JP2013226833A - Polyester resin laminate, method of manufacturing the same, and bag and container using the laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which has biodegradability, and is excellent in processability, and in which the adhesion between the polyester resin layer and a base material layer has been improved, and to provide a bag and a container formed by using the laminate.SOLUTION: A laminate has a base material layer containing a plant-derived component, an outermost layer containing aliphatic polyester, and an intermediate layer that exists between the base material layer and the outermost layer, and is different from the outermost layer. Aliphatic polyester is contained in the intermediate layer, and tensile elasticity of the resin composition that composes the intermediate layer is 300 MPa or less. A bag and a container are formed using the laminate.

Description

  The present invention relates to a polyester resin laminate suitably used as a bag or a container.

  Laminated products such as cups, trays and cartons made of packaging materials such as food, beverages and pharmaceuticals and laminated paper are widely used. Such processed products improve the water resistance, chemical resistance, waterproofness, surface smoothness, glossiness, fragrance retention, processability, etc., so that one or both sides of the paper is used rather than when using the paper alone. In many cases, plastic is laminated on top. In general, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, or the like is used as the plastic to be laminated on paper, and an aluminum foil may be laminated in addition to the plastic.

  Since general-purpose resins such as polyolefin generate a large amount of heat during combustion, incineration of plastic products discarded after use may damage the incinerator. For this reason, plastic products are generally landfilled, but since plastic remains as it is without being decomposed, shortening of the life of the landfill processing site is regarded as a problem. In addition, when it is scattered as dust in the natural environment, it is extremely poor in degradability, which causes environmental pollution and damage to the landscape.

  In addition, due to the recent increase in awareness of environmental issues, a system for collecting milk cartons among laminated papers has been built and paper reuse is progressing, but other laminated papers are incinerated without much progress. Is the actual situation. This recovery is because the laminated paper is immersed in an alkaline aqueous solution and the polyolefin is peeled off, which is a very troublesome and labor-intensive process.

  Against this background, attempts have been made to apply biodegradable resins to laminated papers. For example, Patent Document 1 discloses biodegradable fats that have been polymerized using a chain extender (coupling agent). A laminate of a group polyester is disclosed. Furthermore, Patent Document 2 discloses a method for obtaining a laminate by controlling the resin pressure during processing without using a coupling agent. Patent Document 3 discloses a laminate having a high heat-sealability and excellent workability by controlling the additive viscosity and the melt viscosity before and after heat history without using a coupling agent, and a method for producing the same. .

  However, when a resin is produced by the method disclosed in Patent Document 1 and applied to laminated paper, it is molded at a relatively high temperature in order to obtain a practical adhesive strength between the substrate and the resin. It is necessary to use a resin in which a urethane bond is introduced by the action of a chain extender, causing the phenomenon of fuming and foaming due to thermal decomposition of the urethane bond, deteriorating the working environment, and There was a problem that problems such as odor adsorption occurred. Similarly, even when a laminate is obtained by the method disclosed in Patent Document 2, for example, satisfactory molding conditions have not yet been found in terms of adhesive strength and the like.

  In addition, conventional polyolefin-based laminates have a problem of adsorption of aroma components, and conversely, polyester-based laminates that have low adsorptivity to aroma components and excellent aroma retention have heat sealability. There was a problem of shortage. Therefore, the development of a laminated paper having the performance to satisfy both has been awaited. Here, for example, in the laminate obtained by the method disclosed in Patent Document 3, a laminate having high heat seal strength between the resin layers and excellent biodegradability could be obtained. However, satisfactory molding conditions have not yet been found to obtain sufficient adhesive strength (fiber peeling state) between the resin layer and the base material layer.

  In order to solve these problems, the applicant has disclosed in Patent Document 4 an aliphatic polyester contained in a polyester layer between a base material layer made of a plant-derived material and a polyester layer containing an aliphatic polyester having a predetermined melting point. A laminate provided with an intermediate layer containing a different thermoplastic resin, preferably an acrylic resin, a polyethyleneimine resin, a urethane resin, and a polyester resin different from that used for the polyester layer is disclosed. According to this, it can be set as the laminated body excellent in the practicality and workability as a container or a packaging material, maintaining a biodegradable characteristic.

Japanese Patent Laid-Open No. 6-171050 JP 2006-272712 A JP 2009-51210 A JP 2012-30547 A

  However, when the adhesive layer resin is a polyethyleneimine resin, when the water enters from the end face of the laminate upon contact with water, the polyethyleneimine resin dissolves or swells in the water and the polyester layer is peeled off from the substrate. There was a sex problem. In addition, acrylic resins and urethane resins have odors and safety concerns derived from the solvents and crosslinking agents contained therein.

  In the case of a polyester resin different from that used for the polyester layer, the water resistance, biodegradability and safety are good, but the adhesion to the base material layer is still insufficient.

  Therefore, the present invention is a laminate having a polyester-based resin layer, which has biodegradability, excellent workability, and improved adhesion between the polyester-based resin layer and the base material layer, It aims at providing the bag and container which shape | mold a laminated body.

  As a result of intensive studies to solve the above problems, the present inventors formed an intermediate layer between the base material layer and the aliphatic polyester layer, and contained the specific polyester in the intermediate layer. Thus, the present inventors have found that the adhesion between the base material layer and the aliphatic polyester layer is improved, that excellent workability is obtained, and that good biodegradability is exhibited, and the present invention has been achieved.

  That is, the first present invention comprises a base material layer containing a plant-derived component, an outermost layer containing an aliphatic polyester, and an intermediate layer different from the outermost layer present between the base material layer and the outermost layer. The intermediate layer contains an aliphatic polyester, and the tensile elastic modulus of the resin composition constituting the intermediate layer is 300 MPa or less.

  In the first aspect of the present invention, the plant-derived component is preferably a fiber containing a plant-derived component or a film containing a plant-derived component.

  In the first aspect of the present invention, the aliphatic polyester contained in the outermost layer is preferably formed by polymerizing an aliphatic dicarboxylic acid and an aliphatic diol.

  In the first aspect of the present invention, the polyester contained in the intermediate layer is preferably obtained by polymerizing a dicarboxylic acid and an aliphatic diol.

  The laminate according to the first aspect of the present invention preferably has a thickness of 300 μm or less.

  In the first aspect of the present invention, the tensile elastic modulus of the composition constituting the outermost layer is preferably 400 Mpa or more.

  2nd this invention is a bag in which the laminated body which concerns on 1st this invention was used for at least one part.

  The third aspect of the present invention is a liquid container in which the laminate according to the first aspect of the present invention is used at least in part.

  4th this invention is the lamination | stacking which has the base material layer containing a plant-derived component, the outermost layer containing aliphatic polyester, and the intermediate | middle layer different from the outermost layer which exists between this base material layer and this outermost layer. A method for producing a laminate, wherein the intermediate layer is formed using a resin composition containing an aliphatic polyester and having a tensile modulus of 300 MPa or less.

In the present invention, the “resin composition” constituting the outermost layer or the intermediate layer refers to the entire component contained in the layer, and includes only a single component in addition to a form containing a plurality of types of components. It is a concept including a form that is included (that is, only a predetermined aliphatic aromatic polyester having a tensile modulus of elasticity of 300 MPa or less).
The “tensile modulus” of the resin composition refers to a value measured as follows. That is, an inflation film having a blow ratio of 2.0 and a thickness of 20 to 50 μm is produced by an inflation molding method with a molding temperature of 150 to 180 ° C. for the resin composition constituting the layer. A strip-shaped test piece having a width of 10 mm was prepared from the obtained film, and the initial elasticity was measured at a tensile speed of 1 mm / min with a Tensilon universal testing machine (manufactured by A & D Co., Ltd.) in accordance with JIS K7161. The modulus is measured and this is taken as the tensile modulus.

  In the laminate according to the present invention, an aliphatic polyester is included in the intermediate layer, and the intermediate layer is formed using a resin composition having a tensile elastic modulus of 300 MPa or less. The adhesion between the layer and the outermost layer is improved. In addition, the laminate according to the present invention has biodegradability and excellent workability. That is, according to the present invention, a laminate having biodegradability, excellent processability, and improved adhesion between the polyester resin layer and the base material layer, a bag formed by molding the laminate, A container can be provided.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents. In addition, in this specification, when the expression “to” is used, it is used in a sense including numerical values or physical values before and after that. Further, in this specification, “mol” and “mol” are synonymous, and when “ppm” is simply described, it means “mass ppm”.

  The laminate according to the present invention is a laminate having a base material layer containing a plant-derived component, an outermost layer containing an aliphatic polyester, and an intermediate layer present between the base material layer and the outermost layer. The intermediate layer contains an aliphatic polyester different from the aliphatic polyester contained in the outermost layer, and is characterized in that the tensile elastic modulus of the resin composition constituting the intermediate layer is 300 MPa or less.

(1) Outermost layer The outermost layer is a layer containing an aliphatic polyester. For example, it can be set as the layer which consists of a resin composition which contains aliphatic polyester and other resin other than aliphatic polyester arbitrarily. Here, the content ratio of other resins other than the aliphatic polyester is also arbitrary, but it is preferable that the aliphatic polyester is a main component. Here, the main component means that the content ratio of the aliphatic polyester is the maximum ratio. More preferably, the content ratio of the aliphatic polyester is a majority, and in particular, the resin composition forming the polyester layer is preferably composed only of the aliphatic polyester.

<Aliphatic polyester>
As the aliphatic polyester in the present invention, the molar ratio of the structural unit derived from the aliphatic monomer is the maximum ratio with respect to the entire structure, for example, in addition to the structural unit derived from the aliphatic monomer. It is also possible to use an aliphatic aromatic polyester having a structural unit partially derived from an aromatic monomer. More specifically, aliphatic polyesters, aliphatic aromatic polyesters, and mixtures thereof can be mentioned. Especially, since adhesiveness and moldability are favorable, it is preferable that an aliphatic polyester ratio is high, and it is preferable to consist only of aliphatic polyester especially. In this case, a mixture of plural kinds of aliphatic polyesters can be used as the aliphatic polyester.

  More specifically, preferred aliphatic polyesters in the present invention are those in which the main constituents are aliphatic diol and aliphatic dicarboxylic acid, or the main constituents of aliphatic oxycarboxylic acid such as polylactic acid and polycaprolactam. Is exemplified. Preferably, the main component is formed by polymerizing an aliphatic dicarboxylic acid and an aliphatic diol.

  That is, the aliphatic polyester contained in the outermost layer in the present invention has a diol unit (a structural unit formed from a diol or a derivative thereof) and a dicarboxylic acid unit (a structural unit formed from a dicarboxylic acid or a derivative thereof). Preferably it is a unit. Here, the diol unit and the dicarboxylic acid unit are arbitrary as long as the effects of the present invention are not significantly impaired. Moreover, as for a diol unit and a dicarboxylic acid unit, all may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Among them, the diol unit is preferably formed from a diol represented by the following formula (I) or a derivative thereof (hereinafter, the diol and the derivative are referred to as “diol component” as appropriate). Those formed from a dicarboxylic acid represented by the formula (II) or a derivative thereof (hereinafter, the dicarboxylic acid and the derivative thereof are appropriately referred to as “dicarboxylic acid component”) are preferable.

In the above formula (I), R ¹ represents a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain. In the formula (II), R ² represents a divalent aliphatic hydrocarbon group, and n represents 0 or 1.

In the formula (I), R ¹ is a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, may be a chain aliphatic hydrocarbon group, and may be an alicyclic carbon group. It may be a hydrogen group. Further, it may or may not have a branched chain.

Although the number of carbon atoms in R ¹ is not limited unless significantly impairing the effects of the present invention, when R ¹ is a chain aliphatic hydrocarbon group, the carbon number of R ¹ is usually 2 or more, and usually 10 or less, Preferably it is 6 or less. On the other hand, when R ¹ is an alicyclic hydrocarbon group, the carbon number of R ¹ is usually 3 or more, and usually 10 or less, preferably 8 or less.

  Examples of the diol derivative represented by the formula (I) include ester compounds with acetic acid. Specific examples of the diol represented by the formula (I) and derivatives thereof include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 Preferred examples include 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. Among these, 1,4-butanediol is particularly preferable from the viewpoint of the physical properties of the resulting aliphatic polyester.

In the formula (II), R ² is a divalent aliphatic hydrocarbon group, which may be a chain aliphatic hydrocarbon group or an alicyclic hydrocarbon group. Further, it may or may not have a branched chain.

The carbon number of R ² is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 2 or more and usually 48 or less. However, when R ² is a chain aliphatic hydrocarbon group, R ² is preferably a divalent chain aliphatic hydrocarbon group represented by — (CH ₂ ) _m —. Note that m is an integer of usually 1 or more and usually 10 or less, preferably 6 or less.

When R ² is an alicyclic hydrocarbon group, the carbon number of R ² is usually 3 or more, preferably 4 or more, and usually 10 or less, preferably 8 or less.

  Examples of the derivatives of the dicarboxylic acid represented by the formula (II) include lower alcohol esters and acid anhydrides of the dicarboxylic acid represented by the formula (II). Among these, an ester or acid anhydride with a lower alcohol having 1 to 4 carbon atoms is preferable. Specific examples of the dicarboxylic acid represented by the formula (II) and derivatives thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, heptanedioic acid, octanedioic acid, nonane Diacid, decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, maleic acid, fumaric acid, 1,6-cyclohexane Examples thereof include chain or alicyclic dicarboxylic acids having 2 to 48 carbon atoms, such as dicarboxylic acids and dimer acids. Moreover, these derivatives, for example, esters with lower alcohols such as dimethyl ester and diethyl ester, and acid anhydrides such as succinic anhydride and adipic anhydride are also included. Among these, from the viewpoint of physical properties of the resulting aliphatic polyester, dicarboxylic acids having 12 or less carbon atoms such as succinic acid, adipic acid, and sebacic acid, or acid anhydrides thereof, and esters thereof with these lower alcohols are particularly preferable. A dicarboxylic acid having 4 or less carbon atoms such as succinic acid and its acid anhydride, or a mixture thereof is preferred.

The dicarboxylic acid represented by the above formula (II) and derivatives thereof may be derived from petroleum or from plants. Especially since it can contribute to the reduction of emissions of CO ₂ is preferably one derived from plants. For example, as a raw material for dicarboxylic acid and derivatives thereof, succinic acid converted from a plant raw material or an acid anhydride thereof and an ester with a lower alcohol are preferable.

  The suitable aliphatic polyester used in the present invention may contain other structural units other than the diol units and dicarboxylic acid units as long as the effects of the present invention are not significantly impaired.

  Examples of the structural unit other than the diol unit and the dicarboxylic acid unit include an aliphatic oxycarboxylic acid unit. The aliphatic oxycarboxylic acid unit is formed of an aliphatic oxycarboxylic acid having one hydroxyl group and a carboxylic acid group in the molecule and a derivative thereof (hereinafter referred to as “aliphatic oxycarboxylic acid component” as appropriate). If it is a structural unit, there will be no limitation in particular, A cyclic | annular thing and a chain | strand-shaped thing can be used.

  Examples of the aliphatic oxycarboxylic acid component include α, ω-hydroxycarboxylic acid, α-hydroxycarboxylic acid, and the like, and esters, lactones, lactides, or oxycarboxylic acid polymers of these oxycarboxylic acids. Or a derivative thereof.

  Specific examples of lactones include lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and enanthlactone; 4-methylcaprolactone, 2,2,4-trimethylcaprolactone, 3,3 And methylated lactone such as 5-trimethylcaprolactone.

  Examples of the oxycarboxylic acid include aliphatic oxycarboxylic acids represented by the following formula (III).

In the above formula (III), R ³ represents a divalent aliphatic hydrocarbon group.

In the formula (III), R ³ is a divalent aliphatic hydrocarbon group, which may be a chain aliphatic hydrocarbon group or an alicyclic hydrocarbon group. Further, it may or may not have a branched chain.

  Among the aliphatic oxycarboxylic acids represented by the above formula (III), aliphatic oxycarboxylic acids represented by the following formula (IV) are preferable.

In the above formula (IV), R ⁴ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms. .

  Among these, aliphatic oxycarboxylic acids represented by the following formula (V) are particularly preferable in that the effect of improving the polymerization reactivity is recognized.

In the above formula (V), p represents 0 or an integer of 1 to 10, preferably 0 or an integer of 1 to 5, and more preferably an integer of 1 to 3.

  Specific examples of oxycarboxylic acids, particularly aliphatic oxycarboxylic acids, include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 2-hydroxy3,3-dimethylbutyric acid, 2-hydroxy- Examples also include 3-methylbutyric acid, 2-hydroxyisocaproic acid, 4-hydroxycyclohexanecarboxylic acid, and 4-hydroxymethylcyclohexanecarboxylic acid. Furthermore, derivatives of these lower alkyl esters and intramolecular esters are also included.

  When these compounds have optical isomers, they may be D-form, L-form, or racemate, and the form may be solid, liquid, or aqueous solution.

  Among these, lactic acid or glycolic acid is preferred, and particularly preferred is lactic acid, which is particularly prominent in increasing the polymerization rate during use and is easily available. In addition, as a form of lactic acid, an aqueous solution of 30 to 95% by mass is preferably used because it can be easily obtained.

  One of these aliphatic oxycarboxylic acid components may be used alone, or two or more thereof may be used in any combination and ratio.

  When the aliphatic polyester contains an aliphatic oxycarboxylic acid unit, the amount used is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.1 mass per 100 mass parts of the aliphatic dicarboxylic acid unit. Part or more, preferably 1.0 part by weight or more, more preferably 2.0 parts by weight or more, and usually 100 parts by weight or less, preferably 50 parts by weight or less, more preferably 20 parts by weight or less. If it falls below the lower limit of the above range, there is a possibility that the effect of addition for improving flexibility and polymerization reactivity may not appear, and if it exceeds the upper limit, the odor during the production of the laminate of the present invention becomes a problem, the crystallization temperature. There is a possibility that the roll-off property may be deteriorated by lowering the temperature.

  In addition, the aliphatic polyester includes a group consisting of a trifunctional or higher functional aliphatic polyhydric alcohol unit, an aliphatic polyvalent carboxylic acid unit, and an aliphatic polyvalent oxycarboxylic acid unit as a polyfunctional component unit having three or more functional groups. It is also preferable that at least one unit selected from Thereby, the melt tension of aliphatic polyester improves and the workability to a laminated body can be improved. In addition, a polyfunctional component unit may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  The trifunctional aliphatic oxycarboxylic acid unit forming the polyfunctional component unit includes (i) a type having two carboxyl groups and one hydroxyl group in the same molecule, and (ii) one carboxyl group and hydroxyl group. There are two types in the same molecule, but any type can be used. Specific examples of the compound giving a trifunctional aliphatic oxycarboxylic acid unit include (i) type malic acid and (ii) type glyceric acid.

  Similarly, the tetrafunctional aliphatic oxycarboxylic acid unit forming the polyfunctional component unit includes (i) a type in which three carboxyl groups and one hydroxyl group are shared in the same molecule, and (ii) a carboxyl group 2 There are two types: one that shares two hydroxyl groups and one hydroxyl group in the same molecule, and (iii) one that shares three hydroxyl groups and one carboxyl group in the same molecule. Either type can be used. is there. Specific examples of the compound giving a tetrafunctional aliphatic oxycarboxylic acid unit include (ii) type citric acid and (iii) type tartaric acid.

  When polyfunctional component units are used, the amount used is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 0.001 mol or more, preferably 0.01 mol, per 100 mol of the aliphatic dicarboxylic acid unit. Above, more preferably 0.1 mol or more, and usually 5 mol or less, preferably 2.5 mol or less, more preferably 1 mol or less. Below the lower limit of this range, when the laminate of the present invention is produced by extrusion lamination, the neck of the molten film at the time of production (until the width of the molten film from the T-die of the extruder is in contact with the substrate) The phenomenon of narrowing in space, indicated by the difference between the width of the molten film at the exit of the T-die and the width of the laminated film laminated on the substrate. There is a problem that the difference in thickness becomes large and a stable product cannot be obtained. On the other hand, if the upper limit is exceeded, the possibility of gelation during the reaction increases, the load on the motor of the extruder increases significantly, and the moldability may deteriorate.

  In addition, the aliphatic polyester used for the outermost layer may contain an unsaturated bond for the purpose of appropriately introducing a branched structure and improving processability. The unsaturated bond includes a triple bond in addition to a double bond. Are also included. Examples of the compound that gives such a structural unit having an unsaturated bond include unsaturated dicarboxylic acids and unsaturated diols. Representative examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, 3,6-endomethylene-1,2,3,6-tetrahydro-cis-phthalic acid (nadic acid), dimer acid Etc.

  On the other hand, the unsaturated bond group produced | generated in the manufacturing process of a polymer is also useful for the said objective. The mechanism of unsaturated bond formation is not clear, but in the production process of polymers, fumaric acid, maleic acid, etc. by the generation of terminal vinyl groups by thermal decomposition of the main chain and dehydration of malic acid added as a polyfunctional component The formation of unsaturated bonds due to the conversion reaction into can be considered.

The amount of unsaturated bonds contained in the aliphatic polyester used in the laminate of the present invention is usually 100 μmol / g or less, preferably 80 μmol / g or less, more preferably 60 μmol / g or less, still more preferably 30 μmol / g or less, Preferably it is 20 μmol / g or less. Moreover, it is usually 3 μmol / g or more, more preferably 5 μmol / g or more. If the amount of unsaturated bonds is less than or equal to the lower limit, it is difficult to branch efficiently when branching occurs, and the melt tension cannot be increased. On the other hand, if the upper limit value is exceeded, significant gelation may occur, making it impossible to produce a laminate. In addition, the amount of unsaturated bonds contained in the aliphatic polyester is calculated by NMR measurement such as ¹ H-NMR and ¹³ C-NMR.

  The urethane bond amount in the aliphatic polyester used in the laminate of the present invention is preferably 0.9% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.2% by mass. % Or less, more preferably 0.1% by mass or less, and in particular, it is preferable that the aliphatic polyester does not substantially contain a urethane bond. When the amount of the urethane bond is too large, the phenomenon of fuming or foaming due to thermal decomposition of the urethane bond tends to be difficult to mold.

<Method for producing aliphatic polyester>
As a method for producing such an aliphatic polyester, known methods relating to the production of polyester can be employed. Moreover, the polycondensation reaction in this case can set the appropriate conditions conventionally employ | adopted, and is not restrict | limited in particular. Usually, after the esterification reaction is advanced, the degree of polymerization can be further increased by performing a decompression operation.

  In the production of the aliphatic polyester, when the diol component forming the diol unit is reacted with the dicarboxylic acid component forming the dicarboxylic acid unit, the diol component and the produced aliphatic polyester have a desired composition. Set the amount of dicarboxylic acid component used. Usually, the diol component and the dicarboxylic acid component are in substantially equimolar amounts. However, in this case, the amount of the diol component used is usually 1 to 20 mol% in excess because there is distillation during the esterification reaction.

  When the aliphatic polyester suitable for the present invention contains components (optional components) other than essential components such as aliphatic oxycarboxylic acid units and polyfunctional component units, the aliphatic oxycarboxylic acid units and polyfunctional component units are also respectively A compound (monomer or oligomer) corresponding to each is subjected to the reaction so as to have a desired composition. At this time, there is no restriction | limiting in the time and method of introduce | transducing said arbitrary component into a reaction system, As long as the aliphatic polyester suitable for this invention can be manufactured, it is arbitrary.

  For example, the timing and method for introducing the aliphatic oxycarboxylic acid into the reaction system are not particularly limited as long as it is prior to the polycondensation reaction between the diol component and the dicarboxylic acid component. Examples include a method of mixing in a state dissolved in a solution, and (2) a method of mixing at the same time that the catalyst is introduced into the system when the raw materials are charged.

  The compound that forms the polyfunctional component unit may be introduced at the same time as other monomers and oligomers at the initial stage of polymerization, or after the transesterification reaction and before the start of decompression. From the viewpoint of simplifying the process, it is preferable to charge them simultaneously with the oligomer.

  Aliphatic polyesters are usually produced in the presence of a catalyst. As the catalyst, a catalyst that can be used for producing a known polyester can be arbitrarily selected as long as the effects of the present invention are not significantly impaired. For example, germanium, titanium, zirconium, hafnium, antimony, tin, magnesium, calcium, zinc, and other metal compounds are suitable. Of these, germanium compounds and titanium compounds are preferred.

  Examples of the germanium compound that can be used as the catalyst include organic germanium compounds such as tetraalkoxygermanium, and inorganic germanium compounds such as germanium oxide and germanium chloride. Among these, germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferable from the viewpoint of price and availability, and germanium oxide is particularly preferable.

  Examples of the titanium compound that can be used as the catalyst include organic titanium compounds such as tetraalkoxy titanium such as tetrapropyl titanate, tetrabutyl titanate, and tetraphenyl titanate. Of these, tetrapropyl titanate, tetrabutyl titanate, and the like are preferable from the viewpoint of price and availability.

  Moreover, as long as the object of the present invention is not impaired, the combined use of other catalysts such as metal compounds such as zirconium, hafnium, antimony, tin, magnesium, calcium and zinc is not hindered. In addition, a catalyst may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst used is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.0005% by mass or more, more preferably 0.001% by mass or more, and usually 3%, based on the amount of monomer used. It is not more than mass%, preferably not more than 1.5 mass%. If the lower limit of this range is not reached, the effect of the catalyst may not appear. If the upper limit is exceeded, the production cost may increase, or the resulting polymer may be markedly colored or the hydrolysis resistance may be reduced.

  The introduction timing of the catalyst is not particularly limited as long as it is before the polycondensation, but it may be introduced when the raw materials are charged or may be introduced at the start of pressure reduction. It is preferable to introduce a monomer or oligomer that forms an aliphatic oxycarboxylic acid unit such as lactic acid or glycolic acid at the time of raw material charging, or to dissolve and introduce a catalyst in an aqueous aliphatic oxycarboxylic acid solution. A method in which the catalyst is dissolved and introduced into the aliphatic oxycarboxylic acid aqueous solution is preferable in that the speed increases.

  The reaction conditions such as temperature, polymerization time, and pressure when producing the aliphatic polyester are arbitrary as long as the effects of the present invention are not significantly impaired. However, the reaction temperature of the esterification reaction and / or transesterification reaction between the dicarboxylic acid component and the diol component is usually 150 ° C. or higher, preferably 180 ° C. or higher, and the upper limit is usually 260 ° C. or lower, preferably 250 ° C. or lower. is there. The reaction atmosphere is usually an inert atmosphere such as nitrogen or argon. Furthermore, the reaction pressure is usually normal pressure to 10 kPa, but normal pressure is particularly preferable. The lower limit of the reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 6 hours or shorter, more preferably 4 hours or shorter. When the reaction temperature is too high, excessive generation of unsaturated bonds occurs, gelation caused by unsaturated bonds occurs, and control of polymerization may be difficult.

In addition, in the polycondensation reaction after the ester reaction and / or transesterification reaction between the dicarboxylic acid component and the diol component, the lower limit is usually 0.01 × 10 ³ Pa or more, preferably 0.03 × 10 ³ Pa or more. The upper limit is usually 1.4 × 10 ³ Pa or less, preferably 0.4 × 10 ³ Pa or less. The lower limit of the reaction temperature is usually 150 ° C. or higher, preferably 180 ° C. or higher, and the upper limit is usually 260 ° C. or lower, preferably 250 ° C. or lower. Furthermore, the lower limit of the reaction time is usually 2 hours or more, and the upper limit is usually 15 hours or less, preferably 10 hours or less. When the reaction temperature is too high, excessive generation of unsaturated bonds occurs, gelation caused by unsaturated bonds occurs, and control of polymerization may be difficult.

During the production of the aliphatic polyester, a chain extender such as a carbonate compound or a diisocyanate compound can also be used. The amount is usually 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less, with respect to all monomer units constituting the aliphatic polyester. However, when an aliphatic polyester resin is used in the laminate of the present invention, the presence of diisocyanate or carbonate bond may inhibit biodegradability, so the amount used constitutes the aliphatic polyester. The carbonate bond is less than 1 mol%, preferably 0.5 mol% or less, more preferably 0.1 mol% or less, and the urethane bond is 0.55 mol% or less, preferably based on all monomer units. Is 0.3 mol% or less, more preferably 0.12 mol% or less, still more preferably 0.05 mol% or less. When converted to 100 parts by mass of aliphatic polyester, it is 0.9 parts by mass or less, preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, and further preferably 0.1 parts by mass or less. The carbonate bond amount and the urethane bond amount are calculated by NMR measurement such as ¹ H-NMR and ¹³ C-NMR. If the amount exceeds the upper limit of the amount of urethane bonds, fumes and odors from the molten film from the die outlet may become a problem because of the decomposition of the urethane bonds during the production of the laminate. Cutting may occur and stable molding may not be possible.

  Specific examples of the carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, diamyl carbonate, and dicyclohexyl. Examples include carbonate. In addition, carbonate compounds composed of the same or different hydroxy compounds derived from hydroxy compounds such as phenols and alcohols can be used.

  Specific examples of the diisocyanate compound include 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, Hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, 2,4,6-triisopropylphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, etc. And known diisocyanates.

  Production of high molecular weight polyesters using these chain extenders (coupling agents) can be made using conventional techniques. After the completion of the polycondensation, the chain extender is added to the reaction system without solvent in a uniform molten state and reacted with the polyester obtained by polycondensation.

  More specifically, the end group obtained by catalyzing a diol and dicarboxylic acid (or its anhydride) has a hydroxyl group substantially, and the weight average molecular weight (Mw) is 20,000 or more, preferably Can obtain a polyester resin having a higher molecular weight by reacting the above chain extender with 40,000 or more polyester. A prepolymer having a weight average molecular weight of 20,000 or more is not affected by the remaining catalyst even under severe conditions such as a molten state by using a small amount of a coupling agent. Molecular weight polyesters can be produced. The method for measuring the weight average molecular weight (Mw) is a GPC measurement method in which the solvent is chloroform and the measurement temperature is 40 ° C. The weight average molecular weight is a conversion value by monodisperse polystyrene.

  Therefore, for example, when the above-mentioned diisocyanate is used as a chain extender to further increase the molecular weight of a polyester resin, a prepolymer having a weight average molecular weight of 20,000 or more, preferably 40,000 or more comprising a diol and a dicarboxylic acid. Is preferred. When the weight average molecular weight is 20,000 or less, the amount of diisocyanate used to increase the molecular weight increases, and the heat resistance may decrease. A polyester having a urethane bond having a linear structure linked via a urethane bond derived from diisocyanate is produced.

  The pressure during chain extension is usually 0.01 MPa or more and 1 MPa or less, preferably 0.05 MPa or more and 0.5 MPa or less, more preferably 0.07 MPa or more and 0.3 MPa or less. Most preferred.

  The lower limit of the reaction temperature during chain extension is usually 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 190 ° C. or higher, most preferably 200 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 240 ° C. or lower. More preferably, it is 230 degrees C or less. If the reaction temperature is too low, the viscosity is high and uniform reaction is difficult, and high stirring power tends to be required. If it is too high, gelation and decomposition of the polyester tend to occur simultaneously.

  As for the time for chain extension, the lower limit is usually 0.1 minutes or more, preferably 1 minute or more, more preferably 5 minutes or more, and the upper limit is usually 5 hours or less, preferably 1 hour or less, more preferably 30 minutes or less. Most preferably, it is 15 minutes or less. If the time is too short, the effect of addition tends to be lost, and if it is too long, gelation and decomposition of the polyester tend to occur simultaneously.

  Moreover, you may use an oxazoline compound, a silicate ester, etc. as another chain extender.

As the oxazoline compound, 2,2′-bis (2-oxazoline), 1,3-phenylene-bis (2-oxazoline), 2,2′-m-phenylenebis (2-oxazoline), 2,2′- Examples thereof include bisoxazolines such as p-phenylenebis (2-oxazoline). Examples also include oxazoline group-containing polymers such as oxazoline group-containing polystyrene, oxazoline group-containing acrylic polymers, and oxazoline group-containing styrene-acrylic polymers. Examples of industrially available oxazoline group-containing polymers include Epocross (registered trademark) K series, WS series, and RPS (manufactured by Nippon Shokubai Co., Ltd.).
Specific examples of the silicate ester include tetramethoxysilane, dimethoxydiphenylsilane, dimethoxydimethylsilane, and diphenyldihydroxysilane.

<Properties of aliphatic polyester contained in outermost layer>
The aliphatic polyester contained in the outermost layer has the following properties.
The melting point of the aliphatic polyester (measurement conditions are measured when the temperature is raised from 25 ° C. to 200 ° C. at 10 ° C./min by DSC) is preferably 80 ° C. or higher and 180 ° C. or lower. If the melting point is too low, the heat resistance when hot food or drink is put in applications such as paper cups and paper trays will be insufficient, and the laminated aliphatic polyester composition will peel off, melt, or the joint will peel off. There is a risk of On the other hand, if the melting point is too high, it is necessary to set the heat seal temperature high when the laminated body is secondarily processed into cups, sacks, trays, bags, etc., which may cause problems such as discoloration and shape defects. . More preferably, the melting point is 90 ° C. or higher and 150 ° C. or lower, and particularly preferably the melting point is 100 ° C. or higher and 140 ° C. or lower. By adopting a material having such a melting point, it is possible to obtain a laminate that has sufficient heat resistance and can be easily subjected to secondary processing.

  On the other hand, the crystallization temperature of the aliphatic polyester (measurement conditions measured when DSC is lowered from 200 ° C. to −50 ° C. at 10 ° C./min) is preferably 50 ° C. or more and 100 ° C. or less. If the lower limit is not reached, problems such as sticking to the cooling roll occur when the laminate is extruded, and the temperature of the cooling roll needs to be set to a low temperature in order to avoid this problem. Furthermore, it may take time to bond even during secondary processing of bags, automatic packaging machines, cup making machines, and the like. When the temperature is 98 ° C. or higher, solidification of the molten film starts in the air gap from the die exit to the grounding to the base material, and the adhesive strength with the base material may be weakened. In order to improve roll releasability, a nucleating agent described later may be added to the outermost resin to improve the crystallization temperature.

  The number average molecular weight (Mn) of the aliphatic polyester is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 10,000 or more, preferably 30,000 or more, and usually 200,000 or less. When the number average molecular weight is below the lower limit of the above range, the melt film characteristics at the time of producing the laminate of the present invention may be inferior, for example, the neck-in may be increased. On the other hand, when the upper limit is exceeded, the melt viscosity becomes high and the motor load of the extruder becomes high, which may make it difficult to produce a laminate. The method for measuring the number average molecular weight (Mn) is a GPC measurement method in which the solvent is chloroform and the measurement temperature is 40 ° C. The number average molecular weight is a conversion value by monodisperse polystyrene.

  The melt flow rate (MFR; 190 ° C., 2.16 kg load) of the aliphatic polyester suitably used in the present invention has a usual lower limit of 0.1 g / 10 min or more, preferably 1 g / 10 min or more, more preferably Is 3 g / 10 min or more, more preferably 4 g / 10 min or more. Moreover, it is 20 g / 10min or less, Preferably it is 15 g / 10min or less. If the melt flow rate is below the lower limit of the above range, the motor load during production of the laminate of the present invention may be remarkably increased, and the processing machine may be stopped. May deteriorate (increased neck-in, occurrence of surging).

  Furthermore, the melt flow rate (MFR; 190 ° C., 2.16 kg load) of the aliphatic polyester that has been melted from the die outlet has a usual lower limit of 6 g / 10 min or more, preferably 8 g / 10 min or more. The amount is preferably 10 g / 10 minutes or more, more preferably 12 g / 10 minutes or more. Moreover, it is 35 g / 10min or less, Preferably it is 30 g / 10min or less. If the melt flow rate is below the lower limit of the above range, the motor load during production of the laminate of the present invention may be remarkably increased, and the processing machine may be stopped. May deteriorate (increased neck-in, occurrence of surging).

  Examples of commercially available aliphatic polyesters and aliphatic aromatic polyesters preferably used in the outermost layer include GS Pla (registered trademark) AZ series, AD series, FZ series, FD series, Bionore (Showa Polymer Co., Ltd.) manufactured by Mitsubishi Chemical Corporation. Registered trademark), Laissia (registered trademark) manufactured by Mitsui Chemicals, Ingeo (registered trademark) manufactured by NatureWorks LLC, Ecoflex (registered trademark) manufactured by BASF, Matterby (registered trademark) manufactured by Novamont, Apex manufactured by DuPont, etc. .

<Other resins>
The outermost layer comprises the above-described aliphatic polyester, but may contain other resins other than the aliphatic polyester.

  Examples of other resins include ultra low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polypropylene, ethylene-propylene rubber, polyvinyl acetate, polybutene, Etc. Furthermore, polyamide resins such as 4-nylon, polyamino acid resins such as polyaspartic acid, polyether resins such as polyethylene glycol and polypropylene glycol, polysaccharides such as cellulose and pullulan, and biodegradable resins such as polyvinyl alcohol resin are included. . When these other resins are used, one or more kinds of resins can be used in any combination and ratio. Among them, it is preferable to use a biodegradable resin in combination in that the biodegradation rate of the laminate of the present invention is increased and the deformability after decomposition is improved.

  When a resin other than aliphatic polyester is used in combination, the ratio of the aliphatic polyester is usually 50 parts by mass or more, preferably 70 parts by mass or more with respect to 100 parts by mass of all resin components contained in the outermost layer. This is because if the amount of the aliphatic polyester is increased, the biodegradation rate of the laminate of the present invention is increased, and the deformability after decomposition is improved.

  The resin component of the outermost layer in the laminate of the present invention is preferably composed only of a resin having biodegradability from the viewpoint of degradability. Specifically, it consists only of an aliphatic polyester mainly composed of dicarboxylic acid and diol, or consists of a resin composition composed of an aliphatic polyester mainly composed of dicarboxylic acid and diol and other biodegradable resin. It is more preferable that it consists only of an aliphatic polyester mainly composed of a dicarboxylic acid and a diol. As the biodegradable resin other than the aliphatic polyester mainly composed of dicarboxylic acid and diol, polylactic acid and aliphatic / aromatic polyester are preferable.

  When a resin composition of an aliphatic polyester mainly composed of dicarboxylic acid and diol and other biodegradable resin is used for the polyester layer, the dicarboxylic acid and diol in the polyester layer are mainly used from the viewpoint of workability. The blending amount of the aliphatic polyester as a component is preferably 65 parts by mass or more, more preferably 70 parts by mass or more, and further 75 parts by mass, based on 100 parts by mass of the total amount of the biodegradable resin contained in the polyester layer. In particular, the amount is preferably 90 parts by mass or more. For example, a resin composition containing 70% by mass of an aliphatic polyester mainly composed of dicarboxylic acid and diol and 30% by mass of ECOFLEX (registered trademark) which is polylactic acid or an aliphatic aromatic polyester is completely biodegradable. The resin composition is particularly preferable for the outermost layer because it is a resin composition that has a very small neck-in at the time of molding and has excellent processability.

  In the laminate of the present invention, the water content of the resin composition constituting the outermost layer and the intermediate layer described later is preferably 200 ppm or more and 1500 ppm or less by mass ratio with respect to the resin composition. The lower limit of the water content is more preferably 300 ppm or more, and particularly preferably 400 ppm or more. Further, the upper limit of the water content is more preferably 1200 ppm or less, and particularly preferably 1000 ppm or less. By making the water content of the resin composition constituting the outermost layer and the intermediate layer in such a range, it is effective for suppressing surging during lamination, suppressing foaming phenomenon, and suppressing deterioration of rerollability. Can be improved. A publicly known method can be used as a method of setting the amount of water in the above range. For example, each resin may be dried with a hot air dryer or a hopper dryer so that the water content is in the above range before the laminate is manufactured.

  In the laminate of the present invention, the melt flow rate (MFR: 190 ° C., 2.16 kg load) of the resin composition constituting the outermost layer and the intermediate layer described later is 3 g / 10 min or more and 20 g / 10 min or less. Preferably there is. The lower limit of the MFR of the resin composition is more preferably 4 g / 10 minutes or more, particularly preferably 5 g / 10 minutes or more. Moreover, about the upper limit of MFR of a resin composition, More preferably, it is 17 g / 10min or less, Most preferably, it is 10 g / 10min or less. By setting the MFR of the resin composition constituting the outermost layer or the intermediate layer in such a range, it is effective for suppressing surging during lamination and for suppressing deterioration of roll-off property, and improving workability. Can do.

  Furthermore, in the laminate of the present invention, the tensile elastic modulus of the resin composition constituting the outermost layer is preferably 300 MPa or more, more preferably 350 MPa or more, and further preferably 400 MPa or more. Thereby, it can be set as the laminated body excellent in workability.

  Furthermore, in the laminate of the present invention, the resin composition constituting the outermost layer preferably does not contain the polyester contained in the intermediate layer described later. Thereby, it can be set as the laminated body which was further excellent in workability.

  The low molecular weight oligomer contained in the aliphatic polyester may cause so-called roll dirt that adheres to the chill roll during the molding process, and also exudes to the surface of the molded body with time after molding, which deteriorates heat sealability and appearance. Sometimes. In particular, when the molecular weight of the low molecular weight oligomer is 2000 g / mol or less, particularly 1000 g / mol or less, and the content is 1000 ppm or more, particularly 6000 ppm or more, the heat sealability and appearance deterioration tendency due to oligomer exudation become remarkable ( Hereinafter, “ppm” represents a ratio based on mass.) In particular, when the low molecular weight oligomer is composed of structural units derived from 1,4-butanediol units (BG) and succinic acid (SA), and when these structural units form a cyclic structure, The tendency of appearance deterioration becomes even more pronounced. The cyclic structure mentioned here refers to a structure composed of, for example, two 1,4-butanediol units (BG) and two succinic acid (SA) units. More specifically, the aliphatic polyester is a cyclic dimer oligomer (molecular weight: consisting of two 1,4-butanediol units (BG) and two succinic acid (SA) units as described above. 344 g / mol) is particularly noticeable when it contains 3000 ppm or more. The lower limit of the polyester in terms of mass ratio is not particularly limited, but is usually 500 ppm or more, preferably 1000 ppm or more, more preferably 2500 ppm or more, most preferably 3000 ppm or more, and the upper limit is usually 10,000 ppm or less, preferably 8000 ppm or less. More preferably, it is 6000 ppm or less, Especially preferably, it is 5500 ppm or less, Most preferably, it is 5000 ppm or less. If the content is too small, not only will the equipment and management process be complicated for reduction, it will tend to be economically disadvantageous, but the release of the laminated product from the chill roll (rolling off property) will tend to be poor. There is. On the other hand, when the amount is too large, roll stains during the molding process may become significant, the heat sealability may deteriorate, or the heat sealability may change depending on the elapsed time.

(2) Intermediate layer The intermediate layer is a layer that exists between the base material layer and the outermost layer, contains at least an aliphatic polyester, and is a layer different from the outermost layer. The intermediate layer may contain any composition as long as it contains at least aliphatic polyester and has a resin composition different from that of the outermost layer. The tensile elastic modulus of the resin composition constituting the intermediate layer is 300 MPa or less. It is.

Regarding the aliphatic polyester contained in the intermediate layer, the aliphatic polyester exemplified in the outermost layer can be selected and applied so as to satisfy the above-mentioned conditions. Specifically, it is preferable to use polybutylene succinate, polybutylene adipate, polybutylene succinate adipate, polybutylene adipate terephthalate, polybutylene succinate terephthalate, or a mixture thereof. Or you may mix the aromatic polyester which has a structural unit derived from a terephthalic acid. Among these, those obtained by polymerizing an aliphatic dicarboxylic acid and an aliphatic diol are more preferable.
The polyester contained in the intermediate layer can be produced in the same manner as the outermost aliphatic polyester.

  The resin composition constituting the intermediate layer has a tensile modulus of 300 MPa or less. Preferably it is 290 MPa or less, More preferably, it is 280 MPa or less. When the tensile elastic modulus of the resin composition constituting the intermediate layer is 300 MPa or less, the adhesive strength between the outermost layer and the base material layer can be improved. On the other hand, the tensile elastic modulus of the resin composition constituting the intermediate layer is preferably 50 MPa or more, more preferably 70 MPa or more. Thereby, it can be set as the laminated body excellent in workability.

  The resin composition constituting the intermediate layer may be obtained by mixing two or more types of resins having a tensile modulus of 300 MPa or less, a resin having a tensile modulus of 300 MPa or more, and a tensile modulus. May be obtained by mixing with a resin of 300 MPa or less.

<Properties of polyester contained in the intermediate layer>
The polyester contained in the intermediate layer has the following properties.
The melting point of the polyester is preferably 50 ° C. or higher and 160 ° C. or lower. If the melting point is too low, adhesiveness with the base material becomes insufficient when a hot food or drink is put in applications such as paper cups and paper trays, and the laminated aliphatic polyester composition peels off, melts, or is joined. May peel off. On the other hand, if the melting point is too high, the adhesion to the substrate may be low or may not be developed at all. More preferably, the melting point is 60 ° C. or more and 150 ° C. or less, and particularly preferably, the melting point is 50 ° C. or more and 140 ° C. or less. By adopting a material having such a melting point, it is possible to obtain a laminate that has sufficient heat resistance and can be easily subjected to secondary processing.

  On the other hand, the crystallization temperature of the polyester contained in the intermediate layer (measurement conditions measured when DSC is lowered from 200 ° C. to −50 ° C. at 10 ° C./min) is preferably 20 ° C. or more and 120 ° C. or less. If the value is below the lower limit, there may be a problem that the roll-off property deteriorates. In order to avoid this, it is necessary to set the temperature of the cooling roll to a low temperature. Moreover, when it exceeds an upper limit, adhesiveness with a base material may deteriorate.

  The number average molecular weight (Mn) of the polyester is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 8000 or more, preferably 30000 or more, and usually 200000 or less. When the number average molecular weight is below the lower limit of the above range, the melt film characteristics at the time of producing the laminate of the present invention may be inferior, for example, the neck-in may be increased. On the other hand, when the upper limit is exceeded, the melt viscosity becomes high and the motor load of the extruder becomes high, which may make it difficult to produce a laminate. The method for measuring the number average molecular weight (Mn) is a GPC measurement method in which the solvent is chloroform and the measurement temperature is 40 ° C. The number average molecular weight is a conversion value by monodisperse polystyrene.

  As for the melt flow rate (MFR; 190 ° C., 2.16 kg load) of polyester, the usual lower limit is 0.1 g / 10 min or more, preferably 1 g / 10 min or more, more preferably 3 g / 10 min or more, still more preferably. 5 g / 10 min or more. Moreover, it is 35 g / 10min or less, Preferably it is 20 g / 10min or less. When the melt flow rate is below the lower limit of the above range, the motor load during production of the laminate of the present invention is remarkably increased and the processing machine may stop. On the other hand, when the upper limit is exceeded, the stability of the molten film is deteriorated. (Increase of neck-in and occurrence of surging).

  Examples of commercially available aliphatic aromatic polyesters that are particularly preferably used in the intermediate layer include GS Pla (registered trademark) AD series, FD series, Ecoflex (registered trademark) manufactured by BASF, and Apex manufactured by DuPont (registered). Trademark) and the like.

  The intermediate layer may contain other resins other than polyester as long as the effects of the present invention are not impaired. As for other types and amounts of resins, various resins similar to those described as being applicable to the outermost layer can be applied in the same amounts.

(3) Base material layer The laminate according to the present invention has a base material layer containing a plant-derived component in order to be processed into various applications. The plant-derived component is preferably a fiber containing a plant-derived component or a film containing a plant-derived component. Specifically, paper, paperboard, cotton nonwoven fabric, rayon nonwoven fabric, polylactic acid film, cellulose nitrate film, cellulose acetate film, recycled A cellulose film, a polyglycolic acid film, etc. are mentioned. Among them, from the viewpoint that the obtained laminated film becomes biodegradable as a whole and a packaging material considering the environment can be formed, the base material layer is preferably biodegradable, and is a plant-derived fiber or film. It is preferable. Specific examples include paper, paperboard, pulp non-woven fabric, cotton non-woven fabric, rayon non-woven fabric, and regenerated cellulose film. Paper, paperboard, and regenerated cellulose film are particularly preferable. In addition, a composite film in which starch or chitosan or the like is blended with cellulose acetate, regenerated cellulose or the like that is not biodegradable per se can be used.

Paper substrates include kraft paper, wrapping paper such as pure white roll paper, imitation paper, high-quality paper, medium-quality paper, glassine paper, parchment, art paper, coated paper and other printing / information paper, cup base paper, cardboard base paper, etc. Examples of the processing base paper, Kent paper, Manila cardboard, and coated cardboard. Nonwoven fabrics such as cotton nonwoven fabric and rayon nonwoven fabric are also included in the paper substrate. The basis weight of these paper bases (Japanese Industrial Standard JIS P8124) varies depending on the paper quality, but is generally in the range of 10 to 1000 g / m ² , particularly 30 to 700 g / m ² .

  When the base material layer is a paper base material, since the density of the base material layer is low, the interlaminar strength of the base material is greater than the delamination strength between the outermost layer and the intermediate layer or the delamination strength between the intermediate layer and the base material layer. May be low. Further, when the base material layer is a multilayer paper such as paperboard, the base material layer may have low delamination strength. In these cases, internal destruction occurs in the base material layer. In order to prevent this, it is preferable to improve the dry paper strength of the base material layer.

  As a method for improving the dry paper strength in a paper substrate, there is a method of internally adding a dry paper strength enhancer such as polyacrylamide, cationized starch, and amphoteric starch. The addition amount of the dry paper strength enhancer is usually 0.01 to 0.3% by mass with respect to the absolutely dry pulp. Here, “internal addition” refers to a method of adding an additive to the pulp slurry before papermaking. Further, there is a method of increasing the beating degree of pulp before paper making so that the freeness (CSF) is about 450 to 600 ml. Here, “CSF” refers to Canadian standard freeness normally used in the paper industry. There is also a method of increasing the blending amount of softwood bleached kraft pulp (NBKP) blended into the paper base material.

  Further, since the paper base material is hydrophilic, when the laminate of the present invention comes into contact with water, water penetrates from the end face of the laminate and the base material layer swells to become swollen or wrinkled. The material layer may break and peel off inside the material layer. For applications requiring water resistance, it is preferable to improve the sizing degree and wet paper strength of the paper substrate.

Examples of a method for improving the sizing degree of a paper base material include a method of internally adding an internal sizing agent such as an alkyl ketene dimer. The addition amount of the internally added sizing agent is usually 0.1 to 0.5% by mass with respect to the absolutely dry pulp. In this case, it is also preferable to use a sulfuric acid band in combination.
Examples of the method for improving the wet paper strength include a method of internally adding an internal wet paper strength enhancer such as a polyamide polyamine, a polyamide polyamine epichlorohydrin modified product, or a polyethyleneimine epichlorohydrin modified product. . The addition amount of the internally added wet paper strength enhancer is usually 0.1 to 0.5% by mass with respect to the absolutely dry pulp.

In the paper and paperboard, a filler usually called an additive is blended. In the base material used in the present invention, it is preferable to blend heavy calcium carbonate, titanium oxide, barium sulfate or the like alone or in combination in order to improve the whiteness and opacity of the laminate. Moreover, the compounding quantity of these additives is 1-30 mass% normally with respect to a paper base material.
Other inorganic fillers such as talc, kaolin, calcined kaolin, clay, diatomaceous earth, magnesium carbonate, aluminum hydroxide, magnesium sulfate, silica, aluminosilicate, bentonite, polystyrene particles, urea formalin resin particles, etc. These organic fillers can be appropriately selected and used.
In particular, when increasing the opacity of the laminate, graphite or carbon black may be internally added to the base material layer, or black printing may be performed on the surface of the base material layer.

  A nonwoven fabric can also be used as a base material layer. Specifically, Asahi Kasei Benriese (registered trademark), which is a hydroentangled nonwoven fabric using cotton linter as a raw material, Ono Kinocloth (Kinocloth) (registered trademark), which is an airlaid nonwoven fabric using pulp as a raw material, and rayon as a raw material Omikenshi Pyros (registered trademark), a spunlace nonwoven fabric, Kuraray Kuraflex (registered trademark), a hydroentangled nonwoven fabric made from rayon, and Unitika, a spunbond nonwoven fabric made from polylactic acid Examples include Terramac (registered trademark) manufactured by Shinwa, Hibon (registered trademark) manufactured by Shinwa.

  A film containing a plant-derived component can also be used as the base material layer. Specifically, Cellulose PC-A (registered trademark) manufactured by Daicel Chemical Industries, which is a cellulose acetate film, Lunarle ZT (registered trademark) manufactured by Nippon Shokubai Co., Ltd., NatureFlex NP, NPU, NK, NKR NE manufactured by Innovia Films. Cellulosic films such as series; Novamont's Matterby (registered trademark), which is a blend film of starch and synthetic biodegradable polymer, Delon CC (trade name), manufactured by Aicero Chemical, which is a blend film of chitosan, cellulose and starch, Examples thereof include Kuredux (registered trademark) manufactured by Kuraray Co., Ltd., which is a polyglycolic acid film.

You may vapor-deposit on the film containing a plant-derived component. By performing vapor deposition, an effect of improving the barrier property of the substrate can be obtained.
For example, in the case of providing a metal vapor deposition film, a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method is preferable because it can provide a film with high adhesion to the film and excellent uniformity. Examples of the metal used in the metal vapor deposition film include gold, silver, copper, aluminum or alloys containing these other metal elements, but have a low melting temperature, low cost, and little damage to the substrate. Therefore, aluminum is particularly preferable.

  In the case of providing an inorganic oxide film, a vacuum deposition method, a sputtering method, an ion plating method, a plasma vapor deposition method (CVD), or the like is preferable. Examples of the material used for the inorganic oxide film include aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof. Specific examples of the metal-deposited cellulose film include Cellulose-based NatureFlex NKM, NM, and NKME series manufactured by Innovia Films.

Among the above, the vapor deposition method is preferably a vacuum vapor deposition method from the viewpoint of low cost and little damage to the substrate, and the vapor deposition conditions are appropriately set according to the melting temperature or evaporation temperature of the material to be used. The vacuum degree is preferably 10 ⁻³ to 10 ⁻⁴ Pa and the temperature is 1000 to 1100 ° C.
Although the preferable film thickness of a vapor deposition layer changes according to the use of a barrier film, the film | membrane composition of a vapor deposition film, etc., the range of 1-200 nm is preferable normally. If this deposited layer is too thin, gas barrier properties are not exhibited, and if it is too thick, cracks are likely to occur.
In addition, a metal thin film is formed after surface treatment such as corona discharge treatment, plasma treatment, ozone treatment, or anchor coating with urethane resin, polyester resin, starch resin, polyvinyl alcohol or the like is performed on the film. It is also preferable.

(4) Other layers In the laminate according to the present invention, other resin layers may be provided in addition to the outermost layer and the intermediate layer. In particular, another resin layer may be provided on the surface of the base material layer opposite to the surface on which the intermediate layer is provided. Also in this case, as the resin, the above-described resin and / or other resin can be used in any combination and ratio. Further, from the viewpoint of the decomposition rate of the laminate and the deformability after decomposition, the ratio of the biodegradable resin (particularly aliphatic polyester resin or polylactic acid) to the total resin components contained in the entire laminate is 50 mass. It is preferable to provide another resin layer so as to be at least%, preferably at least 70% by mass. The other resin layer may function as a printing layer. That is, if a printing layer on which printing such as advertisements and pictures is applied on the base material layer and heat-sealing the printing layer and the resin laminated surface at the time of secondary processing, the heat sealing strength can be increased. It is possible to improve the yield of the cup molded product.

<Print layer>
The ink used for the printing layer is mainly composed of an ink vehicle, and if necessary, UV curable monomers, oligomers, and photoinitiators, plasticizers, stabilizers, antioxidants, light stabilizers, UV rays. Add additives such as absorbents, curing agents, cross-linking agents, lubricants, antistatic agents, fillers, etc., and add colorants such as dyes and pigments, and use solvents, diluents, etc. The ink composition is kneaded. In order to improve the heat seal strength of the laminate, a resin such as cellulose acetate resin and polyester polyol and a crosslinking agent such as hexamethylene diisocyanate may be added to the ink composition as necessary.
Using the ink composition, for example, gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. can be used to print characters, figures, symbols, patterns, etc. it can. The cured film thickness of the printing layer is usually 0.1 to 2.0 μm.

  Since the outermost layer of the laminate contains an aliphatic polyester, the outermost layer usually has the above printability. However, as a method of improving the adhesion between the cured printed layer and the outermost layer, the ink vehicle is made of urethane acrylic resin, acrylic type A method of adding a resin, etc .; a method of surface-treating the outermost layer by corona treatment, low-temperature plasma treatment, etc. immediately before printing; a surface of the outermost layer with polyurethane comprising an isocyanate compound such as acrylic polyol, polyvinyl acetal, polyester polyol, polycarbonate polyol, etc. Anchor coating method; Method of using main component of outermost layer resin as aliphatic polyester composed of aliphatic diol and aliphatic dicarboxylic acid; Method of increasing cooling rate immediately after lamination to decrease crystallinity of outermost layer, etc. There is.

(5) Manufacturing method of laminated body The laminated body according to the present invention includes at least a base material layer, an outermost layer, an intermediate layer provided between the base material layer and the outermost layer, and optionally other. And a layer. Hereinafter, a method for producing such a laminate will be described.

In the method for obtaining the laminate of the present invention, an aliphatic aromatic polyester different from the aliphatic polyester contained in the outermost layer is included in the intermediate layer, and a tensile elastic modulus is 300 MPa or less. As long as it constitutes the intermediate layer, a conventional laminating method can be applied without particular limitation.
For example, (1) a wet lamination method in which a water-soluble or water-dispersed resin is applied to a certain layer, the other layers are laminated together in a wet state, and then dried and wound, (2) the resin is heated Then, apply it to the melted layer, paste another layer, and then cool it down to cool and fix the molten resin. (3) Melt the resin and use the film from a slit die such as a T die. Extrusion coating method to apply the extrudate to the base material, (4) melt the resin, apply the extrude on the film from the slit die such as T-die to the layer, separate from the unwinder called sand feeder Extrusion lamination method, which is a method of supplying and laminating at the same time, (5) Extruding several kinds of resin with T die or round die, 1 step Processing techniques such as co-extrusion lamination method that can produce multilayer film, (6) dry lamination method in which resin dissolved in organic solvent is applied to the surface of one layer, dried and other layers are laminated it can.

  As a method for producing the laminate of the present invention, various polyesters described above and other resins added as needed, lubricants, antioxidants, modifiers, nucleating agents, and the like, which will be described later, were blended. A method (extrusion coating method) in which the resin composition is coextruded and laminated on a substrate using an extruder having a hanger coat type T die is particularly preferable. When the extrusion coating method is used, a melt extrusion coating / laminating apparatus usually used for melt extrusion coating / laminating of thermoplastic synthetic resins such as polyethylene can be used.

  For the preparation of the resin composition, all conventionally known mixing / kneading techniques can be applied. As the mixer, a horizontal cylindrical type, V-shaped, double-cone type mixer, a blender such as a ribbon blender or a super mixer, various continuous mixers, or the like can be used. Moreover, as a kneading machine, a batch type kneading machine such as a roll or an internal mixer, a one-stage type, a two-stage type continuous kneading machine, a twin screw extruder, a single screw extruder or the like can be used. Examples of the kneading method include a method in which various additives, fillers, and resins are added and blended when heated and melted. In addition, blending oil or the like can be used for the purpose of uniformly dispersing the various additives.

  About the water content of the raw material resin to be charged, the lower limit is usually 0.1 ppm or more, preferably 0.5 ppm or more, more preferably 1 ppm or more, most preferably 10 ppm or more, in terms of mass ratio with respect to the polyester, The upper limit is usually 3000 ppm or less, preferably 2000 ppm or less, more preferably 1000 ppm or less, particularly preferably 800 ppm or less, and most preferably 500 ppm or less. If the water content is too low, not only will the equipment and management process become complicated and economically disadvantageous, but it will take a long time to dry, and this will cause deterioration of the resin coloring and the formation of bumps. There is a tendency to be caused. On the other hand, if the amount is too large, the molecular weight decreases due to hydrolysis during the molding process, an appropriate melt viscosity cannot be obtained, surging or the like occurs, and the molten film may not be stable.

  In the case of a paper base material, the water content of the base material layer is usually 3 to 10% by mass, preferably 8% by mass or less, and more preferably 6% by mass or less. When the moisture content of the paper base material is larger than this, when laminating the laminate, the resin layer is laminated on the surface of the paper base material by heating and melting the adhesive layer and the outermost layer (hereinafter sometimes referred to as “resin layer”). The base layer is heated by the heat of the layer, and the evaporated water is confined in the resin layer to form bubbles, which may cause “blister”. When the moisture content of the base material layer is high, it is preferable to reduce the moisture content with general drying equipment such as an arch dryer. On the other hand, the moisture content of the paper substrate is preferably 4% by mass or more. If the moisture content of the paper base material is less than this, moisture may be absorbed from the end face of the laminate after lamination to cause the base material layer to swell and curl due to the difference in elastic modulus of the resin layers on both surfaces.

  In the case of a plant-derived resin film, the moisture content of the base material layer is not particularly limited, but the lower limit in terms of mass ratio is usually 0.1 ppm or more, preferably 0.5 ppm or more, more preferably 1 ppm or more, and most preferably Is 10 ppm or more, and the upper limit is usually 3000 ppm or less, preferably 2000 ppm or less, more preferably 1000 ppm or less, particularly preferably 800 ppm or less, and most preferably 500 ppm or less. When the water content is too small, not only does the equipment and the management process become complicated and it tends to be economically disadvantageous, but it also tends to cause coloring of the base material layer because it takes a long time to dry. On the other hand, if the water content is too high, the resin layer may be colored by hydrolysis during the molding process.

  As a method for measuring the water content (moisture content) contained in the polyester resin, 0.5 g of a sample is heated and melted at 200 ° C. using a moisture vaporizer (VA-100 model manufactured by Mitsubishi Chemical Corporation). After vaporizing water, the total amount of water vaporized is quantified by a coulometric titration method based on the principle of the Karl Fischer reaction using a trace moisture analyzer (CA-100, manufactured by Mitsubishi Chemical Corporation). A method for determining the amount of water is mentioned. In the case of measuring the water content contained in the base material layer, for example, a method of drying in an oven at 105 ° C. for 2 hours, measuring the weight loss before and after drying, and calculating the water content can be mentioned.

  The processing temperature of the intermediate layer and the outermost layer (hereinafter sometimes referred to as “resin layer”) varies depending on the type of resin. For example, aliphatic polyester resins and aliphatic aromatic polyesters mainly composed of dicarboxylic acid and diol When resin is used, the inlet temperature of the cylinder in the melt extruder is 100 ° C. to 230 ° C., the set temperature of the extruder die is 230 ° C. to 300 ° C., and the resin temperature immediately below the die is measured at each position from the end to the center. However, it is preferable to control the temperature of each place to an average of ± 10 ° C. For that purpose, it is preferable to control the heat block temperature control set on the die. The central portion was defined as the center position with respect to the width of the laminate product, and the end portion was defined as the position 2 cm away from the width end of the substrate.

  Moreover, in order to suppress the thickness nonuniformity of the resin layer in the width direction, it is preferable to adjust the die temperature. For example, when the die temperature is set so that the resin temperature immediately below the die end is preferably lower than the resin temperature directly below the center of the die by 5 ° C. or more, more preferably 10 ° C. or more. Good. Also, the die temperature may be set so that the temperature is preferably 20 ° C. or lower and more preferably 15 ° C. or lower.

  This thickness unevenness can be suppressed by controlling the temperature of each part of the die. A specific method is described below, but adjustment of the lip opening may be used in combination in order to control the thickness.

  The die has a plurality of heat blocks in order to control the temperature control depending on the size. The temperature adjustment of the heat block is carried out by measuring the temperature of the molten resin flowing out from each heat block portion and based on the deviation from the set temperature and the thickness measurement of the polyester layer.

  When the end portion is thicker than the center portion, the resin temperature at the center portion is kept constant and the resin temperature at the end portion is lowered, so that the temperature setting of the corresponding heat block is lowered and waiting for stabilization. When there are a plurality of heat blocks between the central portion and the end portion, it is preferable to set the temperature setting in an inclined manner.

  Note that if the resin temperature of the aliphatic polyester resin or the composition of it and other resins is too large in the center and at the end, the viscosity of the resin will be different in each part, and it will be pressed as a molten resin layer with a uniform thickness from the die. Since the adhesive strength cannot be obtained and unevenness may occur, it is preferable to precisely perform the temperature adjustment from the viewpoint of producing a high-quality laminate.

  The resin melt-kneaded in the extruder is extrusion-coated on a substrate from a die so as to have a predetermined thickness. As the die, a hanger coat type, a die for coextrusion, or the like can be used. At that time, when the thickness is thick, the touch roll and the air knife are used properly, and when the thickness is thin, the electrostatic pinning is properly used to obtain a uniform thickness. The distance between the die lips is usually 0.2 to 3.0 mm, but is not limited to this depending on the film formation situation.

  When performing melt extrusion, a phenomenon called neck-in in which the film extruded from the T die is narrower than the width of the die exit, or a part called an edge (edge bead) where both sides of the film are thicker than the central part may occur. In order to improve these, it is preferable to dispose a rod rod and an inner deckle inside the die. Thereby, the flow rate of the molten resin can be changed, and the edge beads can be reduced. Further, the thickness distribution of the molded product may be improved by adjusting the lip interval.

  As the rod rod, those having a cross-sectional shape of a round shape, a triangular shape, and a Y shape are used, and those having a shape called a rod rod with a flag are particularly preferably used. By mounting such a rod rod with flag, by extruding from the die extrusion port in a state where the width of the resin film supplied to the die extrusion port is reduced, and as a result, the molten resin immediately after extrusion The film can be prevented from meandering (surging) at the end and can be stably laminated. By installing such a guide plate at the die extrusion port, the side edge of the molten resin film layer is positioned, and the thickness of both side edges of the molten resin film is equal to the center of the film. Can be controlled.

The resin layer that has come out as a molten film from the die outlet is preferably subjected to ozone treatment, and is then pressure-bonded to the substrate between the nip roll and the cooling roll through a predetermined air gap in the laminate processing system. .
The ozone treatment is preferably performed on the intermediate layer side of the resin layer. By treating the surface of the intermediate layer with ozone, the surface of the intermediate layer is oxidized to generate polar groups such as carboxyl groups. When the polar group is present on the surface of the intermediate layer, the affinity with the substrate layer having the same polarity is improved, and the adhesive strength at the interface between the intermediate layer and the substrate layer is improved.
Moreover, when a base material layer is a film, it is also preferable to corona-treat on the surface. By corona-treating the film surface, the film surface is oxidized to generate polar groups such as carboxyl groups. When the corona treatment is performed under nitrogen gas, amino groups and the like are also generated. Combining the corona treatment of the film and the ozone treatment of the intermediate layer has the effect of improving the affinity between the resin layer and the base material layer and improving the adhesive strength at the interface between the intermediate layer and the base material layer.

Low-density polyethylene (LDPE), which is a general-purpose resin, has a wide air gap distance of 120 mm, for example, and promotes the oxidation of LDPE by oxygen in the air in the air gap and improves the surface wettability. It is a known technique to improve the adhesion. However, when manufacturing a laminated body using aliphatic polyester, there is little effect of the adhesive force improvement by oxidation of the molten film surface.
As a result of intensive studies by the present inventors, it has been found that when aliphatic polyester is used as the biodegradable resin, the adhesive force is remarkably improved by narrowing the gap of the air gap. The upper limit of the air gap is 120 mm or less, preferably 100 mm or less, more preferably 90 mm or less, and the lower limit is 50 mm or more, more preferably 60 mm or more. When the upper limit is exceeded, the resin temperature is excessively lowered, and therefore the adhesiveness with the substrate is lowered, which is not preferable. Further, the oxidation is accelerated and the generation of odors such as oxidized odor becomes a problem. On the other hand, when the value is below the lower limit value, it is difficult to install a molten film processing apparatus such as an ozone generator, and the cooling roll and the die are located close to each other, so that the temperature management of the cooling roll may be difficult.

  The nip roll that applies pressure to bond the molten film extruded from the die outlet and the base material is a roll made of rubber, ceramic, or the like. From the point of preventing adhesion of the molten resin, a nip roll made of silicon rubber is used. preferable. Further, the hardness of the nip roll is arbitrarily selected depending on the type of the substrate to be used, and the nip pressure can be arbitrarily adjusted in order to obtain a desired adhesive strength of the laminate. The lower limit value of the nip pressure in the present invention is 0.2 MPa or more, preferably 0.4 MPa or more. The upper limit is 0.5 MPa or less, preferably 0.45 MPa or less. Below the lower limit, the adhesive strength is weak and not practical as a laminate. On the other hand, when the upper limit is exceeded, the nip roll is deformed and the contact area is widened, the pressure per unit area is lowered, and the adhesive force may not be sufficient. Further, the contact position between the molten resin, the base material, and the cooling roll is extremely important because it affects the adhesive force. As for the contact position, when the molten resin comes into contact with the cooling roll before coming into contact with the substrate, the resin is cooled and solidified, and an adhesive force cannot be obtained. Preferably, the molten resin is in contact with the substrate and the cooling roll at the same time.

  The type of chill roll can be arbitrarily selected to obtain a surface overview of the desired outermost layer. For example, there are mirror finishes, semi-matt rolls, mat rolls, and the like. Preferably, a semi-matt roll, further a mat roll or the like is preferably used because the degree of sticking of the laminate is small. The temperature of the cooling roll is preferably 10 ° C. or higher and 35 ° C. or lower. When the upper limit is set, the laminate is likely to stick to the cooling roll, and it becomes difficult to increase the molding speed. If the lower limit is not reached, water droplets may adhere to the cooling roll, which may make operation difficult.

  If the processing speed for producing the laminate is too high, the extrusion amount is large when the resin of the resin layer is extruded from the die, causing a vibration phenomenon called “draw resonance”, and the end portion of the laminate resin is formed on the base layer. It may meander and cause molding defects. By strictly controlling the operating conditions selected as described above, it is possible to manufacture on a normal commercial scale with processing speeds of 20 m / min or more, and further 180 m / min. As a result, for example, a food packaging material that is excellent in heat sealability and can be filled at high speed can be formed.

(6) Additive The laminate of the present invention may contain various additives such as an antioxidant, a lubricant, a terminal blocking agent, and a nucleating agent. In particular, the resin layer (particularly the outermost layer) preferably contains an antioxidant and / or a lubricant.

<Antioxidant>
Any antioxidant can be used as the antioxidant added to the laminate of the present invention as long as the effects of the present invention are not significantly impaired. Specific examples include hindered phenol antioxidants, phosphorus antioxidants, lactone antioxidants; sulfur antioxidants such as dilauryl thiodipropionate and distearyl thiodipropionate. Of these, hindered phenolic antioxidants and phosphorus antioxidants are preferred. These antioxidants may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios. Among these, it is preferable to use a hindered phenol-based antioxidant and a phosphorus-based antioxidant in combination.

Examples of the hindered phenol antioxidant include di-t-butylhydroxytoluene (also known as BHT), 2,2′-methylenebis (4-methyl-6-t-butylphenol), pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate], 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2 , 4,6-triyl) tri-p-cresol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris [(4-t-butyl- 3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (3,5-di-) t-butyl-4-hydro Xylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, calcium diethylbis [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] Methyl] phosphonate, bis (2,2′-dihydroxy-3,3′-di-t-butyl-5,5′-dimethylphenyl) ethane, N, N′-hexane-1,6-diylbis [3- ( 3,5-di-t-butyl-4-hydroxyphenylpropionamide and the like can be mentioned.
Examples of phosphorus antioxidants include tridecyl phosphite, diphenyl decyl phosphite, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, Examples thereof include bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite.
Examples of the lactone antioxidant include a reaction product of 3-hydroxy-5,7-di-t-butyl-furan-2-one and xylene.
Examples of the sulfur-based antioxidant include dilauryl thiodipropionate and distearyl thiodipropionate.

  The amount of the antioxidant used is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 100 ppm or more, preferably 200 ppm or more, and usually 50,000 ppm or less, preferably based on the polyester in the outermost layer and the intermediate layer. It is 10,000 ppm or less, more preferably 5000 ppm or less, still more preferably 1000 ppm or less, and most preferably 800 ppm or less. If the lower limit of this range is not reached, the effect of the antioxidant may be reduced. If the upper limit is exceeded, the manufacturing cost may become too high, or the antioxidant may bleed out, or roll contamination may occur during laminate production. is there.

  Although there is no limitation on the specific method of containing the antioxidant, usually, the resin and the antioxidant are mixed in any step during the production of the laminate, and the antioxidant is added to the resin layer of the laminate. It is made to contain. For example, it is preferable to use a masterbatch containing an antioxidant at a high concentration. This is because the antioxidant can be mixed and diluted so as to have a target concentration, which is simple.

  Although there is no restriction | limiting in content of the antioxidant in a masterbatch, Usually, it is 1 mass% or more, and is 45 mass% or less normally, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less. If the content of the antioxidant is too low, the manufacturing cost will be high, and if the content is too high, the dispersibility of the resin and the antioxidant will be poor, so that the effect of the antioxidant will be maximized. I can't.

  The resin employed as the masterbatch is not particularly limited, but a masterbatch produced using a resin similar to the resin used is usually preferable.

<Lubricant>
Any lubricant can be used as long as the effects of the present invention are not significantly impaired. The lubricant is added for the purpose of discharging stability at the time of producing the laminate, reducing the motor load, increasing the crystallization temperature, and improving the molding stability. In addition to imparting moldability, when used in a layer in contact with a roll mold, it is possible to prevent the layer from sticking or sticking, improving the roll-off property and preventing outstanding roll dirt. To help.

  Specific examples thereof include paraffins such as polyethylene wax, paraffin oil and solid paraffin, higher fatty acids such as stearic acid and palmitic acid, higher alcohols such as palmityl alcohol and stearyl alcohol, fatty acid metal salts, fatty acid esters and fatty acid amides. And waxes such as carnauba wax and montan wax, among which fatty acid amides and fatty acid metal salts are particularly preferred.

  Specific examples of the fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, N-stearyl stearic acid amide, methylol stearic acid amide, methylol behenic acid amide, and dimethylol oil. Amide, dimethyl lauric acid amide, dimethyl stearic acid amide, ethylene bis oleic acid amide, ethylene bis stearic acid amide, ethylene bis lauric acid amide, hexamethylene bis oleic acid amide, butylene bis stearic acid amide, m-xylylene bis stearic acid Amide, m-Xylylenebis-12-hydroxystearic acid amide, N, N'-dioleyl adipic acid amide, N, N'-distearyl adipic acid amide, N, N'-distearyl isophthalic acid amide N, N'-distearyl terephthalic acid amide, N-butyl-N'-stearyl urea, N-propyl-N'-stearyl urea, N-allyl-N'-stearyl urea, N-stearyl-N'-stearyl urea Etc.

  As the fatty acid metal salt, those having 12 to 30 carbon atoms are particularly preferable. Moreover, as a metal seed | species, generally the carboxylate of the 1st-14th group metal element except a hydrogen and carbon in a periodic table is preferable. Particularly preferred are alkali metals, alkaline earth metals, and transition metals of the third to fourth periods of the periodic table. Most preferably, alkaline earth metals of the third to fourth periods are suitably selected. Among the above, the alkali metal carboxylate may deteriorate the resin, depending on the amount used, and may deteriorate the hydrolysis resistance and mechanical properties during the production or after the molding. If the number of carbon atoms of the fatty acid is below the above lower limit, smoke, roll dirt, and bleed-out may be a problem during molding, and if it is more than the upper limit, odor may be a problem due to thermal decomposition during molding. .

  Examples of the above fatty acid metal salts include sodium laurate, potassium laurate, magnesium laurate, calcium laurate, zinc laurate, silver laurate, lithium laurate, lithium myristate, sodium myristate, potassium myristate, myristic Magnesium oxide, calcium myristate, zinc myristate, silver myristate, aluminum myristate, lithium palmitate, potassium palmitate, magnesium palmitate, calcium palmitate, zinc palmitate, copper palmitate, lead palmitate, thallium palmitate , Cobalt palmitate, sodium oleate, potassium oleate, magnesium oleate, calcium oleate, zinc oleate, lead oleate, oleate , Copper oleate, nickel oleate, sodium stearate, lithium stearate, magnesium stearate, calcium stearate, barium stearate, aluminum stearate, thallium stearate, lead stearate, nickel stearate, beryllium stearate, isostearic Sodium acid, potassium isostearate, magnesium isostearate, calcium isostearate, barium isostearate, aluminum isostearate, zinc isostearate, nickel isostearate, sodium behenate, potassium behenate, magnesium behenate, calcium behenate, barium behenate , Aluminum behenate, zinc behenate, nickel behenate, sodium montanate Potassium, potassium montanate, magnesium montanate, calcium montanate, barium montanate, aluminum montanate, zinc montanate, nickel montanate, lithium montanate, sodium octylate, lithium octylate, magnesium octylate, calcium octylate, Barium octylate, aluminum octylate, thallium octylate, lead octylate, nickel octylate, beryllium octylate, sodium 12-hydroxystearate, lithium 12-hydroxystearate, magnesium 12-hydroxystearate, calcium 12-hydroxystearate , 12-hydroxybarium stearate, 12-hydroxyaluminum stearate, 12-hydroxythallium stearate, 12- Lead hydroxystearate, nickel 12-hydroxystearate, beryllium 12-hydroxystearate, sodium sebacate, lithium sebacate, magnesium sebacate, calcium sebacate, barium sebacate, aluminum sebacate, thallium sebacate, lead sebacate , Nickel sebacate, beryllium sebacate, sodium undecylate, lithium undecylate, magnesium undecylate, calcium undecylate, barium undecylate, aluminum undecylate, thallium undecylate, lead undecylate, nickel undecylate, beryllium undecylate, ricinol Acid sodium, lithium ricinoleate, magnesium ricinoleate, calcium ricinoleate, ricinol Barium, aluminum ricinoleic acid, ricinoleic acid thallium, ricinoleic lead, ricinoleic acid nickel, ricinoleic acid beryllium and the like. Among these, calcium stearate, calcium 12-hydroxystearate, calcium montanate, magnesium stearate, magnesium 12-hydroxystearate, magnesium montanate, zinc stearate, zinc 12-hydroxystearate and zinc montanate are preferably used. .

  In addition, a lubricant may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Further, the amount of lubricant used is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 100 ppm or more, preferably 200 ppm or more, and usually 50,000 ppm or less, preferably 10,000 ppm or less, more preferably based on the biodegradable resin. Is 5000 ppm or less, more preferably 1000 ppm or less, and most preferably 800 ppm or less. If the lower limit of this range is not reached, the effect of reducing the motor load, which is the effect of addition as a lubricant, and the contribution to discharge stability may be reduced.If the upper limit is exceeded, the manufacturing cost will be too high, the lubricant bleed out, There is a risk of smoke generation, odor generation, and roll contamination during laminate production.

  Although there is no restriction | limiting in the specific method of containing a lubricant, Usually, in any process at the time of laminated body manufacture, aliphatic polyester and a lubricant are mixed and a lubricant is used for the outermost layer (polyester layer) of a laminated body. It is made to contain. It is preferable to use a masterbatch containing the lubricant at a high concentration because it can be diluted by mixing the lubricant to the target concentration.

  Although there is no restriction | limiting in content of the lubricant in a masterbatch, Usually, it is 1 mass% or more, and is 45 mass% or less normally, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less. If the content of the lubricant is too low, the manufacturing cost increases, which is not suitable for use as a masterbatch. If the content is too high, the dispersibility of the resin and the lubricant becomes poor, so the effect of the lubricant is maximized. It cannot be pulled out to the limit. The resin employed as the masterbatch is not particularly limited, but a masterbatch produced using a resin similar to the resin used is usually preferable from the viewpoint of improving dispersibility.

<End sealant>
As described in JP-A-11-80522, the end-capping agent has a property of reacting with a carboxyl group at the end of the carbon chain of the polyester, and reacts with the carboxy end of the polyester to seal it. It is known to improve the hydrolysis resistance of polyester by stopping. As the terminal blocking agent used in the laminate of the present invention, any compound can be used as long as it is a compound capable of sealing a carboxyl group (carboxy terminal) at the terminal of the carbon chain of the polyester.

  As the end-capping agent used in the present invention, not only the end of the polyester is capped, but also the terminal carboxylic acid produced by thermal decomposition or hydrolysis, or the carboxyl group of an acidic low-molecular compound such as lactic acid or formic acid is also blocked. Those that can be stopped are preferred. Furthermore, it is more preferable that the hydroxyl group terminal in the acidic low molecular weight compound produced by thermal decomposition or hydrolysis can be blocked.

  The terminal blocking agent may be polyfunctional or monofunctional. The polyfunctional end capping agent has the advantage that the physical properties such as melt tension can be maintained when the main chain of the polyester is cut, and the polyfunctional end capping agent becomes a branch point and improved melt tension is recognized. (Neck-in, etc.) is improved. In addition, since the monofunctional end-capping agent has less molecular weight and steric hindrance than the polyfunctional type, it has an advantage that it can quickly react with the carboxy end of the polyester and seal.

  As such a terminal blocker, for example, it is preferable to use at least one selected from the group consisting of a carbodiimide compound, an isocyanate compound, an epoxide compound, and an oxazoline compound.

  A carbodiimide compound is a compound (including a polycarbodiimide compound) having one or more carbodiimide groups in the molecule. Such a carbodiimide compound is an isocyanate using, for example, an organophosphorus compound or an organometallic compound as a catalyst. The compound can be synthesized by decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of 70 ° C. or higher.

  The carbodiimide compound can be used alone, but a plurality of compounds can also be mixed and used.

  In the present invention, it is preferable to use a polycarbodiimide compound, and the degree of polymerization of the lower limit is usually 2 or more, preferably 4 or more, and the upper limit is usually 40 or less, preferably 30 or less. When the degree of polymerization is low, the carbodiimide compound is volatilized during the production of the resin particles, and the effect tends to be low. On the other hand, if the degree of polymerization is too large, dispersibility in the composition becomes insufficient, and the end-capping effect may not be obtained efficiently.

  Examples of industrially available polycarbodiimides include Carbodilite (registered trademark) HMV-8CA (manufactured by Nisshinbo Co., Ltd.), Carbodilite (registered trademark) LA-1 (manufactured by Nisshinbo Co., Ltd.), and Starvacol P (manufactured by Rhein Chemie). And Starvacol P100 (manufactured by Rhein Chemie).

  Examples of the isocyanate compound include cyclohexyl isocyanate, n-butyl isocyanate, phenyl isocyanate, 2,6-diisopropylphenyl isocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, 2,4,6- Examples include triisopropylphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate, tolidine diisocyanate, and hexamethylene diisocyanate.

  Examples of the epoxide compound include butyl phenyl glycidyl ether, resorching glycidyl ether, hydroquinone glycidyl ether, 1,6-hexanediol glycidyl ether, hydrogenated bisphenol A diglycidyl ether, N-glycidyl phthalimide, terephthalic acid diglycidyl ester, and bisphenol A type epoxy. Examples thereof include resins and / or novolac type epoxy resins, ethylene-glycidyl methacrylate-vinyl acetate copolymers, and the like.

  Examples of the oxazoline compound include the bisoxazoline compounds exemplified above and oxazoline group-containing polymers.

  In addition, epoxy compounds such as glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, and alicyclic epoxy compounds, oxazine compounds, and the like can also be used as the end-capping agent. Among these, an epoxy compound and a carbodiimide compound are preferable.

  The said terminal blocker may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  In the laminate of the present invention, the carboxyl terminal or acidic low molecular weight compound may be appropriately sealed according to the application to be used, and the degree of sealing is arbitrary depending on the application. As a specific degree of sealing of the carboxy terminal or acidic low molecular weight compound, from the viewpoint of improving hydrolysis resistance, the acid value of the resin according to the laminate of the present invention is usually 60 μeq / g or less, preferably 30 μeq. / G or less, more preferably 20 μeq / g or less. Here, since the acid value of the resin is a carboxyl group which is a monovalent anion, “eq” is a unit representing “mol”. The acid value of the resin layer may be measured by dissolving the laminate of the present invention in an appropriate solvent and then titrating with an alkali compound solution such as sodium hydroxide having a known concentration, or by NMR. it can. In the present specification, the acid value (AV value) of the resin is measured under the following measurement conditions.

  A resin sample is dissolved by heating in benzyl alcohol, and after cooling, ethanol is added to obtain a sample solution. This is subjected to neutralization titration by potentiometric titration using 0.01N sodium benzyl alcohol solution (containing 10% methanol) to obtain a measured titration value.

  On the other hand, a blank sample in which the sample is not dissolved is prepared, and titration is performed in the same manner as described above to obtain a blank value.

  From the titration result, an acid value (AV value: μeq / g) is calculated using the following formula (VI).

A: Measurement titration value (mL)
B: Blank measured value (mL)
F: Potency of benzyl alcohol solution of 0.01N sodium hydroxide W: Sample mass (g)

  In the present specification, an automatic titrator (Auto Titrator AUT-50 manufactured by Toa DKK Corporation) was used as a measuring device.

  The amount of the end-capping agent used is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.2 parts by mass with respect to 100 parts by mass of the polyester. It is usually 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less. If the lower limit of this range is not reached, the end-capping effect may not appear, and improvement of moldability (such as necking-in and surging of the molten film) may not be observed. If the upper limit is exceeded, production costs may be too high. There is a risk of increased motor load, production of gel, smoke generation during processing and generation of odor from the product during the production of the laminate.

  In addition, within the above range of use amount, the end-capping agent may be added in an amount that quantitatively blocks the end of the polyester, but the end-group is blocked and melted by thermal decomposition during the production of the laminate. In order to exhibit the effect of improving tension and long-term stability, it is desirable that an end-capping agent is present excessively with respect to the polyester terminal. Here, the presence of the end-capping agent in excess means that the end-capping agent is added in excess of the acid value of the substrate resin (that is, the biodegradable resin and other resins used as appropriate).

  Although there is no restriction | limiting in the specific method of containing terminal blocker in the laminated body of this invention, Usually, resin and terminal blocker are mixed and laminated | stacked in any process at the time of laminated body manufacture. A terminal sealing agent is included in the resin layer of the body. For example, it is preferable to use a master batch containing a high concentration of the end capping agent. It is because it can be mixed and diluted so that the content becomes the target concentration.

  Although there is no restriction | limiting in content of the terminal blocker in a masterbatch, Usually, 0.5 mass% or more, and usually 45 mass% or less, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less. . If the content of the end-capping agent is too small, it is not suitable for use as a masterbatch, and if the content is too large, gelation tends to proceed.

  Resin employ | adopted as a masterbatch is not specifically limited, Although the commercially available masterbatch containing carbodiimide may be sufficient, the masterbatch manufactured using resin similar to the polyester resin to be used is preferable.

<Nucleating agent>
The laminate of the present invention may contain a nucleating agent in order to control the crystallization temperature of the resin related to the resin layer during the production of the laminate and improve the workability during molding. The addition of a nucleating agent can be expected to increase the crystallization temperature and improve the roll-off property. As the nucleating agent, either an inorganic nucleating agent or an organic nucleating agent can be used, and the nucleating agent may be used alone or in combination of two or more at any ratio.

  Specific examples of inorganic nucleating agents include talc, kaolin, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, and barium sulfate. And metal salts of aluminum oxide, neodymium oxide and phenylphosphonate. In addition, these inorganic nucleating agents may be modified with an organic substance in order to enhance dispersibility in the composition.

  On the other hand, specific examples of the organic nucleating agent include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, aluminum benzoate, lithium terephthalate, sodium terephthalate, terephthalic acid Potassium, calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, stearin Magnesium oxide, barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate Organic carboxylic acid metal salts such as sodium salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate; organic sulfonic acids such as sodium p-toluenesulfonate and sodium sulfoisophthalate Salts: Carboxylic acid amides such as stearic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide); low density polyethylene, high density polyethylene, polypropylene, poly Polymers such as isopropylene, polybutene, poly-4-methylpentene, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid; Sodium salt or potassium salt of a polymer having a carboxyl group such as sodium salt of rilic acid or methacrylic acid copolymer, sodium salt of styrene-maleic anhydride copolymer (so-called ionomer); benzylidene sorbitol and its derivatives, sodium-2,2 ′ -Phosphorus compound metal salts such as methylenebis (4,6-di-t-butylphenyl) phosphate; 2,2-methylbis (4,6-di-t-butylphenyl) sodium; polyethylene wax . Polyethylene wax is preferably used as a particularly preferred nucleating agent. When this polyethylene wax was used, it was found that GS-Pla crystallization can be promoted, the roll-off property is improved, and the adhesion with the substrate is not inhibited.

  The average particle diameter of the nucleating agent is arbitrary as long as the effects of the present invention are not significantly impaired. Usually, it is 50 μm or less, preferably 10 μm or less. In view of secondary aggregation and handling workability, it is usually 0.1 μm or more, preferably 0.5 μm or more. If the average particle size exceeds the upper limit of the above range, there may be no effect on increasing the crystallization temperature. In addition, when the average particle size of the nucleating agent is less than the lower limit of the above range, the production cost becomes high and handling may be difficult.

  A preferable blending amount of the nucleating agent is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.2 parts by mass with respect to 100 parts by mass of the polyester. Or more, usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and particularly preferably 1.2 parts by mass or less. If the lower limit of this range is not reached, there is a risk that the effect of increasing the crystallization temperature will not appear, and there is a risk that the roll-off property at the time of molding may be deteriorated. The roll dirt of becomes a problem.

<Other additives>
The laminate of the present invention may contain additives other than the above-mentioned antioxidant, lubricant, terminal blocking agent and nucleating agent as long as the effects of the present invention are not significantly impaired. Examples of additives include light stabilizers (light stabilizers), ultraviolet absorbers, compatibilizers, antistatic agents, fillers, colorants, antiblocking agents, mold release agents, antifogging agents, plasticizers, and flame retardants. Etc. In particular, it is preferable to contain 10 ppm or more of any one or more kinds of light stabilizers, compatibilizers, antistatic agents, and fillers.

  Any light-proofing agent can be used as long as the effects of the present invention are not significantly impaired. Specific examples thereof include decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Sebacate, 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4) − Droxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2, 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and the like Agents.

  A single light stabilizer may be used alone, or two or more light stabilizers may be used in any combination and ratio. In particular, it is effective to use a combination of different types of light-proofing agents, and it is also effective to use them in combination with an ultraviolet absorber. Of these, a combination of a hindered amine stabilizer and an ultraviolet absorber is effective.

  Furthermore, the amount of the light-proofing agent used is arbitrary as long as the effects of the present invention are not significantly impaired. However, it is usually 100 ppm or more, preferably 200 ppm or more, and usually 5 parts by mass or less, preferably 1 part by mass or less based on the polyester. More preferably, it is 0.5 parts by mass or less. If the lower limit of this range is not reached, the effect of the light proofing agent may be reduced. If the upper limit is exceeded, the manufacturing cost becomes too high, the heat resistance of the composition is inferior, the bleedout of the light proofing agent, roll dirt, molding processing There is a risk of smoke from time.

  Although there is no limitation on the specific method of containing the light stabilizer, usually, in any step during the production of the laminate, the aliphatic polyester and the light stabilizer are mixed, and the light stabilizer is added to the outermost layer of the laminate. Make it contain. It is preferable to use a masterbatch containing the light-proofing agent at a high concentration because the light-proofing agent can be mixed and diluted so as to have a target concentration and is simple.

  Although there is no restriction | limiting in content of the light-proofing agent in a masterbatch, Usually, it is 1 mass% or more, and is 45 mass% or less normally, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less. If the content of the light stabilizer is too small, the production cost increases, so it is not suitable for use as a masterbatch. If the content is too large, the dispersibility of the resin and the light stabilizer becomes poor. The effect of the agent cannot be maximized.

  Any ultraviolet absorber can be used as long as the effects of the present invention are not significantly impaired. Specific examples thereof include benzotriazoles such as 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol; 2- (4,6-diphenyl) And triazines such as -1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol.

  A ultraviolet absorber may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. In particular, it is effective to use a combination of different types of ultraviolet absorbers.

  The amount of the ultraviolet absorber used is arbitrary as long as the effects of the present invention are not significantly impaired, but are usually 100 ppm or more, preferably 200 ppm or more, and usually 5% by mass or less, preferably 2% by mass or less, more preferably. 0.5% by mass or less. If the lower limit of this range is not reached, the effect of the UV absorber may be reduced. If the upper limit is exceeded, the manufacturing cost becomes too high, the heat resistance of the composition is inferior, the UV absorber bleed-out, fuming, odor There is a risk that rolls will be generated during the production of laminates and laminates.

  The specific method of containing the ultraviolet absorber is not limited, but usually, in any step during the production of the laminate, the aliphatic polyester and the ultraviolet absorber are mixed and ultraviolet rays are added to the outermost layer of the laminate. An absorbent is included. It is preferable to use a masterbatch containing the ultraviolet absorber at a high concentration because the ultraviolet absorber can be mixed and diluted so as to have a target concentration, and it is simple.

  Although there is no restriction | limiting in content of the ultraviolet absorber in a masterbatch, Usually, it is 1 mass% or more, and is 45 mass% or less normally, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less. If the content of the UV absorber is too small, the manufacturing costs will increase, so it is not suitable for use as a masterbatch, and if the content is too high, the dispersibility of the resin and the UV absorber will be poor. The effect of UV absorbers cannot be maximized.

  Any compatibilizer can be used as long as the effects of the present invention are not significantly impaired. Specific examples thereof include an ester group, a carboxylic acid anhydride, an amide group, an ether group, a cyano group, an unsaturated hydrocarbon group, an epoxy group, an acrylic group, a methacryl group, and an aromatic hydrocarbon at the terminal or main chain of the resin. And those having a group introduced therein.

  Examples of the compatibilizer include aliphatic polyesters, polyolefin resins, polyurethane resins, polycarbonate resins, polyethylene terephthalates, polybutylene terephthalates, polyethylene naphthalates, polyarylates, liquid crystal polymers, and other aromatic polyester resins, polyvinyl chloride resins. , SEBS (polystyrene-block-poly (ethylene-co-butylene) -block-polystyrene), SEPS, styrene resins such as polystyrene, nylon 6, nylon 6-6, nylon 6-10, nylon 9, nylon 11, nylon 13, nylon 4, nylon 4-6, nylon 5-6, nylon 12, nylon 10-12, polyamide resin such as aramid, polyacetal resin, polymethyl methacrylate, polymethacrylate Acrylic resins such as tellurium and polyacrylic acid ester, polyethylene glycol, polypropylene glycol, poly 1,3-propanediol, polytetramethylene glycol, polyether resins such as modified polyphenylene ether, polyphenylene sulfide resin, polyether ketone resin, polyether Examples thereof also include graft copolymers with ether ketone resins, block copolymers, multiblock copolymers, random copolymers, and the like.

  As the compatibilizing agent, in addition to the above-mentioned copolymer, a compound containing both the structures of different resins to be blended in the same molecule can be mentioned.

  Also, polyurethane resin, polycarbonate resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, SEBS, SEPS, polystyrene, nylon 6, nylon 6-6, nylon 12, polyacetal resin, polymethyl methacrylate, polymethacrylate, polyacryl Reacts with hydroxyl group, carboxyl group, ester group, alkyl group, alkylene group at the end or side chain of polymer molecule of acrylic resin such as acid ester, polyethylene glycol, polypropylene glycol, poly 1,3-propanediol, polytetramethylene glycol Examples thereof include a polymer having a possible functional group.

  One type of compatibilizer may be used alone, or two or more types may be used in any combination and ratio. In particular, in the laminate of the present invention, the use of a compatibilizer is particularly suitable when the resin layer is composed of two or more kinds of resins (that is, polyester and other resins used as appropriate). The compatibilizer can also be used when the laminate is a multilayer body in which each layer is formed from two or more kinds of resins.

  The amount of the compatibilizer used is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and usually 50 parts. It is not more than part by mass, preferably not more than 30 parts by mass, more preferably not more than 10 parts by mass. If the lower limit of this range is not reached, the adhesive force, which is the effect of the compatibilizer, may be reduced. If the upper limit is exceeded, the production cost may become too high, or the biodegradability may be deteriorated. The compatibilizer is also usually mixed with the resin and the compatibilizer in any step during the production of the laminate so that the compatibilizer is contained in the resin layer of the laminate.

  Moreover, in order to make the laminate of the present invention excellent in antistatic properties, it is also preferable to add a mixture having an antistatic effect that exhibits an antistatic effect to the resin layer. As the mixture, a surfactant type nonionic, cationic or anionic type is suitably selected. One antistatic agent may be used alone, or two or more antistatic agents may be used in any combination and ratio. Nonionic antistatic agents are glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkyldiethanolamine, hydroxyalkyl monoethanolamine, polyoxyethylene alkylamine, polyoxyethylene alkylamine, fatty acid ester There are alkyldiethanolamides, and among them, alkyldiethanolamines are preferable from the viewpoint of expression of the antistatic effect. As the antistatic agent typified by a cationic system, a tetraalkylammonium salt, a trialkylbenzylammonium salt, or the like is selected. Examples of anionic compounds include alkyl sulfonates, alkyl benzene sulfonates, and alkyl phosphates. Of these, alkyl benzene sulfonates are preferable from the viewpoint of kneading properties with a base resin and expression of an antistatic effect.

  The amount of the antistatic agent used is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1000 ppm or more, preferably 3000 ppm or more, and usually 50000 ppm or less, preferably 20000 ppm or less, more preferably 10,000 ppm or less. If the lower limit of this range is not reached, the effect of the antistatic agent may be reduced, and if the upper limit is exceeded, the manufacturing cost becomes too high, the heat resistance of the composition is inferior, the antistatic agent bleed-out, fuming, odor There is a risk that rolls will be generated during the production of laminates and laminates. One antistatic agent may be used alone, or two or more antistatic agents may be used in any combination and ratio.

If the blending amount of the antistatic agent is too small, a substantial effect of improving the antistatic property is not recognized.If the blending amount is too large, the antistatic agent bleeds out to the surface of the laminate, causing stickiness, and printability. It may become defective. Odor and smoke generated during molding may also be a problem. The preferable antistatic performance is that the surface resistivity of the laminate is 1 × 10 ^{8 to} 5 × 10 ¹³ Ω / □, more preferably 1 × 10 ⁸ to 1 × 10 ¹² Ω / □. The surface resistivity is measured according to JIS-K6911 using a resistivity meter.

  The specific method of containing the antistatic agent is not limited, but usually, the aliphatic polyester and the antistatic agent are mixed in any step during the production of the laminate to charge the outermost layer of the laminate. An inhibitor is included. The mixing order and mixing method of the aliphatic polyester and the antistatic agent are not particularly limited, but a masterbatch having a high antistatic agent content, for example, a masterbatch having an antistatic agent content of 5 to 20% by mass. The method of preparing and mixing this with aliphatic polyester is preferable from the viewpoint that the mixture is easily dispersed uniformly. Moreover, about a mixing method, it is preferable to use a twin-screw extruder from viewpoints, such as kneadability. Moreover, you may use a coating type antistatic agent for the resin layer of a laminated body.

  A filler can be added for the purpose of increasing whiteness, increasing opacity, and increasing heat resistance and rigidity. As the filler, conventionally known various fillers can be arbitrarily used as long as the effects of the present invention are not significantly impaired. Fillers are roughly classified into inorganic fillers and organic fillers. These can also be used as one kind or a mixture of two or more kinds.

  Moreover, a functional additive can be mix | blended as a filler and it can also be set as a composition and can also be added to a laminated body. Functional additives include chemical fertilizers, soil conditioners, plant activators and the like.

  Inorganic fillers include mica, talc, titanium oxide, heavy calcium carbonate, diatomaceous earth, allophane, bentonite, zeolite, sepiolite, smectite, kaolin, wollastonite, calcined pearlite, and other processed minerals; glass Carbon; anhydrous silica, silica gel, silicates such as calcium silicate and sodium silicate, oxides such as aluminum oxide, zinc oxide and iron oxide; hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide, magnesium carbonate And carbonates such as light calcium carbonate and ferric carbonate; and other salts such as aluminum phosphate, barium sulfate and potassium titanate. The content of the inorganic filler is usually 1 to 80% by mass, preferably 3 to 70% by mass, and more preferably 5 to 60% by mass with respect to the total amount of the composition material.

  Examples of organic fillers include raw starch, processed starch, pulp, chitin / chitosan, coconut shell powder, wood powder, bamboo powder, bark powder, kenaf, rice husk, and cocoon powder. Moreover, these may be baked and added as a carbide. These may be used alone or as a mixture of two or more. The addition amount of the organic filler is usually 0.01 to 70% by mass with respect to the total amount of the composition material. In particular, this organic filler is used as a green plastic because the organic filler remains in the soil after biodegradation of the polyester composition and also serves as a soil conditioner and compost. .

Among these, in order to increase the opacity of the laminate, it is preferable to use titanium oxide, calcium carbonate, barium sulfate or the like. In order to increase the heat resistance of the laminate, it is preferable to use mica, talc, diatomaceous earth, allophane, bentonite, zeolite, sepiolite, smectite, kaolin and the like. Moreover, in order to improve the flame retardance of a laminated body, it is preferable to use magnesium hydroxide, aluminum hydroxide, etc. In order to obtain an antiblocking effect, it is preferable to use anhydrous silica, silica gel, aluminum oxide, raw starch, and the like.
Some fillers have the properties of soil conditioners such as light calcium carbonate, heavy calcium carbonate (limestone), magnesium carbonate, chitin / chitosan, coconut shell powder, wood powder, rice husk, straw If the biomass-derived polyester composition containing a large amount of these inorganic fillers is dumped in the soil, the inorganic filler after biodegradation remains and functions as a soil conditioner, Increase significance as a green plastic. In the case of applications such as agricultural materials and civil engineering materials that are dumped in the soil, it is necessary to use a layered product to which a material such as a chemical fertilizer, a soil conditioner, or a plant activator is added. It will increase the usefulness of the body.

  A filler may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. Further, the amount of the filler used is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 100 parts by mass of the polyester. 1 part by mass or more, and usually 50 parts by mass or less, preferably 30 parts by mass or less, more preferably 10 parts by mass or less. If the lower limit of this range is not reached, the effect of addition may be reduced, and if it exceeds the upper limit, the manufacturing cost may be increased or the moldability may be deteriorated. You may make it contain these fillers in the resin layer of a laminated body in which process at the time of the laminated body manufacture of this invention. For example, in order to uniformly disperse the polyester resin, a master batch containing a high concentration of filler can be used. The resin employed as the masterbatch is not particularly limited, but a masterbatch produced using a resin similar to the resin used is usually preferable.

  Examples of the colorant include coloring materials and fluorescent brightening agents, and any one can be used as long as the effects of the present invention are not significantly impaired. The colorant may be dye-based or pigment-based. Among the color materials, dye-based color materials have good color developability, and pigment-based color materials have good light resistance. A dye-based color material and a pigment-based color material can also be used in combination. A colorant and a fluorescent brightening agent can be used in combination.

  For example, in order to suppress the yellowness of the laminate and make it closer to white, any of a method of adding a color material to polyester, a method of adding a fluorescent whitening agent, and a method of adding a coloring material and a fluorescent whitening agent may be used. . A pigment-based color material having good light resistance is preferably used as the color material. Moreover, it is possible to control the hue of the laminate by using a combination of a blue pigment and a violet pigment and appropriately adjusting the blending ratio of the two.

Examples of the dye-based color material include C.I. I. Solvent Black 7 (Nigrosine series), C.I. I. Solvent Yellow 21 (pyrazole type), C.I. I. Disperse Yellow 7 (disazo type), C.I. I. Solvent Orange 44 (monoazo type), C.I. I. Disperse Orange 13 (disazo type), C.I. I. Solvent Red 84 (monoazo type), C.I. I. Disperse Red 54 (monoazo type), C.I. I. Solvent Violet 14 (anthraquinone), C.I. I. Disperse Violet 18 (anthraquinone series), C.I. I. Solvent Blue 25 (phthalocyanine series), C.I. I. Disperse Blue 56 (anthraquinone type) and the like can be mentioned.

  Specific examples of the inorganic pigment-based coloring material include chromate salts such as barium yellow (CI pigment Yellow 31), yellow lead (CI pigment Yellow 34), zinc yellow (CI pigment Yellow 36), and the like. Ferrocyanides such as bitumen (CI pigment blue 27); sulfides such as cadmium yellow (CI pigment yellow 42) and cadmium red (CI pigment red 108); iron black (C.I. pigment red 108); Oxides such as I. pigment Black 11) and Bengara (CI pigment Red 101); silicates such as ultramarine (CI pigment Blue 29); or channel black, roller black, disc, gas furnace black , Oil furnace Rack, it can be mentioned thermal black, carbon black such as acetylene black (C.I. Pigment Black 7), and the like.

  Specific examples of organic pigment colorants include C.I. I. pigmentBlack 1 (condensed aniline type), C.I. I. pigment Yellow 12 (monoazo type), C.I. I. pigment Yellow 23 (anthraquinone series), C.I. I. pigment Yellow 109 (isoindolinone series), C.I. I. pigment Yellow 138 (quinophthalone series), C.I. I. pigment Orange 5 (monoazo type), C.I. I. Vat Orange 3 (perinone series), C.I. I. pigment Red 1 (monoazo type), C.I. I. pigment Red 37 (pyrazolone azo type), C.I. I. pigment Red 87 (thioindigo system), C.I. I. pigment Red 224 (perylene type), C.I. I. pigment Violet 19 (quinacridone series), C.I. I. pigment Violet 3 (azomethine series), C.I. I. pigment Violet 37 (dioxazine type), C.I. I. pigment blue 15 (phthalocyanine series), C.I. I. pigment Green 1 (azomethine type) and the like.

  Examples of optical brighteners include C.I. I. Fluorescent Brightening Agent 54 (pyrazoline series), C.I. I. Fluorescent Brightening Agent 86 (stilbene series), C.I. I. Fluorescent Brightening Agent 91 (coumarin type), C.I. I. Fluorescent Brightening Agent 135 (benzoxazole type), C.I. I. Fluorescent Brightening Agent 351 (biphenyl type) and the like.

  The addition amount of the colorant is usually 0.01 parts by mass or more, preferably 0.03 parts or more, and usually 5 parts or less, preferably 1 part or less, relative to 100 parts by mass of the polyester. These colorants may be contained in the resin layer of the laminate in any step during production of the laminate of the present invention. For example, in order to uniformly disperse the polyester resin, a master batch containing a colorant at a high concentration can be used. The resin employed as the masterbatch is not particularly limited, but a masterbatch produced using a resin similar to the resin used is usually preferable.

  In addition, a mold release agent, an antifogging agent, an organic flame retardant, or the like may be used as an additive. Any of these can be used as long as the effect of the present invention is not significantly impaired, and the amount of use thereof is arbitrary as long as the effect of the present invention is not significantly impaired. Furthermore, any of these additives may be used alone, or two or more may be used in any combination and ratio.

(7) Physical properties of the laminate <thickness>
The laminate according to the present invention preferably has an overall thickness of 300 μm or less. More preferably, it is 250 micrometers or less, More preferably, it is 200 micrometers or less. On the other hand, the total thickness of the laminate is preferably 20 μm or more. More preferably, it is 40 micrometers or more, More preferably, it is 70 micrometers or more.
The substrate layer is preferably 10 μm or more and 300 μm or less. In particular, when the laminate of the present invention is used for a bag or a container, paper strength and rigidity are required, and therefore the lower limit of the thickness of the base material layer is more preferably 30 μm or more, and further preferably 50 μm or more. On the other hand, the upper limit of the thickness of the base material layer is more preferably 285 μm and even more preferably 250 μm from the viewpoint that the outer side of the folded part is not easily destroyed when bent during the secondary processing.
The thickness of the resin layer can be controlled by extrusion conditions, particularly by the screw diameter and screw rotation speed of the extruder. The outermost layer is preferably 5 μm or more and 285 μm or less. Above all, the lower limit of the thickness of the outermost layer is more preferably 10 μm or more from the viewpoint of heat sealability, substrate concealability, and mechanical strength. On the other hand, from the viewpoint of production speed due to restrictions on material costs and extrusion conditions, the upper limit of the thickness of the outermost layer is more preferably 250 μm or less, and even more preferably 150 μm or less.
The intermediate layer is preferably 5 μm or more and 285 μm or less. Among these, from the viewpoints of adhesion to the base material layer and mechanical strength, the lower limit of the thickness of the outermost layer is more preferably 10 μm or more. On the other hand, from the viewpoint of production speed due to restrictions on material costs and extrusion conditions, the upper limit of the thickness of the outermost layer is more preferably 200 μm or less, and even more preferably 100 μm or less. By setting it as such thickness, intensity | strength and a softness | flexibility can be made compatible. Also, when laminating resin layers on both sides of the base material layer, curling can be suppressed or the desired curl locality can be imparted by adjusting the elastic modulus of the resin and the thickness of the resin layer. be able to.

<Adhesive strength>
Since the laminate of the present invention is provided with an intermediate layer between the base material and the outermost layer, the adhesive strength between the base material and the outermost layer is high, and the paper fiber is strong enough to adhere to the resin layer. In the case of a product, the outermost layer does not peel off. The adhesive strength of the laminate of the present invention is preferably 1.27 (N / 15 mm) or more, more preferably 1.47 (N / 15 mm) or more, most preferably 1.57 (N / 15 mm) or more. is there. The upper limit is not particularly limited, but is preferably 2.94 (N / 15 mm) or less. Below the preferred lower limit, peeling proceeds with a very weak force, and the peeling type is also interfacial peeling, resulting in poor adhesion, which is not practical as a laminate. The adhesive strength between the resin layer and the paper substrate is determined when peeling is performed at a peeling angle of 180 °, a peeling speed of 300 mm / min, and a test piece width of 15 mm in accordance with JIS Z0237 (“Adhesive tape / adhesive sheet test method”). The peel strength (N / 15 mm).

<Heat seal strength>
The laminate of the present invention is characterized by high heat-sealing strength, and is suitable for high-speed automatic packaging machines and automatic filling machines because it is easy to perform secondary processing. The heat seal strength between the polyester layers according to the laminate of the present invention conforms to the provisions of JIS Z0238, and is at least 6 N / 15 mm, preferably 10 N / 15 mm. On the other hand, the upper limit is preferably 50 N / 15 mm or less, and more preferably 40 N / 15 mm or less. Below the lower limit, peeling proceeds with a very weak force, and the peeling type is also interfacial peeling, poor adhesion, and is not practical as a packaging material, such as breaking the bag. Further, in order to exceed the upper limit value, it is necessary to set the seal pressure, the seal time, and the seal temperature higher than usual, and the productivity during the secondary processing may be lowered.

  The heat seal strength of the polyester layer and the kraft paper is at least 4 N / 15 mm or more, but the upper limit is preferably 10 N / 15 mm or less. Below the lower limit, peeling proceeds with a very weak force, and the peeling type is also interfacial peeling, poor adhesion, and is not practical as a packaging material, such as breaking the bag. Furthermore, complicated operations such as corona treatment and application of an anchor coat agent may be required on the surface of a substrate such as kraft paper. When the upper limit is exceeded, the seal pressure, seal time, and seal temperature must be set higher than usual, which may reduce the productivity during secondary processing.

  The heat seal strength referred to here is a set temperature of 150 ° C., a seal bar width of 5 mm, a seal pressure of 0.1 MPa or more, and a seal time of 0.5 seconds to 1.1 seconds. (Polyester layer) or resin layer (polyester layer) and kraft paper are bonded to each other to produce a strip-shaped test piece having a width of 15 mm, and the heat seal part of the test piece is opened at 180 ° in the center. When the interval is 50 mm or more, both ends of the test piece are attached to the grip of a tensile tester, a tensile load is applied until the heat seal part breaks at a pulling speed of 300 mm / min, and the maximum load (N / 15 mm) is measured Is the value of

  In addition, as described above, in the secondary processing, the heat sealing strength is further improved by interposing another resin layer such as a printing layer between the polyester layer and the base material instead of directly heat sealing. It can also be made. The heat seal strength in this case is about 7.0 to 15.0 N / 15 mm.

  The heat-seal expression temperature of the laminated body of this invention should just be 110 degreeC or more, and especially an upper limit is not set. If the temperature is lower than this temperature, it is necessary to extend the heat sealing time or increase the heat sealing pressure, and the sealing strength may not be obtained.

<Incense retention>
Since the laminate of the present invention contains aliphatic polyester in the outermost layer, the laminate has a property (fragrance retention) that traps various odor components in the container in the container when it is used as a packaging material such as a bag. can do. Here, examples of the odor component include low-molecular-weight terpenes, and malodor-causing substances such as nitrogen-containing compounds such as ammonia. It is known that the principle of increasing the fragrance retention when the outermost layer is a layer containing an aliphatic polyester is generally explained by the solubility parameter, but it is not complete by itself, and the crystallinity is considered. It is necessary and not fully understood.

  In general, a laminate may be imparted with a fragrance by setting a multilayer structure or setting a gas barrier layer. In the laminated body of this invention, since it has high fragrance retention property, a gas barrier layer can be abbreviate | omitted and it can satisfy | fill both high fragrance retention property and high water vapor permeability, and is preferable. In applications that require low water vapor transmission, talc, kaolin, and smectite (including organic smectite) may be added to the resin layer to impart gas barrier properties to the resin layer itself.

<Water vapor permeability>
Water vapor permeability of the laminate of the present invention varies depending on the configuration, when the base material layer of the laminate is paper, it is 1000g ^/ m 2 ^/ 24hr or 4000g ^/ m 2 ^/ 24hr or less. If this upper limit is exceeded when this laminate is used as a packaging material, the amount of moisture from the packaging material may be significantly reduced. Moreover, when it falls below the lower limit, it cannot be achieved under normal molding conditions, and the process such as stretching and thickening of the resin layer may be complicated. The measured value of water vapor permeability is a value obtained by measuring a laminate having a resin layer of 20 μm at a temperature of 40 ° C. and a humidity of 90% RH in accordance with a moisture permeable cup method described in JIS Z0208.

<Biodegradability>
Although the biodegradability of the laminate of the present invention varies depending on the layer configuration, in the case of a laminate in which the base material layer is paper, it is preferable that the resin layer decomposes in the soil under certain specific conditions. In the present invention, biodegradability is evaluated by visually observing a laminate sample after a certain period of time after soil burial, and the sample does not visually maintain the original shape as “with biodegradability”. judge. It should be noted that even if the resin layer disappears and the base material layer remains, it is biodegradable. Although it depends on the use of the laminate, it is preferable that the resin layer disappears within 2 weeks to 5 months. When the laminate of the present invention is used as a compostable paper container or bag, it is preferable that the resin layer has completely disappeared after 3 months of soil embedding, and the resin layer has completely disappeared after 2 months of soil embedding. More preferably.
In the present invention, desired biodegradability can be imparted to the laminate depending on the resin composition of the resin layer and the crystallinity of the resin, the type and amount of additives, the presence or absence of printing (particularly UV varnish), and the like.

(8) Use of laminated body <Secondary processing>
The laminate obtained by the present invention can be subjected to secondary processing into various packaging materials, bag making, cups, trays, cartons and the like. Various types of processing are the same as conventional paper and plastic laminated paper, that is, automatic packaging machines such as three-side seal automatic bag making machines, center seal automatic bag making machines, and standing pouch automatic bag making machines as packaging materials. , Pillow-type automatic filling and packaging machines, three-side seal filling and packaging machines, four-side seal filling and packaging machines and other automatic filling and packaging machines such as flat bags, square bottom bags, turtle shell bags, etc. It can be processed into a shape. Furthermore, it can also process using apparatuses, such as a paper cup molding machine, a punching machine, a sack pasting machine, and a box making machine. In these processing machines, the bonding method of the laminate is adopted by a known technique, but generally a heat sealing method, an impulse sealing method, an ultrasonic sealing method, a high frequency sealing method, a hot air sealing method, a frame sealing method, etc. are adopted. Is done.

Although the heat seal temperature of the laminate of the present invention varies depending on the adhesion method, when a heat-type heat seal tester having a seal bar is used and a paper substrate of 100 to 300 g / m ² or more is used, the heat seal expression temperature is The upper limit is not particularly set, but is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 180 ° C. or lower. Below the lower limit, the adhesive strength may be insufficient. On the other hand, if the upper limit is exceeded, the resin is also melted by heating in the vicinity of the seal portion, the thickness of the resin layer may be reduced, and the seal strength may be reduced.

  The heat seal pressure of the laminate of the present invention varies depending on the bonding method, but when a heating heat seal tester having a seal bar is used, it may be 0.05 MPa or more, preferably 0.1 MPa or more. The upper limit is 0.5 MPa or less, preferably 0.45 MPa or less, more preferably 0.4 MPa or less. Below the lower limit, the adhesive strength may be insufficient. On the other hand, if the upper limit is exceeded, the film thickness at the end of the seal may be reduced, and the seal strength may be reduced.

  The heat seal time of the laminate of the present invention varies depending on the bonding method, but when a heating heat seal tester having a seal bar is used, it may be 0.25 seconds or longer, preferably 0.5 seconds or longer. The upper limit is 3 seconds or less, preferably 2 seconds or less, more preferably 1.5 seconds or less. Below the lower limit, the adhesive strength may be insufficient. On the other hand, if the upper limit is exceeded, the film thickness at the end of the seal may be reduced, and the seal strength may be reduced.

<Specific use>
The laminated body according to the present invention is used for packaging container materials, agricultural / civil engineering / fishery materials, and the like by processing.

  Examples of packaging container materials include shopping bags, various bags, magnetic tape cassette product packaging materials such as video and audio, flexible disk packaging materials, plate making materials, packaging bands, adhesive tapes, tapes, yarns, cups and other liquids. Containers, trays, cartons, lunch boxes, sugar beet containers, food / confectionery packaging materials, food wrap materials, cosmetic / cosmetic wrap materials, diapers, sanitary napkins, pharmaceutical wrap materials, pharmaceutical packaging materials, stiff shoulders Various packaging materials such as food, electronics, medicine, medicine, cosmetics and the like, such as packaging materials for surgical patches applied to the skin and sprains.

  As materials for agriculture, civil engineering and fisheries, for example, films for agriculture and horticulture, wrap films for agricultural chemicals, greenhouse films, fertilizer bags, seedling pots, waterproof sheets, sandbag bags, architectural films, weed prevention sheets And materials used in agriculture, civil engineering and fisheries, such as vegetation nets made of tape and yarn. In addition, it can be used as a garbage bag and a compost bag, and can be suitably used as a material in a wide range.

  In particular, if the biodegradable resin of the polyester layer is an aliphatic polyester mainly composed of dicarboxylic acid and diol, it has a high aroma retention and adsorbability as described above, so that it is a container for liquids such as sake and juices. It is preferable as an interior material such as confectionery and a packaging material. In addition, since malodorous components are not leaked to the outside world, they are suitable for garbage bags that are water-resistant and do not leak odors. Furthermore, since it also has high water vapor permeability, it can be suitably used for food packaging materials such as lunch boxes and rice balls. By using the laminate of the present invention, it is possible to effectively release water vapor generated when warm food is packaged, and to prevent stickiness of the foods contained therein, thereby maintaining the texture.

<Paper recycling>
In the laminate of the present invention, when collecting the laminated paper made of paper as the base material layer, the aliphatic polyester contained in the resin layer is decomposed faster than the paper by immersing the laminated paper in an alkaline solution. Therefore, the defibrated paper fiber can be easily collected. In the case of a polyethylene film, since it does not decompose, it is necessary to separate the film and paper fiber and it is difficult to recycle. However, by using a laminate of the configuration of the present invention using aliphatic polyester, it is easy to reduce the cost. Paper recycling is possible. At this time, an enzyme that promotes the degradation of the aliphatic polyester may be allowed to act in order to promote the degradation.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the following examples are shown in order to explain the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof. In the following description, “part” means “part by mass” unless otherwise specified. Moreover, the physical property of the laminated body in each Example and a comparative example is measured in the following procedure.

(1) Physical property measurement method of resin and type of resin <Melt flow rate (MFR)>
Based on JIS K7210, it measured at 190 degreeC and the load 2.16kg using the melt indexer. The unit is g / 10 minutes.

<Reduced viscosity (ηsp / c)>
The time t (sec) during which the polyester is dissolved in phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) to a concentration of 0.5 g / dL, and the solution drops in the viscosity tube in a 30 ° C. thermostat. Was measured. Further, the time t ₀ (sec) during which only the solvent falls was measured, and the reduced viscosity η _sp / C (= (t−t ₀ ) / t ₀ · C) at 30 ° C. was calculated (C is the concentration of the solution).

^<1 H-NMR>
About 30 mg of the sample was weighed into an NMR sample tube having an outer diameter of 5 mm, and dissolved in 0.75 mL of deuterated chloroform. For this, using a Bruker AVANCE400 nuclear magnetic resonance apparatus, it was analyzed by ¹ H-NMR spectrum at room temperature. The standard of chemical shift was tetramethylsilane (TMS) of 0.00 ppm. The composition ratio of each polymer was calculated.

<Tensile modulus>
With respect to the resin composition constituting the intermediate layer, an inflation film having a blow ratio of 2.0 and a thickness of 20 to 50 μm was produced by an inflation molding method at a molding temperature of 150 to 180 ° C. A strip-shaped test piece having a width of 10 mm was prepared from the obtained film, and the initial elastic modulus was measured at a tensile speed of 1 mm / min with a Tensilon universal testing machine (A & D Co., Ltd.) in accordance with JIS K7161. This was measured and this was taken as the tensile elastic modulus.

<Acid value>
0.5 g of the sample was precisely weighed and placed in a test tube containing 25 mL of benzyl alcohol, and heated in a heating bath at 195 ° C. for 9 minutes to dissolve the sample. After confirming that the sample was completely dissolved and cooled in ice water for 30 to 40 seconds, 2 mL of ethyl alcohol was added. A pH electrode is placed in the sample solution, and while stirring, neutralization titration is performed by potentiometric titration using a 0.01N sodium benzyl alcohol solution (containing 10% methanol) to obtain a measured titration value A (mL). It was. Here, an automatic titration device (Auto Titrator AUT-50 manufactured by Toa DKK Corporation) was used as a measuring device.
On the other hand, a blank sample in which the sample was not dissolved was prepared, and titration was performed in the same manner as described above to obtain a blank measurement value B (mL).
From the titration result, the AV value (μeq / g) was calculated using the formula (VI).

<Use resin>
Details of the resins used in Examples and Comparative Examples are as shown in Table 1 (hereinafter, “GS Pla” in the trade name may be omitted).

  In addition, said polybutylene succinate terephthalate (PBST) was synthesize | combined by the method as described in Example 1 of Unexamined-Japanese-Patent No. 2001-026641.

(2) Evaluation method of molten resin state and roll release property during processing <Resin temperature of molten film>
The resin temperature concerning the polyester layer in each place (each die heat block) was measured with a thermocouple thermometer at the discharge amount at the time of molding.

(3) Evaluation method of laminate <Appearance and stability of molten film>
The state of the molten film was visually observed from the die outlet. The evaluation criteria were as follows.
A (Excellent): The molten film is transparent or translucent, and is in a normal state free from FE (fish eye), foreign matter, and bubbles. There is also very little resonance.
○ (good): The molten film is transparent or semi-transparent, and has some FE (fish eyes), foreign matter, and bubbles, but is within a range that allows resonance at a level that does not cause molding problems.
Δ (possible): The molten film is in a state where there are few FE (fish eyes) and foreign matters, and there is a feeling of opacity. The resonance is also bad.
X (impossible): The molten film has a lot of FE (fish eye) and foreign matters, or there are many bubbles and many film cracks occur, so that the operation is impossible.

<Smoke and odor>
Sensory tests were conducted on the state of fuming from the die outlet and odor. The evaluation criteria were as follows.
◎ (Excellent): There is almost no fuming, no irritating odor that is noticeable to the nose or eyes
○ (Good): Smoke is a little, there is a pungent odor that is noticeable to the nose and eyes, but it does not cause any problems in work.
△ (possible): There is a little smoke, there is an irritating odor that is noticeable to the nose and eyes, and the work is somewhat difficult.
× (No): There is a lot of smoke, there is an irritating odor that is noticeable on the nose and eyes, and molding is impossible.

<Releasing property>
The degree of sticking to the roll when the laminate was separated from the surface of the cooling roll was observed. The evaluation criteria were as follows.
◎ (Excellent): When molded at 100 m / min or more, the laminate peels off from the cooling roll without peeling sound, and the outermost surface of the laminate is clean.
○ (Good): When molded at 100 m / min or more, the laminate has a large peeling sound and the outermost layer surface of the laminate is cloudy, but there is no problem in the range of 100 to 50 m / min.
Δ (possible): Even when molded at 50 m / min or less, the laminated body is slightly separated from the cooling roll, and stringing is seen on the outermost layer surface of the laminated body, or adhesion between the base material and the polyester layer Is broken, or peels off intermittently from the cooling roll, resulting in horizontal streaks entering the laminate.
X (impossible): The laminate is not peeled off from the cooling roll, the base material is cut, and the operation cannot be performed.

(4) Physical property evaluation method of laminate <Adhesiveness between substrate / resin>
The adhesive strength between the resin layer and the paper substrate is indicated by a peel strength (N / 15 mm) when peeled at a peel angle of 180 °, a peel speed of 300 mm / min, and a test piece width of 15 mm. The state was observed. The evaluation criteria of the state were as follows.
Fiber peeling: A state in which cohesive failure of paper is observed over the entire surface of the laminate, no interfacial peeling occurs, and the adhesive strength between the resin layer and the base material layer is sufficient.
Partial fiber peeling: Cohesive failure of paper is observed unevenly, and a part of the laminate is peeled off at the interface.
Interfacial peeling: The paper does not cohesively break, peels off at the interface, and the adhesive strength between the resin layer and the base material layer is weak.
Adhesive failure: A state where there is almost no adhesive strength between paper and resin.

<Thickness unevenness>
The ratio of the average thickness of the central portion to the average thickness within 30 mm from the end portion of the obtained laminate (central maximum thickness / maximum end portion thickness × 100) was evaluated and evaluated. The closer the value is to 100, the less the thickness unevenness. The numerical value of each average thickness is a value obtained by averaging five measured values.

<Punchability>
The punching test was carried out using a 2-hole punch (a punching ability: 16 sheets of 64 g / m ² copy paper). Punching was performed so that the blade of the punch hits the laminated surface, and the number of measurements was 10 times. Comprehensively determine the state of punching.
◎ (Excellent): It can be cut cleanly with a push cutting blade.
○ (Good): The thread is slightly pulled by the press cutting blade.
Δ (possible): The thread is pulled out by the push cutting blade, and 5 or less of 10 pieces are not separated from the surroundings.
X (impossible): There are 5 or more of 10 that cannot be separated from the surroundings with a push cutting blade.

<Biodegradability>
Biodegradability evaluation of the obtained laminate was performed. In the evaluation method, soil having a moisture content of 20% is put in a polyethylene container, samples obtained by punching the laminate into a No. 2 dumbbell shape, and covered with soil having a height of about 1 cm, and a constant temperature of 50 ° C. and 90% RH. It was stored in a constant humidity machine and the change with time was confirmed. The evaluation criteria of the state were as follows.
◎ (Excellent): A state in which the resin layer has completely disappeared in two months after soil embedding.
○ (Good): A state in which the resin layer has almost disappeared in two months after soil embedding.
Δ (possible): The state of the resin layer remains 2 months after the soil is buried, but the resin layer has disappeared after 3 months.
X (impossible): The state in which the shape of the resin layer remains after 3 months have elapsed since the soil was buried.

(5) Manufacture and evaluation result of laminated body (Example 1)
Uses a laminate molding machine capable of laminating two types and two layers (two single-screw extruders with a die width of 500 mm and a screw diameter of Φ40 mm, a combining adapter (two types of two layers), and a three-roll laminator) Then, a cup base paper (250 g / m ² ) was used as a base material.
Aliphatic aromatic polyester (1) (Ecoflex: 100 parts by mass) was used as the resin for the intermediate layer. The extrusion conditions of the intermediate layer are as follows: extruder cylinder set temperature is C1 (hopper side temperature) 230 ° C, C2 (die side temperature) 270 ° C, die part resin temperature (end 250 ° C, central part 260 ° C, end 250 ° C) Set. The tensile elastic modulus of the resin composition constituting the intermediate layer was 70 MPa.
As an outermost layer resin, an aliphatic polyester (3) (FZ91PD: 98 parts by mass) and an antioxidant masterbatch (hereinafter referred to as “antioxidant MB”) (FZ81AN-MB: 2 parts by mass) were dry blended. Used. Extrusion conditions for the outermost layer are as follows: the cylinder set temperature is C1 (hopper side temperature) 230 ° C., C2 (die side temperature) 270 ° C., the die part resin temperature is 250 ° C. at both ends, and the central part 260 ° C. After the discharge state was stabilized, the resin temperature was measured. The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The molten film state of the resin layer was transparent, there were no foreign matters and bubbles, the discharge stability of the extruder was excellent, and the molten film had little resonance. The evaluation of the appearance and stability of the molten film was excellent (◎). In addition, there was some smoke generation, and there was an irritating odor that was noticeable in the nose and eyes, so the evaluation of smoke generation and odor was slightly inferior and acceptable (Δ).

Cup base paper (250 g / m ² , non-laminate type) is fed from a low speed as a base material layer, and is operated at a processing speed of 100 m / min while maintaining the equilibrium moisture content. A laminated body is obtained by laminating a molten film (resin layer) of resin so that the film thickness (operation side: 27 μm, center: 24 μm, drive side: 28 μm) is adjusted while finely adjusting (both ends and center). It was. The discharge of each extruder was adjusted so that the thickness of the resin layer would be the ratio of intermediate layer / outermost layer = 2/8. The air gap (distance from the die outlet to the film film coming into contact with the cooling roll) is 120 mm, the cooling roll is a semi-matt roll with a hard chrome plating treatment, the cooling temperature is 20 ° C., and the nip roll pressure immediately after lamination. Was set to 0.4 MPa.
At the time of laminate molding, it was possible to stably process without peeling noise at a processing speed of 100 m / min, and the evaluation of roll release from the cooling roll was excellent (（).

The obtained laminate was allowed to stand in a thermostatic chamber at 23 ° C. and 50% RH for 2 days, and then the laminate was evaluated.
The evaluation of the adhesiveness between the resin and the base material layer (paper) was as follows: the adhesive strength was 1.64 N / 15 mm, there was no interfacial peeling, and the cohesive failure inside the paper layer was observed uniformly from the end to the center of the laminate. Therefore, the peeled state was “fiber peeling”, and the adhesiveness was at a high level.
Further, the thickness unevenness of the laminate was 93%, which was good with little unevenness.
For the punchability, there was a piece that could not be separated from the surroundings by the punched blade, and the evaluation was acceptable (Δ).
In terms of biodegradability, the shape of the outermost layer of the polyester layer remained almost 2 months after burying the soil, but the paper and the polyester layer were separated, and the decomposition of the intermediate layer progressed. It is considered a thing. In the state after 3 months, all of the polyester had disappeared and it was confirmed that it had biodegradability. Evaluation of biodegradability was acceptable (Δ).
Table 2 shows the layer configuration, the molten resin state, the evaluation of roll release during processing, and the physical property evaluation results of the laminate.

(Example 2)
In Example 1, the resin of the intermediate layer is changed from aliphatic aromatic polyester (1) (Ecoflex: 100 parts by mass) to aliphatic aromatic polyester (2) (PBST: 50 parts by mass) and aliphatic polyester (1) ( (FD92WD: 50 parts by mass) Laminate molding was performed in the same manner as in Example 1 except that the product was changed to a dry blend product. The tensile elastic modulus of the resin composition constituting the intermediate layer was 150 MPa. The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The appearance and stability of the molten film of the resin layer were the same as in Example 1, and the evaluation was excellent (（).
Moreover, there was almost no smoke and odor, and evaluation was excellent ((double-circle)).
The roll-off property at the time of laminate molding was excellent (）) as in Example 1.

The obtained laminate was evaluated in the same manner as in Example 1. The adhesiveness between the resin and the base material layer (paper) was 1.76 N / 15 mm and the peeled state was “fiber peeling”, which was a higher level than in Example 1.
Further, the thickness unevenness of the laminate was 90%, which was slightly lower than that of Example 1, but was good with little unevenness. The punchability was the same as in Example 1, and the evaluation was acceptable (Δ).
In terms of biodegradability, the state of the polyester layer almost decomposed and disappeared when the state after two months after soil embedding was observed, but the paper and polyester layer were separated. This is the decomposition of the intermediate layer. Is considered to have progressed. In the state after 3 months, all of the polyester had disappeared and it was confirmed that it had biodegradability. The biodegradability rate was better than that of Example 1, and the evaluation of biodegradability was good (◯).
Table 2 shows the layer configuration, the molten resin state, the evaluation of roll release during processing, and the physical property evaluation results of the laminate.

(Example 3)
In Example 1, the resin of the intermediate layer is changed from aliphatic aromatic polyester (1) (Ecoflex: 100 parts by mass) to aliphatic aromatic polyester (1) (Ecoflex: 90 parts by mass) and aliphatic polyester (3 ) Laminate molding was carried out in the same manner as in Example 1 except that the dry blend product was changed to (FZ91PD: 10 parts by mass). The tensile elastic modulus of the resin composition constituting the intermediate layer was 300 MPa. The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The molten film state of the resin layer was transparent, there were no foreign matters and bubbles, and the discharge stability of the extruder was excellent, but the resonance of the molten film was a little bad. The appearance and stability of the molten film were slightly lower than in Example 1, but the evaluation was good (◯).
In addition, smoke and odor were the same as in Example 1, and the evaluation was acceptable (Δ).
The roll-off property at the time of laminate molding was the same as in Example 1, and the evaluation was excellent (（).

The obtained laminate was evaluated in the same manner as in Example 1. The adhesiveness between the resin and the base material layer (paper) is 1.56 N / 15 mm, the peeled state is “fiber peeling”, and the adhesive strength between the resin and the paper base material is slightly lower than that of Example 1. However, it was a high level.
Further, the thickness unevenness of the laminate was 90%, which was less than that of Example 1.
The punching performance was such that a small amount of stringing was produced on the small piece punched out by the pressing blade, which was better than Example 1 and the evaluation was good (◯).
In terms of biodegradability, the state of the polyester layer almost decomposed and disappeared when the state after two months after soil embedding was observed, but the paper and polyester layer were separated. This is the decomposition of the intermediate layer. Is considered to have progressed. In the state after 3 months, all of the polyester had disappeared and it was confirmed that it had biodegradability. The biodegradability rate was higher than that of Example 1, and the evaluation of biodegradability was good (◯).
Table 2 shows the layer configuration, the molten resin state, the evaluation of roll release during processing, and the physical property evaluation results of the laminate.

Example 4
In Example 1, the resin in the intermediate layer was changed from aliphatic aromatic polyester (1) (Ecoflex: 100 parts by mass) to aliphatic polyester (1) (FD92WD: 100 parts by mass). Laminate molding was performed in the same manner as described above. The tensile elastic modulus of the resin composition constituting the intermediate layer was 230 MPa. The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The appearance and stability of the molten film of the resin layer were the same as in Example 1, and the evaluation was excellent (（).
Moreover, although there was some smoke generation and some irritating odors on the eyes and nose, the evaluation of smoke generation and odor was good (◯) at a level that is not particularly problematic in work.
The roll-off property at the time of laminate molding was excellent (）) as in Example 1.

The obtained laminate was evaluated in the same manner as in Example 1. The adhesive strength between the resin and the base material layer (paper) is 1.54 N / 15 mm, the peeled state is “fiber peeling”, and the adhesive strength between the resin and the paper base material is slightly lower than that in Example 1. However, it was a high level.
Further, the thickness unevenness of the laminate was 87%, which was slightly lower than that of Example 1, but was good with little unevenness. The punching performance was such that a small amount of stringing was produced on the small piece punched out by the pressing blade, which was better than Example 1 and the evaluation was good (◯).
In terms of biodegradability, the state of the polyester layer almost decomposed and disappeared when the state after two months after soil embedding was observed, but the paper and polyester layer were separated. This is the decomposition of the intermediate layer. Is considered to have progressed. In the state after 3 months, all of the polyester had disappeared and it was confirmed that it had biodegradability. The biodegradability rate was better than that of Example 1, and the evaluation of biodegradability was good (◯).
Table 2 shows the layer configuration, the molten resin state, the evaluation of roll release during processing, and the physical property evaluation results of the laminate.

(Example 5)
Example 1 and Example 1 except that the resin of the intermediate layer was changed from aliphatic aromatic polyester (1) (Ecoflex: 100 parts by mass) to aliphatic polyester (2) (FD99WD: 100 parts by mass) in Example 1. Laminate molding was performed in the same manner. The tensile elastic modulus of the resin composition constituting the intermediate layer was 280 MPa. The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The appearance and stability of the molten film of the resin layer were the same as in Example 1, and the evaluation was excellent (（).
Further, the smoke and odor were the same as in Example 1, and the evaluation was good (◯).
The roll-off property at the time of laminate molding was excellent (）) as in Example 1.

The obtained laminate was evaluated in the same manner as in Example 1. The adhesiveness between the resin and the base material layer (paper) was 1.73 N / 15 mm, the peeled state was “fiber peeling”, and was higher than in Example 1.
Further, the thickness unevenness of the laminate was 93%, which was as good as in Example 1. The punching performance was such that a small amount of stringing was produced on the small piece punched out by the pressing blade, which was better than Example 1 and the evaluation was good (◯).
In terms of biodegradability, the state of the polyester layer almost decomposed and disappeared when the state after two months after soil embedding was observed, but the paper and polyester layer were separated. This is the decomposition of the intermediate layer. Is considered to have progressed. In the state after 3 months, all of the polyester had disappeared and it was confirmed that it had biodegradability. The biodegradability rate was better than that of Example 1, and the evaluation of biodegradability was good (◯).
Table 2 shows the layer configuration, the molten resin state, the evaluation of roll release during processing, and the physical property evaluation results of the laminate.

(Example 6)
In Example 5, the outermost resin was obtained from a dry blend product of aliphatic polyester (3) (FZ91PD: 98 parts by mass) and antioxidant MB (FZ81AN-MB: 2 parts by mass) from aliphatic polyester (3) ( FZ91PD: 68.6 parts by mass), an antioxidant MB (FZ81AN-MB: 1.4 parts by mass) and polylactic acid (Lacia H400: 30.0 parts by mass), except that the dry blend product was used. Lamination was carried out in the same manner as in No. 5. The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The molten film state of the resin layer was translucent, and there were few foreign substances and bubbles, but the resonance of the molten film was poor and was inferior to that of Example 2, but at an acceptable level. Evaluation of the appearance and stability of the molten film was acceptable (Δ).
Moreover, smoke and odor were the same as in Example 5, and the evaluation was good (◯).
The roll release property at the time of laminate molding was the same as in Example 5, and the evaluation was excellent (優秀).

Various evaluations were performed on the obtained laminate in the same manner as in Example 5. The adhesiveness between the resin and the base material layer (paper) was 1.47 N / 15 mm, the peeled state was “fiber peeling”, and the numerical value was lower than that of Example 5, but at a high level.
Further, the thickness unevenness of the laminate was 86%, which was more acceptable than Example 5, but was acceptable. The punchability was superior to that of Example 5, and the evaluation was excellent (◎).
The biodegradability was the same as in Example 5, and the evaluation was good (◯).
Table 2 shows the layer configuration, the molten resin state, the evaluation of roll release during processing, and the physical property evaluation results of the laminate.

(Example 7)
In Example 5, the outermost resin was obtained from a dry blend product of aliphatic polyester (3) (FZ91PD: 98 parts by mass) and antioxidant MB (FZ81AN-MB: 2 parts by mass), polylactic acid (Lacia H400: 100). Laminate molding was carried out in the same manner as in Example 5 except that the weight was changed to (parts by mass). The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The molten film state of the resin layer was translucent, and there were few foreign substances and bubbles, but the resonance of the molten film was poor and inferior to that of Example 5, but at an acceptable level. Evaluation of the appearance and stability of the molten film was acceptable (Δ).
In addition, smoke and odor were good (◯) as in Example 5.
The roll release property at the time of laminate molding was the same as in Example 5, and the evaluation was excellent (優秀).

The obtained laminate was evaluated in the same manner as in Example 5. The evaluation of the adhesion between the resin and the base material layer (paper) was 1.54 N / 15 mm for the adhesive strength and “fiber peeling” for the peeled state, which was lower than that in Example 5, but at a sufficiently high level. It was.
Further, the thickness unevenness of the laminate was 83%, and the end portion was a little thick, but was sufficiently usable. The punchability was improved from that of Example 5 and the evaluation was excellent (（).
In terms of biodegradability, the shape of the outermost layer of the polyester layer remained almost 2 months after burying the soil, but the paper and the polyester layer were separated, and the decomposition of the intermediate layer progressed. It is considered a thing. It was confirmed that all the polyester had disappeared and had biodegradability in the state 3 months after the soil was buried. The biodegradability rate was lower than in Example 5, and the evaluation was acceptable (Δ).
Table 2 shows the layer configuration, the molten resin state, the evaluation of roll release during processing, and the physical property evaluation results of the laminate.

(Comparative Example 1)
In Example 1, the outermost resin layer is made from a dry blend product of aliphatic polyester (3) (FZ91PD: 98 parts by mass) and antioxidant MB (FZ81AN-MB: 2 parts by mass), and the same aliphatic aroma as the intermediate layer. Laminate molding was carried out in the same manner as in Example 1 except that it was changed to group polyester (1) (Ecoflex: 100 parts by mass). The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The appearance and stability of the molten film of the resin layer were the same as in Example 1, and the evaluation was excellent (（).
Moreover, there was fuming, the odor noticed by the nose and eyes was quite bad, and evaluation of fuming and odor was impossible (x).
The roll-off property at the time of laminate molding was remarkably poor, and it was impossible to mold at all, and the evaluation was impossible (x).
Table 2 shows the evaluation results of the layer constitution, the molten resin state, and the roll-off property at the time of processing.

(Comparative Example 2)
In Example 4, the outermost resin is the same aliphatic polyester as the intermediate layer from a dry blend product of aliphatic polyester (3) (FZ91PD: 98 parts by mass) and antioxidant MB (FZ81AN-MB: 2 parts by mass). (1) Laminate molding was performed in the same manner as in Example 4 except that (FD92WD: 100 parts by mass) was changed. The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The appearance and stability of the molten film of the resin layer were the same as in Example 4, and the evaluation was excellent (（).
Moreover, smoke and odor were the same as in Example 4, and the evaluation was good (◯).
Laminate molding discontinuously peels off from the cooling roll even at a processing speed of 50 m / min, and the roll-off property is remarkably bad. Since the processing speed is stable at 10 m / min, the continuous productivity is poor. Yes (△).

The obtained laminate was evaluated in the same manner as in Example 4. The adhesive strength between the resin and the base material layer (paper) is 1.92 N / 15 mm, the peeled state is “fiber peeling”, and the adhesive strength between the resin and the paper base material is higher than that of Example 4, which is very high. It was a high level.
Further, the thickness unevenness of the laminate was 82% and the end portion was slightly thick, but it was in a sufficiently usable state.
The punchability is evaluated by the fact that the same aliphatic polyester (1) as the resin of the intermediate layer is used for the outermost layer, so that it cannot be completely separated even if punched with a press cutting blade. The next processability was poor.
On the other hand, regarding the biodegradability, the shape of the polyester layer almost disappeared when looking at the state one month after burying the soil. The biodegradability rate was higher than that of Example 4, and the evaluation was excellent (◎).
Table 2 shows the layer configuration, the molten resin state, the evaluation of roll release during processing, and the physical property evaluation results of the laminate.

(Comparative Example 3)
In Example 5, the resin of the intermediate layer was changed from aliphatic polyester (2) (FD99WD: 100 parts by mass) to aliphatic polyester (2) (FD99WD: 50 parts by mass) and aliphatic polyester (3) (FZ91PD: 50 parts by mass). Laminate molding was carried out in the same manner as in Example 5 except that the dry blend product was changed to (1). The tensile elastic modulus of the resin composition constituting the intermediate layer was 400 MPa. The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The appearance and stability of the molten film of the resin layer were the same as in Example 5, and the evaluation was excellent (（).
Moreover, smoke and odor were the same as in Example 5, and the evaluation was good (◯).
At the time of lamination molding, when the molding was performed at 100 m / min, a peeling sound was generated from the cooling roll. The evaluation was good (◯).

The obtained laminate was evaluated in the same manner as in Example 5. However, the adhesive strength between the resin and the base material layer (paper) is 1.16 N / 15 mm, and in the peeled state, cohesive failure inside the paper layer is observed unevenly from the end of the laminate to the center. With “partially stripped fibers”, the adhesion was at a low level. Further, the thickness unevenness of the laminate was 93%, which was good as compared with Example 5, with less unevenness.
The punchability was the same as in Example 5, and the evaluation was good (◯).
The biodegradability was higher than that of Example 5 as the polyester layer disappeared completely when the state after two months after soil burial was observed. The evaluation was excellent (◎).
Table 2 shows the layer configuration, the molten resin state, the evaluation of roll release during processing, and the physical property evaluation results of the laminate.

(Comparative Example 4)
Example 1 and Example 1 except that the resin in the intermediate layer was changed from aliphatic aromatic polyester (1) (Ecoflex: 100 parts by mass) to aliphatic polyester (3) (FZ91PD: 100 parts by mass). Laminate molding was performed in the same manner. The tensile elastic modulus of the resin composition constituting the intermediate layer was 550 MPa. The resin temperature at both ends of the die was 225 ° C., and the resin temperature just below the center was 240 ° C.
The molten film state of the resin layer was transparent, there were no foreign matters and bubbles, and the discharge stability of the extruder was excellent, but the resonance of the molten film was a little bad. The appearance and stability of the molten film were slightly lower than in Example 1, but the evaluation was good (◯).
Moreover, smoke generation and odor improved from Example 1, and evaluation was favorable ((circle)).
At the time of laminate molding, the roll-off property from the cooling roll was slightly inferior and a peeling sound was produced at a processing speed of 100 m / min, but it was able to be stably processed, so the evaluation of the roll-off property was good (◯).

The obtained laminate was evaluated in the same manner as in Example 1. Regarding the adhesiveness with the base material layer (paper), the adhesive strength was 0.98 N / 15 mm, and the peeled state was “partially fiber peeling”. The adhesive strength between the resin and the paper substrate was lower than that of Comparative Example 3 and was at a weak level.
Further, the thickness unevenness of the laminate was 90%, good with little unevenness, good punchability (◯), and good biodegradability (◯), both of which were improved from Example 1. Table 2 shows the evaluation results of the molten resin state, the roll-off property during processing, and the physical properties of the laminate.

  As described above, the intermediate layer includes an aliphatic polyester different from the aliphatic polyester contained in the outermost layer, and the intermediate layer is configured using a resin composition having a tensile modulus of 300 MPa or less. The laminate was biodegradable, excellent in processability, and improved in adhesion between the polyester resin layer and the base material layer.

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the present invention is not limited to the embodiments disclosed herein. However, the invention can be appropriately changed without departing from the gist or concept of the invention that can be read from the claims and the entire specification. It should be understood as being included within the scope of the present invention.

Claims (9)

A laminate having a base material layer containing a plant-derived component, an outermost layer containing an aliphatic polyester, and an intermediate layer different from the outermost layer present between the base material layer and the outermost layer, A layered product, wherein the layer contains an aliphatic polyester, and the tensile elastic modulus of the resin composition constituting the intermediate layer is 300 MPa or less. The laminate according to claim 1, wherein the plant-derived component is a fiber containing a plant-derived component or a film containing a plant-derived component. The laminate according to claim 1 or 2, wherein the aliphatic polyester contained in the outermost layer is obtained by polymerizing an aliphatic dicarboxylic acid and an aliphatic diol. The laminate according to any one of claims 1 to 3, wherein the polyester contained in the intermediate layer is obtained by polymerizing a dicarboxylic acid and an aliphatic diol. The laminated body of any one of Claims 1-4 whose thickness is 300 micrometers or less. The laminated body of any one of Claims 1-5 whose tensile elasticity modulus of the resin composition which comprises the said outermost layer is 400 Mpa or more. The bag in which the laminated body of any one of Claims 1-6 was used for at least one part. A liquid container in which the laminate according to any one of claims 1 to 6 is used at least in part. A laminate having a base material layer containing a plant-derived component, an outermost layer containing an aliphatic polyester, and an intermediate layer different from the outermost layer present between the base material layer and the outermost layer, A method for producing a laminate, wherein the intermediate layer is formed using a resin composition containing polyester and having a tensile modulus of 300 MPa or less.