tone decoration sheet at all. In addition, the photo-curing resin composition layer after photo-curing is excellent in scratch resistance, abrasion resistance, chemical resistance, weather resistance, etc., so it is deteriorated or damaged by various scratching factors, harmful drugs, light rays, etc. Can be prevented, and a beautiful metallic appearance can be maintained for a long time.

Next, the manufacturing method of the molded article using the metallic decoration sheet | seat of this invention is demonstrated.
First, the metallic decorative sheet is inserted and arranged so that the thermoplastic acrylic resin sheet side faces the inner wall surface of the mold. When the metallic decorative sheet has a transparent resin composition layer, the transparent resin composition layer side is inserted and disposed so as to face the inner wall surface of the mold. At that time, a necessary portion may be intermittently fed as it is a long sheet (while being unwound from a roll), or the sheets may be separated into sheets and fed one by one.

Then, if necessary, a metallic decorative sheet is preformed. For example, the sheet is preliminarily formed by softening the sheet to a softening point or higher by a heating means such as a hot pack and by following the sheet to the mold shape by vacuum suction through a suction hole provided in the injection molding mold. Can do. In addition, by using a three-dimensional processing mold different from the injection mold, in advance, by a known molding method such as a vacuum molding method, a pressure molding method, a pressure molding method for pressing heated rubber, or a press molding method. The sheet may be preformed in a desired shape in advance, and unnecessary portions may be removed and then loaded into an injection mold. If the sheet is preheated to a temperature lower than the thermal deformation temperature of the sheet before the sheet is inserted into the mold, the heating time to be performed after the sheet is inserted into the mold can be shortened. It becomes possible to improve productivity. Of course, it is also possible to simultaneously perform the molding of the sheet and the integration with the molding resin by the injection pressure of the molding resin described later without preforming the sheet. At this time, the sheet can be preheated and softened in advance.
Thereafter, the mold is closed, a molding resin in a molten state is injected into the cavity, and the resin is solidified to form a resin molded body on which the metallic decorative sheet is arranged on the surface.

  As the molding resin used in the present invention, any resin that can be injection molded can be used regardless of the type. Examples of such molding resins include polyethylene resins, polypropylene resins, polybutene resins, polymethylpentene resins, ethylene-propylene copolymer resins, ethylene-propylene-butene copolymer resins, and olefin thermoplastics. Olefin resins such as elastomers, polystyrene resins, ABS (acrylonitrile / butadiene / styrene copolymers) resins, AS (acrylonitrile / styrene copolymers) resins, acrylic resins, urethane resins, unsaturated polyesters And general-purpose thermoplastic or thermosetting resins such as epoxy resins and epoxy resins. Also, general engineering resins such as polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, polycarbonate-modified polyphenylene ether resins, polyethylene terephthalate resins, polysulfone resins, polyphenylene sulfide resins, polyphenylene oxide resins, polyethers Super engineering resins such as imide resins, polyimide resins, liquid crystal polyester resins, and polyallyl heat resistant resins can also be used. Further, reinforcing materials such as glass fibers and inorganic fillers (talc, calcium carbonate, silica, mica, etc.), composite resins to which modifiers such as rubber components are added, and various modified resins can also be used. In addition, it is preferable to approximate the shrinkage rate after molding of the molding resin to the shrinkage rate of the sheet because problems such as warpage of the molded product and peeling of the sheet can be solved.

Finally, the molded product is taken out from the mold. When a transparent resin composition layer, particularly a photocurable transparent resin composition layer such as the above-described photocurable resin composition layer, is formed on the surface of the thermoplastic acrylic resin sheet, the molded product is removed from the mold. By photoirradiating after taking out, the photocurable transparent resin composition layer on the surface of the molded product is photocured.
Examples of light to be irradiated include electron beams, ultraviolet rays, and γ rays. Irradiation conditions are determined in accordance with the photocuring properties of the photocurable transparent resin composition layer, the amount of irradiation is usually 500~10,000mJ / cm ² approximately. As a result, it is possible to obtain a molded product in which the photocurable transparent resin composition is cured and a hard film is formed on the surface.

  Of the metallic decorative sheet adhered to the molded product, unnecessary portions are appropriately trimmed and removed as necessary. This trimming can be performed after the sheet is inserted and arranged in the mold, or before the light irradiation or after the light irradiation if light irradiation is necessary for the molded product. As a trimming method, a known method such as a method of burning a sheet by irradiating a laser beam or the like, a method of producing a punching die for trimming, punching a sheet by press working, a method of removing the sheet by tearing manually, etc. It can be done by a method.

The molded product of the present invention thus obtained includes automobile interior and exterior, furniture, building materials, bags, home appliances, audio, personal computers, mobile phones, cameras, video cameras, signboards, displays, name plates, frames, pachinko and pachislot, etc. Can be suitably used for members having a metallic appearance, such as amusement products, cosmetic cases, jewelry, tableware and toys.
In addition, although the manufacturing method using injection molding was demonstrated as the manufacturing method of a molded article above, it is also possible to use blow molding instead of injection molding.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. “Parts” in the examples represents “parts by mass”. Abbreviations in the examples are as follows.
Methyl methacrylate MMA
Methyl acrylate MA
n-butyl acrylate n-BA
Styrene St
1,3-butylene glycol dimethacrylate 1,3-BD
Allyl methacrylate AMA
Methyl ethyl ketone MEK
Glycidyl methacrylate GMA
2-hydroxyethyl methacrylate HEMA
Azobisisobutyronitrile AIBN
Cumene hydroperoxide CHP
t-Butyl hydroperoxide t-BH
n-octyl mercaptan n-OM
Ethylenediaminetetraacetic acid disodium EDTA
Hydroquinone monomethyl ether MEHQ
Triphenylphosphine TPP
Acrylic acid AA

Synthesis Example 1 Synthesis of acrylic resin A having radically polymerizable unsaturated group in side chain 50 parts of MEK was placed in a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the temperature was raised to 80 ° C. did. Under a nitrogen atmosphere, a mixture of 79.9 parts of MMA, 20.1 parts of GMA and 0.5 part of AIBN was added dropwise over 3 hours. Thereafter, a mixture of 80 parts of MEK and 0.2 part of AIBN was added and polymerized. After 4 hours, MEK 74.4 parts, MEHQ 0.5 parts, TPP 2.5 parts and AA 10.1 parts were added and stirred at 80 ° C. for 30 hours while blowing air. Subsequently, after cooling, the reaction product was taken out from the flask to obtain a solution of acrylic resin A having a radical polymerizable unsaturated group in the side chain. The polymerization rate of the monomer is 99.5% or more, the polymer solid content is about 35% by mass, the number average molecular weight is about 30,000, the glass transition temperature is about 105 ° C., and the double bond equivalent is an average of 788 g / mol. there were.

Synthesis Example 2 Synthesis of acrylic resin B having alicyclic epoxy group in side chain 3,4-epoxy in 1 L four-necked flask equipped with nitrogen inlet, stirrer, condenser and thermometer under nitrogen atmosphere 100 parts of cyclohexylmethyl methacrylate, 60 parts of MEK and 0.3 part of AIBN were added, the temperature of the hot water bath was raised to 75 ° C. with stirring, and polymerization was carried out at that temperature for 2 hours. Then, 0.7 parts of AIBN was added in 5 portions every 1 hour, and then the temperature in the flask was raised to the boiling point of the solvent and polymerization was conducted at that temperature for another 2 hours. Then, after the temperature in the flask became 50 ° C. or less, 90 parts of MEK was added and the polymerization reaction product was taken out of the flask to obtain a solution of acrylic resin B having an alicyclic epoxy group in the side chain. The polymerization rate is 99.5% or more, the polymer solid content is about 40% by mass, the number average molecular weight is about 12,000, the glass transition temperature is about 73 ° C., the alicyclic epoxy equivalent (side chain alicyclic epoxy). The average molecular weight per group) was 196 g / mol on average.

Synthesis Example 3 Synthesis of surface-treated colloidal silica CS1 Into a flask equipped with a stirrer, a condenser and a thermometer, the components described in Table 1 below were added, and the temperature of the hot water bath was raised to 75 ° C. while stirring, and the temperature was maintained for 2 hours. By making it react, the colloidal silica disperse | distributed in isopropanol and the surface was processed with the silane compound was obtained. Subsequently, the addition of toluene after distilling off isopropanol was repeated, and by completely replacing isopropanol with toluene, colloidal silica CS1 dispersed in toluene and treated with a silane compound was obtained.

注）数値は固形分換算のモル部である。
１）ＩＰＡ−ＳＴ：イソプロパノール分散コロイダルシリカゾル（日産化学工業（株）製），シリカ粒子径＝１５ｎｍ
２）ＫＢＭ５０３：γ−メタクリロイルオキシプロピルトリメトキシシラン（信越化学工業（株）製），分子量＝２４８

Note) The numerical value is the mole part in terms of solid content.
1) IPA-ST: Isopropanol-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd.), silica particle diameter = 15 nm
2) KBM503: γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), molecular weight = 248

Synthesis Example 4 Preparation of Photocurable Resin Composition Solution Light having a composition shown in Table 2 using acrylic resins A and B having a photopolymerizable functional group in the side chain, surface-treated colloidal silica CS1, and a compound shown in Table 2. Curable resin composition solutions 1 to 3 were prepared.

注）数値は固形分換算の質量部である。
１）１−ヒドロキシシクロヘキシルフェニルケトン
２）トリフェニルスルホニウム６フッ化アンチモネート

Note) Numerical values are parts by mass in terms of solid content.
1) 1-hydroxycyclohexyl phenyl ketone 2) triphenylsulfonium hexafluoroantimonate

Synthesis Example 5 Production Example of Thermoplastic Acrylic Resin Sheet (S1 to S4) Production of Rubber-Containing Multistage Polymer (I) After charging 10.8 parts of deionized water in a vessel equipped with a stirrer, 0.3 part of MMA, n -A monomer component consisting of 4.5 parts of BA, 0.2 part of 1,3-BD, 0.05 part of AMA and 0.025 part of CHP was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Industry Co., Ltd., trade name “Phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

  Next, 139.2 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 75 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was dropped into the polymerization vessel over 8 minutes, 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 was dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP. Thereafter, the reaction was continued for 60 minutes to complete the polymerization of the second stage polymer of the elastic polymer (IA-2) to obtain the elastic polymer (IA). 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 dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes to obtain an intermediate polymer (I- B) was formed. The Tg of the intermediate polymer (IB) alone was 60 ° C.

  Subsequently, a monomer component consisting of 57 parts of MMA, 3 parts of MA, 0.264 part of n-OM and 0.075 part of t-BH was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes to obtain 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, this dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and then the nylon mesh was washed in chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. Next, the captured substance after ultrasonic cleaning is put into 150 ml of acetone filtered through a nylon mesh having a mesh size of 25 μm together with the nylon mesh, and this liquid is subjected to ultrasonic treatment for 15 minutes. 150 ml of an acetone dispersion of the trapped material was prepared. Subsequently, 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 of Rubber-Containing Polymer (I ′) In 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. And (i) shown in Table 3 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. The first stage polymer (I′-A-1) latex was obtained. The Tg of the polymer (I′-A-1) alone was 24 ° C.

  Subsequently, 0.6 part 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 4 was used as a monomer component [raw material for water] (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. Then, while stirring at 80 ° C. in a nitrogen atmosphere, the raw material (d) for the hard polymer (I′-C) shown in Table 4 is increased by the rate of increase of the monomer component [raw material (d)] with respect to water. Was continuously added at a rate of 10% / hour and then 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. Moreover, 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 are performed, filtered, washed with water and dried to obtain a powdery rubber-containing polymer. (I ') was obtained. The gel content of the rubber-containing polymer (I ′) was 90%.

Production of thermoplastic polymer (IV) Charge reaction vessel with 200 parts of ion-exchanged water substituted with nitrogen, and further add as an emulsifier 1 part of product name “Latemul ASK” and 0.15 part of potassium persulfate as an emulsifier. It is.
Next, 40 parts of MMA, 2 parts of n-BA and 0.004 part of n-OM were charged, and the mixture was 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) is added to a 0.25% aqueous sulfuric acid solution, and the polymer is 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 of thermoplastic acrylic resin sheet S1 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, Ciba Specialty Chemicals Co., Ltd., trade name “Tinuvin 234” 1.4 parts, Asahi Denka Kogyo Co., Ltd., trade name “ADK STAB AO-50” 0 .1 part and 0.3 part of "Adeka Stub LA-67" manufactured by Asahi Denka Kogyo Co., Ltd. were added and mixed using a Henschel mixer. This mixture [acrylic resin composition (III-1)] is supplied to a degassing extruder [PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.] heated to 230 ° C., kneaded, and 300 mesh. Extruding while removing foreign matter with a screen mesh of Pellets (Pa) was obtained.

The pellets (Pa) produced by the above method were dried overnight at 80 ° C., and a cylinder temperature of 180 to 240 ° C. was used using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm wide T-die. While removing foreign matter with a 500 mesh screen mesh, the extrusion was performed under the conditions of a T die temperature of 240 ° C. and a T die slit width of 0.3 mm. The extruded molten acrylic resin sheet is immediately passed between two metal cooling rolls, the resin is sandwiched without a bank (resin pool), and the surface is transferred without rolling. A thermoplastic acrylic resin sheet (S1) having a thickness of 75 μm was formed by winding on a paper tube with a machine.
In addition, the pencil hardness of this thermoplastic acrylic resin sheet (S1) was H. Further, the maximum peak height (Pp) and maximum valley depth (Pv) of the cross-sectional curve defined in JIS B0601 are more than 50 nm in the thermoplastic acrylic resin sheet (S1) heat-treated at 175 ° C. for 30 seconds. No convex or concave structure was generated.

Production of thermoplastic acrylic resin sheet (S2) 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. And 0.1 part of “Adeka Stub AO-50” manufactured by Asahi Denka Kogyo Co., Ltd., and 0.3 part of “Adekastab 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 extruder [Ikegai Iron Works, PCM-30 (trade name)] heated to 230 ° C., kneaded, and 300 mesh. Extruding while removing foreign matter with a screen mesh of Pellets (Pb) was obtained.

A 75-μm-thick thermoplastic acrylic resin sheet (S2) was formed in the same manner as in the formation of the thermoplastic acrylic resin sheet (S1) except that the pellets (Pb) produced by the above method were used.
The pencil hardness of this thermoplastic acrylic resin sheet (S2) was 2H. Moreover, the maximum peak height (Pp) and the maximum valley depth (Pv) of the cross-sectional curve defined by JIS B0601 are more than 50 nm in the thermoplastic acrylic resin sheet (S2) heat-treated at 175 ° C. for 30 seconds. No convex or concave structure was generated.

Production of Thermoplastic Acrylic Resin Sheet S3 An acrylic resin sheet was formed continuously for 5 days using pellets (Pa) in the same manner as in the production of the thermoplastic acrylic resin sheet S1. In addition, since it was performed without cleaning the lip part of the T die during this continuous film formation, it was visually confirmed that a large amount of foreign matter such as eyes was attached to the lip part after the completion of the continuous film formation. did.
Next, in the same state without cleaning the lip, using the pellet (Pa) again, the thermoplastic acrylic resin sheet (S3) having a thickness of 75 μm was formed in the same manner as the film formation of the thermoplastic acrylic resin sheet S1. A film was formed. Although the obtained thermoplastic acrylic resin sheet (S3) has a die line-like defect in the molten state immediately after being extruded from the T-die, it is die-lined after being surface-transferred between two metal cooling rolls. The defect disappeared and had a smooth surface.

  In addition, the pencil hardness of this thermoplastic acrylic resin sheet (S3) was H. Further, in the thermoplastic acrylic resin sheet (S3) heat-treated at 175 ° C. for 30 seconds, the maximum peak height (Pp) and maximum valley depth (Pv) of the cross-sectional curve defined in JIS B0601 exceed 50 nm ( (100 to 200 nm) Innumerable convex structures or concave structures were generated.

Production of thermoplastic acrylic resin sheet S4 A thermoplastic acrylic resin sheet (S4) is produced in the same manner as the production of the thermoplastic acrylic resin sheet (S3) except that the pellet (Pb) is used instead of the pellet (Pa). A film was formed.
Although the obtained thermoplastic acrylic resin sheet (S4) has a die line-like defect in the molten state immediately after being extruded from the T-die, it is die line-like after surface transfer between two metal cooling rolls. The defect disappeared and had a smooth surface.

In addition, the pencil hardness of this thermoplastic acrylic resin sheet (S4) was 2H. In addition, in the thermoplastic acrylic resin sheet (S4) that is heat-treated at 175 ° C. for 30 seconds, the maximum peak height (Pp) and maximum valley depth (Pv) of the cross-sectional curve defined in JIS B0601 exceed 50 nm ( (100 to 200 nm) Innumerable convex structures or concave structures were generated.
In addition, about the obtained thermoplastic polymer and sheet | seat, various physical properties were measured with the following test methods.

(1) Mass average particle diameter of rubber-containing polymer (I ′) and rubber-containing multistage polymer (I):
About polymer latex of rubber-containing polymer (I ′) and rubber-containing multistage polymer (I) obtained by emulsion polymerization, using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd. It was 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 (mass after extraction) was measured 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) Pencil hardness of thermoplastic acrylic resin sheet:
It measured according to JIS K5400.

(6) Surface shape after heat treatment of thermoplastic acrylic resin sheet:
Non-contact three-dimensional surface shape measuring machine Micromap MM5000-M100 (Ryoka System Co., Ltd., objective lens: x2.5 or 5, intermediate lens: x0.5 or 1, CCD camera: 2/3 ", measurement Mode: Wave mode, data surface correction: quartic function correction), the uneven shape of the surface of the thermoplastic acrylic resin sheet heat-treated at 175 ° C. for 30 seconds was measured, and the maximum cross-sectional curve defined in JIS B0601 The peak height (Pp) and the maximum valley depth (Pv) of the cross-sectional curve were measured.

Example 1
On one side of the thermoplastic acrylic resin sheet (S1), a polyurethane coating agent (trade name Takelac WS6021 manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) is used as an anchor layer using a gravure coater so that the thickness after drying is 2 μm. And dried sufficiently.

Next, an indium film having a purity of 99.99% was deposited on the anchor layer surface of the thermoplastic acrylic resin sheet (S1) by a vacuum deposition method so as to have a thickness of 60 nm. Furthermore, polyurethane adhesive (Takelac A543 (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) as a main agent, Takenate A3 (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) as a curing agent, and ethyl acetate as a diluting solvent on the vapor deposition surface in a mass ratio. 9: 1: 9) was applied so that the thickness after drying was 5 μm, and was sufficiently dried.
The adhesive layer surface of the thermoplastic acrylic resin sheet (S1) having the anchor layer, the indium film, and the adhesive layer obtained in this way and the ABS resin sheet (thickness 150 μm) are passed between the hot press rolls in a bonded state. Thus, a metallic decorative sheet comprising a thermoplastic acrylic resin sheet (S1) / anchor layer / indium film / adhesive layer / ABS resin sheet was obtained. The obtained metallic decorative sheet had an excellent metallic tone, gloss, and mirror appearance.

The metallic decorative sheet is placed in the mold so that the thermoplastic acrylic sheet surface faces the inner wall surface of the mold, and then the sheet is preheated with an infrared heater, and then vacuum suction is performed while further heating is performed. Thus, the metallic decorative sheet was made to follow the mold shape. The shape of this mold is a truncated pyramid, the size of the truncated surface is 100 mm × 100 mm, the size of the bottom surface is 108 mm × 117 mm, the depth is 10 mm, and the radius of curvature of the edge of the truncated surface is Were 3, 5, 7, and 10 mm, respectively. As a result of visual evaluation of the mold following ability at that time, each end portion followed well, had no defects such as cracks, and maintained a good metallic appearance.
Next, in a molding temperature of 200 to 250 ° C. and a mold temperature of 30 to 60 ° C., an in-mold molding is performed using an ABS resin as a molding resin, and the metal tone decorative sheet is adhered to the surface of the molded product. A molded product was obtained. The mold release property of the metallic decorative sheet at that time was good, and there was no foreign matter such as dirt on the mold surface after release.
When various physical properties were evaluated using this metal-molded product, as shown in Table 4, it had an excellent metal-like appearance and also had good physical properties such as surface hardness and scratch resistance.

Method for evaluating physical properties of molded product a) Appearance of molded product:
Visual evaluation was made according to the following criteria.
○: Has a good metallic appearance over the entire surface of the molded product. △: Appearance defects such as a decrease in surface gloss and streaks occur in a part of the molded product. X: A significant decrease in surface gloss over the entire surface of the molded product. Appearance defects such as streaks appear

b) Surface hardness:
In accordance with JIS K 5400, evaluation was performed using Uni (Mitsubishi Pencil Co., Ltd .: trade name) as a pencil.

c) Acid resistance:
The appearance after a spot test of a 47% by mass aqueous sulfuric acid solution at 40 ° C. for 3 hours was visually evaluated according to the following criteria.
○: Good △: Thin trace x: Remarkable trace

d) Scratch resistance:
While applying a load of 0.5 kg, the surface condition when the surface of the molded product was rubbed 20 times with a nylon brush was visually evaluated according to the following criteria.
○: No change in appearance (no scratches)
Δ: Slightly scratched ×: Significantly scratched

e) Abrasion resistance:
The appearance of the molded article after the Taber abrasion test (the test was carried out at a load of 500 g on one side, a CS-10F abrasion wheel, a rotation speed of 60 rpm, and the number of tests 10 times) was visually evaluated according to the following criteria.
○: No whitening of the wear part or very little whitening △: Minor whitening of the wear part ×: Significant whitening of the wear part

f) Weather resistance:
Using a sunshine weatherometer (manufactured by Suga Test Instruments), the appearance when the exposure test was performed for 1500 hours in a cycle of 48 minutes dry and 12 minutes rain was visually evaluated according to the following criteria.
○: Good ×: Whitening or cracking

Example 2
A metallic decorative sheet and a metallic molded article were obtained in the same manner as in Example 1 except that the thermoplastic acrylic resin sheet (S1) of Example 1 was changed to the thermoplastic acrylic resin sheet (S2). Subsequently, when the physical properties were evaluated in the same manner as in Example 1, as shown in Table 4, it had an excellent metallic appearance and also had good physical properties such as surface hardness and scratch resistance.

Comparative Examples 1 and 2
A metallic decorative sheet and a metallic molded article are obtained in the same manner as in Example 1 except that the thermoplastic acrylic resin sheet (S1) of Example 1 is changed to the thermoplastic acrylic resin sheet (S3) or (S4). It was. However, a streak pattern is generated in any of the obtained metal-tone molded products, and a good metal-tone appearance of the metal-tone decorative sheet before molding cannot be reproduced.

Example 3
After stirring said photocurable resin composition solution 1 with a propeller type mixer, it apply | coated with the comma roll coater on the thermoplastic acrylic resin sheet (S1). Subsequently, the solvent was volatilized in a tunnel-type drying furnace, and a photocurable resin composition layer having a thickness of 8 μm was formed on the thermoplastic acrylic resin sheet (S1).
Subsequently, using the PET film subjected to the fine adhesion treatment as a cover film, the cover film is bonded in-line so that the fine adhesion layer of the PET film and the photocurable resin composition layer are in contact with each other, and passed through a press roll to form a roll. Winded up.

  Metallic decoration in the same manner as in Example 1 except that the thermoplastic acrylic resin sheet on which the photocurable resin composition layer thus obtained was laminated was used instead of the thermoplastic acrylic resin sheet (S1). A sheet (photocurable resin composition layer / thermoplastic acrylic resin sheet / anchor layer / indium film / adhesive layer / ABS resin sheet) was obtained. However, the anchor layer, the indium film, and the adhesive layer were formed on the surface opposite to the photocurable resin composition layer.

  Subsequently, after peeling the cover film from the metallic decorative sheet on which the photocurable resin composition layer was laminated, in-mold molding was performed using the ABS resin as a molding resin in the same manner as in Example 1, and molding was performed. I got a product. In addition, when arrange | positioning a metallic decoration sheet | seat in a metal mold | die, it arrange | positioned so that a photocurable resin composition layer might face the inner wall face of a metal mold | die. When the obtained molded product was visually evaluated, each end portion followed well, had no defects such as cracks, and maintained a good metallic appearance. Further, when the molding mold was visually evaluated for dirt, it was found to be free from foreign matters such as dirt.

Next, using a UV irradiation device, the photocurable resin composition layer of the obtained molded product was irradiated with about 700 mJ / cm ² of UV to cure the photocurable resin composition, and the surface physical properties were evaluated. . As shown in Table 5, the adhesiveness between the photocurable resin composition layer and the thermoplastic acrylic resin sheet was good, and had a very good metallic appearance. Furthermore, other physical properties such as scratch resistance, acid resistance and weather resistance were also very good.

  Method for evaluating physical properties of molded article having photocurable resin composition layer on surface

a) Molded product appearance:
The above-described molded product was evaluated by the same method as the a) molded product appearance evaluation method.
b) Pencil hardness test:
Evaluation was performed by the same method as b) the evaluation method of the surface hardness of the molded product described above.

c) Cross-cut peel test:
In accordance with JIS K 5400, 100 square grids with a width of 1 × 1 mm were prepared with a cutter, Nichiban cello tape (registered trademark) was pressure-bonded, and the film appearance after peeling at an angle of 90 degrees was determined according to the following criteria. Visual evaluation was made.
○: No peeling △: Peeling around the grid or slight peeling of the grid *: Peeling around the grid and / or peeling of the grid

d) Acid resistance:
It evaluated by the same method as the evaluation method of c) acid resistance about the molded article mentioned above.
e) Warm water resistance:
The state of the sheet after being immersed in warm water at 40 ° C. for 24 hours was then visually evaluated according to a standard.
○: Good △: Thin whitening ×: Remarkable whitening

  f) Scratch resistance:

Evaluation was made by the same method as the d) scratch resistance evaluation method for the molded article described above.
g) Abrasion resistance:
It evaluated by the same method as the evaluation method of e) abrasion resistance about the molded article mentioned above.
h) Weather resistance:
Evaluation was performed by the same method as the evaluation method of f) weather resistance of the molded article described above.
However, the evaluation criteria depended on the following.
○: Good △: Slightly whitened and gloss decreased ×: Whitened or cracked

Examples 4-8
A metallic decorative sheet and metallic molding, as in Example 3, except that the photocurable resin composition solution 1 of Example 3 and the thermoplastic acrylic resin sheet (S1) were changed to the combinations shown in Table 5. I got a product. Subsequently, physical properties were evaluated in the same manner as in Example 3. As shown in Table 5, the adhesiveness between the photocurable resin composition layer and the thermoplastic acrylic resin sheet was good, and had a very good metallic appearance. Furthermore, other physical properties such as scratch resistance, acid resistance and weather resistance were also very good.

Comparative Examples 3-8
A metallic decorative sheet and metallic molding, as in Example 3, except that the photocurable resin composition solution 1 of Example 3 and the thermoplastic acrylic resin sheet (S1) were changed to the combinations shown in Table 5. I got a product. However, streak patterns are generated in any of the obtained metal-like molded products, and a good metal-like appearance of the metal-like decorative sheet before molding cannot be reproduced.

Example 9
An aluminum film was formed on one surface of a PET film (manufactured by Teijin DuPont Films, Teflex FT3, thickness 25 μm) so as to have a thickness of 50 nm by vacuum deposition.
Next, on the surface of the aluminum film on the PET film, a polyurethane adhesive (Takelac A543 (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) as a main agent, Takenate A3 (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) as a curing agent, and acetic acid as a diluting solvent. A mixed solution in which ethyl was mixed at a mass ratio of 9: 1: 9) was applied so that the thickness after drying was 5 μm, and was sufficiently dried.
The thus obtained aluminum film, the adhesive layer surface of the PET film having the adhesive layer, and the ABS resin sheet (thickness 150 μm) are bonded together and integrated between the hot press rolls, and PET film / aluminum A laminated sheet comprising a film / adhesive layer / ABS resin sheet was obtained.

Next, a polyurethane adhesive is applied to the PET film surface of the laminated sheet so that the thickness after drying is 5 μm and sufficiently dried to form an adhesive layer, and then a thermoplastic acrylic resin sheet is formed on the adhesive layer surface. (S1) is bonded and integrated between the hot press rolls, and a metallic decorative sheet comprising a thermoplastic acrylic resin sheet / adhesive layer / PET film / aluminum film / adhesive layer / ABS resin sheet is formed. Obtained. The obtained metallic decorative sheet had an excellent metallic tone, gloss, and mirror appearance.
Subsequently, a metallic decorative molded product was obtained in the same manner as in Example 1. The mold release property of the metallic decorative sheet at that time was good, and there was no foreign matter such as dirt on the mold surface after release. Moreover, when various physical properties were evaluated using this metal-like molded product, it had an excellent metal-like appearance, and physical properties such as surface hardness and scratch resistance were also good.

Example 10
A metal tone was obtained in the same manner as in Example 10 except that a thermoplastic acrylic resin sheet laminated with a photocurable resin composition layer obtained in the same manner as in Example 3 was used instead of the thermoplastic acrylic resin sheet (S1). A decorative sheet (photocurable resin composition layer / thermoplastic acrylic resin sheet / adhesive layer / PET film / aluminum film / adhesive layer / ABS resin sheet) was obtained. However, the adhesive layer, the PET film, the aluminum film, the adhesive layer, and the ABS resin sheet were formed on the surface opposite to the photocurable resin composition layer. The obtained metallic decorative sheet had an excellent metallic tone, gloss, and mirror appearance.

  Subsequently, after peeling the cover film from the metallic decorative sheet on which the photocurable resin composition layer was laminated, in-mold molding was performed using ABS resin as a molding resin in the same manner as in Example 3, and molding was performed. I got a product. In addition, when arrange | positioning a metallic decoration sheet | seat in a metal mold | die, it arrange | positioned so that a photocurable resin composition layer might face the inner wall face of a metal mold | die. When the obtained molded product was visually evaluated, each end portion followed well, had no defects such as cracks, and maintained a good metallic appearance. Further, when the molding mold was visually evaluated for dirt, it was found to be free from foreign matters such as dirt.

Next, using a UV irradiation device, the photocurable resin composition layer of the obtained molded product was irradiated with about 700 mJ / cm ² of UV to cure the photocurable resin composition, and the surface physical properties were evaluated. As a result, the adhesiveness between the photocurable resin composition layer and the thermoplastic acrylic resin sheet was good, and it had a very good metallic appearance. Furthermore, other physical properties such as scratch resistance, acid resistance and weather resistance were also very good.

Comparative Example 9
A metal decorative sheet and a metal molded product were obtained in the same manner as in Example 9 except that the thermoplastic acrylic resin sheet (S1) of Example 9 was changed to the thermoplastic acrylic resin sheet (S3). However, streaky patterns are generated in the obtained metal-like molded product, and a good metal-like appearance of the metal-like decorative sheet before molding cannot be reproduced.

Comparative Example 10
A metal decorative sheet and a metal molded product were obtained in the same manner as in Example 10 except that the thermoplastic acrylic resin sheet (S1) of Example 10 was changed to the thermoplastic acrylic resin sheet (S3). However, streaky patterns are generated in the obtained metal-like molded product, and a good metal-like appearance of the metal-like decorative sheet before molding cannot be reproduced.
As described above, a thermoplastic acrylic resin in which a convex structure having a height of 50 nm or more or a concave structure having a depth of 50 nm or more is not newly generated on the surface of the metallic decorative sheet even if a specific heat treatment is performed. By using the sheet, it is possible to reproduce the excellent metallic appearance of the metallic decorative sheet even after molding.
On the other hand, when molding is performed using a metallic decorative sheet using a thermoplastic acrylic resin sheet that generates a convex structure having a height of 50 nm or more or a concave structure having a depth of 50 nm or more after the heat treatment, The pattern becomes noticeable and the metallic appearance is spoiled.

The metallic decorative sheet of the present invention has less environmental impact than the conventional wet plating method, and not only can reduce the production cost, but also can be applied to shapes with large deep drawing. Further, even if molded, there is no generation of defects such as streak patterns, and it can be used for the production of molded products having an excellent metallic appearance.
Furthermore, according to the present invention, by forming a specific photocurable resin composition layer on the outermost surface of the metallic decorative sheet, while maintaining the above-described excellent characteristics, scratch resistance and chemical resistance, Durability such as weather resistance can be imparted, and a molded product that retains its excellent metallic appearance over a long period of time can be obtained.

Claims (8)

A metallic decorative sheet having at least a thermoplastic acrylic resin sheet and a metal thin film layer, wherein the thermoplastic acrylic resin sheet satisfies the following conditions.
Condition: When heated at 175 ° C. for 30 seconds, a convex structure having a height of 50 nm or more or a concave structure having a depth of 50 nm or more is not newly generated on the surface of the thermoplastic acrylic resin sheet.   The metal decoration sheet of Claim 1 which has a layer of a transparent resin composition on the thermoplastic acrylic resin sheet surface opposite to the surface where a metal thin film layer exists.   The metal decorative sheet according to claim 2, wherein the transparent resin composition layer is a layer of a cross-linked curable resin composition or a layer of a cross-linked curable resin composition.   The transparent resin composition layer is a layer of a photocurable resin composition containing a thermoplastic resin (a-1) having a photopolymerizable functional group and a photoinitiator (a-2). The metallic decoration sheet of description.   The metallic decorative sheet according to claim 4, wherein the thermoplastic resin (a-1) having a photopolymerizable functional group is an acrylic resin having a photopolymerizable functional group in a side chain.   The metal-tone decoration sheet of Claim 4 or 5 in which a photocurable resin composition layer does not contain crosslinking | crosslinked compounds other than said (a-1).   The metal decoration sheet in any one of Claims 4-6 in which a photocurable resin composition layer contains an inorganic fine particle (a-3) further.   The metal-form molded article which has the metal-tone decorating sheet in any one of Claims 1-7 in the surface layer.