JP2002059524A - Degradable laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is flexible, has high folding strength, is excellent in the bleed-out resistance of a plasticizer at a high temperature, is decomposed in a constant period in a natural environment, for example, in earth, in water, and in the air, is excellent in strength and water resistance, and has a good surface gloss. SOLUTION: The degradable laminate comprises a lactate resin composition containing 100 pts.wt. of a lactate resin and 5-30 pts.wt. of at least one compound selected from a compound (A) expressed by formula (1) (wherein at least one of R1, R2, and R3 is 6-18C acyl and the others are hydrogen or acetyl) and a compound (B) which is the reaction product of the condensate of 1-10 glycerin molecules and a 6-18C carboxylic acid, and a regenerated cellulose film, paper, leather, cloth, or fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate of a lactic acid resin composition having degradability in a natural environment and a regenerated cellulose film (cellophane), leather, paper, cloth or fiber. . More specifically, the present invention relates to a decomposable laminate comprising a lactic acid-based resin composition containing a lactic acid-based resin and a specific glycerin derivative as a plasticizer, and cellophane, paper, leather, cloth or fiber. This laminate has excellent folding strength and can be used for moisture-proof wrapping paper, decorative paper, milk and juice containers, various packaging materials, and the like. These materials are easily decomposed in the natural environment after use.

[0002]

2. Description of the Related Art In recent years, the amount of plastic used for packaging has been increasing due to the problems of aesthetics, hygiene, and packing and transportation of goods. Along with this, the amount of garbage discarded from homes and factories has increased rapidly, and the shortage of land to bury has become a serious problem around large cities. Regenerated cellulose film called cellophane, paper, leather, fabric made from natural fibers or natural fibers is degradable in the natural environment, decomposes over a long period of time even when buried, and emits harmful gases even when incinerated. Does not occur. Some are being recovered and reused from the standpoint of resource protection. For this reason, it is expected to be used as disposable wrapping paper, containers, various types of wrapping materials, etc. instead of plastics having low degradability, and the usage amount will increase.

[0003] Cellophane is originally excellent in transparency, gas impermeability, printability and glossiness, and is in great demand as a packaging material. However, laminates with synthetic polymers are often used for the purpose of compensating for these properties because of their poor moisture-proof properties, low-temperature resistance, strength and heat-sealing properties. Also, since paper and packaging paper, containers, and the like have low strength and low water resistance, a laminated paper in which a polymer and paper are laminated is used for a paper pack or a paper cup for storing milk or juice. Further, glossy laminated paper having a smooth surface has come to be frequently used for book covers, decorative boxes and the like in order to satisfy consumers' aesthetic needs. Leather, cloth, or fiber is also used as a main material or a secondary material in wrapping paper, containers, various packaging materials, and has similar problems.

As polymers used for these applications, polyolefins such as polyethylene and polypropylene, polyesters for paper coating, and the like have been used. However, these polymers are hardly degradable in the natural environment and, when discarded and buried, significantly reduce the rate of degradation of the inherently degradable cellophane, paper, leather, cloth or fiber. Further, when incinerated, a large amount of heat is generated, and thus there is a problem that the combustion furnace is damaged. Alternatively, when recovered and reused, these polymers have caused problems in the separation process.

[0005] From such a background, degradability and / or biodegradability (in the specification of the present application, the function of decomposing by the action of microorganisms and the like in the natural environment and the function of decomposing by the action of enzymes and the like in the living body) As a thermoplastic resin having polylactic acid, a copolylactic acid having a lactic acid component as a main component (for example, a copolymer of lactic acid and another aliphatic hydroxycarboxylic acid), a polylactic acid and another aliphatic polyester. (For example, a mixture of polylactic acid and polybutylene succinate) has attracted attention. Polylactic acid biodegrades 100% within the body of an animal within several months to one year, and when left in wet conditions such as soil or seawater, its strength starts to decrease in about a few weeks, and from about one year to several years. It is characteristic that it disappears without retaining its original form in about a year, and that the decomposition product has the property of becoming lactic acid and / or carbon dioxide and water harmless to the human body.

[0006] Lactic acid, which is a raw material of polylactic acid, is produced by a fermentation method or a chemical synthesis method. Recently, in particular, L-lactic acid has been produced in large quantities by the fermentation method and the price has become low. Development of various applications utilizing the characteristics of polylactic acid having excellent transparency and rigidity is being promoted. However, lactic acid-based resins have high elastic modulus and rigidity and are poor in flexibility. Therefore, it is not suitable for applications requiring flexibility such as polyethylene, polypropylene, soft polyvinyl chloride and the like which are widely used.

In general, as a method of softening a resin, there are known methods such as a method of adding a plasticizer, a method of forming a copolymer, and a method of blending a soft polymer. Among these, as a method of adding a plasticizer, studies on softening using various plasticizers have been made. For example, JP-A-4-335060 discloses a composition in which a plasticizer is added to polylactic acid. As a specific plasticizer,
Diisobutyl adipate and dioctyl sebacate are mentioned. However, these have little plasticizing effect and cannot obtain sufficient flexibility. Furthermore, when these plasticizers are used, bleeding of the plasticizer occurs immediately after molding or over time, and the flexibility, transparency, and the like change. Therefore, it has excellent flexibility and no bleed-out of plasticizer at high temperature.
Therefore, a laminate having a heat-resistant and transparent lactic acid-based resin and paper or the like has not been known.

[0008]

The present invention does not have the above-mentioned disadvantages, ie, has excellent flexibility and water resistance, and as a result,
Lactic acid-based resin and cellophane, paper, which have excellent bending strength, do not bleed out of plasticizers at high temperatures, and therefore have heat resistance and do not cause problems when disposed or incinerated in the natural environment
It is an object of the present invention to provide a laminate made of leather, cloth or fiber.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a lactic acid-based resin composition obtained by adding a specific plasticizer to a lactic acid-based resin is used. As a result, the present inventors have found that a laminate laminated with paper or the like without the above-mentioned defects can be obtained, and the present invention has been completed. Also,
This laminate was found to be excellent in transparency, gloss, water resistance, and bending strength, and was found to have even greater strength, and completed the present invention. In addition, this laminated laminate is excellent in transparency, glossiness, and water resistance, which the lactic acid-based resin originally has,
Can have great strength.

That is, according to the present invention, 100 parts by weight of a lactic acid-based resin is represented by the general formula (1)

[0011]

Embedded image (Wherein at least one of R ₁ , R ₂ and R ₃ has 6 carbon atoms)
(A) and glycerol 1 represented by the formula:
A lactic acid-based resin composition containing 5 to 30 parts by weight of at least one compound selected from compound (B) which is a reaction product of a condensate of 10 to 10 molecules and a carboxylic acid having 6 to 18 carbon atoms; A degradable laminate comprising a cellulose film, paper, leather, cloth or fiber.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The laminate of the present invention, which is flexible, excellent in water resistance and bending strength, and excellent in bleed-out resistance of a plasticizer at high temperature, is obtained by mixing a glycerin ester as a plasticizer with a lactic acid-based resin. The resulting lactic acid-based resin composition is adhered or applied to cellophane, paper, leather, cloth or fiber. In the present invention, the lactic acid-based resin refers to a homopolymer or a copolymer in which the lactic acid component in all the monomer components constituting the resin is at least 50% by weight or more. For example, polylactic acid, lactic acid and aliphatic hydroxycarboxylic acid Copolymers (eg, copolymers of lactic acid and glycolic acid, copolymers of lactic acid and caproic acid, block copolymers of polylactic acid and polycaproic acid, etc.), copolymers of lactic acid and aliphatic polyhydric alcohols and aliphatic polycarboxylic acids (eg, lactic acid and Butanediol, succinic acid and adipic acid copolymers, lactic acid and ethylene glycol, butanediol and succinic acid copolymers, polylactic acid and polybutylene succinate block copolymers, and the like, and mixtures thereof. Furthermore,
It includes a mixture of polylactic acid and an aliphatic polyester (for example, polycaproic acid, polybutylene succinate, polyethylene succinate, a copolymer of β-hydroxybutyric acid and β-hydroxyvaleric acid, and the like). In the case of a mixture, a compatibilizer may be contained. When the lactic acid-based resin is a copolymer, the mode of arrangement of the copolymer may be any mode such as a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. Further, they are at least partially composed of xylylene diisocyanate, 2,4-
It may be cross-linked with a cross-linking agent such as polyvalent isocyanate or cellulose such as tolylene diisocyanate or polysaccharide such as acetyl cellulose or ethyl cellulose, at least a part of which is linear, cyclic, branched or star-shaped. , Three-dimensional network structure, etc., and there is no limitation.

[0013] In the lactic acid resin of the present invention, polylactic acid,
In particular, poly-L-lactic acid, a block copolymer of polylactic acid and poly-6-hydroxycaproic acid, particularly a block copolymer of poly-L-lactic acid and poly-6-hydroxycaproic acid, and a block of polylactic acid and polybutylene succinate Copolymers, especially block copolymers of poly-L-lactic acid and polybutylene succinate, block copolymers of polylactic acid, β-hydroxybutyric acid and β-hydroxyvaleric acid,
Particularly, a block copolymer of poly-L-lactic acid, β-hydroxybutyric acid and β-hydroxyvaleric acid is preferred. Among them, polylactic acid is most preferred.

In the present invention, specific examples of the aliphatic hydroxycarboxylic acid constituting the lactic acid-based resin include, for example, glycolic acid, lactic acid, 3-hydroxy drank acid, 4-hydroxy drank acid, 3-hydroxyvaleric acid, and 4-hydroxyvaleric acid. Hydroxyvaleric acid, 5-hydroxyvaleric lactic acid, 6-hydroxycaproic acid and the like can be mentioned. These may be one kind or a mixture of two or more kinds. When the aliphatic hydroxycarboxylic acid has an asymmetric carbon, L-form, D-form, and a mixture thereof,
That is, it may be racemic.

In the present invention, specific examples of the aliphatic polycarboxylic acid constituting the lactic acid resin include oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and the like. Examples thereof include aliphatic dicarboxylic acids such as sebacic acid, undecanoic acid and dodecane diacid, and anhydrides thereof. These may be one kind or a mixture of two or more kinds.

In the present invention, specific examples of the aliphatic polyhydric alcohol constituting the lactic acid resin include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 4-butanediol, 3-methyl-1,5-pentanediol, 1,6-
Hexanediol, 1,9-nonanediol, neopentyl glycol, tetramethylene glycol, 1,4-
Cyclohexanedimethanol and the like. These may be one kind or a mixture of two or more kinds.

Specific examples of the polysaccharide constituting the lactic acid resin in the present invention include, for example, cellulose, cellulose nitrate, cellulose acetate, methylcellulose, ethylcellulose, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, copper ammonia rayon , Cuprophan, Bemberg®, hemicellulose, starch, amylopectin, dextrin, dextran, glycogen, pectin, chitin, chitosan,
Gum arabic, guar gum, locust bean gum, acacia gum, and the like, and derivatives thereof,
In particular, acetyl cellulose and ethyl cellulose are preferably used. These may be one kind or a mixture of two or more kinds.

The molecular weight of the lactic acid-based resin used in the present invention is not particularly limited as long as it exhibits substantially sufficient mechanical properties, but is generally 1 to 300 as a weight average molecular weight. 10,000 is preferable, 3 to 2,000,000 is more preferable, 5 to 1,000,000 is more preferable, and 7 to 5
More preferably, it is 100,000, most preferably 90,000 to 300,000. In general, when the weight average molecular weight is less than 10,000, mechanical properties are not sufficient. On the contrary, when the molecular weight is more than 3,000,000, handling becomes difficult due to molding processing, and uneconomical in production cost. It may be.

The weight average molecular weight and molecular weight distribution of the lactic acid resin used in the present invention are determined by
Solvent type, catalyst type and amount, reaction temperature, reaction time,
The desired conditions can be controlled by appropriately selecting the reaction conditions such as the method of embedding the solvent distilled off by azeotropic distillation and the degree of solvent drying in the reaction system.

The method for producing the lactic acid resin of the present invention is not particularly limited. For example, as an example of a method for producing a polylactic acid and a lactic acid-based resin having lactic acid as a structural unit, see JP-A-6-6-6.
A method as described in Production Example 1 described below with reference to the method disclosed in Japanese Patent No. 5360 is cited. That is,
Lactic acid and / or an aliphatic hydroxycarboxylic acid other than lactic acid, or an aliphatic diol and an aliphatic dicarboxylic acid,
This is a direct dehydration condensation method in which dehydration condensation is performed as it is in the presence of an organic solvent and a catalyst.

Another example of a method for producing a lactic acid-based resin having lactic acid as a structural unit is described in, for example, JP-A-7-17326.
No. 6, reference is made to the method disclosed therein. That is, this is a method in which a homopolymer of at least two kinds of lactic acid-based resins is copolymerized and transesterified in the presence of a polymerization catalyst.

As another example of the method for producing polylactic acid, for example, a method referring to the method disclosed in US Pat. No. 2,703,316 can be mentioned. That is, once lactic acid and / or hydroxycarboxylic acid other than lactic acid,
This is an indirect polymerization method in which ring-opening polymerization is performed after dehydration to form a cyclic dimer.

In the present invention, for the purpose of imparting flexibility and bending strength to the laminate, a plasticizer represented by the general formula (1):

[0024]

Embedded image (Wherein at least one of R ₁ , R ₂ and R ₃ has 6 carbon atoms)
(A) and glycerol 1 represented by the formula:
At least one compound selected from the compounds (B), which are reaction products of a condensate of 10 to 10 molecules and a carboxylic acid having 6 to 18 carbon atoms, is used.

The added amount of these plasticizers affects the crystallinity, flexibility, heat resistance and the like of the obtained film. If the addition amount is too large, the crystallinity and heat resistance decrease. If the amount is too small, sufficient flexibility cannot be obtained. From this perspective,
The added amount of the plasticizer is preferably 5 to 30 parts by weight based on 100 parts by weight of the aliphatic polyester. More preferably, it is 7 to 20 parts by weight.

The compound (A) used in the present invention is a glycerin ester represented by the general formula (1). Normal,
The acetyl group of the compound is 2 mol or less on average per 1 mol of glycerin. An acyl group having 6 to 18 carbon atoms (hereinafter, referred to as an acyl group)
C6-18 acyl group) is 0.9 mol or more on average to 1 mol of glycerin. Acetyl group and C6-1
The total amount of 8-acyl groups is an average of 2. to 1 mol of glycerin.
It is in the range of 7 to 3.0 mol. Preferably, the total amount of the acetyl group and the C6-18 acyl group is in the range of 2.9 to 3.0 mol on average per 1 mol of glycerin. In addition, from the viewpoint of the plasticizing effect of the resin and the non-bleeding property, the glycerin ester preferably has 8 to 18 carbon atoms of the acyl group among the C6 to 18 acyl groups.

In the general formula (1), R ₁ , R ₂ and R
Esters in which at least one of ₃ is an acyl group having 8 to 18 carbon atoms and the remainder is an acetyl group are more preferred. Particularly preferred compounds (A) include glycerin diacet monocaprylate, glycerin diacet monolaurate and glycerin diacet monooleate. Compound (A) may be used alone or as a mixture.

In the present invention, the compound (B) used as a plasticizer is usually a carboxylic acid having 6 to 18 carbon atoms per 1 mol of a condensate of 1 to 10 molecules of glycerin.
~ 1.2 mol. From the viewpoint of the plasticizing effect of the resin and the non-bleeding property, a condensate of 2 to 10 molecules of glycerin and an ester compound with a carboxylic acid having 8 to 18 carbon atoms are preferable. More preferably, it is an ester with a condensate of 4 to 10 molecules of glycerin. Particularly preferred specific compounds include tetraglycerin caprylate, decaglycerin laurate, and decaglycerin oleate. Compound (B) may be used alone or as a mixture.

Considering the suppression of bleeding of the plasticizer, it is preferable to use the compound (A) and the compound (B) together.
In that case, the mixing weight ratio of (A) to (B) is from 1: 1 to 4:
A range of 1 is preferred. A more preferred mixing weight ratio of (A) to (B) is in the range of 2: 1 to 3: 1.

The lactic acid-based resin composition according to the present invention can be obtained by adding and mixing the lactic acid-based resin with the above-mentioned plasticizer and, if necessary, additives and the like according to the desired molded product.
As a method, after uniformly mixing the lactic acid-based resin and the plasticizer, and optionally other additives using a high-speed stirrer or a low-speed stirrer, a single-screw or multi-screw extruder having a sufficient kneading ability is used. And a method of melt-kneading. The shape of the resin composition according to the present invention is preferably a pellet, a rod, a powder, or the like.

The type of cellophane used in the laminate of the present invention is not particularly limited, and ordinary cellophane, dampproof cellophane and the like are used. The paper used in the present invention includes art paper (coated paper), kraft paper, roll paper, rice paper, other processed base paper, cloth paper, cardboard, and the like. These papers may be papers containing recycled pulp.

The leather used in the present invention is a natural leather, and a thin leather like parchment or a thick leather can also be used. The fiber or cloth used in the present invention is a natural fiber or a cloth using the natural fiber, and its material is cotton, silk, wool, or the like. The fiber may include a thread, and the cloth may include a band. The cloth may be woven or non-woven. These preferably consist only of natural ones, but may also include artificial ones.

As a laminating method, there are known methods such as a solution coating method, a hot melt method, and an extrusion laminating method. The heat melting method is, for example, a method in which a lactic acid resin composition is spread on the surface of paper and then heated and melted or pressed while being heated or melted. For example, a lactic acid-based resin as disclosed in JP-A-10-101911 After emulsifying the composition once to form an emulsion composition, the emulsion composition is applied to the surface of a base material, and dried and melted or pressed while being melted by heating.

When an adhesive is used, glue, gelatin,
It is preferable to use degradable substances such as casein and starch. However, some papers do not use an adhesive in order not to interfere with the degradability. Further, a method of anchor-coating the surface of cellophane, paper, leather, cloth or fiber with an organic titanium compound, an organic silane compound, polyethyleneimine or the like before lamination is also used. In some cases, paper or the like may be previously impregnated with lactic acid, another hydroxycarboxylic acid, lactide, or glycolide, ε-caprolactone, or a mixture thereof.

The decomposable laminate of the present invention may optionally be used by laminating it with another film, for example, an aluminum foil. In the present laminate, since the lactic acid-based resin is easily dissolved under alkaline conditions, cellophane, paper, leather, cloth, or fibers can be easily separated.

[0036]

The method of the present invention will be specifically described below with reference to examples and comparative examples. The method for producing the polylactic acid-based resin used in Examples and Comparative Examples is shown below. All parts in the text are based on weight.

The average molecular weight (weight average molecular weight Mw) of the polymer was measured by gel permeation chromatography using polystyrene as a standard under the following conditions. Equipment: Shimadzu LC-IOAD Detector: Shimadzu RID-6A Column: Hitachi Chemical GL-S350DT-5, GL-S3
70DT-5 Solvent: chloroform Concentration: 1% Injection volume: 20 μl

The bending strength, tensile strength, elongation, plasticizer bleed-out, and water resistance of the film of the obtained laminate were measured as follows. 1) Folding strength of laminate The machine direction (MD) of the laminate and the direction parallel to it (TD)
Was tested according to JISP8115.

2) Water resistance of the film The film was immersed in water at 23 ° C. for 5 days.
The mixture was left overnight at 50 ° C. and 50% RH. The hardness of the obtained molded article was observed. ：: No change △: Slightly hard ×: Clearly hard

3) Bleed-out of plasticizer A film was cut into a size of 45 mm × 30 mm, and two films were stacked on a glass plate. A metal plate was placed thereon, and a 500 g weight was placed thereon, and left for 1 hour in a thermo-hygrostat at a temperature of 80 ° C. and a humidity of 75%. Thereafter, the film was transferred into a desiccator and left at room temperature for 30 minutes. afterwards,
Bleed out of the plasticizer was observed. Bleed of plasticizer ○ ・ ・ ・ No bleed × ・ ・ ・ Bleed

Production Example 1 (Production of Poly-L-lactic acid) 10 kg of 90% L-lactic acid was placed at 150 ° C./5 in a 100 liter reactor equipped with a Dien-Stark trap.
After distilling water while stirring at 0 mmHg for 3 hours, 6.2 g of tin powder was added, and the mixture was further added at 150 ° C / 30 mmHg for 2 hours.
Stir for hours to oligomerize. 28.8 g of tin powder and 21.1 kg of diphenyl ether were added to this oligomer,
An azeotropic dehydration reaction at 150 ° C./35 mmHg was performed, and the distilled water and the solvent were separated by a water separator, and only the solvent was returned to the reactor. After 2 hours, the organic solvent to be returned to the reactor was passed through a column packed with 46 kg of molecular sieve 3A, and then returned to the reactor. The reaction was carried out at 150 ° C./35 mmHg for 40 hours, and the weight average molecular weight was 146,000. A solution of polylactic acid was obtained. Diphenyl ether 44 dehydrated in this solution
After adding kg and diluting, the mixture was cooled to 40 ° C., and the precipitated crystals were filtered, washed three times with 10 kg of n-hexane, and dried at 60 ° C./50 mmHg. 0.5 N of this powder
-Add 12 kg of HCl and 12 kg of ethanol, and add 35
After stirring at 1 ° C. for 1 hour, the mixture was filtered and dried at 60 ° C./50 mmHg to obtain 6.1 kg of white polylactic acid (yield 85%).
%). The weight average molecular weight Mw of this polylactic acid (Polymer B) was 145,000.

Example 1 15 parts by weight of glycerin diacet monocaprylate (hereinafter referred to as "monocaprylate") was mixed with 100 parts by weight of the polylactic acid obtained in Production Example 1 using a Henschel mixer. A composition was obtained. This lactic acid-based resin composition was subjected to T-die molding to obtain a film having a thickness of 30 μm. 1
The film obtained above was superimposed on a kraft paper of about 70 g / m ² of 50 mm × 150 mm and pressed by a hot press at 200 ° C. under a pressure of 30 kg / cm ² for 5 minutes. The adhesion between the paper and the polymer film was good, and a tough laminated laminate with good surface gloss was obtained. Table 1 (Table 1) shows the physical properties of the laminate.

Example 2 Instead of 100 parts by weight of polylactic acid, 70 parts by weight of polylactic acid, polybutylene succinate (Bionole # 3001)
Example 1 except that 30 parts by weight (manufactured by Showa Polymer Co.) was used
In the same manner as in the above, a lactic acid-based resin composition was obtained. This lactic acid-based resin composition was subjected to T-die molding to obtain a film having a thickness of 30 μm. The film obtained above was superimposed on a kraft paper of 150 mm × 150 mm of about 70 g / m ² and pressed by a hot press at 200 ° C. under a pressure of 30 kg / cm ² for 5 minutes. The adhesion between the paper and the polymer film was good, and a tough laminated laminate with good surface gloss was obtained. Table 1 (Table 1) shows the physical properties of the laminate.

Comparative Example 1 A laminate was obtained in the same manner as in Example 1 except that glycerin triacetate (hereinafter, triacetin) was used in place of glycerin diacetmonocaprylate. The adhesion between the paper and the polymer film was good, and a tough laminated laminate with good surface gloss was obtained. Further, Table 1 (Table 1) shows the bending strength of this laminated laminate measured according to JIS P8115.

Comparative Example 2 A laminate was obtained in the same manner as in Example 1 except that glycerin diacet monopropionate (hereinafter referred to as monopropionate) was used instead of glycerin diacet monocaprylate. The adhesion between the paper and the polymer film was good, and a tough laminated laminate with good surface gloss was obtained. In addition, JIS P8
Table 1 (Table 1) shows the bending strength measured according to No. 115.

Comparative Example 3 A laminate was obtained in the same manner as in Example 1 except that tributyl acetylcitrate (hereinafter, referred to as ATBC) was used in place of glycerin diacetomonocaprylate. The adhesion between the paper and the polymer film was good, and a tough laminated laminate with good surface gloss was obtained. Further, Table 1 (Table 1) shows the bending strength of this laminated laminate measured according to JIS P8115.

Comparative Example 4 A laminate was obtained in the same manner as in Example 1 except that glycerin diacetmonocaprylate was not used. The adhesion between the paper and the polymer film was good, and a tough laminated laminate with good surface gloss was obtained. Further, Table 1 (Table 1) shows the bending strength of this laminated laminate measured according to JIS P8115.

[0048]

[Table 1]

[0049]

According to the present invention, it is flexible, has excellent bending strength, has excellent bleed-out resistance of plasticizers at high temperatures, and decomposes in a natural environment such as soil, water, or air within a certain period of time. A laminate having excellent strength, moisture resistance, and good surface gloss can be obtained.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yasuhiro Kitahara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside (72) Inventor Akinori Takehara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals Inc. (72) Inventor Takayuki Kuroki 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi F-term in Mitsui Chemicals, Inc. (reference) 4F100 AH02A AH02H AJ05B AJ10B AK41A BA02 DG01B DG10B DG11B EC03 EC032 EH17 EH172 JC00 YY00A0J047H

Claims (11)

[Claims] [Claim 1] A lactic acid-based resin is used in an amount of 100 parts by weight to the general formula (1). (Wherein at least one of R ₁ , R ₂ and R ₃ has 6 carbon atoms)
(A) and glycerol 1 represented by the formula:
A lactic acid-based resin composition containing 5 to 30 parts by weight of at least one compound selected from compound (B) which is a reaction product of a condensate of 10 to 10 molecules and a carboxylic acid having 6 to 18 carbon atoms; A degradable laminate comprising a cellulose film, paper, leather, cloth or fiber. 2. The decomposable laminate according to claim 1, wherein in formula (1), the acyl group has 8 to 18 carbon atoms. 3. The compound of the formula (1) wherein R ₁ , R ₂ and R ₃
At least one is an acyl group having 8 to 18 carbon atoms,
The decomposable laminate according to claim 1, wherein the remainder is an acetyl group. 4. The decomposable laminate according to claim 3, wherein the compound (A) is at least one compound selected from glycerin diacet monocaprylate, glycerin diacet monolaurate and glycerin diacet monooleate. 5. The decomposable laminate according to claim 1, wherein the compound (B) is an ester obtained by reacting 0.8 to 1.2 mol of a carboxylic acid with respect to 1 mol of a glycerin condensate. 6. The decomposable laminate according to claim 1, wherein the carboxylic acid forming the compound (B) has 8 to 18 carbon atoms. 7. The degradable laminate according to claim 1, wherein the glycerin condensate forming the compound (B) has 2 to 10 glycerin molecules. 8. The decomposable laminate according to claim 7, wherein the glycerin condensate forming the compound (B) has 4 to 10 glycerin molecules. 9. The decomposable laminate according to claim 8, wherein the compound (B) is at least one compound selected from tetraglycerin caprylate, decaglycerin laurate and decaglycerin oleate. 10. The decomposable laminate according to claim 1, comprising both the compound (A) and the compound (B), wherein the weight ratio of (A) to (B) is from 1: 1 to 4: 1. 11. The decomposable resin according to claim 1, wherein the lactic acid resin is at least one polyester selected from polylactic acid and lactic acid and other aliphatic hydroxycarboxylic acid copolymers. Laminate laminate.