GB2425127A

GB2425127A - Resin blend composition, sheet and heat-shrinkable sheet comprising the resin blend composition, and shrink label and package

Info

Publication number: GB2425127A
Application number: GB0614660A
Authority: GB
Inventors: Kouichirou Taniguchi; Takeyoshi Yamada; Toshiaki Ebitani
Original assignee: Mitsubishi Plastics Inc
Current assignee: Mitsubishi Chemical Corp
Priority date: 2003-12-25
Filing date: 2004-12-27
Publication date: 2006-10-18
Anticipated expiration: 2024-12-27
Also published as: GB2425127B; WO2005063887A1; GB0614660D0

Abstract

[PROBLEMS] To obtain a resin blend composition having transparency, impact resistance, flowability, etc. [MEANS FOR SOLVING PROBLEMS] The resin blend composition comprises 1 to 99% by mass polycarbonate resin (b-1) and 1 to 99% by mass polyester resin (b-2), the polyester resin (b-2) being a polyester resin comprising: carboxylic acid monomer units (i) in which 80 to 100 mol% of all the units (i) are accounted for by aromatic dicarboxylic acid units; and glycol monomer units (ii) in which 0.1 to 40 mol% of all the units (ii) are accounted for by 1,4-CHDM units and 0.5 to 15 mol% of all the units (ii) are accounted for by polyalkylene glycol units having a number-average molecular weight of 500 to 3,000.

Description

Ptinted: 11-09-2006 DESC 466O FP366GB

DESCRIPTION

RESIN BLEND COMPOSITION, SHEET AND HEAT-SHRINKABLE SHEET COMPRISING THE RESIN BLEND COMPOSITION, AND SHRINK LABEL

AND PACKAGE OBTAINED WITH THE HEAT-SHRINKABLE SHEET

TECHNICAL FIELD

[00011 The present invention relates to a resin blend composition, a sheet and a heat-shrinkable sheet comprising the resin blend composition, and a shrink label and a package obtained with the heat-shrinkable sheet. More particularly, the present invention relates to a resin blend composition having transparency, impact strength. flowability. and secondary processability, a sheet and a heat-shrinkable sheet comprising the resin blend composition, and a shrink label and a package with the heat-shrinkable composition.

BACKGROUND ART

2] Conventionally, polyvinyl chloride (hereinafter, sometimes, simply referred to also as "PVC") resin, which has transparency and resistance to chemicals and has balanced physical properties, has been used in various applications since it can be controlled to have a wide variety of glass 1 24-07-2006 Printed: 11-09-2006 DESC 0614660 transition temperatures by incorporating therein appropriately selected plasticizers and various additives according to applications. However, PVC resin has a problem that upon its disposal and incineration, it generates gas containing chlorine. Accordingly, vigorous researches on substitutes for PVC resin are being made actively. One of strong candidates of substitutes for PVC resin is a polycarbonate based resin, which is excellent in transparency and impact strength. However, sheets and moldings comprising this resin have poor moldability because of high melt viscosity and hence of low flowability.

Although the polycarbonate based resin, which has glass transition temperature higher than that of the PVC resin, has acceptable heat resistance, it has been difficult to perform secondary process (vacuum forming, pressure forming or the like) within a secondary process temperature range of PVC resin (usually, about 50 C or more and about 100 C or less).

3] To solve the above-mentioned problems of the polycarbonate based resin, many proposals have heretofore been made on resin compositions comprising a polycarbonate based resin to which a polyester based resin is blended.

For example, polycarbonate resin blend composition including a polycarbonate resin and a polyester resin such as polybutylene terephthalate or polyethylene terephthalate are disclosed in Japanese Patent Application Laid-open No. 2 2 24-07-2006 Printed: 11-09-2006 DESC 0614660 58-18391 (cf., claims). The sheets and the like products obtained do not have satisfactory transparency. This could be due to the fact that the ester exchange reaction between the polycarbonate resin and the polyester resin proceeds insufficiently.

4] For this, resin compositions having improved flowability by controlling the ester exchange reaction between the polycarbonate resin and the polyester resin and also having excellent transparency. solvent resistance, and impact resistance are disclosed in Japanese Patent Application Laid-openNo. Hei 10-87973 (cf.,olaims). There have been problems that it has been difficult to control the ester exchange reaction and that it is necessary to use a polycarbonate resin having a functional group at a terminal thereof.

10005] Apolyesterresin consisting of terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol (hereinafter, sometimes, simply referred to as 1,4-CHDM) with the content of 1,4-CHDM being 40 mol% or more is compatibilized with a polycarbonate resin by mere melting and mixing to give a transparent resin composition having a single glass transition temperature and good mechanical properties, asdisciosedinRes, Disci. (UK), 229,182(1983).

6] However, such a polyester resin containing 1,4-CHDM in amounts of 40 mol% or more usually has a glass transition temperature of about 80 C or more and there is 24-07-2006 Printed: 11-09- 2006 DESC 0614660 a limitation in controlling the glass transition temperature of the resin blend composition with a polycarbonate resin to the fabrication temperature range of the PVC resin (usually.

about 50 C or more and about 100 C or less).

7] In addition, Japanese Patent Application Laid-open No. 2002-12748 discloses aresinbiend composition including from 5 mass parts to 95 mass parts of polycarbonate resins and from 5 mass parts to 95 mass parts of polyester resins, with at least one resin of the polyester resins containing a dicarboxylic acid polycondensation component composed of terephthalic acid component and 40 mol% or more of 1,4-CHDM, and the weight ratio of the at least one polyester resin to the total polyesterresin being 10% ormore, intended to improve the flowability of a polycarbonate resin without damaging its transparency and impact resistance. However, this does not have transparency and impact strength with good balance and is unsatisfactory.

8] Further, substitute materials for polyvinyl chloride have been demanded also for heat-shrinkable sheets that are widely used as shrink packages and shrink strapping packages, or shrink labels for plastic containers, broken-piece scattering preventing packages or cap seals of glass bottles. Heat-shrinkable sheets are required to have acceptable shrink finish, low natural shrink ratio (shrinking at temperatures slightly higher than room temperature, for example, in summer seasons, sheets slightly 24-07-2006 Printed: 11-09- 2006 DESC 0614660 shrinking before they are properly used), transparency, nerve of sheet (rigidity at room temperature), excellent mechanical strengths such as rupture resistance, and so on.

9] Further, substitute materials for polyvinyl chloride have been demanded also for sheets for resin-covered metal plates that are employed to increase the design quality of inner and outer package as well as appliance and furniture.

Such sheets for resin-covered metal plates are required to be calenderprocessed in the same temperature range as the polyvinyl chloride (usually, calender machine for flexible polyvinyl chloride is used in many cases at about 200 C as uppermost heating temperature to prevent thermal decomposition of the polyvinyl chloride during long retention in the machine, for example, for coping with troubles and taking into consideration heat generation by shearing with a calendar roll. Also, the sheets for resin-covered metal plates are required to clear a boiling water dipping test, which is one of evaluation items for resin-covered metal plates for building interior.

DISCLOSURE OF THE INVENTION

Problems to Be Solved by the Invention 10010] It is an object of the present Invention to provide a resin blend composition that can be advantageously used as a substitute material for PVC and is excellent in transparency, impact resistance, flowability, and secondary 24-07-2006 Printed: 11-09-2006 DESC 0614660 processability, and a sheet comprising the resin blend composition.

1] Further, it is another object of the present invent ion to provide a heat-shrinkable sheet that comprises a substitute material for PVC and is excellent in shrink finish, natural shrink, transparency, and mechanical strength such as sheet nerve (rigidity at room temperature), and shrink label and package with the heat-shrinkable sheet.

2] Still further, it is another object of the present invention to provide a sheet for resin-covered metal plates that comprises a substitute material for PVC and is excellent in calender processability and boiling water resistance.

Means for Solving the Problems [0013] As a result of extensive studies, inventors of the present invention have found that a resin blend composition comprising a polycarbonate based resin and a specified polyester based resin can solve the above-mentioned problems, thus accomplishing the present invention.

4] That is, the present invention provides a resin blend composition comprising 1 mass% or more and 99 mass% or less of a polycarbonate based resin (b-i), and 1 mass% or more and 99 mass% or less of a polyester based resin (b-2), wherein the polyester based resin (b-2) contains, as a carboxylic acid monomer unit (i), 80 mol% or more and 100 mol% or less of an aromatic dicarboxylic acid unit in total 6 24-07-2006 Printed: 11-09-2006 DESC 0614660 carboxylic acid monomer units (1), and as glycol monomer unit (ii), 0.1 mo].% or more and 40 mol% or less of a i,4-cyclohexanedimethano]. unit, and 0.5 mol% or more and mol% or less of a polyalkylene glycol unit having a number-average molecular weight of 500 or more and 3.000 or less in total glycol monomer units (ii).

5] Here, the polycarbonate based resin (b-i) is preferably an aromatic polycarbonate based resin.

6] The polyester based resin (b-2) may have a glass transition temperature of 0 C or more and 100 C or less as measured by differential scanning calorimeter at a heating rate of 10 C/minute.

7] The resin blend composition may have a single glass transition temperature as measured by differential scanning calorimeter at a heating rate of 10 C/minute, and the glass transition temperature may be positioned between the glass transition temperature of the polycarbonate based resin (b-i) and the glass transition temperature of the polyester based resin (b-2).

8] The resin blend composition may have a glass transition temperature of 50 C or more and 100 C or less, or i00 Cormore and 150 C or less, as measured by differential scanning calorimeter at a heating rate of 10 C/minute.

9] The resin blend composition may comprise 75 mass% or more and 95 mass% or less of the polycarbonate based resin (b-i) and 5 mass% ormore and 25 mass% or less of the polyester 7 24-07-2006 Printed: 11-09-2006 DESC 0614660 based resin (b-2).

0] Alternatively, the resin blend composition may comprise 60 mass% or more and 95 mass% or less of the polycarbonate based resin (b-i) and 5 mass% or more and 40 mass% or less of the polyester based resin (b-2).

1] Alternatively, the resin blend composition may comprise 30 mass% or more and 75 mass% or less of the polycarbonate based resin (b-i) and 25 mass% or more and mass% or less of the polyester based resin (b-2).

2] Alternatively, the resin blend composition may comprise 30 mass% or more and 70 mass% or less of the polycarbonate based resin (b-i) and 30 mass% or more and mass% or less of the polyester based resin (b-2).

3] The sheet of the present invention is made from any one of the above-mentioned resin blend compositions.

100241 The heat-shrinkable sheet of the present invention comprises a sheet made from the resin blend composition that contains 30 mass% or more and 70 mass% or less of the polycarbonate based resin (b-i) and 30 mass% or more and 70 mass% or less of the polyester based resin (b-2), wherein the sheet has been drawn in at least one direction and has a heat shrinkage ratio of 20% or more in at least one direction when dipped in hot water at 80 C for 10 seconds.

5] Here, the heat-shrinkable sheet of the present inventionmaybe suohthat aloss tangent (tanö) curveprepared by dynamic visooelasticity measurement of the 8 24-07-2006 Printed: 11-09-2006 DESC 0614660 heat-shrinkable sheet at a vibrational frequency of 10 Hz has a single peak in a range of 70 C or more and 130 C or less, with a half-value width of the loss tangent curve being 15 C or more.

6] The heat-shrinkable laminate sheet of the present invention includes layers (A) constituting both outer layers, and a layer (B) positioned between the both outer layers, wherein the sheet has been drawn in at least one axial direction and has a heat shrinkage ratio of 20% or more in the main shrinking direction when dipped in hot water at 80 C for 10 seconds, and wherein the layers (A) each comprise a resin composition composed mainly of a thermoplastic polyester based resin (a-i) , and the layer (B) comprises mass% or more and 70 mass% or less of the polycarbonate based resin (b-i) and 30 mass% or more and 70 mass% or less of the polyester based resin (b-2).

7] Here, the thermoplastic polyester based resin (a-i) may be a noncrystalline polyethylene terephthalate resin that contains 15 mol% or more and 50 mol% or less of a i,4- cyclohexanediinethanol unit in the total glycol monomer units in the thermoplastic polyester based resin (a-i).

8] The sheet for resin-covered metal plates of the present invention is obtained by using the resin blend composition that contains 60 mass% or more and 95 mass% or less of the polycarbonate based resin (b-i) and 5 mass% or more and 40 mass% or less of the polyester based resin (b-2).

9 24-07-2006 Printed: 11-09-2006 DESC 0614660 100291 The method of producing a sheet for resin-covered metal plates of the present invention Includes molding the resin blend composition by calender processing method at a temperature ranging from a temperature that is higher than a flow start temperature of the resin blend composition (Ti) by 10 C (I.e., T1+l0 C) to 200 C.

0] The resin-covered metal plate of the present invention is obtained by using a metal plate covered with the sheet for resin-covered metal plates.

1] The shrink label of the present invention Includes one selected from the heat-shrinkable sheet and the heat-shrinkable laminate sheets.

100321 The package of the present invention includes the shrink label attached to an article to be packaged [0033] The molded article of the present invention includes one of the resin blend compositions.

Effects of the Invention [0034] AccordIng to the present invention, resin blend compositions that can be advantageously used as substitute materials for PVC and are excellent In transparency, impact resisitance, flowablilty, and secondary processability and sheets including the resin compositions can be provided.

10035] Further, according to the present invention, heat-shrinkable sheets that are made from substitute materials for PVC and are excellent in shrink finish, natural 24-07-2006 Printed: 11-09-2006 DESC 0614660 shrinkage, transparency, and mechanical strength such as nerve of sheet (rigidity at room temperature), and shrink labels and packages with the heat-shrinkable sheets can be provided.

6] Furthermore, according to the present invention, sheets for resincovered metal plates that are med from substitute materials for PVC and are excellent in low temperature calender processability and boiling water resistance can be provided.

Embodiments for Carrying Out the Invention [0037] Hereinafter, the present invention will be explained in detail.

Note that in the present invention, the upper and lower limits of numerical ranges even when they are slightly outside the numerical ranges specified by the present invention should be construed to be within the scope of equivalents of the present invention as far as similar effects as those obtained within the specified ranges are obtained.

8] [Resin Blend Composition] The resin blend composition of the present invention comprises a polycarbonate based resin (b-i) and a polyester based resin (b-2).

9] The polycarbonate based resin (b-i) used in the present invention is preferably an aromatic polycarbonate 11 24-07-2006 ii Printed: 11-09-2006 DESC 0614660 based resin. The aromatic polycarbonate based resin (b-il) may be either a homopolymer or a copolymer. Further, the aroinaticpoi.ycarbonatebasedresjn (b-li) maybeofabranched structure or of a linear structure, or a mixture of the branched structure and the linear structure.

0] Thearomaticpolycarbonatebasedresjn (b-li) used in the present invention can be produced by any one of known methods such as a phosgene method, an ester exchange method, and a pyridine method.

Hereinafter, as an example, a method of producing aromatic polycarbonate based resin by the ester exchange method is explained.

[00411 The ester exchange method is a production method in which a dihydric phenol and a carbonate diester are subjected to molten ester exchange polycondensation with addition of a basic catalyst and further an acidic substance that neutralizes the basic catalyst.

Representative examples of the dihydric phenol include bisphenols; in particular, 2.2-bis(4-hydroxyplienyl)propane, i.e., bisphenol A is preferably used. Further, a part or whole of bisphenol A may be replaced by one or more other divalent phenol.

Examples of the other divalent phenol include hydroquinone, 4, 4-dihydroxydiphenyl, bis( 4-hydroxyphenyl)alkanes such as bis(4hydroxyphenyl)methane and 1, l-bis( 4-hydroxypheny].)ethane, 12 24-07-2006 Printed: 11-09-2006 DESC 0614660 bis(4-hydroxypbeny]) cycioalkafl such as 1, l-bis(4-hydroxypheny].)cyclohexane compounds such as bis(4hydroxyphenyi)sulfjd bis(4-hydroxyphenyl)suj.f one, bis (4 -hydroxypheny]. sulf oxide, and bis(4-hydroxyphenyl)ether alkylated bisphenols such as 2, 2-bis(3-methyi-4...hydroxypheflyi)propane and 2, 2-bis(3, 5-dimethyl-4-hydorxyphenyl)propane, and halogenated bisphenols such as 2, 2-bjs(3, 5-dibromo-4-hydroxypheny])propane and 2, 2-bis(3, 5-dichloro-4-hydroxypheny].)propane.

10042] Representative examples of the carbonate diester include diphenyl carbonate, ditolyl carbonate, bis(ohlorophenyj) carbonate, m-cresyl carbonate, dinaphthy]. carbonate, bis(bJphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and dicyclohexy]. carbonate. Among these, particularly diphenyl carbonate is preferably used.

3] The aromatic polycarbonate based resin (b-li) that can be used in the present invention has a weight-average molecularweight ofusuallylo, 000 ormore, preferably2O,000 or more and 100,000 or less, preferably 50, 000 or less taking into consideration balance between mechanical properties and molding processability. When the weight-average molecular weight is 10.000 or more, the obtained aromatic polycarbonate based resin will not have a decreased mechanical strength and when the upper limit of the 13 24-07-2006 Printed: 11-09-2006 DESC 0614660 weightaveragemolecu]. arweight is 100,000, appropriate melt viscosity can be obtained so that molding processability can also be maintained, and polymerization is completed in a relatively short time. Accordingly, the upper limit of 100,000 is preferable from the viewpoints of production cycle and cost. Note that in the present invention, the aromatic polycarbonate based resins (b-li) can be used singly or two or more of them can be used as mixtures.

[00441 Then, the polyester based resin (b-2) that constitutes the resin composition of the present invention is explained.

The polyester based resin (b-2) contains, as a carboxylic acid monomer unit (1), 80 mol% or more and 100 mol% or less of an aromatic dicarboxylic acid unit in total carboxylic acid monomer unit (1), and as glycol monomer unit (ii), 0.1 inol% or more and 40 mol% or less of a l,4-cyclohexanedinjetao unit, and 0.5 mol% or more and mol% or less of a polyalkylene glycol unit having a number-average molecular weight of 500 or more and 3.000 or less in total glycol monomer unit (Ii). Note that the polyester based resin (b- 2) may contain one or more other carboxylic acid monomer units and one or more other glycol monomer units as far as the above-mentioned conditions are satisfied.

5] It is desirable that the carboxylic acid monomer unit (i) in the polyester based resin (b-2) contains 80 mol% 14 24-07-2006 Printed: 11-09-2006 DESC 0614660 or more, preferably 85 mol% or more, more preferably 90 mol% or more of an aromatic dicarboxylic acid unit in the total carboxylic acid monomer units (1) in the polyester based resin (b-2). The aromatic dicarboxylic acids impart the obtaIned polyester based resin (b-2) with heat resistance and mechanical strength. When the content of the aromatic dicarboxylic acid unit Is 80 mol% or more in the total carboxylic acid monomer units (i), the obtained polyester based resin (b-2) will have good heat resistance and good mechanical strength. On the other hand, the upper limit of the content of the aromatic dicarboxyllo acid unit Is not particularly limited and the content of the aromatic carboxylic acid unit Is preferably 100 mol% or less.

6] The aromatic dicarboxyllo acids used are not particularly limited and examples thereof Include terephthalic acid, isophthallc acid, naphthalene-1,4- or -2, 6-dicarboxylia acid, anthracenedicarboxylic acid, 4,4 -dlphenyldicarboxylic acid, 4,4' -dlphenyl-ether-dicarboxy].ic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate. The aromatic dicarboxylic acid in the form of ester may be subjected to polymerization in some cases. Although the aromatic dicarboxylates that can be used are not particularly limited, for example, esters of the aromatic dicarboxylic acids are preferable. Specific examples thereof Include lower alkyl esters, aryl esters, carbonate esters, and acid halides.

24-07-2006 Printed: 11-09-2006 DESC 0614660 [0047] Here, the carboxylic acid monomer unit (1) may contain a small amount (usually in a range of less than 20 mol%) of aliphatic dicarboxylic acid unit. The aliphatic dicarboxylic acid is not particularly limited and examples thereof include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecanedjoic acid, dimer acid, 1,3- or 1, 4-oyclohexanedicarboxylic acid, cyclopentanedjcarboxyjjc acid, and 4,4' -dioyclohexyldicarboxyllc acid.

[00481 The glycol monomer unit (ii) used in the polyester based resin (b2), as described above, contains 0.1 mol% or more and 40 mol% or less of a 1,4-CHDM unit, and 0.5 mol% or more and 15 mol% or less of a polyalkylene glycol unit having a number-average molecular weight of 500 or more and 3,000 or less.

100491 As far as the above-mentioned conditions are satisfied, there is imposed no other limitations and examples of the glycol monomer unit (11) that can be used include units of ethylene glycol, diethylene glycol (inclusive of by-produced component), 1,2-propylene glycol, 1,3-propanediol, 2.2-dimethyl-1,3-propanediol, trans- or cys-2,2,4, 4tetramethyl-1, 3-cyclobutanediol, 2.2,4,4-tetramethyl-1,3-cyclobutanedjol 1,4-butanedjol, neopentyl glycol, 1,5-pentanedjol, 1,6-hexanediol, 1,3decamethylene glycol, 16 24-07-2006 Printed: 11-09-2006 DESC 0614660 cyclohexanediol, p- xylenedio]., bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis(2-hydroxyethyl ether).

[0050) These may be used singly or two or more of them may be used as mixtures. Further, the polyester based resin can be imparted with color tone, transparency, heat resistance, impact resistance, and so on. It is preferable to use ethylene glycol as the glycol monomer taking into consideration that it can impart the obtained polyester based resin with heat stability at molding and it is available industrially at low cost.

10051] The 1,4-CHDH unit used in the glycol monomer unit (ii) is to impart the obtained polyester based resin mainly with impact resistance. Conventionally, when it is contemplated to blend a polyester based resin composed of a terephthalic acid unit, an ethylene glycol unit and a 1,4-CHDM unit and a polycarbonate based resin to obtain a resin blend composition, generally the 1, 4-CHDM unit is added in amounts of at least 40 mol% in order to well miscibilize the polyester based resin and the polycarbonate based resin with each other to obtain a resin composition that is transparent and has a single glass transition temperature (Tg) and good mechanical properties (for example, of., Res. Disci. (UK), 229,182 (1983)). However, the polyester based resin that contains 40 mol% or more of 1,4-CHDI4 unit usually has a Pg of about 80 C or more, so that it is difficult to 17 24-07-2006 Printed: 11-09-2006 DESC 0614660 control the Tg of the resin blend composition with the polycarbonate based resin to a temperature range in which secondary process of the PVC resin is carried out (usually, about 50 C or more and about 100 C or less). As a result of extensive studies, the inventors of the present invention have found that a resin blend composition of a polycarbonate based resin and a specified polyester based resin has miscibility even when the content of 1,4-CHDM unit is 40 mol% or less.

2] When the content of 1,4-CHDM unit in the polyester based resin (b2) is 0.1 mol% or more in the glycol monomer unit (ii), the obtained polyester based resin (b-2) can be imparted with impact resistance, and when the upper limit thereof is 40 mol%, the effect of decreasing the glass transition temperature of the obtained polyester based resin (b-2) can be obtained. In the present invention, it is preferable that the content of the 1,4-CRDM unit is 1 mol% or more, more preferably 10 mol% or more and 38 mol% or less, more preferably 35 mol% or less in the total glycol monomer units (ii) in the polyester based resin (b-2). Note that 1,4-CHDMhas two isomers, i.e., cis-andtrans-forms. Either one of them may be used.

10053] The polyalkylene glycol unit having a number-average molecular weight of 500 or more and 3,000 or less contained in the glycol monomer unit (ii) is to impart the obtained polyester based resin mainly with flexibility 18 24-07-2006 Printed: 11-09-2006 DESC 0614660 and lower glass transition temperature (0 C or more and 50 C or less). When the content of the polyalkylene glycol is 0.5 mol% or more in the glycol monomer unit (ii), the obtained polyester based resin can be imparted with flexibility and a lower glass transition temperature. On the other hand, when the upper limit of the content of the polyalkylene glycol is 15 mol%, decreases in heat stability and mechanical strength of the obtained polyester based resin (b-2) can be prevented. In the present invention, it is preferable that the content of the polyalkylene glycol having a number-average molecular weight of 500 or more and 3.000 or less is 1 mol% or more, more preferably 3 mol% or more and 12 mol% or less, more preferably 10 mol% or less in the glyool monomer unit.

4] The polyalkylene glycol has a number-average molecular weight of 500 or more, preferably 800 or more, more preferably 1.000 or more and 3, 000 or less, preferably 2,000 or less. When the number-average molecular weight of the polyalkylene glycol is 500 or more, the obtained polyester based resin (b- 2) can be imparted with sufficient flexibility and when the upper limit of the number-average molecular weight of the polyalkylene glycol is 3, 000, a decrease in miscribility with other component or polymer, stagnation of polymerization reaction, and a decrease in the mechanical strength of the obtained polyester based resin can be prevented.

19 24-07-2006 Printed: 11-09-2006 DESC 0614660 [0055] Further, a mixture of polyalkylene glycols having different number- average molecular weights may be used.

When a plurality of kinds of polyalkylene glycol is used, it is preferable that the number-average molecular weight of it in a state where they are uniformly mixed is in the above-mentioned range. Note that the number-average molecular weight of the polyalkylene glycol can be measured by a generally used method such as gel permeation chromatography.

6] Examples of such polyalkylene glycol include polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymers, polytetramethylene glycol, and polyhexamethylene glycol.

Polytetramethylene glycol is particularly preferable.

These may be used singly or two or more of them may be used as mixtures.

7] Thepolyesterbasedresin (b-2) usedin thepresent invention, as described above, is constituted by a carboxylio acid monomer unit (i) that contains 80 mol% or more and 100 mol% or less of an aromatic dicarboxylic acid unit, and a glycol monomer unit (ii) that contains 0.1 mol% or more and mol% or less of a 1,4-CHDM unit, and 0.5 mol% or more and 15 mol% or less of a polyalkylene glycol unit having a number-average molecular weight of 500 or more and 3.000 or less. To adjust the flexibility, melt viscosity, transparency, mechanical properties, solvent resistance,24-07-2006 Printed: 11-09-2006 DESC 0614660 and so on of the obtained polyester based resin, a small amount (usually about 0.05 to about 2 mol%) of tribasic or higher polybasic carboxylic acid compound and/or a trihydric or higher polyhydric alcohol may further be polymerized with the polyester based resin.

8] Here, the tribasic or higher polybasic carboxylic acid compounds include trimellitic acid, pyromellitic acid, and anhydrides thereof. Trihydric or higher polyhydric alcohols include trimethyloipropane, pentaerythritol, and glycerin. These may be used singly or two or more of them may be used as mixtures. When only the polybasic carboxylic acid compound is used, the content of the polybasic carboxylic acid compound unit is usually 0.05 mol% or more, preferably 0.1 mol% or more and 2 mol% or less, preferably 1 mol% or less in the carboxylic acid monomer unit (i). On the other hand, when only the polyhydric alcohol is used, the content of the polyhydric alcohol unit is usually 0.05 mol% or more, preferably 0.1 mol% or more and 2 mol% or less, preferably 1 mol% or less in the glycol monomer unit (ii).

9] When the polybasic carboxylic acid compound and the polyhydric alcohol are used in combination, the sum of the content of the tribasic or higher polybasic carboxylic acid compound unit in the carboxylic acid monomer unit and the content of the trihydric or higher polyhydric alcohol in the glycol monomer unit is usually 0.05 mol% or more, preferably 0.1 mol% or more and 2 mol% or less, preferably 21 24-07-2006 Printed: 11-09-2006 DESC 0614660 1 mol% or less.

When the content of the polybasic carboxylic acid compound unit and/or polyhydric alcohol unit is 0.05 mol% or more in each of the abovementioned cases, the effect of improvement of the flexibility and melt viscosity of the obtained polyester based resin (b-2) can be obtained sufficiently and when such content is 2 mol% or less, control of the reaction will not become difficult due to gelling and generation of fish eyes in the obtained heat-shrinkable sheet can be prevented.

10060] The resin blend composition of the present invention includes 1 mass% or more and 99 mass% or less of a polycarbonate based resin (b-i), and 1 mass% or more and 99 mass% or less of a polyester based resin (b-2).

It is preferable that the blend ratio of the polycarbonate based resin (bi) and the polyester based resin (b-2) is adjusted as appropriate depending on the target application.

1] For example, to improve the flowability without damaging the features the aromatic polycarbonate based resins inherently have, for example, heat resistance, transparency, and impact strength, a resin blend composition constituted by 75 mass% or more and 95 mass% or less of the polycarbonate based resin (b-i) and 5 mass% or more and 25 mass% or less of the polyester based resin (b-2) may be preferably used.

22 24-07-2006 Printed: 11-09-2006 DESC 0614660 [0062] On the other hand, to impart the resin blend composition with secondary processability (heat shrinking ability, vacuum or pneumatic moldability, etc.) in the secondary process temperature range of the PVC resin (usually, about 50 C or more and about 100 C or less), the blend ratio of the resin blend composition is preferably selected such that the sum of 30 mass% or more and 75 mass% or less of the polycarbonate based resin (b-i) and 25 mass% or more and 70 mass% or less of the polyester based resin (b-2) is 100 mass%. More preferably, the blend ratio of the resin blend composition is selected such that the sum of 40 mass% or more and 70 mass% or less of the polycarbonate based resin (b-i) and30mass% ormoreand6omass% orless of thepolyester based resin (b-2) is 100 mass%.

3] When the resin blend composition of the present invention is used in the formation of heat-shrinkable sheet, it is preferable that the resin blend composition is made from 30 mass% or more and 70 mass% or less of the polycarbonate based resin (b-i) and 30 mass% or more and 70 mass% or less of the polyester based resin (b-2).

4] On the otherhand, when the resin blend composition of the present invention is used in the formation of a sheet for resin-covered metal plates, it is preferable that the resin blend composition is one that includes 60 mass% or more and 95 mass% or less of the polycarbonate based resin (b-i) and 5mass% or more and 40 mass% or less of the polyester 23 24-07-2006 Printed: 11-09-2006 DESC 0614660 based resin (b-2).

10065] The resin blend composition of the present invention has a single glass transition temperature as measured by differential scanning calorimeter at a heating rate of 10 C/minute and the glass transition temperature is preferably between the glass transition temperature of the polycarbonate based resin (b-i) and the glass transition temperature of the polyester based resin (b-2).

6] Here, "has a single glass transition temperature" means that when the resin blend composition is measured of glass transition temperature using a differential scanning calorimeter (DSC) at a heating ratio of 10 C/minute according to Japan Industrial Standard JIS K7121, only one peak that shows glass transition temperature appears. The resin blend composition having a single glass transition temperature results in that the obtained sheet can realize good miscibility and excellent transparency. The good miscibility in the sheet can also be confirmed, for example, by dynamic viscoelasticity measurement as well as by the above-mentioned DSC measurement.

7] The aromatic polycarbonate based resin has a glass transition temperature of usually about 150 C as measured by differential scanning calorimeter, and therefore, for example, to impart the resin blend composition of 30 mass% or more and 75 mass% or less of the polycarbonate based resin (b-i) and 25mass% ormore and lomass% or less of thepolyester 24 24-07-2006 Printed: 11-09-2006 DESC 0614660 based resin (b-2) with secondary processability at the secondary process temperature range of the PVC resin (usually about 50 C or more and about 100 C or less), that is, to make the glass transition temperature of the resin blend composition to 50 C or more and 100 C or less, preferably 55 C or more and 95 C or less, more preferably 60 C or more and 85 C or less, it is preferable that the polyester based resin (b-2) has a glass transition temperature of 0 C or more and 50 C or less, more preferably 5 C or more and 45 C or less. In this case, when the resin blend composition has a glass transition temperature of 50 C or more, sufficient heat resistance can be readily obtained while when the resin blend composition has a glass transition temperature of 100 C or less, heat resistance is good and sufficient secondary processability in the secondary process temperature range of the PVC resin can be readily obtained. Furthermore, when the glass transition temperature of the polyester based resin (b-2) is 0 C or more, there occurs no difficulty of handling due to blocking of pelletized resin and when the glass transition temperature of the polyester resin (b-2) is 50 C or less, the effect of decreasing the glass transition temperature of the resin blend composition can be obtained.

8] When the resin blend composition of the present invention is used in the formation of a sheet for resin-covered metal plates, the resin blend composition preferably has a glass transition temperature of 100 C or 24-07-2006 Printed: 11-09-2006 DESC 0614660 more and 150 C or less as measured by differential scanning calorimeter at a heating rate of 10 C/minute. In this case, the glass transition temperature of the resin blend composition of 100 C or more gives rise to satisfactory results in boilingwater dipping tests and thus is practically preferable.

9] [Heat-shrinkable sheet] Hereinafter, the heat-shrinkable sheet of the present invention is explained. The heat-shrinkable sheet of the present invention can be formed by using a polycarbonate based resin and a polyester based resin. The polyester based resin used here is preferably a resin that can shift the glass transition temperature ascribable to the polycarbonate based resin to a lower temperature side. The polycarbonate based resin may be, for example the polycarbonate based resin (b-i) and the polyester based resin may be, for example, the polyester based resin (b-2).

[00701 The heat-shrinkable sheet of the present invention preferably is one that is obtained by drawing a sheet prepared by using the resin blend composition in at least one direction and that has a heat shrinkage ratio of 20% or more in at least one direction when dipped in hot water at 80 C for seconds. More preferably, the heat-shrinkable sheet of the present invention Is such that a loss tangent (tanb) curve as measured by dynamic viscoelastiolty measurement 26 24-07-2006 Printed: 11-09-2006 DESC 0614660 at a vibrational frequency of 10 Hz has a single peak in a temperature range of 70 C or more and 130 C or less and a half-value width of the loss tangent (tanb) curve is 15 C or more.

[00711 In the present invention, the half-value width of the loss tangent (tanb) curve means an absolute value of a difference in temperature between a lower temperature side and a higher temperature side that indicate 1/2 of the value of the loss tangent (tanö) value at the maximum peak temperature of the loss tangent (tanö) curve. On the other hand, the peak temperature of the loss tangent (tanô) curve refers to a temperature at which first derivation of a variation of tanb versus temperature is zero.

2] Preferably, the heat-shrinkable sheet of the present invention is such that the loss tangent (tanö) curve obtained by dynamic viscoelasticity measurement has a single peak in a temperature range of 70 C or more and 130 C or less.

When the peak temperature of the loss tangent (tanö) curve is 70 C or more, natural shrink ratio can be prevented from becoming too high, so that the heat-shrinkable sheet can be imparted with good dimension stability, and shrink due to an increase in temperature at the time of attaching the sheet does not become too much. On the other hand, when the peak temperature of the loss tangent (tanô) curve is 130 C or less, the heat-shrinkable sheet can be imparted with heat shrinkability without decreasing drawability at 27 24-07-2006 Printed: 11-09-2006 DESC 0614660 low temperatures. In the present invention, the peak temperature of the loss tangent (tanö) curve of the heat-shrinkable sheet is preferably 75 C or more, more preferably 80 C or more and preferably 125 C or less, more preferably 120 C or less.

(0073] The heat-shrinkable sheet of the present invention is preferably such that the half-value width of the loss tangent (tanô) curve is at least 15 C. That is, inthepresent invention, the half-value width of the loss tangent (tanö) curve is 15 C or more, more preferably 17 C or more, particularly preferably 20 C or more. When the half-value width of the loss tangent (tanô) curve is 15 C or more, a heat-shrinkable sheet showing substantially no decrease in transparency and having appropriate miscibility and retaining good shrink finish can be obtained. On the other hand, the upper limit of the half-value width of the loss tangent (tanö) curve is not particularly limited. However, to prevent a decrease in transparency of the sheet due to a decrease in miscibility between the polycarbonate based resin and the polyester based resin, the half-value width of the loss tangent (tanö) curve is 40 C or less, preferably 35 C or less, more preferably 32 C or less, most preferably 30 C or less.

[00741 In order for the loss tangent (tanb) curve of the heat-shrinkable sheet to have a single peak in a temperature range of 70 C or more and 13 0 C or less and for the half-value 28 24-07-2006 Printed: 11-09-2006 DESC 0614660 width of the loss tangent (tanb) curve to be 15 C or more, it is preferable that the resin blend composition to be used in the formation of the sheet has a single peak in the temperature range of 70 C or more and 130 C or less and the half- value width of the loss tangent (tanb) curve is 15 C or more. In the present invention, by blending the polycarbonate basedresin (b-i) andthe polyesterbasedresin (b-2) with appropriately adjusting the blending ratio and so on taking into consideration the degree of miscibility and so on, the shape and half-value width of the loss tangent (tanö) curve of the whole resin blend composition can meet the above- described conditions. For example, when a polycarbonate based resin having a relatively high Tg is used, adding a relatively large amount of a polyester based resin capable of shifting Tg of the polycarbonate based resin toward the lower temperature side results in a decrease of Tg of the whole resin blend composition to prevent abrupt heat shrinkage, so that the shape and half-value width of the loss tangent (tanô) curve of the resin blend composition can be adapted to the above-mentioned conditions, that is, the curve has a single peak in the temperature range of 70 C or more and 130 C or less and the half-value width is 15 C or more.

5] The peak temperature and half-value width of the loss tangent (tanö) curve obtained by dynamic viscoelasticity measurement can be obtained by the following 29 24-07-2006 Printed: 11-09-2006 DESC 0614660 method. That is, a test sample of 4 mm in the longitudinal direction and 60 mm in the traverse direction is cut out of a target to be measured (for example, heat- shrinkable sheet). The test sample is measured for storage modulus (E') and loss elastic modulus (E'') using a viscoelasticity spectrometer DVA-200 (manufactured by IT Measurement Control Co.) under conditions of a vibrational frequency of 10 Hz, a strain of 0.1%, a temperature elevation rate of 3 C/minute, and a chuck interval of 25 mm transversely starting from a temperature of -50 C. Loss tangent (tanö=E''/E') curve is obtained from the obtained data, and then the peak temperature and half- value width of the loss tangent curve are obtained.

6] When the heat-shrinkable sheet of the present invention is formed from, for example, a noncrystalline polyester based resin or a polyester based resin with a relatively low crystallinity, the loss tangent value at the peak temperature of the loss tangent (tanb) curve is preferably 1. 5 or less, more preferably 1.4 or less, and particularly preferably 1.2 or less.

7] [Heat-shrinkable laminate sheet I Hereinafter, the heat-shrinkable laminate sheet of the present invention is explained. The heat-shrinkable laminate sheet of the present invention has layers (A) that constitute both outer layers and a layer (B) positioned 24-07-2006 Printed: 11-092006 DESC 0614660 between the both outer layers.

[00781 The layers (A) each include a resin composition that is mainly composed of a thermoplastic polyester based resin (a-i) containing at least one carboxylic acid monomer unit and at least one glycol monomer unit.

9] Examples of the carboxylic acid monomer unit contained in the thermoplastic polyester based resin (a-i) include units of aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 2chloroterepbthaliC acid, 2,5-dichloroterephthalic acid, 2methylterephthalic acid, 4, 4-stilebenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2, 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylio acid, bisbenzoic acid, bis(p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4, 4-diphenyl-ether-dlcarboxylic acid, 4, 4-diphenoxyethanedicarboxylic acid, 5-sodium (Na) sulfoisophthalate, and ethylene-bis-p-benzoio acid, units of aliphatic dicarboxylic acid such as adipic acid, sebaclo acid, azelaic acid, dodecanedloic acid, 1,3 -cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Among these, terephthalic acid unit is preferable. These carboxylic acid monomer units can be used singly or two or more of them can be used as mixtures.

0] On the other hand, examples of the glycol monomer 31 24-07-2006 Printed: 11-09-2006 DESC 0614660 unit contained in the thermoplastic polyester based resin (a-i) include units of diethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2, 2-dimethyl-1, 3-propanediol, trans- or cis-2,2,4,4-tetramethyl-1,3- cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyolohexanedimetlianol, 1. 3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis(2-hydroxyethyl ether) - Among these, ethylene glycol unit and i,4-oyclohexanedimethanol unit are preferable.

These glycol monomer units can be used singly or two or more of them can be used as mixtures.

1] Examples of the thermoplastic polyester based resin (a-i) that contains such a carboxylic acid monomer unit and such a glycol monomer unit include a polyethylene terephthalate resin, a polypropylene terephthalate resin, a polybutylene terephthalate resin, a polyethylene isophthalate resin, a polyethylene naphthalate resin, a polybutylene naphthalate resin, polyethylene terephthalate/isopbthalate copolymer resin, and a noncrystalline polyethylene terephalate resin containing mol% or more and 50 mol% or less of a 1,4-cyclohexanedimethanol unit in the total glycol monomer units. Further, a thermoplastic polyester based elastomer 32 24-07-2006 Printed: 11-09-2006 DESC 0614660 constituted by an aromatic polyester having a high melting point and high crystallinity as a hard segment and a noncrystalline polyester or a noncrystalline polyether as a soft segment may be blended as appropriate. These may be used singly or two or more of them may be used as mixtures.

2] In the present invention, a noncrystalline polyethylene terephthalate resin containing 15 mol% or more and 50 mol% or less of a 1, 4-cyclohexanedimetbanol unit in the total glyool monomer units is advantageously used as the thermoplastic polyester based resin (a-i). The noncrystalline polyethylene terephthalate resin contains mainly terephthalic acid as the carboxylic acid monomer and mainly ethylene glycol and 1,4-CHDM as the glycol monomer.

3] Here, in the noncrystalline polyethylene terephthalate resin, the content of the 1,4-CHDM unit is preferably 15 mol% or more, more preferably 20 mol% or more and preferably 50 mol% or less, more preferably 40 mol% or less in the total glycol monomer units of the thermoplastic polyester based resin (a-i). When the content of the 1,4-CHDM unit is 15 mol% or more, the problem of printability due to crystallization can hardly occur and embrittlement with time can be prevented. On the other hand, when the upper limit of the content of the 1,4-CHDM unit is 50 mol%, the viscosity of the resin blend composition does not become too high at the time of melt extruding and good film forming property can be obtained. Note that 1, 4-CHDM has two isomers, 24- 07-2006 Printed: 11-09-2006 DESC 0614660 i.e., cis- and trans-forms. Either one of these may be used.

4] The heat-shrinkable laminate sheet of the present invention has layers (A) that constitute a front layer and a back layer and a layer (B) that is an intermediate layer between the both outer layers (A). The layer (B) is made from the resin blend composition of comprises 30 mass% or more and 70 mass% or less of the polycarbonate based resin (b-i) and 30mass% ormore and 70 mass% or less of the polyester based resin (b-2). The polyester based resin (b-2) contains 80 mol% or more and 100 mol% or less of an aromatic carboxylic acid unit as the carboxylic acid monomer unit, and 0. 1 mol% or more and 40 mol% or less of a 1,4-CHDM unit and 0.5 inol% or more and 15 mol% or less of a polyalkylene glycol unit having a number-average molecular weight of 500 or more and 3.000 or less as the glycol monomer unit.

Note that, the polyester based resin (b-2) may contain one or more other carboxylic acid monomer units and one or more other glycol monomer units as far as the above-mentioned conditions are satisfied.

5] The polycarbonate based resin (b-i) that forms the layer (B) is preferably an aromatic polycarbonate based resin (b-li). The layer (B) Is preferably formed from the resin blend composition of the present invention. The polycarbonatebasedresin (b-i) and the polyester basedresin (b-2) may be those described above.

10086] The thermoplastic polyester based resin (a-i) and 34 24-07-2006 Printed: 11-09-2006 DESC 0614660 the polyester based resin (b-2) used in the present invention may, as far as the effects of the present invention are not substantially damaged, contain other polyester resins, polyether, polyamide, polyolef in, polymethyl methacrylate and the like resins, rubbery modifiers of a core-shell type, graft type, or linear random and block copolymers, inorganic particles suchas silica, talc, kaolin, and calcium carbonate, pigments such as titanium oxide and carbon black, flame retardants, weather stabilizers, heat resistant stabilizers, hydrolysis inhibitors (monomer or polymer of carbodilmide compounds), antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, antioxidants and the like additives as appropriate.

[00871 The thermoplastic polyester based resin (a-i) and the polyester based resin (b-2) used in the present invention each can be produced by a known direct polymerization method or ester exchange method. Esterification catalysts and ester exchange catalysts, for example, titanium butoxide, dibutyl tin oxide, magnesium acetate, and manganese acetate, andpolymerization catalysts, for example, titaniumbutoxide, dibutyl tin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide can be used as necessary.

8] The thermoplasticpolyesterbasedresin (a-i) and the polyester based resin (b-2) each have an intrinsic 24-07-2006 Printed: 11-09-2006 DESC 0614660 viscosity of 0.4 dug or more, preferably 0.7 dug or more and 1.5 dug or less, preferably 1.2 dug or less as measured at 30 C In tetrachioroethane/phenol (mass ratio 1/i) as a solvent. When the intrinsic viscosity of each resin is 0.4 dl/g or more, the obtained polyester based resin will not have a decreased humidity resistance or a decreased mechanical strength. On the other hand, when the upper limit of the intrinsic viscosity of each resin is 1.5 dug, polymerization is completed in a relatively short time, so that such upper limit is preferable from the viewpoints of production cycle and cost. Note that in the present invention, these resins can be used singly or two or more of them can be used as mixtures.

10089] The layer (B) that constitutes the heat-shrinkable laminate sheet of the present invention Is preferably made from the resin blend composition of 30 mass% or more and mass% or less of the polycarbonate based resin (b-i) and mass% or more and 70 mass% or less of the polyester based resin (b-2). The polycarbonate based resin (b-i) is preferably the aromatic polycarbonate based resin (b-li).

When the polycarbonate based resin (b-i) is In an amount of 70 mass% or less and the polyester based resin (b-2) is in an amount of 30 mass% or more, the resin blend composition can be adjusted to have a glass transition temperature in a desired range and provides good drawability at low temperatures, so that it can be Imparted with heat 36 24-07-2006 Printed: 11-09-2006 DESC 0614660 shrinkability as specified by the present invention. On the other hand, when the polycarbonate based resin (b-i) is in an amount of 30 mass% or more and the polyester based resin (b-2) is In an amount of 70 mass% or less, the resin blend composition will not have too low a glass transition temperature and provides good natural shrink ratio and suitable nerve of sheet. From these it follows that in the present invention, it is more preferable to use a resin blend composition of 40 mass% or more and 65 mass% or less of the aromatic polycarbonate based resin (b-i) and 35 mass% or more and 60 mass% or less of the polyester based resin (b-2).

Note that in this case, the resin blend composition of the polycarbonate basedresin (b-i) andthepolyesterbasedresln (b-2) has a single glass transition temperature as measured by differential scanning calorimeter at a heating rate of 10 C/minute and that the glass transition temperature is 50 C or more and 100 C or less.

[00901 The glass transition temperature of theresinblend composition of 50 C or more is practically preferable since the obtained heat-shrinkable laminate sheet can be prevented from natural shrinkage, so that a sheet having good dimension stability can be obtained. On the other hand, the glass transition temperature of 100 C or less is preferable since shrink properties such as shrink ratio, shrink start temperature and shrink gradient that enable realization of shrink processing in a relatively short time (on the order 37 24-07-2006 Printed: 11-09-2006 DESC 0614660 of several seconds to ten and several seconds) and imparting high quality shrink finish to the sheet. From these it follows that in the present Invention, the glass transition temperature of the resin blend composition of the polycarbonatebasedresin (b-i) andthepolyesterbasedresifl (b-2) is 55 C or more, more preferably 60 C or more and 95 C or less, more preferably 85 C or less.

(0091] The aromatic polycarbonate based resin used in the layer (B) has a glass transition temperature as measured by differential scanning calorimeter is usually about 150 C.

Therefore, to realize a glass transition temperature of 50 C or more and 100 C or less for the resin blend composition of 30 mass% or more and 70 mass% or less of the polycarbonate based resin (b-i) and 30 mass% or more and 70 mass% or less of the polyester based resin (b-2), the glass transition temperature of the polyester based resin (b-2) preferably is 0 C or more, more preferably 5 C or more and 50 C or less, more preferably 45 C or less. When the glass transition temperature of the polyester based resin (b-2) is 0 C or more, occurrence of blocking In the material pellets can be prevented. On the other hand, the upper limit of the glass transition temperature of the polyester based resin (b-2) of 50 C Is preferable since the glass transition temperature of the resin blend composition can be decreased with ease into a predetermined range.

2] In the present invention, for the purpose of 38 24-07-2006 Printed: 1 1-09-2 006 DESC 0614660 improving or adjusting moldability and various physical properties of resin blendcomposition, heat-shrinkable sheet and so on, the resin blend composition, the heat- shrinkable sheet, and the layers (A) and/or the layer (B) of the heat- shrinkable laminate sheet may, as far as the effects of the present invention are not substantially damaged, contain recycled resins such as cut edges of the sheet produced, for example, by trimming loss (usually added to the layer (B)), resins such as polyester other than the polyester based resin (a-i) and the polyester based resin (b-2), and polyether, polyamide, polyo].ef in, polymethyl methacrylate, rubbery modifiers such as random and block copolymers of a core-shell type, graft type or linear type, inorganic particles such as silica, talc, kaolin, and calcium carbonate, pigments such as titanium oxide and carbon black, flame retardants, weather stabilizers, heat resistant stabilizers, hydrolysis inhibitors (monomer or polymer of carbodlimide compounds, epoxy compounds, oxazoline compounds, etc.), antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, antioxidants and the like additives as appropriate.

3] In the present invention, it is preferable that reactions that occur between the polycarbonate based resin (b-i) and the polyester based resin (b-2) (for example, ester exchange reaction) at the time of melt kneading is inhibited 39 24-07-2006 Printed: 11-09-2006 DESC 0614660 asmuchaspossible. Whenthe reactionproceeds excessively, the obtained resin blend composition not only has deteriorated thermal properties but also causes coloring or foaming phenomenon to occur in the sheet due togeneration of gas, which is not preferable. For this reason, it is preferable that careful attention is paid on the kind of catalyst of material (Ge catalysts are preferably used), the amount of catalyst that remains in the material, or temperature and retention time at the time of melt kneading, and addition of an inhibitor f or ester exchange reaction, such as a phosphorus compound (for example, phosphoric acid or phosphorous acid compound) and so on. The melt kneading temperature, which may be adjusted as appropriate depending on the flow properties and film forming properties of the resin blend composition, is preferably in a range of generally 320 C or less, preferably from 240 C to 280 C.

4] The resin composition of the present invention can be molded into a sheet, film, plate or the like by a known method, for example, an extrusion casting method using a T-die, a calender processing method, an inflation method or the like. In the present invention, film, sheet or plate are collectively referred to as a sheet. The term "sheet" indicates which one of these or a plurality of these may be judged as appropriate.

5] The thickness of the formed sheet Is not particularly limited and usually 5 m or more and 3,000 un 24-07-2006 Printed: 11-09-2006 DESC 0614660 or less. Upon melt kneading, a single screw extruder, a twin screw extruder, a kneader, a mixer and so on that are conventionally used can be employed. Preferably, a twin screw extruder is used from the viewpoints of homogeneous dispersion of the resin blend composition and stability of the mechanical strength of the obtained sheet.

6] In the present invention, the obtained sheet can be subjected to monoaxia]. or biaxial drawing. Further, the sheet can be subjected to surface treatment or surface processing such as printing, embossing, electron beam Irradiation, coating, or vapor deposition.

(0097] The sheet made from the resin composition of the present invention is excellent in transparency, and mechanical properties such as Impact resistance and elongation at break, and has secondary processability in the secondary process temperature range of the PVC resin (usually about 50 C or more and about 100 C or less), so that It can be advantageously used in applications In which the PVC resins have been conventionally used. For example, the sheet of the present invention can be used as building materials, interior parts, transparent sheets, sheets for resin-covered metal plates, sheets for molding (vacuum/pneumatic molding, hot press molding. etc.), color plates, transparent plates, shrink sheets, shrink labels, shrink tubes and so on.

(0098] When the resin blend composition is molded into 41 24-07-2006 Printed: 11-09-2006 DESC 0614660 sheets by a calender processing method, the roll-setting temperature in the calender processing method is adjusted as appropriate depending on the flow properties of the resin blend composition, roll peelability, film-forming speed, and so on and is preferably a temperature of flow start temperature of the resin blend composition (Ti) + 10 C (11+10 C) or more and 250 C or less, preferably a temperature of flow start temperature (Ti) + 10 C (11+10 C) or more and 200 C or less. In particular, if film formation is possible at a rollsetting temperature of 200 C or less, existing calender processing machine for flexible polyvinyl chloride can be used without so much special modification. Further, processing at lower temperatures will give less adverse influences, for example, by hydrolysis. In the case of aromatic polycarbonate based resin alone, the grade of a weight-average molecular weight of 20,000 or more in which impact resistance and mechanical strength are exhibited stably is obtained at a flow start temperature of 190 C or more (about 190 C or more and about 205 C or less) , so that at a roll-setting temperature of 200 C or less, it tends to be difficult to perform stable calender processing.

9] Further, in the present invention, prekneading can be performed prior to the calendar processing. Upon the prekneading, a single screw extruder, a twin screw extruder, a kneader, a mixer and so on that are conventionally used can be employed. While not particularly limited, it is 42 24-07-2006 Printed: 11-09-2006 DESC 0614660 preferable that a twin screw extruder is used from the viewpoints of homogeneous dispersion of the resin blend composition and stability of the mechanical strength of the obtained sheet.

0] Further, when the resin blend composition of the present invention is molded into sheets by a calender processing method, it is preferable that a lubricant is added to the composition in order to increase the roll peelability of the sheet.

Examples of lubricant that can be used include hydrocarbon based lubricants such as paraffin and polyethylene wax, higher fatty acid based lubricants such as stearic acid, metal soap based lubricants such as calcium stearic acid, ester based lubricants such as montanic acid, and organic fine particles such as benzoguanamine, and crosslinked acrylic resins composed mainly of polymethyl methacrylate. Among organic lubricants that provide synergistic effects with the inorganic lubricants, those that increase outside lubricity and have good miscibility with the resin are advantageously used. Besides, the lubricants are required to satisfy conditions that they have heat stability upon melt kneading and montanic acid wax is preferably used in the present Invention.

10101] Here, the montanjc acid wax refers to montan wax of fossil wax containing mainly fatty acids and fatty alcohol having 21 to 34 carbon atoms obtained by solvent extraction 43 24-07-2006 Printed: 11-09-2006 DESC 0614660 of brown coal and waxes obtained by esterification or partial saponification of the montan wax. Specific examples thereof include Hoechst WAX S (manufactured by Hoechst Corporation) obtained by oxidizing montan wax, Hoechst WAX E (manufactured by Hoechst Corporation), i.e., montanic acid diester obtained by esterification of montan wax with ethylene glycol, Hostalub WE4O (manufactured by Hoechst Corporation), i.e., montanic acid diester obtained by esterification of montan waxwlth glycerin, andHoeohst WAXOP (manufacturedbyHoechst Corporation), i.e., partially saponifiedmontanlo acidester obtained by partial esterification of montan wax with butylene glycol and the remainder being saponified with calcium hydroxide.

2] The amount of lubricant to be added is 0.05 mass part or more and 3.0 mass part or less, preferably 0.1 mass part or more and 1.5 mass parts or less per 100 mass parts of the resin blend composition. When the amount of the lubricant to be added is less than 0.05 mass parts, less effect of improvement of roll peelability is obtained. On the other hand, when the amount of the lubricant to be added exceeds 3.0 mass parts, the problems tend to arise undesirably that bleeding to the surface of the sheet occurs and the mechanical strength of sheet is decreased.

[01031 It is important that the heat-shrinkable sheet and heat-shrinkable laminate sheet of the present invention have been drawn at least in one axial direction and exhibit heat 44 24-07-2006 Printed: 11-09-2006 DESC 0614660 shrinkage ratio of 20% or more in a main shrinking direction when dipped in hot water at 80 C for 10 seconds.

4] The condition serves as an index for judging the adaptability of the sheet to shrink processing process so that the sheet can be shrinkprocessed in a relatively short time (on the order of about several seconds to ten and several seconds) when the heat-shrinkable sheet or heat-shrinkable laminate sheet of the present invention is used as a shrink label for PET bottles and the like. For example, the shrink ratio required to heat-shrinkable sheet and the like that is applied to a shrink label for PET bottles may vary depending on the shape thereof and generally about 20% or more and about 40% or less. A heat shrinking machine that is currently used industrially for attaching labels on PET bottles is one that Is called steam shrinker that uses steam as a heating medium with which shrink processing is performed. The heat-shrinkable sheet and heat-shrinkable laminate sheet has to be shrinked sufficiently at a temperature as low as possible from the viewpoint of influence of heat to a target article to be covered.

5] Taking also industrial productivity and soon into consideration, the sheet having a heat shrink ratio of 20% or more tends to be closely attached to the target article to be covered sufficiently within a heat shrinking time.

In the present invention, it is preferable that the heat shrink ratio of the sheet when dipped In hot water at 80 C 24-07-2006 Printed: 11-09-2006 DESC 0614660 for 10 seconds in at least one direction, usually in the main shrinking direction is 30% or more, preferably 40% or more and 70% or less, preferably 65% or less.

6] The heat-shrinkable sheet and heat-shrinkable laminate sheet for shrink label for PET bottles have a heat shrink ratio of preferably 10% or less, more preferably 7% or less in a direction perpendicular to the main shrinking direction when dipped in hot water at 80 C for 10 seconds.

The heat-shrinkable sheet or the like having a heat shrink ratio of 10% or less in the direction perpendicular to the main shrinking direction will neither have a reduced size in the direction perpendicular to the main shrinking direction after shrinking nor tend to cause strains in printed patterns or letters after shrinking, or when the sheet is used as a shrink label for square bottles, occurrence of troubles such as longitudinal dragging can be prevented.

[0107J It is important that the heat-shrinkable sheet and heat-shrinkable laminate sheet of the present invention have a modulus of elongation of 1, 200 MPa or more, preferably 1,800 HPa or more, more preferably 2,000 MPa or more in the direction perpendicular to the main shrinking direction of the sheet from the viewpoint of nerve (rigidity at room temperature). The upper limit of the modulus of elongation of the heat-shrinkable sheet and heat-shrinkable laminate sheet that are usually used is about 4,000 MPa, preferably about 3.000 HPa. The modulus of elongation of the sheet 46 24-07-2006 Printed: 11-09-2006 DESC 0614660 in the direction perpendicular to the main shrinking direction of the sheet of 1,500 MPa or more is preferable, since the nerve (rigidity at room temperature) of the whole sheet can be increased, and when a container such as a PET bottle is covered with a bag-formed sheet by using a labeling machine or the like, the problems of covering the sheet in a slanted manner or a reduction of yield due to firmness failure of the sheet can hardly occur even with a reduced thickness of the sheet. The modulus of elongation can be measured at the condition of 23 C according to the Japan Industrial Standard JIS K7127.

8] Further, the modulus of elongation of the sheet in the main shrinking direction of the sheet is not particularly limited as far as the nerve of the sheet is obtained and is 1,200 MPa or more, preferably 1, 800 MPa or more, more preferably 2.000 MPa or more. The upper limit of the modulus of elongation of the sheet is about 6,000 MPa, preferably about 4,500 Mpa, more preferably about 4.000 MPa. By setting the modulus of elongation in the main shrinking direction of the sheet to 1,200 MPa or more and 6,000 MPa or less, the nerve of the sheet in the both directions can be increased and such modulus of elongation is preferable.

9] The breakage resistance of the heat-shrinkable sheet and heatshrinkable laminate sheet of the present invention is evaluated by modulus of elongation at break.

The sheets have a percentage elongation of 100% or more, 47 24-07-2006 Printed: 11-09-2006 DESC 0614660 preferably 200% or more, more preferably 300% or more in the take-up (flow) direction (MD) of the sheet for use as labels in tensile breakage tests in environment at 0 C. The tensile elongation at break of 100% or more in the environment at 0 C is preferable, since breakage and the like failures of the sheet will not tend to occur in the process of printing/bag formation. In the case of an increased tension on the sheet with an increasing speed of the process such as printing/bag formation, the sheet having an elongation at break of 200% or more is more preferable since the sheet is difficult to be broken.

0] The seal strength of the heat-shrinkable sheet and heat-shrinkable laminate sheet of the present invention is 3N/15 mm width or more, preferably 5N/15 mm width or more, more preferably 7 N/15 mm width or more as measured using a peeling method by a T-type peeling method when peeled in the main shrinking direction in the environment of 23 C and 50% RH at a test speed of 200 mm/minute. While the upper limit of the seal strength is not particularly limited, it is preferably about 15N/15 mm width from viewpoint of solvent resistance of the sheet surface.

1] The sheet, heat-shrinkable sheet, and heat-shrinkable laminate sheet of the present invent ion have transparency such that when a sheet of a thickness of, for example, 50 pun is measured according to the Japan Industrial Standard JIS K 7105, the sheet has a total haze of preferably 48 24-07-2006 Printed: 11-09-2006 DESC 0614660 10% or less, more preferably 7% or less, particularly preferably 5% or less. The total haze of the sheet of 10% or less is preferable since clear display effect can be obtained.

2] The natural shrink ratio of the heat-shrinkable sheet and heatshrinkable laminate sheet of the present invention is desirably as small as possible. Generally, the natural shrink ratio of heat-shrinkable sheet or the like is, for example, 2.0% or less, preferably 1.5% or less, more preferably 1.0% or less after storage at 30 C for 30 days. When the natural shrink ratio of the sheet under the above-mentioned conditions is 2.0% or less, the prepared sheet even after long-term storage can be attached to a container stably, so that no practical problems tend to occur.

3] Then, perforation cutting property of the heat-shrinkable laminate sheet of the present invention is explained.

Here, perforation means perforation formed in cap seals or labels that are attached onto plastic bottles, glass bottles and soon by heat shrinking to impart them with readily opening property or make it easy to peel of f from the bottles or bins when they are recycled. Usually, perforations are formed in a single line or two or more lines. Perforation processing is usually performed by using a perforating blade usually at the time of center seal processing. Length of perforations and intervals between adjacent perforations 49 24-07-2006 Printed: 11-09-2006 DESC 0614660 each is generally about 1 mm or about 0.7 mm. However, the present invention is not limited thereto.

4] The thickness of the heat-shrinkable laminate sheet of the present invention is not particularly limited and is usually 5 m or more, preferably 20 m or more and m or less, preferably 80 m or less. When the thickness of the heat-shrinkable laminate sheet is 5 &m or more, the handleability of sheet is good and on the other hand, the thickness of the heat-shrinkable laminate sheet of 100 tm or less results in good shrink processability of the sheet and is also economically advantageous. Further, the heat-shrinkable laminate sheet of the present invention can be subjected to surface treatment or surface processing, such as corona treatment, printing, coating, vapor deposition and so on and further to bag formation processing by using various solvents or by heat sealing or perforation processing.

5] The thickness of the respective layers that constitute the heatshrinkable laminate sheet of the present invention can be set taking into consideration the above-mentioned effects and actions and is not particularly limited. For example, the ratio of thicknesses of layer (A)/layer (B)/layer (A) is preferably set to be within a range of 1/2/1 to 1/12/1, more preferably 1/3/1 to 1/10/1.

When the ratio of thickness of the layer (B), which is an intermediate layer, is less than 1/2/1, the effects of 24-07-2006 Printed: 11-09-2006 DESC 0614660 improvement of shrink finish and perforation cutting property are not remarkable. Further, the polycarbonate based resin (b-i) that forms the layer (B) generally has poor solvent resistance that is necessary at the time of printing, so that it is preferable that the polyester based resin (b-2) is blended therewith and that the layers (A) are laminated as outer layers. Taking into these in consideration, the thickness of the layer (A) is preferably 1 &m or more, more preferably 3 un or more and the upper limit thereof is preferably 20 pim or less.

6] Then, the production methods for the sheet, heat-shrinkable sheet, and heat-shrinkable laminate sheet of the present invention are explained. The sheet, heat-shrinkable sheet, and heat-shrinkable laminate sheet of the present invention can be produced by conventional methods.

The form of the sheet may be either planar or tubular and planar sheet is more preferable from the viewpoints of, for example, productivity (multiple products can be obtained in the width direction of the original sheet) and enablement of printing on inner surfaces.

7] For example, the method of producing a planar laminate sheet is explained. For example, a monoaxially or biaxially drawn laminate sheet can be obtained by the steps of melt kneading resins as materials by means of a plurality of extruders, coextruding the molten and kneaded 51 24-07-2006 Printed: 11-09-2006 DESC 0614660 resins through a T die, cooling the resins to solidify on a chilled roll (cast roll) to form a laminate, subjecting the laminate to roll drawing in the longitudinal direction and tenter drawing In the transverse direction, then annealing, cooling, and optionally subjecting the resultant to corona discharge treatment.

A tubular sheet produced by a tubular method may be cut open into a planar form. Here, the resin composition and the like as materials may be melt-kneaded in advance and cut into pellets. For example, the pelletlike resin composition may be again melt-extruded to form a heatshrinkable laminate sheet.

8] For melt-kneading, a single screw extruder, a twin screw extruder, a kneader, a mixer and so on can be used and is not particularly limited. Taking Into consideration homogenous dispersion of the resin blend composition, and stability of the mechanical strength and transparency of the obtained heat-shrinkable sheet, and so on, it is preferable that a twin-screw extruder Is used.

9] In the present Invention, it is preferable that reactions (for example, ester exchange reaction) that occur at the time of melt kneading are Inhibited as much as possible.

That is, reactions (ester exchange reaction and so on) that occur between the polycarbonate based resin (b-i) and the polyester based resin (b-2) that constitute the layer (B), and/or the thermoplastic polyester based resin (a-i) that 52 24-07-2006 Printed: 11-09-2006 DESC 0614660 is added as recycle resin or the like preferably are inhibited as much as possible.

0] The reactions that proceed excessively may undesirably lead in some cases to deterioration of the thermal propertIes of the obtained resin blend composition or to coloring or foaming phenomenon due to gas generation in the melt-extruded sheet. For this reason, it is preferable that careful attention is paid on the kind of catalyst of material (Ge catalysts are preferably used), the amount of catalyst that remains in the material, and temperature and retention time at the time of melt kneading. It Is preferable that an Inhibitor for ester exchange reaction, such as a phosphorus based compound (for example, phosphoric acid or phosphorous acid compound) is added as necessary.

1] For example, when a T-die method is used, the molding temperature, which may be adjusted as appropriate depending on the flow properties and film forming properties of the resin blend composition, Is preferably in a range of generally 320 C or less, preferably 240 C or more and 280 C or less. The melt-extruded resin, after being cooled by means of chilled roll, air, water or the like, Is heated again by a suitable method such as hot air, hot water, Infrared radiation, or microwave, and then drawn monoaxially or biaxially by a roll method, a tenter method, a tubular method or the like.

2] While the drawing temperature needs to be varied 53 24-07-2006 Printed: 11-09-2006 DESC 0614660 depending on the glass transition temperature of the resin composition used and properties required for the heat-shrinkable sheet, generally, the drawing temperature Is controlled within the range of 60 C or more and 130 C or less, preferably 70 C or more and 120 C or less. The drawing ratio is determined depending on the properties of the resin composition to be used, drawing means, drawing temperature, and shape of the target product and so on within the range of 1.5 times or more and 10 times or less, preferably 1.7 times or more and 7 times or less In the main shrinking direction monoaxla].].y and/or biaxially as appropriate.

When drawing is performed monoaxially in the transverse direction, it is effective to perform drawing also in the longitudinal direction at a drawing ratio of 1.05 times or more and 1.8 times or less, for example, for improving the mechanical strength of the sheet. Then, for example, for decreasing the natural shrink ratio and improving the heat shrinking properties of the sheet, the drawn sheet is optionally subjected to heat treatment or relaxation treatment at a temperature of about 50 C or more and 100 C orless, andthen is quenchedin atime inwhich theorientation of molecules is not relaxed to obtain a heat - shrinkable sheet.

3] [Sheet for resin-covered metal plates] The resin blend composition of the present invention can be used to form a sheet for resin-covered metal plates.

54 24-07-2006 Printed: 11-09-2006 DESC 0614660 The sheet for resincovered metal plates of the present invention needs to be made from a resin blend composition that contains 60 mass% or more and 95 mass% or less of the polycarbonate based resin (b-i) and 5 mass% or more and 40 mass% or less of the polyester based resin (b-2), and preferably a resin blend composition that contains 65 mass% or more and 90 mass% or less of the polycarbonate based resin (b-i) and 10 mass% ormore and 35mass% or less of thepolyester basedresjn (b-2). The resin blend composition that contains 95 mass% or less of the polycarbonate based resin (b-i) and Smass%ormoreofthepolyesterba$edresjn (b-2) cansuitab].y decrease the flow start temperature of the polycarbonate based resin (b-i), so that calender processing of the resin blend composition can be performed using a calender processing machine for flexible polyvinyl chloride. That is, the bank (resin blend composition) can be regularly and stably rotated in the processing machine.

4] Further, when the amount of the polycarbonate based resin (b-i) is 60 mass% or more and the amount of the polyester based resin (b-2) Is 40 mass% or less, the glass transition temperature of the obtained resin blend composition is not decreased widely, so that satisfactory results can be obtained in boiling water dipping tests and the mechanical strength such as elongation at break is not decreased, so that a decrease in secondary processability does not occur.

Therefore, the obtained resin-covered metal plates can be 24-07-2006 Printed: 11-09-2006 DESC 0614660 subjected to secondary process such as bending.

5] In the present invention, the resin blend composition of the present Invention can be used to form a laminate. For example, a laminate can be formed by laminating on a layer of the resin blend composition of the present Invention a layer of another material and also, the laminate can be formed Into a heat-shrinkable laminate sheet.

The laminate can be constructed such that the layer of the resin blend composition of the present Invention Is arranged as an intermediate layer and layers of another material are arranged on both sides thereof as outer layers.

10126] The sheet for resin-covered metal plates of the present invention can be produced by a known method, for example, an extrusloncastingmethodusingaT_dj, acalender processing method, an Inflation method or the like. Taking into consideration adaptation to multi-item small lot production Involving change of color, a calender processing method Is preferable.

7] The thickness of the sheet for resin-covered metal plates of the present invention is not particularly limited and usually Is 50 p.m or more and 500 pm or less. If the thickness of the sheet is less than 50 pm, when the sheet is used for resin-covered metal plates, the sheet tends to have poor performance as a protective layer for metal plates or poor emboss processability. On the other hand, if the thickness of the sheet exceeds 500 pm, the secondary 56 24-07-2006 Printed: 11-09-2006 DESC 0614660 processabiu.ty of resin- covered decorative metal plate such as punching tends to become poor. Therefore, the thicknesses of the sheet of less than 50 Inn and exceeding 500 itin are not preferable. Further, the sheet may be subjected to surface treatment or surface processing such as printing, emboss processing, electron beam processing, coating, and vapor deposition.

(01281 The obtained sheet for resin-covered metal plates may be used after coloring with, for example, a pigment.

A sheet having excellent transparency can be advantageously used as an overlay sheet for resin-covered metal plates with printing. Here, haze, which is an index of transparency, is preferably small. When the thickness of the sheet is m, the sheet having a haze of usually 5% or less, preferably 4% or less can be used as an overlay sheet for resin- covered metal plates with printing without decreasing design quality, visibility, display effect, and so on.

9] The methods of bonding the sheet for resin-covered metal plates of the present invention and a metal plate include a method in which an adhesive is used, a method in which heat fusion is performed without using adhesives, an extrusion coating method and so on and are not particularly limited. For example, mention may be made of a method of coating an adhesive such as a polyester adhesive or an epoxy adhesive on a bonding surface of the metal plate with the sheet for resin-covered metal plates to cover the resin sheet.

24-07-2006 Printed: 11-09-2006 DESC 0614660 [0130] In this method, a resin-covered metal plate can be obtained by applying an adhesive to a dry thickness of 2 jim or more and 4 ptm or less onto a metal surface on which the sheet for resin-covered metal plates is applied by using a coating machine that is generally employed, such as a reverse coater or a kiss coater, drying and heating the coated surface by means of an infrared heater and a hot air heating furnace, immediately covering the sheet by using a roll laminator while the temperature of the surface of the metal plate is kept at a temperature of about the flow start temperature of the sheet for a resin-covered metal plate + 10 C or more, and cooling the resultant.

1] Examples of the metal plate that can be used for the resin-covered metal plate of the present invention include various steel plates such as hot roll steel plate, cold roll steel plate, molten galvanized steel plate, electro-galvanized steel plate, tined steel plate, and stainless steel plate as well as aluminum plates. These may be used after usual chemical conversion treatment.

[01321 [Shrink label and package] The heat-shrinkable sheet and heat-shrinkable laminate sheet of the present invention each have excellent shrink finish, natural shrink, transparency, and mechanical strengths such as nerve of sheet (rigidity at room temperature) and perforation cutting property, and while 58 24-07-2006 Printed: 11-09-2006 DESC 0614660 their application is not particularly limited, they can be advantageously used in applications f or a shrink label for PET bottles(round or square bottle of about 300 milliliters to about 2 liters), shrink packages for various food and shrink strapping packages, cap seals for various containers, shrink tubes for various food and articles and packages with the shrink label can be obtained. Moreover, the shrink labels and packages of the present invention can be made by a conventional method.

3] Since the heat-shrinkable sheet and heat-shrinkable laminate sheet of the present invention each have excellent shrink finish and shrinking properties, they can be advantageously used as a heat-shrinkable label material for plastic molded articles that could be deformed when heated at high temperatures and in addition, and as a heat-shrinkable label material for packages (containers) that is made from at least one material selected from materials whose coefficient of thermal expansion and water absorption differ extremely from those of the heat-shrinkable laminate sheet, for example, metals, porcelain, glass, paper, polyolef ins such as polyethylene, polypropylene, and polybutene, polymethacrylate resins, polycarbonate based resins, polyester based resins such as polyethylene terephthalate and polybutylene terephthalate, and polyamide based resins.

[01341 The materials that constitute plastic packages for 59 24-07-2006 Printed: 11-09-2006 DESC 0614660 which the heat-shrinkable sheet andheat-shrinkable laminate sheet of the present invention can be used include the above-mentioned resins and in addition thereto polystyrenes, rubber-modified high-impact polystyrenes (HIPS), styrene- butyl acrylate copolymers, styrene-acrylonitrile copolymers, styrene- maleic anhydride copolyiners, acrylonitrile-butadiene-styrene copolymers (ABS), methacrylate-butadiene-styrene copolymers (MBS), polyvinyl chloride resins, phenol resins, urea resins, melamineresins, epoxyresins, unsaturatedpolyesterresins, and silicone resins. These plastic packages can be made from mixtures of two or more of them or can be laminats thereof.

EXAMPLE S

5] Hereinafter, the present invention will be explained in more detail by way of examples. However, the present invention should by no means be construed as being limited thereto. Various measured values and evaluations on the resins, sheets, films indicated in the specification were obtained in the following manner. Here, the direction of flow of sheet (film) from an extruder or calender processing machine is referred to as a longitudinal direction (MD) and the direction perpendicular thereto is referred to as transverse direction (TD).

6] (1) Glass transition temperature (Tg) 24-07-2006 Printed: 11-09-2006 DESC 0614660 Using a differential scanning calorimeter DSC-7 manufactured by Perkin-Elmer Co., 10 mg of a sample was subjected to heat elevation from - 40 C to 250 C at a heating rate of 10 C/minute, holding at 250 C for 1 minute, temperature decrease down to -40 C at a cooling rate of 10 C/minute, holding at -40 C for 1 minute, and then temperature elevation at a heating rate of 10 C/minute and a glass transition temperature (Tg) was determined from the obtained thermogram according to JIS K7121.

7] (2) Compositional analysis of polyester based resin A solution of a polyester based resin in heavy chloroform (solvent) (sample concentration: 100 mg/i milliliter solvent) was used as a sample. The sample solution was analyzed by nuclear magnetic resonance apparatus (NMR) by monitoring 1H. The carboxylic acid monomer unit was expressed in mol% based on the total carboxylic acid monomer units and the glycol monomer unit was expressed In mol% based on the total glycol monomer units.

8] (3) Average refractive index According to the Japan Industrial Standard JIS K7142, measurement was performed using an Abbe refractometer manufactured by Atago Co.., Ltd. with sodium D-line (589 nm) as a light source.

9] 61 24-07-2006 Printed: 11-09-2006 DESC 0614660 (4) Haze According to the Japan Industrial Standards JIS K7105, the haze of the obtained sheet was measured.

[01401 (5) Modulus of elongation According to the Japan Industrial Standards JIS K7127, modulus of elongation of a sample in the transverse direction was obtained under conditions of a temperature of 23 C and a test speed of 5 mm/minute.

1] (6) Tensile strength at break, Elongation at break According to the Japan Industrial Standards JIS K7127, a sample was drawn under conditions of a temperature of 23 C and a test speed of 200 mm/minute and tensile strength at break and elongation at break of the test sample in the transverse direction were measured.

2] (7) Impact resistance Using a hydroshot high speed impact tester ("HTM-l Model" manufactured by Shimadzu Corporation), a sample of mm in the longitudinal direction x 100 mm in the transverse direction was fixed with clamps and a ball of 1/2 inch in diameter was fallen at a falling speed of 3 rn/second onto the center of the sample at a temperature of 0 C to give impact to the sample and energy (kgf*mm) when the sample was broken was measured.

62 24-07-2006 Printed: 11-09-2006 DESC 0614660 [0143] (8) Flow start temperature The obtained sheet was cut with scissors to small pieces, which were dried. Thereafter, using "KOUKA-type flow tester CFT-500C Model" manufactured by Shimadzu Corporation (with a nozzle of 1 mm in inner diameter and 2 mm in length), flow start temperature was measured under conditions of a temperature elevation speed of 3 C/minute and a load of 3.92 MPa (40 kgf/cm2).

4] (9) Measurement of dynamic viscoelasticity A sample of 4 mm in the longitudinal direction x 60 mm in the transverse direction was cut out of the obtained sheet. Using a viscoelasticity spectrometer DVA-200 (manufactured by IT Measurement Co., Ltd.), the sample was measured of storage modulus of elasticity (B') and loss modulus of elasticity (B'') under conditions of avibrational frequency of 10 Hz, a strain of 0.1%, a heat elevation speed of 3 C/minute, and a chuck interval of 25mm in the transverse directionwith starting the temperature elevation from -50 C.

From the obtained data, number of peaks, peak temperature and half-value width and peak value of loss tangential (tanô = E''/E') curve were obtained.

5] (10) Storage modulus of elasticity (B') A sample of 60 mm in the longitudinal direction x 4 63 24-07-2006 Printed: 11-09-2006 DESC 0614660 mm in the transverse direction was cut out of the obtained sheet. Using a viscoelasticity spectrometer DVA-200 (manufactured by IT Measurement Co., Ltd.). the sample was measured under conditions of a vibrational frequency of 10 Hz, a strain of 0.1%. a heat elevation speed of 3 C/minute, and a chuck interval of 25 mm in the longitudinal direction with starting the temperature elevation from -50 C to obtain storage modulus of elasticity (E'). From the obtained data.

the value of storage modulus of elasticity (E') at 25 C was obtained.

10146] (11) Heat shrink ratio A sample of 100 mm in the longitudinal direction x 100 mm in the transverse direction was out out of the obtained sheet. The sample was dipped in hot water bath at 80 C for seconds and then the amount of shrink was measured in the main shrinking direction (transverse direction) and a ratio of the amount of shrink relative to the original size before the shrinking was obtained in terms of %.

Note that negative (-) ratio means that the sample was expanded as compared with the original size.

7] (12) Natural shrink ratio A sample of 1,000 mm in the longitudinal direction x 1.000 mm in the transverse direction was out out of the obtained sheet. The sample was left to stand in a 64 24-07-2006 Printed: 11-09-2006 DESC 0614660 thermostatic chamber with an atmosphere at 30 C for 30 days, and the amount of shrink in the main shrinking direction (transverse direction) was measured and a ratio of the amount of shrink as compared with the original size before the shrinking was obtained in terms of %.

8] (13) Shrink finish A sample of 100 mm in the longitudinal direction x 298 mm in the transverse direction with grating patterns of 10 mm in interval printed thereon was cut out of the obtained sheet. Both ends of the sample in the transverse direction were superposed one on another In a width of 10 mm and sealed with solvent to form a cylindrical structure. The cylindrical sheet was attached onto a PET bottle of a round type having an inner volume of 1.5 liters and the PET bottle was passed through a 3m-long shrinkage tunnel of a steam heating type in 10 seconds without rotating the bottle to cover the sheet on the bottle. In this case, the temperature of steam was 99 C and the temperature of the atmosphere in the tunnel was 90 C to 94 C. The sheet covering the PET bottle was evaluated for shrink finish based on the following evaluation criteria.

Evaluation criteria: "0' Sufficiently shrunk, showing no wrinkles, no pookmarks, deformation of grating patterns raising substantially no practical problem, and adhesion of the sheet 24-07-2006 Printed: 11-09-2006 DESC 0614660 being good.

x Apparently showing a part with insufficient shrink or markedly showing wrinkles, pockmark or deformed grating patterns.

9] (14) Calender processability Using a * 40 mm same direction twin screw extruder (L/D=32), a resin composition was melt-kneaded at 270 C of a cylinder setting temperature and then the resultant was transferred to an L-type calender processing machine having four metal rolls of 250 mm in roll diameter and the resin composition was calendered at a roll setting temperature adjusted within a range of from a temperature that was by 10 C higher than the flow start temperature of the resin composition to 200 C. and calender film forming property of the resin composition was visually evaluated based on the following evaluation criteria.

Evaluation criteria: "0' The rotation of bank (resin composition) was regular and stable, the surface of the obtained sheet having good uniformity in the appearance and thickness.

"x" The rotation of bank was irregular or poor winding onto the roll was showed owing to apparently insufficient heat quantity, thereby giving failure in the surface appearance, such as unevenness or uneven thickness.

0] 66 24-07-2006 Printed: 11-09-2006 DESC 0614660 (15) Boiling water dipping test A sample cut out of the resin-covered metal plate to a size of 60 mm x 60 mm was used. The sample was provided with an outrigger of 6 mm so that the resin-covered side became convex using an Erichsen test machine prescribed in the Japan Industrial Standards JIS K7121. Thereafter, the sample was dipped in boiling water for 3 hours and the surface state of the sample resin sheet after the dipping was visually evaluated based on the following evaluation criteria.

Evaluation criteria: "o" Showing no changes.

"x" Showing surface roughness, swelling or peeling of the resin layer.

1] (16) Pencil hardness Pencil hardness was measured according to the Japan Industrial Standards JIS K5400 8.4 "Pencil scratch value" (tester method).

2] (17) Secondary Processability The obtained resin-covered metal plate was subjected to impact adherence bending tests. The surface state of the resin sheet after the bending test was visually observed and the secondary processability of the resin sheet was evaluated based on the following evaluation criteria.

Evaluation criteria: 67 24-07-2006 Printed: 11-09-2006 DESC 0614660 "o" Showing substantially no changes and being good.

"x' Showing occurrence of cracks or fracture.

Note that the impact adherence bending tests were carried out as follows. Samples of 50 mm x 150 mm were each cut out of the resin-covered metal plate from the longitudinal direction and the transverse direction, respectively and kept at 23 C for 1 hour or more. Thereafter, the samples were bent using a bending tester to 180 (with an inner bending radius of 2 mm), followed by falling a cylindrical weight of 75 mm in diameter with a mass of 5 kg from a height of cm.

10153] (18) Perforation cutting property A heat-shrinkable laminate sheet was formed with perforations (length of perforation: 0.7 mm, interval of perforations: 0.7 mm, a single line) and the sample was attached onto a round PET bottle of an inner volume of 1.5 liters by heat shrinking in the same manner as in the evaluation in "(13) Shrink finish". After it was cooled to room temperature, the perforated portion of the sample was torn by hands and the perforation cutting property was evaluated. In this case, 10 samples were used in the cutting tests and evaluation was performed by sensory tests based on the following evaluation criteria.

Evaluation criteria: 68 24-07-2006 Printed: 11-09-2006 DESC 0614660 "o Eight or more samples were clearly out along the perforation line.

x" Three or more samples did not cut along the perforation line or 3 or more samples were initially cut along the perforation line but in the midway cutting line deviated from the perforation line.

10154] [Example I]

(Example I-i)

As shown in Table 1, a resin blend composition of 75 mass% of a dry aromatic polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., "NOVALEX 7025A", Tg: 149.5 C, average refractive index:i.5858) (hereinafter, sometimes, simply abbreviated as "PC") as polycarbonate based resin (b-i) and 25 mass% of a dry transparent flexible polyester resin (manufactured by Mitsubishi Rayon Co., Ltd., "DAIANITE DN-i24". Tg: 19.1 C.

carboxylic acid monomer unit (i): 100 mol% of terephthalic acid, glycol monomer unit (ii): 66 mol% of ethylene glycol.

2 mol% of diethylene glycol. 26 mol% of 1,4-cyolohexanedimethanol, 6 mol% of polytetramethylene glycol having a number-average molecular weight of 1,000.

average diffractive index: 1.5461) (hereinafter, sometimes, simplyabbreviatedas "PET-i") aspolyesterbasedresln (b-2) was melt-kneaded using a 40 mm same direction twin-screw extruder (L/D=36) with P-die at a setting temperature of 270 C and was subjected to cast film formation with a cast 69 24-07-2006 Printed: 11-09-2006 DESC 0614660 roll at 80 C (in examples other than Example I-i, the temperature of the cast roll was adjusted appropriately at around a temperature of the Tg of the resin blend composition -20 C with confirming the state of adherence of the sheet to the cast roll) to obtain a sheet of 150 itm thick. The obtained sheet was used to evaluate glass transition temperature (Tg) and mechanical strength and so on. The results obtained are shown in Table 1.

[01553

(Example 1-2)

A sheet was obtained in the same manner as in that in example I-i except that the blending ratios of the PC used as the polycarbonate based resin (b-i) and PET-i used as the polyester based resin (b-2) was changed to 90 mass% and 10 mass% respectively as shown in Table 1. The obtained sheet was used to evaluate glass transition temperature (Tg) and mechanical strength and so on. The results obtained are shown in Table 1.

10156)

(Example 1-3)

A sheet was obtained in the same manner as in that in example I-i except that the blending ratios of the PC used as the polycarbonate based resin (b-i) and PET-i used as the polyester based resin (b-2) was changed to 95 mass% and 5 mass% respectively as shown in Table 1. The obtained sheet was used to evaluate glass transition temperature (Tg) and 24-07-2006 Printed: 11-09- 2006 DESC 0614660 mechanical strength and so on. The results obtained are

shown in Table 1.

(0157] (Comparative Example I-i) A sheet was obtained in the same manner as in that in example I-i except that the blending ratios of the PC used as the polycarbonate based resin (b-i) and PET-i used as the polyester based resin (b-2) was changed to 100 mass% and 0 mass%, respectively as shown in Table 1. The obtained sheet was used to evaluate glass transition temperature (Tg) and mechanical strength and so on. The results obtained are shown in Table 1.

(Example 1-4)

A sheet was obtained in the same manner as in that in example I-i except that the blending ratios of the PC used as the polycarbonate based resin (b-i) and PET-i used as the polyester based resin (b-2) was changed to 50 mass% and mass%, respectively as shown in Table 2. Subsequently, the obtained sheet was drawn 3.0 times in the transverse direction using a tenter drawing machine at a drawing temperature of 95 C, and then quenched with cool air to obtain a heat-shrinkable sheet of 50 tm thick. The obtained sheet and heat-shrinkable sheet were appropriately used to evaluate glass transition temperature (Tg) and mechanical strength and so on. The results obtained are shown in Table 71 24-07-2006 Printed: 11-09-2006 DESC 0614660 2.

Note that heat shrink ratio was obtained by cutting a sample of 100 mm in the longitudinal direction x 100 mm in the transverse direction out of the obtained heat-shrinkable sheet, dipping the sample in hot water bath at 80 C for 10 seconds, and then measuring the amount of shrink in the transverse direction and calculating a ratio of the amount of shrink relative to the original size before the shrinking in terms of %. Further, Fig. 1 shows a DSC thermogram of the obtained sheet. Fig. 1 indicates that the sheet has a glass transition temperature at the position of a single peak.

[01591 (Comparative Example 1-2) A sheet was obtained in the same manner as in that in example 1-4 except that PET-i used as the polyester based resin (b-2) was replaced by nonorystalline polyester resin (manufactured by Eastman Chemical Co., Ltd.. EASTAR PETG Copolyester 6763w, Tg: 79.0 C, carboxylic acid monomer unit (i): 100 mol% of terepbthalic acid, glyool monomer unit (ii): 68 mol% of ethylene glycol, 32 mol% of 1, 4-cyclohexanedimethanol, average diffractive index: 1.5667) (hereinafter, sometimes, simply abbreviated as PET-2M), as shown in Table 2. Subsequently, it was tried to draw the obtained sheet 3.0 times in the transverse direction using a tenter drawing machine at a drawing temperature of 95 C, but the drawing was unsuccessful because 72 24-07-2006 Printed: 11-09-2006 DESC 0614660 of breakage of the sheet. Fig. 2 shows a DSC thermogram of the obtained sheet. Fig. 2 indicates that the sheet had glass transition temperature (Tg) at two positions of 79.4 C and 134.8 C.

[Table 1]

Example Comparative

______ _______ _______ Example I ____________ 1 2 3 1 PC (Mass%) 75 90 95 100 PET-i (Mass%) 25 10 5 0 [Evaluation Results] ______ Tg( C) 100.0 125.5 135.4 149.5 Haze (%) 2.5 1. 2 0.8 1.3 Modulus of 2272 2283 2290 2306 Elongation_(MPa) _______ ______ ______ Tensile Strength at 73.1 76.7 77.1 85.5 Break_(MPa) ______ ______ ______ Tensile Elongation 158.3 162.1 165.4 182.1 at_Break_(%) ______ ______ ______ Impact Resistance Fracture Energy 254.5 296.9 331.6 428.3 (kgf*mm) ______ Flow Start 161.5 181.0 183.5 194.9 Temperature_( C) ______ ______ ______ 73 24-07-2006 Printed: 11-09-2006 DESC 0614660 [0161]

[Table 2]

r----_- Example 1-4 ComparativeExample __________________ 1-2 PC (Mass%) 50 50 PET-i (Mass%) 50 PET-2 (Mass%) 50 Drawing Temperature Drawing Ratio _____________ 79.4/134.8 Haze (%) 2.1 (Impossible to draw Modulus of Elongation (MPa) due to breakage) Tensile Strength at Break (MPa) 111.2 Tensile Elongation at Break (%) 76.8 Heat Shrink Ratio (%) (Hot Water Lseconds) at 80 C for 10 47.3 [0162] Tables I. and 2 indicate that the resin blend composition containing the polycarbonate based resin (b-i) and the polyester based resin (b-2) and having a single glass transition temperature exhibited excellent flowability (Examples 1-1 to 1-3) and excellent secondary prooessability (Example 1-4) without considerably damaging the features of the polycarbonate based resin, such as transparency and impact resistance.

On the other hand, in Comparative Example I-i for the resinconsistingofthepolycarbonatebasesjn (b-i) alone, the impact resistance and transparency were good but the flowability was poor. The resin of Comparative Example 1-2 74 24-07-2006 Printed: 11-09-2006 DESC 0614660 resin in which the polyester based resin outside the scope of the present invention was used showed poor miscibility with the polycarbonate based resin, it revealed that it was difficult to impart the resin with secondary processability (heat shrinking property, etc.) in the secondary process temperature range of the PVC resin (usually, about 50 C or more and about 100 C or less).

[01631 [Example II]

(Example 11-1)

As shown in Table 3, a resin blend composition of 50 mass% of a dry aromatic polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., NOVALEX 7025A", Tg: 149.5 C, average refractive index:1.5858) (hereinafter, sometimes, simply abbreviated as PC") as polycarbonate based resin (b-i) and 50 mass% of a dry transparent flexible polyester resin (manufactured by Mitsubishi Rayon Co., Ltd., "DAIANITE DN-124", Tg: 19.1 C.

carboxylic acid monomer unit (i): 100 mol% of terephthalic acid, glycol monomer unit (ii): 66 mol% of ethylene glycol, 2 mol% of diethylene glycol, 26 mol% of 1,4-cyclohexanedimethanol, 6 mol% of polytetramethylene glycol having a number-average molecular weight of 1,000, average refractive index: 1. 5461, intrinsic visxosity 0.94 dl/g) (hereinafter, sometimes, simply abbreviated as "PET-i") as polyester based resin (b-2) was melt-kneaded using a 40 mm same direction twin-screw extruder (L/D=36) 24-07-2006 Printed: 11-09- 2006 DESC 0614660 with a T-die at a setting temperature of 270 C andwas subjected to cast film formation with a cast roll at 50 C (in examples other than Example 11-1, the temperature of the cast roll was adjusted appropriately at around a temperature of the Tg of the resin blend composition -20 C with confirming the state of adherence of the sheet to the cast roll) to obtain a cast sheet of 150 p.m thick. Subsequently, the obtained sheet was drawn 3.0 times In the transverse direction using a tenter drawing machine at a drawing temperature of 95 C.

and then quenched with cool air to obtain a beat-shrinkable sheet of 50 pm thick. The obtained cast sheet was used to evaluate glass transition temperature (Tg) and the obtained heat-shrinkable sheet was used to evaluate mechanical strength and so on. The results obtained are shown in Table 4. Further, Fig. 3 shows a loss tangent curve of the obtained heatshrinkable sheet.

(Example 11-2)

A cast sheet and a heat-shrinkable sheet were obtained In the same manner as in that in Example 11-1 except that the blending ratios of the PC used as the polycarbonate based resin (b-i) and PET-i used as the polyester based resin (b-2) was changed to 60 mass% and 40 mass%, respectively, and the drawing temperature was changed to 105 C as shown in Table 3. The obtained cast sheet was used to evaluate Tg and the heat- shrinkable sheet was used to mechanical strength and 76 24-07-2006 Printed: 11-09-2006 DESC 0614660 so on. Table 4 shows the results obtained. Also, Fig. 3 shows a loss tangent curve of the obtained heat-shrinkable sheet.

5] (Comparative Example 11-i) A cast sheet and a heat-shrinkable sheet were obtained in the same manner as in that in Example 11-1 except that the blending ratios of the PC used as the polycarbonate based resin (b-i) and PET-i used as the polyester based resin (b-2) was changed to 80 mass% and 20 mass%, respectively, and the drawing temperature was changed to 135 C as shown in Table 3. The obtained cast sheet was used to evaluate Tg and the heat- shrinkable sheet was used to mechanical strength and so on. Table 4 shows the results obtained. Also, Fig. 3 shows a loss tangent curve of the obtained heat-shrinkable sheet.

6] (Comparative Example 11-2) A sheet was obtained in the same manner as in that in example 11-1 except that PET-i used as the polyester based resin (b-2) was replaced by noncrystalline polyester resin (manufactured by Eastman Chemical Co., Ltd., "EASTAR PETG Copolyester 6763", Tg: 79.0 C, carboxylic acid monomer unit (1): 100 mol% of terephthalic acid, glycol monomer unit (ii): 68 mol% of ethylene glycol, 32 mol% of 1, 4 -cyolohexanedimethanol, average refractive index: 24-07-2006 Printed: 11-09-2006 DESC 0614660 1.5667) (hereinafter, sometimes, simply abbreviated as "PET-2"), as shown in Table 3. Subsequently, it was tried to draw the obtained sheet 3.0 times in the transverse direction at a drawing temperature of 95 C by using a tenter drawing machine, but the drawing was unsuccessful because of breakage of the sheet. The obtained sheet had glass transition temperature (Tg) at two positions of 79.4 C and 134.8 C.

[01671 (Comparative Example 11-3) A cast sheet and a heat-shrinkable sheet were obtained in the same manner as in that in Example 11-1 except that PET-2 as used in Comparative Example 11-2 was used alone and the drawing temperature was changed to 90 C as shown in Table 3. The obtained cast sheet was used to evaluate Tg and the heat-shrinkable sheet was used to mechanical strength and so on. Table 4 shows the results obtained.

Also, Fig. 3 shows a loss tangent curve of the obtained heat-shrinkable sheet.

[Table 3]

Example II Comparative Example II ______________ 1 2 1 2 3 PC (Mass%) 50 60 80 50 _______ PET-i (Mass%) 50 40 20 _________ _______ PET-2 (Mass%) _____ ______ _______ 50 100 Drawing Temperature ( C) 95 105 135 95 90 Drawing Ratio 3 3 3 3 3 78 24-07-2006 (.0 -p

CD

I-I i-a - 0 o (.0

[Table 41 - 0

Example II Comparative Example II __________________ 1 2 1 2 3 Tg ( C) 64.2 76.5 108.4 79.4 79.0 _____________________________ (Single) (Single) (Single) 134.8 (Single) Number of Peaks of tanô 1 1 1 1 Peak Temperature ( C) 90.5 106.3 132.5 84. 1 Half-Value Width ( C) 26.4 24.9 20.5 13.2 Peak Value of tanö 1.11 1.12 1.22 1.88 Haze (%) 2.1 1.6 1.2 Imposs- 1.3 Modulus of Elongation (MPa) 2543 2628 2680 ible to 2803 Tensile Strength at Break (MPa) 111.2 118.7 125.3 draw 232.5 Tensile Elongation at Break (%) 85.7 91.5 82.8 due to 83. 6 Natural Shrink Ratio (%) 0.8 0.5 0.0 breakage 0.5 Heat ShrinkRatio MD - 1.4 -1.1 0.0 -5.9 (%) TD 47.3 27.5 0.1 57.5 Shrink Finish 0 0 x x Overall Judgment 0 0 x x x N.) 0 0 -.4 0) N.) Printed: 11-09-2006 DESC 0614660 [0170] Tables 3 and 4 indicate that the heat-shrinkable sheet obtained by drawing the resin blend composition containing the polycarbonate based resin (b-i) and the polyester based resin (b-2) showed peak temperature and half-value width of tanö within the predetermined range and had excellent balance between shrink finish, natural shrink, transparency, nerve of sheet (rigidity at room temperature), and mechanical strength such as break resistance (Example

11-1, Example 11-2).

On the contrary, in Comparative Example 11-1 in which Tg was high and the peak temperature of tanö was above 130 C, it was difficult to impart the sheet with heat shrinking property so that the heat-shrinkable sheet could not be used in practice. Further, in Comparative Example Il-i, in which the polyester based resin outside the scope of the present invention was used showed poor miscibility with the polycarbonate based resin (b-i), and it revealed that it was difficult to obtain a heat- shrinkable sheet.

Furthermore, it revealed that in Comparative example 11-3 relating to the resin consisting of the polyester based resin alone, the half-value width of tanb was narrow and the heat-shrinkable sheet obtained by drawing this resin had poor shrink finish.

[Example III]

(Example 111-1)

As shown in Table 5, 1.0 mass part of montan wax 24-07-2006 Printed: 1109-2006 DESC 0614660 (manufactured by Hoechst Corporation, Hoechst WAX OP) as a lubricant was added to 100 mass parts of a resin blend composition of 85 mass% of a dry aromatic polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., "NOVALEX 7025A", Tg: 149.5 C, average refractive index:1.5858, flow start temperature 194.9 C) (hereinafter, sometimes, simply abbreviated as "PC") as polycarbonate based resin (b-i) and 15 mass% of a dry transparent flexible polyester resin (manufactured by Mitsubishi Rayon Co., Ltd..

"DAIANITE DN-124", Tg: 19.1 C, carboxylic acid monomer unit (i): 100 mol%of terephthalic acid, glycol monomer unit (ii): 66 mol% of ethylene glycol, 2 mol% of diethylene glycol, 26 mol% of 1,4-cyclohexanedimethanol, 6 mol% of polytetramethylene glycol having a number- average molecular weight of 1,000, average refractive index: 1.5461, intrinsic viscosity 0.94 dl/g) (hereinafter, sometimes, simply abbreviated as "PET-i") as polyester based resin (b-2) and the resultant was melt-kneaded using a $ 40 mm same direction twin-screw extruder (L/D=32) at a cylinder setting temperature of 270 C, and subsequently transferred to an L-type calender processing machine including four metal rolls having a roll diameter of 250 mm and rolled under the condition of a roll setting temperature of 200 C to obtain a sheet of 150 tm thick. Further, a commercially available polyester based adhesive for polyvinyl chloride-covered metal plates was coated on a metal surface of a galvanized 81 24-07-2006 Printed: 11-09-2006 DESC 0614660 steel plate (of a thickness of 0.5 mm) on which surface the sheet was to be applied to a dry thickness of the adhesive film of about 2 pm to about 4 pm, and then the coated surface was dried and heated with an infrared radiation heater and a hot air oven. While retaining the temperature of the surface of the galvanized steel plate at a temperature of the flow start temperature of the sheet + 10 C or more, the sheet was immediately covered on the metal surface using a roll laminator and cooled to obtain a resin-covered metal plate. The obtained sheet was used to evaluate glass transition temperature (Tg), mechanical strength, and so on. The obtained resin- covered metal plate was used to evaluate service tests. Table 5 shows the results obtained.

Further, overall judgment of the results obtained was also made. Those that showed good results in all of the above-mentioned evaluations and have no problem in practical service were indicated by a symbol o and those that showed failure in any one of the above-mentioned evaluations were indicated by a symbol x.

(Example 111-2)

A sheet of 150 pm thick was obtained in the same manner as in that in Example 111-i except that the blending ratios of the PC used as the polycarbonate based resin (b-i) and PET-i used as the polyester based resin (b-2) were changed to 70 mass% and 30 mass%, respectively, and the roll setting 82 24-07-2006 Printed: 11-09-2006 DESC 0614660 temperature was changed to 185 C as shown in Table 5. Further, a resin-covered metal plate was obtained in the same manner as in that in Example 111-1 using the obtained sheet. The obtained sheet and resin-covered metal plate were used as appropriate to evaluate glass transition temperature (Tg) and mechanical strength and so on as well as to evaluate service tests. Table 5 shows the obtained results put together.

3] (Comparative Example 111-1) A sheet of 150 p.m thick was obtained in the same manner as in that in Example 111-1 except that the blending ratios of the PC used as the polycarbonate based resin (b-i) and PET-i used as the polyester based resin (b-2) were changed to 50 mass% and 50 mass%, respectively, and the roll setting temperature was changed to 175 C as shown in Table 5. Further, a resin-covered metal plate was obtained in the same manner as in that in Example 111-1 using the obtained sheet. The obtained sheet and resin-covered metal plate were used as appropriate to evaluate glass transition temperature (Tg) and mechanical strength and so on as well as to evaluate service tests. Table 5 shows the obtained results put together.

4] (Comparative Example 111-2) In the same manner as in that in Example 111- i. the 83 24-07-2006 Printed: 11-09-2006 DESC 0614660 resin composition was subjected to calender processing except that the blending ratios of the PC used as the polycarbonate based resin (b-i) and PET-i used as the polyester based resin (b-2) was changed to 100 mass% and 0 mass%, respectively as shown in Table 5. However, due to apparently insufficient heat quantity, the sheet showed poor winding onto the roll, and the rotation of the bank was irregular, thus failing to obtain a sheet having good surface appearance.

5] (Comparative Example 111-3) A sheet of 150 iun thick was obtained in the same manner as that in Example 111-i except that PC used as the polycarbonate based resin (b-i) in Example 111-i was used in an amount of 50 mass% and PET-i used as the polyester resin (b-2) in Example 111-1 was replaced by 50 mass% of noncrystalline polyester resin (manufactured by Eastman Chemical Co., Ltd., "EASTAR PETG Copolyester 6763", Tg: 79.0 C, carboxylic acid monomer unit (1): 100 mol% of a terephthalic acid, glycol monomer unit (ii): 68 mol% of an ethylene glycol, 32 mol% of a 1, 4-cyclohexanedimethanol, average refractive index: i.5667) (hereinafter, sometimes, simply abbreviated as "PET-2"), and the roll setting temperature was changed to 195 C as shown in Table 5. Further, a resincovered metal plate was obtained in the same manner as that in Example 111-1 by using the obtained sheet.

84 24-07-2006 Printed: 11-09-2006 DESC 0614660 The obtained sheet and the resin-covered metal plate were used as appropriate to evaluate glass transition temperature (Tg) and mechanical strength and so on as well as to evaluate service tests. Table 5 shows the obtained results put together. The obtained sheet showed glass transition temperature (Tg) at two positions of 79.4 C and 134.8 C. Further the sheet had a haze of 6.5% and hence had poor transparency.

[01761 (Comparative Example 111-4) In the same manner as in that in Example 111- 1, the resin composition was subjected to calender processing except that the PC used as the polycarbonate based resin (b-i) in Example 111-1 was used in an amount of 70 mass% and PET-i used as the polyester based resin (b-2) in Example 111-1 was replaced by 30 mass% of a polyester resin (manufactured by Eastman Chemical Co., Ltd., "EASTAR PCTG Copolyester 5445", Tg: 87.3 C, carboxylic acid monomer unit (1): 100 mol% of terephthalic acid, glycol monomer unit (ii): 35 mol% of ethylene glycol, 65 mol% of 1, 4-cyclohexanedimethanol) (hereinafter, sometimes, simply abbreviated as "PET-3") as shown in Table 5. However, during the calender processing, the sheet was crystallized.

so that a sheet having good surface appearance could not be obtained. Note that DSC measurement of the sheet indicated a crystal melting peak was at 243 C.

24-07-2006 Printed: 11-09-2006 DESC 0614660 [0177]

[Table 5]

j_Example III Comparative Example III 1 2 1 2 3 4 PC (Mass%) 85 70 50 100 50 70 PET-i (Mass%) 15 30 50 _____ _________ PET-2 (Mass%) _______ _______ _________ _________ 50 PET-3 (Mass%) _______ 30 [Evaluation Results of Resin_Sheet] ________ _____ _________ Roll Setting Temperature 200 185 175 200 195 200 ( C) _________ _________ _________ _________ ______ __________ 119.5 100.3 64.2 149.5 79.4 130.8 T 10C' / (Single) (Single) (Single) (Single) 134.8 (Single) Flow Start Temperature 175.2 158.0 145.3 194.9 169.1 178.5 ( C) _________ _________ _________ _________ ______ __________ Calender Process- 0 0 0 X 0 X ability _________ ________ ________ _________ ______ _________ Tensile Impossi- Impossi- Elongation 160.7 168.3 9.8 ble to 209.3 ble to at Break (%) _________ ________ ________ obtain ______ obtain Haze (%) 1.5 2.8 3,3 sheets 6.5 sheets [Results of Evaluation of Resin-Covered Metal Plate] _________ Boiling Water Dipping X 0 Test _________ _________ __________ Pencil B B 3B - 28 - Hardness Fabric 0 -ability 0 0 _________ Overall 0 0 Judgment ________ ________ _________ _________ ______ _________ 86 24-07-2006 Printed: 11-09-2006 DESC 0614660 [0178] TableS indicates that the sheet for the resin-covered metal plate. being made from a resin blend composition containing the polycarbonate based resin and the polyester based resin specified by the present invent ion is excellent in transparency, calenderprocessabilitYatlOWteluPeratures.

boiling water resistance, scratch resistance, and fabrication quality (Example 111-1, Example 111-2).

On the other hand, Comparative Example 111-1 in which the glass transition temperature of the resin was low showed poor evaluation in boiling water dipping tests. Comparative Example 111-2 in which the polycarbonate based resin alone was used showed poor calender processability at low temperatures. In the case where the polyester based resin outside the scope specified by the present invention was used, the resin composition had poor miscibility with the polycarbonate based resin, so that problems occur in that the transparency of the obtained sheet is decreased (Comparative Example 111-3) and that the sheet is crystallized due to insufficient heat quantity during calender processing at low temperatures (Comparative Example 111-4).

[Example IV]

(Example IV-1)

As shown in Table 6, 0.2 mass part of silica (average particle particle diameter: 3 pm) was added to 100 mass parts of a dry noncrystalline polyester resin (manufactured by 87 87 24-07-2006 Printed: 11-09-2006 DESC 0614660 Eastman Chemical Co., Ltd., "EASTAR PETG Copolyester 6763".

Tg: 79.0 C, carboxylic acid monomer unit (1): 100 mol% of terephthalic acid, glycol monomer unit (ii): 68 mol% of ethylene glycol, 32 mol% of 1, 4-cyclohexanedimethanol.

average refractive index: 1.5667) (hereinafter, sometimes, simply abbreviated as "PET-2") as the thermoplastic polyester based resin (a-i) to form a resin composition.

Then, a resin blend composition of 50 inass% of a dry aromatic polycarbonate resin (manufacturedbyMitsubiShi Engineering Plastics Co., Ltd., "NOVALEX 7025A", Tg: 149.5 C, average refractive index:1.5858) (hereinafter, sometimes, simply abbreviated as "PC") as polycarbonate based resin (b-i) and mass% of a dry transparent flexible polyester resin (manufactured by Mitsubishi Rayon Co.. Ltd., "DAIANITE DN-124", Tg: 19. 1 C, oarboxylic acidmonomer unit: 100 mol% of terephthalic acid, glycol monomer unit: 66 mol% of ethylene glycol, 2 mol% of diethylene glycol, 26 mol% of l,4-cyclohexanedimethanol, 6 mol% of polytetramethylene glyco]. having a number-average molecular weight of 1,000, average refractive index: 1.5461, intrinsic viscosity 0.94 dl/g) (hereinafter, sometimes, simply abbreviated as "PET-i") as polyester based resin (b-2) was prepared as a resin blend composition. The resin composition was used as a material for layers (A) and the resin blend composition was used for a layer (B). The resin composition and the resin blend composition were charged in separate $ 40 mm 88 24-07-2006 Printed: 11-09-2006 DESC 0614660 same direction twin-screw extruders (L/D=36), respectively, melt-kneaded at a setting temperature of 270 C, and then coextruded through a three-layer die so that a thickness ratio of the layer was layer (A)/layer (B)/layer (A) = 1/4/1.

The resultant was taken up on a cast roll at 50 C and cooled to solidify to obtain a non-drawn laminate sheet of 500 mm in width and 150 im in thickness. Then the laminate sheet was drawn 3.0 times in the transverse direction monoaxially at a preheating temperature of 110 C and a drawing temperature of 95 C in a tenter drawing machine and then quenched with cold air to obtain a heat-shrinkable laminate sheet of 50 p.m thick. The obtained heat-shrinkable laminate sheet was evaluated for glass transition temperature and mechanical properties and so on. Table 6 shows the results obtained.

Further, overall judgment of the results obtained was also made. Those that showed good results in all of the above-mentioned evaluations were indicated by a symbol o" and those that showed failure in any one of the above-mentioned evaluations were indicated by a symbol "x.

(Example IV-2)

As shown in Table 6, a resin composition was formed by adding 0.2 mass part of silica (average particle diameter: 3pm) to 85 mass parts of PET-2 used in Example IV-1 as the thermoplastic polyester based resin (a-i) and 15 mass parts of a polybutylene terephthalate resin [manufactured by 89 24-07-2006 Printed: 11-09-2006 DESC 0614660 Mitsubishi Engineering Plastics Co., Ltd.. NOVADUR 5008, carboxylic acid monomer unit: 100 mol% terephthalic acid, glycolmonomerunit: 100 mol% 1,4-butanediol. melting point: 225 C, intrinsic viscosity: 0.84 dug] (hereinafter, sometimes, abbreviated as "PET-4"). The resin composition was used as a material for the layer (A).

Then, a resin blend composition comprising 60 mass% of the PC used in Example IV-1 and 40 mass% of PET-i was formed. The resin blend composition was used as a material for the layer (B). These materials were charged in separate same direction twin-screw extruders (L/D=36), respectively, melt-kneaded at a setting temperature of 270 C. and then coextruded through a three-layer die so that a thickness ratio of the layer was layer (A)/layer (B)/layer (A) = 1/4/1.

The resultant was taken up on a cast roll at 50 C and cooled to solidify to obtain a non-drawn laminate sheet of 500 mm in width and 150 m in thickness. Then the laminate sheet was drawn 3.0 times in the transverse direction monoaxially at a preheat ing temperature of 110 C and a drawing temperature of 95 C in a tenter drawing machine and then quenched with cold air to obtain a heat-shrinkable laminate sheet of 50 iun thick. The obtained heat-shrinkable laminate sheet was evaluated in the same manner as in Example IV-1. Table 6 shows the results obtained.

10181] (Comparative Example IV-1) 24-07-2006 Printed: 11-09-2006 DESC 0614660 As shown in Table 6, a non-drawn sheet of 500 mm in width and 150 tm in thickness was obtained in the same manner as in that in Example IV-1 except that no layer (B).

intermediate layer, was provided and the resin composition used as a material for the layer (A) was charged in separate $ 40 mm same direction twin-screw extruders (L/D=36), melt-kneaded at a setting temperature of 270 C, and then extruded through a single-layer die. The resultant was taken up on a cast roll at 50 C and cooled to solidify to obtain a non-drawn sheet of 500 mm in width and 150 pm in thickness.

Then, the sheet was drawn 3.0 times in the transverse direction monoaxially at a preheating temperature of 110 C and a drawing temperature of 95 C in a tenter drawing machine and then quenched with cold air to obtain a heat-shrinkable sheet of 50 pm thick. The obtained heat-shrinkable sheet was evaluated in the same manner as in Example IV-1. Table 6 shows the results obtained.

91 24-07-2006 Printed: 11-09-2006 DESC 0614660 [0182]

[Table 6]

Comparative Example IV Example IV 1 2 1 Layer PET-2 (Mass%) 100 85 100 (A) PET-4 (Mass%) 15 ____________ Layer -PC (Mass%) 50 60 - (B) PET-i (Mass%) 50 40 - Drawing Temperature ( C) 95 95 95 Drawing Ratio 3.0 3.0 3.0 Tg( C) of Resin Blend Composition Constituting 64.2 76.5 - Layer (B) - (Single) (Single) ___________ Haze (%) 2.8 2.9 2.2 Heat Shrink Ratio (%) 48.8 42.3 54.6 Natural Shrink Ratio (%) 0.6 0.5 0.5 Storage Modulus of 2118 2253 1831 Elasticity (E') (MPa) _______ _______ Shrink Finish 0 0 x Perforation Cutting 0 0 x Property _________ __________ _____________ Overall Judgment 0 J 0 x [0183] Table 6 indicates that the heat-shrinkable laminate sheets of the present invention having the predetermined layers (A) that constitute both outer layers and the predetermined layer (B) positioned between the both outer layers had small natural shrink ratios and were excellent in shrink finish, transparency, nerve of the sheet (rigidity at room temperature), and perforation cutting 92 24-07-2006 Printed: 11-09-2006 DESC 0614660 property (Example IV-1, Example IV-2). On the contrary, it revealed that as in Comparative Example IV-1, monolayer heat-shrinkable sheet having only the layers (A) were excellent in the evaluations of transparency and natural shrink ratio but shrink finish and perforation cutting property were poor.

Further, it revealed that the heat-shrinkable laminate sheets of the present invention (sheets of Example IV-1 and Example IV-2) showed good miscibility and excellent transparency even when a recycled resin was added to the layer (A) and/or layer (B). That is, the heat-shrinkable laminate sheets of the present invention were excellent in addition of regenerated material.

INDUSTRIAL APPLICABILITY

10184] The resin compositions of the present invention are excellent in transparency and mechanical properties such as impact resistance, flowability, and elongation at break and have secondary processability in a similar temperature range as the PVC resin, so that they find a wide variety of application and can be advantageously used in those applications in which conventional PVC resins have been used.

For example, they are applied to building materials, interior components, transparent sheets, resin-covered metal plates, molding sheets, color plates, transparent plates, heat-shrinkable sheets, molded articles and so on.

93 24-07-2006 Printed: 11-09-2006 DESC 0614660 The heat-shrinkable sheet and heat-shrinkable laminate sheet of the present invent ion can be used for shrink packages, shrink strapping packages, shrink labels and so on.

BRIEF EXPLANATION OF DRAWINGS

Fig. 1 Is a DSC thermogram illustrating glass transition temperature (Tg) of the sheet obtained in Example 1-4; Fig. 2 is aDSC thermogram illustrating glass transition temperature (Tg) of the sheet obtained in Comparative Example 1-2; and Fig. 3 Is a diagram Illustrating loss tangent (tanô) curves in Examples 11-1 and 11-2 and Comparative Examples Il-i and 11-3.

94 24-07-2006

Claims

Printed: 11-09-2006 CLMS 0614660

Ii] A resin blend composition comprising 1 mass% or more and 99 mass% or less of a polycarbonate based resin (b-i), and 1 mass% or more and 99 mass% or less of a polyester based resin (b-2), wherein the polyesterbased resin (b-2) contains, as a carboxylic acid unit Ci), 80 mol% or more and 100 mol% or less of an aromatic dicarboxylic acid unit in total carboxylic acid monomer units (1), and as glycol monomer unit (ii), 0.1 mol% or more and 40 mol% or less of a 1,4-oyclohexanedimethanol unit, and 0.5 mol% or more and mol% or less of a polyalkylene glycol unit having a number-average molecular weight of 500 or more and 3,000 or less in total glycol monomer units (ii).

121 The resin blend composition according to claim 1, wherein the polycarbonate based resin (b-i) comprises an aromatic polycarbonate based resin.

131 The resin blend composition according to claim 1 or 2. wherein the polyester based resin (b-2) has a glass transition temperature of 0 C or more and 50 C or less as measured by differential scanning calorimeter at a heating rate of 10 C/minute.

24-07-2006 Printed: 11-09-2006 CLMS 0614660 14] The resin blend composition according to any one of claims 1 to 3, wherein the resin blend composition has a single glass transition temperature as measured by differential scanning calorimeter at a heating rate of 10 C/minute and wherein the glass transition temperature is positioned between the glass transition temperature of the polycarbonate based resin (b-i) and the glass transition temperature of the polyester based resin (b-2).

15] The resin blend composition according to any one of claims 1 to 4, wherein the resin blend composition has a glass transition temperature of 50 C or more and 100 C or less as measured by differential scanning calorimeter at a heating rate of 10 C/minute.

[6] The resin blend composition according to any one of claims 1 to 4, wherein the resin blend composition has a glass transition temperature of 100 C or more and 150 C or less as measured by differential scanning calorimeter at a heating rate of 10 C/minute.

[7] The resin blend composition according to any one of claims 1 to 6, wherein the resin blend composition comprises mass% or more and 95 mass% or less of the polycarbonate based resin (b-i) and 5 mass% or more and 25 mass% or less of the polyester based resin (b-2).

2 24-07-2006 Printed: 11-09-2006 CLMS 0614660 (8] The resin blend composition according to any one of claims 1 to 6, wherein the resin blend composition comprises mass% or more and 95 mass% or less of the polycarbonate based resin (b-i) and 5 mass% or more and 40 mass% or less of the polyester based resin (b-2).

[9] The resin blend composition according to any one of claims 1 to 6, wherein the resin blend composition comprises 30 mass% or more and 75 mass% or less of the polycarbonate based resin (b- i) and 25 mass% or more and 75 mass% or less of the polyester based resin (b-2).

[101 The resin blend composition according to any one of claims 1 to 6. wherein the resin blend composition comprises mass% or more and 70 mass% or less of the polycarbonate based resin (b-i) and 30 mass% or more and 70 mass% or less of the polyester based resin (b-2).

[11] A sheet being made from the resin blend composition according to any one of claims 1 to 10.

[121 A heat-shrinkable sheet being obtained by using a sheet made from the resin blend composition according to claim 10. whereIn the sheet has been drawn in at least one direction and the sheet has a heat shrink ratio when dipped in hot 3 24-07-2006 Printed: 11-09-2006 CLMS 0614660 water at 80 C for 10 seconds of 20% or more in at least one direction.

[13] The heat-shrinkable sheet according to claim 12, wherein that a loss tangent (tanö) curve prepared by dynamic viscoelasticity measurement of the heat-shrinkable sheet at a vibrational frequency of 10 Hz has a single peak in a range of 70 C or more and 130 C or less, with a half- value width of the loss tangent curve being 15 C or more.

[14] A heat-shrinkable laminate sheet comprising layers (A) constituting both outer layers, and a layer (B) positioned between the both outer layers, wherein the sheet has been drawn in at least one axial direction and has a heat shrinkage ratio of 20% or more in the main shrink direction when dipped in hot water at 80 C for 10 seconds, and wherein the layers (A) each is made from a resin composition composed mainly of a thermoplastic polyester based resin (a-i). and the layer (B) is made from the resin blend composition according to claim 10.

[15] The heat-shrinkable laminate sheet according to claim 14, wherein the thermoplastic polyester based resin (a-i) comprises noncrystalline polyethylene terephthalate resin that contains 15 mol% or more and 50 mol% or less of a i,4-cyclohexanedimethanol unit in the total glycol monomer 4 24-07-2006 Printed: 11-09-2006 CLMS 0614660 units in the thermoplastic polyester based resin (a-i).

[16] A sheet for a resin-covered metal plate, comprising a sheet made from the resin blend composition according to claim 8.

[17] A method of producing the sheet for a resin-covered metal plate according to claim 16, the method comprising molding the sheet at a temperature ranging from a temperature that is higher than a flow start temperature of the resin blend composition (Ti) by 10 C (i.e., T1+1O C) to 200 C.

1181 A resin-covered metal plate covered with the sheet for a resincovered metal plate according to claim 16.

[19] A shrink label comprising the heat-shrinkable sheet according to claim 12 or 13, or the heat-shrinkable laminate sheet according to claim 14 or 15.

[201 A package having attached thereto the shrink label according to claim 19.

[211 A molded article being obtained by using the resin blend composition according to any one of claims 1 to 10.

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