JP2001162977A - Biodegradable card substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a biodegradable card substrate, constituted of skin layers B laminated on both sides of a core layer A. SOLUTION: The biodegradable card substrate, usable for a biodegradable identification card, is constituted of the core layer A and skin layers B, laminated on both sides of the core layer A. In this case, the core layer A is constituted of a composite having the essential ingredients of the copolymer of 3- hydroxybutyric acid and/or 3-hydroxyvaleric acid and 3-hydroxyvaleric acid as well as a polymeric aliphatic polyester, obtained by the dehydrating polycondensation of a glycol constituent and an aliphatic dicarboxylic acid. The skin layer B is constituted of a composite having the essential ingredients of a polylactic acid and a polymeric aliphatic polyester, obtained by the dehydrating polycondensation of the glycol constituent and the aliphatic dicarboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a biodegradable card base material. More specifically, the present invention relates to a biodegradable card base material having a core layer (A) and a skin layer (B), which have excellent strength, rigidity, suitability for heat fusion processing, and are biodegradable by natural microorganisms.

[0002]

2. Description of the Related Art Conventionally, as a card base material for credit cards, cash cards, consultation tickets, membership cards, etc., printing is performed on both surfaces or one surface in order to impart strength, rigidity and heat-fusibility. A card base material is used which is obtained by laminating a core layer (A) made of a plastic such as polyvinyl chloride and a skin layer (B) made of a plastic such as polyvinyl chloride on which a magnetic stripe is thermocompression-bonded. Was.

It is made of a resin such as polyvinyl chloride,
The molding loss or the like generated when the card whose use is completed or the card base material made of polyvinyl chloride or the like is cut into a card shape is incinerated or landfilled with dust and the like.

However, in the case of incineration, used cards made of plastics, such as polyvinyl chloride, and card bases of molding loss, etc., have high calorie burns and may damage incinerators and the like, and there is a concern that dioxin may be generated. It tends to be problematic. Further, in the case of landfill treatment, there is a problem that plastics such as polyvinyl chloride are hardly decomposed in soil or the like and remain in the soil without being decomposed.

In recent years, as one means for solving the above problems, a biodegradable card base made of a plastic having excellent biodegradability, for example, poly-3-hydroxybutyric acid, polycaprolactone, polylactic acid, etc., is used as a card. It has been proposed to mold. However, card bases formed from poly-3-hydroxybutyric acid are brittle, have poor bending resistance, card bases formed from polylactic acid have poor solvent resistance, and card bases formed from polycaprolactone Has a problem in that it has a low rigidity (Young's modulus) and is not suitable for a card base material.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a card having the following characteristics: static bending strength, interlayer adhesion, warpage, external dimensional stability, laminated storage, nontoxicity, chemical resistance, and light resistance. And a biodegradable card base material which is excellent in temperature and humidity resistance and is biodegraded by microorganisms in a natural environment.

[0007]

The feature of the present invention is that a poly-
82-27% by weight of 3-hydroxybutyric acid and 9-% of polylactic acid
On both surfaces of a core layer (A) composed of a composition containing 40% by weight and 9 to 33% by weight of a high molecular weight aliphatic polyester obtained by dehydration polycondensation of a glycol component and an aliphatic dicarboxylic acid, 99-67% by weight of polylactic acid
And high molecular weight aliphatic polyesters 1-33 obtained by dehydration polycondensation of glycol component and aliphatic dicarboxylic acid
An object of the present invention is to provide a biodegradable card base material obtained by laminating a skin layer (B) composed of a composition containing, by weight, an essential component.

In the biodegradable card base material according to the present invention, the core layer (A) comprises 82 to 27% by weight of poly-3-hydroxybutyric acid, 9 to 40% by weight of polylactic acid, a glycol component and an aliphatic dicarboxylic acid. And 9 to 33% by weight of a high molecular weight aliphatic polyester obtained by dehydration polycondensation of
Other components may be blended within a range that does not impair the characteristics of the above. In addition, the skin layer (B) is a high-molecular aliphatic polyester 1-33 obtained by dehydrating polycondensation of 99-67% by weight of polylactic acid, a glycol component and an aliphatic dicarboxylic acid.
% Of the skin layer (B), and other components may be blended as long as the properties of the skin layer (B) are not impaired. The composition ratio of the composition constituting the core layer and the skin layer in the biodegradable card substrate composed of the core layer (A) and the skin layer (B) is usually at least 50% by weight, more preferably at least 70% by weight. , More preferably at least 85% by weight.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The poly-3-hydroxybutyric acid used for the core layer (A) constituting the biodegradable card base material according to the present invention is a homopolymer of poly-3-hydroxybutyric acid and / or 3-3-hydroxybutyric acid. -Refers to a copolymer of hydroxybutyric acid and 3-hydroxyvaleric acid. The homopolymer of poly-3-hydroxybutyric acid and the copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid are aliphatic polyester-based products having a melting point of 100 to 180 ° C. produced by microorganisms such as hydrogen bacterium Alcaligenes eutrophus. Degradable resins can be exemplified. Such a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid has a 3-hydroxyvaleric acid content of 0 to 20 in consideration of processability.
Molar% is preferred. The content of 3-hydroxyvaleric acid is
There is no particular limitation, but if it exceeds 20 mol%, the crystallinity and melting point tend to decrease and soften.

The polylactic acid used for the core layer (A) and the skin layer (B) of the biodegradable card base material according to the present invention includes, for example, L-lactic acid, D-lactic acid and D, L-lactic acid.
A polymer obtained by directly dehydrating polycondensation of any of lactic acid, or any of these lactic acids and another hydroxycarboxylic acid (eg, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, -Hydroxyvaleric acid, 6-hydroxycaproic acid, etc.), a polymer obtained by ring-opening polymerization of lactide, which is a cyclic dimer of lactic acid, or a polymer obtained by ring-opening polymerization of lactide and hydroxy The ring-opening weight is appropriately determined using a copolymerizable monomer such as a carboxylic acid cyclic ester intermediate [eg, glycolic acid dimer (glycolide), 6-hydroxycaproic acid cyclic ester caprolactone, etc.]. Copolymers obtained by condensation can be exemplified. As understood from this, polylactic acid includes all lactic acid-based polymers, and of course includes copolymers. One or more of these polylactic acids can be used as appropriate.

In the case of direct dehydration polycondensation, the lactic acid or lactic acid and another hydroxycarboxylic acid are azeotropically dehydrated and condensed in the presence of, for example, an organic solvent, particularly a phenyl ether-based solvent, and then the solvent is distilled off azeotropically. A method of returning a substantially anhydrous solvent to a reaction system by removing water can obtain a high-molecular-weight polylactic acid having excellent strength for polymerization, but is not particularly limited to the above method. At this time, the number average molecular weight (Mn) of the polylactic acid according to the present invention is not particularly limited,
The number average molecular weight (Mn) is preferably about 50,000 to 1,000,000. If the number average molecular weight (Mn) is less than 50,000, the strength tends to be weak, and if it exceeds 1,000,000, the moldability tends to be poor.

The polycaprolactone optionally used in the skin layer (B) constituting the biodegradable card base material according to the present invention is obtained by opening ε-caprolactone, which is a cyclic monomer, with an organometallic compound catalyst. An aliphatic polyester represented by the chemical structural formula of Chemical Formula 1 obtained by cycloaddition can be exemplified. Among such polycaprolactones, a polycaprolactone alone or a composition of polycaprolactone and polybutylene succinate is used to prepare a Vicat softening temperature (JI
(Measured by SK-7206). If the Vicat softening temperature is lower than 100 ° C., heat resistance tends to be inferior and moldability tends to decrease. The number average molecular weight (Mn) of polycaprolactone is not particularly limited, but is preferably from 1,000 to 120,000. If the number average molecular weight (Mn) is less than 1,000, strength and rigidity are reduced. If it exceeds 120,000, the moldability tends to be poor.

[0013]

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The high molecular weight aliphatic polyester obtained by dehydration polycondensation of the glycol component and the aliphatic dicarboxylic acid constituting the core layer (A) and the skin layer (B) of the biodegradable card base material according to the present invention. Are tri- or tetra-functional polyhydric alcohols, oxycarboxylic acids and polycarboxylic acids as a glycol component and a dicarboxylic acid (or an acid anhydride thereof), or, if necessary, as a third component. (Or an acid anhydride thereof), which is mainly composed of a polyester obtained by adding at least one polyfunctional component selected from the group consisting of an acid anhydride and esterifying by a dehydration polycondensation reaction, and having a hydroxy group at the terminal of the molecule. Is obtained by further increasing the molecular weight of a high molecular weight polyester prepolymer with a coupling agent (for example, diisocyanate). It can be exemplified those represented by the general formula. At this time, x / y ≧ 1.0, m and n indicate the length of the methylene chain.

[0015]

Embedded image

Although there is no particular limitation, specifically, polyethylene succinate (m = 2, n = 2), polybutylene succinate (m = 4, n = 2), polybutylene succinate adipate (m = 2) 4, n = 2, 4) can be mentioned as preferred.

The number average molecular weight (Mn) of the high molecular weight aliphatic polyester is 5,000 or more, preferably 1
A saturated aliphatic polyester having a melting point of not less than 000 and a melting point of not less than 60 ° C. can be exemplified. Number average molecular weight is 5,000
When the amount is less than 1, when the amount of the coupling agent used for increasing the number average molecular weight in the present invention is small (for example, 0.1 to 5% by weight), there is a tendency that a polyester having good physical properties cannot be obtained. Since the polyester prepolymer having a number average molecular weight of 5,000 or more does not generate a gel during the reaction even under severe conditions such as a molten state,
A good high molecular weight aliphatic polyester can be synthesized.

Further, in the present invention, the number average molecular weight (M
As the polyester prepolymer having n) of 5,000 or more, preferably 10,000 or more, a structure in which the polyester prepolymer is linked via a urethane bond derived from, for example, diisocyanate as a coupling agent; Polyester prepolymer has a long chain branch derived from a polyfunctional component, for example, a structure linked via a urethane bond derived from diisocyanate as a coupling agent, or an oxazoline, a diepoxy compound, an anhydride as a coupling agent When a product is used, a polyester prepolymer having a chain structure via an ester bond can be exemplified.

In the present invention, there is no particular limitation on the glycols constituting the high molecular weight aliphatic polyester to be blended in the core layer (A) and the skin layer (B), and ethylene glycol, 1,4-butanediol, , 6-hexanediol, decamethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol and the like, and these glycols may be used in combination. Among them, 1,4-butanediol can be mentioned as a preferable one.

In the present invention, succinic acid, adipic acid, speric acid, sebacic acid, dodecanoic acid are used as dicarboxylic acids (including acid anhydrides) constituting the high molecular weight aliphatic polyester by reacting with the glycols described above. Succinic anhydride, adipic anhydride and the like, and these dicarboxylic acids may be used in combination. Among them, succinic acid and adipic acid can be mentioned as preferred.

In addition to the above-mentioned glycols and dicarboxylic acids, if necessary, as a third component, a trifunctional polyhydric alcohol component (for example, trimethylolpropane, glycerin or an anhydride thereof) or a tetrafunctional polyhydric alcohol Component (eg, pentaerythrate), trifunctional polyvalent oxycarboxylic acid component (eg, malic acid), tetrafunctional polyvalent oxycarboxylic acid component (eg, citric acid and tartaric acid), and trifunctional polyvalent carboxylic acid (an acid anhydride thereof). (E.g., trimesic acid, propanetricarboxylic acid, etc.) and tetrafunctional polycarboxylic acids (including their acid anhydrides) (e.g., pyromellitic anhydride, benzophenonetetracarboxylic anhydride, cyclopentanetetrahydrate) At least one polyfunctional component selected from carboxylic acid anhydrides, etc. Riesuteru may be synthesized.
The addition of the third component tends to cause long-chain branching in the molecule, which tends to increase the molecular weight and broaden the molecular weight distribution, and can be expected to impart favorable properties to film forming and the like. At this time, the addition amount of the third component is 0.1 to 5 mol% for the trifunctional component with respect to 100 mol% of the total components of the aliphatic dicarboxylic acid (including the acid anhydride) so that gelation does not occur. In the case of a tetrafunctional component, 0.1 to 3 mol% can be exemplified.

Further, the melting point of the high molecular weight aliphatic polyester according to the present invention is 70 to 190 ° C., more preferably 70 to 190 ° C.
The temperature is 150 ° C, particularly preferably 80 to 135 ° C. 70
If the temperature is lower than ℃, the heat resistance is insufficient, and if it exceeds 190 ° C, the production tends to be difficult. A polyester prepolymer for obtaining a polyester having a melting point of 70 ° C. or more;
Is preferably 60 ° C. or higher, but is not particularly limited.

The amount of urethane bonds contained in the high molecular weight aliphatic polyester used in the present invention is 0.03.
To 3.0% by weight, more preferably 0.05 to 2.0% by weight, still more preferably 0.1 to 1.0% by weight. 0.
If the amount is less than 03% by weight, the effect of polymerization by urethane bonds is small, and the moldability tends to be inferior. If the amount exceeds 3.0% by weight, a gel tends to be generated.

In the biodegradable card base material according to the present invention, the core layer (A) is composed of 82 to 27% by weight of poly-3-hydroxybutyric acid, 9 to 40% by weight of polylactic acid, and 9 to 40% of high molecular weight aliphatic polyester. It is molded from a composition containing 33% by weight as an essential component. The compounding ratio of such a composition is poly-3-
When hydroxybutyrate is less than 27% by weight, solvent resistance is poor and printability tends to decrease. When poly-3-hydroxybutyric acid exceeds 82% by weight, tensile strength, rigidity, impact strength and the like are reduced. Tend to. If the high molecular weight aliphatic polyester is less than 9% by weight, the core layer (A)
Printability, (A) layer and (A) layer or (A) layer and (B)
There is a tendency that an improvement in interlayer adhesion with a layer cannot be expected, and 3
If it exceeds 3% by weight, the rigidity tends to decrease. Accordingly, the core layer (A) has the following properties required as a card base material: static bending strength, interlayer adhesion, warpage, appearance dimensional stability, lamination storage property, nontoxicity, chemical resistance, light resistance, It has excellent temperature and humidity resistance and can further contribute to the supportability of the skin layer (B).

The skin layer (B) of the biodegradable card base material according to the present invention comprises a high molecular weight aliphatic polyester 1 obtained by dehydrating polycondensation of 99 to 67% by weight of polylactic acid, a glycol component and an aliphatic dicarboxylic acid. A layer composed of a composition containing -33% by weight as an essential component is preferred. At this time, if the blending amount of the high molecular weight aliphatic polyester is less than 1% by weight, it becomes brittle,
Further, the heat-fusibility between the skin layer (B) and the core layer (A) tends to be insufficient, and if it exceeds 33% by weight, the rigidity tends to decrease.

The other skin layer (B) in the biodegradable card substrate according to the present invention is obtained by dehydrating polycondensation of the above-mentioned polycaprolactone with polylactic acid, a glycol component and an aliphatic dicarboxylic acid. The composition comprising the high-molecular-weight aliphatic polyester and polycaprolactone may be added in an amount of 27% by weight or less to all polymer components.
At this time, if it exceeds 27% by weight, the rigidity is reduced.
It tends to be undesirable as a card.

In the biodegradable card base material according to the present invention, the skin layer (B) is composed of the composition as described above, is laminated on both surfaces of the core layer (A), and the core layer (A)
In order to protect the printing surface on which printing is applied on the surface of the surface and to show the printing more clearly, the transparency tends to be high, and the tendency to contribute to the engraving of embossed characters and the like, the adhesion of the magnetic stripe, etc. is there.

In the biodegradable card base material according to the present invention, the core layer (A) and the skin layer (B) are (B) / (A) /
(B) three-layer structure, or (B) / (A) / (A) /
The four-layer structure (B) can be mentioned as a preferable example.

The biodegradable card base material according to the present invention is (B)
In the case of a four-layer configuration of / (A) / (A) / (B), when it is necessary to print on both surfaces of the (A) / (A) configuration of the core layer, for example, two core layers (A ), One side of the core layer (A) and the other one of the core layers (A) are appropriately printed with images, characters, etc., and the printed surface of each core layer (A) has two skins. By laminating so as to be in contact with the layer (B) and bonding the non-printing surfaces of the core layer (A) together, a biodegradable card substrate having printing on both sides of the core layer can be easily obtained. .

Specifically, for example, first, 82 to 27% by weight of poly-3-hydroxybutyric acid, 9 to 40% by weight of polylactic acid, and a high molecular weight aliphatic polyester obtained by dehydration polycondensation of a glycol component with a dicarboxylic acid At least two core layers (A) each comprising a composition containing 9 to 33% by weight of an essential component, 99 to 67% by weight of polylactic acid, and a high molecular weight fat obtained by dehydration polycondensation of a glycol component and a dicarboxylic acid. At least two skin layers (B) composed of a composition containing 1 to 33% by weight of a group III polyester are essential components. At this time, as the skin layer (B), the total amount of polylactic acid and the high molecular weight aliphatic polyester was 73% by weight or more, and polycaprolactone 27 was used.
It may be a layer made of a composition containing, by weight, not more than an essential component.

Next, images, characters, and the like are printed on one surface of each of the two core layers (A) by, for example, an offset method or a silk screen method. Printing completed 2
One core layer (A) has a printing surface of one core layer (A).
The printed surface of another core layer (A) is arranged on one skin layer (B) so as to be in contact with the other skin layer (B). Print faces face each other,
The core layer (A) / (A) is sandwiched with the skin layer (B) so that (B) / (A) / (A) / (B),
An unbonded biodegradable card base is prepared. The sandwiched biodegradable card base material in the non-adhered state is sandwiched between, for example, mirror plates, and heated, pressed, and cooled to form a biodegradable card base material that can easily see through the printing surface from both sides. An example of the method is as follows.

The biodegradable card base material according to the present invention is not particularly limited. For example, the core layer (A) and the skin layer (B)
Lamination through an adhesive, a co-extrusion method in which layers (A) and (B) are laminated using a co-extrusion die connected to at least two extruders, or at least two types For example, a method of separately forming a card base material, for example, a layer (A) and a layer (B), and laminating them by a thermocompression bonding method can be exemplified.

Among these methods, the thermocompression bonding method can be exemplified as a preferable method. At this time, the pressure is 3-40k
g / cm @ 2, the heating temperature is 140 DEG to 190 DEG C., and the heating and pressurizing time is 30 seconds to 30 minutes, but there is no particular limitation.

The biodegradable card base material according to the present invention has properties as a card base material (static bending strength, interlayer adhesion, warpage, external dimensions, lamination storage property, nontoxicity, chemical resistance, light resistance). , The thickness of the core layer (A), which contributes to supporting the skin layer (B), is as follows.
720 to 480 μm when composed of two sheets, 360 to 240 μm when composed of two sheets, skin layer (B)
Is preferably 20 to 140 μm, but these numerical values are not particularly limited.

In the biodegradable card base material according to the present invention, the composition constituting the core layer (A) and / or the skin layer (B) may be, if desired, an additive and a filler, for example, a heat stabilizer. , Antioxidants, ultraviolet absorbers, antistatic agents,
Lubricants, antibacterial agents, waxes, pigments or dyes, titanium oxide, calcium carbonate, barium sulfate, calcium hydroxide, mica, talc and the like can be added. Also,
Other thermoplastic resins and the like can be blended as needed within a range not to impair biodegradability, and are not particularly limited.

The above-mentioned other thermoplastic resins are not particularly limited, but include other biodegradable resins, such as poly-3-hydroxyvaleric acid, 3-hydroxybutyric acid and 3-hydroxypropionate. A copolymer with a acrylate, a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, a poly-3-hydroxyalkanoate, or the like can be blended as necessary.

In the biodegradable card base material according to the present invention, the method for preparing the composition constituting the core layer (A) and / or the skin layer (B) is not particularly limited. A method commonly used in the production of a composition such as a system resin, for example, a method of blending with a ribbon blender, a Hensel mixer, a tumbler, a kneader,
A method of kneading using a kneader such as a Banbury mixer or a roll, and a method of heating and melting and kneading using a single-screw or twin-screw extruder can be exemplified.

The biodegradable card base material according to the present invention may be provided with a printing layer and a heat-sensitive recording layer as required. In this case, it is preferable to provide between the surface of the core layer (A) and the skin layer (B) or between layers. In the case of a magnetic card, it is preferable to form a magnetic stripe before or after cutting on the surface of the skin layer (B) by an appropriate method.
Also, after cutting the card, if necessary,
It is preferable that an embossed character (including a sign, a symbol, and the like) be imprinted on the surface of the card by an appropriate method, but there is no particular limitation. Furthermore, the biodegradable card base material according to the present invention has a static bending strength, an interlayer adhesion, a warp, which are characteristics of a card.
It has excellent dimensional stability, storage stability, non-toxicity, chemical resistance, light resistance, temperature and humidity resistance, and is biodegradable in nature by microorganisms and the like.

[0039]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. However, the present invention is not limited to the examples described below. In the examples described later, the measurement and evaluation of each item were performed by the methods described below.

[Static bending strength]: JIS X-6301
According to the above-mentioned No. 1, the one with load deformation in the range of 13 to 35 mm and reproducibility within 1.5 mm was regarded as good. [Interlayer adhesion]: The interlayer adhesion strength was measured according to JIS X-6301, and was 6 N / cm or more.

[Warp]: (In the case of a non-embossed card) Place the card on the surface plate,
One end of the long side of the card was fixed to the plane of the surface plate, and the maximum floating distance from the surface plate at the other end was 1.5 mm or less (including the card thickness). (In the case of an embossed card) Place the card on the surface plate with the convex side up and fix one end of the long side of the card to the surface of the surface plate. 2.
5 mm or less (including the thickness of the card and excluding the height of the embossed characters) was regarded as good.

[Appearance dimensional stability]: Those having a card size within the range described below were evaluated as good. Long side: 85.47 to 85.72 mm Short side: 53.92 to 54.03 mm Thickness: 0.68 to 0.84 mm [Lamination storage property]: The state of the card after stacking non-embossed cards is as described below. Was regarded as good. (1) No delamination. (2) No fading or discoloration. (3) No change in surface roughness. (4) There is no movement of the substance from the bonding surface. (5) No deformation. (6) One card can be easily separated from the stacked card group.

[Non-toxicity]: No. 3D-2 of the standard for food and additives (Notification No. 370 of the Ministry of Health and Welfare in 1959)
The test was performed according to a synthetic resin device or a container and packaging. (Operating temperature: 100 ° C or less) As a result, those which conform to the standard value of polyethylene terephthalate were judged to be non-toxic. [Chemical resistance]: After performing the processing described below in accordance with JIS X-6301, the static bending strength, interlayer adhesion, and external dimensions were measured, and those having no change from before the processing were evaluated as good. a) 5% aqueous solution of sodium chloride b) 5% aqueous solution of acetic acid c) 5% aqueous solution of sodium carbonate d) 60% aqueous solution of ethyl alcohol e) 10% aqueous solution of sucrose f) Solution B (according to ISO1817) g) 50% aqueous solution of ethylene glycol h ) Spraying 5% aqueous sodium chloride solution i) 5% aqueous sodium hydroxide solution j) 5% aqueous acetic acid solution For each of a) to g), keep each solution at 20 to 25 ° C and soak the card substrate for 1 minute. h) is maintained for 24 hours after spraying. i) to j) immerse the card substrate for 24 hours.

[Light resistance]: According to JIS X-6301, a fluorescent lamp with an illuminance of 5000 Lux was irradiated for 96 hours, and the static bending strength, interlayer adhesion strength, and external dimensions were measured, and were unchanged from those before irradiation. Was regarded as good.

[Temperature and Humidity Resistance]: According to JIS X-6301, after the card is stored under the following temperature and relative humidity conditions, the external dimensions are the same as before storage, and in the case of a non-embossed card, warpage occurs. In the case of an embossed card having a warpage of not more than 1.5 mm, the one having a warpage of not more than 2.5 mm was regarded as good. (1) -35 ° C (2) 50 ° C (3) 25 ° C5% RH (4) 25 ° C95% RH

[Biodegradability]: size 85.5 × 54 mm
The biodegradable card base material is immersed (retained at 25 ° C) in the returned sludge collected and treated at the Purification Center (Shinagawa Prefectural Sewerage Corporation, Konan Central Office), taken out 28 days later, and the weight loss rate is measured and evaluated. did. After 18 months, the weight loss rate was measured and evaluated. The weight loss rate was defined and calculated as follows.

[0047]

[Formula 1]

Example 1 In a biodegradable card base material comprising (B) layer / (A) layer / (A) layer / (B) layer, a poly-layer was used as a core layer (A).
40% by weight of 3-hydroxyvaleric acid and 32% by weight of polylactic acid obtained by ring-opening polymerization of lactide of L-lactic acid, and 16% by weight of Bionole 1003 (polybutylene succinate (PBS)) manufactured by Showa Polymer Co., Ltd. 8% by weight of talc,
A composition containing 4% by weight of titanium oxide is melt-kneaded using a T-die extruder set at a cylinder temperature of 190 ° C. and a die temperature of 180 ° C., and then extruded onto a cooling roll having a surface temperature of 60 ° C. A sheet with a length of 280 μm was used. As the skin layer (B), 80% by weight of polylactic acid obtained by ring-opening polymerization of lactide of L-lactic acid and Bionole 1003 (polybutylene succinate (PB
S)) 15% by weight, Bionore 3 manufactured by Showa High Polymer Co., Ltd.
003 (polybutylene succinate adipate (PBS
A)) A composition containing 5% by weight is supplied to a T-die extruder set at a cylinder temperature of 210 ° C. and a die temperature of 200 ° C., melt-kneaded, and extruded on a cooling roll having a surface temperature of 50 ° C. And a sheet having a thickness of 100 μm.

An image is printed and printed on the surface of the two sheets to be the core layer (A) obtained above by an offset printing machine, and one printing of the skin layer (B) is performed on the printing surface of one core layer (A). ) And another skin layer (B) was also superimposed on the printed surface of another core layer (A). Thereafter, the non-printed surfaces of the core layer (A) having the layer structure (A) / (B) obtained above are opposed to each other, and the layer (B) / (A) layer / (A) layer /
(B) The four sheets were stacked in a sandwich form so as to form a layer to obtain a non-adhered laminate. Then, the laminate was
After sandwiching between two metal mirror plates, the temperature was raised to 165 ° C. in 20 minutes, and then thermocompression-bonded at that temperature for 5 minutes under a pressure of 5 kg / cm 2, and cooled to 40 ° C. in 20 minutes. / (A) /
(A) / (B) = 100/280/280/100 = 7
A 60 μm biodegradable sheet substrate was formed.

Next, the card obtained by cutting the biodegradable sheet substrate has a static bending strength, interlayer adhesion,
Table 1 shows the characteristics of the card having warpage, external dimensional stability, lamination storage property, nontoxicity, chemical resistance, light resistance, and temperature and humidity resistance. In addition, the weight loss rate after immersing the biodegradable card in the returned sludge described above at 25 ° C. for 28 days was about 5% or less. 15%. It is presumed that it will eventually be decomposed into water and carbon dioxide. (Excluding talc, titanium and printing components.)

Example 2 The skin layer (B) was composed of 80% by weight of polylactic acid obtained by ring-opening polymerization of lactide of L-lactic acid, and Bionore 1003 (Polybutylene succinate (PB
S)) 20% by weight and the total amount of polylactic acid and PBS 10
A biodegradable card was formed in the same manner as in Example 1 except that the composition was 0.04 parts of blue pigment with respect to 0 parts by weight. Static bending strength of biodegradable card, interlayer adhesion,
Table 1 shows the characteristics of the card having warpage, external dimensional stability, lamination storage property, nontoxicity, chemical resistance, light resistance, and temperature and humidity resistance. In addition, the weight loss rate after immersing the biodegradable card in the returned sludge described above at 25 ° C. for 28 days was about 5% or less. 18%. It is presumed that it will eventually be decomposed into water and carbon dioxide.

Example 3 The skin layer (B) was composed of 80% by weight of polylactic acid obtained by ring-opening polymerization of lactide of L-lactic acid, and Bionore 1003 (Polybutylene succinate (PB
S)) 5% by weight, polycaprolactone (PCL) HB0515% by weight, and polylactic acid and P
A biodegradable card was formed in the same manner as in Example 1, except that the composition was composed of 0.04 part of the blue pigment with respect to 100 parts by weight of the total amount of BS and PCL. Static bending strength of biodegradable card, interlayer adhesion, warpage, external dimensional stability,
Table 1 shows the characteristics of the laminated storage, non-toxicity, chemical resistance, light resistance, and temperature and humidity resistance of the card. In addition, the weight loss rate after immersing the biodegradable card in the returned sludge described above at 25 ° C. for 28 days was about 5% or less. 16%. It is presumed that it will eventually be decomposed into water and carbon dioxide.

Example 4 The core layer (B) was composed of 32% by weight of poly-3-hydroxyvaleric acid, 30% by weight of polylactic acid obtained by ring-opening polymerization of lactide of L-lactic acid, and Showa Polymer Co., Ltd. Bionore 3
003 (polybutylene succinate adipate (PBS
A)) A biodegradable card was formed in the same manner as in Example 1 except that the composition was composed of 26% by weight, 8% by weight of talc, and 4% by weight of titanium oxide. Static bending strength of biodegradable card, interlayer adhesion, warpage, external dimensional stability,
Table 1 shows the characteristics of the laminated storage, non-toxicity, chemical resistance, light resistance, and temperature and humidity resistance of the card. In addition, the weight loss rate after immersing the biodegradable card in the returned sludge described above at 25 ° C. for 28 days was about 5% or less. 16%. It is presumed that it will eventually be decomposed into water and carbon dioxide.

Comparative Example 1 A commercially available vinyl chloride card was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0055]

[Table 1]

As is apparent from Table 1, the biodegradable cards comprising the biodegradable card base materials of Examples 1 and 2 containing a high-molecular-weight aliphatic polyester have card properties and have an interlayer adhesion. And it has biodegradability. On the other hand, the vinyl chloride card obtained in Comparative Example 1 had excellent properties as a card, but did not have biodegradability.

[0057]

The card formed from the biodegradable card base material according to the present invention has biodegradability, interlayer adhesion between the core layer (A) and the skin layer (B), and characteristics as a card. Is excellent.

Continued on the front page F term (reference) 2C005 HA10 HA21 JA02 JA08 KA02 KA25 KA40 KA70 LA03 LA22 4F100 AA21H AC10H AK41A AK41B AK41C AK41D AK41J AL01A AL01B AL01C AL01D AL05A AL05B AL05C AL05 BA10 BA07 BA07 BA07 BA07 BA07 BA07 BA07 JK06 YY00A YY00B YY00C YY00D

Claims (9)

[Claims] 1. High molecular weight aliphatic polyester obtained by dehydration polycondensation of 82 to 27% by weight of poly-3-hydroxybutyric acid, 9 to 40% by weight of polylactic acid and glycol component and aliphatic dicarboxylic acid, 9 to 33% by weight. % On both surfaces of a core layer (A) composed of a composition having an essential component of 99% to 67% by weight of polylactic acid and a high molecular weight aliphatic polyester obtained by dehydration polycondensation of a glycol component and an aliphatic dicarboxylic acid. A biodegradable card base obtained by laminating a skin layer (B) comprising a composition containing 1 to 33% by weight as an essential component. 2. The core layer (A) and the skin layer (B) each have a three-layer structure of (B) / (A) / (B) or (B) /
The biodegradable card base material according to claim 1, which has a four-layer structure of (A) / (A) / (B). 3. The skin layer (B) has a total amount of at least 73% by weight of a polylactic acid and a glycol component and a high molecular weight aliphatic polyester obtained by dehydration polycondensation of an aliphatic dicarboxylic acid, and 27% by weight of polycaprolactone. The biodegradable card substrate according to any one of claims 1 and 2, comprising a composition comprising the following as essential components: 4. The glycol component constituting the high molecular weight aliphatic polyester is ethylene glycol, 1.4-butanediol, 1,6-hexanediol, decamethylene glycol, neopentyl glycol, 1,4-cyclohexanediyl. The biodegradable card base material according to any one of claims 1 to 3, wherein the biodegradable card base material is at least one member selected from the group consisting of methanol. 5. The aliphatic dicarboxylic acid constituting the high molecular weight aliphatic polyester is one or two selected from the group consisting of succinic acid, adipic acid, suberic acid, sebacic acid, dodecanoic acid, succinic anhydride and adipic anhydride. 5. The biodegradable card base material according to claim 1, which is at least one kind. 6. A high molecular weight aliphatic polyester comprising at least one glycol component and at least one aliphatic dicarboxylic acid.
The biodegradable card base material according to claim 1, wherein the seed or two or more kinds are a polymer or a copolymer synthesized by dehydration polycondensation. 7. The high-molecular-weight aliphatic polyester is obtained by preparing a third component other than a glycol component and an aliphatic dicarboxylic acid from a trifunctional or tetrafunctional polyhydric alcohol, an oxycarboxylic acid and a polycarboxylic acid or an anhydride thereof. The biodegradable card base material according to any one of claims 1 to 6, further comprising at least one selected polyfunctional functional component. 8. The biodegradable card substrate according to claim 1, wherein the number average molecular weight (Mn) of the high molecular weight aliphatic polyester is 5,000 or more. 9. The biodegradable composition according to claim 1, wherein the high molecular weight aliphatic polyester is at least one selected from polyethylene succinate, polybutylene succinate and polybutylene succinate adipate. Card base material.