WO2007020933A1

WO2007020933A1 - Multilayer sheet and molded body using same

Info

Publication number: WO2007020933A1
Application number: PCT/JP2006/316077
Authority: WO
Inventors: Kazunori Kobashi; Hirofumi Yamada; Toshio Takei; Tsuyoshi Morita
Original assignee: Dainippon Ink And Chemicals, Inc.
Priority date: 2005-08-16
Filing date: 2006-08-16
Publication date: 2007-02-22
Also published as: TW200714465A

Abstract

Disclosed is a multilayer sheet which comprises a layer mainly containing a substantially amorphous polyester resin on at least one side of a layer composed of a styrene resin composition. The multilayer sheet is excellent in heat resistance while having sufficient transparency, impact resistance and abrasion resistance. This multilayer sheet can be used for carrier tapes for blister packages, electronic components and the like.

Description

Laminated sheet and molded body using the same

Technical field

[0001] The present invention relates to a layer (layer (X)) comprising a styrene-based resin composition and a block copolymer having a block copolymer having a polymer block of a conjugation-based monomer. The present invention relates to a novel laminated sheet in which a layer (layer (Y)) made of substantially amorphous polyester resin is laminated on at least one surface, and a molded body using the laminated sheet.

Background art

[0002] Styrenic resin is often used for plastic containers because of its excellent point of processability. In recent years, with regard to problems such as environmental impact, substitution of styrene-based resin to polyester-based resin has been progressing. For example, Patent Literature 1 discloses a styrene-based resin composition. This composition is a combination of a styrene-based copolymer, a polymer block of a styrene-based monomer, and a conjugate block of a conjugated monomer. Combined block force It contains a block copolymer. In this styrene-based resin composition, the styrene-based copolymer is a copolymer of a styrene-based monomer, butyl acrylate, and methyl methacrylate. In the styrene-based resin composition, the polymer block layers of the monomeric monomers form a multilayer structure that is alternately laminated, and the structural units derived from the conjugation-based monomers are mixed in the raw material mass ratio. It is contained at a ratio of ˜25 mass%. Since the styrene-based resin composition is excellent in transparency and impact resistance, it is used in blister packages, carrier tapes, food containers and the like obtained by secondary molding of molding sheets.

However, the resin sheet made of the above-mentioned resin composition is limited in its use because gloss is inferior in scratch resistance compared to a polyester resin sheet.

[0003] Although the polyester-based resin sheet is excellent in gloss, it is inferior in heat resistance, so that it is not used in a high-temperature environment. In addition, Patent Document 2 compensates for the heat resistance of the polyester-based resin sheet, and is transparent. As a styrene-based multilayered resin sheet that has excellent balance of physical properties such as rigidity and impact resistance and satisfies oil resistance and chemical resistance, vinyl aromatic hydrocarbon polymer block, conjugated diene polymer block, conjugated diene and vinyl aromatic On at least one surface of a base material layer comprising a composition of a block copolymer having an aromatic hydrocarbon copolymer block and a butyl aromatic hydrocarbon (meth) acrylate copolymer. A multilayer resin sheet is disclosed in which layers having an amorphous polyester-based polymer strength are laminated. Patent Document 2 describes a specific example in which the block copolymer is used in combination with a binary copolymer such as styrene Z butyl acrylate and styrene Z methyl methacrylate.

[0004] Further, Patent Document 3 discloses a transparent multilayer having oil resistance, gas resistance, and scratch resistance, excellent in both rigidity and impact resistance, and also having good moldability and punchability. As a sheet, the matrix phase is 30 to 70% by weight of the styrene monomer and 70% to 30% by weight of the (meth) acrylic acid alkyl ester monomer. 50 wt%, wherein the butadiene units 80-50 wt% of styrene 'butadiene block rubber 5-15 wt ^_0/0, and rubber-modified styrene the rubber is dispersed in the particle size of 0. 3 to 1. 5 m A multilayer sheet is disclosed in which a system resin is used as a base material layer, and a surface layer made of polyester resin is laminated on one or both sides of the system resin via an adhesive resin layer.

[0005] In Patent Document 3, 42.5% by weight of styrene, 9.1% by weight of butyl acrylate, 38.2% by weight of methyl methacrylate are mixed, and 2.7% by weight of ethylbenzene is further added. to the mixture, the rubber 7.5 wt% dissolved dispersed, to then this was subject to polymerization reaction in a continuous polymerization vessel, rubber-modified styrene polymer 100 weight ^_0/0 obtained, terpene榭脂5. 0 wt ^_0/0 and melt-kneaded, to prepare a rubber-modified styrenic榭脂by further granulating the rubber-modified styrene榭脂, the modified Orefin system榭脂as the adhesive layer, amorphous' property Poriesu An example of producing a three-layer multilayer sheet by co-extrusion with tellurium-based resin is described. In Table 1 of the patent document, it is described that the particle diameter of the rubber dispersed in the rubber-modified styrene-based resin is 0.6 μm.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-250680

Patent Document 2: JP 2001-79993 A Patent Document 3: Japanese Patent Laid-Open No. 10-244635

Disclosure of the invention

Problems to be solved by the invention

[0006] As described above, molding sheets used for blister packages, carrier tapes for electronic components, food containers, and the like have excellent heat resistance, and further transparency, impact resistance, oil resistance, It is necessary to satisfy the required properties such as chemical properties, gas barrier properties, scratch resistance, moldability, and punchability. However, the laminated sheet for molding according to the conventional technique has a problem that, for example, even if the transparency after molding is high, details of an article inside the package are difficult to see and are unclear. In addition to the above issues, there is a new need to make the items inside the package look clearer and more beautiful.

Therefore, the object of the present invention is excellent in heat resistance, and is not limited to a force satisfying transparency, impact resistance and scratch resistance, particularly before being formed into a three-dimensional molded product such as a container. The gloss of the sheet surface is high, and details of the article can be clearly seen through the sheet (image clarity) .In addition, even after being molded into a three-dimensional molded product, the gloss and image clarity before molding are maintained as much as possible. It is providing the laminated sheet which can do. Another object of the present invention is to provide a molded body using a laminated sheet that solves the above problems.

Means for solving the problem

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that a styrene monomer (al), an acrylate monomer (a2), a methacrylic acid ester monomer ( Consists of a styrene copolymer (A) obtained by reacting with a3), a polymer block (bl) of a styrene monomer, and a polymer block (b2) of a conjugation monomer The above-mentioned requirement is obtained by laminating a layer containing a substantially amorphous polyester resin on at least one side of a resin composition comprising a block copolymer (B) as a main component. The inventors have found that it is possible to satisfy the performance, and have completed the present invention.

That is, the present invention provides a layer comprising a substantially amorphous polyester resin (P) as a main component on at least one surface of the layer (X) having a styrene-based resin composition strength (Y )

The styrene-based resin composition is (1) a styrene copolymer (A) obtained by reacting a styrene monomer (al), an acrylate monomer (a2), and a methacrylate ester monomer (a3),

(2) a block copolymer (B) having a polymer block of a styrene monomer (bl) and a polymer block of a conjugated monomer (b2) as main structural units,

(3) Derived from the acrylate monomer (a2) and the methacrylic acid ester monomer (a3) with respect to the total mass of the styrene copolymer (A) and the block copolymer (B). The proportion of the total mass of the structural units is 15% by mass or less,

The present invention provides a laminated sheet characterized by the above.

The present invention further provides a molded body using the laminated sheet.

The present invention further provides a blister package using the laminated sheet.

[0010] As described in the prior art, the polyester resin sheet is excellent in gloss but poor in heat resistance and moldability. However, according to the study by the present inventors, the image clarity was good. Accordingly, the laminated sheets described in Patent Documents 2 and 3 which should improve heat resistance and formability while examining the image clarity of the polyester resin sheet were studied. However, the image of the resin sheet described in the example of Patent Document 3 was poor because the modified olefin-based resin was used as an adhesive layer. In addition, when rubber-modified styrene-based resin and amorphous polyester-based resin are laminated without using this adhesive layer, a laminate that easily peels between the layers is formed, causing a problem in practical use. The image clarity was not satisfactory. Furthermore, the resin sheet described in the example of Patent Document 2 was examined, but it was necessary to further improve the image clarity, which was not a satisfactory level.

Therefore, the present inventors made an effort to improve image clarity in a laminated sheet in which a layer comprising a styrene-based resin composition and a layer containing polyester resin as the main constituents are laminated. In particular,

(1) Styrenic resin composition power

(2) To improve the compatibility between the styrene copolymer and the block copolymer in the styrene resin composition,

(3) A layer composed of a styrene-based resin composition and a layer mainly composed of polyester resin To improve the adhesiveness and make the fluidity of the two oils close to each other during lamination, and to suppress the unstable phenomenon between layers.

Various studies were conducted to achieve the above.

As a result, the above laminated sheet was found, but the laminated sheet of the present invention satisfies transparency, impact resistance and scratch resistance, and the gloss of the sheet surface before molding is high. In addition, the reason is that the image clarity is good and the gloss and image clarity before molding are maintained even after molding.

(1) By using a methacrylic acid ester monomer during the production of the styrene copolymer, the molecular weight of the styrene resin can be reduced and the fluidity can be improved, and the strength and heat resistance can be maintained. The smoothness of the sheet surface at the time of extrusion becomes good, and the roughness of the sheet surface at the time of thermoforming heating can be suppressed. As a result, the smoothness of the molded sheet was maintained, and the image clarity and surface gloss were improved.

(2) Also, by using an acrylate monomer together with a methacrylic acid ester monomer, compatibility with the block copolymer is improved, thereby improving the smoothness of the sheet surface, surface gloss, and image clarity. Became good.

(3) By setting the content ratio of the acrylic ester monomer structural unit and the methacrylic ester monomer structural unit in the styrene-based resin composition to a specific range, a layer comprising a styrene-based resin layer Adhesion with a layer containing polyester resin as the main component has been improved, and the fluidity of the styrene-based resin composition has improved, approaching the fluidity of the polyester resin layer and causing unstable phenomena at the interface. Suppressed.

The invention's effect

The laminated sheet of the present invention is excellent in heat resistance, and is not a force that satisfies transparency, impact resistance, and scratch resistance. In particular, the gloss of the sheet surface before being formed into a three-dimensional molded product such as a container. In addition, the details of the article can be clearly seen through the sheet (image clarity), and even after being formed into a three-dimensional molded product, the gloss and image clarity before molding can be maintained as much as possible. Therefore, when used in a blister package, a carrier tape such as an electronic component, a food container, etc., the articles inside the knocker can be seen more clearly and beautifully. When used for food packaging trays, lids, cups, and various storage trays , It can show the contents of the product neatly and is ideal for visual appeal. Brief Description of Drawings

FIG. 1 is a transmission electron microscope (TEM) photograph of the styrene-based resin composition obtained in Example 1.

FIG. 2 is a process diagram showing an example of a continuous bulk polymerization line incorporating a tubular reactor in which mixing elements are arranged.

Explanation of symbols

[0013] (1): Bra pump

(2): Stirred reactor

(3): Gear pump

(4): Tubular reactor

(5): Tubular reactor

(6): Tubular reactor

(7): Gear pump

(8): Tubular reactor

(9): Tubular reactor

(10): Tubular reactor

(11): Gear pump

(I): Circulation type polymerization line

(II): Polymerization line

BEST MODE FOR CARRYING OUT THE INVENTION

[0014] The laminated sheet of the present invention comprises a layer comprising a substantially amorphous polyester resin (P) as a main component on at least one surface of the layer (X) comprising the styrene-based resin composition ( Y) is a laminated sheet.

[0015] (Styrenic resin composition)

The styrene-based resin composition includes a styrene-based copolymer (A) and a block copolymer (B). The block copolymer (B) comprises a layer of a polymer block (bl) of a styrene monomer in the block copolymer (B) and a polymer block (b2) of a conjugation monomer. ) Layer And the styrenic copolymer (A) penetrates between the network structures to form a continuous layer. Here, the morphology in which the styrene copolymer (A) and the polymer block (bl) of the styrene monomer form a continuous layer, and the block copolymer (B) forms a network structure, Specifically, it can be confirmed by a transmission electron micrograph (TEM) shown in FIG. In FIG. 1, the black portion corresponds to the layer of the polymer block (b2) of the conjugation monomer in the block copolymer (B), and the white circle surrounded by this layer. The portion corresponds to a layer composed of a styrene copolymer (A) and a polymer block (b 1) of a styrene monomer.

The polymer block (bl) of the styrenic monomer and the polymer block (b2) force of the conjugation monomer are composed of the block copolymer (B) itself. ) To form a network structure in which the polymer block (bl) layer and the conjugate block monomer block (b 2) layer intersect! / Speak. In the present invention, the surface impact is caused by allowing the styrene copolymer (A) to exist as a continuous layer between the layers of the polymer block (b2) of a plurality of conjugation monomer monomers so as not to disrupt the network structure as much as possible. Strength is improved. On the other hand, in the case of Patent Document 2 where SBS is used as a block copolymer and a binary copolymer of a styrene monomer and butyl acrylate is used as a continuous layer, the copolymer and Since the block copolymer is easily compatible, the SBS-powered morphology is destroyed, and the surface impact strength of the molded product, especially the molded product made by secondary molding of the molding sheet, is sufficient. It did not reach a certain level.

(Styrene copolymer (A))

The styrene copolymer (A) is a resin obtained by reacting a styrene monomer (al), an acrylate monomer (a 2), and a methacrylate ester monomer (a3). It is.

Adhesiveness with the layer (Y) can be imparted by using the acrylate monomer (a2) as a copolymerization component of the styrene monomer (al). Also, by using the methacrylic acid ester monomer (a3) together with the acrylic acid ester monomer (a2), the molecular weight of the styrene-based resin layer can be suppressed, so the image clarity and transparency of the sheet are also improved. Can be improved. Furthermore, since it is possible to suppress a decrease in heat resistance of the styrene-based resin, the image clarity and gloss are good even after molding. [0017] (Styrene monomer (al))

Styrene monomers (al) are styrene, α-methylol styrene, ο-methylol styrene, m-methylol styrene, p-methylol styrene, ethyl styrene, isobutanol styrene, t-butyl styrene, o Examples include bromostyrene, m-bromostyrene, p-bromostyrene, o-chlorostyrene, m-chlorostyrene, and p-chlorostyrene. Of these, styrene is preferred because of its good reactivity and easy polymerization.

[0018] (Acrylic acid ester monomer (a2))

Preferred examples of the acrylate monomer (a2) include compounds represented by the following formula 1, such as acrylic acid methyl ester, ethyl ester, n-butyl ester, 2-ethylhexyl ester, and the like. It is done. Of these ingredients, butyl acrylate is more preferred for better transparency and greater adhesion to the polyester.

[0019]

(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms which may have a branched chain.)

[0020] The abundance of structural units derived from the acrylate ester ( _a2 ) also affects the formation of the morphology of the styrenic resin composition. As this increases, the polymer block of the styrenic monomer ( bl) and a block copolymer (B) composed of a polymer block (b2) of a conjugation monomer, the surface impact strength is reduced by improving the compatibility. Therefore, the styrene-based resin composition used in the present invention has a structural unit derived from the acrylate ester (a 2) based on the total mass of the styrene-based copolymer (A) and the block copolymer (B). 1.0 to 14.5% by mass is preferable. 1.8 to 10.0% by mass is more preferable 1.8 to 8.0% by mass is more preferable. The structural unit derived from the acrylate ester (a 2) is a structural unit represented by the following formula 3. For example, if the structural unit is derived from butyl acrylate (b), the butyl acrylate The structural site where (b) has undergone an addition reaction is specifically 1-butyloxy-carbo-ethylene.

[0021]

(In the formula, R ¹ represents an alkyl group even if it has a branched chain.)

[0022] (methacrylic acid ester (a3))

As the methacrylic acid ester monomer (a3), a compound represented by the following formula 2 is preferable. For example, methacrylic acid methyl ester, ethyl ester, n-butyl ester, i-butyl ester, t-butyl ester, 2- Ethylhexyl ester etc. are mentioned. Among these components, in order to obtain better transparency, image clarity, and surface impact strength, R ² must be a C 1-4 alkyl group that may have a branched chain. Among the more preferred, methacrylic acid methyl ester is particularly preferred.

[0023] [Chemical 3]

(In the formula, R ² represents an alkyl group having 1 to 8 carbon atoms which may have a branched chain.)

[0024] In addition, since the molecular weight of the styrene-based resin layer can be suppressed by using the methacrylic acid ester monomer (a3), in particular, methacrylic acid methyl ester, it is mapped in a laminated sheet with a polyester resin layer. Excellent in properties, gloss and transparency. Furthermore, since the fluidity is improved by suppressing the molecular weight, an unstable phenomenon between layers at the time of lamination with the polyester resin is less likely to occur, and a sheet having a good appearance can be obtained.

[0025] The styrene-based resin composition used in the present invention comprises a structural unit derived from the methacrylic acid ester monomer (a3), comprising the styrene-based copolymer (A) and the block copolymer (B). It is preferably contained in a proportion of 0.5 to 10.0% by mass with respect to the total mass. 1.5 to 6.5% by mass, more preferably 1.8 to 4.0%. The structural unit derived from the methacrylic acid ester monomer (a3) is a structural unit represented by the following formula 4. For example, if the structural unit is derived from methyl methacrylate, the methyl methacrylate is This refers to a structural site that has undergone an addition reaction, specifically 1-methyl-1 methyloxycarbo-ruethylene.

[0026] [Chemical 4]

[0027] (Composition ratio)

Further, the styrene copolymer (A), styrene monomer (al) seventy-two to eighty-five mass ^_0/0, § acrylic acid ester monomer _(a 2) 5 to 25 wt%, and methacrylic acid esters The monomer (a3) is preferably a copolymer of 3 to 16% by mass. As will be described later, the block copolymer (B) preferably has a polybutadiene block content of 20 to 30% by mass from the viewpoint of surface impact strength of the molded product. By setting the raw material monomer ratio of the styrene copolymer (A) to the above ratio, excellent transparency can be imparted to the molded product. In addition, the balance between surface impact strength and rigidity is further improved.

In particular, from the viewpoint of transparency of the molded article, it is preferable to adjust the monomer ratio as appropriate so that the difference in refractive index from the block copolymer (B) among the above ratios is 0.002 or less. In addition, by using the methacrylic acid ester monomer (a3) in the proportions described above, it is possible to impart excellent heat resistance to the molded product, and it can be used in regions with high temperatures or in summer. It becomes. Furthermore, the molecular weight of the styrenic copolymer (A) can be kept relatively low, while at the same time exhibiting appropriate fluidity at the time of melting and good moldability.

[0028] Such a viewpoint power The styrene copolymer (A) is preferably a styrene copolymer having a weight average molecular weight of 25 X 10 ⁴ to 35 X 10 ^4. G is preferably 5-12gZlOmin! / ,. As described above, since the styrene copolymer (A) can exhibit appropriate fluidity while keeping the molecular weight low, the styrene copolymer (A) and the block copolymer (B) are combined. The temperature conditions for melt kneading can be set low. As a result, the occurrence of gelling can be prevented during melt-kneading, and the appearance of the finally obtained molded article becomes excellent. In addition, the polymer block of styrene monomer (bl) and the block copolymer (B) composed of polymer block force of conjugation monomer (b2) are compatible with each other. It is possible to suppress wrinkles and develop an appropriate morphology to achieve a balance between surface impact strength and rigidity.

[0029] (Styrene copolymer (A) Polymerization method)

Styrene copolymer (A) consists of styrene monomer (al), acrylate monomer (a It can be produced by polymerizing 2) and the methacrylic acid ester monomer (a3) at a predetermined mass ratio by suspension polymerization, bulk suspension polymerization, solution polymerization or bulk polymerization. In the present invention, the continuous block polymerization method is particularly preferable in terms of productivity, cost, and point power excellent in composition uniformity.

[0030] In the present invention, in the continuous bulk polymerization method, in particular, a polymerization line having a polymerization line in which a plurality of tubular reactors are connected in series, and a mixing element is disposed inside the tubular reactor. A continuous bulk polymerization method using an apparatus is preferable because a homogeneous styrene copolymer (A) can be efficiently produced.

The mixing element used here mixes the polymer solution by, for example, changing the flow and flow direction of the polymer solution flowing into the pipe and repeating the division and merging. One set of tubular mixers, Kenix type static mixers, Toray type tubular mixers and the like can be mentioned.

[0031] In addition, in the continuous bulk polymerization method, a raw material component is preliminarily polymerized in the agitation reactor before the raw material components are charged into the polymerization apparatus, and then each of the raw material components is preliminarily polymerized in the agitation reactor. In particular, it is preferable that the uniformity of the styrenic copolymer (A) obtained by introducing the polymerization solution into the polymerization apparatus constituting the continuous bulk polymerization line is further increased. Examples of the stirring reactor that can be used here include a stirring tank reactor, a stirring tower reactor, and the like. The stirring blades in the stirrer include, for example, an anchor type, a turbine type, a screw type, and a double type. Either a bull helical type or log bone type stirring blade can be used.

The temperature conditions for the polymerization of each of the raw material components in a continuous polymerization line connected with a stirred reactor and a continuous bulk polymerization apparatus are as follows. The polymerization conversion rate is 35 to 55% by mass in the initial stage of polymerization. The molecular weight of the styrenic copolymer (A), which can be obtained at 120 to 135 ° C at the stage and 140 to 160 ° C at the subsequent stage of polymerization, is easy to control, and it has excellent productivity. preferable.

[0032] After completion of the polymerization, the polymerization solution is preheated in a preheater and then sent to a devolatilization tank to remove unreacted monomers and solvent under reduced pressure and then pelletized. A styrene copolymer (A) is obtained.

In the continuous bulk polymerization method, the viscosity of the polymerization solution in the tubular reactor is A solvent may be used to lower the temperature. In this case, the amount used is 5 to 20 parts by mass with respect to a total of 100 parts by mass of each raw material component. As the type of solvent, ethylbenzene, toluene, xylene and the like usually used in bulk polymerization are suitable. In addition, it is preferable to add a chain transfer agent for adjusting the molecular weight of the styrene copolymer (A). The addition amount of the chain transfer agent is usually in the range of 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of raw material monomers.

[0033] In the production of the styrene copolymer (A), a polymerization initiator can be appropriately used. Any general-purpose peroxide polymerization initiator can be used as the polymerization initiator. In the present invention, among the known peroxide polymerization initiators, the styrene copolymer (A) can be polymerized three-dimensionally, and the neck-in phenomenon at the time of sheet extrusion can be satisfactorily prevented. 2 Bis (4,4-di-t-butylperoxycyclohexyl) propan is preferred.

[0034] (Block copolymer (B))

The block copolymer (B) has as main structural units a polymer block of a styrene monomer (bl) and a polymer block of a conjugated monomer monomer (b2).

Block copolymer (B)

1) Polymer block of styrene monomer (bl) and polymer block of conjugation monomer (b2) and diblock = 3 polymer,

2) A triblock composed of a polymer block of a styrene monomer (bl), a polymer block of a conjugation monomer (b2), and a polymer block of a styrene monomer (bl) Copolymer,

3) Hydrogenated product of the triblock copolymer,

4) A multi-block copolymer comprising a plurality of polymer block forces exceeding a triblock composed of a polymer block of a plurality of styrene monomers (bl) and a polymer block of a styrene monomer (b 1), as well as

5) A block copolymer having a random copolymer moiety, such as a polymer block of a styrene monomer ((bl) polymer block) and a conjugation monomer (b2). Among these, the triblock copolymer of the above 2) is preferable because the block copolymer (B) has a morphologically excellent surface impact resistance. Regarding the triblock copolymer, the polymer block of the styrene monomer (bl) may be partially copolymerized with a conjugated gen monomer, or a conjugated gen monomer. The polymer block (b2) may be partially copolymerized with a styrene monomer.

[0035] (Styrene monomer (bl))

Here, as the styrene monomer (bl), styrene, α-methyl styrene, ο-methyl styrene, m-methyl styrene, p-methylol styrene, ethyl styrene, isobutino styrene, tert-butyl styrene, o bromo Styrene, m-bromostyrene, p-bromostyrene. Forces such as monochlorostyrene, m-chlorostyrene, p-chlorostyrene, etc. In particular, styrene is mentioned as a general one. Use not only one but also a mixture of two or more.

[0036] (Conjugation monomer (b2))

Examples of the conjugated gen-based monomer (b2) include gen-based monomers such as butadiene, black-opened plane, isoprene, and 1,3-pentagene. Among these, the polybutadiene block is excellent in rubber elasticity expressed by the polymer block, and can be imparted with excellent surface impact strength to the finally obtained styrene-based resin composition of the present invention. Favored ,. These may be used alone or in combination of two or more.

Therefore, the block copolymer (B) is preferably a so-called styrene butadiene copolymer (SBR), and the triblock type is preferably a styrene butadiene styrene copolymer (SBS). Butadiene styrene copolymer (SBS) is preferred.

[0037] (Concentration of polymer block of conjugation monomer (b2))

If the amount of the polymer block of the conjugation monomer (b2) in the block copolymer (B) increases, the rubbery properties of the block copolymer (B) become stronger, and plastic deformation hardly occurs during molding. Therefore, the content of the polymer block of the conjugation monomer (b2) in the block copolymer (B) is preferably 20 to 30% by mass.

The mixing ratio of styrenic copolymer (A) to block copolymer (B) The structural unit derived from the conjugation monomer (b2), which is a raw material component of the body (B), is 10 with respect to the total mass of the styrene copolymer (A) and the block copolymer (B). 0-25. 0% by mass. As a result, it is possible to develop an appropriate morphology and provide a tolerance of surface impact strength and rigidity. Here, the structural unit derived from the conjugated gen monomer refers to an alkylene structure site where the conjugated gen monomer has undergone an addition reaction. For example, 1,3 butadiene is used as the conjugated gen monomer. In this case, it represents butane 1,4 jirou 2 hen and butane 1,2 jiru 3 hen. When the proportion of the structural unit derived from the conjugation monomer (b2) in the styrene-based resin composition of the present invention is less than 10% by mass, sufficient impact strength cannot be imparted to the molded product. . On the other hand, if it exceeds 25% by mass, the composition itself has insufficient rigidity, and drawdown is likely to occur during secondary molding of the molding sheet. Of these, the range of 13 to 25% by mass is particularly preferable, and the range of 13 to 21% by mass is more preferable because the effect of improving the surface impact strength is remarkable.

[0038] Here, the structural unit derived from the conjugation monomer (b2) refers to an alkylene structure site obtained by addition reaction of the conjugation monomer (b2). When 1,3 butadiene is used as a monomer, it represents butane-1,4-diluene 2 and butane-1,2 diluene-3. In addition, the content of the structural unit in the styrene-based resin composition includes a peak derived from a polymer of a styrene-based monomer and a peak derived from a polymer of a conjugated-dene-based monomer in IR measurement. It can be expressed as a mass-based content rate calculated from the relative intensity of.

Here, the structural unit derived from the conjugation monomer (b2), the structural unit derived from the acrylate ester ( _a 2), and the structure derived from the methacrylic acid ester (a3) in the styrene-based resin composition. The unit content can be determined from the area ratio of chemical peaks corresponding to carbon atoms characteristic of each structural unit in C ¹³ -NMR measurement.

[0039] (Production method of block copolymer (B))

The block copolymer (B) can be produced by known methods such as emulsion polymerization and solution polymerization of the styrene monomer (bl) and the conjugated diene monomer (b2). In particular, when producing the triploc copolymer, an organolithium compound or the like in a hydrocarbon-based organic solvent. It is easy to adjust the high molecular weight of the block copolymer (B) by producing a triblock copolymer by solution polymerization of styrene monomer and gen monomer in the presence of Preferable from the point.

[0040] (Melt mixing of styrene copolymer (A) and block copolymer (B))

In addition, a specific method for melt-mixing the styrene copolymer (A) and the block copolymer (B) is, for example, to dry-blend both of them uniformly with a mixer, and then put the mixture into an extruder. And a melt-kneading method, or a styrene-based copolymer (A) and a block copolymer (B) are charged into an extruder and melt-kneaded.

For example, is it possible to dry-blend the pellets or pellets of the styrene copolymer (A) and the block copolymer (B) in advance with a mixer such as a Banbury mixer and put the resulting mixture into an extruder? Alternatively, a method may be mentioned in which the pellets or pearls are directly fed into an extruder and melt kneaded at 190 to 240 ° C. in the extruder. The melt-kneaded mixture may be sheeted as it is, or after being pelletized, it may be melted again with an extruder. Examples of the melt kneading method include a melt kneading method using a single screw and twin screw extruder, a kneader, and an open roll. The resin temperature during extrusion is preferably 230 ° C or lower in order to suppress gel formation and improve the appearance of the molded product.

[0041] The styrene-based resin composition of the present invention is prepared by polymerizing the styrene-based copolymer (A) and the block copolymer (B) from respective raw material components, or by melt-kneading both. In doing so, various additives such as an antioxidant, a release agent, an ultraviolet absorber, a colorant, a heat stabilizer, a plasticizer, and a dye may be mixed as appropriate. Specific examples of such additives include plasticizers such as mineral oil, ester plasticizers, and polyester plasticizers, antioxidants, chain transfer agents, higher fatty acids, higher fatty acid esters, and higher fatty acid metals. Examples thereof include salt and silicone oil, and one or more of these are used in combination.

In the present invention, the styrene monomer block is adjusted to 50% by mass or less for the purpose of further improving the surface impact strength. A block copolymer composed of a polymer block can be added to the styrene resin composition at a ratio of 2 to 15% by mass in the styrene resin composition. [0042] (Substantially amorphous polyester resin (P))

It may be referred to as a substantially amorphous polyester-based resin (hereinafter, polyester) used in the present invention. As the monomer component constituting), terephthalic acid or its isomers (for example, isophthalic acid, phthalic acid, etc.) or derivatives thereof, aliphatic dicarboxylic acids (for example, adipic acid, azelaic acid) , Sebacic acid) or a derivative thereof, naphthalenedicarboxylic acid, and the like.

The glycol (alcohol) component includes ethylene glycol or its derivatives (eg, polyethylene glycol), alkylene glycols (such as trimethylene glycol, tetramethylene glycol, and hexamethylene glycol), and cycloalkyl glycols (such as cyclohexanediol and cyclohexane). Hexane dimethanol, cyclohexane dialkylol, etc.), bishydroxyphenylalkanes, hydrogenated products thereof and the like can be used.

[0043] The polyester resin (P) used in the present invention is substantially amorphous among the polyesters obtained by condensation polymerization of these two components. In particular, an amorphous polyester resin in which the dihydric alcohol component is composed of ethylene glycol and 1,4-cyclohexanedimethanol and the acid component is composed of terephthalic acid is preferable.

The term “substantially amorphous” as used herein means one having a crystallinity of 5% or less as measured by DSC. The polyester resin (P) used in the present invention preferably has a crystallinity of 1% or less. When measuring by the DSC method, measure the melting energy at a heating rate of 10 ° CZ, and use a wide-angle X-ray as a standard for a sample with a clear crystallinity. Specific examples of the polyester resin (P) used in the present invention include Eastman Kodak's trade name “Eastar PE T-G 6763”.

[0044] In the laminated sheet of the present invention, the layer (Y) as a surface layer, the polyester resin (P) constituting the layer (Y) as a lubricant, silica, titanium oxide, calcium carbonate, talc, crosslinked polymer particles, etc. Inorganic and organic inert particles and rubber-modified impact-resistant styrene-based resin (high-impedance polystyrene) can be added to prevent blocking between sheets. In addition, various additives such as an antistatic agent, an antistatic agent, an ultraviolet absorber, a colorant, and a dye may be mixed with the polyester resin (P). [0045] In the present invention, the layer (X) or the layer (Y) is added with petroleum resin, coumarone resin, terpene resin, phenol-modified terpene resin, and the styrenic resin layer and the polyester resin are added. Interlayer adhesion of the oil layer can be improved. A method of blending these additives into a resin composition containing a styrenic copolymer (A) and a block copolymer (B) or a polyester resin (P) is dry blended using a blender. There is a method or a method of pre-pelling with a kneader such as a kinder in advance, and there is no particular limitation.

[0046] (layer thickness)

The thickness of each layer of the laminated sheet of the present invention is not particularly limited, and a thickness of 0.02 to 3 mm that can be appropriately selected according to the purpose of use and application is preferably used. The ratio of the thickness of the layer (Y) to the layer (X) is 0.1 to 50%, more preferably 1 to 20%. It is preferable to use the layer (Y) as a thin film compared to the layer (X), the layer (X) serving as a base material layer, and the layer (Y) serving as a surface layer.

In addition, the laminated sheet in the present invention contains layer (X) and layer (Y) by containing a substantially amorphous polyester resin in the styrene-based resin composition constituting layer (X). Adhesive strength can be increased. At this time, when a crystalline polyester resin is used as the polyester resin, the transparency of the sheet is impaired. It is preferable to use the same polyester resin as the polyester resin (P) constituting the layer (Y) because the adhesion between the layer (X) and the layer (γ) can be further improved. The content of the polyester resin is preferably 0.1 to 20% by mass with respect to 100% by mass of the styrene copolymer (A) + block copolymer (B). If it exceeds 20% by mass, the transparency will decrease, which is preferable.

[0047] In addition, the laminated sheet of the present invention is a styrene-based resin layer that forms the layer (X) after performing the pulverization process without separating the layer (X) and the layer (Y). In production, the pulverized material can be reused. The blended amount of the pulverized product at that time is preferably 30% by mass or less with respect to 100% by mass of the styrene-based resin composition. If the blended amount of the pulverized product exceeds 30% by mass, the physical properties are likely to deteriorate, which is not preferable.

[0048] (Sheet manufacturing method)

In the production method of the laminated sheet of the present invention, the layer (X) and the layer (Y) are melt-extruded using different extruders, laminated with a feed block, and laminated with a flat die. And a method of forming a laminated film in a die using a multi-die. In this way, a sheet suitable for secondary molding with a thickness of 0.02 to 3 mm, preferably 0.03 to Lmm can be produced.

The laminated sheet thus obtained has excellent transparency, image clarity, scratch resistance, gloss, impact resistance (surface impact strength), and molding processability. For example, as for transparency, the sheet haze value using a 0.5 mm thick sheet conforming to JIS K7 105 is 5 or less, and the image clarity (C%) is clear at 50% or more (comb width 0.25 mm). Sheet. In addition, the surface impact strength is 1 J or more in terms of DuPont impact strength on a 0.5 mm thick sheet. In addition, the molded product has excellent heat resistance and does not deform under high temperature and high humidity conditions (for example, temperature 65 ° C, humidity 80%, standing for 8 hours).

(C value: scale of image clarity)

In the present invention, the image clarity (image clarity, comb width 0.25 mm) called C value is preferably 50% or more, more preferably 60% or more. Here, the C value is the image sharpness defined in JIS K7105. In this specification, using the image clarity measuring device (image quality measuring device ICM-1T type manufactured by Suga Test Instruments), the transmission method is used. The value at a measured comb width of 0.25 mm is defined as a C value and defined as a measure of image clarity.

The C value in this image clarity measurement is obtained by the following method.

(1) An optical comb that shines slit-shaped parallel light beams that have passed through extremely thin slits on the laminated film and moves the light that has passed through the laminated film (a chart with a plurality of black lines arranged in parallel at regular intervals) ) Image on top.

(2) Further, a slit-like light image on the optical comb is detected, and the fluctuation of the light quantity is measured as a waveform.

(3) Based on the fluctuation of the light quantity, obtain the C value by the following formula. Image clarity C (%) = [(M-m) / (M + m)] X 100

M: Maximum value of light transmitted through the transparent part of the optical comb

m: Minimum value of light transmitted through opaque part of optical comb The clearer the image of the slit image formed on the optical comb, the higher the image clarity, and the higher the C value. On the other hand, if the slit light is blurred or distorted, the image clarity will be low and the c value will be low.

[0050] The laminated sheet of the present invention can be further shaped into a desired shape by pressure forming, heat pressing or the like. The resulting molded product is excellent in transparency, image clarity, scratch resistance, gloss, impact resistance (surface impact strength), and has good moldability. For example, blister package, food packaging tray, Can be applied to applications such as lids, cups, various storage trays, carrier tapes, etc., especially as a blister package due to its excellent transparency, image clarity, scratch resistance, and good heat resistance. Useful.

Example 1

[0051] Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The following “parts” or “%” are based on mass unless otherwise specified.

[Production of Styrene Copolymer (A)]

The styrene copolymer (A) was produced by using a continuous polymerization apparatus having a polymerization line force shown in the process diagram shown in FIG. The polymerization apparatus consists of a plunger reactor (1), a stirring reactor (2), a gear pump (3), (7), (11), and a tubular reactor (4) with a mixing element inside. ), (5), (6), (8), (9), and (10). In FIG. 2, the arrow indicates the direction of the flow of the polymer solution, and the raw material components are first sent to the agitation reactor (2) by the plunger pump (1), and after initial graft polymerization under agitation. , The gear pump (3) is introduced into a circulation polymerization line (I) composed of a tubular reactor (4), (5), (6) and a gear pump (7). Polymerization is carried out while circulating the polymerization solution in (I). On the other hand, the tubular reactors (8), (9), (10) and the gear pump (11) form a non-circular polymerization line (II), and the polymerization liquid in the circulation line (I) A part flows into this polymerization line (II), and polymerization is carried out in the polymerization line (II) to a desired degree of polymerization.

Here, the polymerization in the cyclic polymerization line (I) is carried out by using a styrene monomer (al), an acrylic ester (a2), and a methacrylic ester (a3) at the outlet of the cyclic polymerization line (I). Is polymerized so that the total polymerization conversion is usually 35 to 55% by mass, preferably 40 to 50% by mass. . The ratio of the flow rate of the polymer solution circulating in the circulation polymerization line (I) to the flow rate of the polymer solution flowing out to the non-circulation type polymerization line (Π), the reflux ratio R, flows into the polymerization line (Π). The flow rate of the mixed solution refluxed in the circulation polymerization line (I) is F1 (liter Z time), and the mixed solution flows out from the circulation polymerization line (I) to the non-circulation polymerization line (Π). When the flow rate is F2 (liters Z time), it is usually adjusted to the range of R = F1 / F2 force ^ ~ 15.

After the completion of the polymerization, the polymerization solution is sent to a preheater and then to a devolatilization tank by a gear pump (11), and after removing unreacted monomers and solvent under reduced pressure, the target styrene copolymer is formed by pelletization. A polymer (A) is obtained.

[0052] (Production of styrene copolymer (A-1))

Prepare a mixed solution consisting of 82 parts of styrene (SM), 12 parts of butyl acrylate (BuA), 6 parts of methyl methacrylate (MMA) and 8 parts of ethylbenzene, and add 100 parts of the monomer mixture as a polymerization initiator. In contrast, 0.025 parts of 2,2-bis (4,4-diperoxycyclohexyl) pour pan and 100 parts of monomer mixture as chain transfer agent, 0.01 parts of n-dodecyl mercabtan In addition, bulk polymerization was continuously performed using the polymerization apparatus under the following conditions. Reaction temperature in stirred reactor (2): 115 ° C

Reaction temperature in circulation polymerization line (I): 132 ° C

Reaction temperature in the polymerization line (Π): 150 ° C

Next, the mixed solution obtained by polymerization was heated to 215 ° C with heat exchange to remove the volatile component under reduced pressure, and then pelletized to produce a styrene copolymer (A —1)

[0053] (Production of styrene copolymer (A-2))

Styrene (SM) 82 parts, Butyl acrylate (BuA) 8 parts, Methyl methacrylate (MMA) 10 parts, Ethylbenzene 9 parts 2,2-bis (4,4-diperoxycyclohexyl) propane, styrene, except that 0.03 part of n-dodecyl mercaptan is added to 100 parts of the monomer mixture as a chain transfer agent. In the same manner as the copolymer (A-1), the styrene copolymer (A-2) shown in Table 1 was obtained.

[0054] (Production of styrene copolymer (A-3)) In a mixed solution consisting of 81 parts of styrene (SM), 16 parts of methyl acrylate, 3 parts of methyl methacrylate, and 9 parts of ethyl benzene, 0.025 part of 2,2 is added to 100 parts of the monomer mixture as a polymerization initiator. —Bis (4,4-di-peroxycyclohexyl) propane, chain transfer agent, 100 parts of monomer mixture with 0.01 part of n-dodecyl mercaptan, shown in the diagram of FIG. Using the polymerization line, bulk polymerization was continuously carried out under the following conditions.

Reaction temperature in stirred reactor (2): 115 ° C

Reaction temperature in circulating polymerization line (I): 132 ° C

Reaction temperature in non-circulation polymerization line (Π): 150 ° C

The mixed solution obtained by polymerization was heated to 215 ° C with heat exchange and after removing volatile components under reduced pressure, the pellets were crushed and styrene copolymers shown in Table 1 (A-3) Got.

[0055] (Production of styrene copolymer (A-4))

In a mixed solution consisting of 78 parts of styrene (SM), 6 parts of butyl acrylate, 16 parts of butyl methacrylate, and 9 parts of ethylbenzene, 0.02 5 parts 2, 2-bis (4,4-di-peroxycyclohexyl) propane, 0.01 parts of n-dodecyl mercaptan was added to 100 parts of the monomer mixture as a chain transfer agent, and is shown in the process diagram of FIG. Bulk polymerization was continuously carried out using the polymerization line under the following conditions.

Reaction temperature in the stirred reactor (2): 119 ° C

Reaction temperature in circulation polymerization line (I): 124 ° C

Reaction temperature in non-circulation polymerization line (Π): 150 ° C

The mixed solution obtained by polymerization was heated to 215 ° C with heat exchange ^ to remove volatile components under reduced pressure, and then pelletized to give the styrenic copolymers shown in Table 1 (A-4) Got.

[0056] (Production of styrene copolymer (A-5))

In a mixed solution of 82 parts of styrene (SM), 12 parts of 2-ethylhexyl acrylate, 6 parts of methyl methacrylate, and 9 parts of ethylbenzene, 100 parts of monomer mixture as a polymerization initiator was added to 0.026. 2, 2-bis (4,4-diperoxycyclohexyl) propane, and 0.01 part of n-dodecyl mercaptan was added to 100 parts of the monomer mixture as a chain transfer agent. Using the polymerization line shown in the process diagram, bulk polymerization was continuously carried out under the following conditions. Reaction temperature in stirred reactor (2): 115 ° C

Reaction temperature in circulating polymerization line (I): 132 ° C

Reaction temperature in non-circulation polymerization line (Π): 150 ° C

The mixed solution obtained by polymerization was heated to 215 ° C with heat exchange ^ to remove volatile components under reduced pressure, and then pelletized to give the styrenic copolymers shown in Table 1 (A-5) Got.

[0057] (Production of styrene copolymer (A-6))

In a mixed solution consisting of 79 parts of styrene (SM), 16 parts of butyl acrylate, 5 parts of methyl methacrylate, and 9 parts of ethylbenzene, 0.03 part of 2,2 is added to 100 parts of the monomer mixture as a polymerization initiator. —Bis (4,4-di-peroxycyclohexyl) propane, chain transfer agent, 100 parts of monomer mixture with 0.01 part of n-dodecyl mercaptan, shown in the diagram of FIG. Using the polymerization line, bulk polymerization was continuously carried out under the following conditions.

Reaction temperature in stirred reactor (2): 115 ° C

Reaction temperature in circulating polymerization line (I): 132 ° C

Reaction temperature in non-circulation polymerization line (Π): 150 ° C

The mixed solution obtained by polymerization was heated to 215 ° C with heat exchange ^, and after removing volatile components under reduced pressure, the mixture was pelleted and styrene copolymers shown in Table 1 (A-6) Got.

[0058] (Production of styrene copolymer (A-7))

In a mixed solution of 79 parts of styrene (SM), 21 parts of butyl acrylate, and 9 parts of ethylbenzene, 0.03 part of 2,2-bis (4, 4 — Di-peroxycyclohexyl) propane, 100 parts of monomer mixture as chain transfer agent, 0.01 parts of n-dodecyl mercaptan was added and the polymerization line shown in the process diagram of FIG. The polymer was continuously bulk polymerized under the conditions.

Reaction temperature in stirred reactor (2): 115 ° C

Reaction temperature in circulating polymerization line (I): 132 ° C

Reaction temperature in non-circulation polymerization line (Π): 150 ° C

The mixed solution obtained by polymerization was heated to 215 ° C with heat exchange and after removing volatile components under reduced pressure, the pellets were crushed and styrene copolymers shown in Table 1 (A-7) Got.

[0059] (Production of styrene copolymer (A-8)) To a mixed solution consisting of 65 parts of styrene (SM), 5 parts of butyl acrylate, 30 parts of methyl methacrylate, and 9 parts of ethylbenzene, 0.02 5 parts 2, 2 Bis (4,4-di-peroxycyclohexyl) propane, 100 parts of monomer mixture as chain transfer agent, 0.01 part of n-dodecyl mercaptan was added and polymerization shown in the process diagram of Figure 2 Using the line, continuous bulk polymerization was performed under the following conditions.

Reaction temperature in stirred reactor (2): 115 ° C

Reaction temperature in circulation polymerization line (I): 123 ° C

Reaction temperature in non-circulation polymerization line (Π): 150 ° C

The mixed solution obtained by polymerization was heated to 215 ° C with heat exchange and after removing volatile components under reduced pressure, the pellets were crushed and styrene copolymers shown in Table 1 (A-8) Got.

[Production of block copolymer (B)]

The styrene-butadiene block copolymer (B) used in the following examples and comparative examples is as follows.

Styrene Butadiene Styrene block copolymer (B-1):

Chevron Phillips SBS (trade name "K Resin XK44J")

Content of the constituent units derived from styrene: 77 weight ^_0/0

Content rate of structural units derived from butadiene: 23% by mass

Styrene Butadiene Block Copolymer (B-2):

SB elastomer made by JSR (trade name “TR2003”)

Content of the constituent units derived from styrene: 43 weight ^_0/0

Content of structural units derived from butadiene: 57% by mass

(Willow by ¹³ C-NMR)

In the structural unit derived from the conjugation monomer in the styrene resin composition obtained in each Example and Comparative Example, the structural unit derived from the methacrylic acid ester (a3), and the acrylic acid ester (a2) The content rate of the derived structural unit was measured as follows.

120 mg of the sample obtained in each example or comparative example was dissolved in 0.5 ml of CDC13, and about 5 mg of a relaxation reagent was filled in a sample tube for measuring NMR. JEOL NMR “GSX— 40 Quantitative ¹³ C-NMR by the gate coupling method was measured by “0”.

The area specific force of the chemical peak shown below The content of each structural unit was determined.

Chemical shift corresponding to each structural unit

Structural unit derived from styrene: 142-146ppm

Structural unit derived from methyl metatalylate and methyl atallylate: 175ppm

Structural unit derived from butyl metatalylate and butyl acrylate: 63ppm

2 Structural unit derived from ethylhexyl acrylate: 39ppm

Structural unit derived from butadiene (butane 1,2 ziru 3 ene): 114 ppm Structural unit derived from butadiene (butane 1,4 jiru 2 ene): 125 to 132 p pm

[Physical property evaluation method]

The physical property evaluation methods of the molding sheets in the following examples and comparative examples are as follows.

(Measurement of haze)

Based on JIS K7105, a haze value representing the transparency of a 0.5 mm-thick sheet test piece was measured using a turbidity and haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.).

Haze value

Less than 5%;

5% or more and less than 7%;

7% or more; X

(DuPont impact strength measurement)

Using a DuPont impact tester (manufactured by Toyo Seiki Seisakusho), weight of 300 g, striker tip radius 6.3 mm, cradle radius 6.3 mm, 50% fracture energy of 0.5 mm thick sheet test piece Asked.

DuPont impact strength

1. 0J or more; 〇

1. Less than 0J, 0.5J or more;

Less than 0.5J; X [0062] (Measurement of scratch resistance)

Using a shaker tester, two 0.5mm thick sheets were superposed on each other (layer (Y)), and the sheets were rubbed together for 3 minutes under a load of 200g. In accordance with this, measurement was performed using an image clarity measuring device (image quality measuring device ICM-1T type manufactured by Suga Test Instruments Co., Ltd.).

60% or more; 〇

60% or less; X

(Measurement of image clarity (C) before heating)

B

In accordance with JIS K7105, the image clarity of a 0.5 mm thick sheet test piece was measured using a image clarity measuring instrument (manufactured by Suga Test Instruments). Tables 2 and 3 show the image clarity when the comb width is 0.25 mm.

The ratio of the dark part of the optical comb to the light part is 1: 1, and the moving speed is lOmmZmin.

(Measurement of image clarity (C) after heating)

A

Using a vacuum forming machine, after heating a 0.5mm thick sheet at a heater set temperature of 375 ° C for 20 seconds, the imageability of the test specimen obtained was in accordance with JIS K7105. It measured using. Tables 2 and 3 show the image clarity when the comb width is 0.25 mm.

[0063] (Ratio of image clarity (C) after heating to image clarity (C) before heating (%))

B A

The ratio (%) of the image clarity (C) after heating to the image clarity (C) before heating is calculated as follows:

B A

Determined by

(c) / (C) (%) = [(C) / (C)] X 100

A B A B

70% or more; 〇

Less than 70%, 60% or more;

Less than 60%; X

(Surface gloss after heating)

After using a vacuum forming machine to heat a 0.5mm thick sheet at the heater set temperature of 375 ° C for 20 seconds, the gloss of the test specimen obtained is in accordance with JIS K7105 and a gloss measuring instrument (manufactured by Nippon Denshoku Industries Co., Ltd.) And measured.

(Heat resistance evaluation) 0. A 4mm thick sheet was formed into a 170 XI 30 X 35 (mm) box using a vacuum forming machine, and this molded product was left in a constant temperature bath at 65 ° C and 80% humidity for 8 hours. Deformation was confirmed. The case where the deformation was not observed in the molded product was marked as ◯, and the case where it was deformed was marked as X.

(Interlayer adhesion)

Using a heat seal tester, a styrene-based resin layer and a polyester resin layer after heat-sealing the surface layers of two sheets of 0.5 mm thickness at a heater temperature of 175 ° C and a seal pressure of ² kgZcm ² The interlayer adhesion was evaluated.

Difficult to remove; 〇

Peeled to some extent, but practically problematic! /, Degree;

Easily peels off; X

[0064] (Example 1)

Styrene-based copolymer (A-1) and styrene-butadiene styrene block copolymer (B-1) and styrene-butadiene block copolymer (B-2) are converted into (A-1) Z (B-1) Z (B — 2) Layer (X) (base material layer), amorphous polyester resin (P) (trade name “Eastar PET-G 6763, manufactured by Eastman Kodak Co., Ltd.”) )) As a layer (Y) (surface layer), and a two-layer laminated sheet for molding with a thickness of 0.5mm (layer (X) thickness Ζlayer (Υ) thickness = 92Z8) is produced using a coextrusion multilayer sheet equipment did.

Various physical properties were measured using the obtained sheet. The measured values are shown in Table 2. The sheet forming conditions are as follows.

Sheet forming machine: 30mm non-vent extruder

65mm non-vent extruder

Cylinder temperature: 30mm extruder 230 ° C

65mm extruder 210. C

T die, feed block set temperature: 230 ° C

Example 2

[0065] Styrene copolymer (A-2) is replaced with block copolymers (B-1) and (B-2) by (A-1) Z (B-l) / (B-2) = 35Z55Z10 (X) (base material layer), amorphous polyester resin (P) (Eastman Kodak Company name “Eastar PET-G” 6763 ”) as layer (Y) (surface layer), and 0.5 mm in thickness (layer (X) thickness Ζ layer (Υ) thickness = 92 Ζ 8) in the same conditions as in Example 1 in the coextrusion multilayer sheet equipment A laminate sheet for molding was prepared and various physical properties were measured. The measured values are shown in Table 2.

Example 3

[0066] Styrene copolymer (A-1), block copolymer (共 -1) and amorphous polyester resin (榭) (Eastman Kodak brand name "Eastar PET-G 6763" ) (8-1) 7 (-1) Z (CP) = 30Z60Z10 is added to the resin composition layer (X) (base material layer) and amorphous polyester resin resin (P) layer (Y) As a (surface layer), a laminated sheet for molding having a thickness of 0.5 mm (layer (X) thickness Z layer (Y) thickness = 92Z8) under the same conditions as in Example 1 in the coextrusion multilayer sheet equipment It was prepared and various physical properties were measured. The measured values are shown in Table 2.

Example 4

[0067] A resin composition layer in which a block copolymer (B-1) is added to a styrene copolymer (A-3) at a ratio of (A-3) Z (B-1) = 50Z50 Layer (X) and amorphous polyester resin (P) as layer (Y) in a co-extrusion multilayer sheet facility with the same conditions as in Example 1 with a thickness of 0.5 mm (layer (X) thickness Z layer A laminate sheet for molding with (Y) thickness = 92/8) was prepared, and various physical properties were measured. The measured values are shown in Table 2.

Example 5

[0068] A resin composition layer obtained by adding block copolymer (8-1) to styrene-based copolymer (A-4) in a ratio of (8-4) 7 (8-1) = 50Z50 Layer (X) and amorphous polyester resin (P) as layer (Y) in a co-extrusion multilayer sheet facility with the same conditions as in Example 1 with a thickness of 0.5 mm (layer (X) thickness Z layer A laminate sheet for molding with (Y) thickness = 92/8) was prepared, and various physical properties were measured. The measured values are shown in Table 2.

Example 6

[0069] To the styrene copolymer (A-5), block copolymers (B-1) and (B-2) are converted into (A-5) Z (Β-1) / (Β-2) = 35Z55Z10 Under the same conditions as in Example 1 using a co-extrusion multilayer sheet equipment, with the resin composition layer added at the ratio of blended as layer (X) and amorphous polyester resin (P) as layer (Y) A laminated sheet for molding with a thickness of 0.5 mm (layer (X) thickness Z layer (Y) thickness = 92/8) It was prepared and various physical properties were measured. The measured values are shown in Table 2.

Example 7

[0070] Block copolymer (B-1) and (B-2) are combined with styrene copolymer (A-6) to (A-5) Z (B-l) / (B-2) = 35Z55ZlO Under the same conditions as in Example 1 using a co-extrusion multilayer sheet equipment, with the resin composition layer added at the ratio of blended as layer (X) and amorphous polyester resin (P) as layer (Y) A laminated sheet for molding having a thickness of 0.5 mm (layer (X) thickness Z layer (Y) thickness = 92/8) was prepared, and various physical properties were measured. The measured values are shown in Table 2.

[0071] (Comparative Example 1)

A block copolymer (B-1) and (B-2) are blended with (A-1) / (B-1) Z (B-2) = 35Z55Z10 to a styrene copolymer (A-1). A single layer sheet having a thickness of 0.5 mm was prepared using a sheet facility, and various physical properties were measured. The measured values are shown in Table 3.

Sheet forming machine: 65mm non-vent extruder

Cylinder temperature: 210 ° C

T die, feed block set temperature: 230 ° C

[0072] (Comparative Example 2)

The block copolymer (B-1) and (B-2) are mixed with the styrene copolymer (A-6) with the formula (A-6) / (B-l) / (B-2) = 35Z55ZlO. Layer (X) (base layer), non-crystalline polyester resin (P) (Eastman's Kodak brand name “Eastar PE TG 6763”) layer (Y) As the (surface layer), a laminated sheet for molding having a thickness of 0.5 mm (layer (X) thickness Z layer (Y) thickness = 92/8) was prepared in the same conditions as in Example 1 using the coextrusion multilayer sheet equipment. The various physical properties were measured. The measured values are shown in Table 3.

[0073] (Comparative Example 3)

A resin composition layer in which the block copolymer (B-1) is added to the styrene copolymer (A-7) at a ratio of (A-7) / (Β-1) = 50Z50 ( X) (base material layer), amorphous polyester resin (P) (Eastman Kodak brand name “Eastar PET-G 6763”) as layer (Y) (surface layer) Using the equipment, a laminated sheet for molding having a thickness of 0.5 mm (layer (X) thickness Z layer (Y) thickness = 92/8) under the same conditions as in Example 1 was measured, and various physical properties were measured. The measured values are shown in Table 3. [0074] [Table 1]

[0075] [Table 2]

Example 1 2 3 4 5 6 7 Layer (X) Copolymer (A-1) 35 30

(Base material layer) Copolymer (A-2) 35

(Part) Copolymer (A-3) 50

Copolymer (A-4) 50

Copolymer (A-5) 35 Copolymer (A-6) 35 Flock copolymer (B-1) 55 55 60 50 50 55 55 Flock copolymer (B-2) 10 10 10 10 Resester resin (P) 10

Layer (Y) Ho. Reester resin (P) 100 100 100 100 100 100 100

(Surface layer)

(Part)

(a2) Content (%) 4.2 2.8 3.6 8.0 3.0 4.2 5.6

( _a3 ) Content (%) 2.1 3.5 1.8 1.5 8.0 2.1 1.75

(b2) Content (%) 18.4 18.4 13.8 11.5 11.5 18.4 18.4 Haze (%) 2.0 3.2 4.9 4.5 4.8 3.7 6.0

〇〇〇〇〇 ∆ τ Uhon impact strength ω 1.4 1.3 1.4 0.6 0.6 1.3 1.0

○ ○ ○ Δ Δ ○ ○ Scratch resistance (%) 73 68 64 65 66 65 64

○ ○ ○ ○ ○ ○ ○ Imageability before heating (C _B ) (%) 84 80 75 78 76 79 73 Image clarity after heating (C _A ) (%) 65 61 54 58 56 55 49

(c _A ) / (C _B ) (%) 77 77 72 74 74 70 67

○ ○ ○ ○ ○ ○ Δ Gloss after heating (%) 176 175 153 171 170 170 166 Heat resistance ○ ○ ○ Δ ○ ○ ○ Interlayer adhesion ○ ○ ○ Δ Δ ○ ○] Comparative Example 1 2 3 Layer (X) Copolymer (A-1) (Part) 35

(Base material layer) Copolymer (A-6) (Part) 35

(Part) Copolymer (A-7) (Part) 50

Flock copolymer (B-1) (part) 55 55 50 Flock copolymer (B-2) (part) 10 10 layers (Y) E Reester resin (P) (Part) None 100 100

(Surface layer)

(Part)

(a2) Content% 4.2 7.35 2.5

(a3) Content% 2.1 0 15.0

(b2) Content% (Hu Tashi) 18.4 18.4 11.5 Haze (%) 3.6 6.8 25.0

〇 Δ X

Tyuhong impact strength (J) 1.4 0.9 0.3

○ Δ X Scratch resistance (%) 54 64 36

X 〇 X

Image clarity before heating (C _B ) (%) 70 72 10 Image clarity after heating (c _A ) (%) 38 42 5

(C _A ) / (C _B ) (%) 54 58 50

X X X

Gloss after heating (%) 157 161 131 Heat resistance ○ X △ Interlayer adhesion ― ○ X Industrial applicability

Since the laminated sheet for molding of the present invention can provide a molded product having excellent heat resistance, it is suitable for use in blister packages, food packaging trays, lid materials, cups, various storage trays, carrier tapes and the like. Very useful.

Claims

Claims [1] A layer (Y) comprising a substantially amorphous polyester resin (p) as a main component is provided on at least one surface of the layer (X) also having a styrene-based resin composition strength. Laminated sheet, wherein the styrene-based resin composition is

(1) a styrene copolymer (A) obtained by reacting a styrene monomer (al), an acrylate monomer (a2), and a methacrylate ester monomer (a3),

A laminated sheet characterized by that.

[2] The styrene-based resin composition contains structural units derived from the acrylate monomer (a2) as a total mass of the styrene-based copolymer (A) and the block copolymer (B). The laminated sheet according to claim 1, which is contained at a ratio of 1.0 to 14.5% by mass relative to the mass.

[3] The styrene-based resin composition contains structural units derived from the methacrylic acid ester monomer (a3) as a total mass of the styrene-based copolymer (A) and the block copolymer (B). The laminated sheet according to claim 1, wherein the laminated sheet is contained at a ratio of 0.5 to 10.0% by mass relative to the mass.

[4] The styrene-based resin composition contains structural units derived from the conjugation monomer (b2) as a total mass of the styrene-based copolymer (A) and the block copolymer (B). The laminated sheet according to claim 1, which is contained in a proportion of 10.0 to 25.0% by mass with respect to the total amount.

[5] The acrylate monomer (a2) is represented by the formula 1

[Chemical 5]

2. The laminated sheet according to claim 1, wherein R ¹ represents a C 1-8 alkyl group which may have a branched chain.

[Chemical 6]

^2. The laminated sheet according to claim 1, wherein R ² represents a C 1-8 alkyl group which may have a branched chain.

7. The laminated sheet according to claim 1, wherein the acrylate monomer (a2) is butyl acrylate.

8. The laminated sheet according to claim 1, wherein the methacrylate (a3) is methyl methacrylate.

[9] A molded body using the laminated sheet according to any one of claims 1 to 8.

[10] A blister rack using the laminated sheet according to any one of claims 1 to 8,