JPH07290645A - Biodegradable metallizing material and production thereof - Google Patents

Abstract

PURPOSE:To obtain a biodegradable metallizing material adjustable in strength, water resistance and moldability and not destructing enviromnent by constituting the same of a laminate consisting of a biodegradable polymer layer composed of specific aliphatic polyester and a metal film which may be partially oxidized. CONSTITUTION:Aliphatic glycol and aliphatic dicarboxylic acid or an anhydride thereof are reacted in the presence or absence of 5 mol% or less of a compd. selected from aliphatic polyol having three or more alcoholic hydroxyl groups, aliphatic polyoxycarboxylic acid having three or more oxycarboxyl groups or an anhydride thereof and aliphatic polycarboxylic acid having three or more carboxyl groups or an anhydride thereof to form aliphatic polyester polyol having a hydroxyl group at its terminal and this aliphatic polyester polyol and polyisocyanate are reacted or subjected to glycol removing reaction under vacuum of 0.005-1mmHg at 160-230 deg.C in the presence of a catalyst to produce aliphatic polyester with a number average mol.wt. of 10000 or more. A biodegradable metallizing material is constituted of a laminate having a biodegradable polymer layer 1 composed of aliphatic polyester and a metal film 2 which may be partially oxidized.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a biodegradable metallizing material and a method for producing the same, and more particularly, to a biodegradable metallizing material which is decomposed by microorganisms when buried in soil and disposed of and does not adversely affect the natural environment. Degradable metallizing material and its manufacturing method.

[0002]

BACKGROUND OF THE INVENTION Metallizing materials such as metallizing films having a metal thin film formed on one surface of a plastic substrate have been known.

Such conventional metallizing materials are
After use, the metallizing material is incinerated or disposed of in the soil. However,
These processes have the following problems.

(1) Problems in Incineration of Metallizing Material When incinerating a metallizing material, energy is required to incinerate the plastic base material. Especially when the plastic substrate is made of vinyl chloride, incineration of the metallizing material generates hydrogen chloride gas, which causes acid rain.

(2) Problems in Disposing Metallizing Material in Soil In recent years, the number of cases in which the metallizing material is buried in the soil and disposed of has increased dramatically. It is becoming difficult to secure land for waste disposal as the number of landfills increases. In addition, the plastic material dumped in the soil
It does not decompose and remains stable for a long period of time, which may damage the natural environment.

Furthermore, if the plastic base material is separated from the metallizing material to be discarded and is reused, the separate collection of the plastic base material entails an enormous cost, resulting in poor marketability. Will cause deterioration of the quality.

[0007]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above. Even when the used metallizing material is discarded in the soil, the natural environment It is an object of the present invention to provide a metallizing material that does not break the metal.

[0008]

SUMMARY OF THE INVENTION The metallizing material according to the present invention comprises:
(I) Fat containing (1) an aliphatic glycol and (2) an aliphatic dicarboxylic acid or an acid anhydride thereof in an amount of 5 mol% or less with respect to the component (2), (3) three or more alcoholic hydroxyl groups. In the presence of at least one compound selected from the group consisting of aliphatic polyols, aliphatic polyoxycarboxylic acids having 3 or more oxycarboxyl groups and their anhydrides, aliphatic polycarboxylic acids having 3 or more carboxyl groups and their anhydrides, or Number average molecular weight 1 obtained by reacting (II) polyisocyanate with an aliphatic polyester polyol having a hydroxyl group at the terminal obtained by reaction in the absence
10,000 or more of the aliphatic polyester (A), or the aliphatic polyester polyol, in the presence of a catalyst.
A biodegradable polymer layer composed of an aliphatic polyester (B) having a number average molecular weight of 10,000 or more obtained by a deglycolization reaction at a temperature of 60 to 230 ° C. and a vacuum of 0.005 to 1 mmHg, and a part thereof. It is characterized by being constituted by a laminated body having a metal thin film which may be oxidized.

The method for producing a metallizing material according to the present invention is characterized in that a metal thin film or a metal oxide thin film is formed on the biodegradable polymer layer by an ion plating method or a sputtering method.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The metallizing material, particularly the metallizing film, according to the present invention will be specifically described below with reference to the drawings.

1 to 3 show specific examples of the metalizing film according to the present invention. In the metallizing film 10 of FIG. 1, the metal thin film 2 is laminated on one surface of the biodegradable polymer layer 1.

Of these, the biodegradable polymer layer 1 is made of the following specific aliphatic polyester. That is, when forming the biodegradable polymer layer 1, the following aliphatic polyester (A) or (B) is used.

Aliphatic polyester (A): (I) (1) An aliphatic glycol and (2) an aliphatic dicarboxylic acid or an acid anhydride thereof in an amount of 5 mol% or less (3) based on the component (2). )
It is selected from an aliphatic polyol having 3 or more alcoholic hydroxyl groups, an aliphatic polyoxycarboxylic acid having 3 or more oxycarboxyl groups and its anhydride, and an aliphatic polycarboxylic acid having 3 or more carboxyl groups and its anhydride. Obtained by reacting (II) a polyisocyanate (including diisocyanate) with an aliphatic polyester polyol having a hydroxyl group at the end obtained by reacting in the presence or absence of at least one compound Aliphatic polyester having a number average molecular weight of 10,000 or more;
For example, the following formula (1):

[0014]

[Chemical 1]

(In the formula, R ¹ and R ² may be the same or different and each is an optionally branched alkylene or cycloalkylene group having 2 to 10 carbon atoms, and R ³ is It is a polyvalent polyisocyanate (including diisocyanate) residue, and m has a number average molecular weight of the polymer represented by the above formula of 10,000 or more, preferably 10,000 to 100,000. The required degree of polymerization, M is 0 or an integer of 1 or more.) And aliphatic polyester (B): 160 to 230 ° C., preferably in the presence of a catalyst, of the aliphatic polyester polyol. Is 180-220 ° C and 0.005-1mmH
g of aliphatic polyester having a number average molecular weight of 10,000 or more obtained by deglycolization reaction under vacuum;

[0016]

[Chemical 2]

(In the formula, R ¹ and R ² may be the same or different and each is an optionally branched alkylene or cycloalkylene group having 2 to 10 carbon atoms, and m is the above. The number average molecular weight of the polymer represented by the formula is 10,000 or more, preferably 10,000 to 10
This is the degree of polymerization required to reach 10,000. ) An aliphatic polyester represented by

In the aliphatic polyesters (A) and (B), R ¹ is an alkylene group represented by (--CH ₂ --CH _2- ) _p (where p is 1 or 2), and R ^{2 is} Is preferably an alkylene group represented by (—CH ₂ —CH ₂ —) _n (where n is 1 or 2), in which case it is crystalline, has a high melting point, and is excellent in moldability. An aliphatic polyester is obtained.

Further, R ¹ is a tetramethylene group, and R ^{1
When 2} is an ethylene group, a high molecular weight, highly crystalline aliphatic polyester is obtained. R ³ is a group derived from the polyisocyanate used when producing the aliphatic polyester. Examples of R ³ include the following formulas:

[0020]

[Chemical 3]

The divalent hydrocarbon group represented by ## STR3 ## may be mentioned, but an aliphatic or alicyclic group, particularly a hexamethylene group is preferable. In this case, an aliphatic polyester having an excellent hue can be obtained. Also, by reacting with polyester diol, R ³
The polyisocyanate that forms the polymer is also advantageous in that it has excellent reactivity with the polyester diol.

The aliphatic glycol used for producing the above aliphatic polyester (A) or (B) is an aliphatic glycol having an alkylene or cycloalkylene skeleton having 2 to 10 carbon atoms, which may be branched. , Ethylene glycol, propylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentenediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-
Octanediol, 1,9-nonanediol, 1,10
-Decanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A or mixtures thereof. Among these, aliphatic glycols having an even number of carbon atoms, such as ethylene glycol,
1,4-butanediol, 1,6-hexanediol,
In particular, ethylene glycol, 1,4-butanediol, and cyclohexanedimethanol have a high melting point and are preferable for synthesizing a film-like aliphatic polyester.

As the aliphatic dicarboxylic acid or its anhydride, an aliphatic dicarboxylic acid having an optionally branched alkylene or cycloalkylene skeleton having 2 to 10 carbon atoms or its anhydride, for example, succinic acid or glutaric acid is used. , Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanecarboxylic acid, dodecanoic acid, succinic anhydride, glutaric anhydride, hydrogenated terephthalic acid or mixtures thereof. Among these, aliphatic dicarboxylic acids having an even number of carbon atoms or anhydrides thereof, such as succinic acid, adipic acid, succinic anhydride, especially succinic acid and succinic anhydride, have a high melting point and are also film-like aliphatic. It is preferable in synthesizing polyester.

In particular, when 1,4-butanediol or ethylene glycol is used as the aliphatic glycol and succinic acid or its anhydride is used as the aliphatic dicarboxylic acid or its anhydride, an aliphatic polyester diol is synthesized. An aliphatic polyester having a melting point (110 to 115 ° C.) similar to that of polyethylene can be synthesized from the aliphatic polyester diol.

When synthesizing the aliphatic polyester polyol as described above, it is preferable to use the aliphatic glycol in a slight stoichiometric excess with respect to the aliphatic dicarboxylic acid or its anhydride. Or 1.05 of aliphatic glycol to 1 mol of its anhydride
It is preferably used in the range of 1.2 mol.

When producing the above aliphatic polyester diol or the above aliphatic polyester (B), a deglycolization reaction occurs after the esterification reaction, and the aliphatic polyester diol or the aliphatic polyester (B) is polymerized. To be done.

In the deglycolization reaction, Ti, Ge, Zn, Fe, Mn, Co, Zr, and
Metal compounds such as V, Ir, La, Ce, Li and Ca,
Preferably, organic acid salts of these metals, such as dibutoxytitanium, diacetoacetoxytitanium ("Narsem titanium" manufactured by Nippon Kagaku Sangyo Co., Ltd.), tetraethoxytitanium, tetrapropoxytitanium and tetrabutoxytitanium, have high catalytic activity. It is preferable because it is available and easily available.

The amount of these catalysts is usually 0.01 to 3 parts by weight, preferably 0.05 parts by weight or less, based on 100 parts by weight of the aliphatic polyester diol. The catalyst may be added from the stage where the esterification reaction is started, or may be added immediately before the deglycolization reaction.

The above esterification reaction is conducted at 160 ° C to 230 ° C.
C., preferably 180.degree. C. to 220.degree. C., under an inert gas atmosphere. When the temperature is lower than 160 ° C, the esterification reaction rate is slow, and when the temperature is higher than 230 ° C, the raw material (aliphatic glycol, aliphatic dicarboxylic acid or its anhydride) and the product [aliphatic polyester (A) or aliphatic polyester (B)] ], At least one of them may decompose. The esterification reaction is carried out until the acid value reaches 15 or less, preferably 10 or less. Upon completion of the esterification reaction, an aliphatic polyester diol having hydroxyl groups at both ends of the molecule and having a number average molecular weight of about 1,000 to 3,000 is obtained. The aliphatic polyester diol having a larger molecular weight is preferable because the molecular weight can be smoothly increased by the deglycolization reaction.

The deglycolization reaction of this aliphatic polyester diol is carried out at 170 ° C. at a reduced pressure of 5 Torr or less.
18 at a reduced pressure of 230 ° C, preferably less than 1 Torr
It is carried out at 0 ° C to 210 ° C.

The aliphatic polyester (A) contains a urethane bond as shown in the above formula (1). This urethane bond is a group derived from polyisocyanate (including diisocyanate), acts to increase the molecular weight of the aliphatic polyester (A), and has a function of increasing the molecular weight of the aliphatic polyester (A) per 5,000. At least one is included.

Diisocyanate is often used as the polyisocyanate. Examples of the diisocyanate used for forming the urethane bond include 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and diphenylmethane diisocyanate. Nart,
1,5-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isophorodi isocyanate. Among them, hexamethylene diisocyanate, its trimer, and a trimethylolpropane adduct are reactive with the above-mentioned aliphatic polyester diol, and an aliphatic polyester (A) produced through a reaction process with this aliphatic polyester diol. Is preferable from the viewpoint of hue.

When it is necessary to improve the toughness and molding processability of the above aliphatic polyesters (A) and (B) as a film, for example, as a raw material for producing these aliphatic polyesters, It is selected from an aliphatic polyol having 3 or more alcoholic hydroxyl groups, an aliphatic polyoxycarboxylic acid having 3 or more oxycarboxyl groups and its anhydride, and an aliphatic polycarboxylic acid having 3 or more carboxyl groups and its anhydride. At least one compound in the above esterification reaction step,
It is usually used in an amount of 5 mol% or less, preferably 1 mol% or less, based on the aliphatic dicarboxylic acid of the above-mentioned component (2) or its anhydride depending on the use of the aliphatic polyester produced.

The biodegradable polymer layer 1 formed of the aliphatic polyester (A) or (B) as described above is
If necessary, a biodegradable polymer other than the above aliphatic polyester, a colorant and the like may be contained.

Specific examples of biodegradable polymers other than the above aliphatic polyesters include the following biodegradable polymers. a) Linear polyester of 3-hydroxybutyric acid and 3-hydroxyvaleric acid (trade name: Biopol, ICI, UK
Note that this linear polyester (Biopol) is made of Al
Obtained by sugar fermentation with caligenes Europhus.

B) Lactic acid-based biodegradable polymer produced by ring-opening polymerization of lactide obtained by lactic acid fermentation of glucose (manufactured by Shimadzu Corporation) c) Natural high levels of starch, polysaccharides, chitin, etc. Biodegradable polymer produced from molecules [for example, pullulan (trade name, manufactured by Hayashibara Laboratory Co., Ltd.)] d) Biodegradable polycaprolactone obtained by ring-opening polymerization of ε-caprolactone e) Polyvinyl alcohol or its modified product Biodegradable polymer (trade name Vitex, manufactured by US Air Products and Chemirkaz) f) Polyether, polyacrylic acid, ethylene / carbon monoxide copolymer, aliphatic polyester / polyamide copolymer, aliphatic polyester / polyolefin Copolymer, aliphatic polyester / aromatic polyester copolymer, aliphatic Biodegradable polymer such as polyester / polyether copolymer g) Biodegradable polymer such as polylactic acid, polybutyric acid, polyglycolide or their derivatives h) Polymer alloy of starch and modified polyvinyl alcohol (trade name: Mataby) , Manufactured by Novamont, USA) etc.

I) Polymer alloy of starch and polyethylene (trade name: Poly Grade II, manufactured by Ampacet; trade name: Polyclean, manufactured by Arcer Daniel Midland Co., USA) j) Composition of silane starch and polyethylene (trade name: Eco Star, manufactured by St. Lawrence Starch) k) Polymer alloy of polycaprolactone and polyethylene (trade name: Biomicron, manufactured by JSP; trade name: Tone, manufactured by Union Carbide Co., USA) Raw consisting of the above biodegradable aliphatic polyester When the biodegradable metallizing film 10, which is a laminate of the degradable polymer layer 1 and the metal thin film 2, is discarded in the soil, the biodegradable polymer layer 1 is decomposed into carbon dioxide and water by microorganisms in the soil. It

Biodegradable polymer layer 1 used in the present invention
The thickness is usually 12 to 250 μm, preferably 25 to 100 μm. Such a biodegradable polymer layer 1 is processed into a film by inflation method or T-die extrusion method from the above biodegradable aliphatic polyester containing other biodegradable polymer, colorant, etc., if necessary,
If necessary, a stretching process is performed as a post process to adjust the film thickness to a desired value.

The metal thin film 2 is, for example, aluminum.
Made of aluminum, brass, chrome, etc., vacuum deposition method, sputtering
Biodegradable poly by ring method or ion plating method
It may be formed on the mer layer 1. Film of the metal thin film 2 in this case
Thickness is usually 50-1000 angstroms, preferred
It is 100 to 300 angstroms. For example,
Form metal thin film 2 on biodegradable polymer layer 1 by vacuum deposition method
When forming, the degree of vacuum is 1 × 10^-Four~ 1 x 10^-Fiveto torr
Adjusted. Such vacuum deposition method, sputtering method
Or biodegradable polymer layer 1 by ion plating method
The metal thin film 2 formed on the top is usually 1 × 10.^-11~ 1
× 10^-14cm³(STP) / cm / cm ²・ Sec ・
It has an oxygen permeability coefficient of cmHg.

It is particularly preferable to form the metal thin film 2 by the sputtering method or the ion plating method. In this case, the metal thin film 2 having excellent adhesion to the biodegradable polymer layer 1, a low gas permeability coefficient, and a low surface electric resistance value can be obtained.

At least a part of the metal thin film 2 may be oxidized. That is, in the biodegradable metallizing film 10, a metal oxide thin film such as silica may be formed on the biodegradable polymer layer 1 instead of the metal thin film 2. However, in this case, it is necessary to form the metal oxide thin film on the biodegradable polymer layer 1 by a sputtering method or an ion plating method from the viewpoint of adhesion with the biodegradable polymer layer 1.

Further, a metal wheel such as an aluminum wheel is used as the metal thin film 2, and the biodegradable polymer layer 1 is extruded and laminated by, for example, a T-die extrusion polylamination method, that is, a metal wheel such as an aluminum wheel is extruded by a T-die extrusion molding machine. Method, heat lamination method, that is, 100 to 100% of the biodegradable polymer layer 1 and the metal wheel.
Biodegradable polymer layer 1 by a method of laminating while heating to a temperature of 300 ° C., a solution casting method, a method of coating a solution of a biodegradable polymer on a metal wheel such as an aluminum wheel with a comma roll coater, and then drying the layer. The biodegradable metallizing film 10 can also be obtained by laminating a metal wheel with a metal wheel.

When the biodegradable metallizing film 10 is thus obtained, the thickness of the metal wheel used as the metal thin film 2 is usually 7 to 120 μm, preferably 7 to 25 μm.

When a metal wheel is used as the metal thin film 2 in the present invention, the metal wheel and the biodegradable polymer layer 1 are used.
It is also possible to form a biodegradable metallizing film by bonding and with an adhesive. As the adhesive in this case,
For example, polyvinyl alcohol, starch, natural rubber, glue,
It is preferable to use an adhesive made of gelatin, casein or the like. In addition, the adhesion amount of this adhesive is usually 1 to 2
It was 0 g / m ^2, preferably from 1 to 5 g / m ^2.

Since the above-mentioned pressure-sensitive adhesive exhibits biodegradability, the biodegradable metallizing film obtained by adhering the metal wheel and the biodegradable polymer layer 1 with such a pressure-sensitive adhesive is a soil. It does not destroy the natural environment even if it is discarded.

In the metallizing film 10 of FIG. 2,
A paper layer 3 is further formed on the biodegradable polymer layer 1 of the metallizing film 10 of FIG. The paper layer 3 is usually 50 to 150 g / m ² , preferably 60 to 150 g / m ² .
100 g / m ² of paper is used.

The metallizing film 10 comprising a laminate of such a metal thin film 2 / biodegradable polymer layer 1 / paper layer 3 has a paper layer 3 on the biodegradable polymer layer 1 of the metallizing film 10 of FIG. Are superposed on each other and laminated by, for example, an extruder at a temperature of 100 to 300 ° C.

Further, the metallizing film 10 shown in FIG.
Then, the metal thin film 2 of the metallizing film 10 of FIG.
The biodegradable polymer layer 1 is further formed thereon.
The metallizing film 10 composed of such a laminate of biodegradable polymer layer 1 / metal thin film 2 / biodegradable polymer layer 1 has the biodegradable polymer layer 1 on the metal thin film 2 of the metallizing film 10 of FIG. Can be obtained by, for example, a method of laminating by the above T-die extrusion polymer laminating method or a heat laminating method, adhering with an adhesive, or forming by a solution casting method. Figure 1
When the biodegradable polymer layer 1 is adhered onto the metal thin film 2 of the metallizing film 10 with the adhesive, it is preferable to use the biodegradable adhesive as described above as the adhesive. In addition, the adhesion amount of this adhesive is usually 1 to 20 g /
m ² and preferably 1 to 5 g / m ² .

The specific examples of the metallizing film according to the present invention have been described above. The metallizing film according to the present invention has a biodegradable polymer layer made of the above-mentioned specific aliphatic polyester and at least a part thereof is oxidized. As long as it is a laminated film containing a metal thin film which may be formed, various embodiments are possible without being limited to the above specific examples.

For example, on the surface of the metal thin film 2 of the metallizing film shown in FIG. 1, the surface of the paper layer 3 of the metallizing film shown in FIG. 2, or the surface of the biodegradable polymer layer 1 of the metallizing film shown in FIG. The adhesive layer may be formed. Further, the biodegradable polymer layer 1 and the pressure-sensitive adhesive layer may be formed in this order on the surface of the paper layer 3 of the metallizing film shown in FIG.
The metallizing film according to the present invention having the pressure-sensitive adhesive layer formed on one surface thereof can be used as a pressure-sensitive adhesive tape or a pressure-sensitive adhesive label body.

Further, an adhesive layer may be formed on both sides of the metallizing film shown in FIGS. The metallizing film according to the present invention having the pressure-sensitive adhesive layer formed on both surfaces of the film as described above can be used as a double-sided pressure-sensitive adhesive tape body.

The metallizing film shown in FIG. 3 is used as a packaging film or the like. The metallizing material according to the present invention is not limited to the above metallizing film, and the biodegradable polymer layer may be a three-dimensional object such as a tubular material or a plate-shaped material.

[0053]

As described above, the metallizing film according to the present invention has a polymer layer and a metal thin film which may be at least partially oxidized, and (I) ( 1) Aliphatic glycol and (2) aliphatic dicarboxylic acid or its acid anhydride, (3) alcoholic hydroxyl group 3
At least 1 selected from aliphatic polyols having 3 or more oxycarboxyl groups, aliphatic polyoxycarboxylic acids having 3 or more oxycarboxyl groups and their anhydrides, and aliphatic polycarboxylic acids having 3 or more carboxyl groups and their anhydrides
Of a number average molecular weight of 10,000 or more obtained by reacting (II) polyisocyanate with an aliphatic polyester polyol having a hydroxyl group at the end, which is obtained by reacting in the presence or absence of a seed compound. Aliphatic polyester (A), or said aliphatic polyester polyol in the presence of a catalyst at a temperature of 160 to 230 ° C. and 0.005
Since a biodegradable polymer layer composed of an aliphatic polyester (B) having a number average molecular weight of 10,000 or more obtained by a deglycolization reaction under a vacuum of 1 mmHg is used, the polymer layer is excellent in biodegradability. To destroy the environment,
It is characterized in that it does not significantly disturb the soil ecosystem and that the mechanical strength, water resistance and moldability can be adjusted according to the type of the aliphatic polyester.

Therefore, according to the present invention, the biodegradability and moldability are excellent, the biodegradable polymer layer and the metal thin film are in close contact with each other, and the mechanical strength and water resistance are dependent on the application. It is possible to provide a metallizing film in which is appropriately adjusted.

Further, when a metal thin film or a metal oxide thin film is formed on the biodegradable polymer layer by an ion plating method or a sputtering method, the adhesion between the biodegradable polymer layer made of the aliphatic polyester and the metal thin film is enhanced. Therefore, the oxygen permeation coefficient of the metallized film can be reduced.

Therefore, according to the method for producing a metallizing film of the present invention, which comprises such a thin film forming process, the metallizing film is excellent in adhesiveness with the biodegradable polymer layer, and gas permeation is excellent. It is possible to provide a metallizing film having a metal thin film having a low coefficient and a low electric resistance value (however, at least a part of the metal thin film may be oxidized).

[0057]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0058]

Example 1 An aliphatic polyester (trade name: Bionole # 3, which is a condensation reaction product of an aliphatic dicarboxylic acid and an aliphatic diol, having a thickness of 50 μm as a biodegradable polymer layer.
000, manufactured by Showa High Polymer Co., Ltd.), and an aluminum layer having a thickness of 200 angstrom was formed by an ion plating method.

After attaching a cellophane tape on the aluminum layer of the metallizing film thus obtained,
This cellophane tape was peeled off from the metallizing film, and the adhesiveness between the biodegradable polymer layer and the aluminum layer was evaluated from the state of the pressure-sensitive adhesive layer of the cellophane tape.

The oxygen permeability coefficient of the metallizing film was measured according to JIS K 7126. Further, the metallizing film is 100 mm ×
The sample obtained by cutting into a size of 100 mm has a depth of 10
It was buried in cm soil and left for 1 month and 3 months and then dug out, and the decomposition rate of the metallizing film was evaluated by the following formula.

[0061]

[Equation 1]

The above results are shown in Table 1.

[0063]

Example 2 A metallizing film was produced in the same manner as in Example 1 except that an aluminum layer was formed on the biodegradable polymer layer by a sputtering method instead of the ion plating method. The adhesion, oxygen permeability coefficient and decomposition rate were measured in the same manner as in Example 1.

The above results are shown in Table 1.

[0065]

Example 3 A metallizing film was produced in the same manner as in Example 1 except that an aluminum layer was formed on the biodegradable polymer layer by a vacuum deposition method instead of the ion plating method, and the obtained metallizing film was obtained. The adhesiveness, oxygen permeability coefficient and decomposition rate of were measured in the same manner as in Example 1.

The above results are shown in Table 1.

[0067]

[Comparative Example] The same as the above example except that a polyethylene terephthalate film (trade name: Torel mirror S-10, manufactured by Toray Industries, Inc.) having the same thickness was used instead of the biodegradable polymer layer. The metallizing film of the comparative example was produced, and the adhesiveness, oxygen permeability coefficient and decomposition rate of the obtained metallizing film were measured in the same manner as in Example 1.

The above results are shown in Table 1.

[0069]

[Table 1]

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a metallizing film according to the present invention.

FIG. 2 is a schematic sectional view of a metalizing film according to the present invention.

FIG. 3 is a schematic sectional view of a metalizing film according to the present invention.

[Explanation of symbols]

 10 ... Metallizing film 1 ... Biodegradable polymer layer 2 ... Metal thin film 3 ... Paper layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08L 67/04 75/06 NFX

Claims (6)

[Claims] 1. An (I) (1) aliphatic glycol and (2) an aliphatic dicarboxylic acid or an acid anhydride thereof are added to the above component (2).
5 mol% or less of (3) an aliphatic polyol having 3 or more alcoholic hydroxyl groups, an aliphatic polyoxycarboxylic acid having 3 or more oxycarboxyl groups and an anhydride thereof, and a fat having 3 or more carboxyl groups Reacting (II) a polyisocyanate with an aliphatic polyester polyol having a hydroxyl group at the end, which is obtained by reacting in the presence or absence of at least one compound selected from group polycarboxylic acids and their anhydrides The aliphatic polyester (A) having a number average molecular weight of 10,000 or more obtained by the above, or the aliphatic polyester polyol,
A temperature of 160-230 ° C. and 0.00 in the presence of a catalyst
A biodegradable polymer layer composed of an aliphatic polyester (B) having a number average molecular weight of 10,000 or more obtained by a deglycolization reaction under a vacuum of 5 to 1 mmHg, and a metal thin film which may be partially oxidized. A biodegradable metallizing material comprising a laminate having 2. The biodegradable metallizing material according to claim 1, wherein the metal thin film is laminated on one surface of the biodegradable polymer layer. 3. The biodegradation according to claim 1, wherein the metal thin film which may be at least partially oxidized and the biodegradable polymer layer are laminated on the paper layer in this order. Metallizing material. 4. The biodegradable meta-material according to claim 1, wherein the biodegradable metallizing material is a laminate of the biodegradable polymer layer / the metal thin film / the biodegradable polymer layer. Rising material. 5. The metal thin film, which may be at least partially oxidized, is a metal thin film or a metal oxide thin film formed by an ion plating method or a sputtering method. The biodegradable metallizing material according to any one of claims. 6. (I) (1) an aliphatic glycol and (2) an aliphatic dicarboxylic acid or an acid anhydride thereof are added to the above component (2).
5 mol% or less of (3) an aliphatic polyol having 3 or more alcoholic hydroxyl groups, an aliphatic polyoxycarboxylic acid having 3 or more oxycarboxyl groups and an anhydride thereof, and a fat having 3 or more carboxyl groups Reacting (II) a polyisocyanate with an aliphatic polyester polyol having a hydroxyl group at the end, which is obtained by reacting in the presence or absence of at least one compound selected from group polycarboxylic acids and their anhydrides The aliphatic polyester (A) having a number average molecular weight of 10,000 or more obtained by the above, or the aliphatic polyester polyol,
A temperature of 160-230 ° C. and 0.00 in the presence of a catalyst
On the biodegradable polymer layer composed of the aliphatic polyester (B) having a number average molecular weight of 10,000 or more obtained by deglycolization under a vacuum of 5 to 1 mmHg, a metal thin film or an ion plating method or a sputtering method is used. A method for producing a biodegradable metallizing material, which comprises forming a metal oxide thin film.