JPWO2016103714A1 - Multi-layer sheet for decoration and three-dimensional molded body - Google Patents

Abstract

Provided is a multilayer sheet for decorating which is excellent in thermoformability and can maintain excellent surface gloss and color depth after thermoforming. The decorative multilayer sheet 1 according to the present invention includes an acrylic resin layer 2 and a base material layer 3, and the acrylic resin layer 2 includes a methacrylic resin (A) and a block copolymer (B). The block copolymer (B) includes a specific amount of a methacrylic acid ester polymer block (b1) and an acrylic acid ester polymer block (b2). Further, the methacrylic resin (A) and the block copolymer (B) have a specific ratio, and the methacrylic acid in one molecule contained in the Mw (A) of the methacrylic resin (A) and the block copolymer (B). Specific range of Mw (b1-total) of ester polymer block (b1) and Mw (b2-total) of acrylate polymer block (b2) in one molecule contained in block copolymer (B) And

Description

  The present invention relates to a decorative multilayer sheet suitable for three-dimensional thermoforming. Moreover, it is related with the three-dimensional molded object which comprises this multilayer sheet for decorating.

  In recent years, for the purpose of improving design and reducing the weight of parts, the demand for three-dimensional molded products mainly made of plastic that can form complex shapes has increased for exterior parts and interior parts such as automobiles, household appliances, and interior furniture. ing. From the viewpoint of providing a design with no joints and a high designability in the three-dimensional molded body, and from the viewpoint of realizing simplification of the processing and assembly process of the molded body, for example, the main resin has a design such as a pattern in advance. An integral molding method in which the decorated decorative sheets made of resin are overlapped and molded at once with a press molding machine or the like has become the mainstream. In this situation, the decorative sheet is required to have performances such as easy moldability, good surface properties, and high designability. In particular, in terms of design, there is an increasing demand for decorative sheets for thermoforming that have excellent surface gloss, such as a piano black design, and have a design with a deep color.

  As the decorative sheet used for the above-mentioned use, a method of laminating a transparent resin layer serving as a protective layer on the outermost surface layer by any method is used. For example, a design such as coating is imparted to the resin sheet as a base material, and a primer layer and a methacrylic transparent resin layer are laminated thereon, or a colored base resin and a methacrylic transparent resin are coextruded. A method of forming a two-layer sheet is disclosed (Patent Documents 1 to 4).

  Since methacrylic resin is inferior in toughness as compared with a base resin such as ABS resin generally used for a molded body, cracking is likely to occur during a molding process involving an abrupt shape change. For this reason, methacrylic resin containing core-shell type particles for improving toughness is generally used (Patent Documents 5 and 6).

  By the way, since the core-shell type particles themselves are crosslinked, they do not have fluidity. Therefore, when the core-shell type particles are blended with the methacrylic resin, a part of the core-shell type particles is formed from the surface of the film formed through a film forming process (for example, melt molding or inflation molding using a T die). It was inevitable that the protrusion protruded, and this reduced the surface smoothness of the methacrylic resin film.

  In addition, a decorative sheet in which a transparent layer containing core-shell type particles is laminated is easily whitened by bending or applying heat when the sheet is subjected to secondary processing. It was necessary to pay attention when.

  Furthermore, the decorative sheet in which the transparent layer containing the core-shell type particles is laminated tends to increase the haze of the transparent layer at the time of thermoforming, and particularly in the case of a decorative sheet having a colored layer on the back of the transparent layer. The color developability and depth of the image will be impaired. In particular, in the above-described piano black decorative film, the haze of the transparent layer is more easily emphasized, and the jet black feeling is greatly impaired. Furthermore, at the time of thermoforming using a mold having a deep drawing portion with a high draw ratio and bending rate, there is a problem that the decorative sheet is likely to be whitened at the deep drawing portion if the molding temperature is low. On the other hand, when the molding temperature is too high, the colored layer is melted, and the design is impaired due to the disorder of the pattern. As a result, there has been a problem that the appropriate temperature condition range of the three-dimensional solid molding becomes narrow and it is difficult to mold a complicated shape.

  In addition, in patent document 7, although it is not the example applied to the decoration use, the example using the acrylic resin composition containing a block copolymer for optical members, such as a light-guide plate, is disclosed.

Japanese Patent No. 5581769 JP 2012-76348 A JP2012-116200A JP2012-213911 Patent No. 5186415 JP 2006-299038 A International Publication No. 2014/073216

  The present invention has been made in view of the above background, and the object of the present invention is to provide a decorative multilayer sheet and a three-dimensional molded product that are excellent in thermoformability and can maintain excellent decorating properties after thermoforming. It is to provide.

  As a result of intensive studies, the present inventors have found that the above problems can be solved in the following aspects, and have completed the present invention.

[1]: A decorative multilayer sheet comprising a laminate including an acrylic resin layer and a base material layer, wherein the acrylic resin layer comprises a methacrylic resin (A) and a block copolymer (B). It is formed using the acrylic resin composition containing this. A methacrylic resin (A) has 80 mass% or more of structural units derived from methyl methacrylate. The block copolymer (B) comprises a methacrylic ester polymer block (b1) containing a structural unit derived from a methacrylic ester and an acrylate polymer block (b2) containing a structural unit derived from an acrylate ester. Independently, it has 1 or more in one molecule and contains 10 to 80% by mass of the methacrylic ester polymer block (b1) and 90 to 20% by mass of the acrylate polymer block (b2). . The methacrylic resin (A) is 10 to 99 parts by mass and the block copolymer (B) is 90 to 1 with respect to 100 parts by mass in total of the methacrylic resin (A) and the block copolymer (B). The weight average molecular weight Mw (A) of the methacrylic resin (A) and the weight average molecular weight Mw (b1) of the methacrylic acid ester polymer block (b1) in one molecule contained in the block copolymer (B). -total), and the weight average molecular weight Mw (b2-total) of the acrylate polymer block (b2) in one molecule contained in the block copolymer (B),
(1) 0.3 ≦ Mw (A) / Mw (b1-total) ≦ 4.0
(2) 30,000 ≦ Mw (b2-total) ≦ 140,000
Multi-layer sheet for decoration satisfying.
[2]: The decorative composite film according to [1], wherein the thickness of the laminate is in a range of 0.05 to 0.5 mm, and the thickness of the acrylic resin layer is 0.03 to 0.25 mm. Layer sheet.
[3]: In the sheet-like acrylic resin layer having a thickness of d1, the acrylic resin layer is 300 mm / sec at a high temperature of 40 ° C. with respect to the glass transition temperature of the resin constituting the acrylic resin layer. The multilayer sheet for decorating according to [1] or [2], in which cracks of 0.05 mm or more do not occur and the following (Formula 1) is satisfied when stretched at a rate of 200%.
<Equation 1> (H2 / d2) − (H1 / d1) <1.20 (Formula 1)
(In the formula, H1 is the haze value of the acrylic resin layer before stretching, d1 is the thickness of the acrylic resin layer before stretching, which is 0.2 mm, and H2 is the acrylic resin layer after stretching. D2 is the thickness of the acrylic resin layer after stretching.)
[4]: At least one surface of the base material layer satisfies at least one of (a) being colored and (b) being provided with a pattern, and the base material layer and the acrylic resin are satisfied. The multilayer sheet for decoration according to any one of [1] to [3], wherein the layers are integrally laminated by an extrusion method.
[5]: At least one surface of the base material layer satisfies at least one of (a) being colored and (b) being provided with a pattern, and a range of 0.03 to 0.1 mm The acrylic resin layer is used, and the glass transition temperature of the resin that constitutes the base material layer and the resin that constitutes the acrylic resin layer is high at 40 ° C. When the laminate is stretched 200% at a speed of 300 mm / sec, no crack of 0.05 mm or more is generated, and the object color display method defined in JIS Z8729 is used from the acrylic resin layer side. The multilayer sheet for decoration according to any one of [1] to [4], which satisfies the following (formula 2) when a certain L ^* a ^* b ^* is measured before and after stretching.
<Equation 2> L ^* 2-L ^* 1 <3.5 (Formula 2)
(L ^* 1 in the formula is the L ^* value of the laminate before stretching, and L ^* 2 is the L ^* value of the laminate after stretching.)
[6]: The decorative multilayer sheet according to any one of [1] to [5], wherein a layer formed from an acrylonitrile-butadiene-styrene copolymer resin is used as the base material layer.
[7]: The decorative multilayer sheet according to any one of [1] to [5], in which a layer formed from an acrylic resin layer is used as the base material layer.
[8]: The decorative multilayer sheet according to any one of [1] to [5], in which a layer formed from a polycarbonate-based resin is used as the base material layer.
[9]: Addition according to any one of [1] to [8], wherein a 60 ° glossiness according to JIS Z8741 on a main surface of the acrylic resin layer not facing the base material layer is 80 or more and 95 or less. Multi-layer sheet for decoration.
[10] The decorative multilayer sheet according to any one of [1] to [9], which is used for interior and exterior of an automobile.

[11]: A three-dimensional molded body comprising the decorative multilayer sheet according to any one of [1] to [10].

  ADVANTAGE OF THE INVENTION According to this invention, there exists an outstanding effect that the multilayer sheet | seat for decorating which can be excellent in thermoformability and can maintain the decorating property after thermoforming, and a three-dimensional molded product can be provided.

It is a partial cross section explanatory view which illustrates the multilayer sheet for decoration concerning the present invention. It is a schematic diagram of the metal mold | die used in order to evaluate simply the moldability of the multilayer sheet for decorating.

  Hereinafter, an example of an embodiment to which the present invention is applied will be described. In addition, the size and ratio of each member in the following drawings are for convenience of explanation, and are not limited to this. Moreover, the numerical value specified by this specification shows the value obtained when it measures by the method described in the Example mentioned later. For example, the weight average molecular weight Mw and the number average molecular weight Mn are standard polystyrene conversion values measured by GPC (gel permeation chromatography), and indicate values obtained when measured by the method described in Examples described later. . “(Meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate.

  The decorative multilayer sheet according to the present invention (hereinafter also referred to as “multi-layer sheet”) comprises a laminate including an acrylic resin layer and a base material layer. As shown in FIG. 1, the multilayer sheet 1 can be composed of two layers of an acrylic resin layer 2 and a base material layer 3. The multilayer sheet may be a laminate in which an acrylic resin layer is sandwiched between a pair of base material layers. The base material layer and the acrylic resin layer may be directly laminated, may be laminated via an adhesive layer, or may be laminated via another layer. The multilayer sheet can further laminate layers other than the acrylic resin layer and the base material layer without departing from the gist of the present invention, and the number of laminated sheets is not particularly limited. The acrylic resin layer may be used for the outermost layer or the inner layer. Moreover, the acrylic resin layer does not need to be provided over the entire main surface of the multilayer sheet, and may be provided in a part thereof. Further, the acrylic resin layer may be used as a single layer or may be used by laminating a plurality of layers. The same applies to the base material layer.

  The acrylic resin layer 2 is formed using an acrylic resin composition containing a methacrylic resin (A) and a block copolymer (B). The block copolymer (B) comprises a methacrylic ester polymer block (b1) containing a structural unit derived from a methacrylic ester and an acrylate polymer block (b2) containing a structural unit derived from an acrylate ester. Each independently has one or more in one molecule. That is, the acrylic resin composition of the present invention comprises a methacrylic resin (A), and a block copolymer (B) having a methacrylic ester polymer block and an acrylic ester polymer block. The acrylic resin composition is a thermoplastic polymer composition.

  The methacrylic resin (A) has a structural unit derived from methyl methacrylate of 80% by mass or more, preferably 90% by mass or more. In other words, the structural unit derived from monomers other than methyl methacrylate in the methacrylic resin (A) is 20% by mass or less, preferably 10% by mass or less. The methacrylic resin (A) may be a polymer having only methyl methacrylate as a monomer.

  Examples of the monomer other than methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-acrylate Butyl, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate; phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-acrylate Hydroxyethyl, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate; acrylate esters such as cyclohexyl acrylate, norbornenyl acrylate, isobornyl acrylate; ethyl methacrylate, n-promethacrylate Pill, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate , Pentadecyl methacrylate, dodecyl methacrylate; phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate; cyclohexyl methacrylate, Methacrylic acid esters other than methyl methacrylate such as norbornyl methacrylate and isobornyl methacrylate; unsaturated compounds such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid and itaconic acid Japanese carboxylic acids; olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as butadiene, isoprene and myrcene; aromas such as styrene, α-methylstyrene, p-methylstyrene and m-methylstyrene Group vinyl compounds; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, and the like.

  The stereoregularity of the methacrylic resin (A) is not particularly limited, and for example, those having stereoregularity such as isotactic, heterotactic and syndiotactic may be used.

  If the value of the weight average molecular weight Mw (A) of the methacrylic resin (A) is small, the impact resistance and toughness of the molded product obtained from the resulting acrylic resin composition tend to decrease. On the other hand, when Mw (A) is large, the fluidity of the acrylic resin composition tends to decrease and the moldability tends to decrease. From these viewpoints, Mw (A) is preferably 30,000 or more and 180,000 or less. Further, Mw (A) is more preferably 40,000 or more, and particularly preferably 50,000 or more. Further, Mw (A) is more preferably 150,000 or less, and particularly preferably 130,000 or less.

  When the ratio of the weight average molecular weight Mw (A) to the number average molecular weight Mn (A) of the methacrylic resin (A), Mw (A) / Mn (A) (hereinafter also referred to as “molecular weight distribution”) is small, the acrylic resin There exists a tendency for the moldability of a resin composition to fall. On the other hand, when Mw (A) / Mn (A) is large, the impact resistance of the molded product obtained from the acrylic resin composition is lowered and tends to be brittle. From this viewpoint, it is preferable that Mw (A) / Mn (A) is 1.03 or more and 2.6 or less. Mw (A) / Mn (A) is more preferably 1.05 or more, and particularly preferably 1.2 or more. Further, Mw (A) / Mn (A) is more preferably 2.3 or less, and particularly preferably 2.0 or less. The molecular weight and molecular weight distribution of the methacrylic resin (A) can be controlled by adjusting the types and amounts of the polymerization initiator and the chain transfer agent.

  The methacrylic resin (A) can be obtained by homopolymerizing a monomer containing 80% by mass or more of methyl methacrylate or copolymerizing with a monomer other than methyl methacrylate. A commercially available product may be used as the methacrylic resin (A). For example, “Parapet H1000B” (MFR: 22 g / 10 min (230 ° C., 37.3 N)), “Parapet GF” (MFR: 15 g / 10 min (230 ° C., 37.3 N)), “Parapet EH” (MFR: 1.3 g / 10 min (230 ° C., 37.3 N)), “Parapet HRL” (MFR: 2.0 g / 10 min (230 ° C., 37.3 N)), “Parapet HRS” (MFR: 2.4 g / 10 minutes (230 ° C., 37.3 N)) and “Parapet G” (MFR: 8.0 g / 10 minutes (230 ° C., 37.3 N)) [all trade names, manufactured by Kuraray Co., Ltd.] and the like.

  The methacrylic acid ester polymer block (b1) is mainly composed of a structural unit derived from a methacrylic acid ester. The proportion of structural units derived from the methacrylic acid ester in the methacrylic acid ester polymer block (b1) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 98% by mass. % Or more.

  Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methacrylic acid. Amyl acid, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, methacrylic acid Examples include 2-hydroxyethyl, 2-methoxyethyl methacrylate, glycidyl methacrylate, and allyl methacrylate. Among these, from the viewpoint of improving transparency and heat resistance, methacrylic acid such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate. Alkyl esters are preferred, and methyl methacrylate is more preferred. A methacrylic acid ester polymer block (b1) can be formed by polymerizing one methacrylic acid ester alone or in combination of two or more.

  The methacrylic acid ester polymer block (b1) may contain a structural unit derived from a monomer other than the methacrylic acid ester as long as the object and effect of the present invention are not hindered. The proportion of structural units derived from monomers other than methacrylate ester contained in the methacrylate polymer block (b1) is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass. Hereinafter, the range is particularly preferably 2% by mass or less.

  Examples of monomers other than methacrylic acid esters include acrylic acid esters, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, Examples thereof include vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride. Monomers other than the methacrylic acid ester can form a methacrylic acid ester polymer block (b1) by copolymerizing one kind alone or two or more kinds together with the aforementioned methacrylic acid ester.

  The methacrylic acid ester polymer block (b1) is preferably composed of a polymer having a refractive index in the range of 1.485 to 1.495 from the viewpoint of increasing the transparency of the acrylic resin layer.

  The weight average molecular weight Mw (b1) of a single unit of the methacrylic acid ester polymer block (b1) is preferably 5,000 or more and 150,000 or less. Further, the lower limit of the weight average molecular weight of the single unit is more preferably 8,000 or more, further preferably 12,000 or more, and the upper limit is more preferably 120,000 or less, and even more preferably 100,000 or less.

  In the block copolymer (B), when there are a plurality of methacrylic acid ester polymer blocks (b1) in one molecule, the composition ratio and molecular weight of the structural units constituting each methacrylic acid ester polymer block (b1) are , May be the same or different from each other.

  The weight average molecular weight Mw (b1-total) per molecule (one polymer chain) of the methacrylic acid ester polymer block (b1) is preferably 12,000 or more and 160,000 or less. The lower limit of Mw (b1-total) is more preferably 15,000 or more, further preferably 20,000 or more, and the upper limit of Mw (b1-total) is more preferably 120,000 or less, and even more preferably 100,000 or less. When the block copolymer (B) has only one methacrylic ester polymer block (b1) in one molecule, the weight average molecular weight Mw of a single unit of the methacrylic ester polymer block (b1) ( b1) becomes Mw (b1-total). Further, when the block copolymer (B) has a plurality of methacrylate polymer blocks (b1) in one molecule, the total weight average molecular weight of each methacrylate polymer block (b1) is Mw. (b1-total). Moreover, when a plurality of methacrylate polymer blocks (b1) having different bonding forms are blended, the ratios blended with respect to the respective methacrylate polymer blocks (b1) are multiplied and totaled. Thus, Mw (b1-total) is obtained.

  In the acrylic resin composition used in the present invention, the ratio of Mw (A) to Mw (b1-total), that is, Mw (A) / Mw (b1-total) is 0.3 or more and 4.0 or less. To do. The lower limit of Mw (A) / Mw (b1-total) is preferably 1.0 or more, more preferably 1.5 or more, and the upper limit is preferably 3.5 or less, more preferably 3.0 or less. . When Mw (A) / Mw (b1) is less than 0.3, the impact resistance of the molded product produced from the acrylic resin composition tends to be lowered, and the surface smoothness tends to be lowered. On the other hand, if Mw (A) / Mw (b1) is too large, the surface smoothness and the haze temperature dependency of a molded product produced from the acrylic resin composition tend to deteriorate. By setting Mw (A) / Mw (b1) to 0.3 or more and 4.0 or less, the dispersed particle diameter of the block copolymer (B) in the methacrylic resin (A) is reduced, and the temperature change Regardless of this, it is possible to show a low haze, and as a result, it is considered that the change in haze is small over a wide temperature range.

  The proportion of the methacrylic ester polymer block (b1) in the block copolymer (B) is preferably 10% by mass or more and 70% by mass or less from the viewpoints of transparency, flexibility, molding processability and surface smoothness. is there. More preferably, it is 25 mass% or more and 60 mass% or less. When the ratio of the methacrylic acid ester polymer block (b1) in the block copolymer (B) is 10% by mass or more and 70% by mass or less, the transparency of the acrylic resin composition of the present invention or a molded product comprising the same, Excellent flexibility, flex resistance, impact resistance, flexibility, etc. When a plurality of methacrylate ester polymer blocks (b1) are contained in the block copolymer (B), the above ratio is calculated based on the total mass of all methacrylate ester polymer blocks (b1).

  The acrylate polymer block (b2) is mainly composed of a structural unit derived from an acrylate ester. The proportion of structural units derived from the acrylate ester in the acrylate polymer block (b2) is preferably 45% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 90% by mass. % Or more.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, acrylic Amyl acid, Isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, acrylic acid Examples include 2-hydroxyethyl, 2-methoxyethyl acrylate, glycidyl acrylate, and allyl acrylate. The acrylate ester polymer block (b2) can be formed by polymerizing one singly or in combination of two or more.

  The acrylic ester polymer block (b2) may contain a structural unit derived from a monomer other than the acrylic ester as long as the object and effect of the present invention are not hindered. The proportion of structural units derived from monomers other than the acrylate ester contained in the acrylate polymer block (b2) is preferably 55% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass. Hereinafter, it is particularly preferably 10% by mass or less.

  As monomers other than the acrylic ester, methacrylic ester, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, vinyl ketone, Examples include vinyl chloride, vinylidene chloride, and vinylidene fluoride. Monomers other than the acrylate ester can be used alone or in combination of two or more, and can be copolymerized with the acrylate ester to form the acrylate polymer block (b2).

The acrylic ester polymer block (b2) is preferably composed of an acrylic acid alkyl ester and a (meth) acrylic acid aromatic ester from the viewpoint of improving the transparency of the acrylic resin composition used in the present invention.
Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and the like. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.

The (meth) acrylic acid aromatic ester means an acrylic acid aromatic ester or a methacrylic acid aromatic ester, and is formed by ester-bonding a compound containing an aromatic ring to (meth) acrylic acid. Examples of such (meth) acrylic acid aromatic esters include phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, styryl acrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, styryl methacrylate, and the like. It is done. Of these, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate are preferred.
When the acrylic acid ester polymer block (b2) is composed of an acrylic acid alkyl ester and a (meth) acrylic acid aromatic ester, the acrylic acid ester polymer block (b2) is a structural unit derived from an acrylic acid alkyl ester. It is preferable to contain 50 to 90% by mass and 50 to 10% by mass of structural units derived from (meth) acrylic acid aromatic ester, and 60 to 80% by mass of structural units derived from alkyl acrylate and (meth) acrylic. It is more preferable that 40-20 mass% of structural units derived from an acid aromatic ester are included.

  The acrylic ester polymer block (b2) is preferably composed of a polymer having a refractive index in the range of 1.485 to 1.495 from the viewpoint of increasing the transparency of the acrylic resin layer.

  The weight average molecular weight Mw (b2) of a single unit of the acrylate polymer block (b2) is preferably 5,000 or more and 120,000 or less. Further, the lower limit of the weight average molecular weight of the single unit is more preferably 15,000 or more, particularly preferably 30,000 or more, the upper limit is more preferably 110,000 or less, and particularly preferably 100,000 or less.

  When there are a plurality of units of the acrylate polymer block (b2) in the block copolymer (B), the composition ratio and molecular weight of the structural units constituting each acrylate polymer block (b2) are It may be the same or different.

  The total weight average molecular weight Mw (b2-total) of the acrylate polymer block (b2) is 30,000 or more and 140,000 or less. The lower limit of Mw (b2-total) is preferably 40,000 or more, more preferably 50,000 or more. Moreover, the upper limit of Mw (b2-total) is preferably 110,000 or less, and more preferably 100,000 or less. When Mw (b2-total) is small, the impact resistance of a molded product produced from the acrylic resin composition tends to decrease. On the other hand, when Mw (b2-total) is large, the surface smoothness of a molded product produced from the acrylic resin composition tends to decrease. When the block copolymer (B) has only one acrylate polymer block (b2) in one molecule, the weight average molecular weight Mw () of a single unit of the acrylate polymer block (b2) b2) becomes Mw (b2-total). Moreover, when a block copolymer (B) has two or more acrylic acid ester polymer blocks (b2) in 1 molecule, the sum total of the weight average molecular weight of each acrylic acid ester polymer block (b2) is Mw. (b2-total). In addition, when a plurality of methacrylate polymer blocks (b2) having different bonding forms are blended, Mw (Mw () is obtained by multiplying by blending ratios of the respective methacrylate polymer blocks (b2). b1-total) is required.

  The weight average molecular weight of the methacrylic acid ester polymer block (b1) and the weight average molecular weight of the acrylate polymer block (b2) were sampled during and after the polymerization in the process of producing the block copolymer (B). Is a value calculated from the weight average molecular weight of the intermediate product and the final product (block copolymer (B)) measured by performing

  The proportion of the acrylate polymer block (b2) in the block copolymer (B) is preferably 10% by mass or more and 60% by mass or less from the viewpoints of transparency, flexibility, molding processability and surface smoothness. More preferably, it is 20 mass% or more and 55 mass% or less. When the ratio of the acrylate polymer block (b2) in the block copolymer (B) is in the range of 10% by mass or more and 60% by mass or less, the acrylic resin composition of the present invention or the molded product comprising the same Excellent impact and flexibility. When the block copolymer (B) contains a plurality of acrylic ester polymer blocks (b2) in one molecule, the above ratio is based on the total mass of all acrylic ester polymer blocks (b2). calculate.

  The bonding form of the methacrylic acid ester polymer block (b1) and the acrylate polymer block (b2) of the block copolymer (B) is not particularly limited. For example, a methacrylic acid ester polymer block (b1) having one end connected to one end of an acrylate polymer block (b2) (diblock copolymer having a (b1)-(b2) structure); methacrylic acid One in which one end of the acrylate polymer block (b2) is connected to each of both ends of the ester polymer block (b1) (triblock copolymer having a structure (b2)-(b1)-(b2)); A triblock copolymer having a (b1)-(b2)-(b1) structure in which one end of a methacrylic acid ester polymer block (b1) is connected to each of both ends of the acrylate polymer block (b2) ) And other methacrylic acid ester polymer blocks (b1) and acrylic acid ester polymer blocks (b2) are connected in series. And the like.

In addition, a block copolymer in which one end of a plurality of block copolymers having a (b1)-(b2) structure is connected to form a radial structure ([(b1)-(b2)-] nX structure); b2)-(b1) block copolymer having one end connected to form a radial structure ([(b2)-(b1)-] nX structure); a plurality of (b1)-(b2 )-(B1) block copolymer having one end connected to form a radial structure ([(b1)-(b2)-(b1)-] nX structure); a plurality of (b2) -Stars such as block copolymers ([(b2)-(b1)-(b2)-] nX structures) in which one end of a block copolymer having the structure (b1)-(b2) is connected to form a radial structure And a block copolymer having a branched structure. Here, X represents a coupling agent residue.
Among these, a diblock copolymer, a triblock copolymer, and a star block copolymer are preferable, and a diblock copolymer having a (b1)-(b2) structure, (b1)-(b2)-(b1 ) Structure triblock copolymer, [(b1)-(b2)-] nX structure star block copolymer, [(b1)-(b2)-(b1)-] nX structure star block copolymer A polymer is more preferred.

Further, the block copolymer (B) may have a polymer block (b3) other than the methacrylic ester polymer block (b1) and the acrylate polymer block (b2).
The main structural units constituting the polymer block (b3) are structural units derived from monomers other than methacrylic acid esters and acrylic acid esters. Examples of such monomers include olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as butadiene, isoprene and myrcene; styrene, α-methylstyrene, p-methylstyrene, m- Aromatic vinyl compounds such as methylstyrene; vinyl acetate, vinyl pyridine, acrylonitrile, methacrylonitrile, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, ε-caprolactone, valerolactone, etc. .

  In the block copolymer (B), the bonding form of the methacrylic ester polymer block (b1), the acrylate polymer block (b2) and the polymer block (b3) is not particularly limited. As a bonding form of the block copolymer (B) comprising the methacrylic ester polymer block (b1), the acrylate polymer block (b2) and the polymer block (b3), for example, (b1)-(b2) Examples thereof include a block copolymer having a structure of-(b1)-(b3) and a block copolymer having a structure of (b3)-(b1)-(b2)-(b1)-(b3). When there are a plurality of polymer blocks (b3) in the block copolymer (B), the composition ratio and molecular weight of the structural units constituting each polymer block (b3) may be the same as each other, May be different.

  The block copolymer (B) may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, or an amino group in the molecular chain or at the molecular chain end as necessary.

The weight average molecular weight Mw (B) of the block copolymer (B) is preferably 52,000 or more and 400,000 or less, more preferably 60,000 or more and 300,000 or less.
If the weight average molecular weight of the block copolymer (B) is small, sufficient melt tension cannot be maintained in melt extrusion molding, and it is difficult to obtain a good plate-shaped product, and the resulting plate-shaped product has a breaking strength. The mechanical properties such as On the other hand, when the weight average molecular weight of the block copolymer (B) is large, the viscosity of the molten resin is increased, and the surface of the plate-like molded body obtained by melt extrusion molding is finely textured and unmelted (high There is a tendency that unevenness due to the (molecular weight body) is generated and it is difficult to obtain a good plate-like molded body.

  The molecular weight distribution of the block copolymer (B) is preferably 1.0 or more and 2.0 or less, more preferably 1.0 or more and 1.6 or less. By having a molecular weight distribution within such a range, in the molded product made of the acrylic resin composition of the present invention, it is possible to make the content of unmelted material that causes blisters extremely small.

  The refractive index of the block copolymer (B) is preferably from 1.485 to 1.495, more preferably from 1.487 to 1.493. When the refractive index is in the range of 1.485 to 1.495, the transparency of the acrylic resin layer is increased. In the present specification, “refractive index” means a value measured at a measurement wavelength of 587.6 nm (d-line) as in the examples described later.

  The manufacturing method of a block copolymer (B) is not specifically limited, The method according to a well-known method is employable. For example, a method of living polymerizing monomers constituting each polymer block is generally used. Examples of such living polymerization methods include anionic polymerization in the presence of mineral acid salts such as alkali metals or alkaline earth metal salts using organic alkali metal compounds as polymerization initiators, and polymerization of organic alkali metal compounds. A method of anionic polymerization in the presence of an organoaluminum compound used as an initiator, a method of polymerization using an organic rare earth metal complex as a polymerization initiator, a method of radical polymerization in the presence of a copper compound using an α-halogenated ester compound as an initiator Etc. In addition, a method of producing a mixture containing the block copolymer (B) used in the present invention by polymerizing monomers constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent, etc. Also mentioned. Among these methods, in particular, the block copolymer (B) can be obtained with high purity, the molecular weight and the composition ratio can be easily controlled, and it is economical. And anionic polymerization in the presence of an organoaluminum compound is preferred.

The acrylic resin composition used in the present invention contains 10 to 99 parts by mass of a methacrylic resin (A) and 90 to 1 parts by mass of a block copolymer (B). Preferably it contains 55 to 90 parts by mass of methacrylic resin (A) and 45 to 10 parts by mass of block copolymer (B), more preferably 70 to 90 parts by mass of methacrylic resin (A) and block copolymer (B 30 to 10 parts by mass.
When the content of the methacrylic resin (A) in the acrylic resin composition is less than that of the block copolymer (B), the surface hardness of the sheet obtained by melt extrusion using a T-die tends to decrease. .

  In the acrylic resin composition used in the present invention, various additives as necessary, for example, an antioxidant, a heat stabilizer, a lubricant, a processing aid, an antistatic agent, as long as the effects of the present invention are not impaired. Antioxidants, colorants, impact resistance aids and the like may be added. In addition, it is preferable not to add a large amount of a foaming agent, a filler, a matting agent, a light diffusing agent, a softening agent, and a plasticizer from the viewpoint of mechanical properties and surface hardness of the decorative multilayer sheet of the present invention.

The antioxidant alone has an effect of preventing oxidative deterioration of the resin in the presence of oxygen. Examples thereof include phosphorus antioxidants, hindered phenol antioxidants, and thioether antioxidants. An antioxidant can be used individually by 1 type or in combination of 2 or more types. Of these, phosphorous antioxidants and hindered phenolic antioxidants are preferred from the viewpoint of preventing the deterioration of optical properties due to coloring, and the combined use of phosphorus antioxidants and hindered phenolic antioxidants is more preferred. preferable.
In the case where a phosphorus antioxidant and a hindered phenol antioxidant are used in combination, the ratio is not particularly limited, but the mass ratio of phosphorus antioxidant / hindered phenol antioxidant, and the lower limit is 1/5. The above is preferable, 1/2 or more is more preferable, the upper limit is preferably 2/1 or less, and more preferably 1/1 or less.

  As the phosphorus-based antioxidant, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by Asahi Denka Co., Ltd .; trade name: ADK STAB HP-10), Tris (2,4-dit -Butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals; trade name: IRUGAFOS168).

  As the hindered phenol-based antioxidant, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals; trade name IRGANOX 1010), Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by Ciba Specialty Chemicals; trade name IRGANOX 1076), 3,9-bis (2,6-di-tert-butyl) -4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (manufactured by ADEKA; trade name: ADK STAB PEP-36) and the like.

The thermal degradation inhibitor can prevent thermal degradation of the resin by scavenging polymer radicals generated when exposed to high heat in a substantially oxygen-free state.
As the thermal degradation inhibitor, 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilizer GM), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy-α-methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumitizer GS) Can be mentioned.

The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. The ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy.
Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, and the like. Among these, benzotriazoles and anilides are preferable. An ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types.

As benzotriazoles, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) 6- (2H-benzotriazol-yl) phenol] (manufactured by Asahi Denka Kogyo Co., Ltd .; trade name ADK STAB LA-31), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN329), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN234).
Examples of the anilides include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan; trade name Sundebore VSU).
Of these ultraviolet absorbers, benzotriazoles are most preferably used from the viewpoint of suppressing resin deterioration due to ultraviolet irradiation.

  The light stabilizer is a compound that is said to have a function of capturing radicals generated mainly by oxidation by light. Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.

The polymer processing aid is a compound that exhibits an effect on thickness accuracy and thinning when molding an acrylic resin composition. The polymer processing aid is polymer particles having a particle diameter of 0.05 to 0.5 μm, which can be usually produced by an emulsion polymerization method.
The polymer particles may be single layer particles composed of polymers having a single composition ratio and single intrinsic viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. May be. Among these, particles having a two-layer structure having a polymer layer having a low intrinsic viscosity in the inner layer and a polymer layer having a high intrinsic viscosity of 5 dl / g or more in the outer layer are preferable.

  The polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g. If the intrinsic viscosity is too small, the effect of improving moldability is low. If the intrinsic viscosity is too large, the melt fluidity of the acrylic resin composition tends to be lowered.

  In addition, the acrylic resin composition used in the present invention may be used by mixing with other polymers other than the methacrylic resin (A) and the block copolymer (B) within a range not impairing the effects of the present invention. it can. Examples of such other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, and high impact polystyrene. , AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin and other styrene resins; methyl methacrylate-styrene copolymer; polyethylene terephthalate, polybutylene terephthalate and other polyester resins; nylon 6, nylon 66, polyamide Polyamides such as elastomers; polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride Polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin; core-shell type acrylic rubber, silicone rubber; styrene thermoplastic elastomer such as SEPS, SEBS, SIS; olefin rubber such as IR, EPR, EPDM, etc. .

The method for preparing the acrylic resin composition used in the present invention is not particularly limited, but, for example, a method of melting and kneading and mixing is recommended in order to improve the dispersibility of each component constituting the acrylic resin composition. . In the method of melt-kneading the methacrylic resin (A) and the block copolymer (B), these and an additive may be mixed at the same time if necessary, and the methacrylic resin (A) together with the additive You may mix with a block copolymer (B) after mixing. The mixing operation can be performed using a known mixing or kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer. In particular, it is preferable to use a twin screw extruder from the viewpoint of improving kneadability and compatibility of the methacrylic resin (A) and the block copolymer (B). The temperature at the time of mixing and kneading should be appropriately adjusted according to the melting temperature of the methacrylic resin (A), block copolymer (B), etc. to be used, and is usually within the range of 110 ° C to 300 ° C. To mix. When melt kneading using a twin screw extruder, it is preferable to use a vent and perform melt kneading under reduced pressure and / or melt kneading under a nitrogen stream from the viewpoint of suppressing coloring. Thus, the acrylic composition of the present invention can be obtained in any form such as pellets or powder. Acrylic compositions in the form of pellets, powders and the like are suitable for use as molding materials.
Further, the block copolymer (B) is dissolved in a mixed solution of an acrylic monomer that is a monomer unit of the methacrylic resin (A) and a solvent such as toluene, and the acrylic monomer is polymerized to block the block copolymer (B). An acrylic resin composition used in the present invention containing the copolymer (B) can also be prepared.

  The base material layer of the multilayer sheet of the present invention is one in which at least one other thermoplastic resin layer or metal and / or metal oxide layer is provided directly or via an adhesive layer. Moreover, the multilayer sheet of the present invention is provided with a base material layer made of non-woody fibers such as a thermoplastic resin, a wooden base material, and kenaf on at least one surface of the above-described decorative multilayer sheet of the present invention. It may be.

  The thickness of the multilayer sheet of the present invention is preferably 500 μm or less. When the thickness is 500 μm or less, secondary workability such as laminating property, handling property, cutting property and punching property is improved, and handling as a sheet becomes easy. Moreover, the unit price per unit area can be set appropriately. The upper limit of the thickness of the multilayer sheet is more preferably 400 μm or less, particularly preferably 300 μm or less, and the lower limit is preferably 50 μm or more, more preferably 100 μm or more. The thickness of the acrylic resin layer is preferably 0.03 mm or more, and preferably 0.25 mm or less. The upper limit of the thickness of the acrylic resin layer is more preferably 0.22 mm or less, particularly preferably 0.2 mm or less, and the lower limit is more preferably 0.04 mm or more, and particularly preferably 0.05 mm or more.

The substrate layer is not particularly limited as long as it does not depart from the gist of the present invention. Preferred examples include polycarbonate resins, polyethylene terephthalate resins, polyamide resins, polyethylene resins, polypropylene resins, polystyrene resins, polychlorinated resins. Examples thereof include thermoplastic resins such as vinyl resins, other acrylic resins, and ABS (acrylonitrile-butadiene-styrene copolymer) resins.
Among these, it is preferable to use a polycarbonate resin, an acrylic resin, or an ABS resin having a good balance of performance such as thermoformability / workability, weather resistance, chemical resistance, and scratch resistance. Furthermore, if a resin-derived gelled product is generated in the multilayer sheet, it becomes a defect of the molded product and leads to a decrease in yield. Therefore, it is possible to use an acrylic resin for the base material layer, which is difficult to cause a gelation reaction structurally of the resin. More preferred. The “acrylic resin” as used herein includes methacrylic resins, acrylic resins, block copolymers thereof, core-shell type particles, and blends thereof.

  The 60 ° glossiness (%) according to JIS Z8741 on the main surface of the acrylic resin layer that does not face the base material layer is preferably 80 or more and 95 or less from the viewpoint of more effective surface glossiness.

The method for producing the multilayer sheet is not particularly limited. For example, (1) A sheet-like acrylic resin layer made of a single layer formed using the acrylic resin composition of the present invention and a sheet-like base material layer formed using a thermoplastic resin are prepared separately. A method of thermocompression bonding with a press machine, a method of laminating simultaneously with compressed air or vacuum forming, a method of laminating with an adhesive / adhesive layer (wet lamination); (2) a thermoplastic resin melt-extruded from a T-die A method of laminating an acrylic resin which is a single layer sheet formed using the acrylic resin composition of the present invention with a base layer (extruded simultaneous dry laminating method); (3) the acrylic resin composition of the present invention And the thermoplastic resin sheet of the present invention from the T-die by a melt-kneading and co-extrusion method using a different extruder and another thermoplastic resin. And a method in which the wood layer to obtain a multilayer sheet laminated and the like.
Among these methods, in the method (1) or (2), surface treatment such as corona treatment may be performed on the bonding surface side of the acrylic resin layer and the base material layer before lamination.

  The production method of the multilayer sheet of the present invention can be carried out using a known method such as an inflation method, a melt casting method, a calendar method, etc. in addition to the T-die method. From the viewpoint that a sheet with good surface smoothness and low haze can be obtained, a method comprising a step of extruding the molten kneaded material from a T-die in a molten state, and bringing both surfaces into contact with a mirror roll surface or a mirror belt surface and molding Is preferred. The roll or belt used at this time is preferably made of metal. When forming the film by bringing both sides of the melt-kneaded product thus extruded into contact with a mirror surface, it is preferable to press and sandwich both surfaces of the sheet with a mirror roll or a mirror belt. The pinching pressure by the mirror roll or the mirror belt is preferably high, and the linear pressure is preferably 10 N / mm or more, and more preferably 30 N / mm or more.

  In the case of the production method by the T-die method, an extruder type melt extrusion apparatus equipped with a single screw or twin screw can be used. The melt extrusion temperature for producing the multilayer sheet of the present invention is preferably 200 to 300 ° C, more preferably 220 to 270 ° C. Further, when melt extrusion is performed using a melt extrusion apparatus, it is preferable to use a vent and perform melt extrusion under reduced pressure or melt extrusion under a nitrogen stream from the viewpoint of suppressing coloring due to deterioration of the resin.

  Further, from the viewpoint of obtaining a sheet having good surface smoothness, good surface gloss, and low haze, the mirror surface roll that sandwiches the sheet or the mirror surface roll that sandwiches the sheet has a surface temperature of at least one of the mirror belt and 60 ° C. or more. Or it is preferable that the surface temperature of both mirror surface belts is 130 ° C. or less. When the surface temperature of both the mirror roll or the mirror belt sandwiching the sheet is less than 60 ° C, the resulting acrylic resin layer tends to lack surface smoothness and haze, and when at least one surface temperature exceeds 130 ° C If the sheet is peeled off from the mirror roll or mirror belt, the surface of the sheet is likely to be rough, and the surface smoothness of the acrylic resin layer of the resulting multilayer sheet will be low. Or the haze tends to increase.

The acrylic resin layer of the multilayer sheet of the present invention is prepared by preparing a sheet-like acrylic resin layer having a thickness of d1 (where d1 = 0.2 mm), and the glass transition of the resin constituting the acrylic resin layer. When the acrylic resin layer is stretched by 200% at a speed of 300 mm / sec at a high temperature of 40 ° C. with respect to the temperature, a crack of 0.05 mm or more does not occur and the following formula 1 is satisfied. It is preferable.
<Equation 3> (H2 / d2) − (H1 / d1) <1.20 (Formula 1)
However, H1 in a formula is the haze value of the acrylic resin layer before extending | stretching, d1 is the thickness of the acrylic resin layer before extending | stretching, H2 is the haze value of the acrylic resin layer after extending | stretching, d2 Is the thickness of the acrylic resin layer after stretching.
By satisfy | filling the said Formula 1, even after thermoforming the multilayer sheet | seat using this acrylic resin layer, the effect that the glossiness which is not different from the shaping | molding can be hold | maintained is acquired. In addition, the acrylic resin layer of this application is not limited to the said thickness. That is, the above conditions specify characteristics obtained when measured under the above conditions, and do not specify any conditions for the acrylic resin layer of the present invention.

  The roughness of the acrylic resin layer of the multilayer sheet of the present invention is preferably 1.5 nm or less, more preferably 0.1 to 1.0 nm. Thereby, it is excellent in surface smoothness, and it is excellent in the handleability at the time of cutting or punching. Furthermore, when used in applications requiring design properties, the surface gloss is excellent, and when printed on the acrylic resin layer of the present invention, the sharpness of the pattern layer and the like is excellent. Become. Moreover, in optical use, it is excellent in optical characteristics such as light transmittance and in shaping accuracy when performing surface shaping. In addition, the roughness of a molded object (film) is the value calculated | required by the method as described in an Example.

  Moreover, it is preferable that the haze temperature dependence of the acrylic resin layer of the multilayer sheet of the present invention is smaller. Thereby, in applications where transparency is required in a wide temperature range or when processing is performed at high temperatures, transparency is not impaired and is advantageous.

In the multilayer sheet of the present invention, the base material layer or the acrylic resin layer may be colored. As a coloring method, a method of coloring the resin itself by adding a pigment or dye to the thermoplastic resin composition itself of the base material layer; coloring a sheet-like acrylic resin layer by immersing it in a liquid in which the dye is dispersed However, it is not particularly limited thereto.
Examples of the pigment used include azo pigments, quinone pigments, phthalocyanine pigments, quinacridone pigments, thioindigo pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, kaolinite, muscovite, talc, calcium carbonate , Anhydrous / hydrous silicic acid, alumina, basic magnesium carbonate, precipitated barium sulfate, titanium dioxide, zinc oxide, lithopone, iron black, graphite, carbon black, yellow lead, yellow iron oxide, titanium yellow, molybdate orange, red Examples thereof include iron oxide, cadmium red, ultramarine blue, bitumen, cobalt blue, chromium oxide, and cobalt green.
Examples of the dye used include azo dyes, acridine dyes, nitroso dyes, nitro dyes, stilbene azo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, quinoline dyes, methine / polymethine dyes, anthraquinone dyes, thiazole dyes, indamine / Indophenol dye, azine dye, oxazine dye, thiazine dye, sulfur dye, aminoketone / oxyketone dye, indigoid dye, phthalocyanine dye, perylene dye, perinone dye and the like.

  Among them, the multilayer sheet of the present invention has a surface gloss after thermoforming, which is a feature of the acrylic resin layer of the present invention, by using a thermoplastic resin colored black with a pigment or dye as a base material layer. It can be suitably used as a piano black-like decorative sheet that is more emphasized and has a more jet-black feel. As the black pigment contained in the base material layer, carbon black is preferably used. Since an appearance defect due to agglomeration or poor dispersion of the carbon black is likely to occur due to the average particle diameter of the carbon black, the average particle diameter of the carbon black is preferably set to 100 nm or more and 30 nm or less.

As a method for coloring the acrylic resin layer of the present invention, a pigment or dye is contained in the composition of the methacrylic resin (A) and the block copolymer (B) itself, and the acrylic resin composition before being formed into a sheet. A method of coloring itself; a dyeing method in which a sheet-like acrylic resin layer is colored by immersing it in a liquid in which a dye is dispersed, is not particularly limited thereto.
By coloring the acrylic resin layer of the present invention, the color tone of the backing layer can be finely adjusted. For example, in the above-mentioned piano black-tone multi-layer sheet, the redness and yellowness of the base material layer can be corrected by adding a blue or green dye to the acrylic resin layer and coloring it, thereby increasing the jet blackness. be able to.

  The multilayer sheet of the present invention may be printed on at least one surface of the acrylic resin layer. Patterns and colors such as pictures, characters and figures are added by printing. The pattern may be chromatic or achromatic. In order to prevent discoloration of the printing layer, printing is preferably performed on the side in contact with another thermoplastic resin or thermosetting resin described later.

In the multilayer sheet of the present invention, at least one surface of the base material layer may be (a) colored or / and (b) patterned. In the case where at least one of the above (a) and (b) is satisfied, the glass transition temperature of the resin constituting the base material layer and the resin constituting the acrylic resin layer is higher than the glass transition temperature of the resin. When the multilayer sheet is stretched 200% at a speed of 300 mm / sec at a high temperature of 0 ° C., cracks of 0.05 mm or more do not occur, and the object color specified in JIS Z8729 from the acrylic resin layer side When L ^* a ^* b ^* , which is the display method of the above, is measured before and after stretching, it is preferable that the following formula 2 is satisfied. For the measurement at this time, the acrylic resin layer having a film thickness in the range of 0.03 to 0.1 mm is used. However, this film thickness is the film thickness at the time of the measurement, and does not define the film thickness of the acrylic resin layer of the present invention.
<Equation 4> L ^* 2-L ^* 1 <3.5 (Formula 2)
However, L ^* ) in a formula is L ^* value of the said laminated body before extending | stretching, L ^* 2 is L ^* value of the said laminated body after extending | stretching.
By satisfy | filling the said Formula 2, even after carrying out the thermoforming of the multilayer sheet | seat using this acrylic resin layer, the effect that the brightness of the color which is not different from a shaping | molding can be hold | maintained can be acquired. In addition, the multilayer sheet of this application is not limited to the said conditions. That is, the above conditions specify characteristics obtained when measured under the above conditions, and do not specify any conditions for the multilayer sheet of the present invention.

  The surface of the multilayer sheet of the present invention has a JIS pencil hardness (thickness: 75 μm), preferably HB or harder, more preferably F or harder, and even more preferably H or harder. . Since the multilayer sheet using the acrylic resin layer having a hard surface is hardly damaged, it is suitably used as a protective sheet in addition to decorating the surface of a molded product that requires design.

  Moreover, in the multilayer sheet of the present invention, when a layer made of metal and / or metal oxide is provided, examples of the metal include aluminum, silicon, magnesium, palladium, zinc, tin, nickel, silver, copper, gold, Indium, stainless steel, chromium, titanium, etc. can be used, and examples of metal oxides include aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, and oxide. Chromium, silicon oxide, cobalt oxide, zirconium oxide, tin oxide, titanium oxide, iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, barium oxide Etc. can be used. These metals and metal oxides may be used alone or in combination of two or more. Among these, indium is preferable because it has an excellent design and is not easily lost in gloss when the laminate is deep-drawn. Aluminum is particularly preferable when it does not require a deep drawing because it has an excellent design and can be obtained industrially at a low cost. As a method of providing these metal and / or metal oxide layers, a vacuum deposition method is usually used, but a method such as ion plating, sputtering, CVD (Chemical Vapor Deposition) may be used. The thickness of the deposited film made of metal and / or metal oxide is generally about 5 to 100 nm. When deep drawing is performed after layer formation, the thickness is preferably 5 to 250 nm.

  The other layer used in the multilayer sheet of the present invention is preferably a layer formed from a transparent resin such as a methacrylic resin from the viewpoint of the design properties of the multilayer sheet. From the standpoint that the multi-layer sheet is not easily scratched and the design property is maintained for a long time, the outermost layer preferably has a high surface hardness and weather resistance. Preferred examples of the outermost layer include a layer made of methacrylic resin or an acrylic resin layer formed using the acrylic thermoplastic resin of the present invention.

(Three-dimensional molded body)
The three-dimensional molded body of the present invention is formed by providing a multilayer sheet on the surface of a three-dimensional molded product. The three-dimensional molded product is not limited as long as it can thermoform the multilayer sheet of the present invention, and is, for example, a thermoplastic resin, a thermosetting resin, a wooden substrate, or a non-wood fiber substrate such as kenaf. The three-dimensional molded product may be made of a plurality of types of materials, but the material covering the multilayer sheet may be selected in consideration of thermoforming of the multilayer sheet.

  The thermoplastic resin of the three-dimensional molded product used in the three-dimensional molded article of the present invention is not particularly limited, but polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, other ( And (meth) acrylic resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, and the like. Examples of other thermosetting resins include epoxy resins, phenol resins, and melamine resins.

  The manufacturing method of the three-dimensional molded body of the present invention is not particularly limited. For example, the three-dimensional molded article of the present invention can be obtained by placing the multilayer sheet of the present invention on the surface of the above-mentioned three-dimensional molded article and vacuum forming, pressure forming, or compression molding under heating. The three-dimensional molded body of the present invention is excellent in surface smoothness, surface hardness, surface gloss, and the like by providing the multilayer sheet of the present invention on the outermost layer of the three-dimensional molded product. Moreover, when printing is performed on the inner side surface of the acrylic resin layer of the multilayer sheet of the present invention, a pattern or the like can be clearly displayed. Moreover, in the multilayer sheet | seat which has a metal layer, the mirror glossiness of the same level as a metal is acquired.

  Among the methods for producing the three-dimensional molded body of the present invention, a preferable method is a method of laminating the multilayer sheet of the present invention as it is or printing on at least one surface and laminating on the surface of the article to be decorated (lamination molding method), A method in which the multilayer sheet of the invention is vacuum- or compressed-air molded in accordance with the shape of the item to be decorated, placed in an injection mold, and then injection-molded to perform a decoration process simultaneously with injection molding (insert) Molding method), a method in which the multilayer sheet of the present invention is formed in a mold cavity for injection molding in a vacuum or pressure, and then injection molding is performed at the same time as the injection molding (in-mold molding method). Can be mentioned.

  Among the methods for producing the three-dimensional molded body of the present invention, a more preferable method is a method generally called three-dimensional surface decoration molding (TOM molding, vacuum / pressure molding method). In this three-dimensional surface decoration molding method, the multi-layer sheet of the present invention is heated in a vacuum state in a mold cavity so as to follow the surface of the article to be decorated, and vacuum drawing from below and pressure molding from above are performed. It is the method of performing the decoration process to to-be-decorated goods by performing simultaneously. This method can form a molded body having a more three-dimensional and complicated shape. For this reason, the multilayer sheet of the present invention will be stretched or bent more locally and the effects of the present invention will be exhibited more remarkably.

The sheet to be inserted into the mold may be a flat sheet as it is, or may be formed into a concavo-convex shape by preforming by vacuum forming, pressure forming or the like.
The preforming of the sheet may be performed by a separate molding machine, or may be preformed in a mold of an injection molding machine used for the injection molding simultaneous bonding method. The latter method, that is, a method in which a sheet is preformed and a molten resin is injected on one side thereof is called an insert molding method.
When using the multilayer sheet of the present invention for the sheet, arrange the acrylic resin layer side of the multilayer sheet of the present invention to be the outermost surface (arrange the base material layer on the other sheet side to be integrated) Is preferred. Thus, the three-dimensional molded object provided with the acrylic resin layer of the multilayer sheet | seat of this invention in the outermost layer can be obtained.

  According to the multilayer sheet of the present invention, it is possible to provide a decorative multilayer sheet and a three-dimensional molded body that are excellent in thermoformability and can maintain excellent decorating properties after thermoforming. That is, according to the multilayer sheet of the present invention, a sheet excellent in transparency, surface hardness, surface smoothness and the like can be provided after thermoforming. Furthermore, since the acrylic resin layer that has less whitening and breakage due to bending and stretching, that is, excellent in whitening resistance and crack resistance, is laminated, it is possible to provide a multilayer sheet excellent in glossiness and color depth. . For this reason, an excellent three-dimensional molded body is obtained by decorating the multilayer sheet of the present invention by adhering to a more complicated three-dimensional three-dimensional structure, for example, a base having a spherical or angular shape by compressed air or vacuum. be able to. According to the three-dimensional molded body of the present invention, there is an excellent effect that it is excellent in thermoformability and can maintain excellent decorating properties after thermoforming.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, this invention is not restrict | limited by a following example. In addition, the present invention includes all aspects that are obtained by arbitrarily combining the above-described items representing technical characteristics such as characteristic values, forms, manufacturing methods, and uses.

  The measurement of physical property values in Examples and Comparative Examples was performed by the following method.

[Weight average molecular weight (Mw) and molecular weight distribution]
The weight average molecular weight (Mw) and molecular weight distribution during and after the polymerization of the block copolymer (B) and the methacrylic resin (A) were determined in terms of polystyrene by GPC (gel permeation chromatography). .
・ Equipment: Tosoh GPC equipment “HLC-8320”
・ Separation column: “TSKguardcolum SuperHZ-H”, “TSKgel HZM-M” and “TSKgel SuperHZ4000” manufactured by Tosoh Corporation are connected in series. ・ Eluent: Tetrahydrofuran ・ Eluent flow rate: 0.35 mL / min
-Column temperature: 40 ° C
・ Detection method: Differential refractive index (RI)

[Composition ratio of each polymer block]
The composition ratio of each polymer block was determined by 1H-NMR (1H-nuclear magnetic resonance) measurement.
・ Equipment: JEOL Nuclear Magnetic Resonance Device “JNM-LA400”
・ Deuterated solvent: Deuterated chloroform

[Method for producing acrylic resin layer (single layer sheet)]
Using an arbitrary acrylic resin composition, it was extruded at a discharge rate of 26 kg / hr using a 50 mmΦ vent type single screw extruder, extruded from a single layer T die having a width of 300 mm at a temperature of 260 ° C., and 80 ° C. and 100 ° C. Were niped with a metal mirror surface roll and taken at a speed of 8.2 m / min to form an acrylic resin layer (single layer sheet) composed of a single layer sheet having a thickness of 200 μm.

[Production method of multilayer sheet]
Using an arbitrary acrylic resin composition, extrusion is performed at a discharge rate of 5 kg / hr using a 30 mmΦ vent type single screw extruder, and at the same time, using a thermoplastic resin for forming an arbitrary base material layer, a 50 mmΦ vent type Was extruded at 23 kg / hr using a single screw extruder. And each was laminated using a multi-manifold die with a width of 300 mm, extruded at a temperature of 260 ° C., nipped with a metal mirror roll at 80 ° C. and 100 ° C., and taken at a speed of 5.9 m / min, A multilayer sheet having a total thickness of 300 μm and an acrylic resin layer of 75 μm was formed.

(Glass-transition temperature)
In accordance with JIS K7121, the resin obtained in each production example was heated once to 230 ° C. using a differential scanning calorimeter (DSC-50 (product number) manufactured by Shimadzu Corporation) and then cooled to room temperature. Thereafter, the DSC curve was measured under the condition of increasing the temperature from room temperature to 230 ° C. at 10 ° C./min. The midpoint glass transition temperature obtained from the DSC curve measured at the second temperature rise was defined as the glass transition temperature in the present invention.

[Stretched molded body preparation method]
A single-layer sheet-like acrylic resin layer and a multilayer sheet prepared under the above-mentioned film forming conditions were cut out respectively to prepare a test piece of 150 mm × 50 mm, and an autograph (manufactured by Shimadzu Corp., Autograph AG-5kN) I set it. Next, with respect to the higher Tg of the resin constituting the acrylic resin layer or the resin constituting the base material layer, in a temperature atmosphere of 40 ° C., a 5 kN load cell, a distance between chucks of 110 mm, and a tensile speed of 300 mm / second. The film was stretched to a stretch rate of 200% to produce a stretch molded body.

[Method for measuring haze of acrylic resin layer]
The acrylic resin layer (single layer sheet) produced under the above-mentioned film forming conditions and the stretched molded body were cut into 30 mm × 30 mm to obtain test pieces. The test piece was set in a haze meter (manufactured by Murakami Color Research Laboratory: HAZE METER HM-150), and haze H1 before stretching and haze H2 after stretching were measured according to JIS-K7136. Using the sheet thickness d1 (mm) before stretching and the sheet thickness d2 (mm) after stretching, the difference in haze before and after stretching defined by the following formula was calculated.
<Equation 5> (H2 / d2) − (H1 / d1)

[Method for measuring pencil hardness of multilayer sheet]
The multilayer sheet produced under the above-mentioned film forming conditions and the stretched molded body were cut out into 30 mm × 30 mm, respectively, and used as test pieces. A test piece is set on a pencil hardness tester (manufactured by Toyo Seiki Seisakusho Co., Ltd .: pencil scratch coating film hardness tester), the pencil hardness is measured according to JIS-K5600-5-4, and the pencil hardness before and after stretching is measured. Compared.

[Color measurement method for multilayer sheets]
A multilayer sheet produced under the above-mentioned film forming conditions and a planar portion of the stretched molded body were cut out as 30 mm × 30 mm test pieces. Set the test piece on the spectrocolorimeter (Nippon Denshoku Kogyo Co., Ltd .: Spectro Photometer SE5000) so that the transparent resin layer side is the measurement surface, and comply with JIS Z8722, C light source, viewing angle 10 degrees, reflection mode ( Under the condition of diffuse reflection, L ^* a ^* b ^* , which is an object color display method defined in JIS Z8729 (2004), was measured from the acrylic resin layer side, and L ^* values before and after stretching were compared. The L ^* value indicates a darker color as the value is smaller.

[Method for producing three-dimensional molded body]
An acrylic resin layer (single layer sheet) and a multilayer sheet prepared under the above-mentioned film forming conditions were cut out into 150 mm × 150 mm to obtain test pieces. Set the test piece on a vacuum forming machine (Yamahachi Teikoku Kogyo Co., Ltd. vacuum adapter I type), and the surface temperature of the sheet will be the higher Tg of the resin constituting the acrylic resin layer or the resin constituting the base material layer. On the other hand, it heated until it became 40 degreeC high temperature. Next, a three-dimensional molded body was molded by pressing against a cubic mold having a width of 50 mm, a depth of 50 mm, and a height of 30 mm shown in FIG. In addition, the multilayer sheet 1 set the test piece so that the acrylic resin layer 2 side might become the surface of a three-dimensional molded object. R in FIG. 2 indicates a radius of curvature (mm).

[Determination method of multi-layer sheet solid molded body torn and corner whitening]
Each side and each apex of the three-dimensional molded body produced under the above-described molding conditions were visually confirmed, and a crack having a width of 0.05 mm or more and a degree of whitening that could be visually confirmed were determined. The discrimination criteria are shown below.
a: No whitening or tearing is observed in each side and each vertex.
b: Whitening is observed on each side and each corner.
c: Whitening and tearing are observed at each side and each corner.

[Measurement method of surface glossiness of multi-layer molded sheet]
Using a gloss checker (GROSS CHECKER IG-331 manufactured by HORIBA) on an arbitrary surface on the acrylic resin layer side of a multilayer sheet three-dimensional molded body produced under the above-described molding conditions, a 60 ° gloss value in accordance with JIS Z8741 (60 ° glossiness) was evaluated. The 60 ° gloss value was measured at 10 different regions on one side of the acrylic resin layer side of the multilayer decorative sheet, and the average value of 10 locations was defined as the surface 60 ° gloss value of the multilayer decorative sheet.

Reference Example 1 [Synthesis of Block Copolymer (B-1)]
A glass-lined 3 m ³ reaction vessel equipped with a brine-cooled jacket and a stirrer that was degassed and purged with nitrogen, was charged with 735 kg of dry toluene, 0.4 kg of hexamethyltriethylenetetramine, and isobutyl bis (2,6 at room temperature). -Di-t-butyl-4-methylphenoxy) 39.4 kg of toluene solution containing 20 mol of aluminum was added, and 1.17 mol of sec-butyllithium was further added. To this, 35.0 kg of methyl methacrylate was added and reacted at room temperature for 1 hour. The polymer contained in the reaction solution was sampled and the weight average molecular weight (hereinafter referred to as Mw (b1-1)) was measured, and it was 40,000. The methyl methacrylate polymer is further block copolymerized with an acrylate ester, whereby the methyl methacrylate polymer is converted into a methacrylate ester polymer block (b1) (hereinafter referred to as “methyl methacrylate polymer block (b1-1)”. ").

  Next, the reaction solution was brought to −25 ° C., and a mixed solution of 24.5 kg of n-butyl acrylate and 10.5 kg of benzyl acrylate was added dropwise over 0.5 hours. Immediately after the dropping, the polymer contained in the reaction solution was sampled and the weight average molecular weight was measured, and it was 80,000. Since the weight average molecular weight of the methyl methacrylate polymer block (b1-1) was 40,000, the weight of the acrylate polymer block (b2) composed of a copolymer of n-butyl acrylate and benzyl acrylate. The average molecular weight (Mw (b2)) was determined to be 40,000.

  Subsequently, 35.0 kg of methyl methacrylate was added, the reaction solution was returned to room temperature, and stirred for 8 hours, whereby the second methacrylate polymer block (b1) (hereinafter, “methyl methacrylate polymer block (b1 -2) "). Thereafter, 4 kg of methanol was added to the reaction solution to stop the polymerization, and then the reaction solution was poured into a large amount of methanol to obtain a block copolymer (B) (hereinafter referred to as “block copolymer”) which is a triblock copolymer. B-1) ") was precipitated, filtered, and isolated by drying at 80 ° C. and 1 torr (about 133 Pa) for 12 hours. The obtained block copolymer (B-1) had a weight average molecular weight Mw (B) of 120,000. Since the weight average molecular weight of the diblock copolymer was 80,000, the weight average molecular weight (referred to as Mw (b1-2)) of the methyl methacrylate polymer block (b1-2) was 40,000. Were determined. Since the weight average molecular weight Mw (b1-1) of the methyl methacrylate polymer block (b1-1) and the weight average molecular weight Mw (b1-2) of the methyl methacrylate polymer block (b1-2) are both 40,000. , Mw (b1) is 40,000, and Mw (b1-total) is 80,000. Table 2 shows the analysis results of the obtained block copolymer (B-1). In Table 2, the structural unit derived from methyl methacrylate is “methyl methacrylate unit”, the structural unit derived from n-butyl acrylate is “n-butyl acrylate unit”, and the structural unit derived from benzyl acrylate. Is expressed as “benzyl acrylate unit”, respectively.

Reference Examples 2 to 4 [Synthesis of Block Copolymers (B-2) to (B-4)]
Conditions other than those shown in Table 1 were the same as in Reference Example 1, and block copolymers (B-2) to (B-4) were synthesized. Table 1 shows the analysis results of the obtained Mw (b1-1), Mw (b2), and the obtained block copolymers (B-2) to (B-6).

Reference Example 5 [Synthesis of Block Copolymer (B-5)]
A glass-lined 3 m ³ reaction vessel equipped with a brine-cooled jacket and a stirrer that was degassed and purged with nitrogen, was charged with 735 kg of dry toluene, 0.4 kg of hexamethyltriethylenetetramine, and isobutyl bis (2,6 at room temperature). -Di-t-butyl-4-methylphenoxy) 39.4 kg of toluene solution containing 20 mol of aluminum was added, and 1.17 mol of sec-butyllithium was further added. To this, 35.0 kg of methyl methacrylate was added and reacted at room temperature for 1 hour. The polymer contained in the reaction solution was sampled and the weight average molecular weight (hereinafter referred to as Mw (b1)) was measured, and it was 40,000. The methyl methacrylate polymer is further block copolymerized with an acrylic ester, whereby the methyl methacrylate polymer is converted into a methacrylate ester polymer block (b1) (hereinafter referred to as “methyl methacrylate polymer block (b1)”). Called).

  Next, the reaction solution was brought to −25 ° C., and a mixed solution of 24.5 kg of n-butyl acrylate and 10.5 kg of benzyl acrylate was added dropwise over 0.5 hours. Thereafter, 4 kg of methanol was added to the reaction solution to stop the polymerization, and then the reaction solution was poured into a large amount of methanol to obtain a block copolymer (B) (hereinafter referred to as “block copolymer (“) ”which is a diblock copolymer. B-5) ") was precipitated, filtered, and isolated by drying at 80 ° C. and 1 torr (about 133 Pa) for 12 hours. The obtained block copolymer (B-5) had a weight average molecular weight Mw (B) of 80,000. Since the weight average molecular weight of the methyl methacrylate polymer block (b1) was 40,000, the weight average molecular weight of the acrylate polymer block (b2) comprising a copolymer of n-butyl acrylate and benzyl acrylate. (Mw (b2)) was determined to be 40,000.

Reference Example 6 [Synthesis of Block Copolymer (B-6)]
567 kg of dry toluene, 0.1 kg of hexamethyltriethylenetetramine, 4.1 mol of isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, 8.3 kg of toluene solution, sec-butyllithium 0 .42 mol, methyl methacrylate polymer block (b1) (hereinafter referred to as “methyl methacrylate polymer block (b1)”) in the same manner as in Reference Example 5 except that 33.3 kg of methyl methacrylate was used. Got. The polymer contained in the reaction solution was sampled and the weight average molecular weight (hereinafter referred to as Mw (b1-1)) was measured, and it was 80,000.

  Next, a block copolymer (B) which is a diblock copolymer was prepared in the same manner as in Reference Example 5 except that n-butyl acrylate was 24.8 kg, benzyl acrylate was 8.5 kg, and methanol was 4 kg. ) (Hereinafter referred to as “block copolymer (B-6)”). The obtained block copolymer (B-6) has a weight average molecular weight Mw (B) of 160,000 and is an acrylate polymer block (b2) comprising a copolymer of n-butyl acrylate and benzyl acrylate. ) Was 80,000 in weight average molecular weight (Mw (b2)).

Reference Example 7 [Synthesis of Methacrylic Resin (A-1)]
Polymerization initiator (2,2′-azobis (2-methylpropionitrile), hydrogen abstraction capacity: 1%, half-life for 1 hour, in a monomer mixture consisting of 95 parts by weight of methyl methacrylate and 5 parts by weight of methyl acrylate (Temperature: 83 ° C.) 0.1 part by mass and 0.77 part by mass of a chain transfer agent (n-octyl mercaptan) were added and dissolved to obtain a raw material liquid.
100 parts by mass of ion-exchanged water, 0.03 parts by mass of sodium sulfate and 0.45 parts by mass of the suspension / dispersant were mixed to obtain a mixed solution. In a pressure-resistant polymerization tank, 420 parts by mass of the mixed liquid and 210 parts by mass of the raw material liquid were charged, and the polymerization reaction was started at a temperature of 70 ° C. while stirring in a nitrogen atmosphere. After 3 hours from the start of the polymerization reaction, the temperature was raised to 90 ° C. and stirring was continued for 1 hour to obtain a liquid in which the bead copolymer was dispersed. Although some polymer adhered to the wall of the polymerization tank or the stirring blade, there was no foaming and the polymerization reaction proceeded smoothly.
The obtained copolymer dispersion is washed with an appropriate amount of ion-exchanged water, and the bead-shaped copolymer is taken out with a bucket-type centrifuge and dried with a hot air dryer at 80 ° C. for 12 hours. (A) (hereinafter referred to as “methacrylic resin (A-1)”) was obtained.
The resulting methacrylic resin (A-1) had a weight average molecular weight Mw (A) of 30,000, a molecular weight distribution of 1.8, and a glass transition temperature (Tg) of 111 ° C.

Reference Example 8 [Synthesis of methacrylic resin (A-2)]
A methacrylic resin (Mw (A) of 80,000, molecular weight distribution of 1.8, and glass transition temperature of 115 ° C.) was used in the same manner as in Reference Example 5 except that the amount of the chain transfer agent was changed to 0.28 parts by mass. A-2) was obtained.

Reference Example 9 [Synthesis of methacrylic resin (A-3)]
Except for changing the amount of the chain transfer agent to 0.16 parts by mass, in the same manner as in Reference Example 5, Mw (A) is 130,000, molecular weight distribution is 1.8, glass transition temperature is 115 ° C. methacrylic resin ( A-3) was obtained.

Example 1
30 parts by mass of the block copolymer (B-1) and 70 parts by mass of the methacrylic resin (A-2) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting. The glass transition temperature was 115 ° C.
Using the obtained acrylic resin composition, a 200 μm-thick transparent resin single-layer sheet was formed by the above-described method, and the obtained transparent resin single-layer sheet was stretched by the above-described method. Haze was measured by the method described above. Further, using the obtained methacrylic resin composition and the carbon black-containing black original ABS resin “330 ABS” (Tg: 100 ° C.) manufactured by Techno Polymer Co., the total thickness of 300 μm and the acrylic resin layer of 75 μm. A co-extruded multilayer sheet was formed, the obtained multilayer sheet was stretched by the above-described method, and the pencil hardness before and after stretching and the colorimetric value L value were measured by the above-described method. Moreover, the surface glossiness (%) of the multilayer sheet solid molded body obtained by vacuum-molding the multilayer sheet by the above-mentioned method was measured, and the presence or absence of breakage or whitening was visually evaluated. The results are shown in Table 3.

(Example 2)
10 parts by mass of the block copolymer (B-2) and 90 parts by mass of the methacrylic resin (A-2) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 3.

(Example 3)
10 parts by mass of the block copolymer (B-6) and 90 parts by mass of the methacrylic resin (A-3) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 3.

Example 4
30 parts by mass of block copolymer (B-5) and 70 parts by mass of methacrylic resin (A-2) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 3.

(Example 5)
20 parts by mass of block copolymer (B-5) and 80 parts by mass of methacrylic resin (A-3) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 3.

(Example 6)
20 parts by mass of block copolymer (B-6) and 80 parts by mass of methacrylic resin (A-3) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 3.

(Example 7)
20 parts by mass of block copolymer (B-5) and 80 parts by mass of methacrylic resin (A-2) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 3.

(Example 8)
20 parts by mass of block copolymer (B-5) and 80 parts by mass of methacrylic resin (A-2) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting. Also, Sumika Stylon Polycarbonate Co., Ltd., "Caliber 301-8" (Tg: 150 degrees) 98 parts by mass, black chemical "Mitsubishi Carbon Black" 1.0 parts by mass, black dye manufactured by LANXESS 0.3 parts by mass of “MACROLEX Green G” and 0.7 parts by mass of “MACROLEX Green 5B” manufactured by LANXESS were melt kneaded at 250 ° C. with a twin screw extruder. Then, the pellet of the black polycarbonate resin composition was manufactured by extruding and cut | disconnecting. Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 3.

Example 9
20 parts by mass of block copolymer (B-5) and 80 parts by mass of methacrylic resin (A-2) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Further, 49 parts by mass of a crosslinked rubber particle compounded resin “Parapet GR-100” manufactured by Kuraray Co., Ltd., 49 parts by mass of methacrylic resin (A-3), and 1.0 part by mass of “Mitsubishi Carbon Black” manufactured by Mitsubishi Chemical Corporation as a black pigment. As a black dye, 0.3 parts by mass of “MACROLEX Green G” manufactured by LANXESS and 0.7 parts by mass of “MACROLEX Green 5B” manufactured by LANXESS were melt-kneaded at 230 ° C. with a twin screw extruder. Then, the pellet of the black acrylic resin composition was manufactured by extruding and cut | disconnecting. Tg was 108 ° C.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 3.

(Example 10)
Molding was performed in the same manner as in Example 7 except that 40 parts by mass of the block copolymer (B-5) and 60 parts by mass of the methacrylic resin (A-2) were used, and each physical property was measured. The results are shown in Table 3.

(Comparative Example 1)
In place of the block copolymer (B), 20 parts by mass of a crosslinked rubber particle-containing resin “Parapet GR-100” manufactured by Kuraray Co., Ltd. and 80 parts by mass of a methacrylic resin (A-2) are 230 by a twin screw extruder. Melted and kneaded at a temperature of ° C. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 4.

(Comparative Example 2)
In place of the block copolymer (B), 30 parts by mass of a crosslinked rubber particle-containing resin “Parapet EB-SN” manufactured by Kuraray Co., Ltd. and 70 parts by mass of a methacrylic resin (A-2) are 230 by a twin screw extruder. Melted and kneaded at a temperature of ° C. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 4.

(Comparative Example 3)
20 parts by mass of the block copolymer (B-2) and 80 parts by mass of the methacrylic resin (A-1) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 4.

(Comparative Example 4)
20 parts by mass of the block copolymer (B-4) and 80 parts by mass of the methacrylic resin (A-1) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 4.

(Comparative Example 5)
20 parts by mass of the block copolymer (B-3) and 80 parts by mass of the methacrylic resin (A-3) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 4.

(Comparative Example 6)
20 parts by mass of the block copolymer (B-4) and 80 parts by mass of the methacrylic resin (A-2) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the acrylic resin composition was manufactured by extruding and cutting.
Using this pellet, a transparent resin single-layer sheet and a co-extruded multi-layer sheet and a multi-layer sheet three-dimensional molded body were molded in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 4.

From these results,
(1) 0.3 ≦ Mw (A) / Mw (b1-total) ≦ 4.0
(2) 30,000 ≦ Mw (b2-total) ≦ 140,000
The methacrylic resin (A) is 10 to 99 parts by mass with respect to 100 parts by mass in total of the methacrylic resin (A) and the block copolymer (B), and the block copolymer (B It can be seen that the decorative multilayer sheet produced using the acrylic resin composition blended at 90 to 1 part by mass exhibits excellent decorating properties. In other words, when molded into a complex three-dimensional solid shape that tends to increase the local stretch ratio and bending rate, it suppresses breakage and whitening during molding, and has excellent surface smoothness, surface hardness, and color depth. Can be maintained.

  This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2014-266122 for which it applied on December 26, 2014, and takes in those the indications of all here.

  The multilayer sheet or three-dimensionally molded article of the present invention utilizes a good handleability, a good surface smoothness and a high surface hardness, and various moldings requiring high design properties and high optical properties. It can be used for goods. Specifically, billboard parts such as advertising towers, stand signboards, sleeve signboards, billboard signs, and rooftop signs; display parts such as showcases, dividers, and store displays; fluorescent lamp covers, mood lighting covers, lamp shades, and light ceilings Lighting parts such as light walls and chandeliers; Interior parts such as furniture, pendants and mirrors; Building parts such as doors, domes, safety window glass, partitions, staircases, balcony stools, and roofs of leisure buildings; , Pilot visor, motorcycle, motor boat windshield, bus shading plate, automobile side visor, rear visor, head wing, headlight cover, automobile interior parts, automotive exterior parts such as bumpers and molds; Nameplate, stereo cover, TV protective mask, vending machine, mobile phone Electronic equipment parts such as personal computers; medical equipment parts such as incubators and X-ray parts; equipment-related parts such as machine covers, instrument covers, experimental devices, rulers, dials, observation windows; road signs, guide plates, curved mirrors, soundproofing Traffic related parts such as walls; other decorative films on the surface of greenhouses, large aquariums, box aquariums, bathroom components, clock panels, bathtubs, sanitary, desk mats, game parts, toys, masks for face protection when welding, etc. Protective film, wallpaper; marking film; liquid crystal protective film, light guide film, Fresnel lens, lenticular lens, front film of various displays, optical related parts such as diffusion film, etc.

1 Multi-layer sheet 2 Acrylic resin layer 3 Base material layer 4 Solid mold

Claims (11)

It is a multilayer sheet for decoration consisting of a laminate including an acrylic resin layer and a base material layer,
The acrylic resin layer is formed using an acrylic resin composition containing a methacrylic resin (A) and a block copolymer (B),
The methacrylic resin (A) has a structural unit derived from methyl methacrylate of 80% by mass or more,
The block copolymer (B) comprises a methacrylic ester polymer block (b1) containing a structural unit derived from a methacrylic ester and an acrylate polymer block (b2) containing a structural unit derived from an acrylate ester. Independently, it has one or more in one molecule, and 10 to 80% by mass of the methacrylic ester polymer block (b1) and 90 to 20% by mass of the acrylate polymer block (b2). ,
The methacrylic resin (A) is 10 to 99 parts by mass and the block copolymer (B) is 90 to 1 with respect to 100 parts by mass in total of the methacrylic resin (A) and the block copolymer (B). Mass part,
The weight average molecular weight Mw (A) of the methacrylic resin (A), the weight average molecular weight Mw (b1-total) of the methacrylic ester polymer block (b1) in one molecule contained in the block copolymer (B), and When the weight average molecular weight Mw (b2-total) of the acrylate polymer block (b2) in one molecule contained in the block copolymer (B) is obtained,
(1) 0.3 ≦ Mw (A) / Mw (b1-total) ≦ 4.0
(2) 30,000 ≦ Mw (b2-total) ≦ 140,000
Multi-layer sheet for decoration satisfying. The thickness of the laminate is in the range of 0.05 to 0.5 mm,
The multilayer sheet for decoration according to claim 1, wherein the acrylic resin layer has a thickness of 0.03 to 0.25 mm. In the sheet-like acrylic resin layer having a thickness of d1, the acrylic resin layer is formed at a speed of 300 mm / sec at a rate of 300 mm / sec at a high temperature of 40 ° C. with respect to the glass transition temperature of the resin constituting the acrylic resin layer. The decorative multilayer sheet according to claim 1 or 2, wherein a crack of 0.05 mm or more does not occur and the following (Formula 1) is satisfied.
<Equation 1> (H2 / d2) − (H1 / d1) <1.20 (Formula 1)
(In the formula, H1 is the haze value of the acrylic resin layer before stretching, d1 is the thickness of the acrylic resin layer before stretching, which is 0.2 mm, and H2 is the acrylic resin layer after stretching. D2 is the thickness of the acrylic resin layer after stretching.) At least one surface of the base material layer satisfies at least one of (a) being colored and (b) being provided with a pattern,
The multilayer sheet for decoration according to any one of claims 1 to 3, wherein the base material layer and the acrylic resin layer are integrally laminated by an extrusion method. At least one surface of the base material layer satisfies at least one of (a) being colored and (b) being provided with a pattern,
Using the acrylic resin layer in the range of 0.03-0.1 mm,
The speed of the laminate is 300 mm / sec at a high temperature of 40 ° C. with respect to the glass transition temperature of the resin constituting the base material layer and the resin constituting the acrylic resin layer having a high glass transition temperature. When the film was stretched by 200%, cracks of 0.05 mm or more did not occur, and L ^* a ^* b ^* , which is the object color display method specified in JIS Z8729, was stretched before and after stretching from the acrylic resin layer side. The multilayer sheet for decorating of any one of Claims 1-4 which satisfy | fills the following formula | equation 2 when measured by (5).
<Equation 2> L ^* 2-L ^* 1 <3.5 (Formula 2)
(L ^* 1 in the formula is the L ^* value of the laminate before stretching, and L ^* 2 is the L ^* value of the laminate after stretching.)   The multilayer sheet for decorating of any one of Claims 1-5 using the layer formed from the acrylonitrile-butadiene-styrene copolymer resin as the said base material layer.   The multilayer sheet for decorating of any one of Claims 1-5 using the layer formed from the acrylic resin layer as the said base material layer.   The multilayer sheet for decorating of any one of Claims 1-5 using the layer formed from the polycarbonate-type resin as the said base material layer.   The multi-layer for decoration according to any one of claims 1 to 8, wherein a 60 ° glossiness according to JIS Z8741 on a main surface of the acrylic resin layer not facing the base material layer is 80 or more and 95 or less. Sheet.   The multilayer sheet for decoration according to any one of claims 1 to 9, which is used for an interior and exterior of an automobile.   The three-dimensional molded object which comprises the multilayer sheet for decorating of any one of Claims 1-10.

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