TW201630750A - Multi-layer sheet and three-dimensional molded body for decoration - Google Patents

Abstract

Provided is a multi-layer sheet for decorative which is excellent in thermoformability and which can maintain excellent surface gloss and color depth even after thermoforming. The multi-layer sheet 1 for decoration of the present invention comprises the acrylic resin layer 2 and the base material layer 3, and the acrylic resin layer 2 is composed of a composition containing the methacrylic resin (A) and the block copolymer (B). Formed, the block copolymer (B) contains a specific amount of the methacrylate polymer block (b1) and the acrylate polymer block (b2). In addition, the methacrylic resin (A) and the block copolymer (B) are contained in a specific ratio, and the Mw (A) and the block copolymer (B) of the methacrylic resin (A) are contained. Mw (b1-total) of the methacrylate polymer block (b1) in one molecule, and Mw of the acrylate polymer block (b2) in one molecule contained in the block copolymer (B) (b2-total) is set to a specific range.

Description

Multi-layer sheet and three-dimensional molded body for decoration

The present invention relates to a multi-layer sheet for decoration suitable for stereo thermoforming. Further, a three-dimensional molded body including the plurality of sheets for the decoration is provided.

In recent years, in the exterior decoration and interior decoration parts of automobiles, household electrical appliances, interior decoration furniture, etc., the three-dimensional molded products mainly composed of plastics having a complicated shape are used for the purpose of design improvement or weight reduction of parts. need to be improved. From the viewpoint of the design of the three-dimensional molded body without seams and the high design, and the simplification of the processing and assembly steps of the molded body, for example, a resin which is designed in advance to impart a pattern to the resin to be the main body is provided. The integrated molding process in which the decorative sheets are overlapped and formed by a press molding machine or the like is becoming mainstream. In this case, the decorative sheet is required to have properties such as easy formability, good surface properties, and high design properties. In particular, in terms of design, for example, a design such as a Piano Black style has an excellent surface gloss, and the design of a thermoforming decorative sheet having a deep design in color is required to be improved.

For the decorative sheet used in the above application, a method of laminating a transparent resin layer serving as a protective layer on the outermost surface layer by some methods can be used. For example, a method of imparting design to a resin sheet to be a substrate, a laminate of a primer layer and a methacrylic transparent resin, or a method of bonding a colored substrate resin by co-extrusion has been disclosed. A method of forming a two-layer sheet from a methacrylic transparent resin (Patent Documents 1 to 4).

Compared with a base resin such as an ABS resin generally used for a molded article, the methacrylic resin is deteriorated in toughness, so that cracks are likely to occur during molding processing due to a rapid shape change. Therefore, in order to improve the toughness, a methacrylic resin containing core-shell type particles is generally used (Patent Documents 5 and 6).

However, the core-shell particles themselves have no fluidity due to cross-linking. Therefore, in the case where the core-shell type particles are blended with the methacrylic resin, it is unavoidable to protrude the core-shell from the surface of the film formed through the film forming step (for example, melt forming or aerating forming using a T-die) A part of the type of particles lowers the surface smoothness of the methacrylic resin film.

Further, since the decorative sheet containing the transparent layered layer of the core-shell type particles is easily whitened by bending or heating during the secondary processing of the sheet, it is necessary to pay attention to the operation or step of the sheet.

Further, when the decorative sheet containing the transparent laminated layer containing the core-shell type particles is heated, the haze of the transparent layer is likely to increase, and in particular, when the decorative layer of the colored layer is provided on the back surface of the transparent layer, Damage to the color or depth of the color. Among them, especially in the aforementioned piano black In the color tone decorative film, it is easy to further emphasize the haze of the transparent layer, and the black feeling is greatly impaired. Further, in the case of hot forming of a mold having a shape in which a deep stretched portion having a high elongation or a high bending ratio is used, there is a problem that the decorative sheet is easily whitened in the deep drawn portion when the molding temperature is low. Conversely, when the forming temperature is too high, since the colored layer continues to melt, the design is degraded due to the disorder of the design pattern. As a result, the range of suitable temperature conditions for the three-dimensional three-dimensional forming is narrowed, and the formation of complicated shapes is difficult.

Further, Patent Document 7 is not an example suitable for decorative use, but an example in which an acrylic resin composition containing a block copolymer is used for an optical member such as a light guide plate is disclosed.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5581769

[Patent Document 2] Japanese Patent Laid-Open No. 2012-76348

[Patent Document 3] Japanese Patent Laid-Open No. 2012-116200

[Patent Document 4] Japanese Patent Laid-Open No. 2012-213911

[Patent Document 5] Japanese Patent No. 5186415

[Patent Document 6] Japanese Patent Laid-Open No. 2006-299038

[Patent Document 7] International Publication No. 2014/073216

The present invention has been made in view of the above circumstances, and an object thereof is to provide excellent thermoformability and dimensionality after thermoforming. A multi-layer sheet and a three-dimensional molded article with excellent decorative finish.

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

[1] A multi-layer sheet for decorative decoration comprising a multi-layer sheet for decoration comprising a laminate of an acrylic resin layer and a base layer, wherein the acrylic resin layer contains a methacrylic resin (A) And an acrylic resin composition of the 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) is a methacrylate polymer block (b1) having one or a plurality of structural units derived from methacrylate independently in one molecule, and a structure containing an acrylate. The acrylate polymer block (b2) of the unit, and the methacrylate polymer block (b1) is contained in a proportion of 10 to 80% by mass, and the acrylate polymer block is contained in a ratio of 90 to 20% by mass ( 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 of the total of the methacrylic resin (A) and the block copolymer (B). The weight average molecular weight of the methacrylic resin (A) is Mw (A) and the weight of the methacrylate polymer block (b1) in one molecule contained in the block copolymer (B). When the average molecular weight is Mw (b1-total) and the weight average molecular weight of the acrylate polymer block (b2) in one molecule contained in the block copolymer (B) is Mw (b2-total), Satisfied: (1) 0.3 ≦ Mw (A) / Mw (b1-total) ≦ 4.0

(2) 30,000 ≦ Mw (b2-total) ≦ 140,000.

[2] The multi-layer sheet for decorative decoration according to [1], wherein the laminated body has a film thickness of 0.05 to 0.5 mm, and the acrylic resin layer has a thickness of 0.03 to 0.25 mm.

[3] The multi-layer sheet for decoration of [1] or [2], wherein the glass transition temperature of the resin constituting the acrylic resin layer in the acrylic resin layer having a thickness of d1 In the case where the acrylic resin layer is stretched by 200% at a temperature of 300 mm/sec at a high temperature of 40 ° C, cracking of 0.05 mm or more does not occur, and the following Formula 1 is satisfied.

(H2/d2)-(H1/d1)<1.20 (Equation 1)

(H1 in the formula is a haze value of the acrylic resin layer before stretching, d1 is a thickness of the acrylic resin layer before stretching of 0.2 mm, and H2 is a haze value of the acrylic resin layer after stretching. D2 is the thickness of the aforementioned acrylic resin layer after stretching)

[4] The multi-layer sheet for decoration according to any one of [1] to [3] wherein at least one side of the substrate layer satisfies: (a) is colored, and (b) is provided with at least one pattern In one case, the base material layer and the acrylic resin layer are integrally laminated by an extrusion molding method.

[5] The multi-layer sheet for decorative decoration according to any one of [1] to [4] wherein at least one side of the base material layer satisfies: (a) is colored, and (b) is provided with at least one pattern In the case where the acrylic resin layer in the range of 0.03 to 0.1 mm is used, the glass transition temperature of the resin having a high glass transition temperature among the resin constituting the base layer and the resin constituting the acrylic resin layer is used. When the laminate is extended by 200% at a high temperature of 40 ° C at a speed of 300 mm/sec, no turtle of 0.05 mm or more is produced. When the display method L*a*b* of the object color defined by JIS Z8729 is measured from the side of the acrylic resin layer before and after the stretching, the following formula 2 is satisfied.

L ^* 2-L ^* 1<3.5 (Formula 2)

(L ^* 1 in the formula is the L ^* value of the layered body before stretching, and L ^* 2 is the L* value of the layered body after stretching)

[6] The multi-layer sheet for decoration of any one of [1] to [5], wherein a layer formed of an acrylonitrile-butadiene-styrene copolymer resin is used as the base material layer.

[7] The multi-layer sheet for decoration of any one of [1] to [5], wherein a layer formed of an acrylic resin layer is used as the base material layer.

[8] The plurality of sheets for decorative use according to any one of [1] to [5], wherein a layer formed of a polycarbonate resin is used as the base material layer.

[9] The multi-layer sheet for decorative decoration according to any one of [1] to [8] wherein, in the main surface of the acrylic resin layer which is not opposed to the base material layer, 60° of JIS Z8741 The gloss is 80 or more and 95 or less.

[10]: The multi-layer sheet for decoration of any one of [1] to [9], which is used for interior and exterior decoration of a car.

[11] A three-dimensional molded article comprising the plurality of layers for decorative of any one of [1] to [10].

According to the present invention, it is possible to provide an excellent effect of providing a multi-layer sheet for decoration and a three-dimensional molded article which are excellent in thermoformability and which can maintain excellent decorative properties after thermoforming.

1‧‧‧multilayer sheet

2‧‧‧Acrylic resin layer

3‧‧‧Substrate layer

4‧‧‧Three-dimensional molding die

Fig. 1 is a cross-sectional explanatory view showing a part of a plurality of sheets for decoration of the present invention.

Fig. 2 is a schematic view of a mold used for the simple evaluation of the formability of a plurality of sheets for decoration.

[Formation of the Invention]

Hereinafter, an example of an embodiment to which the present invention is applied will be described. In addition, the size or ratio of each member in the following drawings is for convenience of description, and is not limited to this. Moreover, the specific numerical value in this specification shows the value obtained by the measurement of the method of the Example mentioned later. For example, the weight average molecular weight Mw and the number average molecular weight Mn are values in terms of standard polystyrene measured by GPC (gel permeation chromatography), and are values obtained by measurement by the method described in the examples below. Moreover, the term "(meth)acrylic acid" means acrylic acid and methacrylic acid, and the term "(meth)acrylate" means acrylate and methacrylate.

The multi-layer sheet for decoration (hereinafter also referred to as "plural layer sheet") of the present invention includes a laminate including an acrylic resin layer and a base material layer. As shown in FIG. 1, the plurality of layers 1 may be composed of two layers of the acrylic resin layer 2 and the base layer 3. Further, as the plurality of sheets, a laminate in which an acrylic resin layer is sandwiched between a pair of base material layers can be used. The base material layer and the acrylic resin layer may be laminated directly, or may be laminated via an adhesive layer, or may be laminated via another layer. The plurality of sheets may further laminate the acrylic resin layer and the substrate layer without departing from the scope of the present invention. The layer other than the layer of the plurality of layers is not particularly limited. The acrylic resin layer can be used in the outermost layer or in the inner layer. Further, it is not necessary to cover that the main surface of the plurality of sheets is entirely provided with the acrylic resin layer, and it may be provided on a part thereof. Further, the acrylic resin layer may be used in a single layer or in a plurality of layers. The same applies to the substrate layer.

The acrylic resin layer 2 is formed by using an acrylic resin composition containing a methacrylic resin (A) and a block copolymer (B). The block copolymer (B) is a methacrylate polymer block (b1) having one or a plurality of structural units derived from a methacrylate, and a structural unit derived from an acrylate, each of which has one or a plurality of molecules. Acrylate polymer block (b2). That is, the acrylic resin composition of the present invention contains a methacrylic resin (A) and a block copolymer (B) having a methacrylate polymer block and an acrylate polymer block. The acrylic resin composition is a thermoplastic polymer composition.

The methacrylic resin (A) has 80% by mass or more of a structural unit derived from methyl methacrylate, and preferably has 90% by mass or more. In other words, the structural unit of the monomer other than methyl methacrylate of 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 the methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and acrylic acid second. Ester, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate; phenyl acrylate, benzoyl acrylate Ester, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate; cyclohexyl acrylate, acrylic acid Ester ester, acrylic acid Acrylates such as esters; ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, Tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, methacrylic acid Dodecyl ester; phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, methacrylic acid Glycidyl ester, allyl methacrylate; cyclohexyl methacrylate, methacrylic acid Ester, methacrylic acid a methacrylate other than methyl methacrylate such as an ester; an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid or itaconic acid; ethylene, propylene, 1-butene, isobutylene, Olefins such as 1-octene; conjugated dienes such as butadiene, isoprene, and myrcene; styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, etc. Aromatic vinyl compound; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, etc. .

The stereoregularity of the methacrylic resin (A) is not particularly limited, and for example, a stereoregularity having the same row, miscellaneous row, or opposite row can be used.

Weight average molecular weight of methacrylic resin (A) When the value of Mw (A) is small, the impact resistance or toughness of the molded article obtained from the obtained acrylic resin composition tends to be lowered. On the other hand, when Mw (A) is large, the fluidity of the acrylic resin composition tends to decrease, and the moldability tends to be lowered. From the viewpoints of the above, 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) of the methacrylic resin (A) to the number average molecular weight Mn (A) Mw (A) / Mn (A) (hereinafter, also referred to as "molecular weight distribution") is small, The molding processability of the acrylic resin composition tends to decrease. On the other hand, when Mw (A) / Mn (A) is large, the impact resistance of the molded article obtained from the acrylic resin composition tends to be lowered and become brittle. From this viewpoint, Mw (A) / Mn (A) is preferably 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 or molecular weight distribution of the methacrylic resin (A) can be controlled by adjusting the type or amount of the polymerization initiator and the chain transfer agent.

The methacrylic resin (A) is obtained by separately polymerizing a monomer containing 80% by mass or more of methyl methacrylate or copolymerizing with a monomer other than methyl methacrylate. A commercially available product can 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: 1.3g/10 minutes (230°C, 37.3N)), “Parapet HRL” (MFR: 2.0g/10 minutes) Clock (230°C, 37.3N)), “Parapet HRS” (MFR: 2.4g/10 minutes (230°C, 37.3N)) and “Parapet G” (MFR: 8.0g/10 minutes (230°C, 37.3N) ) [all product names, manufactured by Kuraray Co., Ltd.], etc.

The methacrylate polymer block (b1) is a constituent unit mainly composed of a structural unit derived from methacrylate. The proportion of the structural unit derived from methacrylate in the methacrylate polymer block (b1) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, particularly preferably It is 98% by mass or more.

Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methacrylic acid. Isobutyl ester, second butyl methacrylate, third butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, methyl 2-ethylhexyl acrylate, pentadecyl methacrylate, dodecyl methacrylate, methacrylic acid Ester, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate And allyl methacrylate and the like. Among these, from the viewpoint of improving transparency and heat resistance, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methacrylic acid are preferred. Butyl ester, cyclohexyl methacrylate, methacrylic acid An alkyl methacrylate such as an ester is more preferably methyl methacrylate. The methacrylate may be polymerized in a single type or in combination of two or more kinds to form a methacrylate polymer block (b1).

The methacrylate polymer block (b1) as long as it does not interfere with this The object and effect of the invention may include a structural unit derived from a monomer other than methacrylate. The proportion of the structural unit derived from the monomer other than the methacrylate contained in the methacrylate polymer block (b1) is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass. % or less is particularly preferably in the range of 2% by mass or less.

Examples of the monomer other than the methacrylate include an acrylate, an unsaturated carboxylic acid, an aromatic vinyl compound, an olefin, a conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, and A. Acrylamide, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, and the like. A monomer other than the methacrylate may be copolymerized with the above-mentioned methacrylate by a single type or a combination of two or more types to form a methacrylate polymer block (b1).

The methacrylate polymer block (b1) is preferably a polymer having a refractive index in the range of 1.485 to 1.495, and is preferably from the viewpoint of improving the transparency of the acrylic resin layer.

The weight average molecular weight Mw (b1) of the single unit of the methacrylate 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, still more preferably 100,000 or less.

In the block copolymer (B), in the case where the methacrylate polymer block (b1) is plural in a molecule, the composition of the structural unit constituting the respective methacrylate polymer block (b1) The ratio or molecular weight may be the same or different.

Each molecule of the methacrylate polymer block (b1) ( The weight average molecular weight Mw (b1-total) of one polymer chain is preferably set to 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, further preferably 100,000 or less. The block copolymer (B) is a case where only one methacrylate polymer block (b1) is present in one molecule, and the weight average molecular weight Mw of a single unit of the methacrylate polymer block (b1) (b1) is Mw (b1-total). Further, the block copolymer (B) is a case where a plurality of methacrylate polymer blocks (b1) are present in one molecule, and the weight average molecular weight of each of the methacrylate polymer blocks (b1) The total is Mw (b1-total). Further, in the case of blending a plurality of methacrylate polymer blocks (b1) having different bonding forms, the ratio of the blending is multiplied by the respective methacrylate polymer block (b1) and the total is added. Wait, and find Mw (b1-total).

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 set to 0.3 or more and 4.0 or less. 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 article made of the acrylic resin composition tends to decrease, and the surface smoothness tends to be lowered. On the other hand, when Mw (A) / Mw (b1) is too large, the surface smoothness of the molded article produced from the acrylic resin composition and the temperature dependence of the haze tend to deteriorate. It has been found that by setting Mw (A) / Mw (b1) to 0.3 or more and 4.0 or less, the dispersed particle diameter in the methacrylic resin (A) of the block copolymer (B) can be reduced, regardless of the temperature. The change shows that low haze becomes possible, and the result is at a wide range of temperatures The change in haze in the range becomes smaller.

The ratio of the methacrylate polymer block (b1) in the block copolymer (B) is preferably 10% by mass or more and 70% by mass from the viewpoints of transparency, flexibility, moldability, and surface smoothness. %the following. More preferably, it is 25 mass% or more and 60 mass% or less. When the ratio of the methacrylate polymer block (b1) in the block copolymer (B) is 10% by mass or more and 70% by mass or less, the acrylic resin composition of the present invention or a molded article containing the same It is excellent in transparency, flexibility, bending resistance, impact resistance, flexibility, and the like. In the case where the block copolymer (B) contains a plurality of methacrylate polymer blocks (b1), the above ratio is calculated based on the total mass of all the methacrylate polymer blocks (b1).

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

Examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, second butyl acrylate, and acrylic acid. Butyl ester, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, acrylic acid Ester, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate, allyl acrylate, and the like. The acrylate can be polymerized by one type alone or in combination of two or more types to form an acrylate polymer block (b2).

The acrylate polymer block (b2) may contain a structural unit derived from a monomer other than the acrylate as long as it does not impair the object and effect of the present invention. The ratio of the structural unit derived from the monomer other than the acrylate contained in the acrylate polymer block (b2) is preferably 55 mass% or less, more preferably 50 mass% or less, still more preferably 40 mass% or less. It is particularly preferably 10% by mass or less.

Examples of the monomer other than the acrylate include methacrylate, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, and methyl group. Acrylamide, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, and the like. The acrylate polymer block (b2) can be formed by copolymerizing one or a combination of two or more kinds of acrylates together with the above acrylate.

The acrylate polymer block (b2) preferably contains an alkyl acrylate and an (meth) acrylate 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. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.

The (meth)acrylic aromatic ester means an aromatic acrylate or an aromatic methacrylate, and an aromatic ring-containing compound forms an ester bond with (meth)acrylic acid acrylate. Examples of the (meth)acrylic acid aromatic ester include phenyl acrylate, benzyl acrylate, and benzene acrylate. Oxyethyl ester, styrene acrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, styrene methacrylate, and the like. Among them, preferred are phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate.

Where the acrylate polymer block (b2) comprises an alkyl acrylate and an (meth)acrylic acid aromatic ester, the acrylate polymer block (b2) preferably contains 50 to 90% by mass of an alkyl group derived from acrylic acid. The structural unit of the ester and the structural unit derived from the (meth)acrylic acid aromatic ester in an amount of 50 to 10% by mass, more preferably 60 to 80% by mass of the structural unit derived from the alkyl acrylate, and 40 to 20% by mass A structural unit derived from a (meth)acrylic aromatic ester.

The acrylate polymer block (b2) is preferably a polymer having a refractive index of 1.485 to 1.495, and is preferably from the viewpoint of improving the transparency of the acrylic resin layer.

The weight average molecular weight Mw (b2) of the 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, and the upper limit is more preferably 110,000 or less, particularly preferably 100,000 or less.

In the case where the number of units of the acrylate polymer block (b2) in the block copolymer (B) is plural, the composition ratio or molecular weight of the structural units constituting the respective acrylate polymer block (b2) may be the same as each other. It can also be 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. Further, the upper limit of Mw (b2-total) is preferably 110,000 or less, more preferably 100,000 or less. When Mw (b2-total) is small, the impact resistance of the molded article made of the acrylic resin composition tends to decrease. On the other hand, when Mw (b2-total) is large, the surface smoothness of the molded article produced from the acrylic resin composition tends to be lowered. The block copolymer (B) contains only one acrylate polymer block (b2) in one molecule, and the weight average molecular weight Mw (b2) of a single unit of the acrylate polymer block (b2) is Mw (b2-total). Further, in the case where the block copolymer (B) has a plurality of acrylate polymer blocks (b2) in one molecule, the total weight average molecular weight of each acrylate polymer block (b2) is Mw (b2) -total). Further, in the case of blending a plurality of methacrylate polymer blocks (b2) having different bonding forms, by multiplying the blend ratio of the respective methacrylate polymer blocks (b2) and totaling this Wait, and find Mw (b1-total).

Further, the weight average molecular weight of the methacrylate polymer block (b1) and the weight average molecular weight of the acrylate polymer block (b2) are in the process of polymerizing and polymerizing the block copolymer (B). The value calculated by the weight average molecular weight of the intermediate product and the final product (block copolymer (B)) measured after sampling.

The ratio 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, moldability, 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 10% by mass or more, 60% by mass In the range of % or less, the acrylic resin composition of the present invention or a molded article containing the same is excellent in impact resistance, flexibility, and the like. When the block copolymer (B) contains a plurality of acrylate polymer blocks (b2) in one molecule, the above ratio is calculated based on the total mass of all the acrylate polymer blocks (b2).

The bonding form of the methacrylate polymer block (b1) and the acrylate polymer block (b2) of the block copolymer (B) is not particularly limited. For example, a terminal (the diblock copolymer of the (b1)-(b2) structure) in which the acrylate polymer block (b2) is bonded to one end of the methacrylate polymer block (b1); One end of the acrylate polymer block (b2) is bonded to both ends of the methacrylate polymer block (b1) (triphenyl copolymer of (b2)-(b1)-(b2) structure One end of the methacrylate polymer block (b1) (the (b1)-(b2)-(b1)-structured triblock is attached to both ends of the acrylate polymer block (b2) A block copolymer of a structure in which a methacrylate polymer block (b1) such as a copolymer) is linearly bonded to an acrylate polymer block (b2).

Further, a block copolymer in which a plurality of (b1)-(b2) structures are connected to each other to form a radial structure ([(b1)-(b2)-]nX structure); One end of the block copolymer of the (b2)-(b1) structure is joined to form a radial structure of the block copolymer ([(b2)-(b1)-]nX structure); plural (b1) One end of the block copolymer of the structure of (b2)-(b1) is joined to form a block copolymer of a radial structure ([(b1)-(b2)-(b1)-]nX structure); a plurality of The block copolymer of the (b2)-(b1)-(b2) structure is joined to form a radial structure of the block copolymer ([(b2)-(b1)-(b2)-]nX structure), etc. Star block copolymer, or A block copolymer or the like having a branched structure. Further, X here represents a coupling agent residue.

Among these, a diblock copolymer, a triblock copolymer, a star block copolymer, more preferably a diblock copolymer of the (b1)-(b2) structure, (b1)-( a triblock copolymer of b2)-(b1), a star block copolymer of [(b1)-(b2)-]nX structure, [(b1)-(b2)-(b1)-]nX structure Star block copolymer.

Further, the block copolymer (B) may have a polymer block (b3) other than the methacrylate polymer block (b1) and the acrylate polymer block (b2).

The main structural unit constituting the polymer block (b3) is a structural unit of methacrylate and a monomer other than the acrylate. Examples of the monomer include olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; conjugated dienes such as butadiene, isoprene, and myrcene; and styrene; An aromatic vinyl compound such as α-methylstyrene, p-methylstyrene or m-methylstyrene; vinyl acetate, vinyl pyridine, acrylonitrile, methacrylonitrile, vinyl ketone, chlorine Ethylene, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, ε-caprolactone, valerolactone, and the like.

The bonding form of the methacrylate polymer block (b1), the acrylate polymer block (b2), and the polymer block (b3) in the block copolymer (B) is not particularly limited. The binding form of the block copolymer (B) containing the methacrylate polymer block (b1), the acrylate polymer block (b2), and the polymer block (b3) may, for example, be (b1) a block copolymer of the structure -(b2)-(b1)-(b3), (b3)-(b1)-(b2)-(b1)-(b3) Structured block copolymers and the like. In the case where the block copolymer (B) has a plurality of polymer blocks (b3), the composition ratio or molecular weight of the structural units constituting the respective polymer blocks (b3) may be the same or different.

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

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.

When the weight average molecular weight of the block copolymer (B) is small, and sufficient melt tension cannot be maintained in the melt extrusion molding, it is difficult to obtain a good plate-like formed body, and the mechanical properties such as the fracture strength of the obtained plate-shaped formed body are obtained. The tendency of physical decline. On the other hand, when the weight average molecular weight of the block copolymer (B) is large, the viscosity of the molten resin becomes high, and the surface of the plate-shaped formed body obtained by melt extrusion is caused by fine wrinkles. The unevenness of the uneven or unmelted material (high molecular weight body) does not favor a good plate-shaped formed body.

Further, 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 in such a range, the content of the unmelted material which causes microbumping in the molded article containing the acrylic resin composition of the present invention can be extremely small.

The refractive index of the block copolymer (B) is preferably 1.485 to 1.495, more preferably 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 becomes high. In addition, the "refractive index" in this specification is an example as mentioned later, and means the measurement. The value measured at a constant wavelength of 587.6 nm (d line).

The method for producing the block copolymer (B) is not particularly limited, and a method according to a well-known method can be employed. For example, a method of living-polymerizing a monomer constituting each polymer block is generally used. In the method of living polymerization, for example, an anionic polymerization method in the presence of a mineral acid salt such as an alkali metal or an alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator; and an organic alkali metal are used. a method for polymerizing a compound as a polymerization initiator, an anionic polymerization in the presence of an organoaluminum compound; a method for polymerizing using an organic rare earth metal complex as a polymerization initiator; using an α-halogenated ester compound as a starter, A method of radical polymerization in the presence of a copper compound. Further, a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent may be used to polymerize a monomer constituting each block to produce a mixture containing the block copolymer (B) used in the present invention. Method etc. Among these methods, in particular, since the block copolymer (B) is obtained in high purity, the molecular weight or the composition ratio is easily controlled, and economical, and an organic alkali metal compound is used as a polymerization initiator, in the organoaluminum compound. In the presence of, an anionic polymerization method is preferred.

The acrylic resin composition used in the present invention contains 10 to 99 parts by mass of the methacrylic resin (A) and 90 to 1 part by mass of the block copolymer (B). It is preferably 55 to 90 parts by mass of the methacrylic resin (A) and 45 to 10 parts by mass of the block copolymer (B), more preferably 70 to 90 parts by mass of the methacrylic resin (A). ) with 30 to 10 parts by mass of the block copolymer (B).

When the content of the methacrylic resin (A) in the acrylic resin composition is small relative to the block copolymer (B), there is a surface hardness of the sheet obtained by melt extrusion molding using a T-die. The tendency to decline.

In the acrylic resin composition used in the present invention, various additives such as an antioxidant, a thermal stabilizer, a slip agent, a processing aid, an antistatic agent, and the like may be added as needed within a range not impairing the effects of the present invention. Antioxidants, colorants, anti-crushing additives, etc. Further, from the viewpoints of mechanical properties and surface hardness of the plurality of sheets for decorative of the present invention, it is preferred that a foaming agent, a filler, a matting agent, a light diffusing agent, a softening agent or a plasticizer are not added in a large amount.

The antioxidant has an effect of preventing oxidative degradation of the resin by the monomer in the presence of oxygen. For example, a phosphorus-based antioxidant, a hindered phenol-based antioxidant, a thioether-based antioxidant, or the like can be given. The antioxidant may be used alone or in combination of two or more. Among these, from the viewpoint of preventing the effect of deterioration of optical characteristics due to coloring, a phosphorus-based antioxidant or a hindered phenol-based antioxidant is preferable, and a phosphorus-based antioxidant and a hindered phenol-based antioxidant are more preferably used in combination.

When a phosphorus-based antioxidant and a hindered phenol-based antioxidant are used in combination, the ratio thereof is not particularly limited, and the lower limit of the phosphorus-based antioxidant/hindered phenol-based antioxidant is preferably 1/5 or more. Preferably, it is 1/2 or more, and the upper limit is preferably 2/1 or less, more preferably 1/1 or less.

Examples of the phosphorus-based antioxidant include 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite (manufactured by Asahi Kasei Co., Ltd.; trade name: ADEKA STAB HP- 10), ginseng (2,4-di-t-butylphenyl) Phosphite (manufactured by CIBA SPECIALTY CHEMICALS; trade name: IRUGAFOS 168).

Examples of the hindered phenol-based antioxidant include pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by CIBA SPECIALTY CHEMICALS; trade name IRGANOX 1010) Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured by CIBA SPECIALTY CHEMICALS; trade name IRGANOX1076), 3,9-double (2,6 -Di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphate siro[5.5]undecane (made by ADEKA); trade name: ADEKA STAB PEP-36) and so on.

The thermal deterioration preventing agent can prevent thermal deterioration of the resin by capturing polymer radicals generated by exposure to high heat in a state of substantially no oxygen.

As the thermal deterioration preventing agent, 2-t-butyl-6-(3,-t-butyl-5'-methyl-hydroxybenzyl)-4-methylphenyl acrylate ( Sumitomo Chemical Co., Ltd.; trade name Sumilizer GM), 2,4-di-third amyl-6-(3',5'-di-third-pentyl-2'-hydroxy-α-methylbenzyl Phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.; trade name Sumilizer GS).

The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. The ultraviolet absorber is a compound having a function of mainly converting light energy into heat energy.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, and trisole. Classes, benzoates, salicylates, cyanoacrylates, oxalic acid anilines, malonic esters, formazan and the like. Among these, benzotriazoles and anilines are preferred. The ultraviolet absorbers may be used alone or in combination of two or more.

As the benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)6-(2H-benzotriazol-yl) can be mentioned. Phenol] (made by Asahi Denki Kogyo Co., Ltd.; trade name ADEKA STAB LA-31), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl) Phenol (manufactured by CIBA SPECIALTY CHEMICALS; trade name TINUVIN 329), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (CIBA SPECIALTY) Produced by CHEMICALS; trade name TINUVIN234).

The aniline may, for example, be 2-ethyl-2'-ethoxy-oxabenzidine (manufactured by Clariant and Japan; trade name Sandeyuboa VSU).

Among these ultraviolet absorbers, benzotriazoles are preferably used from the viewpoint of suppressing deterioration of the resin due to irradiation with ultraviolet rays.

The light stabilizer is a compound mainly having a function of capturing a radical generated by oxidation by light. As a suitable light stabilizer, a hindered amine such as a compound having a 2,2,6,6-tetraalkylpiperidine skeleton can be mentioned.

The polymer processing aid is a compound which exhibits the effects of thickness precision and film formation when forming an acrylic resin composition. The polymer processing aid is usually a polymer particle having a particle diameter of 0.05 to 0.5 μm which can be produced by an emulsion polymerization method.

The polymer particles may be a single layer particle containing a polymer having a single composition ratio and a single ultimate viscosity, or may be a multilayer particle containing two or more kinds of polymers having different composition ratios or ultimate viscosity. Among them, can be listed It is preferred that the layer has a polymer layer having a low ultimate viscosity and a two-layer structure having a polymer layer having a high ultimate viscosity of 5 dl/g or more in the outer layer.

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

Moreover, the acrylic resin composition used in the present invention can be used in combination with other polymers other than the methacrylic resin (A) and the block copolymer (B), within the range not impairing the effects of the present invention. Examples of the other polymer include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polydecene; ethylene-based ionic polymers; Styrene, styrene-maleic anhydride copolymer, impact-resistant polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, styrene resin such as MBS resin; methyl methacrylate- Styrene copolymer; polyester resin such as polyethylene terephthalate or polybutylene terephthalate; polyamide of nylon 6, nylon 66, polyamine elastomer, etc.; polycarbonate , polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, Poly-xyloxy modified resin; core-shell type acrylic rubber, polyoxyxene rubber; styrene-based thermoplastic elastomer such as SEPS, SEBS, SIS, etc.; olefin-based rubber such as IR, EPR, EPDM, and the like.

The method of preparing the acrylic resin composition used in the present invention is not particularly limited, in order to improve the constitution of the acrylic resin. For the dispersibility of each component of the product, a method of mixing by, for example, melt kneading is recommended. The method of melt-kneading the methacrylic resin (A) and the block copolymer (B) may be mixed with the additive as needed, or the methacrylic resin (A) may be mixed with the additive, and then The block copolymer (B) is mixed. The mixing operation can be carried out using a known mixing or kneading device such as a kneader ruder, an extruder, a mixing roll, a Banbury internal kneader or the like. In particular, from the viewpoint of improving the kneadability and compatibility of the methacrylic resin (A) and the block copolymer (B), a biaxial extruder is preferably used. The temperature during mixing/kneading is preferably adjusted according to the melting temperature of the methacrylic resin (A), the block copolymer (B), and the like, and is usually in the range of 110 ° C to 300 ° C. mixing. In the case of melt kneading using a biaxial extruder, it is preferable to carry out melt kneading under reduced pressure and/or melt kneading under a nitrogen flow from the viewpoint of suppressing coloration. In this way, the acrylic composition of the present invention can be obtained in any form such as pellets or powder. An acrylic composition in the form of pellets, powder or the like is suitably used as a molding material.

Further, the block copolymer (B) is dissolved in a mixed solution of a monomer unit of the methacrylic resin (A) and a solvent such as toluene, and the acrylic monomer can be prepared by polymerizing the acrylic monomer. The acrylic resin composition used in the present invention containing the block copolymer (B).

The base layer of the plurality of layers of the present invention is provided with at least one layer of a layer of another thermoplastic resin layer or a metal and/or a metal oxide, directly or via an adhesive layer. Further, the plurality of layers of the present invention may be provided with a non-wood fiber such as a thermoplastic resin, a wooden substrate or a kenaf on at least one surface of the above-mentioned plurality of decorative layer sheets of the present invention. Dimensional base layer of the fabric.

The thickness of the plurality of sheets of the present invention is preferably 500 μm or less. When the thickness is 500 μm or less, secondary workability such as build-up property, handleability, cutting property, and punching property is good, and workability as a sheet becomes easy. Further, the unit price per unit area can be appropriately set. The upper limit of the thickness of the plurality of sheets is more preferably 400 μm or less, particularly preferably 300 μm or less, and the lower limit is preferably 50 μm or more, and more preferably 100 μm or more. Further, 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 base material layer is not particularly limited as long as it does not deviate from the gist of the present invention, and preferred examples thereof include a polycarbonate resin, a polyethylene terephthalate resin, a polyamide resin, and a poly Thermoplastic resin such as ethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, other acrylic resin, or ABS (acrylonitrile-butadiene-styrene copolymerization) resin .

Among these, a polycarbonate resin, an acrylic resin, or an ABS resin having a good balance of performance surfaces such as thermoformability, workability, weather resistance, chemical resistance, and scratch resistance is preferably used. In addition, when a gelate derived from a resin is generated in a plurality of sheets, the disadvantage of being a molded article is implicated in a decrease in yield. Therefore, it is more preferable to use an acrylic resin which is less likely to cause a gelation reaction in a resin structure. On the substrate layer. In addition, the "acrylic resin" as used herein includes methacrylic resin and propylene. An olefinic resin, a block copolymer of these, a core-shell type particle, and the like.

The 60° gloss (%) of JIS Z8741 in the main surface of the acrylic resin layer which does not face the base material layer is preferably 80 or more and 95 or less from the viewpoint of more effectively extracting surface glossiness.

The manufacturing system of the plurality of sheets is not particularly limited. For example, (1) a sheet-like acrylic resin layer comprising 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 in advance. a method of hot pressing of a press machine, performing vacuum pressing or vacuum forming, a method of laminating, a method of laminating via a bonding/adhesion layer (wet lamination method), and (2) heat of melting by a T-die A method of forming a base layer of a plasticized resin, and laminating an acrylic resin using a single-layer sheet formed of the acrylic resin composition of the present invention (extrusion simultaneous dry lamination method); (3) by using the present invention A co-extrusion method in which an acrylic resin composition and another thermoplastic resin are melt-mixed using different extruders, and an acrylic resin layer of the present invention is laminated from a T-die to contain a thermoplastic resin. A method of a plurality of sheets of a base material layer of a resin sheet or the like.

Among these methods, the method of (1) or (2) can apply a surface treatment such as corona treatment to the bonding surface side of the acrylic resin layer and the base material layer before lamination.

The method for producing the plurality of sheets of the present invention can be carried out by a well-known method such as an inflation method, a melt casting method or a curtain coating method in addition to the T-die method. From the viewpoint of obtaining a sheet having good surface smoothness and low haze, it is preferred to contain the above melted kneaded material in a molten state. A method of forming a step from a T-die extrusion to form a surface thereof in contact with a surface of a mirror roll or a surface of a mirror surface. The rolls or belts used at this time are preferably made of metal. In the case where the both sides of the thus-extruded molten kneaded material are brought into contact with the mirror surface to form a film, it is preferred to press the both sides of the sheet with a mirror roll or a mirror belt under pressure. The holding pressure of the mirror roll or the mirror belt is preferably high, and the line pressure is preferably 10 N/mm or more, and more preferably 30 N/mm or more.

In the case of the manufacturing method of the T-die method, an extruder-type melt-squeezing device or the like with a uniaxial or biaxially extruded propeller can be used. The melt extrusion temperature for producing the plurality of sheets of the present invention is preferably from 200 to 300 ° C, more preferably from 220 to 270 ° C. Further, in the case of melt-squeezing using a melt-squeezing device, it is preferable to use a vent pipe, melt-extrude under reduced pressure, or melt-extrude under a nitrogen stream from the viewpoint of suppressing coloring due to deterioration of the resin. Pressure.

Further, from the viewpoint of obtaining a sheet having good surface smoothness, good surface gloss, and low haze, it is preferable that the surface temperature of at least one of the mirror roll or the mirror strip for holding the sheet is 60 ° C or higher. Further, the surface temperature of both the mirror roll holding the sheet or the mirror belt is set to 130 ° C or lower. When the surface temperature of both the mirror roll or the mirror belt of the sheet is less than 60 ° C, the surface of the obtained acrylic resin layer is less likely to be smooth and haze, and when at least one of the surface temperatures exceeds 130 At °C, since the sheet is too close to the mirror roll or the mirror belt, the surface of the sheet is easily cracked when the sheet is peeled off from the mirror roll or the mirror strip, and the surface of the acrylic layer of the plurality of sheets obtained is smooth. The tendency to become less or to increase the haze.

In the acrylic resin layer of the plurality of sheets of the present invention, a sheet-like acrylic resin layer having a thickness of d1 (however, d1 = 0.2 mm) is prepared, and the glass transition temperature of the resin constituting the acrylic resin layer is When the acrylic resin layer is stretched by 200% at a speed of 300 mm/sec at a high temperature of 40 ° C, cracking of 0.05 mm or more is not caused, and the following formula 1 is satisfied.

(H2/d2)-(H1/d1)<1.20 (Equation 1)

However, H1 in the formula is the haze value of the acrylic resin layer before stretching, d1 is the thickness of the acrylic resin layer before stretching, H2 is the haze value of the acrylic resin layer after stretching, and d2 is the elongation after stretching The thickness of the acrylic resin layer.

By conforming to the above formula 1, it is possible to obtain an effect of maintaining a glossiness which does not change before molding even after thermoforming a plurality of layers of the sheet using the acrylic resin layer. Further, the acrylic resin layer of the present invention is not limited to the above thickness. In other words, the above conditions are properties specified in the case of measuring under the above conditions, and the conditions of the acrylic resin layer of the present invention are not particularly limited.

The roughness of the acrylic resin layer of the plurality of sheets of the present invention is preferably 1.5 nm or less, more preferably 0.1 to 1.0 nm. Thereby, surface smoothness is excellent, and workability at the time of cutting, or punching is excellent. In addition, in the case of being used for the purpose of designing, the surface gloss is excellent, and in the case of printing on the acrylic resin layer of the present invention, the sharpness of the pattern layer or the like is excellent. Moreover, in optical use, optical characteristics, such as a light transmittance, and the shaping|molding precision at the time of surface shaping are excellent. Further, the roughness of the molded body (film) is as described in the examples. The value obtained by the method.

Further, the acrylic resin layer of the plurality of sheets of the present invention preferably has a lower haze temperature dependency. Therefore, it is advantageous in that the use of transparency is required in a wide temperature range or in the case of processing at a high temperature without impairing transparency.

The base layer or the acrylic resin layer of the plurality of sheets of the present invention can be colored. In the coloring method, the thermoplastic resin composition of the base material layer itself contains a pigment or a dye to color the resin itself, and the flaky acrylic resin layer is immersed in a liquid in which the dye is dispersed. The dyeing method of coloring or the like is not particularly limited thereto.

Examples of the pigment to be used include an azo pigment, an anthraquinone pigment, a phthalocyanine pigment, a quinophthalone pigment, a thioindole pigment, an isoindolinone pigment, and Pigments, lanthanide pigments, kaolinite, muscovite, talc, calcium carbonate, anhydrous/aqueous citric acid, alumina, basic magnesium carbonate, precipitated barium sulfate, titanium dioxide, zinc oxide, zinc antimony white, iron black, graphite , carbon black, chrome yellow, yellow iron oxide, titanium yellow, molybdenum chrome orange, red iron oxide, cadmium red, ultramarine blue, indigo, cobalt blue, chromium oxide, cobalt green and the like.

Further, as the dye to be used, for example, an azo dye, an acridine dye, a nitroso dye, a nitro dye, a stilbene azo dye, a ketimine dye, a triphenylmethane dye, a dibenzo Piper dye, quinoline dye, methine/polymethine dye, anthraquinone dye, thiazole dye, indamine/indophenol dye, hydrazine dye, Dye, thiophene Dyes, sulphur dyes, oxyketone dyes, anthraquinone dyes, anthraquinone dyes, anthraquinone dyes, anthrone dyes, and the like.

Here, the multi-layer sheet of the present invention can be used as a base layer of a thermoplastic resin which is colored black by a pigment or a dye, and the surface of the acrylic resin layer of the present invention is thermoformed. The gloss is more emphasized, and it is suitable for use as a decorative sheet of piano black tone which is more excellent in black feeling. As the black pigment contained in the substrate layer, carbon black is suitably used. The carbon black is likely to be aggregated due to the average particle diameter of the carbon black or the appearance defect due to poor dispersion, and the average particle diameter of the carbon black is preferably 100 nm or more and 30 nm or less.

In the coloring method of the acrylic resin layer of the present invention, the composition of the methacrylic resin (A) and the block copolymer (B) itself contains a pigment or a dye, and the acrylic before the flaking is used. A method of coloring the resin composition itself, a dyeing method in which a sheet-like acrylic resin layer is immersed in a liquid in which a dye is dispersed, and coloring, etc., but is not particularly limited thereto.

By coloring the acrylic resin layer of the present invention, the color tone of the back surface layer can be finely adjusted. For example, the plurality of sheets of the piano black tone described above can be colored by including the blue or green dye in the acrylic resin layer, and the redness or yellowness of the base material layer can be corrected, so that the black feeling can be further improved.

The plurality of layers of the sheet of the present invention can be printed on at least one side of the acrylic resin layer. Patterns and colors such as patterns, characters, graphics, and the like are given by printing. The pattern can be colored or achromatic. In order to prevent discoloration of the printing layer, the printing system is preferably carried out on the side in contact with other thermoplastic resin or thermosetting resin to be described later.

The plurality of layers of the present invention can have at least one side of the substrate layer For (a) colored, or / and set (b) pattern. In the case where at least one of the above (a) and (b) is satisfied, the glass transition temperature of the resin having a high glass transition temperature among the resin constituting the base material layer and the resin constituting the acrylic resin layer is 40 When the plurality of sheets are stretched by 200% at a speed of 300 mm/sec, the crack of 0.05 mm or more is not generated, and the display of the object color defined by JIS Z8729 is measured from the side of the acrylic resin layer before and after the stretching. In the case of the method L*a*b*, it is preferred to satisfy the following formula 2. Further, in the measurement at this time, the film thickness of the acrylic resin layer was in the range of 0.03 to 0.1 mm. However, the film thickness is the film thickness at the time of the measurement, and the thickness of the acrylic resin layer of the present invention is not limited.

L ^* 2-L ^* 1<3.5 (Formula 2)

However, L ^* 1 in the formula is the L ^* value of the layered body before stretching, and L ^* 2 is the L* value of the layered body after stretching.

By conforming to the above formula 2, even if the plurality of sheets using the acrylic resin layer are thermoformed, the effect of color brightness which is not changed before molding can be maintained. Further, the plurality of sheets of the present invention are not limited to the above conditions. That is, the above conditions are specific to the characteristics obtained in the case of the above-described conditions, and there are no conditions for the plurality of sheets of the invention of the present invention.

The JIS pencil hardness (thickness 75 μm) of the surface of the plurality of sheets of the present invention is preferably HB or harder, more preferably F or harder, further preferably H or harder. Since a plurality of sheets of a surface-hard acrylic resin layer are not easily damaged, they are suitable for use as a protective sheet in addition to the surface of a molded article requiring design.

Further, in the plurality of layers of the present invention, the metal and/or are provided. Or in the case of a layer composed of a metal oxide, for the metal, for example, aluminum, bismuth, magnesium, palladium, zinc, tin, nickel, silver, copper, gold, indium, stainless steel, chromium, titanium, etc. may be used. As the metal oxide, for example, alumina, zinc oxide, cerium oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, chromium oxide, cerium oxide, cobalt oxide, zirconium oxide, tin oxide, or the like can be used. Titanium oxide, iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, cerium oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, cerium oxide, and the like. These metals and metal oxides may be used alone or in combination of two or more. Among these, indium has excellent design properties, and it is preferable that the laminate is not easily lost in gloss even when it is formed by deep drawing. Further, since aluminum has excellent design properties and can be industrially inexpensive, it is particularly preferable in the case where deep drawing is not required. As a method of providing a layer of such a metal and/or metal oxide, a vacuum deposition method is usually used, and a method such as ion plating, sputtering, or CVD (Chemical Vapor Deposition) can be used. The thickness of the deposited film containing a metal and/or a metal oxide is generally about 5 to 100 nm. In the case of performing deep drawing after formation of a layer, it is preferably 5 to 250 nm.

The other layer used for the plurality of layers of the present invention is preferably a layer formed of a transparent resin such as a methacrylic resin from the viewpoint of designability of the plurality of layers. From the viewpoint that it is difficult to cause damage to the plurality of sheets and the design is durable, the outermost layer is preferably one having high surface hardness and weather resistance. The preferred layer of the outermost layer may, for example, be a layer containing a methacrylic resin or an acrylic resin layer formed using the acrylic thermoplastic resin of the present invention.

(three-dimensional molded body)

In the three-dimensional molding system of the present invention, a plurality of sheets are formed on the surface of a three-dimensional molded article. The three-dimensional molded article is not limited as long as it can thermoform the plurality of layers of the present invention, and is not limited, for example, a non-wood fiber substrate such as a thermoplastic resin, a thermosetting resin, a wood substrate or kenaf. The three-dimensional molded product may be of a plurality of materials, but the surface of the plurality of laminated sheets should be selected in consideration of the plurality of layers of the sheet.

The thermoplastic resin of the three-dimensional molded article used in the three-dimensional molded article of the present invention is not particularly limited, and examples thereof include a polycarbonate resin, a polyethylene terephthalate resin, a polyamide resin, and a polyethylene resin. Polypropylene resin, polystyrene resin, polyvinyl chloride resin, other (meth)acrylic resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, and the like. The other thermosetting resin may, for example, be an epoxy resin, a phenol resin, a melamine resin or the like.

The manufacturing method of the three-dimensional molded body of the present invention is not particularly limited. For example, the three-dimensional molded body of the present invention can be obtained by disposing the plurality of sheets of the present invention on the surface of the above-mentioned three-dimensional molded article, vacuum forming/pressure forming/compression molding under heating. The three-dimensional molding system of the present invention is excellent in surface smoothness, surface hardness, surface gloss, and the like by providing the plurality of sheets of the present invention on the outermost layer of the three-dimensional molded article. Moreover, in the case where printing is performed on the inner side surface of the acrylic resin layer of the plurality of layer sheets of the present invention, the pattern or the like can be clearly displayed. Further, in a plurality of sheets having a metal layer, specular gloss at the same level as that of the metal can be obtained.

Preferred method among the methods for producing a three-dimensional molded body of the present invention The method of laminating the plurality of sheets of the present invention directly or on at least one side and laminating to the surface of the ornamented article (stacking forming method); forming a vacuum or pressure forming by matching the shape of the ornament to be added The plurality of sheets of the present invention are placed in a mold for injection molding, followed by injection molding, and a method of performing decorative processing simultaneously with injection molding (embedded molding method); by vacuum or pressure in the cavity of the injection molding die The plurality of layers of the sheet of the present invention are formed by a blank, followed by injection molding, a method of performing decorative processing simultaneously with injection molding (in-mold forming method), and the like.

Among the methods for producing a three-dimensional molded article of the present invention, a further preferred method is generally referred to as a three-dimensional surface decorative molding (TOM forming, vacuum/pressure forming method). The 3-dimensional surface finish forming method heats the plurality of layers of the present invention under vacuum in a mold cavity and along the surface of the ornamented surface, simultaneously vacuum suction from below, and from above Pressure forming, and the method of adding ornaments to the jewelry. This method can form a more compact and complex shaped shaped body. Therefore, the plurality of layers of the present invention can be locally stretched more widely or greatly bent, and the effects of the present invention can be more significantly exerted.

The sheet to be inserted into the mold may be flat, or may be formed by preliminary molding such as vacuum forming or pressure forming to impart uneven shape.

The preliminary forming of the sheet may be carried out by another molding machine, or may be pre-formed in a mold of an injection molding machine which is used for injection molding at the same time. The latter method, that is, a method of preparing a molten resin on one side after preliminary preparation of a sheet is referred to as an insert molding method.

In the case where the plurality of sheets of the present invention are used for the sheet, it is preferred that the side of the acrylic resin layer of the plurality of sheets of the present invention is the outermost sheet. Surface (the substrate layer is disposed on the other sheet side of the integration). In this way, a three-dimensional molded body of an acrylic resin layer in which the plurality of layers of the present invention are provided on the outermost surface layer can be obtained.

According to the plurality of sheets of the present invention, it is possible to provide a multi-layer sheet for decoration and a three-dimensional molded body which are excellent in thermoformability and which can maintain excellent decorative properties after thermoforming. That is, according to the plurality of sheets of the present invention, it is possible to provide a sheet excellent in transparency, surface hardness, surface smoothness, and the like after thermoforming. In addition, whitening or cracking due to bending or stretching is small, that is, an acrylic resin layer excellent in whitening resistance and crack resistance, and a plurality of sheets having excellent glossiness or color depth can be provided. . Therefore, an excellent three-dimensional molded body can be obtained by densely laminating and laminating the plurality of layers of the present invention by a vacuum/vacuum on a more complicated three-dimensional three-dimensional structure, for example, a spherical or angular shape. According to the three-dimensional molded article of the present invention, it is excellent in thermoformability and excellent in decorative properties after thermoforming.

[Examples]

The present invention will be more specifically described below by way of examples and comparative examples. Further, the present invention is not limited by the following examples. Further, the present invention includes all aspects in which the technical characteristics of the characteristic values, the form, the manufacturing method, and the use described above are arbitrarily combined.

The measurement of the physical property values in the examples and the comparative examples was carried out by the following method.

[Weight average molecular weight (Mw) and molecular weight distribution]

The weight average molecular weight (Mw) and molecular weight distribution of the block copolymer (B) and the methacrylic resin (A) during and after the polymerization are The molecular weight was determined by GPC (gel permeation chromatography) in terms of polystyrene.

. Device: GPC device "HLC-8320" manufactured by TOSOH Corporation

. Separation column: "TSKguardcolum SuperHZ-H", "TSKgel HZM-M" and "TSKgel SuperHZ4000" manufactured by TOSOH Co., Ltd.

. Solvent: tetrahydrofuran

. Dissolution agent flow rate: 0.35mL/min

. Column temperature: 40 ° C

. Detection method: differential refractive index (RI)

[Structure ratio of each polymer block]

The composition ratio of each polymer block was determined by 1H-NMR (1H-nuclear magnetic resonance) measurement.

. Device: Nuclear Magnetic Resonance Device "JNM-LA400" manufactured by JEOL

. Heavy solvent: chloroform

[Method for Producing Acrylic Resin Layer (Single Layer Sheet)]

Using an arbitrary acrylic resin composition, a 1-mm extruder with a 50 mmΦ vent tube type was extruded at a discharge amount of 26 kg/hr, and a single-layer T-die having a width of 300 mm was extruded at a temperature of 260 ° C at 80 ° C. The metal mirror roll of 100 ° C was sandwiched and taken back at a speed of 8.2 m/min to form an acrylic resin layer (single layer sheet) comprising a single-layer sheet having a thickness of 200 μm.

[Method of Manufacturing Multiple Layer Sheets]

Using an arbitrary acrylic resin composition, a 30 mm Φ vented 1-axis extruder was used to press at a discharge amount of 5 kg/hr, and a thermoplastic resin for forming an arbitrary base material layer was used, using a 50 mm Φ snorkel. formula The 1-axis extruder was extruded at 23 kg/hr. Moreover, by laminating it using a hole multi-manifold mold having a width of 300 mm and pressing at a temperature of 260 ° C, it was sandwiched at a metal mirror roll of 80 ° C and 100 ° C and taken back at a speed of 5.9 m / min to A plurality of sheets having a total thickness of 300 μm and an acrylic resin layer of 75 μm were formed.

(glass transition temperature)

The resin obtained in each of the production examples was subjected to a differential scanning calorimeter (DSC-50 (product number), manufactured by Shimadzu Corporation) in accordance with JIS K7121. The temperature was raised to 230 ° C at a time, followed by cooling to room temperature, and then, at 10 ° C. The temperature was raised from room temperature to 230 ° C, and the DSC curve was measured. The intermediate point glass transition temperature obtained from the DSC curve measured at the second temperature rise is taken as the glass transition temperature of the present invention.

[Method for producing an elongated molded body]

A single-layer sheet-like acrylic resin layer and a plurality of layer sheets produced by the above-described film forming conditions were cut out to prepare a test piece of 150 mm × 50 mm, and mounted on an automatic plotter (Automatic plotter AG manufactured by Shimadzu Corporation) -5kN). Next, the Tg is higher with respect to any of the resin constituting the acrylic resin layer or the resin constituting the base material layer, and the temperature is 40 ° C, and the distance between the dynamometers at a height of 10 kN and the distance between the chucks is 110 mm. The elongation was extended to 200% at 300 mm/sec to produce an elongated molded body.

[Method for Measuring Haze of Acrylic Resin Layer]

The acrylic resin layer (single-layer sheet) produced by the above-described film forming conditions and the stretched molded body thereof were cut out to have a size of 30 mm × 30 mm as a test piece. The test piece was attached to a haze meter (manufactured by Murakami Color Technology Research Institute: HAZE METER HM-150), and the pre-extension was measured in accordance with JIS-K7136. Haze H1, haze H2 after stretching. 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.

(H2/d2)-(H1/d1)

[Method for Measuring Pencil Hardness of Multiple Layer Sheets]

The plurality of sheets produced by the above-described film forming conditions and the stretched molded body thereof were cut out to have a size of 30 mm × 30 mm, respectively, as test pieces. The test piece was attached to a pencil hardness tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.: pencil scratch coating hardness tester), and the pencil hardness was measured in accordance with JIS-K5600-5-4, and the pencil hardness before and after the extension was compared.

[Color measurement method of multiple layers of sheets]

A test piece was cut out by cutting a flat portion of the plurality of sheets produced by the film forming conditions described above and a flat portion of the stretched molded body by 30 mm × 30 mm. The test piece was attached to a spectrophotometer (Spectro Photometer SE5000, manufactured by Nippon Denshoku Industries Co., Ltd.) so that the transparent resin layer side became a measurement surface, and the C light source, the viewing angle of 10 degrees, and the reflection mode (diffusion reflection) were used in accordance with JIS Z8722. Under the conditions, the display method L ^* a ^* b ^* of the object color defined in JIS Z8729 (2004) was measured from the side of the acrylic resin layer, and the L ^* value before and after the extension was compared. The smaller the L ^* value, the darker color.

[Method of Manufacturing Three-Dimensional Molded Body]

An acrylic resin layer (single layer sheet) produced by the above-described film forming conditions and a plurality of sheets were cut out to have a size of 150 mm × 150 mm as a test piece. The test piece is attached to a vacuum forming machine (manufactured by Yamato Tooth Industries Co., Ltd., vacuum type I), and has a higher Tg with respect to any of the resin constituting the acrylic resin layer or the resin constituting the base material layer. Surface temperature system It is heated to a high temperature of 40 °C. Next, a three-dimensional molded body was molded by pressing a cubic mold having a width of 50 mm, a depth of 50 mm, and a height of 30 mm as shown in FIG. 2 and vacuum suctioning from below. Further, the plurality of sheets 1 were attached with a test piece so that the side of the acrylic resin layer 2 became the surface of the three-dimensional molded body. R in Fig. 2 represents the radius of curvature (mm).

[Method for Discrimination of Crack and Corner Whitening of Multi-Layer Sheet Three-dimensional Shaped Body]

The sides and the apex portions of the three-dimensional molded body produced by the above-described molding conditions were visually observed, and the degree of cracking and whitening which was visually confirmed to be 0.05 mm or more in width was determined. The discrimination criteria are shown below.

a: No whitening or cracking is visible on each side and each vertex.

b: Whitening is seen on each side and corners.

c: Whitening and cracking are seen on each side and corners.

[Method for Measuring Surface Gloss of Multi-Layer Sheet Three-dimensional Shaped Body]

The 60° gloss value was evaluated in accordance with JIS Z8741 using a gloss meter (GROSS CHECKER IG-331, manufactured by HORIBA) on any surface of the acrylic resin layer side of the plurality of layered three-dimensional molded articles produced by the above-mentioned molding conditions. ° gloss). The 60° gloss value was measured in 10 different fields on one side of the acrylic resin layer side of the plurality of decorative sheets, and the average value at 10 points was taken as the surface 60° gloss value of the plurality of decorative sheets.

Reference Example 1 [Synthesis of Block Copolymer (B-1)]

The inside was degassed, and 735 kg of dry toluene and 0.4 kg of hexamethyltriethylenetetramine were added at room temperature in a ³ m ³ reaction vessel with a nitrogen-filled brine-cooled casing and a glass lining of a stirrer. And 39.4 kg of a toluene solution containing 20 mol of isobutylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum, and further, 1.17 mol of a second butyllithium was added. 35.0 kg of methyl methacrylate was added thereto, and the mixture was reacted at room temperature for 1 hour. When the polymer contained in the reaction liquid was sampled and the weight average molecular weight (hereinafter referred to as Mw (b1-1)) was measured, it was 40,000. The methyl methacrylate polymer is obtained by further copolymerizing an acrylate block to form the methyl methacrylate polymer into a methacrylate polymer block (b1) (hereinafter, referred to as "methyl group". Methyl acrylate polymer block (b1-1)").

Next, the reaction liquid was set to -25 ° C, and a mixture of 24.5 kg of n-butyl acrylate and 10.5 kg of benzyl acrylate was dropped over 0.5 hours. After the dropping, the polymer contained in the reaction liquid was immediately sampled, and when the weight average molecular weight was measured, it was 80,000. Since the weight average molecular weight of the methyl methacrylate polymer block (b1-1) is 40,000, the acrylate polymer block (b2) comprising a copolymer of n-butyl acrylate and benzyl acrylate is determined. The weight average molecular weight (Mw (b2)) was 40,000.

Next, 35.0 kg of methyl methacrylate was added, the reaction solution was warmed to room temperature, and stirred for 8 hours to form a 2-pack methacrylate polymer block (b1) (hereinafter, referred to as "methyl group". Methyl acrylate polymer block (b1-2)"). Then, 4 kg of methanol was added to the reaction solution to terminate the polymerization, and then the reaction solution was poured into a large amount of methanol to form a block copolymer (B) of a triblock copolymer (hereinafter referred to as "block copolymer (B). -1)") was precipitated, filtered, and dried at 80 ° C for 1 hour at 1 torr (about 133 Pa). The weight average molecular weight Mw (B) of the obtained block copolymer (B-1) was 120,000. Due to the weight average molecular weight of the diblock copolymer At 80,000, it was determined that the weight average molecular weight (referred to as Mw (b1-2)) of the methyl methacrylate polymer block (b1-2) was 40,000. The weight average molecular weight Mw (b1-1) of the methyl methacrylate polymer block (b1-1) and the weight average molecular weight Mw of the methyl methacrylate polymer block (b1-2) (b1-2) ) is 40,000 together, so Mw(b1) is 40,000 and Mw(b1-total) is 80,000. The analysis results of the obtained block copolymer (B-1) are shown in Table 2. Further, in Table 2, the structural unit derived from methyl methacrylate was designated as "methyl methacrylate unit", and the structural unit derived from n-butyl acrylate was designated as "n-butyl acrylate unit", from acrylic acid. The structural unit of benzyl ester is indicated as "benzyl methacrylate unit".

Reference Example 2 to 4 [Synthesis of Block Copolymer (B-2) to (B-4)]

The conditions other than those shown in Table 1 were the same as in Reference Example 1, and the block copolymers (B-2) to (B-4) were synthesized. The analysis results of Mw (b1-1), Mw (b2) and the obtained block copolymers (B-2) to (B-6) obtained in Table 1 are shown in Table 2.

Reference Example 5 [Synthesis of Block Copolymer (B-5)]

The inside was degassed, and 735 kg of dry toluene and 0.4 kg of hexamethyltriethylenetetramine were added at room temperature in a ³ m ³ reaction vessel with a nitrogen-filled brine-cooled casing and a glass lining of a stirrer. And 39.4 kg of a toluene solution containing 20 mol of isobutylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum, and further, 1.17 mol of a second butyllithium was added. 35.0 kg of methyl methacrylate was added thereto, and the mixture was reacted at room temperature for 1 hour. When the polymer contained in the reaction liquid was sampled and the weight average molecular weight (hereinafter referred to as Mw (b1)) was measured, it was 40,000. The methyl methacrylate polymer is obtained by further copolymerizing an acrylate block to form the methyl methacrylate polymer into a methacrylate polymer block (b1) (hereinafter, referred to as "methyl group". Methyl acrylate polymer block (b1)").

Next, the reaction liquid was set to -25 ° C, and a mixture of 24.5 kg of n-butyl acrylate and 10.5 kg of benzyl acrylate was dropped over 0.5 hours. Then, 4 kg of methanol was added to the reaction solution to terminate the polymerization, and then the reaction solution was poured into a large amount of methanol to form a block copolymer (B) of a diblock copolymer (hereinafter referred to as "block copolymer (B). -5)") was precipitated, filtered, and dried at 80 ° C for 1 hour at 1 torr (about 133 Pa). The weight average molecular weight Mw (B) of the obtained block copolymer (B-5) was 80,000. Since the weight average molecular weight of the methyl methacrylate polymer block (b1) is 40,000, the weight average of the acrylate polymer block (b2) of the copolymer comprising n-butyl acrylate and benzyl acrylate is determined. The molecular weight (Mw (b2)) was 40,000.

Reference Example 6 [Synthesis of Block Copolymer (B-6)]

In addition to 567 kg of dry toluene, 0.1 kg of hexamethyltriethylenetetramine, 4.1 mol of isobutylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum, 8.3 kg A methacrylate polymer block (b1) was obtained in the same manner as in Reference Example 5 except that a toluene solution, 0.42 mol of a second butyllithium, and 33.3 kg of methyl methacrylate were used (hereinafter, referred to as "A". Methyl acrylate polymer block (b1)"). When the polymer contained in the reaction liquid was sampled and the weight average molecular weight (hereinafter referred to as Mw (b1-1)) was measured, it was 80,000.

Next, a block copolymer of a diblock copolymer was obtained by the same method as Reference Example 5 except that n-butyl acrylate was 24.8 kg, benzyl acrylate was 8.5 kg, and methanol was 4 kg. B) (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 a weight average molecular weight of the acrylate polymer block (b2) of a copolymer comprising n-butyl acrylate and benzyl acrylate. (Mw(b2)) is 80,000.

Reference Example 7 [Synthesis of Methacrylic Resin (A-1)]

0.1 parts by mass of a polymerization initiator (2,2'-azobis(2-methylpropionitrile) is added to a monomer mixture containing 95 parts by mass of methyl methacrylate and 5 parts by mass of methyl acrylate. The hydrogen transfer energy: 1%, 1 hour and a half period temperature: 83 ° C) and 0.77 parts by mass of a chain transfer agent (n-octyl mercaptan) were 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 a suspension dispersant were mixed to obtain a mixed solution. 420 parts by mass of the mixed liquid and 210 parts by mass of the raw material liquid were fed into the pressure-resistant polymerization tank, and the temperature was 70 ° C while stirring in a nitrogen atmosphere. Start the polymerization. After the start of the polymerization reaction, the temperature was raised to 90 ° C over 3 hours, followed by stirring for 1 hour to obtain a liquid in which the bead copolymer was dispersed. Further, a plurality of polymers were adhered to the wall surface of the polymerization tank or the stirring blade, but no foaming occurred, and the polymerization reaction was smoothly carried out.

The obtained copolymer dispersion was washed with an appropriate amount of ion-exchanged water, and the bead-like copolymer was taken out by a bucket centrifuge and dried by a hot air dryer at 80 ° C for 12 hours to obtain bead-like methacrylic acid. Resin (A) (hereinafter referred to as "methacrylic resin (A-1)").

The obtained 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 (A-2) having a Mw (A) of 80,000, a molecular weight distribution of 1.8, and a glass transition temperature of 115 ° C was obtained 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.

Reference Example 9 [Synthesis of methacrylic resin (A-3)]

A glass transition temperature of Mw (A) of 130,000 and a molecular weight distribution of 1.8 of 115 ° C methacrylic resin (A-3) was obtained in the same manner as in Reference Example 5 except that the amount of the chain transfer agent was changed to 0.16 parts by mass.

(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, pellets of the acrylic resin composition were produced by extrusion and cutting. The glass transition temperature was 115 °C.

Using the obtained acrylic resin composition to form a film by the aforementioned method A transparent resin single-layer sheet having a thickness of 200 μm was used to extend the obtained transparent resin single-layer sheet by the above-described method, and the haze before and after stretching was measured by the aforementioned method. In addition, the obtained methacrylic resin composition and ABS resin "330ABS" (Tg: 100 ° C) manufactured by Techno Polymer Co., Ltd., which is black-colored and colored with carbon black, were used to prepare a film having a total thickness of 300 μm and an acrylic resin. A plurality of layers of 75 μm co-extruded sheets were stretched, and the obtained plurality of sheets were stretched in the aforementioned manner, and the pencil hardness and the color measurement value L values before and after the extension were measured by the aforementioned methods. Moreover, the surface glossiness (%) of the obtained multi-layer sheet three-dimensional molded body was measured by vacuum-molding a plurality of layers of the sheet by the above-described method, and the presence or absence of cracking 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, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets, and a plurality of sheet-like three-dimensional molded bodies, 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, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets, and a plurality of sheet-like three-dimensional molded bodies, and the respective physical properties were measured. The results are shown in Table 3.

(Example 4)

30 parts by mass of the block copolymer (B-5) and 70 parts by mass of the methacrylic resin (A-2) were melt-kneaded at 230 ° C by a twin-screw extruder. Then, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets, and a plurality of sheet-like three-dimensional molded bodies, and the respective physical properties were measured. The results are shown in Table 3.

(Example 5)

20 parts by mass of the block copolymer (B-5) and 80 parts by mass of the methacrylic resin (A-3) were melt-kneaded at 230 ° C by a twin-screw extruder. Then, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets, and a plurality of sheet-like three-dimensional molded bodies, and the respective physical properties were measured. The results are shown in Table 3.

(Example 6)

20 parts by mass of the block copolymer (B-6) and 80 parts by mass of the methacrylic resin (A-3) were melt-kneaded at 230 ° C by a twin-screw extruder. Then, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets, and a plurality of sheet-like three-dimensional molded bodies, and the respective physical properties were measured. The results are shown in Table 3.

(Example 7)

20 parts by mass of the block copolymer (B-5) and 80 parts by mass of the methacrylic resin (A-2) were melt-kneaded at 230 ° C by a twin-screw extruder. Then, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets, and a plurality of sheet-like three-dimensional molded bodies, and the respective physical properties were measured. The results are shown in Table 3.

(Example 8)

20 parts by mass of the block copolymer (B-5) and 80 parts by mass of the methacrylic resin (A-2) were melt-kneaded at 230 ° C by a twin-screw extruder. Then, pellets of the acrylic resin composition were produced by extrusion and cutting. Further, 98 parts by mass of a polycarbonate "Caliber 301-8" (Tg: 150 degrees) manufactured by Susedron Polycarbonate Co., Ltd., and 1.0 part by mass as a black pigment, were melt-kneaded at 250 ° C by a twin-screw extruder. "Mitsubishi Carbon Black" manufactured by Mitsubishi Chemical Corporation, "MACROLEX Green G" manufactured by LANXESS Co., Ltd., 0.3 parts by mass of black dye, and "MACROLEX Green 5B" manufactured by LANXESS Co., Ltd., 0.7 parts by mass. Then, pellets of a black polycarbonate resin composition were produced by extrusion and cutting. Using the pellets, a plurality of sheets and a plurality of sheet-shaped three-dimensionally formed bodies were co-extruded with a transparent resin single-layer sheet 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 the block copolymer (B-5) and 80 parts by mass of the methacrylic resin (A-2) were melt-kneaded at 230 ° C by a twin-screw extruder. Then, pellets of the acrylic resin composition were produced by extrusion and cutting.

Further, 49 parts by mass of a crosslinked rubber particle-blending resin "Parapet GR-100" manufactured by Kuraray Co., Ltd. and 49 parts by mass of methacrylic resin (A-3) were melt-kneaded at 230 ° C by a twin-screw extruder. "Mitsubishi carbon black" manufactured by Mitsubishi Chemical Corporation as 1.0 part by mass of black pigment "MACROLEX Green G" manufactured by LANXESS Co., Ltd., which is 0.3 parts by mass of black dye, and "MACROLEX Green 5B" manufactured by LANXESS Co., Ltd., 0.7 parts by mass. Then, pellets of a black acrylic resin composition were produced by extrusion and cutting. The Tg is 108 °C.

Using the pellets, a plurality of sheets and a plurality of sheet-shaped three-dimensionally formed bodies were co-extruded with a transparent resin single-layer sheet in the same manner as in Example 1, and the respective physical properties were measured. The results are shown in Table 3.

(Embodiment 10)

Each of the physical properties was measured 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. The results are shown in Table 3.

(Comparative Example 1)

In the block copolymer (B), 20 parts by mass of a crosslinked rubber particle-blended resin "Parapet GR-100" manufactured by Kuraray Co., Ltd., and 80 parts by mass were melt-blended at 230 ° C by a twin-screw extruder. Methacrylic resin (A-2). Then, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets and a plurality of sheet-like three-dimensional molded bodies, and the respective physical properties were measured. The results are shown in Table 4.

(Comparative Example 2)

In the block copolymer (B), 30 parts by mass of a crosslinked rubber particle-blending resin "Parapet EB-SN" manufactured by Kuraray Co., Ltd., and 70 parts by mass were melt-blended at 230 ° C by a twin-screw extruder. Methacrylic resin (A-2). Then, by extrusion and cutting, an acrylic resin composition is produced. Pellet.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets and a plurality of sheet-like three-dimensional molded bodies, 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, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets and a plurality of sheet-like three-dimensional molded bodies, 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, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets and a plurality of sheet-like three-dimensional molded bodies, 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, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets and a plurality of sheet-like three-dimensional molded bodies, 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, pellets of the acrylic resin composition were produced by extrusion and cutting.

Using the pellets, in the same manner as in Example 1, a transparent resin single-layer sheet was co-extruded to form a plurality of sheets and a plurality of sheet-like three-dimensional molded bodies, and the respective physical properties were measured. The results are shown in Table 4.

From these results, it is known to meet: (1) 0.3 ≦ Mw (A) / Mw (b1-total) ≦ 4.0

(2) 30,000 ≦ Mw (b2-total) ≦ 140,000

In addition, 100 parts by mass of the methacrylic resin (A) and the block copolymer (B) are used, and the methacrylic resin (A) is used in an amount of 10 to 99 parts by mass, and the block copolymer (B) is used. The multi-layer sheet for decoration produced by 90 to 1 part by mass of the blended acrylic resin composition exhibits excellent decorative properties. In other words, it is known that when a complex three-dimensional three-dimensional shape in which the elongation or the bending rate of the partial portion is likely to be high is formed, cracking or whitening at the time of molding is suppressed, and excellent surface smoothness, surface hardness, and a sense of depth of color can be maintained.

[Industrial availability]

The multi-layer sheet or the three-dimensional molded article of the present invention exhibits excellent handleability, good surface smoothness, and high surface hardness, and can be used for various molded articles requiring a desired molded article or a high optical property. Specifically, it is suitable for kanban parts such as advertising towers, standing kanbans, side kanbans, crossbeams, roof kanbans, etc.; display parts of display cabinets, partitions, store displays, etc.; fluorescent lamp covers, atmosphere lighting covers, light transmission Lighting parts such as hoods, illuminated ceilings, illuminating walls, chandeliers, etc.; interior fittings for furniture, ornaments, mirrors, etc.; doors, semi-circular roofs, safety glazing, next door, stairway panels, balcony clusters, leisure Building parts such as roofs of buildings; aircraft windshields, sun visors for pilots, motorcycles, motorboat windshields, bus visors, side visors for automobiles, rear visors, front fenders, headlights, Automotive exterior components such as automotive interior components, bumpers or molds, etc. Conveyor-related parts; electronic image parts for audio image with brand name, stereo casing, TV protective cover, vending machine, mobile phone, personal computer, etc.; medical machine parts such as incubator and X-ray machine parts; mechanical casing, Machine-related parts such as instrument casings, experimental devices, rulers, dials, observation windows, etc.; traffic-related parts such as road signs, guide plates, curved mirrors, soundproof walls, etc.; other, greenhouses, large sinks, tank sinks, bathroom components, clocks Surface decorative film and protective film and wallpaper for panels, bathtubs, sanitary equipment, table mats, game parts, toys, masks for face protection during welding, marking films, liquid crystal protective films, light guiding films, Fresnel lenses Optically related parts such as lenticular lenses, front films of various displays, and diffusion films.

1‧‧‧multilayer sheet

2‧‧‧Acrylic resin layer

3‧‧‧Substrate layer

Claims (11)

A multi-layer sheet for decoration, comprising a multi-layer sheet for decoration comprising a laminate of an acrylic resin layer and a base layer, wherein the acrylic resin layer contains a methacrylic resin (A) and a block. The acrylic resin composition (B) is formed of an acrylic resin composition of the copolymer (B), and the methacrylic resin (A) has 80% by mass or more of a structural unit derived from methyl methacrylate, and the block copolymer (B) is in one molecule. Each of the methacrylate polymer block (b1) containing one or more structural units derived from methacrylate, and the acrylate polymer block (b2) containing a structural unit derived from an acrylate, Further, the methacrylate polymer block (b1) is contained in a proportion of 10 to 80% by mass, and the acrylate polymer block (b2) is contained in a ratio of 90 to 20% by mass based on the methacrylic resin (A). 100 parts by mass of the block copolymer (B), 10 to 99 parts by mass of the methacrylic resin (A), and 90 to 1 part by mass of the block copolymer (B), and a methacrylic resin The weight average molecular weight of (A) is set to Mw (A) and one of the block copolymer (B) The weight average molecular weight of the methacrylate polymer block (b1) in the molecule is set to Mw (b1-total), and the acrylate polymer block in one molecule contained in the block copolymer (B) (b2) When the weight average molecular weight is Mw (b2-total), it satisfies: (1) 0.3 ≦ Mw (A) / Mw (b1-total) ≦ 4.0 (2) 30,000 ≦ Mw (b2-total) ≦ 140,000. The plurality of sheets of the decoration of claim 1 wherein the film of the laminate is The thickness of the acrylic resin layer is 0.03 to 0.25 mm in a range of 0.05 to 0.5 mm. The plurality of sheets for the decoration of claim 1 or 2, wherein the glass-like temperature of the resin having the thickness of d1 is 40 ° C with respect to the glass transition temperature 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, cracking of 0.05 mm or more does not occur, and the following (Formula 1) is satisfied: (H2/d2)-(H1/d1)< 1.20 (Formula 1) (H1 in the formula is a haze value of the acrylic resin layer before stretching, d1 is a thickness of the acrylic resin layer before stretching of 0.2 mm, and H2 is the acrylic resin layer after stretching) The haze value, d2 is the thickness of the acrylic resin layer after stretching). The plurality of sheets for the decoration of claim 1 or 2, wherein at least one side of the substrate layer satisfies at least one of (a) colored, and (b) provided with a pattern, by extrusion molding The base material layer and the acrylic resin layer are integrally laminated. The plurality of sheets of the decorative item according to claim 1 or 2, wherein at least one side of the substrate layer satisfies: (a) colored, and (b) at least one of the patterns, used in the range of 0.03 to 0.1 mm The acrylic resin layer has a glass transition temperature of a resin having a high glass transition temperature among the resin constituting the base layer and the resin constituting the acrylic resin layer, and is 300 mm/at a high temperature of 40 ° C. When the speed of the sec is 200%, the cracking of 0.05 mm or more is not caused, and the display method L*a*b* of the object color defined by JIS Z8729 is measured from the side of the acrylic resin layer before and after the stretching. The following formula (Equation 2) is satisfied: L ^* 2-L ^* 1 < 3.5 (Formula 2) (where L ^* 1 in the formula is the L* value of the layered body before stretching, and L ^* 2 is the layered layer after stretching L* value of the body). A plurality of sheets for the decoration of claim 1 or 2, wherein a layer formed of an acrylonitrile-butadiene-styrene copolymer resin is used as the aforementioned substrate layer. A plurality of sheets for the decoration of claim 1 or 2, wherein a layer formed of an acrylic resin layer is used as the substrate layer. The plurality of sheets for the decoration of claim 1 or 2, wherein a layer formed of a polycarbonate resin is used as the base material layer. The multi-layer sheet for decoration of claim 1 or 2, wherein the 60° gloss of JIS Z8741 is 80 or more and 95 or less in the main surface of the acrylic resin layer which is not opposed to the base material layer. A multi-layer sheet for the decoration of claim 1 or 2 is used for interior and exterior decoration of a car. A three-dimensional molded body comprising the plurality of layers for decorative of any one of claims 1 to 10.