JP2016049629A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a biodegradable laminate having sufficient adhesiveness, roll separability and die-stamping property.SOLUTION: There is provided a laminate having a polyester layer comprising a resin composition containing an aliphatic polyester, and a substrate layer containing a cellulose component. In the laminate, a tensile strain at break in a resin flow direction (MD) of the polyester layer measured by a tensile test based on JIS K7127 is 220% or less.SELECTED DRAWING: None

Description

  The present invention relates to a laminate, and more specifically, a laminate having a polyester layer comprising a resin composition containing an aliphatic polyester and a base material layer containing a cellulose component, wherein the polyester layer has specific tensile properties. It relates to a laminated body.

  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.

  General-purpose resins such as the above-mentioned polyolefin and polyvinyl chloride have a high calorific value at the time of combustion. Therefore, incineration treatment of discarded plastic products may damage the incinerator and does not have sufficient exhaust gas treatment equipment. In such a case, toxic gases such as chlorine and dioxin may be discharged into the atmosphere. Therefore, in some areas, plastic products are collected separately and landfilled. However, since many of the general-purpose resins remain in the form as they are without being decomposed even in the soil, shortening the life of the landfill treatment 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.

  Therefore, in recent years, attempts have been made to apply biodegradable resins to laminated paper so that decomposition occurs together with paper. For example, Patent Document 1 discloses that a laminate having biodegradability can be produced by laminating aliphatic polyester and paper. Patent Documents 2 and 3 describe that a laminate having excellent adhesion and punchability can be produced by using a specific resin for the intermediate layer between the base material layer and the aliphatic polyester layer. . However, even if a laminated body was manufactured according to the description in Patent Documents 1 to 3, it was not possible to obtain a laminated body having sufficient adhesiveness, punchability, and the like.

Japanese Patent Laid-Open No. 6-171050 JP 2012-30547 A JP 2013-226833 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminate that is biodegradable and has sufficient adhesiveness, roll-off property, and punchability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that in a laminate having a polyester layer containing an aliphatic polyester and a base material layer containing a cellulose component, the resin flow direction (MD) of the polyester layer It was found that the punching property of the laminate was improved by adjusting the tensile property of the material to a specific value or less, and the present invention was achieved.

That is, the gist of the present invention resides in the following [1] to [11].
[1] A layered product having a polyester layer comprising a resin composition containing an aliphatic polyester and a base material layer containing a cellulose component, the resin flow of the polyester layer measured by a tensile test in accordance with JIS K7127 A laminate having a tensile fracture strain in the direction (MD) of 220% or less.
[2] The laminate according to [1], wherein the tensile breaking strain in the direction perpendicular to the resin flow of the polyester layer (TD) is 50% or less as measured by a tensile test according to JIS K7127.
[3] The tensile breaking strength in the resin flow direction (MD) of the polyester layer measured by a tensile test according to JIS K7127 is 36 MPa or less, and the tensile breaking strength in the direction perpendicular to the resin flow (TD) is 32 MPa or less. A laminate according to [1] or [2].
[4] The laminate according to any one of [1] to [3], in which the aliphatic polyester includes an aliphatic dicarboxylic acid unit and an aliphatic diol unit as main structural units.
[5] The laminate according to any one of [1] to [4], wherein the aliphatic polyester includes a succinic acid unit and a 1,4-butanediol unit as main structural units.
[6] The laminate according to any one of [1] to [5], wherein the resin composition contains a filler.
[7] The laminate according to any one of [1] to [6], wherein the tensile modulus of the resin composition is 400 MPa or more.
[8] The laminate according to any one of [1] to [7], wherein the base material layer is paper.
[9] The laminate according to any one of [1] to [8], which has a thickness of 300 μm or less.
[10] A bag in which the laminate according to any one of [1] to [9] is used at least in part.
[11] A liquid container in which the laminate according to any one of [1] to [9] is used at least in part.

The laminated body of the present invention has a remarkably improved secondary processability such as punchability than before by disposing a polyester layer having specific tensile properties made of a resin composition containing an aliphatic polyester. It is. Moreover, by using the resin composition which concerns on this invention, the release roll property in extrusion molding is also improved, and the workability to a laminated body is also improving.
The laminate of the present invention has biodegradability, is excellent in processability to the laminate, and is excellent in secondary processability of the laminate, and can be particularly suitably used as a bag or a container.

It is the schematic which shows one Embodiment of the melt-extrusion coating-lamination apparatus 100 used for manufacture of the laminated body of this invention.

  Hereinafter, embodiments of the present invention will be described in more detail. However, the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents and is within the scope of the gist thereof. Various modifications can be made.

  The laminate of the present invention is a laminate having a polyester layer made of a resin composition containing an aliphatic polyester and a base material layer containing a cellulose component, and measured by a tensile test in accordance with JIS K7127. It is characterized in that the tensile breaking strain in the resin flow direction (MD) of the layer is 220% or less. Hereinafter, the polyester layer and the base material layer will be described first, and then the layer structure, production method, application and the like of the laminate will be described in more detail.

(1) Polyester layer <Tensile physical properties of the polyester layer>
First, in the present invention, “tensile breaking strain” means that a polyester layer peeled from a base material layer of a laminate is pulled at a constant speed, and the elongation applied to the test piece is measured during that time. ". The “tensile breaking strength” means the strength at break by measuring the load at break. These tensile properties are values measured by a tensile test according to JIS K7127. The test piece used in the test is a JIS No. 2 dumbbell, the test speed is 500 mm / min, and the distance between chucks is 80 mm. Details of measurement methods other than the above conditions will be described in the Examples section.

  As described above, in the laminate of the present invention, the tensile breaking strain in the resin flow direction (MD) of the polyester layer (hereinafter sometimes referred to as “tensile breaking strain (MD)”) is 220% or less. The tensile breaking strain (MD) is preferably 210% or less, more preferably 170% or less, and still more preferably 100% or less. Although a minimum is not specifically limited, Usually, it is 2% or more, Preferably it is 5% or more, More preferably, it is 7% or more. By setting the tensile breaking strain (MD) within the above range, secondary workability such as punchability of the laminate can be remarkably improved.

  The tensile breaking strain in the direction perpendicular to the resin flow of the polyester layer (TD) (hereinafter sometimes referred to as “tensile breaking strain (TD)”) is usually 50% or less, preferably 45% or less, more preferably. 30% or less. Although a minimum is not specifically limited, Usually, it is 2% or more, Preferably it is 5% or more, More preferably, it is 20% or more. By setting the tensile breaking strain (TD) to the above range, the secondary workability such as punchability of the laminate can be further improved.

  Furthermore, in the laminate of the present invention, the tensile break strength in the resin flow direction (MD) of the polyester layer (hereinafter sometimes referred to as “tensile break strength (MD)”) is 36 MPa or less, and is perpendicular to the resin flow. The tensile breaking strength in the direction (TD) (hereinafter sometimes referred to as “tensile breaking strength (TD)”) is preferably 32 MPa or less.

The tensile strength at break (MD) is more preferably 34 MPa or less, still more preferably 32 MPa or less, and the lower limit is not particularly limited, but is usually 25 MPa or more, preferably 28 MPa or more, more preferably 30 MPa or more. Further, the tensile breaking strength (TD) is more preferably 31 MPa or less, still more preferably 30 MPa or less, and the lower limit is not particularly limited, but is usually 25 MPa or more, preferably 28 MPa or more, more preferably 29 MPa or more.
By setting the tensile strength at break to the above range, secondary workability such as punchability of the laminate can be further improved.

  As will be described later, the tensile properties of the polyester layer, such as tensile breaking strain and tensile breaking strength, include an aliphatic polyester in the resin composition constituting the polyester layer, and further contain a filler as necessary. The extrusion can be controlled as described above by raising the cooling roll temperature above a specific value.

<Resin composition of polyester layer>
A polyester layer is a layer which consists of a resin composition which contains additives, such as other resins other than aliphatic polyester, and various fillers, while containing aliphatic polyester. The content ratio of other resins and additives other than the aliphatic polyester is also arbitrary, but it is preferable to use the aliphatic polyester as a main component. Here, the main component means that the content ratio of the aliphatic polyester in the resin composition becomes the maximum ratio. Further, the content ratio of the aliphatic polyester is preferably more than 50% by mass, more preferably 70% by mass or more, and usually 99.5% by mass or less, preferably 90% by mass or less.

<Aliphatic polyester>
Aliphatic polyester may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The aliphatic polyester is preferably biodegradable. ,
The aliphatic polyester is preferably produced using a part or all of a raw material obtained from biomass resources.

  As the aliphatic polyester in the present invention, the molar ratio of the aliphatic structural unit is the maximum ratio with respect to the entire structural unit of the aliphatic polyester. For example, in addition to the aliphatic structural unit, partially aromatic Those containing an aliphatic aromatic polyester having a structural unit are also included. More specifically, aliphatic polyesters, aliphatic aromatic polyesters, and mixtures thereof can be mentioned. Among them, in order to improve the adhesion and moldability, the aliphatic polyester ratio is preferably more than 50% by mass, more preferably 70% by mass or more, but only the aliphatic polyester is particularly preferable. preferable.

  In the present invention, a preferred aliphatic polyester is formed of a structural unit whose main structural unit is an aliphatic diol component (hereinafter sometimes referred to as “aliphatic diol unit”) and an aliphatic dicarboxylic acid component. Examples thereof include structural units (hereinafter sometimes referred to as “aliphatic dicarboxylic acid units”).

  Here, in this specification, the “main structural unit” means 50 mol% or more with respect to the total amount of each structural unit. Further, the content of each structural unit is preferably 60 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more.

  The aliphatic diol component includes aliphatic diols and derivatives thereof. Specific examples include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, and 1,5-pentane. Preferred examples include diol, 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.

  The aliphatic dicarboxylic acid component includes aliphatic dicarboxylic acids and derivatives thereof. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, heptanedioic acid, octane. Diacid, nonanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, maleic acid, fumaric acid, 1 , 6-cyclohexanedicarboxylic acid, dimer acid, etc., C2-C48 chain or alicyclic dicarboxylic acid. Examples of these derivatives also include esters with alcohols having 1 to 4 carbon atoms such as dimethyl ester and diethyl ester, and acid anhydrides such as succinic anhydride and adipic anhydride. Among these, succinic acid, adipic acid, sebacic acid or their acid anhydrides, and esters thereof with alcohols having 1 to 4 carbon atoms are preferred from the viewpoint of the physical properties of the resulting aliphatic polyester, and in particular, succinic acid, anhydrous Succinic acid or a mixture thereof is preferred.

  More specifically, as the aliphatic polyester, those in which main structural units are a succinic acid unit and a 1,4-butanediol unit are particularly preferable. Polybutylene succinate has higher affinity and penetrability with woody components (lignin and cellulose) than poly (butylene adipate terephthalate) and polylactic acid, and tends to have higher adhesion to the base material layer.

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

  Examples of the structural unit other than the aliphatic diol unit and the aliphatic 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 sometimes referred to as “aliphatic oxycarboxylic acid component”). The structural unit is not particularly limited, and a cyclic unit or a chain unit 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 the aliphatic oxycarboxylic acid include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, Examples also include 2-hydroxyisocaproic acid, 4-hydroxycyclohexanecarboxylic acid, 4-hydroxymethylcyclohexanecarboxylic acid and the like. 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.

  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 used in the present invention includes a trifunctional or higher aliphatic polyhydric alcohol unit, an aliphatic polyvalent carboxylic acid unit, and an aliphatic polyvalent oxycarboxylic acid as a polyfunctional component unit having three or more functional groups. It is also preferred that at least one unit selected from the group consisting of units is present. 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.

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 this lower limit, when the laminate of the present invention is produced by extrusion molding, a neck-in (
The phenomenon that the width of the molten film coming out from the T-die of the extruder becomes narrower in the space until it comes into contact with the substrate, the width of the molten film at the exit of the T-die and the width of the laminated film laminated on the substrate, The difference is shown. ) Increases, or the difference between the film thickness at the end and the thickness at the center increases, and a stable product may not be obtained. On the other hand, if the upper limit is exceeded, the possibility of gelation during the polymerization reaction increases, the load on the motor of the extruder increases remarkably, and the moldability may deteriorate.

  The aliphatic polyester according to the present invention can be obtained by employing a known method relating to the production of polyester. Moreover, the polycondensation reaction in this case should just set the appropriate conditions employ | adopted conventionally, 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.

  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.

  The number average molecular weight (Mn) of the aliphatic polyester is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 10,000 or more, preferably 30,000 or more, and usually 200,000 or less. If the number average molecular weight is below the lower limit, the properties of the molten film during production of the laminate of the present invention may be deteriorated, for example, the neck-in may be increased. On the other hand, if the upper limit is exceeded, the melt viscosity becomes high and the motor load of the extruder becomes high, so that the processing machine stops and it may be difficult to produce a laminate. The method for measuring the number average molecular weight (Mn) is a gel permeation chromatograph (GPC) measurement method using chloroform as a solvent and a measurement temperature of 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 is usually 0.1 g / 10 min or more, preferably 1 g / 10 min or more, more preferably 3 g / It is 10 minutes or more, more preferably 4 g / 10 minutes or more, and usually 45 g / 10 minutes or less, preferably 30 g / 10 minutes or less. If the melt flow rate is lower than the lower limit, the motor load during the production of the laminate of the present invention is 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 resin composition exiting from the die outlet is usually 6 g / 10 minutes or more, preferably 8 g / 10 minutes or more, more preferably 10 g / 10 minutes or more. More preferably, it is 12 g / 10 min or more, and is usually 40 g / 10 min or less, preferably 30 g / 10 min or less. If the melt flow rate is lower than the lower limit, the motor load during the production of the laminate of the present invention is remarkably increased, and the processing machine may be stopped. May deteriorate (increased neck-in, occurrence of surging).

Moreover, as an aliphatic polyester resin used by this invention, you may use a commercial item.
Examples of the aliphatic polyester mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid include GS Pla (registered trademark) AZ series, AD series, FZ series (polybutylene succinate resin) and FD manufactured by Mitsubishi Chemical Corporation. Series (Polybutylene succinate adipate resin), Bionore (registered trademark) manufactured by Showa Denko KK, and aliphatic polyester mainly composed of oxycarboxylic acid are Raisia (registered trademark) manufactured by Mitsui Chemicals, manufactured by Nature Works Ingeo (registered trademark).

<Other resins>
The above-mentioned aliphatic polyester becomes a laminate by laminating the resin composition containing the polyester as a polyester layer on the base material layer. The polyester layer may contain other resins other than the aliphatic polyester.

  Examples of other resins include polyethylene terephthalate, polybutylene terephthalate, ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, ethylene-propylene rubber, polyvinyl acetate, Examples include polybutene. Further, polyamide resins such as 6-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 can be mentioned. . 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 the 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 the total resin components contained in the polyester 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.

  In the present invention, the resin component of the polyester layer is preferably made of only a resin having biodegradability from the viewpoint of degradability. Specifically, the polyester layer is composed only of an aliphatic polyester having an aliphatic dicarboxylic acid unit and an aliphatic diol unit as main structural units, or a fat having an aliphatic dicarboxylic acid unit and an aliphatic diol unit as main structural units. It is preferably composed of a resin composition of an aliphatic polyester and other biodegradable resin, and more preferably composed of only an aliphatic polyester having an aliphatic dicarboxylic acid unit and an aliphatic diol unit as main structural units. As the biodegradable resin other than the aliphatic polyester having an aliphatic dicarboxylic acid unit and an aliphatic diol unit as main structural units, polylactic acid and aliphatic aromatic polyester are preferable.

  In the case of using a resin composition of an aliphatic polyester mainly composed of an aliphatic dicarboxylic acid unit and an aliphatic diol unit and a biodegradable resin other than the polyester layer, from the viewpoint of workability, the polyester layer The blending amount of the aliphatic polyester having the aliphatic dicarboxylic acid and the aliphatic diol as the main structural units is preferably 65% by mass or more based on the total amount of the biodegradable resin contained in the polyester layer, and is 70% by mass. More preferably, it is more preferably 75% by mass or more, and particularly preferably 90% by mass or more. For example, 70 to 95% by mass of an aliphatic polyester having an aliphatic dicarboxylic acid unit and an aliphatic diol unit as main structural units, and 30 to 5% by mass of ECOFLEX (registered trademark) which is polylactic acid or an aliphatic aromatic polyester. The resin composition to be contained is particularly preferable as a polyester layer because it is a complete biodegradable resin composition but has a very small neck-in at the time of molding and an excellent processability.

<Additives>
In the present invention, the polyester layer is not particularly limited as long as it contains an aliphatic polyester, and may contain various additives such as known antioxidants, lubricants, modifiers, and nucleating agents. In particular, the polyester layer preferably contains various fillers.

  The filler is roughly classified into an inorganic filler and an organic filler, and an inorganic filler is preferable. These additives can be used alone or as a mixture of two or more.

Examples of inorganic fillers include anhydrous silica, mica, talc, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, Wollastonite, calcined perlite, silicates such as calcium silicate, sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate, calcium hydroxide, ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, barium sulfate, etc. Examples include salts. Among these, talc, calcium carbonate, titanium oxide, anhydrous silica, and wollastonite are preferable, and talc and calcium carbonate are more preferable.
A commercial item can be used for these inorganic fillers. Specifically, for example, nanotalc [Nanoace (registered trademark) series] manufactured by Nippon Talc Co., Ltd., fine talc [microace (registered trademark) series], LMS100, PKP series manufactured by Fuji Talc Industrial Co., Ltd. and the like can be mentioned.

The physical properties of the inorganic filler are not particularly limited, but the particle diameter D50 (laser diffraction method) is usually 0.5 μm or more, preferably 1.0 μm or more, and usually 25 μm or less, preferably 10 μm or less. The apparent density (JIS K5101) is usually 0.08 g / mL or more, preferably 0.1 g / mL or more, and usually 0.55 g / mL or less, preferably 0.17 g / mL or less. Furthermore, the specific surface area (BET method) is usually 4.0 m ² / g or more, preferably 9 m ² / g or more, and usually 24 m ² / g or less, preferably 16 m ² / g or less. By using the inorganic filler having the physical properties in the above range, the moldability such as the roll-off property and the secondary workability such as the punching property can be further improved.

  The content of the inorganic filler is usually 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, with respect to 100 parts by mass of the resin of the polyester layer. Moreover, it is 80 mass parts or less normally, Preferably it is 70 mass parts or less, More preferably, it is 60 mass parts or less, More preferably, it is 20 mass parts or less. If the content of the inorganic filler is less than the lower limit, there is no effect of addition, and the roll-off property and punchability may be deteriorated. On the other hand, if the upper limit is exceeded, dispersion failure due to aggregation of inorganic fillers, reduction in processing speed due to deterioration of spreadability, deterioration of adhesion to the substrate, and heat seal strength may be reduced. Therefore, by using the inorganic filler in the above range, it is possible to further improve secondary processability such as moldability such as roll-off property and punchability.

  Some inorganic fillers, such as calcium carbonate and limestone, have properties of soil improvers. If a polyester composition derived from biomass containing a particularly large amount of these inorganic fillers is dumped in the soil, Since the inorganic filler after biodegradation remains and functions as a soil conditioner, the significance as a green plastic is increased. 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.

  Examples of the organic filler include raw starch, processed starch, pulp, chitin / chitosan, coconut powder, wood powder, bamboo powder, bark powder, and powders such as kenaf and straw. These may be used alone or as a mixture of two or more. The addition amount of the organic filler is usually 0.01 parts by mass or more, preferably 1 part by mass or more, and usually 70 parts by mass or less, preferably 20 parts by mass or less with respect to 100 parts by mass of the resin of the polyester layer. It is. In particular, this organic filler filler increases its role 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.

  Moreover, in this invention, it is preferable that a polyester layer exists in the outermost layer of the single side | surface of a laminated body, or the outermost layer of both surfaces.

  The laminate having the above layer configuration can be produced by preparing a polyester layer resin composition and using a known method. For example, as will be described later, two or more types of co-extrusion dies as a die shape, a tandem method in which a T-die extruder is arranged in series, or a method of laminating a laminate product twice with a single-layer extruder may be used.

  Furthermore, in the present invention, the melt flow rate (MFR; 190 ° C., 2.16 kg load) of the resin composition constituting the polyester layer is usually 6 g / 10 min or more and 40 g / 10 min or less. The lower limit of the MFR of the resin composition is preferably 8 g / 10 minutes or more, more preferably 10 g / 10 minutes or more, and further preferably 12 g / 10 minutes or more. Moreover, the upper limit of MFR of a resin composition becomes like this. Preferably it is 30 g / 10min or less, More preferably, it is 25 g / 10min or less. By making MFR of the resin composition which comprises a polyester layer into such a range, it is effective in suppression of the surging at the time of a lamination process, suppression of the deterioration of reroll property, and can make workability favorable.

  Moreover, in this invention, the tensile elasticity modulus of the resin composition which comprises a polyester layer is 400 MPa or more normally, Preferably it is 450 MPa or more, More preferably, it is 480 MPa or more. Although an upper limit is not specifically limited, Usually, it is 1000 MPa or less, Preferably it is 900 MPa or less, More preferably, it is 800 MPa or less. If the tensile modulus is too low, the punchability may be deteriorated, and if it is too high, the laminate may be easily cracked when bent. The tensile elastic modulus is a value measured by a method based on JIS K7127.

(2) Base material layer The laminated body of this invention has a base material layer containing a cellulose component at least with a polyester layer. Although it will not specifically limit as a base material if a cellulose component is included, The thing chosen from paper, a nonwoven fabric, and a cellulose nanofiber sheet is preferable, and especially paper is especially preferable. When using a biodegradable aliphatic polyester resin film or sheet as a base material together with a base material containing a cellulose component such as paper, the resulting laminated film (laminated body) becomes biodegradable as a whole. The packaging material can be formed in consideration of the environment. Specific examples of the paper substrate include kraft paper, imitation paper, roll paper, medium quality paper, board, glassine paper, parchment, art paper, board paper, and cardboard base paper. 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 .

  In the laminate of the present invention, other resin layers may be provided in addition to the polyester layer. Also in this case, as the resin, the above-described aliphatic polyester (biodegradable resin) and / or other resins 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 to the total resin components contained in the entire laminate is usually 50% by mass or more, preferably 70% by mass or more. It is preferable to provide another resin layer. The other resin layer may function as a printing layer. In other words, by providing a printing layer with advertisements, pictures, etc. printed on the base material layer and heat-sealing the printed layer and the resin laminate surface during secondary processing, the heat seal strength can be increased. Thus, the yield of the cup molded product can be improved.

(3) Manufacturing method of laminated body In this invention, although the manufacturing method of a laminated body is not specifically limited, For example, it is preferable to manufacture by extrusion molding.

As the extrusion molding method, for example, known techniques described in “Latest Laminating Handbook” (1989 Processing Technology Research Society) can be adopted. Specifically, for example, (a) an extrusion coating method in which a resin composition is melted and applied onto a substrate by extrusion onto a film from a slit die such as a T die, (b) the resin composition is melted, and T An extrusion lamination method, which is a method of applying a layer extruded from a slit die such as a die onto a film, supplying another layer from an unwinder called a sand feeding machine, and bonding them together, (c) Examples include a co-extrusion lamination method in which several resin compositions are extruded with a round die and a multilayer film can be produced in one step.

  In the present invention, a resin composition containing the above-described aliphatic polyester, other resins added as necessary, various fillers, lubricants, antioxidants, modifiers, nucleating agents, and other desired additives. Particularly preferred is a method (extrusion coating method) of extrusion lamination on a substrate using an extruder having a hanger coat type T die. 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.

  The extruded molten film (polyester layer) is applied with pressure in order to adhere to the substrate, and is cooled and solidified with a cooling roll.

  Any conventionally known mixing / kneading techniques can be applied to the preparation of the resin composition. 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. As the kneader, a batch kneader such as a roll or an internal mixer, a single-stage or two-stage continuous kneader, 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 thermoplastic 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.

  The surface temperature of the cooling roll before the polyester layer contacts is usually 36 ° C. or higher, preferably 38 ° C. or higher, more preferably 40 ° C. or higher. Although an upper limit is not specifically limited, Usually, it is 80 degrees C or less, Preferably it is 70 degrees C or less, More preferably, it is 55 or less. If the upper limit is set, the laminate tends to stick to the cooling roll, and it may be difficult to increase the molding speed. On the other hand, when the lower limit is not reached, the adhesiveness, release property and punching property of the laminate may be lowered.

  In the present invention, the tensile break strain in the resin flow direction (MD) of the polyester layer is 220% or less, so that the laminate has excellent secondary workability such as adhesiveness, moldability such as roll-off property, and punchability. The detailed mechanism by which the laminated body can be obtained is unknown, but the laminated body in which the temperature of the cooling roll is raised, the degree of crystallinity is raised and the tensile breaking strain (MD) is reduced, and the tensile breaking strain (by adding filler) The laminate with a reduced MD) has a reduced punching property due to a decrease in the elongation of the film, and the polyester layer has specific physical properties, so that the adhesion of the base material layer is improved, and the punching property is improved. It is considered that a laminate having excellent next processability was obtained.

Hereinafter, the present invention will be described more specifically with reference to the apparatus of FIG. 1 given as an example of the embodiment.
FIG. 1 is a schematic view of a melt extrusion coating and laminating apparatus 100 used for manufacturing a laminate of the present invention. However, the laminate of the present invention does not necessarily have to be manufactured by an apparatus including all of the processes and components described in FIG. 1, and the number of steps can be increased or decreased as appropriate.

The illustrated apparatus 100 is supplied from a base material supply system 10 that supplies a base material fed from a base material feeding portion 11 to a laminating portion via an anchor coat portion 12, and a hopper 21 equipped with an autoloader, a dryer, and the like. A molten resin supply system 20 comprising an extruder 25 having a screw portion in a heating cylinder 22 for extruding and conveying the raw material resin to be melt kneaded, a crosshead portion (not shown), an adapter portion 23 and a die portion 24; And a laminate processing system 30 that press laminates the resin layer (polyester layer) melt-extruded on the substrate and the substrate.

  The base material installed in the base material feeding part 11 of the base material supply system 10 is applied to the base material with a liquid paint obtained by diluting an adhesive or binder resin with an organic solvent or the like in the anchor coat part 12, and is 100 to 120 ° C. And dried for 10 seconds to 5 minutes. Then, a corona discharge treatment is optionally performed. For the same purpose, chemical etching treatment such as flame plasma treatment and chromic acid treatment, surface treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sandblasting may be optionally performed.

  On the other hand, in the molten resin supply system 20, the raw material of the polyester layer containing the aliphatic polyester is put into the hopper 21 and melt-kneaded in the extruder 25. Many aliphatic polyesters have relatively high hygroscopicity, and aliphatic polyesters are also hydrolyzable, so moisture management is necessary, and the resin is previously dehumidified and dried with a hot air drier, vacuum drier, etc. It is preferable. Moreover, when putting resin pellets into the extruder 25, it is preferable to be in a nitrogen atmosphere, and it is also preferable that the hopper 21 includes a hopper dryer. From the viewpoint of resin dehydration, if the film is formed by a vent type twin-screw extruder, the dehydration effect is high and the drying step can be omitted, so that efficient film formation is possible.

  The processing temperature of the polyester layer varies depending on the type of resin. For example, when an aliphatic polyester having an aliphatic dicarboxylic acid unit and an aliphatic diol unit as the main structural unit is used, the inlet temperature of the cylinder in the melt extruder is set to 100 ° C to 230 ° C., set temperature of the die 24 of the extruder 25 is 230 ° C. to 300 ° C., and the resin temperature immediately below the die 24 is measured at each location from the end to the center, and the temperature at each location is ± 10 ° C. of the average It is preferable to control. For this purpose, it is preferable to control the die temperature using a heat block 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 polyester layer, it is preferable to adjust the die temperature. For example, the resin temperature containing the aliphatic polyester immediately below the end of the die is preferably 5 ° C. or more lower than the resin temperature immediately below the center of the die, more preferably 10 ° C. or more. Set the die temperature. 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. Although the specific method is shown below, in order to control thickness, you may use adjustment of a lip opening together.
Depending on its size, the die has a plurality of heat blocks to control the temperature. 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.

  It should be noted that if the resin temperature of the composition of the aliphatic polyester or other resin is too large at the central part and at the end part, the viscosity of the resin will be different in each part, and it will be pressed as a molten resin layer having a uniform thickness from the die 24. 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 25 is extrusion-coated on the substrate from the die 24 so as to have a predetermined thickness. As the die 24, a hanger coat type, a co-extrusion die, 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 or an inner deckle inside the die 24. 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 (polyester layer) that has come out as a molten film from the outlet of the die 24 is subjected to ozone treatment, and then is laminated between the nip roll 31 and the cooling roll 32 via a predetermined air gap G in the laminate processing unit system 30. Crimped to the substrate. In low density polyethylene (LDPE), which is a general-purpose resin, the air gap G is usually set to 120 mm. In the air gap G, the oxygen in the air promotes the oxidation of LDPE and improves the wettability of the surface. Increasing adhesion is a known technique. 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.

  When aliphatic polyester is used, the adhesive force is remarkably improved by narrowing the gap of the air gap G. The upper limit of the air gap G is usually 120 mm or less, preferably 100 mm or less, more preferably 90 mm or less, and the lower limit is usually 50 mm or more, preferably 60 mm or more. If the upper limit is exceeded, the resin temperature will be too low, which may reduce the adhesion to the substrate, and oxidation may be promoted, causing the generation of odors such as oxidized odors. On the other hand, if the value is below the lower limit, it is difficult to install a molten film processing apparatus such as an ozone generator, and the cooling roll 32 and the die 24 are located close to each other, so that the temperature management of the cooling roll 32 may be difficult. is there.

The nip roll 31 for applying pressure to bond the molten film extruded from the outlet of the die 24 and the base material is a roll made of rubber or ceramic, and is made of silicon rubber from the viewpoint of preventing the adhesion of the molten resin. Nip rolls are preferred. Further, the hardness of the nip roll 31 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 of the nip pressure is usually 0.2 MPa or more, preferably 0.4 MPa or more. Moreover, an upper limit is 0.5 MPa or less normally, Preferably it is 0.45 MPa or less. Below the lower limit, the adhesive strength of the laminate may not be sufficient. On the other hand, when the upper limit is exceeded, the nip roll 31 is deformed and the contact area is widened, the pressure per unit area is lowered, and the adhesive strength of the laminate may not be sufficient. Further, the contact position between the molten resin, the base material, and the cooling roll 32 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 32 before coming into contact with the substrate, the resin is cooled and solidified, and an adhesive force may not be obtained. Preferably, the molten resin contacts the substrate and the cooling roll 32 at the same time.

  The kind of the cooling roll 32 can be arbitrarily selected in order to obtain the surface appearance of the target resin layer (polyester 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. Moreover, it is preferable that the temperature of the cooling roll 32 is 36 degreeC or more as above-mentioned.

  By strictly controlling the processing speed for producing the laminate to the operating conditions selected as described above, the processing speed is usually 20 m / min or more, preferably 80 m / min or more, more preferably 120 m / min or more, and further Production on a normal commercial scale of preferably 180 m / min or more is possible. 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.

(4) Thickness of polyester layer and laminate In the laminate of the present invention, the thickness of the resin layer (polyester layer) is not particularly limited, but is preferably 5 µm or more, more preferably 8 µm or more, and further preferably 15 µm or more. The upper limit is usually 100 μm or less, preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. When the upper limit is exceeded, the resin layer may be stretched and uncut after the roll of the laminate product, the roll-off property, the heat sealability is deteriorated, or punching may occur. On the other hand, if the value is below the lower limit, it depends on the performance of the extruder, but the discharge is not stable, thickness unevenness may occur, and the adhesive strength and heat seal strength may be insufficient.

  In addition, the thickness of each layer in the case where the resin layer is composed of two kinds is arbitrary. For example, the laminate is made of polyester layer (A) / polyester layer (B) / base material, and the polyester layer is divided into two layers. When arranged separately (in this case, examples of the polyester layer (A) include polybutylene succinate, and examples of the polyester layer (B) include a polybutylene succinate adipate copolymer having excellent adhesion, Aliphatic-aromatic copolymer polyesters, etc.), and the composition ratio of polyester layer (B) / polyester layer (A) is usually 5/95 to 95/5, preferably 5/95 to 50/50, More preferably, it is 5 / 95-25 / 75, More preferably, it is 10 / 90-20 / 80.

  Although the thickness of a laminated body is not specifically limited, Usually, it is 300 micrometers or less, Preferably it is 280 micrometers or less, More preferably, it is 200 micrometers or less, Usually, 40 micrometers or more, Preferably it is 50 micrometers or more, More preferably, it is 55 micrometers or more.

(5) Use of laminated body The laminated body of this invention is used for packaging container materials, agricultural / civil engineering / fishery materials, etc. by processing.

  Examples of packaging container materials include shopping bags, various bag making, 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, trays, Applicable to cartons, lunch boxes, prepared food containers, food and confectionery packaging materials, food wrap materials, cosmetic and cosmetic wrap materials, diapers, sanitary napkins, pharmaceutical wrap materials, pharmaceutical packaging materials, stiff shoulders, sprains, etc. Various packaging materials such as foods, electronics, medical care, medicines, cosmetics and the like such as packaging materials for surgical patches to be used.

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, when the polyester layer is an aliphatic polyester having a dicarboxylic acid unit and a diol unit as main structural units, it has a high aroma retention and adsorbability as described above. It is preferable as interior materials and packaging materials such as 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.

  The said material should just be what the laminated body of this invention is used for at least one part. Among these materials, various bags and containers are preferable, and a liquid container is particularly preferable as the container.

(6) Paper recycling In the laminate of the present invention, when recovering the laminated paper composed of the resin layer (polyester layer) and paper, the aliphatic polyester is more than the paper by immersing the laminated paper in an alkaline solution. Since it is quickly decomposed, the opened paper fibers can be easily recovered. In the case of polyethylene film, it is difficult to separate the film and paper fiber because it does not decompose, but it is difficult to recycle paper at low cost by using a laminate of the present invention that uses aliphatic polyester. Can be done. At this time, an enzyme that promotes the degradation of the aliphatic polyester may be allowed to act in order to promote the degradation. In addition, since the base material has a resin layer in the present invention, the base material and the polyester layer can be easily separated by using a solvent that dissolves the resin component used in the resin layer (polyester layer). Can do.

  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 describe the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof.

(1) Raw material used Resin (aliphatic polyester); GS Pla FZ71PL MFR = 22 g / 10 min (@ 190 ° C., 2.16 kgf) manufactured by Mitsubishi Chemical Corporation
Inorganic fillers;
Filler A: manufactured by Nippon Talc Co., Ltd. Microace (registered trademark) K-1 Particle size D50 (laser diffraction method) 8.0 μm, apparent density (JIS K5101) 0.25 g / mL, specific surface area (BET method) 7.0 m ² / G
Filler B: Nihon Talc Co., Ltd. Microace (registered trademark) SG-95 Particle diameter D50 (Laser diffraction method) 2.5 μm, Apparent density (JIS K5101) 0.11 g / mL, Specific surface area (BET method) 15.0 m ² / G

  The details of the composition of the resin layers (outermost layers) of Examples and Comparative Examples are as shown in Table 1.

(2) Evaluation method of molten resin state and roll-off property during processing <Appearance and stability of molten film>
The state of the molten film was visually evaluated from the die outlet. The evaluation criteria were as follows.
(Excellent): The molten film is transparent, translucent, or milky white, and is in a normal state without significant aggregation of FE (fish eye), foreign matter, and filler, and without bubbles. It is also excellent without resonance.
○ (Good): The molten film is transparent, translucent, or milky white, and there is no significant aggregation of FE (fish eye), foreign matter, and filler, and there are a few bubbles, but within a range where resonance is allowed at a level that does not cause molding problems. It is.
Δ (possible): The molten film is in a state where there is no significant aggregation of FE (fish eye) or filler with few foreign matters, but the resonance is poor.
X (impossible): The molten film has a lot of FE (fish eye) and foreign matters, or there is significant aggregation of the filler, there are many bubbles and many film cracks occur, and the film cannot be processed.

<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): Little smoke, no irritation to the nose or eyes.
○ (Good): Smoke is slight and there is a slight irritation to the nose and eyes, but at a level that does not cause a problem in work.
△ (possible): Smoke is somewhat, there is irritation to the nose and eyes, work is a little difficult.
× (No): Smoke is abundant, there is irritation to 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 peeling sound and film properties were confirmed while gradually changing the take-up speed under the same extrusion conditions. The evaluation criteria were as follows.
◎ (Excellent): When molded at 15 m / min or more, the film peels off from the cooling roll without peeling sound, and the film surface is clean.
○ (Good): When molded at 15 m / min or more, the peeled sound of the laminate was small and the surface of the laminate was slightly rough.
Δ (possible): When molded at 15 m / min or more, the laminate does not peel off from the cooling roll, and even when molded at 10 m / min or less, the laminate is hardly separated from the cooling roll. A state in which stringing is observed on the surface, or strips are intermittently peeled off from the cooling roll and horizontal stripes enter the laminate.
X (impossible): The state in which the laminate is not peeled off from the cooling roll and cannot be operated.

(3) Evaluation method of physical properties of laminate <Punching property>
The punching property was a punching test using a two-hole punch (a punching ability: 64 g / m ² plain paper 16 sheets). As the punching direction of the blade, punching was performed so that a cylindrical punch blade progressed from the base material surface of the laminated body toward the resin layer, 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.

<Tensile properties of polyester layer>
The tensile test of the resin layer film part (polyester layer) of the obtained laminate was performed, and the tensile breaking strain and the tensile breaking strength were evaluated.
The resin layer was peeled from the laminate in the following procedure.
When the laminate is immersed in water at room temperature and the paper is sufficiently swollen, it is carefully peeled off so that excessive force is not applied to the resin layer, and left in a humidity-controlled room at 23 ° C. and 50% RH for 1 day. do it,
A film for a tensile test was prepared. The test method was an elongation test based on JIS K7127. The test piece was punched with a JIS No. 2 dumbbell. The test direction was 5 sheets each in the direction of the resin flow (MD) and the direction perpendicular to the resin flow (TD). The tensile tester was AGS100 manufactured by Shimadzu Corporation, the test speed was 500 mm / min, and the distance between chucks was 80 mm. For tensile properties, the tensile breaking strength and tensile breaking strain in each direction were measured, and the average tensile breaking strain and average tensile breaking strength were determined from these values. Units are expressed in% and MPa, respectively. The tensile breaking strain was calculated by the following formula.
Tensile breaking strain (%) = [movement distance (mm) / distance between chucks (80 mm)] × 100
The average tensile breaking strain and the average tensile breaking strength are shown by the value obtained by MD and TD and the average value thereof.

(4) Manufacture and evaluation results of laminate <Manufacture of resin composition>
Using aliphatic polyester (GS Pla), filler A and filler B, a resin composition was produced with a biaxial kneader (TEX30α manufactured by Nippon Steel Works) so as to have the composition ratio described in Table 1. . The kneading conditions were a cylinder set temperature of 190 ° C., a rotation speed of 200 rpm, and a discharge of 25 kg / h. The obtained resin composition was pelletized after the molten strand was cooled with water, dried under a nitrogen stream at 70 ° C., and used as a raw material for a film laminate.

<Example 1>
A laminate was produced from the resin composition using a single-layer T-die molding machine (die slip width 300 mm, screw diameter 50 mmφ, L / D 28) equipped with a substrate feeding machine and a take-up machine. Extrusion conditions were set such that the extruder cylinder set temperature was C1 (hopper side temperature) 200 ° C., C2 (die side temperature) 250 ° C., and die part resin temperature (end 250 ° C., central part 250 ° C., end 250 ° C.). A laminate was produced at a take-up speed of 15 m / min using an extruder rotating speed of 15 rpm, an air gap width of 120 mm, and a semi-matt roll having a radius of 150 mm as a cooling roll. The cooling temperature at this time was set to 50 ° C.

The base material is a corona-treated cup base paper (250 g / m ² , non-laminate type), which is fed out from a low speed and brought into contact with the molten film of the resin composition. A laminate was manufactured by sandwiching at a pressure of 4 MPa, and then setting the take-up speed to a predetermined speed.

  The moldability and secondary processability of the obtained laminate were evaluated, and the results are shown in Table 1.

<Examples 2-6, Comparative Examples 1-3>
A laminate was manufactured and evaluated in the same manner as in Example 1 except for the conditions shown in Table 1. The results are shown in Table 1.
In addition, the adhesiveness between the resin and the base material layer (paper) in all the examples and comparative examples in the present invention has sufficient resistance when the resin layer is peeled by hand, and the adhesiveness is at a high level. It was.

G Air gap 10 Base material supply system 11 Base material feeding part 12 Anchor coat part 20 Molten resin supply system 21 Hopper 22 Heating cylinder 23 Adapter part 24 Die part 25 Extruder 30 Laminating part system 31 Nip roll 32 Cooling roll 100 Melt extrusion coating・ Laminating equipment

Claims (11)

  A laminate having a polyester layer made of a resin composition containing an aliphatic polyester and a base material layer containing a cellulose component, the direction of resin flow of the polyester layer measured by a tensile test in accordance with JIS K7127 ( MD) is a laminate having a tensile strain at break of 220% or less.   The laminate according to claim 1, wherein the tensile breaking strain in the direction perpendicular to the resin flow of the polyester layer (TD) measured by a tensile test according to JIS K7127 is 50% or less.   The tensile break strength in the resin flow direction (MD) of the polyester layer measured by a tensile test according to JIS K7127 is 36 MPa or less, and the tensile break strength in the direction perpendicular to the resin flow (TD) is 32 MPa or less. Item 3. A laminate according to item 1 or 2.   The laminate according to any one of claims 1 to 3, wherein the aliphatic polyester contains an aliphatic dicarboxylic acid unit and an aliphatic diol unit as main structural units.   The laminate according to any one of claims 1 to 4, wherein the aliphatic polyester contains a succinic acid unit and a 1,4-butanediol unit as main structural units.   The laminate according to any one of claims 1 to 5, wherein the resin composition contains a filler.   The laminated body of any one of Claims 1-6 whose tensile elasticity modulus of a resin composition is 400 Mpa or more.   The laminate according to any one of claims 1 to 7, wherein the base material layer is paper.   The laminate according to any one of claims 1 to 8, having a thickness of 300 µm or less.   The bag in which the laminated body of any one of Claims 1-9 is used for at least one part.   A liquid container in which the laminate according to claim 1 is used at least in part.

Images