JP2002356542A - Polyhydroxyalkanoate-containing card - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a card capable of preventing environmental pollution arising from its disposal, by using a card comprising a biodegradable plastic having an excellent processability on extrusion molding, mechanical characteristics, heat resistance. SOLUTION: The mono- or multi-layered card comprises at least a polyhydroxyalkanoate having a monomer unit represented by the formula (1) (the monomer unit is at least one selected from the group consisting of monomer units specifying as: R1 is a hydrogen atom and a is an integer of 5 to 10 R1 is a halogen atom and a is an integer of 1 to 10, R1 is a chromophore and a is an integer of 1 to 10, R1 is a carboxyl group and a is an integer of 1 to 10 or R1 is a glycidyl group and a is an integer of 1 to 7).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a card used for various plastic cards such as a credit card, a cash card, an ID card and the like and various prepaid cards such as a telephone card (registered trademark) and a shopping card. By using a card substrate using a so-called biodegradable degradable plastic material, which can be substituted for a card substrate such as a polyvinyl chloride card,
The present invention relates to a card capable of preventing the destruction of the natural environment and promoting pollution elimination. Furthermore, the present invention relates to a card having improved physical properties such as mechanical strength and storage stability.

[0002]

2. Description of the Related Art In recent years, various plastic cards such as credit cards, cash cards, and ID cards, and various disposable prepaid cards such as telephone cards, shopping cards, commuter passes, and pass tickets have been adopted in various fields and industries. In particular, among these various cards, so-called prepaid cards (prepaid cards) in which a certain unit amount is paid in advance and value information corresponding to the amount is recorded as a card which is most frequently used. This card has value information and identification information printed or printed on the card base via a read / write device as picture / character information, and a magnetic or optical recording unit provided on the card base. Since the information is recorded as read information, mechanical characteristics called gate characteristics, such as durability, bending resistance, and stiffness, are required to enable use in the read / write device. As a material which satisfies such conditions and is easy to manufacture, polyethylene terephthalate (PET) resin or the like is widely used as a card base material. As a base material for general cards such as credit cards, cash cards, and ID cards, polyvinyl chloride resin is widely used.

After this type of card is sold or lent to a user, most of the card is discarded when the user finishes using the card. The disposal of such cards after use is conventionally disposed of by incineration or landfill as waste, but plastic waste generates a large amount of combustion energy by incineration. There is a problem such as durability of the steel, a problem of processing cost by installing a high heat resistance furnace, and a problem of air pollution due to generation of harmful combustion gas such as carbon monoxide, sulfur compound, chlorine gas, dioxin and the like. In the landfill process, the plastic material remains almost permanently without being decomposed and is deposited as waste at the disposal site, which has become a social problem as a garbage problem. Moreover, since plastic materials exist underground in their original form,
There is a risk that the ground of the landfill will not be stable and that it will adversely affect various types of natural creatures in the land and area where the plastic material is landfilled.

As a countermeasure against the above-mentioned problem, a card using paper as a card base material has been conventionally used.
In particular, paper is one of card materials suitable for solving environmental problems such as the trash problem discussed above in recent years, since it is easy to dispose such as incineration and landfill and the production cost is low. However, when paper is used as a card base, durability, bending resistance, water resistance, chemical resistance,
In consideration of suitability as a card such as waterproofness, surface smoothness, glossiness, workability, etc., the function is inferior in all respects,
The use of paper alone has been limited to only temporary use such as toll tickets, admission tickets, and tickets. In order to solve these problems, it is conceivable to laminate an outer layer other than plastic such as a synthetic resin such as polyethylene, polypropylene, polyvinyl chloride, or polyethylene terephthalate or an aluminum foil as a protective layer on a paper base, but these are discarded. It has a drawback that it is not excellent in properties and does not differ much from the plastic card described above.

Therefore, Japanese Patent Application Laid-Open No. 57-150393 and
JP-A-59-220192, JP-A-51-93991, JP-A-Showa 6
As described in Japanese Patent Application Laid-Open No. 3-260912 and Japanese Patent Application Laid-Open No. 57-150393, plastics that can be decomposed under natural environment such as light or underground have been developed, and are used for disposable product packages, Some have been commercialized. In the field of cards, JP-A-5-42786 and JP-A-5-85088 describe the use of biodegradable or photodegradable plastics for card substrates. Japanese Patent Application Laid-Open No. 6-9788 discloses a card having a biodegradable resin layer on one or both sides of a paper base material, which has characteristics as a conventional plastic card and has excellent disposability. However, in view of the suitability as a card such as durability, bending resistance, water resistance, chemical resistance, waterproofness, surface smoothness, glossiness and workability, the function was still insufficient.

For example, among currently available biodegradable resins, biodegradable resins satisfying mechanical properties such as bending resistance and rigidity required as a card by itself are described as follows.
For example, a polymer sheet mainly containing polylactic acid or a copolymer of lactic acid and oxycarboxylic acid can be used.
However, these biodegradable resins have a drawback that they are hydrolyzed during storage and become brittle, which has been a problem in terms of water resistance. The hydrolysis can be solved by removing the residual catalyst and unreacted monomers used in the synthesis, but on the other hand, in the polylactic acid-based polymer, the polymer chain is degraded by the initial hydrolysis. It is biodegradable after shortening and reducing the molecular weight, and under normal conditions such as suppressing hydrolysis, biodegradation becomes extremely slow, and it is necessary to accelerate decomposition under heating conditions such as compost equipment. The problem that biodegradation is difficult occurs.

On the other hand, for example, 3-hydroxy-n-butyric acid and 3-hydroxy-n-butyric acid
Copolymers with hydroxy-n-valeric acid (hereinafter sometimes abbreviated as PHB / V) and other aliphatic polyesters are
Although it has excellent biodegradability, it has mechanical properties similar to polyethylene and has softness, but it is inferior in mechanical strength such as durability, bending resistance, rigidity, etc. required for machine reading / writing. ing. For example, poly-ε-caprolactone has a low melting point of 60 ° C., and if it exceeds about 50 ° C., stickiness and softening become severe, and a molded product of itself alone has low practicality. Also, these aliphatic polyesters,
Even if other biodegradable resins or inorganic additives (e.g., calcium carbonate, magnesium carbonate, calcium sulfide, etc.) are added, the durability, bending resistance, stiffness, etc., are lower than those of the materials used for current cards. The problem is that the mechanical properties of the above are inferior.

As another problem, a new card which solves the above-mentioned problems can also be provided with embossing on a card base so that characters and numerical information can be provided as uneven characters. It is naturally required to have a conventional card function, such as being able to provide a visible information display unit at least in part. In other words, even when a resin made of a different material from the conventional material is used for the card base material, it is possible to provide a card that can provide functionality that is not inferior to that of a conventional card made of PET resin or vinyl chloride resin. It is important to use it in a wide range of fields and applications.

In recent years, as one method for solving environmental pollution caused by waste such as plastic molded articles,
It has been proposed to use plastics decomposable by microorganisms and the like as described above as molding materials. For example, as a high molecular compound derived from a microorganism, poly-3-hydroxy-n-butyric acid (hereinafter sometimes abbreviated as PHB) or a copolymer of 3-hydroxy-n-butyric acid and 3-hydroxy-n-valeric acid is used. Coalescence
(Hereinafter sometimes abbreviated as PHB / V), poly-hydroxyalkanoates such as poly-ε-caprolactone (hereinafter P
HA), polysaccharides such as bacterial cellulose and pullulan, and polyamino acids such as poly-γ-glutamic acid and polylysine are known. In particular, PHA can be used for various products by melt processing and the like, as well as conventional plastics, and has excellent biocompatibility, and is also expected to be applied as a soft medical member or the like.

(Biosynthesis of PHA) It has been reported that many microorganisms produce PHA and accumulate in the cells. For example, Alcaligenes eutrophus H16 strain
(Alcaligenes eutropus H16, ATCC No. 17699),
Methylobacterium sp., Paracoccus sp., Alcaligenes sp.
aligenes sp.), Pseudomonas sp.
Production of PHB / V by microorganisms has been reported (JP-A-5-74492, JP-B-6-15604, JP-B-7-15604).
-14352, Japanese Patent Publication No. 8-19227). In addition, Comamonas acidovorans IFO 13852 strain (Comamo
nas acidovorans IFO 13852) is disclosed to produce PHA having 3-hydroxy-n-butyric acid and 4-hydroxy-n-butyric acid as monomer units (JP-A-9-1918).
No. 93). In addition, Aeromonas Cavier
onas caviae) to produce a copolymer of 3-hydroxy-n-butyric acid and 3-hydroxyhexanoic acid (JP-A-5-93049, JP-A-7-265065).

[0011] The biosynthesis of PHB and PHB / V is based on (R) -3-hydroxybutyryl CoA or (R) -3- produced from various carbon sources through various metabolic pathways in vivo.
The reaction is carried out by an enzymatic polymerization reaction using hydroxyvaleryl CoA as a substrate. CoA is a coenzyme A (co
enzyme A), and its chemical structure is as follows.

[0012]

[Formula 10]

However, these linear aliphatic polyesters, which are copolymers of 3-hydroxybutyric acid and / or 3-hydroxyvaleric acid, are liable to be thermally decomposed because their melting points and thermal decomposition temperatures are close to each other. And the extrusion processability is poor. In addition, the linear aliphatic polyester has high crystallinity, so that it is hard, brittle, has small elongation, and tends to have poor mechanical properties. Therefore, this is not preferable as a material as a molded product by itself.

(Mcl-PHA) In recent years, a medium-chain length of 3 to 12 carbon atoms has been considered.
Polyhydroxyalkanoate composed of hydroxyalkanoic acid units (hereinafter sometimes abbreviated as mcl-PHA)
Research on has been energetically conducted.

For example, in Japanese Patent Publication No. 2642937, Pseudomonas oleovorans ATCC 29347 strain (Ps
It is disclosed that by providing acyclic aliphatic hydrocarbons to Eudomonas oleovorans ATCC 29347), PHA having a monomer unit of 3-hydroxyalkanoic acid having 6 to 12 carbon atoms is produced. Also,
Appl. Environ. Microbiol., 58, 746 (1992), Pseudomonas resinov
orans) produce PHA using octanoic acid as a single carbon source and 3-hydroxy-n-butyric acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid, and 3-hydroxydecanoic acid as monomer units, It has been reported to produce PHA using hexanoic acid as a single carbon source and using 3-hydroxy-n-butyric acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid, and 3-hydroxydecanoic acid as units. Here, it is considered that the introduction of the 3-hydroxyalkanoic acid monomer unit having a longer chain length than the raw material fatty acid is via a fatty acid synthesis pathway.

Int. J. Biol. Macromol., 16 (3), 119 (1
994) includes Pseudomonas sp. 61-3 strain (Pseudomonas s.
p.strain 61-3), using sodium gluconate as a single carbon source, 3-hydroxy-n-butyric acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid, 3-hydroxydecanoic acid, and 3-hydroxydodecanoic acid 3-hydroxyalkanoic acid and 3-hydroxy-5-cis-decenoic acid, 3
It has been reported that PHA is produced using 3-hydroxyalkenoic acid as a unit, such as -hydroxy-5-cis-dodeceneic acid.

However, these mcl-PHAs are:
Like the above-mentioned poly-ε-caprolactone, it has a low melting point, and if it exceeds about 50 ° C., stickiness and softening become severe, and a molded product of itself alone has low practicality.

(Unusual-PHA) By the way, the above PHA
Is a PHA composed of a monomer unit having an alkyl group in a side chain (hereinafter may be abbreviated as “usual-PHA”).
However, in consideration of a wider range of applications, for example, application as a card base material, substituents other than an alkyl group (e.g., phenyl group, unsaturated hydrocarbon, ester group, allyl group,
PHA in which a cyano group, a halogenated hydrocarbon, an epoxide, or the like is introduced into a side chain (hereinafter, sometimes abbreviated as unusual-PHA) is extremely useful.

Examples of the biosynthesis of unusual-PHA having a phenyl group include, for example, Macromolecules, 24, 525.
6-5260 (1991), Macromol. Chem., 191, 1957-196.
5 (1990), Chirality, 3, 492-494 (1991), etc., report that Pseudomonas oleovorans produces PHA containing 3-hydroxy-5-phenylvaleric acid unit from 5-phenylvaleric acid. . Also, Macromol
ecules, 29, 1762-1766 (1996).
Oleobolans is reported to produce PHAs containing 3-hydroxy-5- (4-tolyl) valeric acid units from 5- (4-tolyl) valeric acid (5- (4-methylphenyl) valeric acid). . Further, Macromolecules, 32, 2889-2895
(1999) included Pseudomonas oleovorans
From (2,4-dinitrophenyl) valeric acid to 3-hydroxy-
5- (2,4-dinitrophenyl) valeric acid unit and 3-
It is reported to produce PHA containing a hydroxy-5- (4-nitrophenyl) valeric acid unit.

Further, unusual-PH having a phenoxy group
Examples of A include Macromol. Chem. Phys., 195, 1
In 665-1672 (1994), Pseudomonas oleovorans was able to convert 3-hydroxy-5- from 11-phenoxyundecanoic acid.
It is reported to produce PHA containing a phenoxyvaleric acid unit and a 3-hydroxy-9-phenoxynonanoic acid unit. Also, Macromolecules, 29, 3432-3
In 435 (1996), Pseudomonas oreobolans
PHA containing 6-phenoxyhexanoic acid to 3-hydroxy-4-phenoxybutyric acid unit and 3-hydroxy-6-phenoxyhexanoic acid unit; 8-phenoxyoctanoic acid to 3-hydroxy-4-phenoxybutyric acid unit, 3-hydroxy A PHA containing a 6-phenoxyhexanoic acid unit and a 3-hydroxy-8-phenoxyoctanoic acid unit is converted from 11-phenoxyundecanoic acid to a 3-hydroxy-5-phenoxyvaleric acid unit and a 3-hydroxy-7-phenoxyheptanoic acid unit PHAs containing
Has been reported to produce. In addition, Can.J.Mi
crobiol., 41, 32-43 (1995)
Oleobolans ATCC 29347 and Pseudomonas putida KT2442 (Pseudomonas putida KT244)
2) reported that PHA containing 3-hydroxy-p-cyanophenoxyhexanoic acid units or 3-hydroxy-p-nitrophenoxyhexanoic acid units was produced from p-cyanophenoxyhexanoic acid or p-nitrophenoxyhexanoic acid. ing. Patent No. 2989175 discloses 3-
Hydroxy-5- (monofluorophenoxy) valeric acid unit or 3-hydroxy-5- (difluorophenoxy)
Homopolymer composed of valeric acid units, at least 3-
A copolymer containing a hydroxy-5- (monofluorophenoxy) pentanoate unit or a 3-hydroxy-5- (difluorophenoxy) pentanoate unit and a method for producing the same are described. It is said that stereoregularity and water repellency can be imparted while maintaining excellent workability.

In addition, an unusual-containing cyclohexyl group
Examples of PHA include Macromolecules, 30, 1611-1.
In 615 (1997), Pseudomonas oleovorans was obtained from cyclohexylbutyric acid or cyclohexylvaleric acid.
There is a report that HA will be produced.

The biosynthesis of these mcl-PHA and unusual-PHA is produced from various alkanoic acids as raw materials through various metabolic pathways in vivo (for example, β-oxidation system and fatty acid synthesis pathway) (R). It is carried out by an enzymatic polymerization reaction using -3-hydroxyacyl CoA as a substrate. Here, in the case of going through the fatty acid synthesis pathway, (R) -3-
(R) -3-Hydroxyacyl CoA converted from hydroxyacyl-ACP (ACP is an acyl carrier protein) serves as a substrate for an enzymatic polymerization reaction.

[0023]

As described above, the conventional card uses polyvinyl chloride or PET, which is difficult to dispose, as the card base material. And may cause various environmental problems. Further, since cards are used in large quantities and the amount of use tends to increase year by year, urgent measures for disposal of discarded cards are strongly desired. The present invention has been made to solve the above problems, and has as its object to provide a card capable of preventing the occurrence of various environmental problems due to disposal.

Furthermore, extrusion processability, mechanical properties,
Another object of the present invention is to provide a molded product made of a biodegradable plastic having excellent heat resistance and the like. In addition, it satisfies the mechanical characteristics required for machine reading and writing, such as durability, bending resistance, rigidity, etc., as well as recording and visual information display functions, which are the functions of conventional cards. It is intended to provide a card that enables the user to be satisfied.

As described above, by applying the biotechnological technique to the synthesis of the card base material, it is possible to synthesize a new card base material which is difficult to realize by the conventional organic synthesis technique. . Also, in many cases, the production process that required a multi-stage reaction in the conventional organic synthetic chemistry method can be realized with only one stage, which simplifies the production process, reduces costs, and shortens the required time. And other effects can also be expected. Furthermore, it is possible to reduce the use of organic solvents, acids and alkalis, surfactants, etc., set mild reaction conditions, synthesize from non-petroleum-based raw materials and low-purity raw materials (* notes), etc. It is possible to provide a card composed of a resource recycling type synthesis process. (* Note: In biotechnological synthesis processes, in general, because of the high substrate specificity of the catalytic enzyme,
Even if low-purity raw materials are used, a desired reaction can be selectively advanced. Therefore, the use of waste and recycled materials can be expected. )

[0026]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, at least a part of the card base material is represented by the formulas [1] to [7]. By using a polyhydroxyalkanoate containing at least a monomer unit, the present inventors have found that a biodegradable molded product excellent in extrusion processability, mechanical properties, heat resistance, and the like can be obtained, and have reached the present invention.

That is, according to the present invention, at least a part of a card base material used for a card having a single layer or a plurality of layers comprises a polyhydroxy resin comprising at least a monomer unit represented by the formulas [1] to [7]. A card comprising an alkanoate.

[0028]

[Formula 11]

(Where the monomer unit is represented by R
The combination of 1 and a is at least one selected from the group consisting of any of the following monomer units.

R1 is a hydrogen atom (H) and a is 5 to 10
A monomer unit in which R1 is a halogen atom and a is an integer of 1 to 10, R1 is a chromophore and a is 1 to 1
R1 is a monomer unit that is any of the integers 0
A monomer unit wherein R1 is a carboxyl group and a is any integer from 1 to 10,

[0031]

[Formula 12]

A monomer unit wherein a is any integer from 1 to 7. )

[0033]

[Formula 13]

(Where b represents any one of integers from 0 to 7, and R2 represents a hydrogen atom (H), a halogen atom, -CN,-
_{NO 2, -CF 3, -C 2} F 5, represents any one selected from the group consisting of -C ₃ F _7. )

[0035]

[Formula 14]

(Where c represents any one of integers from 1 to 8, and R3 represents a hydrogen atom (H), a halogen atom, -CN,-
It represents any one selected from the group consisting of NO ₂ , —CF ₃ , —C ₂ F ₅ , and —C ₃ F ₇ . )

[0037]

[Formula 15]

(Where d represents any one of integers from 0 to 7, and R4 represents a hydrogen atom (H), a halogen atom, -CN,-
It represents any one selected from the group consisting of NO ₂ , —CF ₃ , —C ₂ F ₅ , and —C ₃ F ₇ . )

[0039]

[Formula 16]

(Wherein, e represents any one of integers from 1 to 8, and R5 represents a hydrogen atom (H), a halogen atom, -CN,-
_{NO 2, -CF 3, -C 2} F 5, -C 3 F 7, -CH 3, -C 2 H 5, -C 3 H
₇ represents any one selected from the group consisting of ₇ . )

[0041]

[Formula 17]

(Where f represents any one of integers from 0 to 7).

[0043]

[Formula 18]

(Where g represents an integer of 1 to 8). The present invention also provides that the card substrate containing the polyhydroxyalkanoate covers the entire periphery of the card. It is a featured card.

Further, the present invention provides a polyhydroxyalkanoate, a polylactic acid, a polylactic acid, and a polyhydroxyalkanoate, wherein the card substrate containing the polyhydroxyalkanoate comprises at least the polyhydroxyalkanoate and a monomer unit represented by the formula [8]. A card as a base material obtained by kneading at least one selected from -ε-caprolactone and a photodegradable resin.

[0046]

[Formula 19]

(However, the monomer unit is at least one selected from the group consisting of monomer units in which a is any integer from 0 to 4.) A copolymer of ethylene and carbon monoxide, a mixture of polyethylene and an organic acid metal salt,
A card which is at least one selected from a mixture of polypropylene and a metal salt of an organic acid, and wherein the metal salt of the organic acid is at least one selected from iron stearate, cerium stearate, and cobalt stearate.

Further, the card base material containing the polyhydroxyalkanoate is a base material obtained by kneading a polyhydroxyalkanoate and a filler, and the filler is made of calcium carbonate, mica, calcium silicate, white carbon, asbestos, and clay. (Firing), at least one selected from glass fibers, and further a card obtained by kneading a polyhydroxyalkanoate and a filler and then biaxially stretching the card.

The present invention also provides a card wherein the polyhydroxyalkanoate has a number average molecular weight of 10,000 to 1,000,000.

Further, according to the present invention, at least one selected from a magnetic recording layer, a heat-sensitive recording layer, and a visible information display layer is formed on at least a part of the card base material. A card characterized by being at least one selected from an embossed character layer, a thermosensitive recording display layer, a reversible thermosensitive recording display layer, and a magnetic recording display layer.

[0051]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <Construction of Card> The card of the present invention will be described in detail with reference to the drawings. FIG. 1 is a plan view showing one embodiment of the card of the present invention, FIG. 2 is a cross-sectional view of FIG. 1, FIG. 3 is a cross-sectional view showing another embodiment of the card of the present invention, and FIG. FIG. 7 is a cross-sectional view showing one embodiment of another configuration of the card of FIG.

The card of the present invention can be formed as a card base body having a laminated structure in which the base material of a card is formed of only one sheet of a single layer base material, or the base materials of a plurality of sheets are laminated. You may comprise.

The card of the present invention uses, as a sheet, a substrate comprising PHA containing at least the monomer units represented by the formulas [1] to [7] as the substrate constituting the card substrate body. is there. Examples of the laminated structure of the base material in these card base bodies include, for example, P having a white color.
A single-layer HA sheet, or a PHA sheet having a white color and laminated by being sandwiched between two transparent PHA sheets from above and below,
Further, there may be mentioned, for example, a laminate in which two laminated PHA sheets having a white color are interposed and sandwiched between two transparent PHA sheets from above and below.

<PHA as a base material of the card of the present invention> Here, PHA has a basic skeleton as a biodegradable resin, is highly safe, and has an effect of not adversely affecting human bodies and the environment. Can be expected. PHA, like conventional plastics, can be used for the production of various products by melt processing, etc., and, unlike synthetic polymers derived from petroleum, has the remarkable property that it can be decomposed by living organisms. I have. Therefore, when disposed, PHA is biodegraded and is taken into the material cycle in the natural world. Therefore, PHA may remain in the natural environment and cause pollution like many synthetic polymer compounds conventionally used. No,
Its safety is extremely high. Furthermore, by performing biodegradation treatment, there is no need to perform combustion treatment, so it is an effective material from the viewpoint of preventing air pollution and global warming.
It can be used as a plastic that enables environmental conservation.

The PHA represented by the formulas [1] to [7] of the present invention will be specifically described. PH used in the present invention
A is a polyester resin having 3-hydroxyalkanoate as a monomer unit. Here, when such a compound is produced using a microorganism, the polyester resin is an isotactic polymer consisting only of the R-form. For example, it is not necessary to use an isotactic polymer, and an atactic polymer can be used. Further, PHA is obtained by a chemical synthesis method in which a lactone compound is subjected to ring-opening polymerization using an organometallic catalyst (for example, an organic catalyst containing aluminum, zinc, tin, etc.).
It is also possible to get

In the present invention, in the side chain structures represented by the formulas [1] to [5], R1 to R5 are each a hydrogen atom, a halogen atom, a cyano group, a nitro group, a nitro group, a perfluoroalkyl group, an epoxy group. , An alkyl group or the like, and one or more atoms or functional groups selected from the group. In addition, as a specific example of the halogen atom,
Examples include fluorine, chlorine, and bromine. here,
For the side chain structures represented by the formulas [1] to [5], for example, R
By having a structure in which 1 to R5 are substituted with a fluorine atom, it is possible to further reduce the environmental dependency. In the case of substitution with a fluorine atom, a monomer unit containing a fluorine atom may be contained in the polymer in an amount of 1 mol% or more, and the ratio may be selected in consideration of desired environmental dependence. Regarding the substitution positions of R1 to R5, it is possible to obtain a PHA consisting of a corresponding monomer unit at any of the ortho, meta and para positions, but it is possible to obtain a functional or physical property such as any isomer. When there is no significant difference, a substituent at the meta-position or para-position can be suitably used in terms of yield or ease of incorporation into a polymer.

As the PHA of the present invention, it is possible to use a random copolymer or a block copolymer containing a plurality of the above monomer units, and to control the physical properties of the PHA by utilizing the characteristics of each monomer unit and the functional group contained therein. And a plurality of functions can be provided, and a new function can be expressed by utilizing an interaction between functional groups. Furthermore, by appropriately controlling the amount and order of addition of the monomer compounds, it is also possible to synthesize a block copolymer having an arbitrary order and composition ratio. Further, if necessary, after PHA is synthesized or during the synthesis, chemical modification or the like may be further performed.
As described above, when the PHA of the present invention is produced using a microorganism, the PHA may contain the various monomer units described above. However, when the PHA is designed to contain an appropriate number in consideration of the required polymer functionality, physical properties, and the like. good. In general, it is expected that the object of the present invention can be sufficiently achieved by including the above-mentioned about 6 types of monomer units. However, if delicate functionality and control of physical properties are desired, more types of monomer units can be used. It is also possible to configure.

The softening point of PHA in the present invention is as follows:
Preferably, the temperature is at least 50 ° C. or higher.

The PHA having the desired physical properties can be obtained by selecting the culture conditions and the like of the microorganism capable of synthesizing the PHA in the present invention. For example, the number average molecular weight can be controlled by controlling the culture time and the like. In addition, the number average molecular weight can be controlled by removing low molecular weight components using means such as solvent extraction and reprecipitation. Here, the softening point has a correlation with the molecular weight of PHA. Further, the softening point can be controlled by controlling the type / composition ratio of the monomer units in the PHA. In addition, the PH of the present invention
A has a number average molecular weight Mn of preferably 10,000 to 1,000,000. If Mn is less than 10,000, the softening point is lowered, and practicality is impaired. On the other hand, if it exceeds 1,000,000, the viscosity at the time of melting becomes high, and the workability in the manufacturing process is deteriorated.

<Examples of PHA and its manufacturing method>
Here, the synthesis of the PHAs of the formulas [1] to [7]
Can be produced by culturing a microorganism which can be produced from the corresponding alkanoic acid in a medium containing the corresponding alkanoic acid. The culturing method and the like will be described later.

For example, from 5- (4-fluorophenyl) valeric acid (FPVA) represented by the following formula [10], 3-hydroxy-5- (4-fluorophenyl) represented by the following formula [9] By culturing a microorganism capable of producing a polyhydroxyalkanoate containing a valeric acid (3HFPV) monomer unit, it is possible to produce a polyhydroxyalkanoate containing a 3HFPV monomer unit.

[0062]

[Formula 20]

Further, from 5- (4-trifluoromethylphenyl) valeric acid (CF ₃ PVA) represented by the following formula [12], 3-hydroxy-5- (4) represented by the following formula [11] is obtained. By culturing a microorganism capable of producing a polyhydroxyalkanoate containing (trifluoromethylphenyl) valeric acid (3HCF ₃ PV) monomer unit, it is possible to produce a polyhydroxyalkanoate containing 3HCF ₃ PV monomer unit. is there.

[0064]

[Formula 21]

A 4-hydroxy-4-phenoxybutyric acid (PxBA) represented by the following formula [14] is converted to a polyhydroxyalkano containing a 3-hydroxy-4-phenoxybutyric acid (3HPxB) monomer unit represented by the following formula [13]: By culturing a microorganism capable of producing an ate, it is possible to produce a polyhydroxyalkanoate containing a 3HPxB monomer unit.

[0066]

[Formula 22]

Further, from 4-cyclohexylbutyric acid (CHBA) represented by the following formula [16], 3-cyclohexylbutyric acid (CHBA) represented by the following formula [15] is obtained.
By culturing a microorganism capable of producing a polyhydroxyalkanoate containing a hydroxy-4-cyclohexylbutyric acid (3HCHB) monomer unit, it is possible to produce a polyhydroxyalkanoate containing a 3HCHB monomer unit.

[0068]

[Formula 23]

Further, from a 5-benzoylvaleric acid (BzVA) represented by the following formula [18], a polymer containing a 3-hydroxy-5-benzoylvaleric acid (3HBzV) monomer unit represented by the following formula [17] is obtained. By culturing a microorganism capable of producing hydroxyalkanoate, it is possible to produce polyhydroxyalkanoate containing 3HBzV monomer units.

[0070]

[Formula 24]

Further, from 5- (4-fluorobenzoyl) valeric acid (FBzVA) represented by the following formula [20], 3-hydroxy-5- (4-fluorobenzoyl) represented by the following formula [19] By culturing a microorganism capable of producing a polyhydroxyalkanoate containing a valeric acid (3HFBzV) monomer unit, it is possible to produce a polyhydroxyalkanoate containing a 3HFBzV monomer unit.

[0072]

[Formula 25]

Further, from a 5-thienyl valeric acid (TVA) represented by the following formula [22], a poly (meth) acrylate containing a 3-hydroxy-5-thienyl valeric acid (3HTV) monomer unit represented by the following formula [21]: By culturing a microorganism capable of producing hydroxyalkanoate, it is possible to produce polyhydroxyalkanoate containing 3HTV monomer units.

[0074]

[Formula 26]

Further, from a 5-benzoylvaleric acid (ToVA) represented by the following formula [24], a polymer containing a 3-hydroxy-5-benzoylvaleric acid (3HToV) monomer unit represented by the following formula [23] is obtained. By culturing a microorganism capable of producing hydroxyalkanoate, it is possible to produce polyhydroxyalkanoate containing 3HToV monomer units.

[0076]

[Formula 27]

(Microorganism) As the PHA of the present invention, a microorganism appropriately selected from microorganisms producing PHA, or a microorganism synthesized by a transformant into which a PHA synthase gene of those microorganisms has been introduced can be used.

Microorganisms that synthesize PHA include PHB
And PHB / V-producing bacteria. Examples of such microorganisms include Aeromonas sp., Alcaligenes sp., And Chromium sp.
romatium sp.), Comamonas sp.
Methylobacterium sp., Paracoccus sp., Pseudomonas sp.
udomonas sp.), a strain of Bulk hordelia cepacia KK01 isolated by the present inventors (Burkhos sp.
lderia cepacia KK01), Ralstonia eutropha TB64 strain (Ralstonia eutropha TB64), Alcaligenes sp. TL2 strain (Alcaligenes sp. TL2), and the like. The KK01 strain has the deposit number FER
As MBP-4235, the TB64 strain has the deposit number FERM B
P-6933, strain TL2 was deposited under accession number FERM BP-69.
13 have been deposited at the Patent Microorganisms Depositary Center of the Biotechnology and Industrial Technology Research Institute of the Ministry of Economy, Trade and Industry.

Mcl-PHA and unusual-PHA producing bacteria can be used. Examples of such microorganisms include Pseudomonas oleovorans, Pseudomonas reginovabolans, Pseudomonas sp. 61-3, Pseudomonas putida KT2442, Pseudomonas Pseudomonas putida P9 strain isolated by the present inventors in addition to Aeruginosa and the like.
1), Pseudomonas chicory eye H45 strain (Pseudomona
s cichorii H45), Pseudomonas chicory eye YN
2 strains (Pseudomonas cichorii YN2) and 161 strains of Pseudomonas jessenii P
161) and the like, and JP-A-2001-78753.
Publication No. 3 (Burkhoderia genus OK3 strain)
lderia sp.OK3, FERM P-17370), JP 2001-699A
No. 68, Burkholderia sp.
Burkholderia microorganisms such as kholderia sp. OK4 and FERM P-17371) can be used. In addition to these microorganisms, Aeromonas ssp.
p.) and Comamonas sp.
It is also possible to use microorganisms that produce -PHA or unusual-PHA.

The P91 strain has a deposit number of FERM BP-73.
The H45 strain as accession number FERM BP-7374; the YN2 strain as accession number FERM BP-7375;
The P161 strain has a deposit number of FERM BP-7376, based on the Budapest Treaty on the International Recognition of Deposit of Microorganisms for Patent Procedures, based on the Research Institute of Biotechnology, National Institute of Advanced Industrial Science and Technology (formerly the Ministry of Economy, Trade and Industry). It has been deposited internationally at the Patented Microorganisms Depositary.

The YN2 strain, H45 strain, P91 strain and P161
Show details about the strain. <Bacteriological properties of YN2 strain> (1) Morphological properties Cell shape and size: bacilli, 0.8 μm × 1.5-2.0 μm Cell polymorphism: no Motility: yes Sporulation: no Gram stain : Negative Colony shape: Circular, whole edge smooth, low convex, surface smooth, glossy, translucent (2) Physiological properties Catalase: Positive oxidase: Positive O / F test: Reduction of oxidized (non-fermentative) nitrate: Negative Indole production: Positive Glucose acidification: Negative Arginine dihydrolase: Negative urease: Negative Esculin hydrolysis: Negative Gelatin hydrolysis: Negative β-galactosidase: Negative Fluorescent dye production on King's B agar: Positive 4% NaCl Growth: Positive (weak growth) Accumulation of poly-β-hydroxybutyric acid: Negative (*) Hydrolysis of Tween 80: Positive * Judged by staining nutrient agar culture colonies with Sudan Black. (3) Substrate utilization glucose: positive L-arabinose: positive D-mannose: negative D-mannitol: negative N-acetyl-D-glucosamine: negative maltose: negative potassium gluconate: positive n-capric acid: positive adipic acid : Negative dl-malic acid: Positive Sodium citrate: Positive Phenyl acetate: Positive <Bacteriological properties of H45 strain> (1) Morphological properties Cell shape and size: Bacillus, 0.8 μm × 1.0-1.2 μm cells Polymorphism of: No Motility: Yes Sporulation: No Gram stain: Negative Colony shape: Round, whole edge smooth, low convex, surface layer smooth, gloss, cream color (2) Physiological properties Catalase: Positive oxidase: Positive O / F test: Oxidized nitrate reduction: Negative Indole formation: Negative Glucose acidification: Negative Arginine dihydrolase: Negative urease: Negative Esculin hydrolysis: Negative gelatin Hydrolysis: Negative β-galactosidase: Negative Fluorescent dye production in King's B agar: Positive Growth in 4% NaCl: Negative Accumulation of poly-β-hydroxybutyric acid: Negative (3) Substrate utilization glucose: Positive L- Arabinose: negative D-mannose: positive D-mannitol: positive N-acetyl-D-glucosamine: positive Maltose: negative potassium gluconate: positive n-capric acid: positive adipic acid: negative dl-malic acid: positive sodium citrate: Positive phenyl acetate: Positive <Bacteriological properties of strain P91> (1) Morphological properties Cell shape and size: Bacillus, 0.6 μm × 1.5 μm Cell polymorphism: No Motility: Yes Sporulation: No Gram stain: negative Colony shape: round, whole edge smooth, low convex, surface layer smooth, gloss, cream color (2) Physiological properties Catalase: Positive oxidase: Positive O / F test: Reduction of oxidized nitrate : Negative Indole production: Negative Glucose acidification: Negative Arginine dihydrolase: Positive urease: Negative Esculin hydrolysis: Negative Gelatin hydrolysis: Negative β-galactosidase: Negative Fluorescent dye production on King's B agar: Positive (3) Substrate Glucose: Positive L-arabinose: negative D-mannose: negative D-mannitol: negative N-acetyl-D-glucosamine: negative Maltose: negative potassium gluconate: positive n-capric acid: positive adipic acid: negative dl- Malic acid: Positive Sodium citrate: Positive Phenyl acetate: Positive (2) Physiological properties Catalase: Positive oxidase: Positive O / F test: Reduction of oxidized nitrate: Positive Indole formation: Negative Glucose acidification: Negative Arginine dihydrolase: Positive urease: Negative Esculin hydrolysis: Negative gelatin hydrolysis : Negative β-galactosidase: Negative Fluorescent dye production in King's B agar: Positive (3) Substrate utilization glucose: Positive L-arabinose: Positive D-mannose: Positive D-mannitol: Positive N-acetyl-D-glucosamine : Positive Maltose: Negative Potassium gluconate: Positive n-capric acid: Positive Adipic acid: Negative dl-malic acid: Positive Sodium citrate: Positive phenyl acetate: Positive <Culture substrate> Acetyl-CoA or energy source in the method of the present invention Substrates that can effectively supply a carbon source include yeast extract, polypeptone, and meat extract. Scan (e.g. beef extract), it is possible to use the medium for components derived from natural products, such as casamino acids, further, sugars, TCA
Organic acids generated as intermediates in the circuit and organic acids or their salts, amino acids or their salts formed through one- or two-step biochemical reactions from the TCA cycle, such as acetyl-CoA or energy sources without passing through the β-oxidation system. Any compound that can supply a carbon source can be appropriately selected according to its usefulness as a substrate for the strain used.

When the proportion of the desired bulky monomer may be low, a straight-chain alkanoic acid having 4 to 12 carbon atoms or a salt thereof may be used as the substrate. However, in this case, a simple monomer having no substituent and a straight chain (hereinafter, mc
It should be noted that the ratio (abbreviated as l) increases.

Among these, saccharides include glyceraldehyde, erythrose, arabinose, xylose,
Aldoses such as glucose, galactose, mannose and fructose, glycerol, erythritol,
One or more compounds selected from alditols such as xylitol, aldonic acids such as gluconic acid, uronic acids such as glucuronic acid and galacturonic acid, and disaccharides such as maltose, sucrose and lactose can be suitably used.

Examples of the organic acid or a salt thereof include pyruvic acid, oxaloacetic acid, citric acid, isocitric acid, ketoglutaric acid, succinic acid, fumaric acid, malic acid, lactic acid, and the like. One or more compounds can be suitably used.

Further, as the amino acid or a salt thereof, one or more compounds selected from glutamic acid, aspartic acid and a salt thereof can be suitably used.

Among these, it is preferable to use polypeptone or a saccharide, and among the saccharides, it is more preferable to use at least one selected from the group consisting of glucose, fructose and mannose. These substrates are usually 0.1% to 5% (w / v) per medium, more preferably
Desirably, it is contained at a rate of 0.2% to 2%.

<Culture In general> By culturing these microorganisms in a medium containing a desired alkanoate for introducing a monomer unit and the growth substrate of the present invention, the desired P
HA can be produced. Such a PHA is generally composed of only the R-form and is an isotactic polymer.

The usual culture of microorganisms used in the method for producing PHA of the present invention, for example, the preparation of a preserved strain, the culture for ensuring the number of cells and the active state, and the like, may adversely affect the growth and survival of the microorganism. Unless otherwise, any type of medium such as a general natural medium or a synthetic medium supplemented with nutrients can be used. Culture conditions such as temperature, aeration and stirring are appropriately selected depending on the microorganism used. For example, types such as batch culture, fed-batch culture, semi-continuous culture, and continuous culture are not limited. As a form of the liquid batch culture, there are a method of supplying oxygen by shaking with a shaking flask and a method of supplying oxygen by stirring and aeration using a jar fermenter. Further, a multi-stage system in which these steps are connected in a plurality of stages may be adopted.

When PHA is produced using the above-mentioned PHA-producing microorganism, for example, the microorganism is grown in an inorganic medium containing alkanoic acid such as octanoic acid or nonanoic acid, and the logarithmic growth phase to the early stage of the stationary phase. For example, a method of extracting the desired PHA by collecting the microorganisms by the centrifugation or the like can be used. When culturing is performed under the above conditions, mcl-PHA derived from the added alkanoic acid is synthesized in the cells.

The inorganic medium used in the above-mentioned culturing method contains a component capable of growing microorganisms, such as a phosphorus source (for example, phosphate) or a nitrogen source (for example, ammonium salt or nitrate). Any medium may be used as long as it is an inorganic salt medium, for example, MSB medium, E medium (J. Biol. C)
218, 97-106 (1956)), M9 medium and the like. Note that M9 used in the embodiment of the present invention
The composition of the medium is as follows. [M9 medium] Na ₂ HPO ₄ : 6.2 g KH ₂ PO ₄ : 3.0 g NaCl: 0.5 g NH ₄ Cl: 1.0 g (pH 7.0 in 1 liter of medium) Further, for good growth and production of PHA synthase In the above-mentioned mineral salt medium, 0.3
% (V / v) is preferably added. (Trace component solution) nitrilotriacetic _{acid: 1.5g MgSO 4: 3.0g MnSO 4} : 0.5g NaCl: 1.0g FeSO 4: 0.1g CaCl 2: 0.1g CoCl 2: 0.1g ZnSO 4: 0.1g CuSO 4: 0.1g AlK (SO ₄ ) ₂ : 0.1 g H ₃ BO ₃ : 0.1 g Na ₂ MoO ₄ : 0.1 g NiCl ₂ : 0.1 g (in 1 liter) The culture temperature should be such that the above strains can grow well. Good, for example, about 15 to 40 ° C, preferably about 20 to 35 ° C.

<Recovery of PHA> For obtaining PHA from the culture solution according to the present invention, a commonly used method can be applied. When PHA is secreted into the culture solution, an extraction and purification method from the culture solution is used, and when PHA is accumulated in the cells, an extraction and purification method from the cells is used. For example, for the recovery of PHA from cultured microbial cells of microorganisms, extraction with an organic solvent such as chloroform, which is usually performed, is the simplest, but dioxane, tetrahydrofuran, acetonitrile, and acetone may be used in addition to chloroform. . In environments where organic solvents are difficult to use, treatment with a surfactant such as SDS,
Treatment with enzymes such as lysozyme and treatment with chemicals such as EDTA, sodium hypochlorite, hydrogen peroxide, and ammonia removes bacterial components other than PHA, and recovers only PHA by removing intracellular components. A method can also be adopted.

[0092] In addition, culture of microorganisms, PHA by microorganisms
Production and accumulation in cells, and PHA from cells
Is not limited to the above method. For example, as the microorganism used in the method for producing PHA according to the present invention, other than the above-mentioned four strains, the same microorganism having the ability to produce PHA according to the present invention similar to these four strains can be used. .

<Biosynthesis Using Transformant> A desired PHA can be produced using a transformant in which the PHA synthase gene of the above-mentioned PHA-producing bacterium has been introduced into another microorganism. is there. Cloning of the PHA synthase gene, preparation of an expression vector, and preparation of a transformant can be performed according to a standard method. In a transformant obtained by using a bacterium such as Escherichia coli as a host, a natural medium or a synthetic medium, for example,
LB medium, M9 medium and the like. The culture temperature is
The microorganism is grown aerobically for 8 to 27 hours at a temperature in the range of 25 to 37 ° C. to promote the growth of the microorganism. Thereafter, the cells are collected, and PHA accumulated in the cells can be collected. The medium contains
If necessary, antibiotics such as kanamycin, ampicillin, tetracycline, chloramphenicol, and streptomycin may be added. When an inducible promoter is used in the expression vector, expression may be promoted by adding an inducer corresponding to the promoter to the medium when culturing the transformant. For example, isopropyl-β-D-thiogalactopyranoside (IPTG), tetracycline, indoleacrylic acid (IAA) and the like can be mentioned as the inducer.

<Substrate of Card> The card according to the present invention comprises a substrate which constitutes a card substrate main body and contains at least a monomer unit represented by any one of formulas [1] to [7].
A can be mixed with PHA, polylactic acid, poly-ε-caprolactone, a photo-decomposable resin or the like containing at least the monomer unit represented by the formula [8].

The PHA containing at least the monomer unit represented by the formula [8] is synthesized by a microorganism as described above and has biodegradability.

(Other Biodegradable Plastics) Polylactic acid can be polymerized by polycondensation because lactic acid as a monomer compound has a hydroxyl group and a carboxyl group in the molecule. However, dehydration condensation has a molecular weight of 4
Since only oligomers with a low degree of polymerization of less than 000 can be obtained,
Once an oligomer of lactic acid is obtained, a polymer can be obtained by a ring-opening polymerization method (indirect method). Further, a method using a catalyst, JP-A-59-96123, JP-A-63-289020
The polymer can be obtained by a known method such as a method of obtaining polylactic acid having a molecular weight of 4000 or more by heating and pressurizing in an inert gas atmosphere (direct method).

Poly-ε-caprolactone is a cyclic monomer
Is obtained by ring-opening polymerization of ε-caprolactone
it can. Poly-ε-caprolactone has a density (23 ° C) of 1.145 g.
/ cm ^Three, Melt flow index (MFI) 0.1-30
More preferably, from the viewpoint of extrusion processability, 1 to 10, crystallization
Temperature (TC) about 22 ° C, weight average molecular weight 40,000-100,000
The degree can be exemplified as preferable.

Further, a commercially available biodegradable plastic can be kneaded and used together with the PHA of the present invention. For example, thermoplastic polyester from ICI, trade name "Biopol", starch / modified PVA from Novamoat,
Product name "Mater-Bi", starch / modified PVA type from Warner Lambert, product name "Novon", lactic acid type from Shimadzu Corporation, product name "Lacty", lactic acid type from Mitsui Toatsu Kogyo, product name "Lacia"", Polycaprolactone from UCC, dicarboxylic acid / diol system from Nippon Polyolefin Co., Ltd., trade name" Bionore "and the like.

(Photodegradable resin) As the degradable resin,
By using a photodegradable resin in addition to the PHA of the present invention,
A degradable resin having both photodegradability and microbial degradability can be obtained.

The photodegradable resin includes, for example, a copolymer of ethylene and carbon monoxide. This ethylene / carbon monoxide copolymer has 2
It is said to decompose by cleavage between the third and third carbons by light. And the decomposition rate can be adjusted by the content of carbon monoxide in the copolymer. Normal,
The density of ethylene / carbon monoxide copolymer is 0.89 ~ 0.95g / c
m ³ , and the content of carbon monoxide is about 0.1 to 10 mol%. Ethylene / carbon monoxide copolymer as described above, for example, ethylene and carbon monoxide at a temperature of 230 ℃,
It can be produced by coexisting under the condition of a pressure of about 200 MPa (≒ 2000 atm). Further, as a photodegradable degradable polyolefin resin, polyethylene (density 0.
870 to 0.950 g / cm ³ , melt flow index (MFI)
0.4 to 40) or a mixture of polypropylene (density 0.88 to 0.91 g / cm ³ , melt flow index (MFI) 0.2 to 50) and a metal salt of an organic acid. Examples of the organic acid metal salt include iron stearate, cerium stearate, cobalt stearate, and the like. The mixing amount of the organic acid metal salt is preferably about 1 to 5000 ppm. These degradable resins are
A single substance may be used, or two or more kinds may be mixed, and may be appropriately selected according to necessary properties such as strength and decomposability.

Further, if necessary, a non-degradable resin such as polyethylene may be mixed with the PHA of the present invention or a mixture of the PHA of the present invention and the above-mentioned degradable resin. It is preferable that the total amount of the decomposable resin is 100% by mass and the amount of the degradable resin mixed is 5% by mass or more. When the mixing amount of the degradable resin is less than 5% by mass, the degradability becomes insufficient.

(Method of Preparing Composition) The PHA of the present invention and the various decomposable resins described above, for example, a PHA containing at least a monomer unit represented by the formula [8], polylactic acid, poly-ε-caprolactone, The method for preparing a composition comprising a photodecomposable resin and the like is a method commonly used in a method for producing a composition comprising a conventional polyolefin resin and the like, for example, mixing by a ribbon blender, a Henschel mixer, a kneader, a Banbury mixer. , Kneading with a roll or the like, and heat-melting kneading using a single-screw or twin-screw extruder or the like.

The composition can be prepared by controlling the crystallinity, for example, to form a tough plastic with improved brittleness while maintaining the hardness, and to suppress deterioration during thermoforming. Is possible. At this time, the compounding ratio of the resin to be kneaded, kneading conditions and the like may be set according to the characteristics of the desired composition.

(Additives, etc.) In order to improve the mechanical properties, the PHA of the present invention is used as a filler as an inorganic filler such as calcium carbonate, mica, calcium silicate, white carbon, asbestos, clay (fired), glass fiber Add (1)
To 30% by mass, preferably 5 to 10% by mass), kneading, and further biaxial stretching. As a result, mechanical properties such as stiffness, durability, moldability, mechanical strength, hardness, impact strength, dimensional stability, bending resistance, etc. and surface smoothness, gloss, water resistance, waterproofness It is possible to give the same properties as PET resin, vinyl chloride resin and the like.

The composition of the present invention may contain, if desired, various additives and fillers such as heat stabilizers, antioxidants, antistatic agents, pigments or dyes, lubricants, nucleating agents and the like. Agents, fillers such as calcium carbonate, barium sulfate, magnesium hydroxide, talc and the like can be added.
More specifically, it is possible to add 0.05 to 3 parts by mass of a coloring inhibitor, 0.05 to 3 parts by mass of an antioxidant, 0.05 to 0.5 parts by mass of a lubricant, an organic pigment and an inorganic pigment. As for the whitening of the sheet, a white sheet can be produced by mixing titanium.

(Molding Method) There is no particular limitation on the method for producing a card comprising the composition containing PHA of the present invention, and known methods such as compression molding, injection molding, extrusion molding, lamination molding, and inflation molding are known. It is possible to manufacture a card by the method described above.

For example, melt extrusion may be performed by a known method using an extruder equipped with a T die or an annular die to form a flat card. The molded product of the present invention may be produced by a calendering method, a hot stamping method, a hot roll pressing method or the like in addition to the extrusion method described above, and there is no particular limitation. Further, if necessary, the film may be uniaxially or biaxially stretched by a known method, and there is no particular limitation. The thickness of the card, which is a molded product of the present invention, may be appropriately selected depending on the application, and generally, 20
0 to 800 μm can be exemplified.

<Representative Embodiment of Card> (Embodiment 1) An example of a representative embodiment of the card of the present invention will be described with reference to FIGS. Card base body 2
Is a white plastic sheet 3 made of the PHA of the present invention.
The concave and convex characters 4 are formed on a part of the card base body 2 by embossing. In addition, the card base body 2
A visible information display layer 6 composed of a reversible thermosensitive recording display layer 5 is provided on a part of the surface of. Visible information display layer 6
Is not limited to the reversible thermosensitive recording display layer, and a recording display layer such as a thermosensitive recording display layer or a magnetic recording display layer may be provided. The magnetic recording display layer is formed by attaching microcapsules containing oil and magnetic flakes to the surface of a transparent substrate with a transparent binder to form a microcapsule layer, and then forming the magnetic flakes on the surface of the transparent substrate. When oriented parallel to the surface, it reflects visible incident light to visually display the bright colors of the magnetic flakes, and reflects the incident light when the magnetic flakes are oriented perpendicular to the surface of the transparent substrate. First, the dark color (for example, black) of the magnetic sheet is visually displayed, and the visible display is performed by contrast between the colors. The card base body 2 of the present invention
The white plastic sheet 3 made of HA has a property of not exhibiting flexibility when heated below 50 ° C.

(Embodiment 2) Another embodiment of the card of the present invention will be described with reference to FIG. 3. The card base body 2 is made of a white plastic made of two laminated PHAs of the present invention. Sandwiching the sheets 3a and 3b, two transparent plastic sheets 7a made of the PHA of the present invention;
7b are laminated and closely integrated. An embossed character 4 is formed on a part of the card base body 2 by embossing, and a visible information display layer 6 composed of a reversible thermosensitive recording display layer 5 is formed on a part of the surface of the transparent plastic sheet 7a. Is provided. A white plastic sheet 3a, 3b and a transparent plastic sheet 7a made of the PHA of the present invention as the card base body 2;
7b is made of a material which does not exhibit flexibility when heated at less than 50 ° C.

Printing Layer A printing layer 8 displaying various pictures, patterns, marks, etc. is provided on the surface of the white plastic sheets 3a, 3b. The printing layer 8 is a white plastic sheet 3
There is no particular limitation on the combination of the resins a and 3b as long as the combination satisfies the adhesiveness, physical properties, and the like, and known materials can be used. Specifically, a polyurethane resin, a polyester resin, a vinyl chloride resin, a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer, a polystyrene resin, an acrylic resin, a butyral resin, or the like may be appropriately selected and used for pigments, dyes, and the like. If necessary, a plasticizer or an additive may be added. In addition, as a method of providing the printing layer 8, printing can be performed on the surfaces of the white plastic sheets 3a and 3b using a known printing method such as a gravure coating method, a screen printing method, an offset method, and a roll coating method. The printed layer 8 may be provided with a picture or pattern on the entire surface of the white plastic sheets 3a and 3b, or may be printed with characters and the like as necessary.

Magnetic Layer When a magnetic stripe layer, which is a magnetic layer, is formed on the surface of the transparent plastic sheet 7a, the magnetic material may be appropriately selected according to the system used, and is 7.9 to 320 kA / m. (100 to 4000 (Oe)) in consideration of necessary physical characteristics and the like. As a method for providing a magnetic stripe layer on the surface of the transparent plastic sheet 7a, a magnetic paint may be applied by a known method, or may be formed by forming a transfer sheet once and then forming the transfer sheet on the transparent plastic sheet 7a. It may be formed by thermal transfer.

(Embodiment 3) Another embodiment of the card of the present invention will be described with reference to FIG. FIG.
1 is a cross-sectional view of a card according to the present invention.
The transparent plastic sheets 7a and 7b are laminated and closely integrated on both sides of a white plastic sheet 3 made of polylactic acid. The PHA of the present invention is used as a material constituting the transparent plastic sheets 7a and 7b. The white plastic sheet 3 made of polylactic acid has excellent mechanical properties and excellent biodegradability,
On the other hand, moisture resistance is weak, and hydrolysis occurs when a simple substance is exposed to a state of high temperature and high humidity. By covering both sides of the white plastic sheet 3 or the entire periphery with the transparent plastic sheets 7a and 7b that block humidity, the card can be used as a card having excellent mechanical properties in normal use.
At the time of disposal, the transparent plastic sheets 7a and 7b on the surface are biodegraded in soil, activated sludge, and compost, and when the humidity is no longer blocked, the white plastic sheet 3 is hydrolyzed and completely decomposed by biodegradation. It is.

The transparent plastic sheets 7a and 7b are made of PHA containing at least the monomer units represented by the formulas [1] to [7]. By coating, it is possible to suppress the hydrolysis of the white plastic sheet 3 due to the moisture barrier property of the transparent plastic sheets 7a and 7b when using the card.

Here, the PHA or other resin of the present invention used for the sheet constituting the base material body may be formed by kneading a filler. The method of kneading the filler includes dry blending, melt blending and the like. The molding method of the kneaded resin includes T-die extrusion, calender roll molding, and the like. By appropriately selecting, for example, a sheet-like base material used for the transparent plastic sheets 7a and 7b can be molded. is there. Further, after the above-mentioned sheet-shaped base material is melt-extruded or by biaxial stretching under heating, stiffness, moldability, mechanical strength,
Mechanical properties such as hardness, impact strength, dimensional stability, and bending resistance can be further improved.

Lamination method White plastic sheet 3 and transparent plastic sheet 7
The lamination method of each of the sheets a and 7b includes dry lamination, wet lamination, and heat fusion lamination. To form the transparent plastic sheets 7a and 7b around the white plastic sheet 3, the white plastic sheet 3
The white plastic sheet 3 can be inserted between the transparent plastic sheets 7a and 7b, which are slightly larger than the transparent plastic sheets 7a and 7b, and can be performed by heat / pressure fusion lamination.

Further, in the present invention, the base material may have a structure other than the above-mentioned laminated structure, and the core sheet may be subjected to addition of a filler and / or biaxial stretching, or only one of them. Each of the sheet-shaped substrates prepared by changing the compounding ratio may be prepared and laminated,
In any case, the mechanical strength can be maintained.

The base material produced by the above method can be printed and processed in the same manner as in the case of the conventional paper / plastic card, and can be printed on the base material by a printing method such as offset printing, screen printing, or gravure printing. Thus, the card of the present invention can be manufactured by, for example, printing characters, patterns, and the like, and processing the characters into a card size using a punching machine.

Magnetic Recording Layer Further, the card of the present invention has a magnetic recording layer 9 as shown in FIG.
An information recording layer capable of mechanically recording and reproducing data such as digital information such as a digital information and a heat-sensitive recording layer can be formed. It is also possible to stack a plurality of different magnetic recording layers 9 and an information recording layer comprising a heat-sensitive recording layer on the same card.

The method for forming the magnetic recording layer 9 is well known, such as applying a coating liquid in which a magnetic recording material is dispersed in a binder or the like, or laminating sheets on which the magnetic recording layer is formed.
Similarly, a method of forming a heat-sensitive recording layer is also known, and can be formed by applying a heat-sensitive recording material, for example, a coating liquid composed of a heat-sensitive leuco dye, a heat-sensitive diazo dye, or the like, or a thin film of a low-melting metal such as tin or aluminum.

[0120]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. All parts in the following formulations are parts by mass.

Example 1 0.5% of D-glucose and 5-
Pseudomonas chicoryi YN2 strain in 20 L of M9 medium containing 0.1% of (4-fluorophenyl) valeric acid (FPVA)
(Pseudomonas cichorii YN2, FERM BP-737
5) was inoculated, and cultured under aeration and agitation at 30 ° C., 80 rotations / min, and aeration of 2.5 L / min. After 48 hours, the cells were collected by centrifugation, and resuspended in 20 L of M9 medium containing 0.5% of D-glucose and 0.1% of FPVA without a nitrogen source (NH ₄ Cl). The cells were cultured with aeration and agitation at 80 rotations / minute and aeration of 2.5 L / minute. After 48 hours, the cells were collected by centrifugation, 1 g was collected from the collected wet cells for analysis and evaluation, washed once with cold methanol, and then freeze-dried to obtain freeze-dried pellets.

The remaining wet bacterial cells were suspended in 500 mL of an aqueous solution of about 1.7% sodium hypochlorite, and were suspended at about 4 ° C. for 2 hours.
The PHA was extracted by shaking for an hour. PHA by centrifugation
Was collected and dried, resulting in 0.87 g of P / L of medium.
HA was obtained. This PHA was used as Exemplified Compound 1.

Note that M9 used in the embodiment of the present invention
The composition of the medium is as follows. Na ₂ HPO ₄ : 6.2 g KH ₂ PO ₄ : 3.0 g NaCl: 0.5 g NH ₄ Cl: 1.0 g (pH 7.0 in 1 liter of culture medium) This lyophilized pellet is suspended in 20 mL of chloroform, and is suspended at 60 ° C. for 20 hours. The PHA was extracted by stirring. The extract was filtered through a membrane filter having a pore size of 0.45 μm, concentrated by a rotary evaporator, and the concentrated solution was reprecipitated in cold methanol. Further, only the precipitate was recovered and dried under vacuum to obtain PHA.

The composition of the obtained PHA was analyzed as follows. That is, about 10 mg of PHA was put into a 25 mL eggplant-shaped flask, dissolved in 2 mL of chloroform, and dissolved in 3 mL of chloroform.
2 mL of a methanol solution containing% sulfuric acid was added, and the mixture was reacted at 100 ° C. under reflux for 3.5 hours. After completion of the reaction, 10 mL of deionized water was added, and the mixture was vigorously shaken for 10 minutes. Then, the lower chloroform layer separated into two layers was taken out and dehydrated with magnesium sulfate. -MS, Shimadzu QP-50
50, Column: DB-WAX (J & W, 0.32mm × 30m),
EI method) to identify the methyl esterified product of the PHA monomer unit. As a result, in the PHA monomer unit, 96% was 3HFPV and 4% was 3-HFPV.
PHA having a high ratio of 3HFPV monomer units, which are hydroxybutyric acid units and desired monomer units derived from FPVA, were obtained in high yield.

The molecular weight of the PHA was determined by gel permeation chromatography (GPC; Tosoh HLC-8).
020, column; polymer laboratory PLgel MIXED
As a result of evaluation using -C (5 μm) and a solvent; (chloroform, polystyrene conversion), Mn = 71,500, Mw = 158,000
Met.

Example 2 3-Hydroxy-5 was obtained under the same conditions as in Example 1 except that 5- (4-trifluoromethylphenyl) valeric acid (CF ₃ PVA) was used instead of FPVA.
-(4-trifluoromethylphenyl) valeric acid (3HCF ₃ P
V) When PHA containing a monomer unit was synthesized,
0.12 g of PHA was obtained per 1 L of the medium. This P
HA was designated as Exemplified Compound 2.

When the obtained PHA was analyzed and evaluated in the same manner as in Example 1, 17% of the PHA monomer units were 3HCF ₃ PV, and 83% were 3-hydroxybutyric acid, 3-hydroxyhexanoic acid, 3HCF ₃ PV monomer, which is one or more units of 3-hydroxyoctanoic acid, 3-hydroxydecanoic acid, 3-hydroxydodecanoic acid and 3-hydroxydodesenic acid, and is a desired monomer unit derived from CF ₃ PVA PHA containing the unit was obtained in high yield. The molecular weight is Mn = 65,
200, Mw = 117,000.

(Example 3) 3-Hydroxy-4-phenoxybutyric acid (3HPxB) was prepared under the same conditions as in Example 1 except that 4-phenoxybutyric acid (PxBA) was used instead of FPVA.
When PHA containing a monomer unit was synthesized, 0.15 g of PHA was obtained per 1 L of the medium volume. This PHA
Was set as exemplary compound 3.

The obtained PHA was analyzed and evaluated in the same manner as in Example 1. As a result, 95% of the PHA monomer units were PxBA and 5% were 3-hydroxybutyric acid units, which were derived from PxBA. A PHA having a high ratio of 3HPxB monomer units, which is a desired monomer unit, was obtained in high yield. The molecular weight is Mn = 71,
500, Mw = 158,000.

Example 4 The same conditions as in Example 1 were used except that 4-cyclohexylbutyric acid (CHBA) was used instead of FPVA, and 3-hydroxy-4-cyclohexylbutyric acid (3
When PHA containing an HCHB) monomer unit was synthesized, 0.79 g of PHA was obtained per liter of medium solution.
This PHA was used as Exemplified Compound 4.

The obtained PHA was analyzed and evaluated in the same manner as in Example 1. As a result, 98% of the PHA monomer units were 3HCHB and 2% were 3-hydroxybutyric acid units, which were derived from CHBA. A PHA having a high ratio of 3HCHB monomer units, which is a desired monomer unit, was obtained in high yield. The molecular weight is Mn
= 92,200 and Mw = 218,000.

Example 5 3-Hydroxy-5-benzoylvaleric acid (3HB) was prepared under the same conditions as in Example 1 except that 5-benzoylvaleric acid (BzVA) was used instead of FPVA.
zV) When PHA containing a monomer unit was synthesized,
0.55 g of PHA was obtained per liter of medium solution. This P
HA was designated as Exemplified Compound 5.

The obtained PHA was analyzed and evaluated in the same manner as in Example 1. As a result, 88% of the PHA monomer units were 3HBzV, and 12% were 3-hydroxybutyric acid, 3-hydroxyhexanoic acid, and 3-hydroxyhexanoic acid. PHA having a high ratio of 3HBzV monomer units, which are one or more units of hydroxyoctanoic acid, 3-hydroxydecanoic acid, 3-hydroxydodecanoic acid and 3-hydroxydodesenic acid, and are desired monomer units derived from BzVA
Was obtained in high yield. The molecular weight is Mn = 325,000, M
w = 1,240,000.

Example 6 3-Hydroxy-5- (4-fluorobenzoyl) was prepared under the same conditions as in Example 1 except that 5- (4-fluorobenzoyl) valeric acid (FBzVA) was used instead of FPVA. ) PHA containing valeric acid (3HFBzV) monomer unit was synthesized.
35 g of PHA was obtained. This PHA was designated as Exemplified Compound 6.

When the obtained PHA was analyzed and evaluated in the same manner as in Example 1, 79% of the PHA monomer units were 3HFBzV, and 21% were 3-hydroxybutyric acid, 3-hydroxyhexanoic acid, and 3-hydroxyhexanoic acid. P is a unit having at least one of hydroxyoctanoic acid, 3-hydroxydecanoic acid, 3-hydroxydodecanoic acid and 3-hydroxydodeceneic acid, and a high proportion of 3HFBzV monomer units, which are desired monomer units derived from FBzVA.
HA was obtained in high yield. The molecular weight is Mn = 285,00
0, Mw = 833,000.

(Example 7) A 3-hydroxy-5-thienylvaleric acid (3HTV) monomer unit was used under the same conditions as in Example 1 except that 5-thienylvaleric acid (TVA) was used instead of FPVA. When PHA was synthesized, 0.85 g of PHA was obtained per 1 L of the medium solution volume. This PHA was designated as Exemplified Compound 7.

The obtained PHA was analyzed and evaluated in the same manner as in Example 1. As a result, 97% of the PHA monomer units were 3HTV and 3% were 3-hydroxybutyric acid units, which were derived from TVA. A PHA having a high ratio of 3HTV monomer units, which is a desired monomer unit, was obtained in high yield. The molecular weight is Mn = 75,00
0, Mw = 185,000.

Example 8 3-Hydroxy-5-thienoylvaleric acid (3HT) was used under the same conditions as in Example 1 except that 5-thienoylvaleric acid (ToVA) was used instead of FPVA.
oV) When PHA containing a monomer unit was synthesized,
0.15 g of PHA was obtained per liter of medium solution. This P
HA was designated as Exemplified Compound 8.

The obtained PHA was analyzed and evaluated in the same manner as in Example 1. As a result, 62% of the PHA monomer units were 3HToV, and 38% were 3-hydroxybutyric acid, 3-hydroxyhexanoic acid, and 3-hydroxyhexanoic acid. PHA having a high ratio of 3HToV monomer units, which are one or more units of hydroxyoctanoic acid, 3-hydroxydecanoic acid, 3-hydroxydodecanoic acid, and 3-hydroxydodesenic acid, and are desired monomer units derived from ToVA
Was obtained in high yield. The molecular weight is Mn = 105,000, M
w = 252,000.

Hereinafter, specific embodiments of the card of the present invention will be described in detail with reference to the drawings.

Example 9 First, Exemplified Compound 1 synthesized in Example 1 was subjected to sheet processing by an extruder at a resin processing temperature of 140 ° C. and an extrusion speed of 30 m / min.
0.1 mm transparent plastic sheets 7a and 7b were produced. Next, 10% by mass of titanium was added to Exemplified Compound 1 and white plastic sheets 3a and 3b having a thickness of 0.28 mm were produced in the same manner as described above.

Next, two sheets of the above-prepared white plastic sheets 7a and 7b each having a thickness of 0.28 mm and cut into a size of 100 mm × 200 m were prepared, and two sheets were formed on one side of each sheet. Then, on the side corresponding to the front and back of the card, the thickness of 1μ
The printed layer 8 was provided by printing m patterns and characters. that time,
The ink for UVS card, which is an offset ink, is used in consideration of the adhesion between the printing ink and the sheet.
(Manufactured by The Inc.).

Next, two white plastic sheets 3a,
3b and two transparent plastic sheets 7a and 7b are superimposed and heated by a hot press at a heating temperature of 150 ° C. and a heating time.
Thermocompression bonding was performed under a pressure of 9.8 MPa (9.8100 kg / cm ² ) for 10 minutes to integrate. And 86m by the punching machine
The card base material 2 as shown in FIG. 3 was produced by punching out to a size of mx 54 mm.

Next, in order to provide the reversible thermosensitive recording layer 5 which is the visible information display layer 6 on a part of the surface of the transparent plastic sheet 7a of the card substrate 2, a coating for a reversible thermosensitive recording layer having the following composition was prepared. The protective coating was applied to the surface of the transparent plastic sheet 7a by a bar coat printing method so that the thickness of the reversible thermosensitive recording layer was 10 μm and the thickness of the protective layer was 2 μm.

[0145] After providing the reversible thermosensitive recording layer 5 on the card base material 2,
An embosser (DC900 manufactured by Nippon Data Card Co., Ltd.) is used to form embossed characters 4 on the card base 2.
The card of Example 9 was produced by forming uneven characters 4 using (0).

(Examples 10 to 16) First, Exemplified Compounds 2 to 8 synthesized in Examples 2 to 8 were processed into a sheet by an extrusion molding machine under the conditions of a resin processing temperature of 140 ° C. and an extrusion speed of 30 m / min. 0.1mm transparent plastic sheet 7a, 7
b was prepared. Next, 10% by mass of titanium was added to Exemplified Compounds 2 to 8, and white plastic sheets 3a and 3b having a thickness of 0.28 mm were produced in the same manner as described above. Hereinafter, the cards of Examples 10 to 16 were produced in the same procedure as in Example 9.

Example 17 Exemplified Compound 3 was added with a density of 1.145 g /
cm ³ , melting point 60 ° C, melt flow index (MFI)
No. 4 and poly-ε-caprolactone were blended so that the mass ratio became 50/50. Next, this mixture was supplied to a twin-screw extruder at a cylinder temperature and a die temperature of 180 ° C., and was melt-kneaded to obtain a composition adjusted to pellets.

The pellets obtained above were supplied to an extruder equipped with a T die, melt-kneaded at a die temperature of 180 ° C., and extruded into a flat shape into a white plastic sheet 3 having a thickness of 0.28 mm.

(Comparative Example 1) The card of Comparative Example 1 was a biodegradable resin (trade name, polycaprolactone) manufactured by Daicel Chemical Industries, Ltd.
The sheet is processed with an extruder at a resin processing temperature of 120 ° C and an extrusion speed of 30 m / min.
The transparent plastic sheets 7a and 7b were manufactured. next,
10% by mass of titanium is added to the resin, and a white plastic sheet 3a having a thickness of 0.28 mm is formed in the same manner as described above.
3b was produced. Hereinafter, the card of Comparative Example 1 was manufactured by the same manufacturing procedure as in Example 9.

Comparative Example 2 Density: 1.25 g / cm ³ , Melting Point: 144
C., supplying a copolymer linear polyester of 3-hydroxybutyric acid and 3-hydroxyvaleric acid having a melt flow index (MFI) of 12 to an extruder equipped with a T die,
Melt and kneaded at a die temperature of 180 ° C and extruded into a flat shape.
It was molded into a white plastic sheet 3 having a thickness of 0.28 mm.

Next, the ninth embodiment manufactured as described above was used.
The following evaluation items were tested to compare and evaluate the quality of the 11 types of cards of Comparative Examples 1 and 2 and Cards of Comparative Examples 1 and 2.

Evaluation items [Microbial degradability]: The period of time from burying in soil to completely disappearing was measured. [Tensile strength]: Measured and evaluated according to JIS K-6732. [Hardness (waist)]: Sensory evaluation was performed.

…: Suitable for cards. △… Can be used for cards. ×… Not suitable for cards. [Brittleness]: Fold the sheet half way back and forth 10 times and evaluate the condition.

…: No crack. Δ: There are slight cracks. ×
... with cracks. [Stackiness]: Sensory evaluation of the bear after standing for 5 days at 40 ° C., 90% RH.

…: No stickiness. △: Slightly sticky. ×: There is stickiness. [Emboss height]: Measured before and after transfer of the colored ribbon.

…: 0.45 mm or more. ×: Less than 0.45 mm. [Card warpage]: Measured before and after recording on the heat-sensitive recording layer.

…: Less than 2.0 mm. ×: 2.0 mm or more. [Emboss Crack]: Immediately after the formation of the protrusion, the crack of the protrusion was visually determined.

…: No crack. Δ: Slight cracking. ×
... with cracks.

Here, the measurement of the emboss height and the warpage of the card was performed by a measuring method according to JIS X6301. The colored ribbon was transferred by a rubber roller under the following conditions. Transfer temperature 120 ° C, transfer pressure: 4
90kPa (≒ 5kg / cm ² ), transfer time 3 seconds. The recording condition of the thermosensitive recording layer was 8 dot /
An image was formed with an applied energy of 0.30 mJ / dot using a mm line type thermal head. Table 1 shows the test results.

[0160]

[Table 1]

Example 18 60% by mass of polylactic acid having a number average molecular weight of 150,000 and 35% by mass of mica as an additive (HA
R 160 Shiraishi Industry Co., Ltd., titanium oxide 5% by mass (200 ° C
(24 hours drying) after kneading with a vent type extruder, extruding this to a specified thickness at a processing temperature of 200 ° C. with a T-die melt extruder, biaxially stretching, and further calendering,
A white plastic sheet 3 having a thickness of 0.28 mm having improved surface smoothness was prepared, and a transparent plastic sheet 7 having a thickness of 0.1 mm obtained by melt-extruding Exemplified Compound 6 was obtained.
Cards were prepared by laminating a and 7b on both sides of a white plastic sheet and heating and laminating them.

[0162] The sheet was subjected to 48 ° C in an environment of 40 ° C and 90% humidity.
After standing for a while, there was no change in the bending strength and no off-flavor was generated. That is, the transparent plastic sheets 7a, 7
Hydrolysis does not occur in the white plastic sheet 3 made of polylactic acid due to the lamination of b, and the mechanical strength can be maintained.

A magnetic paint having the following composition was formed on this sheet by knife coating to form a black magnetic recording layer of about 10 μm, and a magnetic field orientation in a horizontal magnetic field of about 0.3 T (= 3000 gauss) was applied. For 3 minutes.

Magnetic paint Magnetic powder (139 kA / m (≒ 1750 Oe): barium ferrite) 100 parts by mass Vinyl chloride-vinyl acetate copolymer (VAGF: manufactured by Union Carbide) 20 parts by mass Polyurethane resin (Nipporan 2304: Nippon Polyurethane Industry Co., Ltd. 30 parts by mass Hexamethylene diisocyanate (Coronate HX: Nippon Polyurethane Industry Co., Ltd.) 2 parts by mass Carbon black (# 3000: Mitsubishi Kasei Co., Ltd.) 5 parts by mass Dispersant (Garfax RE-610: Toho Chemical Co., Ltd.) 3 parts by mass Dilution solvent (toluene / MEK / MIBK) 100 parts by mass This sheet was processed into a card size of 57.5 mm in length x 85.0 mm in width according to the cyber spring standard to obtain a card. This card,
2m at gate with card read / write device
After passing through the card at / sec and repeating this about 500 times, there was no card abnormality such as card jam. Next, immerse this card in water for 30 seconds, wipe off the water,
Similarly, the card passed through the gate, but no card abnormality such as a card jam occurred. The stiffness at this time is 32 N / m (≒ 3
3gf / cm) (short side), and there was no change before and after immersion in water. Further, when the card was buried in field soil and the state of decomposition was observed, after 10 months, the card had been decomposed to a state where its shape was not maintained, leaving the magnetic recording layer.

[0165]

As described above in detail, in the card of the present invention, even if the card is discarded in the natural world, each of the base materials constituting the card base body is decomposed in the natural world, so that the discarded card can be left alone. It is possible to reduce the burden on the environment even when the processing is performed, and it is possible to configure a card function required for a conventional card, for example, an embossed portion in which characters, numeral information, and the like are formed unevenly on a card base material. In addition, the present invention provides a card having a quality that is not inferior to conventional vinyl chloride resin cards in required specifications such as that a visible information display layer can be formed on at least a part of the card. It is a card that can be widely used in various fields and applications. In addition, the card of the present invention requires less large-scale disposal equipment for disposal of discarded cards, and has a less adverse effect on the ground when discarded cards are buried underground than conventional cards. The card of the present invention can be widely and suitably used for a card system using various plastic cards such as a credit card, a cash card, and an ID card.

[Brief description of the drawings]

FIG. 1 is a plan view showing one embodiment of a card of the present invention.

FIG. 2 is a sectional view of FIG.

FIG. 3 is a sectional view showing another embodiment of the card of the present invention.

FIG. 4 is a cross-sectional view showing one embodiment of another configuration of the card of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Card 2 Card base material 3 White plastic sheet 3a White plastic sheet 3b White plastic sheet 4 Uneven characters 5 Reversible thermosensitive recording layer 6 Visible information display layer 7a Transparent plastic sheet 7b Transparent plastic sheet 8 Printing layer 9 Magnetic recording layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/26 C08K 3/26 3/34 3/34 3/36 3/36 5/098 5/098 7 / 14 7/14 C08L 23/06 C08L 23/06 23/12 23/12 67/04 67/04 73/00 73/00 (72) Inventor Kei Takashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Within Canon Inc. (72) Inventor Etsuko Sugawa 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term within Canon Inc. (reference) 2C005 HA10 HA21 HB01 HB04 HB14 HB20 JA02 JA03 JA08 JA09 JB04 KA15 KA40 4F100 AA03A AA03B AA08A AA08B AC05A AC05B AG00A AG00B AK01A AK01B AK04A AK04B AK07A AK07B AK41A AK41B AL05A AL05B BA02 BA04 BA06 EH17 EJ17 EJ42 GB90 JC00A JC00B JJ03 JK01 4J002 CF023 01 AD01 AE03 AE05 EA02 EA05 EB01 EC10 ED01 ED03 EE01 EE04 EF01 EF02 EG09 FC38

Claims (11)

[Claims] 1. A card comprising a single layer or a plurality of layers, wherein at least a part of a card base material used for the card is
A card comprising a polyhydroxyalkanoate comprising at least the monomer units represented by the formulas [1] to [7]. Embedded image (However, the monomer unit is at least one selected from the group consisting of monomer units in which the combination of R1 and a is any of the following. R1 is a hydrogen atom (H) and a is from 5 to A monomer unit in which R1 is a halogen atom and a is any of integers from 1 to 10, R1
Is a chromophore and a is a monomer unit in which a is any integer from 1 to 10, R1 is a carboxyl group and a is a monomer unit in which a is any integer from 1 to 10,
R1 is: And a is a monomer unit wherein a is any integer from 1 to 7. ) (Where b represents any integer from 0 to 7;
2 is a hydrogen atom (H), a halogen atom, —CN, —NO ₂ , —CF ₃ ,
It represents any one selected from the group consisting of -C ₂ F ₅ and -C ₃ F ₇ . ) (Where c represents an integer of 1 to 8;
3 is a hydrogen atom (H), a halogen atom, —CN, —NO ₂ , —CF ₃ ,
It represents any one selected from the group consisting of -C ₂ F ₅ and -C ₃ F ₇ . ) (Where d represents an integer of 0 to 7;
4 is a hydrogen atom (H), a halogen atom, —CN, —NO ₂ , —CF ₃ ,
It represents any one selected from the group consisting of -C ₂ F ₅ and -C ₃ F ₇ . ) (Where e represents any one of integers from 1 to 8;
5 is a hydrogen atom (H), a halogen atom, —CN, —NO ₂ , —CF ₃ ,
_{-C 2 F 5, -C 3 F} 7, -CH 3, -C 2 H 5, represents any one selected from the group consisting of -C ₃ H _7. ) (Where f represents any integer from 0 to 7). (Where g represents any one of integers from 1 to 8). 2. The card according to claim 1, wherein the card substrate containing the polyhydroxyalkanoate covers the entire periphery of the card. 3. A card substrate comprising the polyhydroxyalkanoate and a polyhydroxyalkanoate having the formula
Polyhydroxyalkanoate, polylactic acid, poly-ε- at least comprising a monomer unit represented by [8]
3. The card according to claim 1, wherein the card is a base material obtained by kneading at least one selected from caprolactone and a photodegradable resin. Embedded image (However, the monomer unit is at least one selected from the group consisting of monomer units in which a is any integer from 0 to 4.) 4. The photo-decomposable resin is at least one selected from a copolymer of ethylene and carbon monoxide, a mixture of polyethylene and an organic acid metal salt, and a mixture of polypropylene and an organic acid metal salt. The card according to claim 3. 5. The card according to claim 4, wherein the organic acid metal salt is at least one selected from iron stearate, cerium stearate, and cobalt stearate. 6. The card according to claim 1, wherein the card substrate containing the polyhydroxyalkanoate is a substrate obtained by kneading a polyhydroxyalkanoate and a filler. 7. The method according to claim 1, wherein the filler is calcium carbonate, mica, calcium silicate, white carbon, asbestos, porcelain clay.
The card according to claim 6, wherein the card is at least one selected from (firing) and glass fiber. 8. The card according to claim 6, wherein the card substrate containing the polyhydroxyalkanoate is obtained by kneading a polyhydroxyalkanoate and a filler and then biaxially stretching the card. 9. The card according to claim 1, wherein the polyhydroxyalkanoate has a number average molecular weight of 10,000 to 1,000,000. 10. At least a part of the card base material,
10. The card according to claim 1, wherein at least one selected from a magnetic recording layer, a thermosensitive recording layer, and a visible information display layer is formed. 11. The visual information display layer according to claim 10, wherein the visible information display layer is at least one selected from a concavo-convex character layer formed by embossing, a thermosensitive recording display layer, a reversible thermosensitive recording display layer, and a magnetic recording display layer. card.