JP2012213912A - Acrylic multilayer body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic multilayer body having excellent dimension stability, thermal shrinkage resistance, impact resistance, crack resistance and flexibility, and usable in a roll-like form without causing inter-layer separation nor cracking of a film, and an acrylic multilayer body excelling in surface scratch resistance and surface smoothness.SOLUTION: This acrylic multilayer body is selected from a multilayer body including an acrylic resin composition layer (I) having tensile elasticity of 1-1,000 MPa, and resin composition layers (II) where a ratio of tensile elasticity to that of the acrylic resin composition layer (I) is 2 to 500, and having one of the acrylic resin composition layers (II) arranged on each of both the principal surfaces of the acrylic resin composition layer (I), and a multilayer body including one acrylic resin composition layer (I) on each of both the principal surfaces of the resin composition layer (II).

Description

  The present invention relates to an acrylic multilayer.

A methacrylic resin-based sheet or film made of methacrylic resin is excellent in transparency, light resistance, and surface scratch resistance, and has been widely used for roofing materials, automotive lamp covers, signboards, light guide plates for display devices, etc. ing. In addition, polycarbonate resin sheets or films made of polycarbonate resin or the like are used as various optical members by taking advantage of excellent transparency and low water absorption. However, methacrylic resin-based and polycarbonate resin-based sheets or films are inferior in impact resistance and flexibility, and thus have a drawback that the sheet may break or cannot be rolled.
On the other hand, as a sheet or film excellent in transparency, impact resistance and flexibility, an acrylic block copolymer or a resin composition containing the acrylic block copolymer, an acrylic resin composition containing acrylic rubber particles, or a plasticizer and a methacrylic resin Sheets or films made of an acrylic resin composition such as an acrylic resin composition containing bismuth are known (Patent Documents 1 to 8). However, these sheets or films have a problem that they are poor in surface scratch resistance and dimensional stability. Moreover, the said patent document is disclosing that these sheets or films can be laminated | stacked on the base material which consists of another polymer, a fabric, etc. However, these laminates may cause delamination and have room for improvement.

Japanese Patent Application Laid-Open No. 11-349782 JP 2007-182585 A JP 2009-125985 A International Publication No. 2010/055798 Pamphlet International Publication No. 2009/054553 Pamphlet JP 2008-93921 A JP 2002-291353 A JP 2009-91531 A JP 2005-515281 A JP-A-11-335432 JP 11-292940 A

Macromol. Chem. Phys. 2000, 201, p. 1108 to 1114

  An object of the present invention is an acrylic type which has excellent dimensional stability, heat shrinkage resistance, impact resistance, crack resistance and flexibility, and can be used as a roll without delamination or film cracking. It is to provide a multilayer body. Another object of the present invention is to provide an acrylic multilayer having excellent surface scratch resistance and surface smoothness in addition to the above.

That is,
[1] A resin composition having a tensile modulus ratio of 2 or more and 500 or less between the acrylic resin composition layer (I) having a tensile modulus of 1-1000 MPa and the acrylic resin composition layer (I). Layer (II), and a multilayer body including one resin composition layer (II) on each side of the main surface of the acrylic resin composition layer (I) and the main surface of the resin composition layer (II) An acrylic multilayer selected from a multilayer having one acrylic resin composition layer (I) on both sides;
[2] The acrylic multilayer of [1], wherein the acrylic resin composition layer (I) is composed of either an acrylic block copolymer or a resin composition containing the acrylic block copolymer;
[3] The acrylic multilayer of [1] or [2], wherein the resin composition layer (II) is made of a resin composition selected from a methacrylic ester polymer composition or a polycarbonate resin composition.
[4] Any of [1] to [3], wherein the difference in refractive index between the resin compositions constituting the acrylic resin composition layer (I) and the resin composition layer (II) is 0.05 or less. Acrylic multilayer.
[5] The total thickness ratio (layer ratio) of the acrylic resin composition layer (I) relative to the thickness of the entire acrylic multilayer is in the range of 0.5 to less than 0.95 [1] to [4] ] The acrylic multilayer body in any one of.
[6] The total thickness ratio (layer ratio) of the acrylic resin composition layer (I) to the thickness of the entire acrylic multilayer body is in the range of 0.05 or more and less than 0.5 [1] to [4 ] The acrylic multilayer body in any one of.
[7] One or more acrylic resin composition layers (I) are provided on both sides of the main surface of the resin composition layer (II), and the outermost layer of the acrylic multilayer is the acrylic resin composition layer (I). [1] to [6] of any one of the acrylic multilayers;
[8] One or more resin composition layers (II) are provided on both sides of the main surface of the acrylic resin composition layer (I), and the outermost layer of the acrylic multilayer is the resin composition layer (II). [1]-[6] acrylic multilayers;
About.

  According to the present invention, an acrylic multilayer having excellent dimensional stability, heat shrinkage resistance, impact resistance, crack resistance and flexibility, and can be used as a roll without delamination or film cracking. Can provide the body. Furthermore, an acrylic multilayer having excellent surface scratch resistance and surface smoothness can be provided.

Hereinafter, the present invention will be described in detail.
The acrylic multilayer of the present invention comprises an acrylic resin composition layer (I) and a resin composition layer (II), and a resin composition on both surfaces of the main surface of the acrylic resin composition layer (I). The multilayer body is selected from a multilayer body including one layer (II) and a multilayer body including one acrylic resin composition layer (I) on both surfaces of the main surface of the resin composition layer (II).

The tensile elastic modulus of the acrylic resin composition layer (I) used in the present invention is 1-1000 MPa, preferably 50-500 MPa. When the tensile modulus is smaller than the above range, the resulting acrylic multilayer has insufficient mechanical strength such as tensile strength, resulting in insufficient impact resistance. In addition, the acrylic resin composition layer (I) cannot retain its shape, and there is a problem that the acrylic resin composition layer (I) protrudes from the end face of the acrylic multilayer. When the tensile elastic modulus is larger than the above range, the acrylic multilayer of the present invention has insufficient flexibility and is inferior in impact resistance. Therefore, when a product is used as a roll, cracks and curling occur.
Here, the tensile elastic modulus of the acrylic resin composition layer (I) is a value measured at 23 ° C. under a tensile speed of 300 mm / min in accordance with the method described in ISO527-3.

  The acrylic resin composition constituting the acrylic resin composition layer (I) contains an acrylic block copolymer, an acrylic graft copolymer, an acrylic block copolymer, or an acrylic graft copolymer. Examples thereof include a composition, a composition containing acrylic rubber particles, and a composition of a methacrylic acid ester polymer and a plasticizer.

  The acrylic block copolymer and the acrylic graft copolymer are polymer blocks having a glass transition temperature of less than 25 ° C. made of a (meth) acrylic acid ester polymer (hereinafter sometimes referred to as a soft block). And a polymer block having a glass transition temperature of 25 ° C. or higher (hereinafter sometimes referred to as a hard block).

  The mass ratio of the hard block and the soft block of the acrylic block copolymer and acrylic graft copolymer is not particularly limited, and the tensile modulus of the acrylic resin composition layer (I) used in the present invention is the above. However, usually, soft block / hard block = 15/80 to 85/15 is preferable, 25/75 to 75/25 is more preferable, and 30/70 to 60/40 is further preferable. When the ratio of the soft block / soft block is smaller than the above range, the flexibility of the acrylic resin composition layer (I) tends to be insufficient. When the ratio of the soft block / soft block of the hard block is larger than the above range, it becomes difficult to form an acrylic block copolymer, an acrylic graft copolymer, and a resin composition containing them into a pellet shape. , Tend to be inferior in handleability.

  As the polymer that forms the soft block, a (meth) acrylic acid ester-based polymer having a glass transition temperature of less than 25 ° C. can be selected, and methacrylic acid is a specific example of the monomer constituting the polymer. n-butyl, 2-ethylhexyl methacrylate, dodecyl methacrylate, benzyl methacrylate, phenylethyl methacrylate, 2-methoxyethyl methacrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylic acid Examples include 2-ethylhexyl, dodecyl acrylate, benzyl acrylate, phenylethyl acrylate, 2-methoxyethyl acrylate, and the like. The said (meth) acrylic acid ester may be used individually by 1 type, and may mix and use 2 or more types.

  As the polymer that forms the hard block, a (meth) acrylic acid ester-based polymer having a glass transition temperature of less than 25 ° C. can be selected, and methacrylic acid is a specific example of the monomer constituting the polymer. Examples include methyl, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and isobornyl acrylate. The said methacrylic acid ester or acrylic acid ester may be used individually by 1 type, and may mix and use 2 or more types.

  The polymer that forms the soft block may contain a structural unit derived from the (meth) acrylic acid ester that constitutes the polymer that forms the hard block, as long as the properties of the soft block are not impaired. The polymer that forms the hard block may contain a structural unit derived from a (meth) acrylic acid ester that constitutes the polymer that forms the soft block as long as the properties of the hard block are not impaired. .

  In addition to the (meth) acrylic acid ester, other monomers may be copolymerized as long as the properties of the soft block and the hard block are not impaired. Examples of the copolymerizable monomer include methacrylic acid; methacrylic acid ester having a reactive group such as glycidyl methacrylate, allyl methacrylate, 2-hydroxyethyl methacrylate, trimethoxysilylpropyl methacrylate, and N-isopropylamide methacrylate. Acrylic acid; glycidyl acrylate, allyl acrylate, 2-hydroxyethyl acrylate, trimethoxysilylpropyl acrylate, acrylic acid ester having a reactive group such as N-isopropylamide; styrene, α-methylstyrene, p -Aromatic vinyl compounds such as methylstyrene; nitriles such as acrylonitrile and methacrylonitrile; vinyl acetate; olefins such as ethylene, propylene and 1-butene; vinyl chloride; vinylidene chloride; Vinylidene; butadiene, a conjugated diene such as isoprene; and maleic anhydride and the like.

  The weight average molecular weight of the acrylic block copolymer and the acrylic graft copolymer is preferably 10,000 to 500,000 from the viewpoint of improving the melt extrusion moldability of the acrylic multilayer of the present invention. 30,000 to 150,000 are more preferable. If the weight average molecular weight of the acrylic block copolymer and acrylic graft copolymer is less than 10,000, sufficient melt tension cannot be maintained in melt extrusion molding, resulting in reduced thickness accuracy and good acrylic copolymer. It is difficult to obtain a layered body. On the other hand, if the viscosity is larger than 500,000, the viscosity of the molten resin becomes high, and unevenness due to unmelted material (high molecular weight) is generated on the surface of the acrylic multilayer obtained by melt extrusion molding. There exists a tendency for a system multilayer to be hard to be obtained. The molecular weight distribution (ratio of weight average molecular weight / number average molecular weight) is preferably from 1.01 to 1.50, from the viewpoint of improving the transparency of the acrylic multilayer of the present invention. 35 is more preferable. By taking such a range, the content of the unmelted material which is the cause of the occurrence of the irregularities in the acrylic multilayer of the present invention can be made extremely small.

  Examples of the acrylic block copolymer include soft block-hard block diblock copolymer, hard block-soft block-hard block triblock copolymer, hard block-soft block-hard block-soft. Examples include block tetrablock copolymers and their star copolymers. Among these, a triblock copolymer or a mixture of a triblock copolymer and a diblock copolymer is more preferable.

  Examples of the block copolymerization method include a method using a polymer having a terminal reactive group as a polymerization initiator, a polymerization terminator, and a chain transfer agent, and living polymerization, and living polymerization is more preferable. Living polymerization includes living radical polymerization, living cation polymerization, and living anion polymerization, but living radical polymerization and living anion polymerization are more preferable, from the viewpoint of transparency of the resulting acrylic block copolymer. The living anionic polymerization method is most preferred. Examples of the living radical polymerization method include a control radical polymerization method (CRP) using a stable nitroxy group compound as in Patent Document 9 and an atom transfer radical polymerization method (ATRP) as in Non-Patent Document 1. Examples of the living anion polymerization method include a polymerization method using an organoaluminum compound as described in Patent Document 10, a polymerization method using an organic samarium complex, and a polymerization method using an alkoxy lithium such as lithium chloride and lithium methoxyethoxide. . Among the above polymerization methods, the atom transfer radical polymerization method and the living anion polymerization method using an organoaluminum compound are preferable, the molecular weight and molecular weight distribution are excellently controlled, and the content of the acrylic block copolymer other than the target block structure The living anionic polymerization method using an organoaluminum compound is more preferable because the structure is more controlled, the transparency and the melt fluidity are excellent, and the amount of unreacted monomers and oligomer components are small.

  Examples of the graft copolymerization method include a method in which a polymer having a polymerization reactive group at a terminal and forming a hard block is used as a macromonomer and copolymerized with a monomer forming a soft block. Polymerization of the macromonomer includes radical polymerization, anionic polymerization, and cationic polymerization. Moreover, the method of polymerizing the monomer which forms a hard block from the side chain of the polymer which forms a soft block is mentioned.

  Although the said acrylic resin composition may consist only of the said acrylic block copolymer and an acrylic graft copolymer, the resin composition containing either or both of these may be sufficient. In that case, the ratio of the total mass of the acrylic block copolymer and the acrylic graft copolymer is preferably 15 to 100 mass%, more preferably 30 to 100 mass%, and more preferably 50 to 100 mass% in the acrylic resin composition. Is more preferable. In addition to the acrylic block copolymer and acrylic graft copolymer, the components that may be included include other polymers, polymer processing aids, colorants, tackifying resins, plasticizers, fillers, etc. Can be mentioned.

  Examples of other polymers include methacrylic acid ester polymers. Methacrylic acid ester polymers are methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate. , Methacrylate polymer having no functional group such as benzyl methacrylate, phenylethyl methacrylate and isobornyl methacrylate. In addition to the methacrylic acid ester, methacrylic acid having a functional group such as 2-methoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, 2-hydroxyethyl methacrylate, trimethoxysilylpropyl methacrylate, N-isopropylamide methacrylate. Acid ester; acrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, acrylic acid Benzyl, phenylethyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate, allyl acrylate, 2-hydroxyethyl acrylate, trimethoxy acrylate Acrylic acid esters such as propylpropyl and acrylic acid N-isopropylamide; aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene; nitriles such as acrylonitrile and methacrylonitrile; vinyl acetate; ethylene, propylene, 1- Olefins such as butene; vinyl chloride; vinylidene chloride; vinyl fluoride; vinylidene fluoride; conjugated dienes such as butadiene and isoprene; and maleic anhydride may be copolymerized in a small amount.

  When the resin composition containing either or both of the acrylic block copolymer and the acrylic graft copolymer contains a methacrylic ester polymer, the resin composition of the methacrylic ester polymer The content of is preferably 85% by mass or less, more preferably 70% by mass or less, and further preferably 50% by mass or less.

  As the acrylic resin composition layer (I) used in the present invention, a composition containing acrylic rubber particles may be used. Acrylic rubber particles are particles having an elastic polymer mainly composed of an acrylate ester, and have a single-layer structure composed only of the elastic polymer, a multi-layer structure having the elastic polymer layer, and the like. . As the acrylic rubber particles, an elastic polymer mainly composed of an acrylate ester has a carbon-carbon double bond, and may be post-crosslinked. This elastic polymer mainly composed of an acrylate ester is typically a co-polymer of 40% by mass or more and less than 99.99% by mass of an acrylate ester and 0.01% by mass or more and less than 60% by mass of another monomer. It is a polymer. The polyfunctional monomer may be included in the range of 49.99% by mass or less. Here, “mainly composed of an acrylate ester” means that among all the components, the acrylate ester is the component having the largest mass ratio.

  As said acrylic acid ester, acrylic acid alkyl ester is preferable, 1-8 are preferable and, as for carbon number of the alkyl group of acrylic acid alkyl ester, 4-8 are more preferable. Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. Examples of the other monomers include methacrylic acid esters such as methyl methacrylate; conjugated dienes such as butadiene and isoprene; aromatic vinyls such as styrene; and nitriles such as acrylonitrile. Moreover, as a polyfunctional monomer, (meth) acrylic acid ester of polyhydric alcohols such as ethylene glycol di (meth) acrylate and butanediol di (meth) acrylate; Meth) acrylic acid alkenyl ester; aromatic divinyl compounds such as divinylbenzene.

  When the acrylic rubber particles have a multilayer structure, the acrylic rubber particles may have a two-layer structure or a three-layer structure or more. In the case of a two-layer structure, an example is one in which an elastic polymer mainly composed of an acrylate ester is used as an inner layer and a polymer mainly composed of a methacrylic ester is used as an outer layer. In the case of a three-layer structure, a polymer mainly composed of acrylic acid ester and methacrylic acid ester is an inner layer, an elastic polymer mainly composed of acrylic acid ester is an intermediate layer, and a polymer mainly composed of methacrylic acid ester What is used as an outer layer is mentioned. From the viewpoint of the flexibility and film-forming property of the resulting acrylic resin composition layer (I), the acrylic rubber particles preferably have a single-layer structure or a two-layer structure. The rubber particles preferably have a structure of three or more layers.

  Among the acrylic rubber particles, the acrylic rubber particles having a single layer structure or a multilayer structure are prepared by, for example, dissolving an acrylic ester, other monomers, and, if necessary, a polyfunctional polymer by a known method. It can be obtained by polymerization, emulsion polymerization, suspension polymerization or bulk polymerization. Among these, in the case of emulsion polymerization, the polymerization temperature is usually in the range of 10 to 100 ° C. Examples of the emulsifier used include alkali metal salts of aliphatic carboxylic acids such as sodium oleate, sodium laurate, and sodium stearate; sulfate esters of aliphatic alcohols such as sodium lauryl sulfate; rosinates such as potassium rosinate. An alkyl allyl sulfonic acid such as dodecylbenzene sulfonic acid; As a polymerization initiator used in emulsion polymerization, a radical polymerization initiator is generally used. As the radical polymerization initiator, for example, a peroxide such as persulfate, azobisisobutyronitrile, benzoyl peroxide and the like can be used alone. Moreover, the redox initiator by the combination of organic hydroperoxides, such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, and reducing agents, such as a transition metal salt, can also be used. For acrylic rubber particles having a multilayer structure of two or more layers, a predetermined amount of a predetermined monomer mixture is sequentially polymerized in accordance with a known emulsion polymerization method so that a predetermined polymer layer is externally exposed from the center of the particle. It is obtained by forming in a stepwise manner (for example, see Patent Document 11).

  The elastic polymer mainly composed of the acrylate ester has a carbon-carbon double bond, and the post-crosslinked acrylic rubber particles are obtained by dissolving the elastic polymer in a monomer and crosslinking during polymerization. The elastic polymer can be produced by a method of crosslinking during melt kneading.

When the elastic polymer mainly composed of the acrylate ester has a carbon-carbon double bond, the polymer is, for example, an acrylate ester, other monomers, and a polyfunctional polymer as required. It can be obtained by radical polymerization or anionic polymerization. The other monomer is preferably a polyfunctional monomer having two or more double bonds in order to contain a carbon-carbon double bond. For example, (meth) acrylic acid ester of polyhydric alcohol described above, ( Examples include meth) acrylic acid alkenyl esters, aromatic divinyl compounds, and conjugated dienes. Among them, conjugated dienes are preferable.
As a polymerization method, anionic polymerization is preferable because a carbon-carbon double bond can be more efficiently contained. The form of copolymerization may be any of random copolymerization, block copolymerization, and graft copolymerization, but block copolymerization is preferred.

  In the present invention, when the acrylic resin composition constituting the acrylic resin composition layer (I) contains acrylic rubber particles, the content is determined by the tensile elastic modulus of the acrylic resin composition layer (I). Although it will not specifically limit if it becomes in the range prescribed | regulated by this invention, Typically, 30 mass%-100 mass% are preferable, 40 mass%-100 mass% are more preferable, 50 mass%-100 mass% are further preferable. If the content of the acrylic rubber particles is within the above range, the flexibility of the acrylic resin composition layer (I) and the melt fluidity, workability, and tensile strength at break of the acrylic resin composition can be achieved.

  The composition containing the acrylic rubber particles may further contain a methacrylic acid ester polymer. As a blending method in that case, a method of blending acrylic rubber particles with a methacrylic acid ester polymer, or a method of blending acrylic rubber particles having a polymerization reactive group (or a polymer serving as a precursor thereof) with a methacrylic acid ester type. Examples thereof include a method obtained by mixing with a monomer and crosslinking and finely dispersing a rubber component simultaneously with polymerization.

  When using a composition of a methacrylic ester polymer and a plasticizer as the acrylic resin composition constituting the acrylic resin composition layer (I), the plasticizer used is, for example, dibutyl phthalate (DBP). ), Phthalate plasticizers such as diisobutyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate (DINP); polyester plasticizers such as Polycizer W230-S (Dainippon Ink Co., Ltd.); And citric acid ester plasticizers such as tributyl acid (ATBC). The said plasticizer may be used individually by 1 type, and may mix and use 2 or more types.

  The content of the methacrylic ester polymer in the composition of the methacrylic ester polymer and the plasticizer is such that the tensile elastic modulus of the acrylic resin composition layer (I) used in the present invention falls within the above range. However, 40 to 95% by mass is preferable, 60 to 90% by mass is more preferable, and 70 to 85% by mass is more preferable.

  Moreover, 5 mass%-60 mass% are preferable, as for content of a plasticizer, 10 mass%-40 mass% are more preferable, and 15% mass%-30 mass% are further more preferable. When the content of the plasticizer is larger than the above range, the tensile strength is lowered, and it becomes difficult to form the acrylic resin composition used in the present invention into a pellet shape, and the handling property tends to be inferior. When content of a plasticizer is smaller than said range, the flexibility of acrylic resin composition layer (I) becomes inadequate.

  The method of blending the plasticizer into the methacrylic acid ester polymer is not particularly limited, but it may be dissolved in a methacrylic acid ester monomer and polymerized, or may be melt-kneaded with the methacrylic acid ester polymer. When a plasticizer is dissolved in a methacrylic acid ester monomer and polymerized, a cross-linking reaction may be performed simultaneously with the polymerization reaction to increase heat resistance.

  The acrylic resin composition used in the present invention may contain other polymers as long as the transparency and tensile elastic modulus of the acrylic resin composition layer (I) are not affected. As such other polymer, a material having good compatibility with the acrylic polymer used in the present invention is preferable. For example, ethylene-vinyl acetate copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer are used. Examples thereof include a polymer, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polylactic acid, rosin acid ester, and poly α-methylstyrene.

  The resin composition layer (II) used in the present invention has a tensile modulus ratio with the acrylic resin composition layer (I) of 2 to 500, preferably 3 to 300. Here, in the present invention, the ratio of the tensile modulus is obtained by dividing the value of the tensile modulus of the resin composition layer (II) by the value of the tensile modulus of the acrylic resin composition layer (I) (resin composition The tensile elastic modulus of the physical layer (II) / the tensile elastic modulus of the acrylic resin composition layer (I)). When the tensile modulus ratio of the resin composition layer (II) of the present invention is smaller than the above range, the effect of improving the surface properties and rigidity of the acrylic multilayer of the present invention is insufficient. Inferior in resistance and impact resistance. When the tensile modulus ratio is larger than the above range, the difference in tensile modulus between the acrylic resin composition layer (I) and the resin composition layer (II) constituting the acrylic multilayered body of the present invention is large. Since it becomes too much, a crack and a crack generate | occur | produce in resin composition layer (II) at the time of roll winding, and peeling between layers arises.

  Here, the tensile elastic modulus of the resin composition layer (II) is a value measured at 23 ° C. under a tensile speed of 300 mm / min in accordance with the method described in ISO527-3.

  The tensile elastic modulus of the resin composition layer (II) used in the present invention is preferably 1200 MPa or more and 3000 MPa or less, and more preferably 1500 MPa or more and 2500 MPa or less, from the viewpoint of improving surface scratch resistance.

  The resin composition layer (II) used in the present invention is preferably made of a transparent resin or a composition thereof in order to make use of the transparency and light guide performance of the acrylic resin composition layer (I). Here, transparent means that the haze measured according to the method of JISK7136 is 3.0% or less, and the total light transmittance measured according to the method of JISK7361-1 is 85% or more. Examples of materials that satisfy such requirements include methacrylate ester polymers, methyl methacrylate-styrene copolymer (MS) resins, polycarbonate resins, polyethylene resins, polypropylene resins, cycloolefin resins, polyethylene terephthalate (PET). ), Styrene resin, polylactic acid, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinyl butyral, polyvinyl acetal, polyvinyl chloride (PVC), polyvinylidene chloride, polyfluoride Examples include vinyl (PVDF), polyvinylidene fluoride, styrene-conjugated diene block copolymers and their hydrogenated (SEBS, SEEPS, SEPS, etc.) resins, thermoplastic polyurethane resins, and resin compositions containing these. It is. These resins may be used alone or in combination of two or more. Among these resins, from the viewpoint of adhesion to the acrylic resin composition layer (I) used in the present invention, a methacrylic ester polymer or a composition thereof, a methyl methacrylate-styrene copolymer (MS) Resin, polycarbonate resin, polylactic acid, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinyl butyral, polyvinyl acetal, polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl fluoride (PVDF), polyvinylidene fluoride, styrene-conjugated diene block copolymers and hydrogenated products thereof (SEBS, SEEPS, SEPS, etc.) and thermoplastic polyurethane resins are preferred, and from the viewpoint of weather resistance and optical properties, methacryl Acid ester polymer or composition thereof, meta Methyl acrylic acid - styrene copolymer (MS) resins, polycarbonate resins, polylactic acid, polyvinyl butyral, polyvinyl acetal, polyvinyl fluoride (PVDF), polyvinylidene fluoride is more preferable.

  In addition, the methacrylic ester polymer or its composition, polylactic acid and polyvinyl butyral are excellent in compatibility with the acrylic resin composition constituting the acrylic resin composition layer (I) used in the present invention. , End portions produced during the production of the acrylic multilayer (the portion called the ear after cutting to a specified width, including both the acrylic resin composition layer (I) and the resin composition (II)), etc. Can be collected and reused together, which is excellent from the viewpoint of manufacturing cost and effective use of resources. In particular, a methacrylic ester polymer composition is most preferable from the viewpoint of preventing thermal deterioration during reuse.

The composition of the methacrylic ester polymer is a composition containing the methacrylic ester polymer described above, and the ratio of the tensile elastic modulus to the acrylic resin composition layer (I) is within the above range. There is no particular limitation. The resin composition layer (II) is used in the acrylic resin composition layer (I) because the tensile modulus of elasticity of the resin composition layer (II) is easy to adjust and the difference in refractive index from the acrylic resin composition layer (I) is small. Among the same compositions as the acrylic resin composition, an acrylic block copolymer or acrylic graft copolymer and its composition, a composition of a methacrylic ester polymer and acrylic rubber particles, a methacrylic ester You may use the composition of a polymer and a plasticizer, adjusting a composition ratio etc. suitably.
In this case, 50-100 mass% is preferable and, as for content of the methacrylic ester polymer in a composition, 70-100 mass% is more preferable.

  Among the transparent resins described above, methyl methacrylate-styrene copolymer (MS) resin, polycarbonate resin, polyvinyl fluoride (PVDF), and polyvinylidene fluoride suppress dimensional changes at the time of water absorption and high humidity and high temperature. be able to. In particular, the polycarbonate resin is most preferable in applications where dimensional stability is required because it is excellent in optical transparency, dimensional stability due to water absorption or heat, and impact resistance and has a low resin cost.

  The acrylic multilayer of the present invention includes a multilayer having one resin composition layer (II) on both sides of the main surface of the acrylic resin composition layer (I), and a resin composition layer (II). It is selected from a multilayer body comprising one acrylic resin composition layer (I) on each of the main surfaces.

  The number of layers constituting the acrylic multilayer of the present invention is 3 or more. In the case of two layers, a difference in physical properties between the upper layer and the lower layer occurs, and disadvantages such as warpage of the multilayer body due to the influence of heat or water absorption occur. The upper limit of the number of layers of the acrylic multilayered body of the present invention is not particularly limited, and may be a multilayered body of about 3 to 7 layers or a multilayered multilayered body of several tens to several hundreds of layers.

  The difference in refractive index between the resin composition layer (II) and the acrylic resin composition layer (I) is preferably 0.05 or less, more preferably 0.03 or less. When the refractive index difference is larger than the above range, when an acrylic multilayer is used as an optical member such as a light guide member, loss due to reflection between layers increases, resulting in inferior light guide distance and light emission hue. .

The method for adjusting the difference in refractive index is not particularly limited, but the polymer monomer constituting either or both of the acrylic resin composition layer (I) and the resin composition layer (II) is selected. Examples thereof include a method of adjusting and a method of adjusting using a refractive index adjusting agent. Examples of the refractive index adjusting agent include aromatic organic phosphorus compounds, silica-containing composite oxide spherical fine particles, rosins such as rosin, hydrogenated rosin, and disproportionated rosin, styrene resins, α-methylstyrene resins, and the like. Can be mentioned. Of these, rosins are preferred, and disproportionated or hydrogenated rosins purified by an operation such as distillation, recrystallization or extraction are more preferred from the viewpoint of suppressing light deterioration, coloring, and generation of bubbles due to impurities. Specific examples of the rosins include Pine Crystal KE-100, Pine Crystal KE-311, Pine Crystal KE-359, Pine Crystal KE-604, and Pine Crystal D-6250 (all manufactured by Arakawa Chemical Industries, Ltd.). It is done.
When the refractive index adjusting agent is contained, the content can be adjusted according to the refractive index, but 1 to 30% by mass is preferable and 3 to 20% by mass is more preferable from the viewpoint of suppressing light resistance deterioration and coloring.

  The resin composition layer (II) and the acrylic resin composition layer (I) may contain a light diffusing agent, a filler, an ultraviolet absorber, a fluorescent agent, a bluing agent, an antistatic agent, etc., if necessary. You may use thing.

  The total thickness ratio of the acrylic resin composition layer (I) to the total thickness of the acrylic multilayer body of the present invention (layer ratio of the acrylic resin composition layer (I)) is 0.05 or more and 0.95. Is preferably less than 0.1 and more preferably less than 0.1 and less than 0.9. When the layer ratio of the acrylic resin composition layer (I) is within the above range, the acrylic multilayer body of the present invention is excellent in flexibility and impact resistance, and in dimensional stability and heat shrinkage resistance. Also excellent. In applications where rigidity, dimensional stability, and heat shrinkability are more required, the layer ratio of the acrylic resin composition layer (I) is preferably 0.05 or more and less than 0.5, preferably 0.1 or more and 0.00. More preferably, it is less than 3. In applications where more flexibility and impact resistance are required, the layer ratio of the acrylic resin composition layer (I) is preferably 0.5 or more and less than 0.95, preferably 0.7 or more and 0.9 or less. More preferably.

  The total thickness ratio of the resin composition layer (II) to the total thickness of the acrylic multilayer of the present invention (layer ratio of the resin composition layer (II)) is preferably 0.05 or more and less than 0.95. More preferably, it is 0.1 or more and less than 0.9. When the layer ratio of the resin composition layer (II) is within the above range, the acrylic multilayer of the present invention is excellent in dimensional stability and heat shrinkage resistance, and is also excellent in flexibility and impact resistance. It will be. In applications that require more rigidity, dimensional stability, and heat shrinkage resistance, the layer ratio of the resin composition layer (II) is preferably 0.5 or more and less than 0.95, and 0.7 or more and 0.9 or less. It is more preferable that In applications that require more flexibility and impact resistance, the layer ratio of the resin composition layer (II) is preferably 0.05 or more and less than 0.5, and preferably 0.1 or more and less than 0.3. Is more preferable.

  The acrylic multilayer of the present invention is a multilayer having one acrylic resin composition layer (I) on both sides of the main surface of the resin composition layer (II), and is the outermost layer of the acrylic multilayer. When the outer layer is the acrylic resin composition layer (I), the acrylic multilayer is excellent in dimensional stability and excellent in impact resistance and flexibility. When the acrylic resin composition layer (I) is the outermost layer, the layer ratio of the acrylic resin composition layer (I) is 0.5 or more and less than 0.95, more preferably 0.7 or more and less than 0.9. And the effect of said resin composition layer (II) can be expressed, without impairing the softness | flexibility and flexibility of acrylic resin composition layer (I). In addition, the acrylic multilayer is excellent in flexibility and hard to break, and thus can be formed into a roll shape, and is excellent in transportability and molding processability.

  In particular, when the tensile modulus of the acrylic resin composition layer (I) is 1 to 100 MPa, an optical double-sided pressure-sensitive adhesive sheet or cushion material such as a flat panel display is utilized by utilizing surface adhesiveness and excellent transparency. Useful as. In this case, the resin composition layer (II) has a small optical distortion in order to maintain the uniformity of the display surface. Specifically, the resin composition layer (II) has a retardation of 10 nm or less, preferably 5 nm or less. Is preferably used. When the retardation is within the above range, the quality of the display screen is preferable. As resin which comprises said resin composition layer (II), the said methacrylic ester polymer composition or polycarbonate resin is preferable.

  Furthermore, the acrylic multilayer body of the present invention imparts an optical phase difference depending on the application, and can be used as a transparent adhesive sheet with an optical phase difference function. For example, when the resin composition layer (II) imparted with a ¼λ phase difference by oblique stretching is used, it is useful for a 3D display screen.

  The acrylic multilayer of the present invention is a multilayer having one resin composition layer (II) on both sides of the main surface of the acrylic resin composition layer (I), and the acrylic multilayer When the outermost layer is the resin composition layer (II), it is excellent in dimensional stability and impact resistance, and is excellent in rigidity, surface scratch resistance, surface antifouling resistance and the like. Moreover, since it has excellent surface smoothness and flexibility while having rigidity on the surface, it is also possible to produce an acrylic multilayer using a metal elastic roll or the like. The range of the layer ratio of the acrylic resin composition layer (I) is not particularly limited, but when the layer ratio of the acrylic resin composition layer (I) is 0.1 or more and less than 0.5, the acrylic resin composition of the present invention The multilayer body is useful as “acrylic tempered glass” in which the fragments are not scattered when the resin composition layer (II) is broken. On the other hand, when the layer ratio of the acrylic resin composition layer (I) is in the range of 0.5 or more and less than 0.9, it is useful as a “hard coat soft acrylic sheet” that is flexible but has excellent surface scratching properties. It is.

  The production method for obtaining the acrylic multilayer of the present invention includes a melt extrusion method using a feed block or a multi-manifold die, and further using a film forming apparatus such as a T-die extrusion molding machine or an inflation molding machine. It is done. Specifically, the method using a multi-manifold die is, for example, multi-layer melt extrusion using a multi-manifold T die, and at least one side, preferably both sides, of the resulting laminated sheet is brought into contact with a roll or belt. A film can be formed. The method using the above-described multi-manifold T-die is preferable in that an acrylic multilayer having good surface properties can be obtained. These roll surfaces or belt surfaces preferably have a mirror surface for imparting smoothness to the sheet surface, but with an optical pattern using a roll or belt having a surface shaped optical pattern. You may manufacture as a multilayer body.

  The shape of the acrylic multilayer of the present invention is not limited, and examples thereof include a sheet shape, a film shape, a rod shape, a tube shape, and a fiber shape.

  When the acrylic multilayer body of the present invention is in the form of a sheet or film, the thickness is not particularly limited, but is preferably 0.01 to 10 mm, more preferably 0.05 to 5 mm, and further preferably 0.1 to 3 mm. preferable.

  When the acrylic multilayered body of the present invention is in the form of a sheet or film, the form in the previous stage applied to various uses is not particularly limited, but the form overlaid on a sheet, the form wound up in a roll, etc. Is mentioned. Since the acrylic multilayer of the present invention is excellent in flexibility, it can be easily wound up into a roll shape. If it is in a roll shape, continuous processing is possible, transportation efficiency is good, etc. This is preferable from the viewpoint of improving productivity.

  The acrylic multilayered body of the present invention can be further used by being laminated with other layers. Examples of the layer to be laminated include metal films such as aluminum, zinc oxide, silver, indium oxide, titanium oxide, and tin oxide: carbon nanotubes; various paints; hard coat layers.

   The acrylic multilayered body of the present invention is suitably used as a sheet for bonding to various molded bodies, for example, automobile interiors, exteriors of household electrical appliances, transparent substrates of display members, and the like. At that time, at least one surface of the acrylic multilayer can also be decorated, for example, as a method for applying a pattern by printing or a thin film made of metal or metal oxide by vapor deposition. Examples thereof include a method of forming and imparting a metallic luster. The method of bonding sheets is preferably an injection molding simultaneous bonding method.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this invention is not limited to these Examples. Various physical properties in Examples and Comparative Examples were measured or evaluated by the following methods.

(1) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the acrylic block copolymer and acrylic resin are converted to standard polystyrene by gel permeation chromatography (hereinafter abbreviated as GPC). Calculated as molecular weight.
-Equipment: GPC equipment "HLC-8020" manufactured by Tosoh Corporation
Separation column: “TSKgel GMHXL”, “G4000HXL” and “G5000HXL” manufactured by Tosoh Corporation are connected in series. Eluent: Tetrahydrofuran Eluent flow rate: 1.0 ml / min Column temperature: 40 ° C.
・ Detection method: Differential refractive index (RI)

(2) PMMA content in acrylic block copolymer (content of methyl methacrylate units, mass%)
^It was determined by ¹ H-NMR measurement.

(3) Tensile modulus Obtained in the raw material resin (hereinafter referred to as raw material resin) constituting the acrylic resin composition layer (I) or the resin composition layer (II) shown in Table 1 below and in Example 4. The tensile modulus of the acrylic multilayer was measured. The measurement sample was a 1 mm thick sheet molded at an appropriate temperature of each resin with a press molding machine for the raw material resin, and multilayer melt extrusion was carried out at a cylinder temperature and a die temperature of 220 ° C. with a T-die extruder. Using the molded multilayer body having the thickness described in Tables 2 to 4, the measurement was performed at a measurement temperature of 23 ° C. and a tensile speed of 300 mm / min according to the method described in ISO 527-3.

(4) Surface hardness of the raw material resin The surface hardness of the raw material resin was measured according to JISK6253 using a durometer hardness test and using an A-type hardness meter and a D-type hardness meter (manufactured by Kobunshi Keiki Co., Ltd.).

(5) Refractive Index of Raw Material Resin The refractive index of the raw material resin was measured by a V-block method at a measurement temperature of 25 ° C. by cutting a sample from a 0.2 mm thick sheet molded by a press molding machine. The measurement wavelength is d-line 587.6 nm.

(6) Average thickness of each layer of acrylic multilayer and layer ratio of acrylic resin composition layer (I) Cut out the cross section of the acrylic multilayer obtained in the following examples or comparative examples, It magnified with the optical microscope and the thickness of each layer was measured using reflected light. The average thickness was a value obtained by measuring the thicknesses at arbitrary three locations. The layer ratio of the acrylic resin composition layer (I) was calculated by the following formula (A).
Formula (A): Layer ratio of acrylic resin composition layer (I) = Thickness of acrylic resin composition layer (I) / Total thickness of acrylic multilayer

(7) Tensile modulus ratio of acrylic multilayered layer Using the tensile modulus of the raw material resin measured in (3), the resin composition layer (II) with respect to the tensile modulus of acrylic resin composition layer (I) The elastic modulus ratio was calculated by the following equation (B).
Formula (B): Tensile modulus ratio = tensile modulus of resin composition layer (II) / tensile modulus of acrylic resin composition layer (I)

(8) Surface pencil hardness of acrylic multilayer body Using the acrylic multilayer body obtained in the following examples or comparative examples, the surface pencil hardness was measured at a temperature of 23 ° C. according to JISK5600-5-4. did.

(9) Roll processability of acrylic multilayer body When the acrylic multilayer body obtained in the following examples or comparative examples is wound into a roll, and the multilayer body wound into a roll The state at the time of unwinding was visually evaluated, and this was used as an index of roll processability.
○: Cracks and cracks do not occur on the surface and the end of the multilayer body when rolled up and stored in a rolled state. And when unwinding a multilayer body from a roll state, there is no sticking of multilayer bodies, and a crack and a crack do not generate | occur | produce on a sheet | seat surface and an edge part.
X: When wound up in a roll state or stored in a roll state, cracks or cracks occur on the surface or end of the multilayer body. In addition, when the multilayer body is unwound from the roll state, a peeling mark defect is generated on the surface of the multilayer body or cracks or cracks are generated on the surface of the multilayer body or at the end due to the adhesion between the multilayer bodies.

(10) Falling ball impact test of acrylic multilayers Using the acrylic multilayers obtained in the following examples or comparative examples, 50 mm long and 50 mm wide test pieces were cut out and weighed at 23 ° C and 50 g in weight. The steel ball (diameter 23 mm) was evaluated by a falling ball impact test method in which the steel ball was dropped from a height of 400 mm.
○: The sheet is not broken, or even if it is broken, no debris is scattered ×: The sheet is broken, and the debris is scattered

(11) Thermal shrinkage ratio of acrylic multilayer body Using the acrylic multilayer body obtained in the following Examples or Comparative Examples, a test piece having a length of 100 mm and a width of 100 mm was cut out, and after 85 ° C. for 24 hours. The heat shrinkage rate was calculated by the following formula (C) according to JISK7133.
Formula (C): Thermal shrinkage ratio of acrylic multilayered layer = [(side dimension before test (device flow direction) −side size after heating) / side size before test (device flow direction)] × 100

[Raw materials used in Examples]
Below, the detail of raw material resin used by the Example and the comparative example is shown. Table 1 shows physical property values measured using them.
Raw material resin (1): acrylic block copolymer In the presence of isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, sec-butyllithium is used as a polymerization initiator in toluene. Monomer (methyl methacrylate, n-butyl acrylate, methyl methacrylate) corresponding to each block was added in succession and living anion polymerization was performed. After removing the aluminum and lithium used, acrylic was removed using a devolatilizing twin-screw extruder. A triblock copolymer was obtained.
The structure of the resulting acrylic block copolymer was a triblock copolymer of methyl methacrylate polymer block (PMMA) -n-butyl acrylate polymer block (PnBA) -methyl methacrylate polymer block (PMMA). PMMA content 44 mass%, weight average molecular weight 63000, molecular weight distribution (weight average molecular weight / number average molecular weight) 1.15, tensile elastic modulus 200 MPa, surface hardness (A) 86, refractive index 1.48.
Raw material resin (2): acrylic block copolymer Living anionic polymerization was carried out in the same manner as the raw material resin (1) to obtain the following acrylic triblock copolymer.
The structure of the resulting acrylic block copolymer is a triblock copolymer of PMMA-PnBA-PMMA, having a PMMA content of 32% by mass, a weight average molecular weight of 62,000, and a molecular weight distribution (weight average molecular weight / number average molecular weight). .19, tensile modulus of elasticity 20 MPa, surface hardness (A) 65, refractive index 1.47.
Raw material resin (3): acrylic triblock copolymer resin composition With respect to 10 parts by mass of the raw material resin (1) (acrylic block copolymer), a commercially available methacrylate polymer: “Parapet GF: 5 parts by mass of “Kuraray Co., Ltd.” was kneaded at 210 ° C. using a twin screw extruder.
The resulting acrylic triblock copolymer resin composition had a tensile modulus of 300 MPa, a surface hardness (A) of 93, and a refractive index of 1.48.
Raw material resin (4): acrylic triblock copolymer resin composition With respect to 10 parts by mass of the raw material resin (1) (acrylic block copolymer), a commercially available methacrylate polymer: “Parapet GF: 15 parts by mass of Kuraray Co., Ltd. was kneaded at 210 ° C. using a twin screw extruder.
The obtained acrylic triblock copolymer resin composition had a tensile modulus of elasticity of 900 MPa, a surface hardness (A) of 98, and a refractive index of 1.48.
Raw material resin (5): Multilayered crosslinked rubber particle resin Sodium dodecylbenzenesulfonate is used as an aqueous emulsifier, potassium peroxodisulfate is used as a polymerization initiator, and polyoxyethylene alkyl sodium phosphate is used as a monomer phase emulsifier. -The first layer was formed by emulsion polymerization of 30 parts by weight of butyl, 14 parts by weight of methyl methacrylate, 6 parts by weight of styrene, and 0.2 parts by weight of allyl methacrylate. Next, 20 parts by mass of n-butyl acrylate, 10 parts by mass of methyl methacrylate, 4 parts by mass of styrene and 0.1 part by mass of allyl methacrylate were dropped and polymerized to form a second layer. Furthermore, 24 parts by mass of methyl methacrylate, 1.3 parts by mass of methyl acrylate, and 0.25 part by mass of n-octyl mercaptan were subjected to dropwise polymerization to form a third layer. The obtained latex was cooled to −30 ° C. for 24 hours for freeze aggregation, and then the aggregate was melted and taken out. It dried under reduced pressure at 50 degreeC for 2 days, and obtained the powdery three-layer type multilayer structure crosslinked rubber particle.
The obtained multilayer structure crosslinked rubber particles had a tensile elastic modulus of 5 MPa, a surface hardness (A) of 70, and a refractive index of 1.49.
Raw material resin (6): Composition of multilayer structure cross-linked rubber particle resin and methacrylic acid ester polymer The commercially available methacrylic acid ester weight is used with respect to 20 parts by mass of the raw material resin (5) (multilayer structure cross-linked rubber particle). Combined: 80 parts by mass of “Parapet GF: manufactured by Kuraray Co., Ltd.” was kneaded at 230 ° C. using a twin screw extruder.
The obtained composition had a tensile modulus of elasticity of 2300 MPa, a surface hardness (D) of 75, and a refractive index of 1.49.
・ Raw material resin (7): Acrylic resin “Parapet GF: Kuraray Co., Ltd.”. Tensile modulus 3300 MPa, surface hardness (D) 80, refractive index 1.49.
Raw material resin (8): Polycarbonate resin “Panlite K-1300Y: manufactured by Teijin Chemicals Limited”. Tensile modulus 2400 MPa, surface hardness (D) 70, refractive index 1.59.

[Examples 1-6, Comparative Examples 1-4]
Using the feed resin method, the surface layer material is arranged on both sides of the intermediate layer material using the above-mentioned raw material resin using a φ40 mm single screw extruder (main extruder) and φ22 mm single screw extruder (sub extruder). Extrusion was performed by a T-die extruder at a cylinder temperature and a die temperature of 220 ° C. so that the three-layer structure was formed, and then cooled so that one side was in contact with the polishing roll, thereby producing a sheet-like multilayered body. Test pieces were collected from the obtained multilayered body, and the average thickness, tensile modulus ratio, surface pencil hardness, roll workability, falling ball impact property, and heat shrinkage rate of each layer were measured or evaluated. The obtained results are shown in Tables 2 to 4.

  From the results of Table 2 above, the acrylic multilayers obtained in Examples 1 to 3 have excellent balance between surface scratch resistance and roll processability, whereas Comparative Examples 1 and 2 are multilayers. When unwinding the multilayer body from the roll due to surface sticking, a release mark defect occurs on the surface of the multilayer body (zipping occurs when the sheets are strongly stuck together, leaving a mark on the surface). No. 3, because the ratio of the tensile elastic modulus of the resin composition layer (II) to the tensile elastic modulus of the acrylic resin composition layer (I) is larger than 500, so that there are defects such as cracks and cracks during storage of the roll-shaped multilayered body. There has occurred. Further, from Table 3, when the acrylic multilayer obtained in Example 4 is used, since the acrylic resin composition layer (I) as an intermediate layer becomes a cushioning material, impact resistance is improved. The outermost resin composition layer (II) has an excellent scattering prevention effect. Further, from Table 4, the acrylic multilayers obtained in Examples 5 and 6 have excellent dimensional stability due to the effect of the resin composition layer (II) as an intermediate layer, whereas Comparative Example 4 Since the acrylic resin layer (I) is a single layer, the thermal contraction rate is increased. In all of the examples and comparative examples, the heat shrinkage rate was a positive value and did not become a negative value (the film would expand).

  The acrylic multilayer of the present invention has excellent dimensional stability, heat shrinkage resistance, impact resistance, crack resistance and flexibility, and is used as a roll without delamination or film cracking. In addition, it has excellent surface scratch resistance. For this reason, it is suitably used as various molded articles, for example, a sheet for bonding to the interior of an automobile, the exterior of a home appliance, the transparent substrate of a display member, and the like.

Claims (8)

  Resin composition layer (II) in which the ratio of the tensile modulus of elasticity between the acrylic resin composition layer (I) having a tensile modulus of 1-1000 MPa and the acrylic resin composition layer (I) is 2 or more and 500 or less And the acrylic resin composition layer (I) on both sides of the main surface of the acrylic resin composition layer (I) on both sides of the main surface of the resin composition layer (II). Acrylic multilayers selected from multilayers each having one resin-based resin composition layer (I).   2. The acrylic multilayer according to claim 1, wherein the acrylic resin composition layer (I) is composed of either an acrylic block copolymer or a resin composition containing the acrylic block copolymer.   The acrylic multilayer according to claim 1 or 2, wherein the resin composition layer (II) is made of a resin composition selected from a methacrylic acid ester polymer composition or a polycarbonate resin composition.   The refractive index difference of each resin composition which comprises acrylic resin composition layer (I) and resin composition layer (II) is 0.05 or less, The acrylic compound in any one of Claims 1-3 Layered body.   The total thickness ratio (layer ratio) of the acrylic resin composition layer (I) with respect to the thickness of the entire acrylic multilayer body is in the range of 0.5 or more and less than 0.95. The acrylic multilayer as described.   The total thickness ratio (layer ratio) of the acrylic resin composition layer (I) with respect to the thickness of the entire acrylic multilayer body is in the range of 0.05 or more and less than 0.5. The acrylic multilayer as described.   One or more acrylic resin composition layers (I) are provided on both surfaces of the main surface of the resin composition layer (II), and the outermost layer of the acrylic multilayer is the acrylic resin composition layer (I). Item 7. The acrylic multilayer according to any one of Items 1 to 6.   2. The resin composition layer (II) is provided on each of the main surfaces of the acrylic resin composition layer (I) at least one layer, and the outermost layer of the acrylic multilayer is the resin composition layer (II). The acrylic multilayered body in any one of -6.