JP5954034B2 - Laminate and container - Google Patents

Description

  The present invention relates to a polyester resin laminate having heat resistance, transparency and recyclability. Specifically, the present invention relates to a polyester-based resin laminate that does not deform even in a relatively high temperature range and does not impair the transparency even when recycled end mills and the like, and a container made of this laminate.

  Currently, polyolefin-based resins, polyethylene terephthalate-based resins, polycarbonate-based resins, polyethylene naphthalate-based resins, and the like are used as constituent materials for packaging containers for foods and the like. Among these resins, polyolefin-based resins are relatively inexpensive, but there is a disadvantage that the flavor of the contents is impaired due to adsorption of the low molecular weight compound to the resin, and the flavor retention is poor. Although polycarbonate resin is excellent in transparency and heat resistance, there is a concern that bisphenol A contained as a residual monomer may adversely affect the human body. Is being avoided and its application is being limited to the industrial field. Therefore, at present, containers made of polyester resins such as polyethylene terephthalate resins are mainly used as food packaging materials.

  Among various polyester resins, polyethylene terephthalate resin is most widely used as a constituent material of packaging containers for foods and the like because it is excellent in glossiness, transparency and aroma retention, and is inexpensive. However, while having these excellent points, the polyethylene terephthalate resin is inferior in heat resistance, so that it cannot withstand heating by a microwave oven.

For this reason, development of a packaging member having both fragrance retention, transparency and heat resistance is desired, and a laminate of a polyethylene terephthalate resin and a polycarbonate resin has been proposed as a packaging material that meets this demand. .
For example, Patent Document 1 discloses a technique of laminating a polycarbonate resin film on both sides of a polyethylene terephthalate resin film. In Patent Document 2, an amorphous polyethylene terephthalate resin sheet and a polycarbonate resin sheet are laminated. In Patent Document 3, a mixture of a polyethylene terephthalate resin and a polycarbonate resin is used as an intermediate layer, and a polycarbonate system is used on one or both sides. A technique for laminating a resin is disclosed. Further, in Patent Document 4, a recycled polyethylene terephthalate resin and a polycarbonate resin are each modified with an amorphous polyethylene terephthalate resin and laminated to form a heat-resistant laminate.

Japanese Patent Laid-Open No. 62-181129 JP 10-1003006 A Japanese Patent Laid-Open No. 11-77938 JP 2006-231822 A

  Any of the techniques described in Patent Documents 1 to 4 is effective as a technique for improving the heat resistance of the laminate. However, in recent years, from the viewpoints of soaring raw material prices linked to naphtha prices and environmental protection, scraps and defective products generated when secondary processing of raw sheets into packaging containers, as well as returns from the market, etc. There is a demand for pulverizing and melting waste materials and the like (hereinafter, these may be referred to as “end materials”) and utilizing them as a recycling layer. In the laminated body of polycarbonate-type resin and polyethylene terephthalate-type resin as described in Patent Documents 1 to 4, the recycled layer that is a mixture of these layers is extremely devitrified, and thus obtained by recycling. There is a problem that the transparency of the container is impaired.

  The present invention has been made in view of such various problems, and the problem is that the food packaging has excellent heat resistance and transparency, and does not impair the transparency even when recycling scraps and the like. It is providing the laminated body suitable for a use, and the container which consists of this laminated body.

  As a result of intensive studies in view of the above problems, the present inventor used an alicyclic polyester resin as an adhesive resin, and a polyethylene terephthalate resin layer and an aromatic polycarbonate resin through an alicyclic polyester resin layer. Laminate with laminated layers is excellent in heat resistance and transparency, and does not impair transparency even when recycling scraps, etc., and exhibits high performance as food containers and food packaging materials, etc. The present invention has been completed.

  That is, the gist of the present invention is the following [1] to [11].

[1] The following layer (A), layer (B) and layer (C) are laminated in this order, and the thickness ratio of layer (B) to layer (C) [thickness of layer (B)] / [ The thickness of the layer (C)] is 2/98 to 25/75.
Layer (A): Layer comprising a terephthalic acid-derived unit and a unit derived from ethylene glycol and diethylene glycol as main constituent units and comprising a polyester resin having a glass transition temperature of 45 to 90 ° C. Layer (B): 1, 4 -Layer comprising a unit derived from cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol as main constituent units, and composed of an alicyclic polyester resin having a melting point of 160 to 240 ° C. Layer (C): aromatic Layer made of polycarbonate resin

[2] The thickness ratio [the thickness of the layer (A)] / [the thickness of the layer (C)] of the layer (A) and the layer (C) is 90/10 to 10/90, according to [1]. Laminated body.

[3] The laminate according to [1] or [2], wherein the aromatic polycarbonate-based resin of the layer (C) includes a structural unit derived from bisphenol A.

[4] The laminate according to any one of [1] to [3], further having the following layer (D).
Layer (D): The resin (a) is 10 to 90% by weight, the resin (b) is 1 to 19 parts by weight and the resin (c) is 100% by weight of the total of the following resins (a) to resin (c). Layer composed of a resin composition containing 9 to 89% by weight Resin (a): A unit derived from terephthalic acid and a unit derived from ethylene glycol and diethylene glycol as main constituent units, and a glass transition temperature of 45 to 90 Polyester resin at 0 ° C. Resin (b): an alicyclic compound having a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol as main constituent units and having a melting point of 160 to 240 ° C. Polyester resin Resin (c): Aromatic polycarbonate resin

[5] The laminate according to any one of [1] to [4], wherein the total thickness is 100 to 2000 μm.

[6] A container comprising the laminate according to any one of [1] to [5].

[7] A packaging material comprising the laminate according to any one of [1] to [5].

[8] A food container comprising the laminate according to any one of [1] to [5].

[9] A food packaging material comprising the laminate according to any one of [1] to [5].

[10] The food container according to [8], wherein the layer (A) is configured as an innermost layer in contact with the contents.

[11] The food packaging material according to [9], wherein the layer (A) is configured as an innermost layer in contact with the contents.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which is excellent in heat resistance and transparency, and is suitable for a food container, a food packaging material, etc. without impairing transparency, even if a scrap is recycled.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

The laminate of the present invention comprises the following layer (A), layer (B) and layer (C) laminated in this order, and the thickness ratio between the layer (B) and the layer (C) [of the layer (B) Thickness] / [thickness of layer (C)] is 2/98 to 25/75.
Layer (A): Layer comprising a terephthalic acid-derived unit and a unit derived from ethylene glycol and diethylene glycol as main constituent units and comprising a polyester resin having a glass transition temperature of 45 to 90 ° C. Layer (B): 1, 4 -Layer comprising a unit derived from cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol as main constituent units, and composed of an alicyclic polyester resin having a melting point of 160 to 240 ° C. Layer (C): aromatic Layer made of polycarbonate resin

In some cases, the laminate of the present invention further comprises the following layer (D), preferably between the layer (A) and the layer (B), or between the layer (C) and the layer (B). Have. Here, the layer (D) corresponds to a recycled layer formed by using the end material of the laminate of the present invention formed by laminating the layers (A) to (C).
Layer (D): The resin (a) is 10 to 90% by weight, the resin (b) is 1 to 19 parts by weight and the resin (c) is 100% by weight of the total of the following resins (a) to resin (c). Layer composed of a resin composition containing 9 to 89% by weight Resin (a): A unit derived from terephthalic acid and a unit derived from ethylene glycol and diethylene glycol as main constituent units, and a glass transition temperature of 45 to 90 Polyester resin at 0 ° C. Resin (b): an alicyclic compound having a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol as main constituent units and having a melting point of 160 to 240 ° C. Polyester resin Resin (c): Aromatic polycarbonate resin

[Layer (A)]
The layer (A) includes a unit derived from terephthalic acid and a unit derived from ethylene glycol and diethylene glycol as main constituent units, and has a glass transition temperature of 45 to 90 ° C. (hereinafter referred to as “resin”). (A) may be referred to as “).
Here, “include as a main structural unit” means 50 mol% or more of the total structural units of the resin (a), and the resin (a) according to the present invention constitutes the resin (a). As a dicarboxylic acid component, a unit derived from terephthalic acid is contained in a unit derived from all dicarboxylic acid components in an amount of 50 mol% or more, and as a diol component, a unit derived from all diol components is composed of a unit derived from ethylene glycol and a unit derived from diethylene glycol. It is an amorphous polyester resin containing 50 mol% or more.

  The dicarboxylic acid component constituting the resin (a) preferably contains 90 mol% or more of units derived from terephthalic acid in the units derived from all dicarboxylic acid components from the viewpoint of heat resistance and transparency, and particularly 95 to 100 mol. % Is preferable.

  In the resin (a), other dicarboxylic acid components used in addition to terephthalic acid include, for example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1, Alicyclic dicarboxylic acids such as 5-decahydronaphthalenedicarboxylic acid; phthalic acid, isophthalic acid, phenylenedioxydicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′- Aromatic dicarboxylic acids such as diphenyl ketone dicarboxylic acid, 4,4′-diphenoxyethane dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid; succinic acid, glutaric acid, adipic acid, pimelin Acid, suberic acid, azelaic acid, sebacic acid, undecadi Examples thereof include aliphatic dicarboxylic acids such as carboxylic acid and dodecadicarboxylic acid; alkyl esters having 1 to 4 carbon atoms of these dicarboxylic acids, and dicarboxylic acid derivatives such as halides. These may be used alone or in combination of two or more.

  On the other hand, the higher the ratio of the units derived from ethylene glycol and diethylene glycol in the units derived from all diol components constituting the resin (a), the better the transparency and heat resistance. It is preferable to contain 55 mol% or more in the unit derived from all diol components, and it is particularly preferable to contain 60 to 100 mol%.

  Examples of diol components other than ethylene glycol and diethylene glycol that can be used in the resin (a) include 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentanedimethanol bis (hydroxy 5-membered ring diols such as methyl) tricyclo [5.2.1.0] decane and 1,3-cyclopentanedimethanolbis (hydroxymethyl) tricyclo [5.2.1.0] decane; 1,2-cyclohexane Diol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis- (4-hydroxy (Cyclohexyl) -propane and other 6-membered ring diols; Aliphatic diols such as lenglycol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol; xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2 -Bis (4'-hydroxyphenyl) propane, 2,2-bis (4'-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid, etc. Aromatic diols and the like. These may be used alone or in combination of two or more.

  The glass transition temperature of the resin (a) is 45 ° C. or higher, more desirably 55 ° C. or higher. If the glass transition temperature of the resin (a) is less than the above lower limit, the heat resistance is poor, which is not preferable. On the other hand, the upper limit of the glass transition temperature of the resin (a) is 90 ° C. The glass transition temperature can be measured by a conventional method using, for example, a differential scanning calorimeter (DSC) or the like, and usually the variation of heat flow when measured at a heating rate of 10 ° C./min. It means the temperature of the point. The glass transition temperature of the resin (a) can be controlled by appropriately selecting and using the dicarboxylic acid component and the diol component described above.

  In addition, the intrinsic viscosity (IV) of the resin (a) is arbitrary, but a lower one is preferable in view of easy molding because the melt viscosity is low. Specifically, the intrinsic viscosity (IV) obtained by measuring the resin (a) with a phenol / tetrachloroethane (weight ratio 1/1) mixed solvent as a solvent using an Ubbelohde viscometer at 30 ° C. It is preferably 1.5 dl / g or less. On the other hand, from the viewpoint of physical properties such as strength of the laminate, the intrinsic viscosity (IV) of the resin (a) is preferably 0.3 dl / g or more.

  The resin (a) is generally obtained by esterification or transesterification and polycondensation reaction of a dicarboxylic acid component mainly composed of terephthalic acid and a diol component mainly composed of ethylene glycol and diethylene glycol. The temperature condition of the esterification reaction or transesterification reaction is usually 200 to 300 ° C. In order to obtain a sufficient reaction rate, it is preferable to use a catalyst. The catalyst is not particularly limited as long as it is a catalyst used in ordinary esterification reaction or transesterification reaction and polycondensation reaction, and widely known catalysts can be adopted. Specific examples include titanium compounds, antimony compounds, tin compounds, and the like.

  Polyester resins having the above-described properties suitable as the resin (a) are commercially available. For example, “Easter (registered trademark) Polyester” manufactured by Eastman Chemical Co., Ltd. Trademark) ”.

  As the resin (a), one type of resin may be used alone, or two or more types having different physical properties such as a dicarboxylic acid component, a diol component, or a glass transition temperature may be mixed and used.

[Layer (B)]
The layer (B) includes a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol as main constituent units, and has an alicyclic polyester resin (hereinafter referred to as a melting point of 160 to 240 ° C.). The alicyclic polyester resin may be referred to as “resin (b)”).
Here, “include as a main structural unit” means that it is 50 mol% or more of the total structural units of the resin (b), and the resin (b) according to the present invention constitutes the resin (b). As a dicarboxylic acid component, a unit derived from 1,4-cyclohexanedicarboxylic acid is contained in a unit derived from all dicarboxylic acid components in an amount of 50 mol% or more, and as a diol component, a unit derived from 1,4-cyclohexanedimethanol is derived from all diol components. Is an alicyclic polyester resin containing 50 mol% or more in the unit.

  The resin (b) is preferably a proportion of units derived from 1,4-cyclohexanedicarboxylic acid in units derived from all dicarboxylic acid components and a proportion of units derived from 1,4-cyclohexanedimethanol in units derived from all diol components. However, each is preferably 60 mol% or more, and this ratio is more preferably 70 mol% or more, and particularly preferably 80 mol%. The upper limit is 100 mol%. The higher the proportion of units derived from 1,4-cyclohexanedicarboxylic acid in units derived from all dicarboxylic acid components in the resin (b) and units derived from 1,4-cyclohexanedimethanol in units derived from all diol components, It is preferable in terms of heat resistance of the laminate.

  Examples of dicarboxylic acid components other than 1,4-cyclohexanedicarboxylic acid that can be used for the resin (b) include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-decahydronaphthalene. Alicyclic dicarboxylic acids such as dicarboxylic acid and 1,5-decahydronaphthalenedicarboxylic acid; terephthalic acid, phthalic acid, isophthalic acid, phenylenedioxydicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether Aromatic dicarboxylic acids such as dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid, 4,4′-diphenoxyethane dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid; succinic acid , Glutaric acid, adipic acid, pimelic acid, suberic acid, Examples thereof include chain aliphatic dicarboxylic acids such as xeraic acid, sebacic acid, undecadicarboxylic acid, and dodecadicarboxylic acid; alkyl esters having 1 to 4 carbon atoms of these dicarboxylic acids, and dicarboxylic acid derivatives such as halides. These may be used alone or in combination of two or more.

  Of these dicarboxylic acid components, chain aliphatic dicarboxylic acid, alicyclic dicarboxylic acid or derivatives thereof are preferably used.

  When the dicarboxylic acid component is an alicyclic dicarboxylic acid, it is desirable that the ratio of the trans isomer in the alicyclic dicarboxylic acid is higher in terms of the heat resistance of the resin (b). In this respect, the lower one is preferable. Specifically, the proportion of the trans isomer is preferably 60 mol% or more, more preferably 70 mol% or more, and on the other hand, it is preferably 98 mol% or less.

  On the other hand, examples of diol components other than 1,4-cyclohexanedimethanol that can be used for the resin (b) include 1,2-cyclopentanediol, 1,3-cyclopentanediol, and 1,2-cyclopentane. 5-membered ring diols such as dimethanol bis (hydroxymethyl) tricyclo [5.2.1.0] decane, 1,3-cyclopentanedimethanol bis (hydroxymethyl) tricyclo [5.2.1.0] decane; 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2-bis- (4-hydroxycyclohexyl)- 6-membered ring diol such as propane; ethylene glycol, trimethylene glycol, Tetramethylene glycol such as 1,4-butanediol; chain aliphatic diols such as pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol, polytetramethylene ether glycol; Lenglycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone And aromatic diols such as bis (4-β-hydroxyethoxyphenyl) sulfonic acid. These may be used alone or in combination of two or more.

  Of these, chain aliphatic diols such as pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, and diethylene glycol are preferable from the viewpoint of imparting flexibility.

  When the diol component is an alicyclic diol, the proportion of the trans isomer in the alicyclic diol is 60 mol% or more for the same reason as the proportion of the trans isomer contained in the alicyclic dicarboxylic acid component described above. Preferably, it is 70 mol% or more, and more preferably 98 mol% or less.

  Further, a part of the unit derived from the diol component constituting the resin (b) is replaced with a unit derived from a polyalkylene polyol, that is, the resin (b) is a dicarboxylic acid mainly composed of 1,4-cyclohexanedicarboxylic acid. Flexibility is improved by using a polyether ester block copolymer with a hard segment and a polyalkylene polyol as a soft segment. Therefore, it is preferable. As the polyalkylene polyol used here, polyalkylene glycol such as polyethylene glycol is preferable, and polytetramethylene ether glycol is particularly preferable.

In this case, the amount of the unit derived from the polyalkylene polyol in the resin (b) is preferably larger in terms of the flexibility of the resin (b) and the adhesive performance with the resin (a). When the number of units is excessively large, the melting point of the resin (b) is lowered, and thus heat resistance and transparency may be impaired. For this reason, the content of the unit derived from the polyalkylene polyol contained in the resin (b) in the total resin (b) is preferably 3% by weight or more, and more preferably 6% by weight or more. On the other hand, the content is preferably 30% by weight or less, and more preferably 25% by weight or less. In addition, content of the unit derived from the polyalkylene polyol in resin (b) can be calculated from the preparation ratio at the time of manufacture, or can be quantified by an instrumental analysis method such as ¹ H-NMR spectrum analysis.

  Regarding the molecular weight of the polyalkylene polyol, the number average molecular weight is preferably 200 or more from the viewpoint of toughness and impact resistance, while the number average molecular weight is preferably 3000 or less from the viewpoint of polymerization reactivity. preferable.

The melting point of the resin (b) is required to be 160 ° C. or higher and 240 ° C. or lower from the viewpoint of balance between workability and transparency. The melting point of the resin (b) is adjusted appropriately for the types of the dicarboxylic acid component and the diol component described above, the ratio of the trans alicyclic dicarboxylic acid in the dicarboxylic acid component, the ratio of the trans alicyclic diol in the diol component, and the like. It is controllable by doing.
The melting point of the resin (b) is detected by a differential scanning calorimeter (DSC), and usually means the temperature at the top of the melting peak when measured at a heating rate of 10 ° C./min.

  In addition, the intrinsic viscosity (IV) of the resin (b) is arbitrary, but a lower one is preferable because the melt viscosity is also low, so that the molding process is easy. Specifically, the intrinsic viscosity (IV) determined by measuring the resin (b) with a phenol / tetrachloroethane (weight ratio 1/1) mixed solvent as a solvent using an Ubbelohde viscometer at 30 ° C. It is preferably 1.5 dl / g or less. On the other hand, from the viewpoint of physical properties such as strength of the laminate of the present invention, the intrinsic viscosity (IV) of the resin (b) is preferably 0.5 dl / g or more.

  The resin (b) preferably has a higher melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg measured in accordance with test condition 4 of JIS K7210 in terms of workability and is small in terms of mechanical strength. Is preferred. Specifically, the MFR of the resin (b) at 230 ° C. and a load of 2.16 kg is preferably 1 g / 10 min or more, more preferably 5 g / 10 min or more, and on the other hand, 200 g / 10 min or less. Is preferably 100 g / 10 min or less.

  Resin (b) is generally an esterification or transesterification reaction and polycondensation of a dicarboxylic acid component having 1,4-cyclohexanedicarboxylic acid as a main component and a diol component having 1,4-cyclohexanedimethanol as a main component. Obtained by reaction. The temperature condition of the esterification reaction or transesterification reaction is usually 200 to 300 ° C. In order to obtain a sufficient reaction rate, it is preferable to use a catalyst. The catalyst is not particularly limited as long as it is a catalyst used in ordinary esterification reaction or transesterification reaction and polycondensation reaction, and widely known catalysts can be adopted. Specific examples include titanium compounds, antimony compounds, tin compounds, and the like. When polycondensation is carried out using a transesterification reaction, a dimethyl dicarboxylate component is used in place of the dicarboxylic acid component described above. In particular, the composition derived from 1,4-cyclohexanedicarboxylic acid has 1,4 as its raw material. -Dimethyl cyclohexanedicarboxylate is used.

  As the resin (b), one type of resin may be used alone, or two or more types having different physical properties such as a dicarboxylic acid component, a diol component, or a melting point may be used.

  The resin (b) may be a branched alicyclic polyester obtained by copolymerizing a trifunctional or higher polyfunctional compound. Examples of the trifunctional or higher polyfunctional compound include compounds having three or more hydroxyl groups such as trimethylolpropane, polyoxypropylenetriol, pentaerythritol, sorbitol, 1,2,4-benzenetricarboxylic acid, butanetetracarboxylic Acid, cyclohexane-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid And compounds having three or more carboxyl groups such as. The amount of its use is 0.01-10 mol% normally with respect to all the raw materials, Preferably it is 0.1-3 mol%.

[Layer (C)]
The layer (C) is a layer made of an aromatic polycarbonate resin (hereinafter sometimes referred to as “resin (c)”).

  The resin (c) is a linear or branched thermoplastic polymer or copolymer usually obtained by using an aromatic dihydroxy compound and a carbonate precursor as raw materials. In addition to the above aromatic dihydroxy compound, a trifunctional or higher polyfunctional aromatic compound may be used as the raw material for the resin (c).

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetra Bromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ) Octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3) , 5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis ( , 5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1- Bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2,2-bis (4 -Hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, bis such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane And (hydroxyaryl) alkanes.

  Moreover, as aromatic dihydroxy compounds other than the above, for example, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy) Bis (hydroxyaryl) cycloalkanes exemplified by phenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3- Cardo structure-containing bisphenols exemplified by methylphenyl) fluorene; dihydroxydiaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether; '-Dihydroxydiphenyl sulfide, 4,4'-dihydride Dihydroxy diaryl sulfides exemplified by xy-3,3′-dimethyldiphenyl sulfide; dihydroxy exemplified by 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc. Diaryl sulfoxides; dihydroxy diaryl sulfones exemplified by 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, etc .; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, etc. Is mentioned.

  Among the above, as the aromatic dihydroxy compound, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. preferable. An aromatic dihydroxy compound may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate and the like. Specific examples thereof include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl such as dimethyl carbonate and diethyl carbonate. Carbonates; dihaloformates of dihydric phenols and the like. These carbonate precursors may be used alone or in combination of two or more.

  The resin (c) may be a branched aromatic polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4, 6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, In addition to polyhydroxy compounds such as 1,1,1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7 -Dichloro isatin, 5-bromo isatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is usually 0.01 to 10 mol%, preferably based on the aromatic dihydroxy compound. 0.1 to 2 mol%.

  Examples of the method for producing the resin (c) include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Industrially, an interfacial polymerization method or a melt transesterification method is advantageous.

  The molecular weight of the resin (c) is a viscosity average molecular weight (Mv) converted from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent from the viewpoint of mechanical strength and fluidity (ease of molding processability). ) Is usually 10,000 to 50,000, preferably 12,000 to 40,000, and more preferably 14,000 to 30,000. Resin (c) is good also as a viscosity average molecular weight in said range by mixing 2 or more types of aromatic polycarbonate resin from which a viscosity average molecular weight differs. Moreover, you may mix the aromatic polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

  In addition, the resin (c) preferably has a higher melt flow rate (MFR) at 300 ° C. and 1.20 kg load measured in accordance with test condition 4 of JIS K7210 in terms of workability and is small in terms of mechanical strength. Is preferred. Specifically, the MFR of the resin (c) at 300 ° C. and 1.20 kg load is preferably 0.1 g / 10 min or more, more preferably 1 g / 10 min or more, while 100 g / 10 min or less. It is preferable that it is 50 g / 10 min or less.

  The terminal hydroxyl group concentration of the resin (c) is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. The lower limit is 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly for an aromatic polycarbonate resin produced by a transesterification method. By setting the terminal hydroxyl group concentration to 10 ppm or more, a decrease in molecular weight can be suppressed, and mechanical properties tend to be further improved. Further, when the terminal hydroxyl group concentration is within a range not exceeding 1000 ppm, the residence heat stability and the color tone tend to be further improved.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the aromatic polycarbonate resin, and the measuring method is a colorimetric determination (Macromol. Chem. 88 215) by the titanium tetrachloride / acetic acid method. (Method of (1965)).

  As the aromatic polycarbonate-based resin as the resin (c), one kind may be used alone, or two or more kinds having different raw material compounds or different physical properties such as viscosity average molecular weight may be mixed and used. .

  Resin (c) can also be obtained as a commercial item. Examples of commercially available products include Iupilon (registered trademark) series manufactured by Mitsubishi Engineering Plastics.

[Other ingredients]
The layer (A), the layer (B), and the layer (C) are each formed of the above-described resin (a), resin (b), and resin (c). The resin (a), the resin (b), a resin other than the resin (c), additives, and the like may be included as long as the effects are not significantly disturbed. That is, the layer (A), the layer (B), and the layer (C) may be formed of a resin composition mainly composed of the resin (a), the resin (b), and the resin (c). Good.

  Examples of the resin other than the resins (a) to (c) used for forming each layer include an ethylene / vinyl acetate copolymer, an ethylene / acrylic acid copolymer, a propylene homopolymer, a propylene / ethylene copolymer, Propylene copolymers such as propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer; polyphenylene ether resins; polyamide resins such as nylon 66 and nylon 11; polyethylene terephthalate, polybutylene terephthalate, etc. Polyester resins (however, except those respectively contained in the resins (a) to (c)), thermoplastic resins such as polymethyl methacrylate resins, acrylic / methacrylic resins, and the like.

Examples of additives include various heat stabilizers, antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, light stabilizers, crystal nucleating agents, impact modifiers, pigments, lubricants, antistatic agents, Examples include flame retardants, flame retardant aids, fillers, compatibilizers, and tackifiers.
These other resins, additives and the like may be used alone or in combination of two or more in any combination and ratio.

  Examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and the like.

  Flame retardants are roughly classified into halogen-based flame retardants and non-halogen-based flame retardants, and non-halogen-based flame retardants are preferable in terms of the environment. Non-halogen flame retardants include phosphorus flame retardants, hydrated metal compounds (aluminum hydroxide and magnesium hydroxide) flame retardants, nitrogen-containing compounds (melamine and guanidine) flame retardants and inorganic compounds (borate and molybdenum) Compound) flame retardant and the like.

  Fillers are roughly classified into organic fillers and inorganic fillers. Examples of the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir husk, bran, and modified products thereof. Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon Examples thereof include black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, and carbon fiber.

  Even when components such as resins and additives other than the resins (a) to (c) are used for forming the layers (A) to (C), the contents of the resins (a) to (c) in each layer are From the standpoint of ease of expression of the excellent effects of the invention, it is preferably 60% by weight or more, and more preferably 80% by weight or more. This upper limit is usually 100% by weight.

[Thickness ratio of each layer]
In the laminate of the present invention, the thickness ratio of layer (B) to layer (C) [thickness of layer (B)] / [thickness of layer (C)] (hereinafter “layer (B) / layer (C)” Is a range of 2/98 to 25/75. Even if the layer (B) / layer (C) is larger than the above range, the layer (B) is thick and the layer (C) is thin, it is smaller than the above range, and the layer (B) is thin and the layer (C ) Is too thick, the transparency of the recycled layer obtained by recycling the end material of the laminate of the present invention, that is, the transparency of the layer (D) described later is impaired.

  By setting the layer (B) / layer (C) in the above range, a recycled layer having excellent transparency can be obtained. Further, if the layer (B) as the adhesive resin layer is thinner than the above range, the transparency of the recycled layer is inferior, and if the layer (C) as the heat-resistant resin layer is thin, the transparency of the recycled layer is lowered. At the same time, deformation occurs when the container is heated, which is not preferable. On the other hand, if these layers are too thick, the total thickness of the laminate becomes too thick, which is not preferable in terms of reduction in thickness and weight and material cost. A more preferable layer (B) / layer (C) is 5/95 to 20/80.

  In the laminate of the present invention, the thickness ratio of layer (A) to layer (C) [thickness of layer (A)] / [thickness of layer (C)] (hereinafter referred to as “layer (A) / layer (C ) ”May be abbreviated as“. ”Is preferably in the range of 90/10 to 10/90. When the layer (A) / layer (C) is in the above range, a recycled layer obtained by utilizing the end material of the laminate of the present invention, that is, a layer (D) described later having better transparency It tends to be.

  By setting the layer (A) / layer (C) in the above range, a recycled layer having excellent transparency can be obtained. Further, when the layered product of the present invention is used for food packaging applications, for example, the layer (A) is a layer that comes into contact with the contents as the innermost layer. Inferior content preservation. On the other hand, if the layer (C) as the heat-resistant resin layer is thin, deformation occurs when the container is heated, which is not preferable. On the other hand, if these layers are too thick, the total thickness of the laminate becomes too thick, which is not preferable in terms of reduction in thickness and weight and material cost. More preferable layer (A) / layer (C) is 80/20 to 20/80, and more preferably 70/30 to 30/70.

[Layer (D)]
In the layer (D), the resin (a) is 10 to 90% by weight, the resin (b) is 1 to 19 parts by weight, and the resin (c) with respect to the total of 100% by weight of the following resins (a) to resin (c). ) Is a layer made of a resin composition containing 9 to 89% by weight.
Resin (a): Polyester resin containing a unit derived from terephthalic acid and a unit derived from ethylene glycol and diethylene glycol as main constituent units and having a glass transition temperature of 45 to 90 ° C. Resin (b): 1,4-cyclohexanedicarboxylic acid An alicyclic polyester-based resin having an acid-derived unit and a 1,4-cyclohexanedimethanol-derived unit as main constituent units and having a melting point of 160 to 240 ° C. Resin (c): Aromatic polycarbonate-based resin

The details of the resins (a) to (c) are as described above for the resins constituting the layers (A) to (C).
That is, the layer (D) is a recycled layer formed by pulverizing and melting the ends of the laminate of the present invention formed by laminating the layers (A) to (C), and preferably the above-mentioned layer ( B) / layer (C) and layer (A) / layer (C), when the end materials of the laminate of the present invention constituted by the thickness ratio are recycled, the resins (a) to (a) in the layer (D) The content ratio of c) is in the above range, and the layer (D) containing the resins (a) to (c) at such ratio is excellent in transparency, and the layers (A), (B), and (C ) And can be easily laminated.

  The content ratios of the resins (a) to (c) in the layer (D) are more preferably resin (a): 10 to 90% by weight, resin (b): 1 to 17% by weight, resin (c): 9 to 79% by weight, particularly preferably resin (a): 20 to 80% by weight, resin (b): 1 to 15% by weight, resin (c): 20 to 79% by weight (however, resin (The total of (a) to (c) is 100% by weight.)

  In addition, the layer (C) may contain the above-mentioned other resin, additive, etc. similarly to the layers (A) to (C). However, in this case, the total content of the resins (a) to (c) in the layer (D) is preferably 60% by weight or more, and particularly preferably 80 to 100% by weight.

  The layered product of the present invention is characterized in that the layer (D) which is a recycling layer of the mill ends is excellent in transparency. Regarding the transparency of this layer (D), when measuring haze and total light transmittance according to JIS K7136 for the layer (D) having a thickness of 2 mm, the haze is 40% or less, particularly 20% or less. The transmittance is preferably 80% or more, particularly 85% or more.

[Layer structure and thickness and total thickness of each layer]
The laminate of the present invention is formed by laminating the layer (A), the layer (B) and the layer (C) in this order, and the layer (A) is excellent in aroma retention, safety, etc. When the laminate is used for food packaging and the like, it is used as the innermost layer in contact with the contents. The layer (C) contributes to heat resistance and transparency, and the layer (B) functions as an adhesive resin layer between these layers (A) and (C).

  Each layer of the layer (A), the layer (B), and the layer (C) is used to effectively exhibit each function without excessively increasing the total thickness of the laminate of the present invention. ) / Layer (C) and layer (A) / layer (C) in the thickness ratio range, the thickness of the layer (A) is preferably 10 to 1960 μm, particularly preferably 30 to 980 μm, and the thickness of the layer (B). Is preferably 2 to 370 μm, more preferably 4 to 185 μm. The thickness of the layer (C) is preferably 10 to 1960 μm, particularly preferably 30 to 980 μm.

  Moreover, when the laminated body of this invention has a layer (D) further, when a layer (D) has more resin (a) than resin (c), a layer (D) is a layer (A) and a layer (B ) Is preferably provided between the layer (A) and the layer (B), and the laminate of the present invention comprises the layer (A), the layer (D), and the layer (B). The layer (C) is preferably laminated in this order. On the other hand, in the layer (D), when the resin (c) is more than the resin (a), the layer (D) has excellent adhesion performance to the layer (C) and the layer (B). The layered product of the present invention is preferably provided between the layer (C) and the layered product of the layer (A), the layer (B), the layer (D), and the layer (C) in this order. It is preferable that Furthermore, since the layer (D) is made of a resin composition containing the resins (a) to (c), it can be used in place of any of the layers (A) to (C).

The layer (D) is used for the purpose of achieving effective use of resources, reduction of material costs, and reduction of waste materials by recycling of the end materials of the laminate of the present invention.
In order to increase the recycling rate without impairing the transparency and hue of the resulting laminate, the thickness of the layer (D) is preferably 10 to 1000 μm, particularly 30 to 500 μm, and particularly preferably 30 to 200 μm.

  Further, the total thickness of the laminate of the present invention composed of layers (A) to (C) or layers (A) to (D) varies depending on the use of the laminate, but is usually 100 to 2000 μm, particularly 100. It is preferable that it is -1000 micrometers, especially 100-500 micrometers. If the total thickness of the laminate is equal to or more than the above lower limit value, it tends to ensure the thickness required for each of the layers (A) to (C), and the mechanical strength, handleability, and molding of the laminate are likely to be ensured. It tends to be favorable in terms of properties. On the other hand, when the total thickness of the laminate is not more than the above upper limit value, it is preferable in terms of reducing the thickness and weight and reducing the material cost. In addition, the laminated body of this invention may have other layers, such as a barrier layer other than layer (A)-(D), in the range which does not exceed the summary of this invention.

[Manufacturing method of laminate]
In producing the laminate of the present invention, the resin (a), the resin (b), and the resin (c) constituting the layer (A), the layer (B), and the layer (C) are added to the above-described other resins and additives. Etc. are used as a resin composition, and each of the resins (a) to (c) and the compounding agent are mixed using various known techniques such as a tumbler blender, a V blender, a ribbon blender, a Henschel mixer, etc. Then, after mixing, pellets of the resin composition can be prepared and used by a technique of melt kneading with a single screw extruder, twin screw extruder, Banbury mixer, kneader or the like, and granulating or pulverizing.

  About a layer (D), the end material etc. of the laminated body of this invention can be grind | pulverized and used.

The laminate of the present invention consisting of layers (A) to (C) can be produced, for example, by the following method.
(1) Using a three-layer co-extruder, the constituent materials (resins (a) to (c) or compositions thereof) of each layer are co-extruded to form a three-layer laminate.
(2) A film or sheet of the layer (A) or the layer (C) that has been extrusion molded in advance is subjected to coextrusion lamination using a two-layer coextrusion machine to form a three-layer laminate.
(3) The layer (B) is extrusion-molded between a film or sheet of the layer (A) and the layer (C) that has been previously extruded to form a three-layer laminate.
(4) A laminate or layer (A) of a layer (B) and a layer (C) obtained separately by two-layer extrusion molding with respect to a film or sheet of the layer (A) or layer (C) which has been previously extruded. ) And layer (B).
(5) Layers (A) to (C) that are separately extruded are laminated and bonded in the order of layer (A) / layer (B) / layer (C).

  Further, the laminate of the present invention having a layer (D) can also be produced in the same manner as described above except that the layer (D) is further interposed.

  When manufacturing the laminated body of this invention especially using a multilayer T-die coextrusion molding machine, the cylinder temperature of each layer extruder is 250-290 degreeC in a layer (A), 190-230 degreeC in a layer (B), layer (C) is preferably 250 to 290 ° C, and layer (D) is preferably 250 to 290 ° C, and the die temperature is preferably set to 250 to 290 ° C.

[Physical properties of laminates]
The laminate of the present invention has a feature of excellent transparency and heat resistance, and the transparency can be evaluated by haze and total light transmittance according to JIS K7136. For example, when a laminate having a thickness of 200 μm is measured, the haze is preferably 10% or less, particularly 5% or less, and the total light transmittance is preferably 85% or more, particularly 86% or more. .

  In addition, the laminate of the present invention preferably has a heat resistance of a high temperature tensile modulus measured according to JIS K6251 by a method described in the section of the below-described example, of 400 MPa or more, particularly 500 MPa or more.

[Use of laminate]
The laminate of the present invention can be used in various applications as a film or sheet having a total thickness of 100 to 2000 μm. In particular, the layer (A) has excellent fragrance retention and safety, transparency and heat resistance. Due to the characteristics of the layer (C) having excellent properties, it is suitably used for food packaging applications including various beverages such as various containers such as food containers, various packaging materials such as food packaging materials and the like. However, the laminate of the present invention is not limited to food packaging applications, and is also useful as containers for chemicals, cosmetics, and various packaging materials.

  In any case, the laminate of the present invention is usually used so that the layer (A) is the innermost layer in contact with the contents.

  The laminate of the present invention produced by the above-described method is further used as various containers and packaging materials by thermoforming into a desired shape by vacuum forming, pressure forming or the like.

  In the laminate of the present invention, paper, a nonwoven fabric, a resin film, a metal layer, a printed layer, and the like may be further formed on the layer (C) as necessary in various containers and packaging materials. .

  EXAMPLES Hereinafter, although this invention is demonstrated still in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

  In the examples and comparative examples of the present invention, the following raw materials were used.

In the following, the glass transition temperature of the resin (a) is the temperature at the inflection point of heat flow when measured with a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min.
Further, the intrinsic viscosity (IV) of the resin (a) and the resin (b) is a value measured at 30 ° C. using an Ubbelohde viscometer with a phenol / tetrachloroethane (weight ratio 1/1) mixed solution as a solvent. It is.
The melting point of the resin (b) is the temperature at the top of the melting peak when measured with a differential scanning calorimeter (DSC) at a rate of temperature increase of 10 ° C./min, and the melt flow rate (MFR) is JIS K7210 It is a value at 230 ° C. and a load of 2.16 kg measured according to test condition 4.
Further, the viscosity average molecular weight (Mv) of the resin (c) is a value converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and the melt flow rate (MFR) is JIS K7210. It is a value at 300 ° C. and a load of 1.20 kg measured according to test condition 4, and the terminal hydroxyl group concentration is measured by colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method. It is a thing.

<Layer (A): Resin (a)>
(A-1) Nippon Unipet Co., Ltd. Polyethylene terephthalate resin homopolymer
"Unipet (registered trademark) RT553C"
Glass transition temperature = 81 ° C.
Intrinsic viscosity (IV) = 0.85 dl / g
(A-2) Polyethylene terephthalate resin by Eastman Chemical Co.
"Eastar (registered trademark) Copolyester GN001"
Dicarboxylic acid component: 100 mol% terephthalic acid
Diol component: 65.3 mol% ethylene glycol
Diethylene glycol 2.5 mol%
1,4-cyclohexanedimethanol 32.2 mol%
Glass transition temperature = 72.7 ° C.
Intrinsic viscosity (IV) = 0.65 dl / g

<Layer (B): Resin (b)>
(B-1) Alicyclic polyester: a copolymer of 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol as a hard segment, and polytetramethylene ether glycol (number average molecular weight 1000) as a soft segment Polyether ester block copolymer
Content of units derived from polytetramethylene ether glycol
= 15% by weight (quantified by ¹ H-NMR)
Trans rate of 1,4-cyclohexanedicarboxylic acid = 80%
Trans ratio of 1,4-cyclohexanedimethanol = 69%
Melting point = 202 ° C.
MFR (230 ° C., 2.16 kg load) = 35 g / 10 min

<Layer (C): Resin (c)>
(C-1) Bisphenol A type aromatic polycarbonate resin “Iupilon (registered trademark) S-2000” manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight (Mv) = 25000
MFR (300 ° C., 1.20 kg load) = 9 g / 10 min

[Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2]
Based on the layer configuration shown in Table-1A, co-extrusion molding was performed using a multilayer T-die molding machine (multi-layer T-die film manufacturing apparatus manufactured by Pla Giken Co., Ltd.), and this was taken up on a cast roll at 30 ° C. The thickness and the thickness ratio are values shown in Table-1A, and a laminate having a total thickness of 200 μm was obtained. The layers (A) to (C) were laminated so that the layer (B) entered between the layers (A) and (C). Regarding the extruder for forming each layer, the layer (A) extruder is 230 to 260 ° C, the layer (B) extruder is 190 to 210 ° C, and the layer (C) extruder is 250 to 280 ° C. The temperature was set. The temperature of the die was set to 250 to 280 ° C.

  The obtained laminate was evaluated as follows, and the results are shown in Table 1A.

(1) Transparency: haze and total light transmittance The haze and total light transmittance of a laminate having a total thickness of 200 μm were measured according to JIS K7136. Moreover, transparency was evaluated according to the following criteria from haze and total light transmittance.
○: Haze of 10% or less and total light transmittance of 85% or more ×: Outside the above range

(2) Heat resistance: High-temperature tensile elastic modulus Measured according to JIS K6251. Specifically, the laminate was punched in the MD direction (sheet take-off direction) into a No. 3 dumbbell test piece, and this was pulled at a rate of 1 mm / min by an autograph in a thermostatic chamber adjusted to 80 ° C., From the tensile stress at a displacement of 0 to 0.5 mm, the high temperature tensile modulus of the laminate was calculated. Moreover, this high temperature tensile elasticity modulus is so preferable that the value is high, and heat resistance was evaluated by the following judgment criteria.
A: High-temperature tensile elastic modulus is 500 MPa or higher. O: High-temperature tensile elastic modulus is 450 MPa or higher and lower than 500 MPa. Δ: High-temperature tensile elastic modulus is 400 MPa or higher and lower than 450 MPa. X: High-temperature tensile elastic modulus is lower than 400 MPa.

[Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2]
Assuming that the laminates formed in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2 were recycled as layers (D), respectively, and used at the thickness ratios described in Table-1A. Recycled pellets were obtained by melting and kneading the constituent resins of each layer using a twin-screw extruder with a cylinder temperature of 260 ° C. at the blending ratio shown in Table-1B corresponding to the resin ratio. The recycled pellets were molded into an 80 mm × 120 mm × 2 mm plate with an injection molding machine. The injection molding conditions were resin temperature: 200 to 280 ° C., injection time: 2 to 20 seconds, mold temperature: 40 to 70 ° C., cooling time: 10 to 40 seconds.
The obtained plate was evaluated as follows, and the results are shown in Table 1-B.

(3) Recyclability: haze and total light transmittance Using the obtained plate, the haze and total light transmittance in the thickness (2 mm) direction were measured according to JIS K7136, and the recyclability was evaluated based on the following criteria. did.
○: Haze of 20% or less and total light transmittance of 85% or more Δ: Haze of 40% or less and total light transmittance of 85% or more ×: Haze outside the above range

  Tables 1A and 1B show that Examples 1-1 to 1-4 corresponding to the laminate of the present invention are excellent in heat resistance, transparency, and recyclability. In Comparative Examples 1-1 and 1-2, the thickness ratio of the layer (B) and the layer (C) [thickness of the layer (B)] / [thickness of the layer (C)] is the specified range of the laminate of the invention. It can be seen that Comparative Example 1-1 is inferior in heat resistance and recyclability, and Comparative Example 1-2 is inferior in recyclability.

  Since the laminate of the present invention has excellent transparency, heat resistance, and recycling characteristics, it is expected to be applied to various members including food packaging containers.

Claims (11)

The following layer (A), layer (B) and layer (C) are laminated in this order, and the thickness ratio of layer (B) to layer (C) [thickness of layer (B)] / [layer (C )]] Is 2/98 to 25/75.
Layer (A): Layer comprising a terephthalic acid-derived unit and a unit derived from ethylene glycol and diethylene glycol as main constituent units and comprising a polyester resin having a glass transition temperature of 45 to 90 ° C. Layer (B): 1, 4 -Layer comprising a unit derived from cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol as main constituent units, and composed of an alicyclic polyester resin having a melting point of 160 to 240 ° C. Layer (C): aromatic Layer made of polycarbonate resin   The laminate according to claim 1, wherein the thickness ratio of the layer (A) to the layer (C) [thickness of the layer (A)] / [thickness of the layer (C)] is 90/10 to 10/90.   The laminate according to claim 1 or 2, wherein the aromatic polycarbonate-based resin of the layer (C) includes a structural unit derived from bisphenol A. Furthermore, the laminated body of any one of Claims 1 thru | or 3 which has the following layer (D).
Layer (D): The resin (a) is 10 to 90% by weight, the resin (b) is 1 to 19 parts by weight and the resin (c) is 100% by weight of the total of the following resins (a) to resin (c). Layer composed of a resin composition containing 9 to 89% by weight Resin (a): A unit derived from terephthalic acid and a unit derived from ethylene glycol and diethylene glycol as main constituent units, and a glass transition temperature of 45 to 90 Polyester resin at 0 ° C. Resin (b): an alicyclic compound having a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol as main constituent units and having a melting point of 160 to 240 ° C. Polyester resin Resin (c): Aromatic polycarbonate resin   The laminated body of any one of Claims 1 thru | or 4 whose total thickness is 100-2000 micrometers.   A container comprising the laminate according to any one of claims 1 to 5.   The packaging material which consists of a laminated body of any one of Claims 1 thru | or 5.   A food container comprising the laminate according to any one of claims 1 to 5.   A food packaging material comprising the laminate according to any one of claims 1 to 5.   The food container according to claim 8, wherein the layer (A) is configured as an innermost layer in contact with the contents.   The packaging material for foodstuffs of Claim 9 comprised as the innermost layer which the said layer (A) contacts with the contents.