JP2009051210A - Biodegradable resin laminate and its manufacturing process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate containing a biodegradable resin, which has also a superior workability while keeping a biodegradability. <P>SOLUTION: The biodegradable resin laminate has a resin layer containing the biodegradable resin, and has a heat-sealing strength of the laminate of 10 N/15 mm or more. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminate having a resin layer containing a biodegradable resin and a method for producing the same.

  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 poorly decomposable, 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 uses a chain extender (coupling agent) to increase the molecular weight to a specific viscosity range. Biodegradable aliphatic polyester laminates are disclosed. Furthermore, Patent Document 2 discloses a method for obtaining a laminate by controlling the resin pressure during processing without using a coupling agent.
Japanese Patent Laid-Open No. 6-171050 JP 2006-272712 A

  According to the inventor's study, when a resin is produced by the method disclosed in Patent Document 1 and applied to laminated paper, it is necessary to mold at a relatively high temperature in order to obtain a practical adhesive strength. In particular, the use of a resin in which a urethane bond has been introduced by the action of a chain extender has caused problems such as fuming and foaming due to thermal decomposition of the urethane bond, and the molding cannot be performed. Similarly, even in the method disclosed in Patent Document 2, a satisfactory molding condition has not yet been found. Therefore, it has been desired to set more detailed manufacturing conditions.

  In addition, conventional polyolefin-based laminates have a problem of adsorption of aroma components. Conversely, polyethylene terephthalate-based laminates that have low adsorptivity to aroma components and excellent fragrance retention are heat-sealable. There was a problem of shortage. Therefore, the development of a laminated paper having the performance to satisfy both has been awaited.

  Then, an object of this invention is to provide the laminated body which contains the biodegradable resin excellent in workability, maintaining a biodegradable characteristic.

  As a result of intensive studies to solve the above problems, the present inventors have found that excellent workability can be obtained by employing a resin having specific physical properties. It has also been found that by adopting a specific type of resin, it is possible to achieve both excellent processability and fragrance retention.

A first aspect of the present invention is a biodegradable resin laminate having a resin layer containing a biodegradable resin, and the heat seal strength of the laminate measured by the following method (A) is 10 N. / 15mm or more is provided and the said subject is solved.
(Method (A): The above-mentioned two laminates were measured with a heat seal tester under the conditions of 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. The resin layer surfaces are bonded together to create a strip-shaped test piece having a width of 15 mm, and the heat seal strength is measured with a Tensilon universal testing machine at a pulling speed of 300 mm / min.)

  According to this invention, a laminate excellent in biodegradability and processability can be provided.

In this embodiment, the heat seal strength of the laminate measured by the following method (B) is preferably 4 N / 15 mm or more.
(Method (B): resin layer and craft of laminate in heat seal tester under conditions of set temperature 150 ° C., seal bar width 5 mm, seal pressure 0.1 MPa or more, seal time 0.5 seconds to 1.1 seconds. Adhesion with paper makes a strip-shaped test piece with a width of 15 mm, and measures the heat seal strength with a Tensilon universal testing machine at a pulling speed of 300 mm / min.)

  By doing in this way, the laminated body which was excellent in workability can be provided.

  In this embodiment, the resin layer is made of a biodegradable resin that is an aliphatic polyester mainly composed of a dicarboxylic acid and a diol, or is made of a resin composition of the aliphatic polyester and another biodegradable resin. Is preferred.

  Here, “consisting of” means that other resin components are not included as the type of resin, and a small amount of other resin components that are unintentionally contained in the biodegradable resin or in the resin. Any additive component contained in may be contained.

  By doing in this way, it can be set as the laminated body which made the outstanding workability and aroma retention property compatible.

  The biodegradable resin other than the aliphatic polyester mainly composed of dicarboxylic acid and diol is preferably polylactic acid or aliphatic / aromatic polyester.

  By doing in this way, it can be set as the laminated body which was excellent in workability.

  Moreover, it is preferable that the urethane bond amount in aliphatic polyester is 0.90 mass% or less.

  By doing in this way, the laminated body which was excellent in workability can be provided.

  The resin layer preferably contains an antioxidant and / or a lubricant, and the lubricant is a fatty acid metal salt, and the fatty acid constituting the fatty acid metal salt has a carbon chain having 12 to 30 carbon atoms, More preferably, the metal constituting the fatty acid metal salt is any one of alkali metals, alkaline earth metals, and transition metals in the third to fourth periods of the periodic table.

  By doing in this way, it can be set as the laminated body which was excellent in workability.

  Moreover, it is preferable that a laminated body has a base material, and it is preferable that a base material contains at least 1 sort (s) chosen from paper, a nonwoven fabric, a polylactic acid film, and a polyglycolic acid film.

  By doing in this way, it can be set as the laminated body excellent in especially biodegradability.

The second aspect of the present invention is a method for producing a laminate having a resin layer comprising an aliphatic polyester containing at least a dicarboxylic acid and a diol as main components, wherein the resin layer comprises the following (1) to (1) to The present invention solves the above problems by providing a method for producing a laminate, which is characterized by being molded by an extrusion coating method under conditions that satisfy (6).
(1) The blending amount of the aliphatic polyester mainly composed of dicarboxylic acid and diol in the resin layer is 65 parts by mass or more, with 100 parts by mass of the total amount of the biodegradable resin contained in the resin layer.
(2) The temperature of the die of the melt extruder is 230 ° C. or higher and 300 ° C. or lower.
(3) The resin temperature directly under the die is ± 35 ° C. of the die set temperature.
(4) In order to laminate the resin layer on the substrate, the nip pressure when the substrate and the resin layer are pressed between the cooling roll and the nip roll is 0.2 MPa or more and 0.45 MPa or less.
(5) The air gap, which is the distance from the die outlet to the contact with the cooling roll, is 50 mm or more and 120 mm or less.
(6) The MI (melt index; 190 ° C., 2.16 kg load) of the raw resin is 3 g / 10 min or more and 20 g / 10 min or less, and the MI of the molten resin at the die outlet is 6 g / 10 min or more and 35 g / 10 min or less.

  According to this invention, it is possible to efficiently produce a high-quality laminate that achieves both excellent workability and fragrance retention.

  In this embodiment, the amount of urethane bonds in the aliphatic polyester is preferably 0.90% by mass or less.

  By doing in this way, workability can be made more excellent.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body suitable for the packaging material use which has the outstanding workability while having biodegradability can be provided. In addition, if the biodegradable resin component is an aliphatic polyester mainly composed of a dicarboxylic acid and a diol or a composition containing the aliphatic polyester, it is excellent in fragrance retention for an aroma component, so that it is particularly used for food packaging materials. It can be set as the laminated body suitable for. Furthermore, according to the second aspect of the present invention, smoke generation during processing, motor load, sticking to a cooling roll, and the like can be reduced, which is a conventional problem such as odor during processing and insufficient adhesive force. It is possible to efficiently manufacture a high-quality laminate while overcoming the above problems.

  Such an operation and a gain of the present invention will be clarified from the best mode for carrying out the invention described below.

  The biodegradable resin laminate of the present invention (hereinafter also simply referred to as a laminate) has a resin layer containing at least a biodegradable resin. Hereinafter, first, a biodegradable resin serving as a resin layer will be described, and then a laminate of the present invention using the resin will be described in detail.

(1) Biodegradable resin The biodegradable resin as the main component of the resin layer is not limited as long as it is a resin having biodegradability, and any known biodegradation is possible as long as the effects of the present invention are not significantly impaired. Resin can also be used. Moreover, biodegradable resin may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Furthermore, the biodegradable resin may be produced using a raw material partially or entirely obtained from biomass resources.

  Specific examples of biodegradable resins include aliphatic polyester resins, aliphatic / aromatic polyesters, polyamide resins such as 4-nylon, polyamino acid resins such as polyaspartic acid, and polyethers such as polyethylene glycol and polypropylene glycol. Examples thereof include resins, polysaccharides such as cellulose and pullulan, and polyvinyl alcohol resins. Of these, aliphatic polyester resins are preferred because of good moldability.

  In addition, biodegradable resin is not necessarily limited to these examples, The manufacturing method may also be manufactured using any well-known technique, and commercially available biodegradable resin may be used. For example, if an aliphatic polyester resin and aliphatic / aromatic polyester are taken as examples, GS Pla (registered trademark) manufactured by Mitsubishi Chemical Corporation, Bionore (registered trademark) manufactured by Showa Polymer Co., Ltd., and Lacia (registered trademark) manufactured by Mitsui Chemicals, Inc. ), Ecoflex (registered trademark) manufactured by BASF, and Matabi (registered trademark) manufactured by Novamont.

  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 constituents are aliphatic diols and aliphatic dicarboxylic acids.

  That is, the aliphatic polyester suitable for the biodegradable resin in the present invention includes 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). Is an essential constituent 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 a diol represented by the following formula (I) or a derivative thereof (hereinafter, the diol and its derivative are referred to as “diol component” as appropriate), and the dicarboxylic acid unit is represented by the following formula: Those formed from the dicarboxylic acid represented by (II) or a derivative thereof (hereinafter appropriately referred to as “dicarboxylic acid component”) are preferred.

(In Formula (I), R ¹ represents a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain. In Formula (II), R ² represents a divalent aliphatic hydrocarbon group. Represents a 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 of the formula (I) include ester compounds with acetic acid.

  Specific examples of the diol represented by the above formula (I) and derivatives thereof include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 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 of the formula (II) include lower alcohol esters and acid anhydrides of the dicarboxylic acid of the formula (II). Of these, lower alcohol esters or acid anhydrides having 1 to 4 carbon atoms are preferred.

  Specific examples of the dicarboxylic acid represented by the above formula (II) and derivatives thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, heptanedioic acid, octanedioic acid, 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-cyclohexane Usually, a chain or alicyclic dicarboxylic acid having 2 to 48 carbon atoms, such as dicarboxylic acid and dimer acid, may be mentioned. 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. Of these, succinic acid, adipic acid, sebacic acid or acid anhydrides thereof, and esters thereof with these lower alcohols are preferred from the viewpoint of the physical properties of the resulting aliphatic polyester, and in particular, succinic acid, succinic anhydride, or these 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 raw materials for dicarboxylic acids and derivatives thereof, succinic acid converted from plant raw materials or acid anhydrides thereof, and esters with these lower alcohols are preferred.

  The aliphatic polyester suitable as the biodegradable resin 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 formula (III), R ³ represents the same substituent as R ² in formula (II) above.)

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

（式（ＩＶ）において、Ｒ^４は、水素原子または炭素数１〜１０の直鎖もしくは分岐アルキル基を表わす。）

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

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

（式（Ｖ）において、ｐは、０または１〜１０の整数を表わし、好ましくは０または１〜５の整数を表わす。）

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

  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 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 type (i) include structural units formed from malic acid and the like, and specific examples of the type (ii) include structural units formed from glyceric acid and the like.

  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 include units formed from citric acid and 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, exceeding the upper limit is not preferable because there is a problem that the possibility of gelation during the reaction increases, the load on the motor of the extruder increases remarkably, and the moldability deteriorates.

  As a method for producing the 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 of introducing the aliphatic oxycarboxylic acid into the reaction system are not particularly limited as long as it is before the polycondensation reaction between the diol component and the dicarboxylic acid component. For example, (1) the catalyst is preliminarily used as the aliphatic oxycarboxylic acid. 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, unless the objective of this invention is impaired, combined use of another catalyst is not prevented. 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 effects of the present invention are not significantly impaired. 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.

Further, in the polycondensation reaction after the ester reaction and / or transesterification reaction between the dicarboxylic acid component and the diol component, the lower limit of the pressure 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 the 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, more 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 HNMR and ¹³ CNMR. Exceeding the upper limit of the amount of urethane bonds causes decomposition of the urethane bonds during production of the laminate, causing problems with fumes and odors from the molten film from the die outlet, causing film breakage due to foaming in the molten film, and stable molding There are things that cannot be done.

  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 diinocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, 2,4,6-triisopropylphenyl diisocyanate, 4,4'- Examples include known diisocyanates such as diphenylmethane diisocyanate and tolidine diisocyanate.

  Production of high molecular weight polyesters using these chain extenders (coupling agents) can be made using conventional techniques. After the completion of 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 be obtained by reacting the above chain extender with 40,000 or more polyester to obtain a higher molecular weight polyester resin. 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, in the case of further increasing the molecular weight using the above-mentioned diisocyanate as a chain extender, a prepolymer having a weight average molecular weight composed of diol and dicarboxylic acid of 20,000 or more, preferably 40,000 or more is preferable. When the weight average molecular weight is 20,000 or less, the amount of diisocyanate used for increasing the molecular weight is increased, and the heat resistance is lowered, which is not preferable. 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, and most preferably 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 a dioxazoline, a silicate ester, etc. as another chain extender.

  Specific examples of the silicate ester include tetramethoxysilane, dimethoxydiphenylsilane, dimethoxydimethylsilane, and diphenyldihydroxysilane.

  The melting point of the aliphatic polyester preferable as the biodegradable resin used in the present invention is 85 ° C to 200 ° C. If the melting point is less than 85 ° C, the heat resistance when warm food or drink is put in applications such as paper cups and paper trays is insufficient, and the laminated aliphatic polyester composition peels off, melts, or the joints peel off. This is not preferable. On the contrary, if the melting point exceeds 200 ° C., it is not preferable because the heat seal temperature needs to be set high when the laminate is secondarily processed into a cup, sack, tray, bag or the like. The melting point is preferably 90 to 150 ° C, more preferably 100 to 140 ° C. The crystallization temperature is preferably 70 to 100 ° C. 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 is not preferable because it takes time to bond even in the secondary processing of bag making, automatic packaging machines, cup making machines and the like. Further, when the temperature is 98 ° C. or higher, there is a problem in that solidification of the molten film starts between the air gap from the die outlet to the grounding to the base material, and the adhesive force with the base material becomes weak.

  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 index (MI; 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 / min. It is 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 index falls below the lower limit of the above range, the motor load during production of the laminate of the present invention may increase significantly, and the processing machine may stop.On the other hand, if the melt index exceeds the upper limit, the molten film Since stability (increased neck-in and occurrence of surging) may deteriorate, it is not preferable.

  Further, the melt index (MI; 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, more preferably 10 g. / 10 min or more, more preferably 12 g / 10 min or more. Moreover, it is 35 g / 10min or less, Preferably it is 30 g / 10min or less. If the melt index falls below the lower limit of the above range, the motor load during production of the laminate of the present invention may increase significantly, and the processing machine may stop.On the other hand, if the melt index exceeds the upper limit, the molten film Since stability (increased neck-in and occurrence of surging) may deteriorate, it is not preferable.

  The aliphatic polyester that is preferably used in the present invention may contain an unsaturated bond, and the unsaturated bond includes a triple bond as well as a double bond. Examples of such structural units 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.

  Unsaturated linking groups generated in the polymer manufacturing process are also useful. Although the mechanism of formation is not clear, the formation of unsaturated vinyl groups by the conversion reaction to fumaric acid or maleic acid by the dehydration of malic acid added as a polyfunctional component is generated by thermal decomposition of the main chain and malic acid. Conceivable. These unsaturated bonds may be used singly or may be in the form of two or more types contained in the polymer in an arbitrary ratio.

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. The amount of unsaturated bonds is calculated by NMR measurement such as ¹ HNMR and ¹³ CNMR.

  Further, the urethane bond amount in the aliphatic polyester used in the laminate of the present invention is preferably 0.90% by mass or less, more preferably 0.50% 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.

(2-1) Laminate Raw Material and Method for Producing Laminate The above-described biodegradable resin is made into a laminate by being laminated as a resin layer. The resin layer may contain other resins.

  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, and the like. Is mentioned. When using these, 1 or more types of resin can be used together by arbitrary combinations and a ratio.

  When these resins other than aliphatic polyester are used in combination, the ratio of the biodegradable resin 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 resin layer. To do. This is because if the amount of the biodegradable resin is increased, the decomposition rate of the laminate of the present invention is increased, and the deformability after decomposition is improved.

  The resin component of the resin layer of the laminate of the present invention is preferably composed only of a biodegradable resin from the viewpoint of degradability. Specifically, the resin layer is made of only an aliphatic polyester mainly composed of dicarboxylic acid and diol, or an aliphatic polyester mainly composed of dicarboxylic acid and diol and other biodegradable resin. The composition is preferably composed of an aliphatic polyester mainly composed of dicarboxylic acid and diol, and more preferably composed of an aliphatic polyester. 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 resin layer, the dicarboxylic acid and diol in the resin layer are mainly used from the viewpoint of processability. 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 resin 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 a dicarboxylic acid and a diol and 30% by mass of ECOFLEX (registered trademark), which is polylactic acid or an aliphatic / aromatic polyester, has a complete life. Although it is a decomposable resin composition, it is a resin composition that is particularly preferable for the resin layer because it is a resin that has a very small neck-in during molding and has excellent processability.

  The laminate of the present invention preferably has a substrate in order to be processed for various uses. As the base material, resin film bodies and sheet bodies that are usually used as outer layer materials in heat-sealing food packaging materials, laminated bodies of aluminum foil and resin films, non-woven cloth, cellophane, synthetic paper, paper, etc. Is mentioned. As resin films and resin sheet bodies as base materials, not only synthetic resin base materials such as polypropylene, polyester, polyethylene, polyamide, but also films and sheet bodies made of aliphatic polyester resins such as polylactic acid and polyglycolic acid are used. can do.

Especially, it is preferable that the base material of the laminated body of this invention is a thing chosen from paper, a nonwoven fabric, a polylactic acid film, and a polyglycolic acid film. When using a biodegradable aliphatic polyester resin film, sheet, paper, etc. as the base material, the resulting laminated film will be biodegradable as a whole and form an environmentally friendly packaging material. it can. 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 addition, as a constituent layer of the laminate of the present invention, for example, other resin layers such as a printing layer and a gas barrier layer can be arbitrarily set, and a multilayer structure can be taken. It is preferable that the layer containing the aliphatic polyester mainly composed of dicarboxylic acid and diol is in the outermost layer on one side or the outermost layer on both sides of the laminate. In particular, polybutylene succinate and polybutylene succinate adipate copolymer.

  When a layer containing a resin other than the resin layer is provided, the above-described biodegradable resin and / or other resin can be used in any combination and ratio as the resin. However, 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 including the substrate and the resin layer is preferably 50% by mass or more, preferably Is preferably provided with another resin layer so as to be 70% by mass or more.

  The method for obtaining the laminate of the present invention is not particularly limited as long as it satisfies a specific physical property value and may be a commonly used method. For example, known techniques described in "Latest Laminating Handbook" (1989 Processing Technology Research Society) can be employed. The processing methods are listed as follows: (1) A wet lamination method in which a water-soluble or water-dispersed adhesive is applied to a certain layer, the other layers are laminated together in a wet state, and then dried and wound. 2) A hot melt lamination method in which an adhesive is heated (120 ° C. to 160 ° C.) and applied to a melted layer, another layer is bonded, and then the adhesive is hardened and bonded by instantaneous cooling, (3) There is an extrusion coating method in which a resin is melted and extruded onto a film from a slit die such as a T die, and (4) a resin is melted and extruded onto a film from a slit die such as a T die. Extrusion lamination method, which is a method of coating layers and supplying another layer from an unwinder called a sand feeder and bonding them together (5) T Co-extrusion lamination method that can extrude several kinds of resins with a round die and produce a multilayer film in one step, (6) Apply an adhesive dissolved in an organic solvent on the surface of a layer, dry it, etc. (7) Non-solvent to obtain a laminate by applying a urethane-based adhesive to a layer that has been dissolved by heating without a solvent, and then applying another layer with a heating roll. (8) Processing techniques such as thermal lamination, in which a layer is impregnated or coated with a hot melt type, thermosetting type, or thermoplastic type adhesive and the other layer is pressure-bonded with a heating roll. Can be used.

Adhesives in the case of dry lamination include one-component reaction type in which an isocyanate group is incorporated at the end of polyether polyurethane polyisocyanate, polyester polyurethane polyisocyanate, etc., polyester resin such as polyester polyol, polyester polyurethane polyol, etc. Examples thereof include a two-component reaction type urethane system in which a main component having a hydroxyl group of a polyether resin such as an ether polyurethane polyol and a curing agent having an isocyanate group are mixed. The application amount of these adhesives is preferably about 1 to 5 g / m ² .

  As a manufacturing method of the laminate of the present invention, the biodegradable resin described above, other resins added as necessary, lubricants, antioxidants, modifiers, nucleating agents, and the like, which will be described later, are used. A method of extrusion laminating the blended resin composition on a base material using an extruder having a hanger coat type T-die (extrusion coating method), or the above-described biodegradable resin of the present invention by inflation molding or T-die A method of obtaining a laminate by an adhesive or flame treatment after forming a film by a film forming method is preferred, and an extrusion coating method is particularly preferred from the viewpoint of productivity and physical properties of the obtained laminate. 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.

  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. 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 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.

  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 under the conditions including all of the treatments and parts described in FIG. 1, and the number of steps can be increased or decreased as appropriate.

  The illustrated apparatus 100 is a raw material resin supplied from a base material supply system 10 that is supplied from a base material supply part 11 and supplied to a laminating part via an anchor coat part 12, and a hopper 21 equipped with an autoloader, a dryer, and the like. A molten resin supply system 20 composed of an extruder 25 having a screw portion in a heating cylinder 22, a crosshead portion (not shown), an adapter portion 23, and a die portion 24, and a base material. It has a laminate processing system 30 for pressing and laminating the melt-extruded resin layer and the substrate.

  The base material installed in the base material feeding part 11 of the base material supply system 10 is provided with an anchor coat layer in the anchor coat part 12 and subjected to corona discharge treatment. Although this treatment is not essential, it is preferable in that the adhesion with the resin layer can be improved. For the same purpose, chemical etching treatment such as flame plasma treatment, chromic acid treatment, surface treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sand blasting may be performed. Examples of the adhesive for the anchor coat layer include urethane-based, imine-based, butadiene-based, and titanate-based adhesives.

  On the other hand, in the molten resin supply system 20, the raw material for the resin layer containing the biodegradable resin is put into the hopper 21 and melt-kneaded in the extruder 25. Many biodegradable resins have relatively high hygroscopicity, and aliphatic polyesters are also hydrolyzable, so moisture management is necessary, and the resin is dehumidified and dried in advance with a hot air dryer or vacuum dryer. It is preferable to keep it. Further, when the resin pellets are charged into the extruder 25, it is preferably in a nitrogen atmosphere, and it is also preferable that the hopper 21 is fully equipped with 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 water content of the raw material resin to be added is not particularly limited with respect to the polyester in terms of mass ratio, but is usually 0.1 ppm or more, preferably 0.5 ppm or more, more preferably 1 ppm or more, most preferably 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 lot of time to dry, so coloring of biodegradable resin and generation of scum etc. Tend to cause deterioration. On the other hand, when the amount is too large, the molecular weight decreases due to hydrolysis during molding, an appropriate melt viscosity cannot be obtained, and the molten film may not be stable.

  As a method for measuring the water content (water content), a water vaporizer (VA-100 model manufactured by Mitsubishi Chemical Corporation) was used to heat and melt a 0.5 g sample at 200 ° C. to vaporize water in the sample. Thereafter, the amount of water in the sample is determined by quantifying the total amount of water vaporized by a coulometric titration method based on the principle of the Karl Fischer reaction using a trace moisture measuring device (CA-100 model manufactured by Mitsubishi Chemical Corporation). A method is mentioned.

  The processing temperature of the resin layer varies depending on the type of the resin. For example, when an aliphatic polyester resin mainly composed of dicarboxylic acid and diol is used for the resin layer of the present invention, the inlet temperature of the cylinder in the melt extruder is 100 ° C. It is preferable to set the temperature of the die 24 of the extruder 25 to 230 ° C. to 230 ° C. to 300 ° C., and the resin temperature just below the die 24 to the die setting temperature of ± 35 ° C. When the resin temperature of the aliphatic polyester resin and the composition of the resin and other resins reaches a high temperature state of 320 ° C. or more, which is the usual melt extrusion temperature of polyethylene, the viscosity of the resin becomes too low and more uniform than the die 24. It cannot be extruded as a thick molten resin layer.

  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 It is possible to prevent meandering (surging) of the film ears and perform stable laminating. By installing such a guide plate in the die extrusion port, the side edge of the molten resin film layer is positioned and the film thickness of both side edges of the molten resin film is made equal to the center of the film. It has a function to control.

  The resin layer that has come out as a molten film from the outlet of the die 24 is subjected to ozone treatment, and then bonded to the base material between the nip roll 31 and the cooling roll 32 through a predetermined air gap G in the laminate processing unit system 30. Is done. 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 by the 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 G. The upper limit value of the air gap G is 120 mm or less, preferably 100 mm or less, more preferably 90 mm or less, and the lower limit value 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, if the value is below the lower limit, it becomes 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 becomes difficult. It is not preferable.

  The nip roll 31 to which pressure is applied in order to bond the molten film extruded from the outlet of the die 24 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 preferred. Further, the hardness of the nip roll 31 is arbitrarily selected depending on the type of the substrate to be used, but 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, if 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 force 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. If the molten resin comes into contact with the cooling roll 32 before the molten resin comes into contact with the substrate, the resin is cooled and solidified, and an adhesive force cannot be obtained. Preferably, the substrate and the cooling roll 32 are in contact at the same time.

  The kind of the cooling roll 32 can be arbitrarily selected in order to obtain a surface overview of the target resin 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 32 is preferably 10 ° C. or higher and 35 ° C. or lower. If the upper limit is set, the laminate is likely to stick to the cooling roll 32, and it becomes difficult to increase the molding speed. On the other hand, if the value is below the lower limit, water droplets may adhere to the cooling roll 32, which is not preferable.

  By strictly controlling the processing speed for producing the laminate to the operating conditions selected as described above, the processing speed can be produced on a normal commercial scale of 20 m / min or more, and further 180 m / min. is there. As a result, it is possible to form a food packaging material that is excellent in heat sealability and can be filled at high speed.

  The laminate of the present invention may contain various additives such as an antioxidant, a lubricant, a modifier, and a nucleating agent. In particular, the resin layer preferably contains an antioxidant and / or a lubricant.

  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 thereof include BHT, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, octadecyl- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris [(4-tert-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-tert-butyl-4-hydroxybenzyl) -1,3,5 − Ryadin-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-tert-butyl-5,5'-dimethylphenyl) ethane, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl Hindered phenol antioxidants such as -4-hydroxyphenylpropionamide, tridecyl phosphite, diphenyl decyl phosphite, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4, 4'-diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous Reaction of phosphorus antioxidants such as bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 3-hydroxy-5,7-di-tert-butyl-furan-2-one with xylene Examples include lactone antioxidants such as products, sulfur antioxidants such as dilauryl thiodipropionate, distearyl thiodipropionate, etc. These antioxidants may be used alone or in combination. In addition, two or more kinds may be used in any combination and ratio.

  The amount of the antioxidant used is arbitrary as long as the effects of the present invention are not significantly impaired, but with respect to the biodegradable resin, it is 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, it is 5000 ppm or less, More preferably, it is 1000 ppm or less, Most preferably, it is 800 ppm or less. If the lower limit of this range is not reached, the effect of the antioxidant may be reduced, and 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. In the present specification, “ppm” represents a ratio based on mass.

  Although there is no limitation on the specific method of containing the antioxidant, usually, in any step during the production of the laminate, the biodegradable resin and the antioxidant are mixed to form a resin layer of the laminate. An antioxidant is included. 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 antioxidant content is too low, the manufacturing cost will increase, and if the content is too high, the dispersibility of the biodegradable resin and the antioxidant will be poor, so the effect of the antioxidant will be maximized. Can not be pulled out.

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

  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 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, fatty acid amides, and the like. Examples thereof include waxes such as carnauba wax and montan wax, and among these, fatty acid metal salts are particularly preferable.

  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-xylylene bis-12 hydroxystearic acid amide, N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl isophthalic acid amide, , N'- distearyl terephthalic acid amide, N- butyl -N 'stearylurea, N- propyl -N' stearylurea, N- allyl -N 'stearylurea, N- stearyl -N' stearyl urea.

  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 not more than 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 the molding. .

  Examples of the fatty acid metal salt include sodium laurate, potassium laurate, potassium hydrogen laurate, magnesium laurate, calcium laurate, zinc laurate, silver laurate, lithium laurate, lithium myristate, sodium myristate, Potassium hydrogen myristate, magnesium myristate, calcium myristate, zinc myristate, silver myristate, aluminum myristate, lithium palmitate, potassium palmitate, magnesium palmitate, calcium palmitate, zinc palmitate, copper palmitate, palmitate Lead acid, thallium palmitate, cobalt palmitate, sodium oleate, potassium oleate, magnesium oleate, calcium oleate, zinc oleate Lead oleate, thallium oleate, copper oleate, nickel oleate, sodium stearate, lithium stearate, magnesium stearate, calcium stearate, barium stearate, aluminum stearate, thallium stearate, lead stearate, nickel stearate , Beberium stearate, sodium isostearate, potassium isostearate, magnesium isostearate, calcium isostearate, barium isostearate, aluminum isostearate, zinc isostearate, nickel isostearate, sodium behenate, potassium behenate, magnesium behenate, behenine Calcium acid, Barium behenate, Aluminum behenate, Zinc behenate, Behe Nickelate, sodium montanate, potassium montanate, magnesium montanate, calcium montanate, barium montanate, aluminum montanate, zinc montanate, nickel montanate, lithium montanate, sodium octylate, lithium octylate, octylic acid Magnesium, calcium octylate, barium octylate, aluminum octylate, thallium octylate, lead octylate, nickel octylate, bevelium octylate, sodium 12-hydroxystearate, lithium 12-hydroxystearate, magnesium 12-hydroxystearate , Calcium 12-hydroxystearate, barium 12-hydroxystearate, aluminum 12-hydroxystearate, 12-hydroxy Thallium stearate, lead 12-hydroxystearate, nickel 12-hydroxystearate, bebelium 12-hydroxystearate, sodium sebacate, lithium sebacate, magnesium sebacate, calcium sebacate, barium sebacate, aluminum sebacate, sebacin Thallium acid, lead sebacate, nickel sebacate, bevelium sebacate, sodium undecylate, lithium undecylate, magnesium undecylate, calcium undecylate, barium undecylate, aluminum undecylenate, thallium undecylate, lead undecylenate, nickel undecylenate , Bebelium undecylate, sodium ricinoleate, lithium ricinoleate, magnesium ricinoleate, ricino Calcium Le, barium ricinoleate, aluminum ricinoleate, ricinoleic acid thallium, ricinoleic lead, ricinoleic acid nickel, Beberiumu ricinoleic acid 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, there may be a reduction in the contribution to motor load and discharge stability, which is the effect of addition as a lubricant. If the upper limit is exceeded, the manufacturing cost will be too high, or the lubricant may bleed out or produce smoke. Odor may be generated and roll stains may occur during laminate production.

  Although there is no restriction on the specific method of containing the lubricant, usually, in any step during the production of the laminate, the resin and the lubricant are mixed so that the resin layer of the laminate contains the lubricant. . 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.

  A modifier (carboxyl group reactive modifier) is known to improve hydrolysis resistance as described in JP-A-11-80522. As the modifier used in the laminate of the present invention, any compound can be used as long as the biodegradable resin can seal the carboxyl group (carboxy terminus) at the end of the carbon chain. For example, what is used as sealing agent of the carboxyl terminal of a polymer can be used arbitrarily.

  In addition, as a modifier used in the present invention, not only the terminal of the resin is sealed, but also a terminal carboxylic acid generated by thermal decomposition or hydrolysis, or a carboxyl group of an acidic low molecular compound such as lactic acid or formic acid. What can be sealed is 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 modifier may be polyfunctional or monofunctional. Multifunctional modifiers have the advantage of maintaining physical properties such as melt tension when the main chain of the biodegradable resin is cleaved, and the modifier becomes a branching point and improves melt tension. In). In addition, since the monofunctional modifier has less molecular weight and steric hindrance than the polyfunctional type, it has an advantage that it can quickly react with the end of the biodegradable resin and can be sealed.

  As such a modifier, for example, at least one selected from the group consisting of a carbodiimide compound, an isocyanate compound, an epoxide compound, and an oxazoline compound is preferably used.

  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 base 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 diinocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, 2,4, Examples include 6-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 2,2'-m-phenylenebis (2-oxazoline) and 2,2'-p-phenylenebis (2-oxazoline).

  In addition, epoxy compounds such as glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, and alicyclic epoxy compounds, oxazine compounds, and the like are also included as modifiers. Among these, an epoxy compound and a carbodiimide compound are preferable.

  The said modifier 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 carboxyl terminal and acidic low molecular weight compound, from the viewpoint of improving hydrolysis resistance, the acid value of the resin layer of the laminate of the present invention is usually 50 μeq / g or less, preferably 30 μeq. / G or less, more preferably 20 μeq / g. Here, “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) is measured under the following measurement conditions.

  0.5 g of a sample is precisely weighed, put 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 is completely dissolved, the sample is cooled in ice water for 30 to 40 seconds, and then 2 mL of ethyl alcohol is added. While stirring, place a pH electrode in the sample solution, and start neutralization titration by potentiometric titration using a benzyl alcohol solution of 0.01N sodium hydroxide (10% methanol solution).

  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.

Ａ：測定滴定値（ｍＬ）
Ｂ：ブランク測定値（ｍＬ）
Ｆ：０．０１Ｎ水酸化ナトリウムのベンジルアルコール液の力価
Ｗ：試料質量（ｇ）

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 modifier 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, particularly preferably 0.00 parts by mass, based on 100 parts by mass of the biodegradable resin. It is 2 parts by mass or more, 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 an increase in motor load, production of gelation, 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 modifier may be added in an amount that quantitatively blocks the terminal of the polyester acid, 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 the tension and long-term stability, it is desirable that the modifier is present in excess relative to the polyester terminal. Here, the presence of the modifying agent in excess means that the modifying 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 limitation on the specific method of incorporating the modifier into the laminate of the present invention, usually, in any step during the production of the laminate, the biodegradable resin and the modifier are mixed, A modifier is contained in the resin layer of the laminate. For example, it is preferable to use a masterbatch containing a modifier at a high concentration. 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 modifier in a masterbatch, Usually, it is 0.5 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 modifying 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 biodegradable resin to be used is preferable.

  The laminate of the present invention may contain a nucleating agent in order to control the crystallization temperature during production of the laminate and improve 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 singly or in combination of two or more at an arbitrary 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 organic nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, oxalic acid Calcium, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearin Barium acid, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, Organic carboxylic acid metal salts such as luminium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate; organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate; stearamide , Carboxylic acid amides such as 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, polyisopropylene, polybutene, Polymers such as poly-4-methylpentene, polyvinylcycloalkane, polyvinyltrialkylsilane, and high melting point polylactic acid; ethylene-acrylic acid or methacrylic Sodium salt or potassium salt of a polymer having a carboxyl group such as sodium salt of acid copolymer, sodium salt of styrene-maleic anhydride copolymer (so-called ionomer); benzylidene sorbitol and its derivatives, sodium-2,2′-methylenebis (4 , 6-di-t-butylphenyl) phosphate and the like; and 2,2-methylbis (4,6-di-t-butylphenyl) sodium; polyethylene wax and the like.

  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. When the average particle diameter exceeds the upper limit of the above range, there is no effect in increasing the crystallization temperature, which is not preferable. Further, 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 becomes difficult, which is not preferable.

  The preferred 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, particularly preferably 0.00 parts by mass, based on 100 parts by mass of the biodegradable resin. It is 2 parts by mass 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.

  The laminate of the present invention may contain additives other than the antioxidants, lubricants, modifiers, and nucleating agents as long as the effects of the present invention are not significantly impaired. For example, ultraviolet absorbers, light stabilizers (light-proofing agents), antistatic agents, antiblocking agents, mold release agents, antifogging agents, crystal nucleating agents, plasticizers, colorants, fillers, compatibilizing agents, flame retardants, etc. Is mentioned. In particular, it is preferable to contain 10 ppm or more of any one or more of a heat stabilizer, a light stabilizer, an antistatic agent, a compatibilizer, a crystal nucleating agent, and a filler.

  Any light-proofing agent can be used as long as the effects of the present invention are not significantly impaired. Specific examples thereof include decanoic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, a 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-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl) Ru-4-hydroxyphenyl) 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 Hindered amine stabilizers.

  A light stabilizer 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 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, but usually 100 ppm or more, preferably 200 ppm or more, and usually 5 parts by mass or less, preferably 1 with respect to the biodegradable resin. It is 0.5 parts by mass or less, more preferably 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 restriction | limiting in the specific method of containing a light resistance agent, Usually, resin and a light resistance agent are mixed in any process at the time of laminated body manufacture, and a light resistance agent is included in the resin layer of a laminated body. Like that. 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-resistant 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 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol, 2- (4,6-diphenyl-1,3, 5-triazin-2-yl) -5-[(hexyl) oxy] phenol and the like.

  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 incorporating the ultraviolet absorber is not limited, but usually, in any step during the production of the laminate, the resin and the ultraviolet absorber are mixed, and the ultraviolet absorber is added to the resin layer of the laminate. It is made to contain. 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. Examples include those obtained by reacting groups.

  Examples of the compatibilizing agent include aliphatic polyesters, polyolefin resins, polyurethane resins, polycarbonate resins, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, 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 resin such as tellurium and polyacrylic acid ester, polyethylene glycol, polypropylene glycol, poly 1,3-propanediol, polytetramethylene glycol, polyether resin 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, when the resin layer (that is, the biodegradable resin and other resins appropriately used) is composed of two or more kinds of resins, the use of a compatibilizing agent is particularly suitable. is there. 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. Or you may have a resin layer which has this compatibilizing agent between different layers.

  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 such as glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkyldiethanolamine, hydroxyalkyl monoethanolamine, polyoxyethylene alkylamine, polyoxyethylene alkylamine fatty acid ester alkyl There are diethanolamides, and among them, alkyldiethanolamines are preferred from the standpoint 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.

When the blending amount of the antistatic agent is too small, the substantial effect of improving the antistatic property is not recognized. When the blending amount is too large, stickiness occurs on the surface of the obtained laminate, and bleeding out becomes a problem. Odor and smoke generated during molding are also problematic. 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 / □. Using a resistivity meter, measurement is performed according to JIS-K6911.

  The mixing order and mixing method of the resin and the antistatic agent are not particularly limited, but a master batch having a high content of the mixture, for example, a master batch having a content of the mixture of 5 to 20% by mass is prepared. A method of mixing the resin and the resin 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.

  Any filler can be used as long as the effects of the present invention are not significantly impaired. Examples thereof include pigments for coloring, fillers that increase heat resistance and rigidity, and processing stabilizers.

  Any pigment can be used as long as the effects of the present invention are not significantly impaired. The pigment may be an inorganic pigment or an organic pigment. Specific examples of inorganic pigments include chromates such as chrome yellow, zinc yellow and barium yellow, ferrocyanides such as bitumen, sulfides such as cadmium yellow and cadmium red, oxides such as iron black and brown, Examples thereof include silicates such as ultramarine blue, or carbon black such as channel black, roller black, disc, gas furnace black, oil furnace black, thermal black, and acetylene black. Specific examples of organic pigments include azo pigments such as monoazo pigments, disazo pigments, azo lakes, condensed azo pigments, chelate azo pigments, or phthalocyanines, anthraquinones, perylenes, perinones, thioindigos, quinacridones, Examples thereof include polycyclic pigments such as dioxazine, isoindolinone, and quinophthalone.

  Moreover, conventionally well-known various fillers and functional additives can be mix | blended and it can be set as a composition, and can also be added to a laminated body. As functional additives, chemical fertilizers, soil conditioners, plant activators, and the like can be added. 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.

  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, wallastenite. , Calcinated perlite, silicates such as calcium silicate and sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate and calcium hydroxide, salts such as ferric carbonate, zinc oxide, iron oxide, aluminum phosphate and barium sulfate Is mentioned. Content of an inorganic type filler is 1-80 mass% normally with respect to the total amount of composition substances, Preferably it is 3-70 mass%, More preferably, it is 5-60 mass%. 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 can also be used as one kind or a mixture of two or more kinds. 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 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.

  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, relative to 100 parts by mass of the biodegradable resin. More preferably, it is 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 manufacture of the laminated body of this invention.

  In addition, as described above, an antiblocking agent, a release agent, an antifogging agent, a crystal nucleating agent, a colorant, a flame retardant, and 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.

  Although the thickness of the resin layer of the laminate of the present invention is not particularly limited, it is generally preferably 5 μm or more and 300 μm. Moreover, when heat seal strength is calculated | required by a use application, 10 micrometers or more and 50 micrometers or less are preferable, and it is preferable that the thickness nonuniformity of the resin layer shall also be 20% or less. Below the lower limit, the heat seal strength may be insufficient, which is not preferable. When the upper limit is exceeded, the molding time becomes long and the molding cycle becomes long when secondary processing such as bag making and filling packaging is performed. On the other hand, if the thickness unevenness exceeds the upper limit value, the strength of the heat seal portion becomes uneven, which is not preferable.

(2-2) Physical properties of laminate <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 secondary processing is easy. The heat seal strength between the resin layers of the laminate of the present invention is at least 10 N / 15 mm or more, and the upper limit is preferably 25 N / 15 mm or less. Below the lower limit, peeling proceeds with a very weak force, and the peeling type is also interfacial peeling, the adhesive strength is weak, and it is not practical as a packaging material such as breaking the bag. On the other hand, when the value exceeds the upper limit value, it is necessary to set the seal pressure, the seal time, and the seal temperature higher than usual, which is not preferable because the productivity during the secondary processing may be lowered.

  The heat seal strength of the resin layer and the kraft paper is at least 4 N / 15 mm or more, and 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, the adhesive strength is weak, and it is not practical as a packaging material such as breaking the bag. Furthermore, since a corona treatment is required on the surface of a substrate such as kraft paper, the operation becomes complicated, which is not preferable. On the other hand, when the value exceeds the upper limit value, it is necessary to set the seal pressure, the seal time, and the seal temperature higher than usual, which is not preferable because the productivity during the secondary processing may be lowered.

  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. This is a value when a resin layer and kraft paper are bonded to each other, a strip-shaped test piece having a width of 15 mm is prepared, and the heat seal strength is measured with a Tensilon universal testing machine at a pulling speed of 300 mm / min.

  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 not preferable because it requires an extension of the heat sealing time and an increase in the heat sealing pressure, and the sealing strength may not be obtained.

<Adhesive strength>
When the laminate of the present invention has a base material layer, the lower limit value of the adhesive strength between the base material and the resin layer is 0.1 N or more, more preferably 0.3 N or more, and most preferably 0.8 N or more. . Moreover, a preferable upper limit is 2.0 N or less. Below the preferred lower limit, peeling proceeds with a very weak force, the peeling type is also interfacial peeling, and the adhesive strength is weak, which is not practical as a laminate. If the upper limit is exceeded, the paper fibers are peeled off while causing so-called paper peeling, but this is not a problem in practice.

<Incense retention>
In the laminate of the present invention, when the biodegradable resin of the resin layer is an aliphatic polyester mainly composed of a dicarboxylic acid and a diol, a laminate having an aroma retaining property against various odor components can be obtained. Examples of odor components include low-molecular weight terpenes and substances causing malodor such as nitrogen-containing compounds such as ammonia. Although it is known that the principle is generally explained by the solubility parameter, it is not complete by itself, it is necessary to consider crystallinity and the like, and it is not completely understood.

  Generally, in a laminated body, an aroma retaining property may be imparted by setting a multilayer structure or setting a gas barrier layer. In the laminate of the present invention, it is preferable to use an aliphatic polyester mainly composed of a dicarboxylic acid and a diol as the biodegradable resin because it has high aroma retention and the gas barrier layer can be omitted.

The index of fragrance retention is indicated by a permeability coefficient (g / m ² / day) for limonene, which is an aroma component. The range of the transmission coefficient is 600 g / m ² / day or less, preferably 400 g / m ² / day or less, more preferably 200 g / m ² / day or less. The normal lower limit range is 10 g / m ² / day or more, more preferably 50 g / m ² / day or more, and still more preferably 100 g / m ² / day or more. When the upper limit is exceeded, the odor component may be released to the outside through the laminate, which is not preferable. A numerical value less than the lower limit cannot be achieved under normal molding conditions, and is not preferable because it complicates processes such as stretching and thickening of the resin layer.

<Adsorption>
In the laminate of the present invention, when the biodegradable resin of the resin layer is an aliphatic polyester mainly composed of dicarboxylic acid and diol, the adsorptivity to various odor components can also be reduced. As the odor component, a component having a small adsorption amount to a resin of a medicinal component such as a low molecular weight terpene or vitamin is preferable. As with fragrance retention, it is known that it is generally explained by solubility parameters, but it is not complete by itself, and crystallinity and the like need to be considered and is not fully understood.

  The range of the amount of adsorption in the adsorptivity test (see the adsorptivity test method in the following examples) is preferably 5000 ppm or less, more preferably 4000 ppm or less. The normal lower limit range is 100 ppm or more, more preferably 2000 ppm or more, and still more preferably 3000 ppm or more.

  When this laminate is used as a packaging material, if the upper limit is exceeded, the amount of aroma components adsorbed on the resin layer of the laminate is large, which is not preferable because the amount of aroma components from the package is reduced. A numerical value less than the lower limit cannot be achieved under normal molding conditions, and is not preferable because it complicates processes such as stretching and thickening of the resin layer.

<Water vapor permeability>
Water vapor permeability of the laminate of the present invention may vary depending on the configuration, paper and, in the case of laminated paper consisting of an aliphatic polyester composed mainly of dicarboxylic acid and diol, 1000g ^/ m 2 ^/ 24hr or 4000g ^{/ m} 2 ^/ 24 hours or less. When this laminated body is used as a packaging material, if this upper limit is exceeded, the amount of water from the packaging material is remarkably reduced, which is not preferable. On the other hand, if the value is below the lower limit, it cannot be achieved under normal molding conditions, and the process such as stretching and thickening of the resin layer becomes complicated, which is not preferable. 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.

(2-3) Use of laminate <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 bonding method, when a heating type heat seal tester having a seal bar is used, it may be higher than the heat seal expression temperature, and the upper limit is not particularly set. Is 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. If it is below the lower limit, it may not be adhered, which is not preferable. On the other hand, if the value exceeds the upper limit value, the resin is also melted by heating in the vicinity of the seal portion, the film pressure of the resin layer is thinned, 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 0.4 MPa or less, more preferably 0.3 MPa or less. If it is below the lower limit, it may not be adhered, which is not preferable. On the other hand, if the upper limit is exceeded, the membrane pressure 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. If it is below the lower limit, it may not be adhered, which is not preferable. On the other hand, if the value exceeds the upper limit, the film pressure at the end of the seal may be thinned 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 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 / confectionery packaging materials, food wrap materials, cosmetic / 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 biodegradable resin of the resin layer is an aliphatic polyester mainly composed of a dicarboxylic acid and a diol, it has high aroma retention and adsorbability as described above, so that sake, juices, confectionery, etc. Preferred as interior material and 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 the biodegradable resin is an aliphatic polyester, when collecting the laminated paper composed of a resin layer and paper, the aliphatic polyester is made into paper by immersing the laminated paper in an alkaline solution. Since the paper fiber is decomposed more quickly, the opened paper fiber 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 using 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.

  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.

<Melt index (MI)>
Based on JIS K7210, it measured at 190 degreeC and the load 2.16kg using the melt indexer. The unit is g / 10 min.
<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 set to 0.00 ppm of TMS.

<Appearance and stability of molten film>
The state of the molten film was visually observed from the die outlet.
A: The molten film is transparent and is in a normal state free of FE (fish eye), foreign matter and bubbles.
There is also very little surging.
○: The molten film is transparent, FE (fish eye), foreign matter, and bubbles are few, and it is within a range where surging is allowed at a level at which there is no problem in molding.
Δ: The molten film is opaque, and there are many FE (fish eyes) and foreign matters. There are also many surgings.
X: 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.

<Odor>
Sensory tests were conducted on the state of fuming from the die outlet and odor.
○: Smoke is low and there is no irritating odor that is noticeable to the nose or eyes.
Δ: Smoke is generated slightly, but there is a slight irritating odor that is noticeable in the nose and eyes, but it does not cause a problem in work.
X: There is smoke and there is an irritating odor that is noticeable to the nose

<Releasing properties>
The degree of sticking from the cooling roll was observed.
A: The molten film is transparent and is in a normal state free of FE (fish eye), foreign matter and bubbles.
There is also very little surging.
○: The molten film is transparent, FE (fish eye), foreign matter, and bubbles are few, and it is within a range where surging is allowed at a level at which there is no problem in molding.
Δ: The molten film is opaque, and there are many FE (fish eyes) and foreign matters. There are also many surgings.
X: 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.

<Neck-in N. I. >
Trimming was performed so that the thickness accuracy was within a range of ± 3 μm in consideration of thickness unevenness of the laminate, and the effective width of the product was measured.
◎: 95% or more ○: 80% or more Δ: 75% or more ×: No molded product is obtained

<Comprehensive evaluation of moldability>
The overall appearance and stability of the molten film, odor, release property, and NI were comprehensively judged.
A: Very good moldability.
○: Good moldability.
Δ: Although there are some problems, it is a moldable level.
X: There is a serious problem in moldability.

<Adhesive strength>
The adhesive strength between the resin layer and the paper substrate was shown as the strength when peeled at a peeling angle of 180 °, a peeling speed of 300 mm / min, and a test piece width of 15 mm, and the state of peeling between the resin layer and paper was observed.
A: Interfacial peeling did not occur, and cohesive failure of paper was observed.
B: Although there was no problem in practical use, the interface was not peeled off, and a cohesive failure of the paper with slight paper peeling was observed. C: The adhesive strength between the resin and the paper substrate was a weak level, and the interface peeled. Was observed.

<Heat seal strength>
The heat seal strength was determined according to JIS Z 1526. Regarding the preparation of the test piece and the measurement of the heat seal strength, a sample which was allowed to stand at 23 ° C. and 50% RH for 1 day or longer was used as a condition adjustment of the sample.
As a test piece, use a flat part with a membrane pressure of 20 μm as the test piece, cut out vertically and horizontally 15 cm, heat seal one end with a heat sealer so that the resin layer part is aligned, and form a strip with a width of 15 mm. What was cut out was used. At this time, the one sealed at right angles to the film flow direction was defined as the longitudinal seal strength. On the contrary, what was sealed parallel to the film flow direction was defined as the transverse seal strength.
Heat sealing was performed using a single-sided heating bar sealer with a seal bar width of 5 mm at a seal temperature of 150 ° C., a seal pressure of 0.2 MPa, and a seal time of 1 second.
The heat seal strength is a value (N / 15 mm) obtained by measuring the load at a tensile speed of 300 mm / min with a peel angle of 180 degrees using a Tensilon universal testing machine.

<Heat seal strength with paper>
Similar to the above-described conditions for measuring the heat seal strength between the resin layers, the resin layer and the kraft paper were overlapped for heat seal, and the heat seal strength was measured.

(Production Example 1: Preparation of polycondensation catalyst)
62.0 parts by mass of magnesium acetate tetrahydrate was added to a glass eggplant-shaped flask equipped with a stirrer, and 250 parts by mass of absolute ethanol (purity 99% or more) was further added. Furthermore, 41.0 parts by mass of ethyl acid phosphate (mixing mass ratio of monoester and diester was 45:55) was added, and the mixture was stirred at 23 ° C. After confirming that magnesium acetate was completely dissolved after 15 minutes, 75.0 parts by mass of tetra-n-butyl titanate was added. Stirring was further continued for 10 minutes to obtain a uniform mixed solution. This mixed solution was transferred to an eggplant-shaped flask and concentrated under reduced pressure by an evaporator in an oil bath at 60 ° C. After about 1 hour, most of the ethanol was distilled off, leaving a translucent viscous liquid. The temperature of the oil bath was further raised to 80 ° C., and further concentration was performed under a reduced pressure of 667 Pa. The viscous liquid gradually changed from the surface to a powder form, and after about 2 hours, it was completely powdered. Then, it returned to normal pressure using nitrogen, and cooled to room temperature, and pale yellow powder was obtained. The metal element analysis value of the obtained catalyst is as follows: titanium atom content is 10.3 mass%, Mg atom content is 6.8 mass%, phosphorus atom content is 7.8 mass%, Ti / P = 0.85 and Mg / P = 1.1. In addition, a mass reduction rate during production of 39% with respect to the total mass of the raw material excluding the ethanol solvent was observed. Further, a powdery catalyst was dissolved in 1,4-butanediol to prepare a titanium atom of 34000 ppm. The storage stability in 1,4-butanediol was good, and the catalyst solution stored at 40 ° C. under a nitrogen atmosphere did not show the formation of precipitates for at least 40 days. The catalyst solution had a pH of 6.1. In this catalyst solution, absorption derived from alkoxide groups of ethanol, butanol and 1,4-butanediol was not observed on NMR, and it was found that no organic alkoxide group was bonded to the titanium metal of this catalyst. did.

[Production Example 2: Production of aliphatic polyester resin]
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer and a vacuum outlet, 100 parts by mass of succinic acid, 88.5 parts by mass of 1,4-butanediol, and 0.37 parts by mass of malic acid are used as raw materials. The system was placed in a nitrogen atmosphere by nitrogen-vacuum substitution.
Next, the temperature was raised to 230 ° C. over 2.5 hours while stirring in the system to carry out an esterification reaction. Thereafter, the catalyst solution was added. The amount added was 50 ppm as titanium atoms per polyester resin obtained. Thereafter, the mixture was reacted for 6.5 hours under reduced pressure while raising the temperature to 250 ° C. to obtain a white polyester resin. The final pressure reduction degree was 0.07 × 10 ³ Pa. The reduced viscosity (ηsp / c) of the obtained polyester was 2.5, and the acid value of the obtained polyester was 35 μeq / t. MI was 3 g / 10 min.

[Production Example 3: Production of additive masterbatch]
In each Example and Comparative Example, a master batch (MB) of the additive to be used was manufactured in advance so that various additives could be added to the resin at an arbitrary concentration during the laminate molding. As the resin, the resin used in each example and comparative example was used (see the column of resin in Tables 1 and 2). The additives used are as shown in Tables 1 and 2. Specifically, 99 parts by mass of resin and 1 part by mass of various additives are dry blended so that the concentration of various additives MB is 1% by mass, and the kneading temperature is set to 190 ° C. Extruded into a shape, pellets were obtained with a pelletizer, and dried with a hot air dryer under a nitrogen stream at 80 ° C. to obtain MBs of various additives.

[Production of biodegradable resin laminate]
(Example 1)
Dry blend of 95 parts by mass of aliphatic polyester AZ91T (GS-Pla (MI = 3) manufactured by Mitsubishi Chemical Corporation) and 5 parts by mass of CaSt ₂ so that the final concentration of calcium stearate (CaSt ₂ ) is 500 ppm. A hanger coat type T die with a width of 360 mm was used for a single screw extruder with a screw diameter of 40 mmφ, and the cylinder set temperature was C1 (hopper side temperature) 230 ° C., C2 (die side temperature) 280 ° C., and die part temperature 280 ° C. The resin was extruded, the discharge was kept constant at an extruder rotation speed of 100 rpm, and the molten film was awaited for stabilization. After stabilization, the resin temperature (260 ° C.) immediately below the die, resin pressure (9.6 MPa), MI of the raw material resin (6 g / 10 min), and MI of the molten resin at the die outlet (9 g / min) were measured, and the film stability , And odor were observed. The results are shown in Table 1.
Kraft paper (70 g / m ² ) as a base material is fed out at a speed of 50 m / min, subjected to corona treatment (55 W / m ² ), and this is finely adjusted to a film thickness of 20 μm. A laminate was obtained by laminating a molten resin film. The air gap was 120 mm, a mat roll was used as the cooling roll, the cooling temperature was 30 ° C., and the nip roll pressure was set to 0.4 MPa. Table 1 summarizes the roll-off properties from the cooling roll at the time of molding. The obtained laminate was allowed to stand in a thermostatic chamber at 23 ° C. for 2 days, and then the adhesive strength, the state of peeling, the heat seal strength between the laminate layers, and the heat seal strength between the laminate layers and the kraft paper were measured. The physical property evaluation results of the laminate are also shown in Table 1.

  At the time of laminate molding, the molten film was transparent, and had excellent molding stability without blisters, bubbles or smoke. Although the odor was slightly attached to the nose, it was at a level that was not particularly problematic for work. Further, the resin pressure of the extruder was constant at 9.6 MPa, the discharge stability was excellent, and the surging of the molten film was small. The adhesive strength between the resin and the paper substrate was at a level that does not cause any problems in actual use, and the interface was not peeled off, and cohesive failure of the paper was observed. The heat seal strength between the resin layers was 12 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 7 (N / 15 mm).

(Example 2)
Laminate molding was carried out in the same manner as in Example 1 except that CaSt ₂ of Example 1 was changed to magnesium stearate (MgSt ₂ ) and the nip pressure was changed from 0.4 MPa to 0.25 MPa. The results are shown in Table 1. The molten film was transparent and was excellent in molding stability without any buoyancy, bubbles or smoke. Although the odor was slightly attached to the nose, it was at a level that was not particularly problematic for work. The resin pressure of the extruder was constant at 9.7 MPa, the discharge stability was excellent, and the surging of the molten film was small. The MI of the raw material resin was 6 g / 10 min, and the MI of the molten resin at the die outlet was 9.5 g / min. Although the adhesive strength between the resin and the paper substrate is at a level that does not cause any problem in practical use, cohesive failure of the paper with slight peeling of the paper was observed without interfacial peeling. The heat seal strength between the resin layers was 10 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 8 (N / 15 mm).

(Example 3)
Laminate molding was carried out in the same manner as in Example 1 except that CaSt ₂ of Example 1 was changed to zinc stearate (ZnSt ₂ ) and the air gap was changed from 120 mm to 90 mm. The results are shown in Table 1. The molten film was transparent and was excellent in molding stability without any buoyancy, bubbles or smoke. Although the odor was slightly attached to the nose, it was at a level that was not particularly problematic for work. Further, the resin pressure of the extruder was constant at 9.6 MPa, the discharge stability was excellent, and the surging of the molten film was small. The MI of the raw material resin was 6 g / 10 min, and the MI of the molten resin at the die outlet was 9.5 g / min. Although the adhesive strength between the resin and the paper base material is at a level that does not cause a problem in practical use, the interfacial peeling did not occur, and cohesive failure of the paper was observed. The heat seal strength between the resin layers was 18 (N / 15 mm), and the heat seal strength between the resin layers and the kraft paper was 7 (N / 15 mm).

Example 4
A laminate was prepared in the same manner as in Example 3 except that AZ91T in Example 3 was changed to the aliphatic polyester obtained in Production Example 2. The results are shown in Table 1. The molten film was transparent and had excellent molding stability without bubbles, smoke generation and odor. Further, although the resin pressure of the extruder was higher than those of Examples 1 to 3, the pressure was constant at 10 MPa and the discharge stability was excellent. There was little surging of the molten film. The MI of the raw material resin was 4 g / 10 min, and the MI of the molten resin at the die outlet was 11.5 g / min. Although the adhesive strength between the resin and the paper base material is at a level that does not cause a problem in practical use, the interfacial peeling did not occur, and cohesive failure of the paper was observed. The heat seal strength between the resin layers was 17 (N / 15 mm), and the heat seal strength between the resin layers and the kraft paper was 8 (N / 15 mm).

(Example 5)
The final concentration of ZnSt ₂ in Example 4 was changed from 500 ppm to 800 ppm, the air gap was changed from 90 mm to 120 mm, and laminate molding was performed in the same manner as in Example 4 except that. The results are shown in Table 1. The molten film was transparent and had excellent molding stability without bubbles, smoke generation and odor. Although the resin pressure of the extruder was higher than those of Examples 1 to 3, it was at a level with no particular problem in operation because it was constant at 9.8 MPa and excellent in discharge stability. There was little surging of the molten film. The MI of the raw material resin was 4 g / 10 min, and the MI of the molten resin at the die outlet was 12 g / min. Although the adhesive strength between the resin and the paper base material is at a level that does not cause any problem in practical use, cohesive failure causing slight paper peeling was observed without interfacial peeling. The heat seal strength between the resin layers was 14 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 7 (N / 15 mm).

(Example 6)
Antioxidant A (Irganox 1330 (manufactured by Ciba Geigy)) MB was added to Example 3 and blended so that the final addition concentration was 800 ppm, and laminate molding was performed in the same manner as Example 3. The results are shown in Table 1. The molten film was transparent and was excellent in molding stability without any buoyancy, bubbles or smoke. Although the odor was slightly attached to the nose, it was at a level that was not particularly problematic for work. Further, the resin pressure of the extruder was constant at 9.6 MPa, the discharge stability was excellent, and the surging of the molten film was small. The MI of the raw material resin was 6.5 g / 10 min, and the MI of the molten resin at the die outlet was 15 g / min. Although the adhesive strength between the resin and the paper base material is at a level that does not cause a problem in practical use, the interfacial peeling did not occur, and cohesive failure of the paper was observed. The heat seal strength between the resin layers was 19 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 6 (N / 15 mm).

(Example 7)
ZnSt ₂ MB of Example 4 was changed to antioxidant A (Irganox 1330 (manufactured by Ciba Geigy)) MB, blended so that the final added concentration was 800 ppm, and laminate molding was performed in the same manner as Example 4. The results are shown in Table 1. The molten film had high transparency and was excellent in molding stability without bubbles, smoke and odor. In particular, the odor was the lowest in this example, was constant at 9.7 MPa, and was excellent in discharge stability. There was little surging of the molten film. The MI of the raw material resin was 4.0 g / 10 min, and the MI of the molten resin at the die outlet was 18 g / min. Although the adhesive strength between the resin and the paper base material is at a level that does not cause a problem in practical use, the interfacial peeling did not occur, and cohesive failure of the paper was observed. The heat seal strength between the resin layers was 19 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 8.

(Example 8)
The cylinder set temperatures were set to C1 (hopper side temperature) 190 ° C., C2 (die side temperature) 230 ° C., and die part temperature 235 ° C. so that the resin temperature of Example 6 was changed from 260 ° C. to 220 ° C. Laminate molding was performed in the same manner as described above. The results are shown in Table 1. The molten film was transparent, and had excellent molding stability with no irregularities, bubbles, smoke or odor. Moreover, the resin pressure of the extruder was constant at 12 MPa, the discharge stability was excellent, and the surging of the molten film was small. The MI of the raw material resin was 6.5 g / 10 min, and the MI of the molten resin at the die outlet was 7 g / min. Although the adhesive strength between the resin and the paper substrate is at a level that does not cause any problems in actual use, cohesive failure of the paper with slight paper peeling was observed without interfacial peeling. The heat seal strength between the resin layers was 10 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 5 (N / 15 mm).

Example 9
The cylinder set temperatures were set to C1 (hopper side temperature) 240 ° C., C2 (die side temperature) 280 ° C., and die part temperature 295 ° C. so that the resin temperature of Example 6 was changed from 260 ° C. to 280 ° C. Laminate molding was performed in the same manner as described above. The results are shown in Table 1. The molten film was transparent and was excellent in molding stability without any buoyancy, bubbles or smoke. Although the odor was somewhat attached to the nose, it was at a level that was not particularly problematic for work. Further, the resin pressure of the extruder was constant at 8.5 MPa, the discharge stability was excellent, and the surging of the molten film was small. The MI of the raw material resin was 6.5 g / 10 min, and the MI of the molten resin at the die outlet was 20 g / min. Although the adhesive strength between the resin and the paper substrate is at a level that does not cause any problems in actual use, cohesive failure of the paper with slight paper peeling was observed without interfacial peeling. The heat seal strength between the resin layers was 18 (N / 15 mm), and the heat seal strength between the resin layers and the kraft paper was 7 (N / 15 mm).

(Example 10)
Was added ZnSt ₂ masterbatch so that the final concentration of ZnSt ₂ to 500ppm in Example 7, further cylinder temperature so that the resin temperature to 220 ° C. from 260 ° C. C1 (hopper side temperature) 190 ° C., C2 (Die side temperature) 230 ° C. and die part temperature 235 ° C. were set, and laminate molding was carried out in the same manner as in Example 7. The results are shown in Table 1. The molten film was transparent, and had excellent molding stability with no irregularities, bubbles, smoke or odor. Further, the resin pressure of the extruder was constant at 9.9 MPa, the discharge stability was excellent, and the surging of the molten film was small. The MI of the raw material resin was 6.2 g / 10 min, and the MI of the molten resin at the die outlet was 25 g / min. Although the adhesive strength between the resin and the paper substrate is at a level that does not cause any problems in actual use, cohesive failure of the paper with slight paper peeling was observed without interfacial peeling. The heat seal strength between the resin layers was 15 (N / 15 mm), and the heat seal strength between the resin layers and the kraft paper was 7 (N / 15 mm).

(Example 11)
The cylinder set temperature was set to C1 (hopper side temperature) 240 ° C., C2 (die side temperature) 285 ° C., and die part temperature 300 ° C. so that the resin temperature of Example 10 was changed from 260 ° C. to 280 ° C. Example 7 Laminate molding was performed in the same manner as described above. The results are shown in Table 1. The molten film was transparent, and had excellent molding stability with no irregularities, bubbles, smoke or odor. Further, the resin pressure of the extruder was constant at 8.4 MPa, the discharge stability was excellent, and the surging of the molten film was small. The MI of the raw material resin was 6.2 g / 10 min, and the MI of the molten resin at the die outlet was 28 g / min. Although the adhesive strength between the resin and the paper substrate is at a level that does not cause any problems in actual use, cohesive failure of the paper with slight paper peeling was observed without interfacial peeling. The heat seal strength between the resin layers was 19 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 8 (N / 15 mm).

Example 12
Using a hanger coat type T die with a width of 360 mm in a single-screw extruder with a screw diameter of 40 mmφ, Bionore 1010 (MI = 11, manufactured by Showa Polymer Co., Ltd., an aliphatic polyester), an aliphatic polyester. Set the cylinder set temperature to C1 (hopper side temperature) 220 ° C, C2 (die side temperature) 260 ° C, die part temperature 260 ° C, extrude the resin, make the discharge constant at the extruder rotation speed 100rpm, and stabilize the molten film waited. After stabilization, the resin temperature (240 ° C.) and the resin pressure directly under the die were measured, and film stability and odor were observed. Although the odor was slightly attached to the nose, it was at a level that was not particularly problematic for work. Moreover, the resin pressure of the extruder was constant at 10 MPa, the discharge stability was excellent, and the surging of the molten film was small. The MI of the raw material resin was 11 g / 10 min, and the MI of the molten resin at the die outlet was 17 g / 10 min. Although the adhesive strength between the resin and the paper substrate is at a level that does not cause a problem in practical use, partial peeling of the interface was observed. The heat seal strength between the resin layers was 10 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 5 (N / 15 mm).

(Example 13)
Irganox 1330, which is antioxidant A in Example 7, was changed to antioxidant B (Irganox HP2410 (manufactured by Ciba Geigy)), and laminate molding was performed in the same manner as in Example 7. The results are shown in Table 1. The result was almost the same as in Example 7, and was practical as a laminate.

(Example 14)
Irganox 1330, which is antioxidant A in Example 7, was changed to antioxidant C (Irganox 3114 (manufactured by Ciba Geigy)), and laminate molding was performed in the same manner as in Example 7. The results are shown in Table 1. The result was almost the same as in Example 7, and was practical as a laminate.

(Example 15)
The air gap in Example 7 was changed to 120 mm, and laminate molding was performed in the same manner as in Example 7. The results are shown in Table 1. As for the processing status, there was little ear shaking, the film formability was good, and the molding processability was equivalent to that of Example 7. Compared to Example 7, although the neck-in was somewhat larger, it was practical as a laminate. The heat seal strength between the resin layers was 12 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 6.5 (N / 15 mm).

(Example 16)
To 68 parts of the aliphatic polyester of Production Example 2, 7 parts of 1% MB of antioxidant A (Irganox 1330 (Ciba Geigy)) and 25 parts of polylactic acid (Lacia H-400, Mitsui Chemicals) are dry blended and mixed. The smelting temperature was 190 ° C. and extruded into a strand shape with a twin screw extruder, and pellets were obtained with a pelletizer. This was dried at 80 ° C. with a hot air dryer under a nitrogen stream to obtain a resin composition. Using this resin composition, a hanger coat type T die having a width of 360 mm is used in a single screw extruder having a screw diameter of 40 mmφ, the cylinder set temperature is C1 (hopper side temperature) 220 ° C., C2 (die side temperature) 260 ° C., the die part The temperature was set to 275 ° C., the resin was extruded, the discharge was kept constant at an extruder rotation speed of 100 rpm, and the molten film was awaited for stabilization. After stabilization, the resin temperature (270 ° C.) and the resin pressure (9.6 MPa) directly under the die are measured, and the MI of the raw material resin (6.6 g / 10 min) and the molten resin MI at the die outlet (12 g / min) are measured. The film stability and odor were observed. Further, this resin was used for laminate molding in the same manner as in Example 7. The results are shown in Table 2. As for the processing status, there was little ear shaking, the film formability was good, and the molding processability was equivalent to that of Example 7. Further, the neck-in was small and the processing stability was good, so that it was practical as a laminate. The heat seal strength between the resin layers was 12 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 6.5 (N / 15 mm). The average resin thickness of the obtained laminate was 20 μm, and the product effective width in the range of thickness accuracy ± 5 μm was 97%. The evaluation of neck-in was ◎.

(Example 17)
To 63 parts of the aliphatic polyester of Production Example 2, 7 parts of 1% MB of antioxidant A (Irganox 1330 (manufactured by Ciba Geigy)) and 30 parts of polylactic acid (Lacia H-400, Mitsui Chemicals) are added, A resin composition having 30% by mass of lactic acid was obtained. This was molded in the same manner as in Example 16. The results are shown in Table 2. As for the processing status, there was little ear shaking and the film forming property was good. In addition, the neck-in was small and the processing stability was good. The result was almost the same as in Example 15, and was practical as a laminate. The average resin thickness of the obtained laminate was 20 μm, and the product effective width in the range of thickness accuracy ± 5 μm was 97%. The evaluation of neck-in was ◎.

(Example 18)
Molding was performed in the same manner as in Example 17 except that the polylactic acid of Example 17 was changed to modified PBT (Ecoflex, manufactured by BASF Corporation, urethane bond amount 0.45% by mass). The results are shown in Table 2. The processing situation at this time had little ear shaking and good film formability. In addition, the neck-in was small and the processing stability was good. The results were almost the same as in Example 17, and were practical as a laminate. The obtained laminate had an average resin thickness of 20 μm, and an effective product width in the range of thickness accuracy of ± 5 μm was 98%. The evaluation of neck-in was ◎.

(Comparative Example 1)
Using a hanger coat type T die with a width of 360 mm in a single-screw extruder with a screw diameter of 40 mmφ, Bionore 1010 (MI = 11, manufactured by Showa Polymer Co., Ltd., an aliphatic polyester), an aliphatic polyester. , Set the cylinder set temperature to C1 (hopper side temperature) 230 ° C, C2 (die side temperature) 280 ° C, die part temperature 285 ° C, extrude the resin, make the discharge constant at the extruder rotation speed 100rpm, and stabilize the molten film waited. After stabilization, the resin temperature immediately below the die was measured at 262 ° C., the resin pressure (9.7 MPa), and the film stability and odor were observed. The results are shown in Table 1. During the stabilization of the molten film, bubbles entered (foamed) into the molten film, causing film cracking, and in the vicinity of the die, there was a lot of fuming from the molten resin, and the irritating odor was severe, so molding was stopped. The MI of the raw material resin was 11 g / 10 min, and the MI of the molten resin at the die outlet was 38 g / min. Bionore 1010 is an aliphatic polyester obtained by chain-extending a polymer composed of main raw materials of succinic acid and 1,4-butanediol with hexamethylene diisocyanate.

(Comparative Example 2)
Laminate molding was performed in the same manner as in Example 2 except that the additive MB of Example 2 was removed and the nip pressure was changed from 0.25 MPa to 0.15 MPa. The results are shown in Table 1. The molten film was transparent and was excellent in molding stability without any buoyancy, bubbles or smoke. Although the odor was somewhat attached to the nose, it was at a level that was not particularly problematic for work. Moreover, although the resin pressure of the extruder was 11 MPa, the resin pressure and the current value of the motor load were not stable, and the discharge stability was not good. There was also surging of the molten film. The MI of the raw material resin was 4 g / 10 min, and the MI of the molten resin at the die outlet was 38 g / min. Separation from the cooling roll was poor and long-time molding was difficult. The adhesive strength between the resin and the paper substrate was such that interface peeling occurred and the adhesive strength was low. The heat seal strength between the resin layers was 8 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 8 (N / 15 mm).

(Comparative Example 3)
Laminate molding was carried out in the same manner as in Example 3 except that the final concentration of ZnSt ₂ in Example 3 was changed from 500 ppm to 5000 ppm and the nip pressure was changed from 0.25 MPa to 0.15 MPa. The results are shown in Table 1. The molten film was transparent, and there was no generation of blisters or bubbles, and the molding stability was excellent. Smoke was somewhat high and odor was slightly attached to the nose, but it was at a level that was not a problem for work. Further, the resin pressure of the extruder was constant at 10 MPa, the discharge stability was excellent, and the surging of the molten film was small. The MI of the raw material resin was 6 g / 10 min, and the MI of the molten resin at the die outlet was 18 g / min. Although the adhesive strength between the resin and the paper base material is at a level that does not cause a problem in practical use, the interfacial peeling did not occur, and cohesive failure of the paper was observed. The heat seal strength between the resin layers was 6 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 8 (N / 15 mm). Moreover, although the roll release property was very excellent, roll stains appeared remarkably about 15 minutes after the operation.

(Comparative Example 4)
Laminate molding was carried out in the same manner as in Example 1 except that CaSt ₂ in Example 1 was changed to LiSt. The results are shown in Table 1. During the stabilization of the molten film, it was observed that bubbles entered the foamed film (foaming), causing film cracking and a decrease in molecular weight. Further, the resin pressure of the extruder at that time was 8.9 MPa. The MI of the raw material resin was 6 g / 10 min, and the MI of the molten resin at the die outlet was 40 g / min.

(Comparative Example 5)
Laminate molding was carried out in the same manner as in Example 7 except that the nip pressure in Example 7 was changed from 0.4 MPa to 0.15 MPa. The results are shown in Table 1. The molten film had high transparency and was excellent in molding stability without bubbles, smoke and odor. In particular, the odor was the smallest in this example, the resin pressure was constant at 9 MPa, and the discharge stability was excellent. There was little surging of the molten film. However, interfacial peeling occurred between the resin and the paper substrate, and the adhesive strength was low. The heat seal strength between the resin layers was 6 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 6 (N / 15 mm).

(Comparative Example 6)
The raw material resin was changed to Novatex LC720 (MI = 9.5) manufactured by Nippon Polyethylene Co., Ltd., which is a low density polyethylene, and the cylinder set temperatures in Example 1 were C1 (hopper side temperature) 230 ° C., C2 (die side temperature) 295 C. and a die part temperature of 300.degree. C., and the resin temperature was changed to 270.degree. The results are shown in Table 1. The resin pressure was constant at 7.2 MPa and the discharge stability was excellent. The heat seal strength between the resin layers was 8 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 1 (N / 15 mm) or less.

(Comparative Example 7)
The cylinder set temperatures were set to C1 (hopper side temperature) 230 ° C., C2 (die side temperature) 295 ° C., and die part temperature 300 ° C. so that the resin temperature of Example 7 was changed from 260 ° C. to 325 ° C. Laminate molding was performed in the same manner as described above. The results are shown in Table 1. The molten film was transparent, free from bumps and bubbles, and excellent in molding stability. However, smoke and odor were the worst in this example. Also, although the resin pressure of the extruder is constant at 7.6 MPa and the discharge stability is excellent, the surging of the molten film is large, the neck-in is large, the ears are thick, the thickness is uneven, and the adhesive strength is also in the center. There was a big difference at the edge. The MI of the raw material resin was 6 g / 10 min, and the MI of the molten resin at the die outlet was 38 g / min. The adhesive strength between the resin and the paper substrate was at a weak level, and interface peeling was observed. The heat seal strength between the resin layers was 6 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 5 (N / 15 mm).

(Comparative Example 8)
The final concentration of the antioxidant A in Example 7 was changed from 800 ppm to 5000 ppm, and laminate molding was performed. The results are shown in Table 1. The molten film was transparent, free from bumps and bubbles, and excellent in molding stability. However, the smoke was terrible. In addition, although the resin pressure of the extruder is constant at 7.0 MPa and excellent discharge stability, the surging of the molten film is large, the neck-in is large, the ears are thick, the thickness is uneven, and the adhesive strength is also in the middle. There was a big difference at the edge. The MI of the raw material resin was 7 g / 10 min, and the MI of the molten resin at the die outlet was 35 g / min. The adhesive strength between the resin and the paper substrate was at a weak level, and interface peeling was observed. The heat seal strength between the resin layers was 9 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 5 (N / 15 mm).

(Comparative Example 9)
7 parts of 1% MB of antioxidant A (Irganox 1330) and 40 parts of polylactic acid (Lacia H-400, manufactured by Mitsui Chemicals) were added to 53 parts of the aliphatic polyester of Production Example 2 of Example 16. A 30% by mass resin composition was obtained. This was molded in the same manner as in Example 16. The results are shown in Table 2. As for the processing status, there was little ear shaking and the film forming property was good. In addition, the neck-in was small and the processing stability was good. The result was almost the same as in Example 16, and was practical as a laminate. The average resin thickness of the obtained laminate was 20 μm, and the product effective width in the range of thickness accuracy ± 5 μm was 97%. The evaluation of neck-in was ◎. The adhesive strength between the resin and the paper substrate was at a weak level, and interface peeling was observed. The heat seal strength between the resin layers was 9 (N / 15 mm), and the heat seal strength between the resin layer and the kraft paper was 2 (N / 15 mm).

(Comparative Example 10)
A resin composition obtained by changing the modified PBT of Example 18 (Ecoflex, manufactured by BASF Corp., urethane bond amount: 0.45% by mass) to 45% by mass was obtained. This was molded in the same manner as in Example 17. The results are shown in Table 2. Smoke and odor were very bad, and it was observed that bubbles entered the foamed film (foaming) during the stabilization of the melted film, resulting in film cracking and a decrease in molecular weight. This seems to be due to the decomposition of urethane bonds contained in Ecoflex.

[Performance test of laminated body as packaging material]
A performance test as a packaging material was performed on the laminates of Example 6, Example 7, and Comparative Example 6 from the laminates prepared above. Evaluation methods and results are as follows.

<Incense retention test>
Put 50g of aroma components (D-limonene, manufactured by Wako Pure Chemical Industries, Ltd.) into a 50ml sample bottle, and cover the top of the sample bottle with a laminate with the resin layer down, 23 ° C, 50% RH Left in a constant temperature room. With the passage of time, the amount of decrease in the fragrance component was measured, and the transmission coefficient was determined by the following equation. The results are shown in Table 3.
Reduction amount per day (g) / effective area (m ² ) = permeation coefficient (g / m ² / day)

<Adsorption test>
The film portion of the laminate after the fragrance retention test was extracted with an organic solvent, and the amount of the fragrance component was quantified by GC (gas chromatography) by the following description method.
About 1.5 (± 0.5) g of the sample was filled in a heat desorption tube (TERS tube manufactured by GERSTEL), and quartz wool (manufactured by GLsciences) was packed at both ends. This TDS tube was inserted into a heat desorption apparatus (TDS3 manufactured by GERSTEL) at 40 ° C., and the inside of the tube was replaced with helium. Thereafter, the temperature of the TDS tube was increased to 280 ° C. at a rate of 60 ° C./min, and heat extraction was performed at this temperature for 10 minutes. During this heating period, GC injection (CIS4 manufactured by GERSTEL) filled with quartz wool was cooled to −150 ° C. to collect volatile components generated from the sample. The components collected by cooling at the GC inlet were vaporized by rapidly heating the collected portion (CIS4) to 320 ° C. and introduced into the GC column.
Separately, to prepare a calibration curve, prepare approximately 800 μg / mL and 8000 μg / mL solutions of D-limonene using hexane (Wako Pure Chemicals, reagent grade) as a solvent as a standard solution for quantification, and add 1 μL of these solutions. The sample was added to a TDS tube filled with quartz wool, DTE sampling was performed at 280 ° C. for 5 minutes, and a calibration curve was prepared by GC / IIS measurement under the same conditions as the sample. Using this calibration curve, the amount of aroma components adsorbed by the laminate was quantified. The results are shown in Table 3.

<Biodegradability test>
Gardening soil was put in a sealed plastic container of 30 cm × 30 cm × 10 cm to a height of about 6 cm, a 4 cm × 4 cm test piece was placed on the soil, and the soil was placed thereon so as to have a height of about 1 cm. It was placed in a constant temperature and humidity chamber at 50 ° C. and 90% RH, and the mass change and shape change of the laminated paper were measured over time. The results are shown in Table 3.
A: There is a hole in the film in one month, and the film is hardly shaped.
X: The state in which the shape of the film part is maintained even after one month.

  As is clear from Table 3, the laminate of the present invention has a very low permeability coefficient and adsorption amount compared to the laminate of Comparative Example 6, is excellent in biodegradability, and is a laminate suitable for packaging materials. It turns out that it is a body.

<Odor sensory test>
For the laminates obtained in Example 6, Example 7 and Comparative Example 6, each laminate was formed into a 10 cm x 11 cm three-sided sealing bag with a heat sealing machine, and 0.5 g of limonene was impregnated with 1 g of absorbent cotton. A sample bottle was prepared, packed in a bag, the upper part was heat-sealed, and an odor sensory test was performed for each change over time.
As a result, the limonene odor was strongly felt from the laminate having polyethylene as the resin layer. However, the limonene odor was suppressed in the laminates having the aliphatic polyester resin layers of Example 6 and Example 7. Next, the aroma component was taken out, fresh air was put into the bag, and an odor sensory test was conducted. When the resin layer was made of polyethylene, the limonene odor was felt very strongly, and the limonene was adsorbed on the resin. On the other hand, when the resin layer was made of aliphatic polyester, the limonene odor was reduced compared to the resin layer made of polyethylene.

<Sensory test of odor level>
The laminated body obtained in Example 7 and Comparative Example 6 was molded into a square-bottom bag, and 5 g of garbage such as tea husk, coffee residue, vegetable scraps, fish internal organs, etc. were put in the bag, and the upper part was heat sealed. A sensory test for malodor was conducted for each change.
As a result, the laminate having the polyethylene of Comparative Example 6 as the resin layer felt bad odor, while the odor of the resin layer of Example 7 made of aliphatic polyester was suppressed.

<Water vapor permeability test>
A center seal bag of 10 cm × 11 cm was prepared from the laminates obtained in Example 7 and Comparative Example 6 with a pulse heat sealer, and rice balls made with freshly cooked rice were packaged. After standing for 60 minutes and opening the bag, it was confirmed that the resin layer had a lot of water droplets attached to the polyethylene bag, and the rice balls on the contents were so wet that it was easily deformed. On the other hand, the bag with the resin layer made of aliphatic polyester had fewer water droplets than the one made of polyethylene, and the shape of the rice ball on the inside was maintained, which felt delicious.

  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. The biodegradable resin laminate and the method for producing the same can also be modified as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification. It should be understood as encompassed by the scope.

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

Explanation of symbols

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 biodegradable resin laminate having a resin layer containing a biodegradable resin, wherein the laminate has a heat seal strength of 10 N / 15 mm or more measured by the following method (A).
(Method (A): The above-mentioned two laminates were measured with a heat seal tester under the conditions of 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. The resin layer surfaces are bonded together to create a strip-shaped test piece having a width of 15 mm, and the heat seal strength is measured with a Tensilon universal testing machine at a pulling speed of 300 mm / min.) The laminate according to claim 1, wherein the heat seal strength of the laminate measured by the following method (B) is 4 N / 15 mm or more.
(Method (B): resin layer and craft of laminate in heat seal tester under conditions of set temperature 150 ° C., seal bar width 5 mm, seal pressure 0.1 MPa or more, seal time 0.5 seconds to 1.1 seconds. Adhesion with paper makes a strip-shaped test piece with a width of 15 mm, and measures the heat seal strength with a Tensilon universal testing machine at a pulling speed of 300 mm / min.) The resin layer is made of a biodegradable resin that is an aliphatic polyester mainly composed of dicarboxylic acid and diol, or biodegradable other than the aliphatic polyester and an aliphatic polyester mainly composed of dicarboxylic acid and diol. The laminate according to claim 1 or 2, comprising a resin composition with a functional resin. The laminate according to claim 3, wherein the biodegradable resin other than the aliphatic polyester mainly composed of the dicarboxylic acid and the diol is polylactic acid or an aliphatic / aromatic polyester. The laminate according to claim 3 or 4, wherein the amount of urethane bonds in the aliphatic polyester is 0.90 mass% or less. The laminate according to any one of Claims 1 to 5, wherein the resin layer contains an antioxidant and / or a lubricant. The lubricant is a fatty acid metal salt, the fatty acid constituting the fatty acid metal salt has a carbon chain having 12 to 30 carbon atoms, and the metal constituting the fatty acid metal salt is from the third period to the fourth period of the periodic table. The laminate according to claim 6, wherein the laminate is any one of alkali metals, alkaline earth metals, and transition metals. It has a base material, The laminated body of any one of Claims 1-7 characterized by the above-mentioned. The laminate according to claim 8, wherein the substrate contains at least one selected from paper, nonwoven fabric, polylactic acid film, and polyglycolic acid film. A method for producing a laminate having a resin layer containing an aliphatic polyester containing at least a dicarboxylic acid and a diol as main components, wherein the resin layer satisfies the following (1) to (6): A method for producing a laminate, which is formed by an extrusion coating method.
(1) The blending amount of the aliphatic polyester mainly composed of dicarboxylic acid and diol in the resin layer is 65 parts by mass or more, with 100 parts by mass of the total amount of the biodegradable resin contained in the resin layer.
(2) The temperature of the die of the melt extruder is 230 ° C. or higher and 300 ° C. or lower.
(3) The resin temperature directly under the die is ± 35 ° C. of the die set temperature.
(4) In order to laminate the resin layer on the substrate, the nip pressure when the substrate and the resin layer are pressed between the cooling roll and the nip roll is 0.2 MPa or more and 0.45 MPa or less.
(5) The air gap, which is the distance from the die outlet to the contact with the cooling roll, is 50 mm or more and 120 mm or less.
(6) The MI (melt index; 190 ° C., 2.16 kg load) of the raw resin is 3 g / 10 min or more and 20 g / 10 min or less, and the MI of the molten resin at the die outlet is 6 g / 10 min or more and 35 g / 10 min or less. The method for producing a laminate according to claim 10, wherein an amount of urethane bonds in the aliphatic polyester is 0.90 mass% or less.

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