JPH09157424A - Information recording card comprising lactic acid-based polyester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject card excellent in biodegradability, solvent resistance, heat resistance, etc., having low combustion calorie in burning and free from occurrence of poisonous gas by using a crystallized and/or drawn lactic acid-based polyester as a support. SOLUTION: In this recording card, at least part of the support is composed of a crystallized and/or drawn lactic acid-based polyester. Furthermore, the polyester is preferably a crystallized polyester. In the polyester, deactivation treatment of a polymerization catalyst is preferably carried out, especially by using chelating agent and/or acidic phosphoric acid ester and the polyester consists essentially of (A) >=70wt.% structural component derived from L-lactic acid or D-lactic acid, (B) a structural component derived from a dicarboxylic acid and (C) a structural component derived from a diol and the components B and C have preferably each an aliphatic structure.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a small amount of calories burned even when incinerated after use, and has biodegradability which is decomposed in a natural environment even when it becomes landfill or scattered dust. In addition, the present invention relates to an information recording card having excellent heat resistance, solvent resistance and the like.

[0002]

2. Description of the Related Art Information recording cards are widely used in daily social life such as telephone cards, shopping cards, cash cards, credit cards, facility use cards, guarantee cards and ID cards. Such an information recording card is composed of a non-magnetic support, an information recording section, a printing layer and the like. As the non-magnetic support, a plastic such as polyethylene terephthalate or polyvinyl chloride is selected according to the purpose of use of the card, period or frequency, and is molded and used in a thickness of 100 to 800 μm.

Although some of these information recording cards are collected after use, most of them are processed by incineration or landfill. In the incineration process, these plastics burn large calories, which causes problems such as damage to the incinerator and generation of harmful gas, and in the landfill process,
Because these plastics are extremely stable in the natural environment and do not decompose and remain as they are, confidentiality cannot be maintained,
It lacks the stability of the ground, causes a shortage of landfills, and when scattered, it remains as semi-permanent garbage, causing social problems that damage the environment.

In order to solve such a problem, a so-called eco-friendly card has been developed, which has a low calorific value and decomposes in the natural world. Japanese Patent Laid-Open No. 7-1790
Japanese Patent Publication No. 84 discloses a magnetic card made of a polymer composed of α-oxy acid such as L-lactic acid and glycolic acid.

However, these polylactic acid and copolymers of lactic acid and glycolic acid are easily corroded by a solvent and have low heat resistance. Therefore, when used as a support of an information recording card, the information recording card There is a problem that the support is invaded by the solvent or is deformed when the above is manufactured.

In addition, since these polymers generally have a large amount of residual lactide, they are easily subjected to thermal decomposition during molding, resulting in a decrease in molecular weight and insufficient strength, and residual lactide is volatilized during molding, resulting in a product. Since it adheres to the molding equipment and molding equipment, its use is greatly restricted. The main reason for this is that residual lactide reacts with water in the air to form an organic acid, which hydrolyzes and cuts the polymer chain.

[0007]

The solvent resistance, heat resistance, mechanical strength, and durability are the same as those of current information recording cards, but the calories burned during incineration are low, and the heat stability during molding is stable. It has good properties, processability, and storage stability during use, is naturally decomposed even if it is abandoned in the natural world after use, and does not generate harmful gas even if it is incinerated. It is to provide an information recording card with a small amount.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an information recording card using a crystallized and / or stretched lactic acid-based polyester as a support is biodegradable,
It has been found that the solvent resistance, heat resistance, etc. are excellent, and when the lactic acid-based polyester is subjected to deactivation treatment of the polymerization catalyst contained therein beforehand, the information recording card obtained therefrom has thermal stability, It was found that the storage stability and the like were also improved, and the present invention was completed.

That is, the present invention is an information recording card characterized in that at least a part of the support is composed of crystallized and / or stretched lactic acid-based polyester, and particularly lactic acid-based polyester is crystallized. It is an information recording card characterized in that it has been recorded.

In the information recording card of the present invention, at least a part of its support is composed of crystallized and / or stretched lactic acid-based polyester, and the lactic acid-based polyester is subjected to deactivation treatment of the polymerization catalyst. In particular, the information recording card is characterized in that the polymerization catalyst is deactivated by using a chelating agent and / or an acidic phosphoric acid ester.

The information recording card of the present invention is an information recording card characterized in that the lactic acid-based polyester used contains the structural component (A) derived from lactic acid as an essential component, and particularly the structural component derived from lactic acid. (A) is an information recording card containing 70% by weight or more of a structural component derived from L-lactic acid or D-lactic acid.

Further, in the information recording card of the present invention, the lactic acid-based polyester used comprises a structural component (A) derived from lactic acid and a structural component (B) derived from dicarboxylic acid.
A structural component (B) derived from a diol and a structural component (C) derived from a dicarboxylic acid are included as an essential component. The component (C) includes an information recording card characterized by having an aliphatic structure. Further, the information recording card of the present invention is an information recording card characterized by being particularly in the form of a magnetic card.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The contents of the present invention will be described below in detail. First, the crystallized and / or stretched lactic acid-based polyester used in the present invention will be described. The crystallized lactic acid-based polyester has excellent properties such as solvent resistance and heat resistance as compared with an amorphous one. These performances are required in the manufacturing process and use of the information recording card, and in order to obtain excellent performance as an information recording card, the lactic acid-based polyester used has a crystallinity of 5% or more, preferably 10%. % Or more, more preferably 20% or more.

The crystallinity varies depending on the crystallization method of the lactic acid-based polyester, constituent components, residual volatile components, additives, etc. The crystallization method is generally the lactic acid-based polyester extruded by an extruder. Annealing is performed by heating with hot air or infrared irradiation in a heating oven. The conditions are usually 40 to 150 ° C.
It takes 10 seconds to 30 minutes, and some crystallize at room temperature.

Further, the solvent resistance and heat resistance of the stretched lactic acid-based polyester are not so excellent as those of the crystallized one, but the higher the draw ratio, the better the tendency tends to be.
The stretched lactic acid-based polyester has tensile strength, rigidity,
It has the advantage of excellent mechanical properties such as folding endurance and impact strength. The preferred stretch ratio of the lactic acid-based polyester used in the information recording card of the present invention is generally about 1.5 to 8 times, more preferably 2 to 5 times.

Stretching can be carried out uniaxially or biaxially, but biaxially stretched ones are preferable because they are excellent in solvent resistance, heat resistance and mechanical properties. Regarding the biaxial stretching method of the lactic acid-based polyester, the lactic acid-based polyester is continuously polymerized after polymerization, or after being pelletized, passed through an extruder, and the polymer discharged from the tea die or the circular die is biaxially stretched by a tenter machine. Or stretched with an inflation machine.

The temperature conditions are such that the glass transition point of the lactic acid-based polyester is above the melting point. In addition, the lactic acid-based polyester used in the present invention, in addition to performance, after being uniaxially or biaxially stretched from the viewpoint of the manufacturing process and productivity,
Crystallization by heating or the like is particularly preferable.

The lactic acid-based polyester used in the present invention is characterized in that the polymerization catalyst used in the polymerization of the lactic acid-based polyester is deactivated with a deactivator. The deactivation treatment of the polymerization catalyst suppresses the decomposition of the lactic acid-based polyester and the formation of lactide by the polymerization catalyst in the molding and processing of the lactic acid-based polyester,
Greatly improves thermal stability and improves moldability.

After that, by further devolatilizing and removing the residual volatile components, especially the residual lactide, the lactic acid-based polyester used in the information recording card of the present invention can be machined for processability, storage stability, tensile strength, rigidity and the like. It improves the physical characteristics. There are various methods for deactivating the polymerization catalyst, but deactivating with a chelating agent or acidic phosphoric acid ester is effective.

The chelating agent and the acidic phosphoric acid ester are used during the polymerization of the lactic acid-based polyester and form a complex with the metal ion of the polymerization catalyst contained in the polymer to lose the catalytic activity.

Next, a method for producing a lactic acid-based polyester used for the support of the present invention or a deactivation treatment of a polymerization catalyst, particularly a method for producing a lactic acid-based polyester deactivated with a chelating agent and / or acidic phosphoric acid ester will be described in order. explain. The manufacturing method thereof is not particularly limited, but its main method is exemplified.

As a method for producing a lactic acid-based polyester consisting only of a lactic acid component, as disclosed in JP-A-6-172502, lactic acid is directly dehydrated and polycondensed in the presence of a solvent, or Polymer, 20. Vol. 1, page 1459 (1979), by ring-opening polymerization of lactide in the presence of a ring-opening polymerization catalyst. It is then preferable to remove residual volatiles, especially residual lactide.

Further, a lactic acid component and a dicarboxylic acid component,
As a method for producing a lactic acid-based polyester containing a diol component as an essential component, a method comprising subjecting a polyester composed of a dicarboxylic acid component and a diol component, and lactide to a copolymerization or transesterification reaction in the presence of a ring-opening polymerization catalyst,

[0024] As described in JP-A-7-172425, lactic acid, a dicarboxylic acid component, and a diol component are subjected to dehydration and depolyglycol condensation polymerization in the presence of a catalyst and a solvent. An ester of polylactic acid obtained as a raw material, or polylactic acid obtained by polycondensation of lactic acid in the presence or absence of a solvent, and polyester comprising a dicarboxylic acid component and a diol component in the presence of an ester exchange catalyst It is manufactured by a method of exchanging. It is then preferable to remove residual volatiles, especially residual lactide.

Further, as a method for producing a lactic acid-based polyester consisting of only the deactivated lactic acid component of the polymerization catalyst,
After dehydration polycondensation of lactic acid in the presence of an esterification catalyst or a solvent, or after ring-opening polymerization of lactide in the presence of a ring-opening polymerization catalyst, a chelating agent and / or acid phosphates are reacted, and then Manufactured by removing residual volatile components, especially residual lactide.

Further, as a method for producing a lactic acid-based polyester in which a lactic acid component, a dicarboxylic acid component, and a diol component, which have been subjected to a deactivation treatment of a polymerization catalyst, are essential components, a polyester comprising a dicarboxylic acid component and a diol component is used. Polycondensation of lactic acid, dicarboxylic acid component and diol component by dehydration and deglycolization after copolymerization or transesterification of lactide with lactide in the presence of a ring-opening polymerization catalyst. After the reaction, the chelating agent and / or the acidic phosphoric acid ester is reacted, and then the residual volatile components are removed to produce the resin.

Alternatively, an ester of polylactic acid obtained from lactide as a raw material, or polylactic acid obtained by polycondensation of lactic acid in the presence or absence of a solvent, and a polyester composed of a dicarboxylic acid component and a diol component After transesterification in the coexistence of an exchange catalyst, a chelating agent and / or an acidic phosphoric acid ester is reacted, and then, residual volatile components are removed to produce the product.

Further, the polyester composed of a dicarboxylic acid component and a diol component used when producing the lactic acid-based polyester is polycondensed by dehydration and deglycolization of the dicarboxylic acid component and the diol component in the presence of an esterification catalyst. It can be produced by a method of polycondensation of a dicarboxylic acid component and a diol component as disclosed in JP-A-7-172425 in the presence of a catalyst for dehydration and deglycolization.

A lactic acid component, a dicarboxylic acid component, a diol component used in the production of the lactic acid-based polyester of the present invention,
A chelating agent, acidic phosphoric acid esters, polyester composed of a dicarboxylic acid component and a diol component, etc. will be described.

Examples of the lactic acid component used in the present invention include lactic acid and lactide which is a dehydrated cyclic dimer of lactic acid. Lactic acid is a monomer having stereoisomers, L-lactic acid, D-
Lactic acid is present. A polymer containing only L-lactic acid or D-lactic acid is highly crystallized to obtain excellent solvent resistance and heat resistance.

L-lactide and D are lactides.
-Lactide, there are isomers of MESO-lactide,
A polymer containing only L-lactide or D-lactide is also highly crystallized and excellent solvent resistance and heat resistance can be obtained. Therefore, the lactic acid-based polyester can realize preferable polymer characteristics by combining these two kinds of lactic acid or three kinds of lactide.

In particular, since the information recording card of the present invention is required to have solvent resistance and heat resistance, it is preferable that lactic acid has a high optical activity. Specifically, as the lactic acid component, it is preferable that 70% by weight or more of L-form or D-form is contained in the total lactic acid component. In order to obtain further excellent solvent resistance and high heat resistance, it is preferable that L-form or D-form is contained in an amount of 80% by weight or more as lactic acid.

Regarding lactide, L-lactide or D-lactide is 70% by weight in the total lactide.
It is preferable to include the above. In order to obtain further excellent solvent resistance and high heat resistance, it is preferable that L-lactide or D-lactide be contained in an amount of 80% by weight or more based on the total lactide. Commercially, L-lactic acid is cheaper and higher in purity by fermentation synthesis. Therefore, L-lactic acid is used as the lactic acid of the lactic acid-based polyester and L-lactic acid is used as the lactide.
-Preference is given to using lactide.

Specific examples of the dicarboxylic acid component include aromatic dicarboxylic acid components such as phthalic anhydride, isophthalic acid, terephthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid and p-phenylenediacetic acid. , M-phenylenediglycolic acid, p-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p,
p'-dicarboxylic acid, diphenyl-m, m'-dicarboxylic acid, ο, ο'-diphenyl-p, p'-diphenyldicarboxylic acid, diphenyl-4,4'-diacetic acid,

Diphenylmethane-p, p'-dicarboxylic acid, diphenylethane-m, m'-dicarboxylic acid, stilbenedicarboxylic acid, 1,1'-diphenylethane-
p, p'-dicarboxylic acid, diphenylbutane-p, p '
-Dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, p-carboxyphenoxyacetic acid,

P-carboxyphenoxybutyric acid, p-
Carboxyphenoxyvaleic acid, p-carboxyphenoxycaproic acid, p-carboxyphenoxyheptanoic acid, p-carboxyphenoxyundecanoic acid, 1,2
-Diphenoxypropane-p, p'-dicarboxylic acid,
1,3-diphenoxypropane-p, p'-dicarboxylic acid, 1,4-diphenoxybutane-p, p'-dicarboxylic acid, 1,5-diphenoxypentane-p, p'-dicarboxylic acid, 1, 6-diphenoxypentane-p, p'-
Dicarboxylic acid, p- (p-carboxyphenoxy) benzoic acid,

P- (p-Carboxybenzyloxy) benzoic acid, 1,2-bis (2-methoxyphenoxy) ethane-p, p'-dicarboxylic acid, 1,3-bis (2-methoxyphenoxy) propane- p, p'-dicarboxylic acid, 1,4-bis (2-methoxyphenoxy) butane-p, p'-dicarboxylic acid, 1,5-bis (2-methoxyphenoxy) -3-oxapentane-p, p'-dicarboxylic acid, etc.

Further, malonic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, which are aliphatic dicarboxylic acid components,
Undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, citraconic acid, diglycolic acid, cyclohexa-3,5-diene-1,2-carboxylic acid, malic acid, citric acid, trans-hexahydroterephthalic acid, cis-hexahydroterephthalic acid, dimer acid, and the like, and mixtures thereof.

In particular, when an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms is used, it is excellent in biodegradability and flexibility. When an aromatic dicarboxylic acid is used, rigidity and heat resistance are excellent, but biodegradability deteriorates. Therefore, the amount of the aromatic dicarboxylic acid used in combination with the aliphatic dicarboxylic acid is 2%.
0 wt% or less, preferably 10 wt% or less, more preferably 5 wt% or less. Use of maleic anhydride, fumaric acid, dimer acid or the like having a double bond is excellent in heat resistance.

The diol component may be of any type, but is not limited to ethylene glycol, propylene glycol, trimethylene glycol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol. , Butane-2,3-diol, 2,2-dimethylpropane-1,3-diol, cis-2-butene-
1,4-diol, trans-2-butene-1,4-
Diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol,

Heptamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, tridecamethylene glycol, eicosamethylene glycol, trans-1,4-cyclohexanedimethanol, 2, 2,4, -trimethylpentane-1,3-diol, hydrogenated bisphenol A, p-xylylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and the like, and a mixture thereof.

Further, when polyoxyalkylene having many ether-bonded oxygen atoms is used as the diol component, the flexibility is excellent. For example, polyethylene glycol, polypropylene glycol, polybutylene glycol, polypentanediol, polytetramethylene glycol, a block copolymer of polyethylene glycol and polypropylene glycol and the like can be mentioned.

The dicarboxylic acid component and the diol component are copolymerized with the lactic acid component for the purpose of increasing the flexibility and strength of the lactic acid-based polyester, and have the effect of improving the folding strength and impact resistance. . When an aliphatic dicarboxylic acid component and an aliphatic diol component are used as the dicarboxylic acid component and the diol component, the lactic acid-based polyester obtained is excellent in biodegradability and flexibility, and when a component having a branched chain is used. It tends to be excellent in transparency.

The chelating agent used as a deactivator for the polymerization catalyst includes an organic chelating agent and an inorganic chelating agent. Organic chelating agents have low hygroscopicity and are excellent in thermal stability. Examples of the organic chelate that can be used include, but are not limited to, amino acids, phenols, hydroxycarboxylic acids, diketones, amines, oximes, phenanthrolines, pyridine compounds, dithio compounds, N-containing phenols as coordinating atoms, and coordination atoms. Examples of the atom include N-containing carboxylic acids, diazo compounds, thiols, and porphyrins.

Specifically, the amino acid is glycine,
Leucine, alanine, serine, α-aminobutyric acid, acetylaminoacetic acid, glycylglycine, glutamic acid, etc.
As phenols, alizarin, t-butylcatechol, 4-isopropyltropolone, chromotropic acid,
Tyrone, oxine, propyl gallate and the like, hydroxycarboxylic acids such as tartaric acid, oxalic acid, citric acid, monooctyl citrate, dibenzoyl-D-tartaric acid, diparatoluoyl-D-tartaric acid, etc.

The diketones include acetylacetone, hexafluoroacetylacetone, benzoylacetone,
Amines such as theoyltrifluoroacetone and trifluoroacetylacetone; oximes such as ethylenediamine, diethylenetriamine, 1,2,3-triaminopropane, thiodiethylamine, triethylenetetramine, triethanolamine, tetraethylenepentamine, and pentaethylenehexamine; Such as dimethylglyoxime, α, α-furyldioxime, salicylaldoxime,

Phenanthrolines include neocuproin and 1,10-phenanthroline, pyridine compounds include 2,2-bipyridine and 2,2 ′, 2 ″ -terpyridyl, and dithio compounds include xanthogenic acid, diethyldithiocarbamic acid and toluene. Coordinating atom N-containing phenols such as 3,4-dithiol include o-aminophenol, oxine, nitroso R salt, 2-nitroso-5-dimethylaminophenol, 1-nitroso-2-
Naphthol, 8-selenoquinoline, etc.

Examples of the carboxylic acid containing a coordination atom N include quinaldic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, trans-cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, Aniline diacetate, 2-sulfoaniline diacetate, 3-sulfoaniline diacetate, 4-sulfoaniline diacetate, 2-aminobenzoic acid-N, N-diacetate, 3-aminobenzoic acid-N, N-diacetate , 4-aminobenzoic acid-
N, N-diacetate, methylamine diacetate, β-alanine-
N, N-diacetate,

Examples of diazo compounds such as β-aminoethylsulfonic acid-N, N-diacetate and β-aminoethylphosphonic acid-N, N-diacetic acid include diphenylcarbazone, magneson, dithizone, eriochrome black T, -(2
Thiols, such as -thiazolylazo) resorcinol and 1- (2-pyridylazo) -2-naphthol, such as thiooxin, thionalide, and 1,1,1-trifluoro-4-.
(2-thienyl) -4-mercapto-3-butene-2-
On, 3-mercapto-p-cresol, etc.

Examples of the porphyrins include tetraphenylporphine and tetrakis (4-N-methylpyridyl) porphine, and other examples include cupron, murexide, polyethyleneimine, polymethylacryloylacetone, and polyacrylic acid, and mixtures thereof. .

Among these, nitrile triacetic acid, ethylenediamine diacetate, tetraethylene pentaacetic acid and the like are used as organic chelating agents which efficiently coordinate with the metal ions of the catalyst contained in the lactic acid-based polyester and suppress the cleavage of polymer terminals. Min, hydroxyethyl ethylenediamine triacetic acid,
N-containing carboxylic acids such as ethylenediaminetetraacetic acid, trans-cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and triethylenetetraminehexaacetic acid;

Examples include hydroxycarboxylic acids such as tartaric acid, dibenzoyl-D-tartaric acid, diparatoluoyl-D-tartaric acid, citric acid, and monooctyl citrate. In particular, the above-mentioned carboxylic acid containing a coordinating atom N is excellent in thermal stability and storage stability, and hydroxycarboxylic acid is characterized by little coloring.

The inorganic chelating agent has a high hygroscopic property, and if it absorbs moisture, it has no effect. Specific examples include phosphoric acids such as phosphoric acid, phosphorous acid, pyrophosphoric acid, and polyphosphoric acid.

The acidic phosphoric acid ester used in the present invention includes acidic phosphoric acid ester, phosphonic acid ester, alkylphosphonic acid and the like and mixtures thereof.
Specifically, as the acidic phosphate ester, monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, diethyl phosphate, monopropyl phosphate, dipropyl phosphate, monoisopropyl phosphate, diisopropyl phosphate, monobutyl phosphate, Dibutyl phosphate, monopentyl phosphate, dipentyl phosphate, monohexyl phosphate, dihexyl phosphate, monooctyl phosphate, dioctyl phosphate, mono-2-ethylhexyl phosphate, di2-ethylhexyl phosphate,
Monodecyl phosphate,

Didecyl phosphate, monoisodecyl phosphate,
Diisodecyl phosphate, monoundecyl phosphate, diundecyl phosphate, monododecyl phosphate, didodecyl phosphate,
Monotetradecyl phosphate, ditetradecyl phosphate, monohexadecyl phosphate, dihexadecyl phosphate, monooctadecyl phosphate, dioctadecyl phosphate, monophenyl phosphate, diphenyl phosphate, monobenzyl phosphate, dibenzyl phosphate, etc.

Examples of the phosphonate ester include monomethyl phosphonate, monoethyl phosphonate, monopropyl phosphonate, monoisopropyl phosphonate, monobutyl phosphonate, monopentyl phosphonate, monohexyl phosphonate, monooctyl phosphonate, monoethylhexyl phosphonate, Monodecyl phosphonate, monoisodecyl phosphonate, monoundecyl phosphonate, monododecyl phosphonate, monotetradecyl phosphonate, monohexadecyl phosphonate, monooctadecyl phosphonate, monophenyl phosphonate, monobenzyl phosphonate, etc.,

As the alkylphosphonic acid, monomethylphosphonic acid, dimethylphosphonic acid, monoethylphosphonic acid, diethylphosphonic acid, monopropylphosphonic acid, dipropylphosphonic acid, monoisopropylphosphonic acid, diisopropylphosphonic acid, monobutylphosphonic acid, Dibutylphosphonic acid, monopentylphosphonic acid, dipentylphosphonic acid, monohexylphosphonic acid, dihexylphosphonic acid, isooctylphosphonic acid, dioctylphosphonic acid, monoethylhexylphosphonic acid, diethylhexylphosphonic acid, monodecylphosphonic acid, didecylphosphonic acid ,

Monoisodecylphosphonic acid, diisodecylphosphonic acid, monoundecylphosphonic acid, diundecylphosphonic acid, monododecylphosphonic acid, didodecylphosphonic acid, monotetradecylphosphonic acid, ditetradecylphosphonic acid, monohexadecylphosphonic acid Acid, dihexadecylphosphonic acid, monooctadecylphosphonic acid, dioctadecylphosphonic acid, monophenylphosphonic acid,
Mention may be made of diphenylphosphonic acid, monobenzylphosphonic acid, dibenzylphosphonic acid, etc., and mixtures thereof.

The acidic phosphoric acid ester component has good solubility in an organic solvent and therefore has excellent workability and excellent reactivity with a lactic acid-based polyester. Among them, acidic phosphates have a great effect on deactivating the catalyst.

The polyester composed of a dicarboxylic acid component and a diol component used in the production of lactic acid-based polyester has a weight average molecular weight of 10,000 to 400,000, preferably 2
It is preferably from 10,000 to 300,000. If it is less than 10,000, the mechanical strength of the lactic acid-based polyester obtained therefrom is insufficient. If it exceeds 400,000, its productivity and moldability are poor, which is not preferable. Further, when a polyester which is solid at room temperature is used as this polyester, bleeding from the obtained lactic acid-based polyester tends to decrease, which is preferable.

Next, the composition of the constituent components of the lactic acid-based polyester of the present invention will be described in order. The ratio of the lactic acid or lactide (f) of the present invention to the dicarboxylic acid component and the diol component (g) is not particularly limited, but (f) / (g) is preferably 99/1 to 10/90 weight. Parts, in order to obtain a high melting point, (f) / (g) is 9
It is preferably 9/1 to 40/60 parts by weight. Furthermore, in order to obtain high rigidity, (f) / (g) is 99 /
1 to 70/30 parts by weight, and in order to obtain excellent flexibility, (f) / (g) is preferably 70/30 to 40/60 parts by weight.

Further, the addition amount of the chelating agent and / or the acidic phosphoric acid ester used for the deactivation treatment of the polymerization catalyst varies depending on the kind, the kind and the amount of the catalyst contained in the lactic acid-based polyester. It is preferable to add 0.001 to 5 parts by weight to 100 parts by weight. Any chelating agent or acidic phosphoric acid ester can minimize the breaking of the polymer chain, and it is possible to use a mixture of an organic chelating agent, an inorganic chelating agent, and acidic phosphoric acid esters. .

However, if a chelating agent or acidic phosphoric acid ester is excessively added, the lactic acid type polyester chain is cleaved during storage, the molecular weight and viscosity are lowered, and the performance of the present invention may not be obtained. , It is necessary to add an appropriate amount.

As the polymerization catalyst used in the production of the lactic acid-based polyester of the present invention, known ring-opening polymerization catalysts,
Esterification catalyst, polymerization catalyst such as transesterification catalyst, tin, zinc, lead, titanium, bismuth, zirconium,
Examples thereof include metals such as germanium and cobalt and compounds thereof, and particularly preferred are metal organic compounds, carbonates, and halides.

Specifically, tin octoate, tin chloride, zinc chloride, zinc acetate, lead oxide, lead carbonate, titanium chloride, diacetoacetoxyoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, germanium oxide, Zirconium oxide and the like are suitable. The addition amount is preferably 0.001 to 2 parts by weight based on 100 parts by weight of the reaction components. From the viewpoint of reaction rate, coloring and the like, the amount of addition is more preferably 0.002% by weight to 0.5% by weight.

Further, as the esterification catalyst used in the production of the polyester composed of the dicarboxylic acid component and the diol component, metals such as tin, zinc, titanium, zirconium and the compounds thereof are preferable. Specifically, tin octanoate is used. , Tin chloride, zinc chloride, zinc acetate, diacetoacetoxyoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, zirconium oxide, etc. 0.001 to 2 parts by weight, preferably 0. It is preferable to add 002 to 0.5 part by weight from the beginning of the esterification or immediately before the deglycolization reaction.

The reaction temperature at the time of producing the lactic acid-based polyester of the present invention varies depending on the kind, amount and combination of the lactic acid component, the dicarboxylic acid component and the diol component, but is usually 125 ° C to 250 ° C, preferably 140 ° C. ~ 230
° C, more preferably 150 ° C to 200 ° C.

A solvent can be used in order to reduce the viscosity in the polymerization step, increase the stirring efficiency, and obtain good quality. The solvent that can be used is not particularly limited, but benzene, toluene, ethylbenzene, xylene,
Preferred are cyclohexanone, isopropyl ether, diphenyl ether and the like. The amount added varies depending on the production method, production conditions, type and composition of the reaction components, but is usually 100 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the reaction components.

In order to suppress the decomposition and coloration of the lactic acid type polyester, the reaction is carried out in an atmosphere of an inert gas such as nitrogen or argon without any contact with the outside air, and the raw material used is dried to remove water before the reaction. I need to keep it.

The lactic acid-based polyester thus obtained preferably has a high molecular weight to some extent, and specifically has a weight average molecular weight of 40,000 to 400,000, preferably 50,000 to 400,000, and further preferably. It is 100,000 to 350,000.
If it is less than 40,000, the strength as an information recording card is insufficient, and if it exceeds 400,000, there is a problem in molding and production efficiency, which is not preferable.

Further, in order to increase the molecular weight of the polyester used in the present invention, lactic acid, a dicarboxylic acid component, and a lactic acid-based polyester containing a diol component as structural units, a high molecular weight agent can be reacted. . This high molecular weight agent also has the effect of suppressing a decrease in molecular weight due to heat in the molding process. The timing of addition of the high molecular weight agent is not limited to any step such as before, during, and after the polymerization, a devolatilization step after the polymerization, an extrusion step, and a processing step.

Examples of the high molecular weight agent include polyvalent carboxylic acid, metal complex, epoxy compound, isocyanate and the like, or a mixture thereof. Examples of the polycarboxylic acid include (phthalic anhydride), hexahydrophthalic acid, (maleic anhydride), maleic acid, trimethyladipic acid, (trimellitic anhydride), pyromellitic dianhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, Epicron 4400 manufactured by Dainippon Ink and Chemicals, etc.
And mixtures thereof. In particular, carboxylic acids having three or more functional groups are effective in increasing the molecular weight.

Examples of the metal complex include lithium formate, sodium methoxide, potassium propionate, magnesium ethoxide, calcium propionate, manganese acetylacetonate, cobalt acetylacetonate, zinc acetylacetonate, cobalt acetylacetonate, and iron acetylacetonate. And aluminum acetylacetonate, aluminum isopropoxide, tetrabutoxytitanium, and the like, and mixtures thereof. Particularly, divalent or higher valent metal complexes show a great effect.

As the epoxy compound, bisphenol A type diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, terephthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, ο-
Diglycidyl phthalate, 3,4-epoxycyclohexylmethyl-3,4 epoxycyclohexanecarboxylate, bis (3,4 epoxycyclohexyl)
Adipate, tetradecane-1,14-dicarboxylic acid glycidyl ester and the like can be used.

As the isocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate,
1,5-naphthylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, diisocyanate-modified polyether, diisocyanate-modified polyester, polyhydric alcohol-modified bifunctional isocyanate, polyisocyanate-modified polyether, And polyesters modified with polyvalent isocyanates and mixtures thereof.

Among these high molecular weight agent components, polyvalent carboxylic acids and metal complexes are preferable in terms of safety and coloring, and aliphatic compounds are preferable in terms of biodegradability. Also,
The amount of the high molecular weight agent added varies depending on the type,
0.001 to 100 parts by weight of lactic acid-based polyester
It is preferable to add 5 parts by weight, more preferably 0.01 to 2 parts by weight. If the amount exceeds 5 parts by weight, the lactic acid-based polyester is not preferable because it gels, colors, or causes a decrease in viscosity.

Further, if an acidic substance such as polyvalent carboxylic acid remains in an unreacted state, the lactic acid type polyester chain is cleaved during storage, so it is not preferable to add it in excess, but less than 0.001 part by weight. Does not show a sufficient effect for increasing the molecular weight.

During the production of the lactic acid-based polyester of the present invention, a hydroxycarboxylic acid component other than lactic acid, a cyclic ester other than lactide, etc. may be added to 100 weight% of the lactic acid-based polyester depending on the purpose such as softening, mechanical strength and heat resistance. 1 to 50 parts by weight, preferably 1 to 25 parts by weight can be added to the parts. The timing of the addition is not particularly limited, but it is preferable to add it during the production of a lactic acid-based polyester containing lactic acid or lactide as a structural unit.

Specifically, hydroxycarboxylic acid components other than lactic acid include glycolic acid, dimethyl glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropanoic acid. , 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 2-hydroxycaproic acid, 3-hydroxycaproic acid, 4-hydroxycaproic acid, 5-hydroxycaproic acid, 6 -Hydroxycaproic acid,

Cyclic esters other than lactide, such as 6-hydroxymethylcaproic acid, include glycolide and β-.
Methyl-δ-valerolactone, γ-valerolactone, γ
-Undecalactone, epsilon-caprolactone, etc. are mentioned.

Further, an alcohol component such as stearyl alcohol, trimethylolethane, trimethylolpropane, pentaerythritol or glycerin can be added as a viscosity modifier within a range that does not impair the effects of the present invention. In addition, known and commonly used antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, flame retardants, etc. before, during, after polymerization, devolatilization step after polymerization, added to the extrusion step and the like Is also good.

The addition amount of them is 10
0.01 to 5 parts by weight per 0 parts by weight is preferred. Specifically, as an antioxidant, 2,6-di-t-butyl-
p-cresol, butylated hydroxyanisole, 2,
6-di-t-butyl-4-ethylphenol, distearyl 3,3'-thiodipropionate, dilauryl 3,
3'-thiodipropionate and the like, and heat stabilizers such as triphenyl phosphite, trilauryl phosphite and trisnonyl phenyl phosphite,

As the ultraviolet absorber, pt-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone and the like are used. As the antistatic agent, N, N-bis (hydroxyethyl) alkylamine, alkylamine, alkylallyl sulfonate, alkyl sulfonate, etc., and as the flame retardant, hexabromocyclododecane, tris- (2,3 -Dichloropropyl) phosphate, pentabromophenyl allyl ether and the like.

Further, known and commonly used lubricants and waxes may be added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of lactic acid type polyester. Lubricants, as waxes, for example, paraffin oil, paraffin such as solid paraffin, stearic acid, higher fatty acids such as palmitic acid, palmityl alcohol, higher alcohols such as stearyl alcohol, calcium stearate, zinc stearate, barium stearate, Fatty acid metal salts such as aluminum stearate, magnesium stearate and sodium palmitate; fatty acid esters such as butyl stearate, glycerin monostearate and diethylene glycol monostearate;

Waxes such as stearamide, methylenebisstearamide, ethylenebisstearamide, ethylenediamide of oxystearic acid, fatty acid amides such as methylolamide, oleylamide and erucylamide, waxes such as carnauba wax, montan wax and the like. A mixture may be mentioned. Further, a colorant, a crystallization accelerator, etc. can be added.

The lactic acid-based polyester of the present invention can be produced by using an ordinary reaction apparatus, but generally, in the high viscosity region where the viscosity of the polymerization solution exceeds 1,000 poise, not only the heat of polymerization but also the stirring shearing force is remarkable. Due to the heat generation, it is preferable to use a static mixer that has a small shearing force and acts uniformly. The static mixer is usually tubular, and multiple static mixers are connected in a line, and the raw material is continuously supplied from the raw material charging port under an inert gas atmosphere, and the reaction product moves continuously in the static mixer. Thus, it is possible to carry out the reaction continuously, from raw material charging to reaction and pomerization without any contact with the outside atmosphere.

In addition, a continuous stirred tank reactor, continuous polymerization by so-called CSTR, continuous polymerization by a combination of CSTR and static mixer, continuous reaction by a twin-screw extruder, etc. are also effective. These reactions can be carried out from raw material preparation to reaction and polymerization without any exposure to the outside atmosphere.

Volatile components such as unreacted components, solvents, and odorous components in the obtained lactic acid-based polyester are removed by using a devolatilization device such as a devolatilization tank, a film evaporator, and an extruder with a vent attached after the reaction process. To remove it, dissolve it in a good solvent and then remove it by precipitating it in a poor solvent, or use a solvent such as alcohol, ketone, hydrocarbon, etc., without dissolving it, dip or disperse it and then extract and remove it. However, the moldability and heat resistance of lactic acid-based polyester,
It is preferable from the viewpoint of improving storage stability and the like.

By these devolatilization methods, volatile components such as unreacted components, solvents and odor components in the lactic acid-based polyester can be significantly reduced. Usually 2 to 5 in lactic acid based polyester
The amount of lactide remaining by about 10% by weight can be reduced to 1.0% by weight or less and, if necessary, 0.5% by weight or less.

The lactic acid-based polyester used for the support of the information recording card of the present invention is thermoplastic, and the support can be easily molded, and the support can be prepared by laminating the lactic acid-based polyester alone or appropriately, or Further, it is formed into a predetermined thickness by being composite-laminated with a paper having poor water resistance and mechanical strength, a polymer alloy containing starch as a main component (Matterby of Japan Synthetic Chemical Industry, Nobon of Chisso, etc.) and the like. The thickness of the support can be set arbitrarily, but is usually 100 to 800 μm, preferably 150 to 350 μm.

An information recording section is formed on such a support. The type and shape of the information recording section used in the present invention is not particularly limited as long as it can record and reproduce information. Although the information recording portion in the example described below has a card shape, the present invention is not limited to this and may be formed in a desired shape.

More specifically, when the information recording portion is a magnetic recording layer, for example, γ-Fe ₂ O ₃ and Co deposited γ-Fe _{2
O 3, Fe 3 O 4,} Fe-Cr, Fe-Co, Co-C
A dispersion prepared by dispersing a magnetic material such as r, Co-Ni, Ba-ferrite, Sr-ferrite, CrO ₂ in a suitable resin or ink vehicle is prepared by a gravure method, a roll method,
The magnetic recording layer can be formed by coating according to a known coating method such as the Nifedge method.

Further, Fe, Fe--Cr, Fe--Co, C
The magnetic recording layer can be formed by using a metal or alloy such as o-Cr, or an oxide thereof, by a vacuum deposition method, a sputtering method, a plating method, or the like. Alternatively, a magnetic tape piece prepared in advance may be attached to a support to form it. Alternatively, a magnetic transfer foil may be prepared and formed by a transfer method.

Further, known recording means such as a heat-sensitive recording layer, a heat-sensitive rewrite layer, an optical recording layer, a program layer discharge recording layer, a bar code, an IC chip and a semiconductor chip can be formed as the information recording section. Of these, the heat-sensitive recording layer is a heat-sensitive transfer (sublimation transfer type or melt transfer type),
It can be appropriately selected from known recording means such as heat-sensitive color development and heat-sensitive destruction according to the purpose of use.

Further, the heat-sensitive rewrite layer may be one capable of stably recording and erasing by heat. Specifically, at least one aliphatic carboxylic acid selected from an aliphatic monocarboxylic acid and an aliphatic dicarboxylic acid and an organic low molecular compound having a polyoxyethylene chain are dispersed in a matrix material made of a resin. And a film-forming polymer substance containing a liquid crystal substance.

An information recording card using the lactic acid-based polyester of the present invention as a support has, inter alia, mechanical properties, durability, heat resistance and solvent resistance required for a magnetic card or its support, and , Shows biodegradability that can be decomposed by microorganisms in the natural world, and can be used for various information recording cards such as book purchase cards, telephone cards, shopping cards, cash cards, highway cards, facility use cards, guarantee cards, IC cards, etc. You can

[0097]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. All parts in the examples are on a weight basis unless otherwise specified. The molecular weight, residual lactide, melting point, thermal stability, tensile strength, durability, biodegradability test and storage stability were measured by the following methods.

The molecular weight was measured by gel permeation chromatography (GPC) and shown as a polystyrene conversion value. Residual lactide was measured by high performance liquid chromatography. Melting point: Differential scanning calorimeter D manufactured by Seiko
It was measured using a SC-200 model under the condition of a heating rate of 10 ° C./min, and determined from the obtained melting endothermic curve.

Thermal stability is 220 μm for 250 μm sheets.
The reduction rate of the weight and the molecular weight after standing for 10 minutes under a reduced pressure of 5 ° C. at 5 ° C. was measured. The tensile strength is JIS-C2
318 test method. With respect to durability, a magnetic card reader type was repeatedly run for 3000 passes, and the running property of the card and the presence or absence of an abnormality in the reproduction signal were evaluated. For the magnetic output characteristics, the reproduction output level and the output fluctuation rate were measured with a magnetic card reader / writer. Here, reproduction output level = sum of peak voltage values / number of peaks, output fluctuation rate = (peak voltage maximum value−peak voltage minimum value) × 100 / reproduction output level.

[0100] The biodegradability test was carried out by Shinki Gosei Co., Ltd. Composting container Tombo Miracle Component 10 with a capacity of 100 liters
Type 0 was used, and 50 kg of garbage was put therein, the magnetic card prepared was placed, and further garbage was put into a thickness of about 5 cm. On top of that, 500 g of Nyxaminone, a fermentation accelerator manufactured by Aron Kasei Co., was sprinkled and evaluated. The device was installed outdoors. One month after the start of the test, the test piece was taken out and evaluated in the following four stages.

⊚: The image is in a tattered state where the original shape is not retained. ○: The original shape is kept but the appearance is white and brittle. Δ: There is no change in appearance and there is little decrease in strength. X: No change at all.

The storage stability is as follows:
The rate of decrease in molecular weight when left for 3 months at 50% humidity is shown.

Reference Example 1 1 molar equivalent of dicarboxylic acid component and 1.3 molar equivalent of diol component were charged, and the temperature was raised from 150 ° C. to 10 ° C. in 1 hour in a nitrogen atmosphere. The temperature was raised to 220 ° C. while distilling off the generated water, and after the distillation of water stopped, 70 pp of titanium tetraisopropoxide was added.
m, and a polycondensation reaction by glycol removal was performed for 4 hours while reducing the pressure to 0.5 torr. Furthermore, after the distillation of glycol stopped, the reaction was carried out at 230 ° C. for 1 hour to obtain a polyester.

Reference Example 2 A dicarboxylic acid component of 1 molar equivalent and a diol component of 1.3 molar equivalent were charged, and the temperature was raised from 150 ° C. to 10 ° C. per hour in a nitrogen atmosphere. The temperature was raised to 220 ° C. while distilling off the generated water, and after the distillation of water stopped, 70 pp of titanium tetraisopropoxide was added.
m, and a polycondensation reaction by glycol removal was performed for 4 hours while reducing the pressure to 0.5 torr. Further, after the distillation of glycol was stopped, the reaction was carried out at 230 ° C. for 1 hour,
The temperature was lowered to 0 ° C., and then a high molecular weight agent was added and reacted for 1 hour to obtain a polyester.

Reference Example 3 Polyester obtained by the production method of Reference Example 1 (25 mol% terephthalic acid, 25 mol% isophthalic acid, 20 mol% ethylene glycol, 30 mol% neopentyl glycol, weight average molecular weight 55, Four
00) 20 parts, L-lactide 78 parts, and D-lactide 2 parts were charged in a reaction kettle and placed under an inert gas atmosphere for 1
Melt and mix at 70 ° C for 1 hour to add tin octoate 0.04
Part of the mixture was added, and the mixture was reacted at the same temperature for 6 hours, then devolatilized and pelletized.

Lactic acid-based polyester pellets 1 thus obtained
After blending 0.1 part of pyrophosphoric acid and 3 parts of titanium oxide with 00 parts, the mixture was supplied to a sheet extruder with a vent set at 180 ° C., melt-kneaded, devolatized at a reduced pressure of 5 torr, extruded, and rolled. After casting, use a stretching roll set at 70 ° C and a tenter set at 65 ° C for 2.5 mm each in length and width.
After being biaxially stretched twice, it was annealed and crystallized in an oven at 90 ° C. to obtain a sheet having a thickness of 200 μm.

The weight average molecular weight of the obtained sheet was 13
It was 5,000. Its appearance was white, odorless, and 0.1% residual lactide. The melting point is 159
The reduction rate of weight and molecular weight in the thermostability test at 1 ° C. was 1% and 1%, respectively.

Reference Example 4 Polyester obtained by the production method of Reference Example 1 (50 mol% sebacic acid, 50 mol% ethylene glycol, weight average molecular weight 46,000) 10
Parts, 85 parts of L-lactide, 5 parts of DL-lactide and 15 parts of toluene as a solvent were charged into a reaction kettle, and they were melt-mixed under an inert gas atmosphere at 170 ° C. for 1 hour to obtain tin octanoate. 0.03 part of was added and reacted at the same temperature for 6 hours, then heated to 200 ° C., devolatilized under reduced pressure of 5 torr, and pelletized.

Lactic acid-based polyester pellets 1 thus obtained
180 parts after blending 3 parts of titanium oxide with 00 parts
It is supplied to a sheet extruder with a vent set at 1, melt-kneaded, devolatilized at a reduced pressure of 5 torr, extruded, cast by a roll, and then stretched vertically and horizontally by a stretching roll set at 70 ° C and a tenter set at 65 ° C. After biaxially stretching each 2.5 times,
Annealing and crystallization were performed in an oven at 90 ° C. to obtain a sheet having a thickness of 200 μm.

The weight average molecular weight of the obtained sheet was 11
It was 5,000. Its appearance was white, odorless, and residual lactide was 0.9%. The melting point is 169.
The reduction rates of the weight and the molecular weight in the heat stability test at 2 ° C were 2% and 2%, respectively, indicating excellent stability.

Reference Example 5 Polyester (50 mole% azelaic acid, 50 mole% ethylene glycol, 0.2% hexamethylene diisocyanate / polyester of azelaic acid and ethylene glycol) obtained by the production method of Reference Example 2, weight Average molecular weight 116,000) 30 parts,
70 parts of L-lactide and 15 parts of toluene as a solvent were charged into a reaction kettle, and they were melt-mixed under an inert gas atmosphere at 170 ° C. for 1 hour to obtain tin octoate 0.03.
After adding 6 parts and reacting at the same temperature for 6 hours, the temperature was raised to 200 ° C., the mixture was devolatilized under reduced pressure of 5 torr, and pelletized.

Lactic acid-based polyester pellets 1 thus obtained
After blending 0.2 parts of ethylenediaminetetraacetic acid and 3 parts of titanium oxide with respect to 00 parts, the mixture was fed to a sheet extruder with a vent set at 180 ° C., melt-kneaded, devolatilized at a reduced pressure of 5 torr, extruded, and rolled. After casting, the film was biaxially stretched 2.5 times in both length and width with a stretching roll set at 70 ° C. and a tenter set at 65 ° C., then annealed and crystallized in an oven at 90 ° C. to a thickness of 200 μm. Got the sheet.

The weight average molecular weight of the obtained sheet was 14
It was 3,000. Its appearance was white, odorless, and residual lactide was 0.1% or less. The melting point is 1
At 70 ° C., the weight and molecular weight reduction rates in the thermal stability test were all 1% or less, and the stability was extremely excellent.

Reference Example 6 Polyester obtained by the production method of Reference Example 1 (sebacic acid: 50 mol%, molecular weight: 100)
0 polypropylene glycol 25 mol%, propylene glycol 25 mol%, weight average molecular weight 41,000)
15 parts, 85 parts of L-lactide, and 15 parts of toluene as a solvent were charged into a reaction kettle, and an inert gas atmosphere was added.
Melt and mix at 170 ° C for 1 hour, and add tin octoate to 0.0
After adding 3 parts and reacting at the same temperature for 6 hours, it was devolatilized and pelletized.

Lactic acid-based polyester pellets 1 thus obtained
To 00 parts, 0.2 parts pyromellitic dianhydride, 0.1 part of a mixture of monododecyl phosphate and didodecyl phosphate, and 3 parts of titanium oxide were blended, and then supplied to a sheet extruder with a vent set at 180 ° C. Melt-knead, devolatilize at a reduced pressure of 5 torr, extrude, cast with rolls, then 70 ° C
The film was biaxially stretched 2.5 times in each of the lengthwise direction and the transverse direction with a stretching roll set to No. 2 and a tenter installed at 65 ° C., and then annealed and crystallized in an oven at 90 ° C. to obtain a sheet having a thickness of 200 μm.

The weight average molecular weight of the obtained sheet was 14
It was 4,000. Its appearance is white, odorless,
Residual lactide was less than 0.1%. Further, the melting point was 168 ° C., and the weight and molecular weight reduction rates in the thermal stability test were all 1% or less, and the stability was extremely excellent.

Reference Example 7 3 mol% of sebacic acid, 4 mol% of propylene glycol and 94 mol% of L-lactic acid were placed in a reaction kettle and heated at 150 ° C. to 1 ° C. under an inert gas atmosphere.
The mixture was heated and stirred while the temperature was raised by 7 ° C each time. The temperature was raised to 200 ° C. while distilling off the produced water, and 0.007 parts of tetraisopropoxytitanium was added after the distilling of water was stopped, and the mixture was stirred under reduced pressure to 0.5 torr. After the distillation of glycol stopped, the reaction was continued at 210 ° C. for 1 hour. Hexamethylene diisocyanate 0.2 part and phosphoric acid mono 2- to 100 parts of the obtained polyester
After adding 0.1 part of a mixture of ethylhexyl and di2-ethylhexyl phosphate and reacting at 170 ° C. for 30 minutes,
The temperature was raised to 200 ° C., the mixture was devolatilized under reduced pressure of 5 torr, and pelletized.

The lactic acid-based polyester pellets thus obtained were blended with 3 parts of titanium oxide per 100 parts thereof, and then blended to give 1 part.
It is supplied to a vented sheet extruder set at 80 ° C, melt-kneaded, devolatilized at a reduced pressure of 5 torr, extruded, cast on a roll, and then lengthwise by a stretching roll set at 70 ° C and a tenter installed at 65 ° C. After being biaxially stretched 2.5 times each in the transverse direction, they were annealed and crystallized in an oven at 90 ° C. to obtain a sheet having a thickness of 200 μm.

The weight average molecular weight of the obtained sheet was 10
It was 3,000. Its appearance is white, odorless,
Residual lactide was less than 0.1%. Further, the melting point was 147 ° C., and the weight and molecular weight reduction rates in the thermal stability test were all 1% or less, and the stability was extremely excellent.

(Reference Example 8) 98 parts of L-lactide and D
-2 parts of lactide and 15 parts of toluene as a solvent are charged into a reaction vessel, melt-mixed at 170 ° C for 1 hour in an inert gas atmosphere, and 0.03 part of tin octoate is added thereto.
After reacting at 75 ° C. for 6 hours, devolatilized and pelletized.

70 parts of the obtained polylactic acid pellets and the polyester (40 mol% of dodecanedicarboxylic acid, 10 mol% of adipic acid, 50 mol% of hexanemethylene glycol, weight average molecular weight of 4) obtained by the production method of Reference Example 1
5,000) 30 parts, aluminum isopropoxide 0.5 part, citric acid 0.1 part, and titanium oxide 3 parts are blended, and then supplied to a sheet extruder with a vent set at 180 ° C. and melt-kneaded. After devolatilizing at a reduced pressure of 5 torr, extruding, casting with a roll, a stretching roll set at 70 ° C. and a tenter installed at 65 ° C. set both the vertical and horizontal directions to 2.5.
After being biaxially stretched twice, it was annealed and crystallized in an oven at 90 ° C. to obtain a sheet having a thickness of 200 μm.

The weight average molecular weight of the obtained sheet was 12
It was 1,000. Its appearance is white, odorless,
The residual lactide was 0.1%. The melting point is 16
The reduction rates of the weight and the molecular weight in the 3 ° C. heat stability test were 1% and 1%, respectively, and the stability was considerably excellent.

Reference Example 9 95 parts of L-lactide and D
A reaction vessel was charged with 5 parts of L-lactide and 15 parts of toluene as a solvent, and melt-mixed at 170 ° C. for 1 hour under an inert gas atmosphere.
After reacting at 75 ° C. for 6 hours, devolatilized and pelletized.

80 parts of the obtained polylactic acid pellets, 20 parts of the polyester (50 mol% sebacic acid, 50 mol% ethylene glycol, weight average molecular weight 46,000) obtained by the production method of Reference Example 1, phosphorus 0.1 part of a mixture of acid monohexadecyl and dihexadecyl phosphate and 3 parts of titanium oxide are blended, supplied to a sheet extruder with a vent set to 180 ° C., melt-kneaded, and devolatilized at a reduced pressure of 5 torr, After extrusion and casting with a roll, the film was biaxially stretched 2.5 times in both length and width with a stretching roll set at 70 ° C. and a tenter set at 65 ° C. to obtain a sheet having a thickness of 200 μm.

The weight average molecular weight of the obtained sheet was 13
It was 5,000. Its appearance is white, odorless,
Residual lactide was less than 0.1%. Further, the melting point was 160 ° C., and the weight and molecular weight reduction rates in the thermal stability test were all 1% or less, and the stability was extremely excellent.

Reference Example 10 95 parts of L-lactide,
5 parts of D-lactide and 15 parts of toluene as a solvent were charged into a reaction kettle, and melt-mixed at 170 ° C. for 1 hour under an inert gas atmosphere, and 0.03 part of tin octoate was added to give 1 part.
After reacting at 75 ° C. for 6 hours, devolatilized and pelletized.

85 parts of the obtained polylactic acid pellets, 15 parts of the polyester (50 mole% azelaic acid, 50 mole% ethylene glycol, weight average molecular weight 42,000) obtained by the production method of Reference Example 1 and phosphorus were used. After blending 0.1 part of the mixture of monododecyl acidate and didodecyl phosphate,
The mixture was supplied to a vented twin-screw extruder set at 180 ° C., melt-kneaded, and pelletized. The obtained pellet was dissolved in chloroform, precipitated in methanol, filtered, and then heated at 200 ° C for 5
It was devolatilized under a reduced pressure of torr.

Further, the obtained lactic acid-based polyester 100
After blending 3 parts of titanium oxide with 3 parts, it is fed to a sheet extruder with a vent set at 180 ° C, melt-kneaded, devolatilized at a reduced pressure of 5 torr, extruded, cast on a roll, and then set at 70 ° C. The film is stretched biaxially 2.5 times in each of the length and width with a drawing roll and a tenter installed at 65 ° C, and then 90 ° C.
Annealed and crystallized in an oven at a thickness of 200
A sheet of μm was obtained. The weight average molecular weight of the obtained sheet was 131,000.

The appearance was white, had no odor, and the residual lactide was 0.1% or less. The melting point is 151.
The reduction rates of the weight and the molecular weight in the temperature stability test at 0 ° C. were all 1% or less, and the stability was extremely excellent.

Reference Example 11 95 parts of L-lactide,
5 parts of DL-lactide and 15 parts of toluene as a solvent are charged into a reaction vessel, and heated at 170 ° C. under an inert gas atmosphere.
Melt for hours, add 0.03 parts of tin octoate,
After reacting at 175 ° C. for 6 hours, it was devolatilized and pelletized.

100 parts of the obtained polylactic acid pellet was blended with 0.1 part of a mixture of monohexadecyl phosphate and dihexadecyl phosphate and 3 parts of titanium oxide.
It is supplied to a sheet extruder with a vent set to 0 ° C, melt-kneaded, devolatilized at a reduced pressure of 5 torr, extruded, cast on a roll, and then lengthwise by a stretching roll set at 70 ° C and a tenter installed at 65 ° C. After being biaxially stretched 2.5 times each in the transverse direction, they were annealed and crystallized in an oven at 90 ° C. to obtain a sheet having a thickness of 200 μm.

The weight average molecular weight of the obtained sheet was 15
It was 7,000. Its appearance is white, odorless,
Residual lactide was less than 0.1%. Further, the melting point was 161 ° C., and the weight and molecular weight reduction rates in the thermal stability test were all 1% or less, and the stability was extremely excellent.

(Reference Example 12) 98 parts of L-lactide,
2 parts of D-lactide and 15 parts of toluene as a solvent were charged into a reaction vessel, melt-mixed at 170 ° C. for 1 hour in an inert gas atmosphere, and 0.03 part of tin octoate was added.
After reacting at 75 ° C. for 6 hours, devolatilized and pelletized.

100 parts of the obtained polylactic acid pellets were blended with 0.1 part of didecylphosphonic acid and 3 parts of titanium oxide, and then fed to a sheet extruder with a vent set at 180 ° C. and melt-kneaded. After devolatilization at a reduced pressure of 5 torr, extrusion, casting with a roll, annealing and crystallization in an oven at 90 ° C., and a sheet having a thickness of 200 μm was obtained.

The weight average molecular weight of the obtained sheet was 15
It was 7,000. Its appearance is white, odorless,
Residual lactide was less than 0.1%. Further, the melting point was 161 ° C., and the weight and molecular weight reduction rates in the thermal stability test were 1% and 1%, respectively.

Reference Example 13 100 parts of 90% L-lactic acid was charged into a reaction kettle, dehydrated for 3 hours at 150 ° C. under reduced pressure of 50 torr, 0.2 parts of tin powder was added, and the same temperature, 3
It was dehydrated for 2 hours under a reduced pressure of 0 torr. Next, as a solvent, 350 parts of diphenyl ether and 1 part of tin powder were added, and a column filled with 100 parts of molecular sieve was assembled so that the solvent distilled out by reflux would return to the inside of the system at 130 ° C. and 12 torr. Then, dehydration condensation was carried out for 55 hours. After completion of the reaction, 1.5 parts of trans-cyclohexanediaminetetraacetic acid was added, and after stirring for 20 minutes, the obtained polylactic acid was dissolved in chloroform, precipitated in methanol, filtered, and then removed under reduced pressure at 200 ° C. and 5 torr. I was excited.

Further, with respect to 100 parts of the obtained polylactic acid,
After blending 3 parts of titanium oxide, the mixture was fed to a sheet extruder with a vent set at 180 ° C, melted and kneaded, and the degree of vacuum was 5 torr.
After devolatilizing with, extruding, and casting with a roll, 70
Vertical with a stretching roll set at ℃ and a tenter set at 65 ℃
The film was biaxially stretched 2.5 times in the transverse direction and then annealed and crystallized in an oven at 90 ° C. to obtain a sheet having a thickness of 200 μm.

The weight average molecular weight of the obtained sheet was 10.
6,000. Its appearance is white, odorless,
Residual lactide was less than 0.1%. In addition, the melting point was 170 ° C., and the weight and molecular weight reduction rates in the thermal stability test were all 1% or less, and the stability was extremely excellent.

Reference Example 14 96 parts of L-lactide,
2 parts of D-lactide, 2 parts of glycolide, and 15 parts of toluene as a solvent were charged into a reaction kettle and melt-mixed at 170 ° C. for 1 hour under an inert gas atmosphere, and 0.03 part of tin octoate was added. After reacting at 175 ° C. for 6 hours, it was devolatilized and pelletized.

Lactic acid-based polyester pellets 1 thus obtained
Aluminum isopropoxide 0.8 against 100 parts
Part, tartaric acid 0.1 part, titanium oxide 3 parts after blending 1
It is supplied to a vented sheet extruder set at 80 ° C, melt-kneaded, devolatilized at a reduced pressure of 5 torr, extruded, cast on a roll, and then lengthwise by a stretching roll set at 70 ° C and a tenter installed at 65 ° C. After being biaxially stretched 2.5 times each in the transverse direction, they were annealed and crystallized in an oven at 90 ° C. to obtain a sheet having a thickness of 50 μm.

The weight average molecular weight of the obtained sheet was 15
It was 3,000. Its appearance is white, odorless,
The residual lactide was 0.1%. The melting point is 15
At 5 ° C., the weight and molecular weight reduction rates in the thermal stability test were 1% and 1%, respectively.

Example 1 As the support, the lactic acid type polyester sheet obtained in Reference Example 3 was used. First,
The following materials were dispersed and mixed by a ball mill for 24 hours to prepare a magnetic paint.

MC-127 (Ba ferrite magnetic powder manufactured by Toda Kogyo Co., Ltd.): 100 parts VAGH (vinyl chloride / vinyl acetate copolymer manufactured by UCC): 15 parts T-5206 (Polyurethane manufactured by Dainippon Ink and Chemicals, Inc.) Resin): 15 parts Toluene: 50 parts Methyl ethyl ketone: 50 parts Cyclohexanone: 50 parts

A coating consisting of 100 parts of the magnetic coating prepared above and 3 parts of BURNOCK D-750 (polyisocyanate manufactured by Dainippon Ink and Chemicals, Inc.) was used and applied to a thickness of 10 μm with a bar coater. Oriented magnet (magnetic field strength of 2,000 gauss) for undried magnetic recording layer
After the orientation treatment in (1), the magnetic recording layer was formed by drying for 1 minute in a hot air dryer at a temperature of 100 ° C.

Next, the following materials were stirred and mixed by a dispersion stirrer for 1 hour to prepare a protective coating material. BM-1 (Sekisui Chemical Co., Ltd. butyral resin) 100 parts, High Wax 220MP (Mitsui Petrochemical Co., Ltd. low molecular weight polyethylene) 5 parts, toluene 100 parts, methyl ethyl ketone 100 parts, cyclohexanone 100 parts.

Using the protective coating material prepared above, the magnetic recording layer was coated with a bar coater to a thickness of 2 μm and then dried for 1 minute in a hot air dryer at a temperature of 100 ° C. to form a protective layer. Further, after printing DieCure RT-8 black (offset ink manufactured by Dainippon Ink and Chemicals, Inc.) in a thickness of 2 μm on the surface of the support opposite to the coated surface, it was punched out into a card shape to obtain a magnetic card. . The magnetic card thus obtained did not have streaks or unevenness on the coated surface caused by the solvent being applied to the support during the coating of the magnetic paint, and there was no warpage caused by thermal deformation during drying. Tables 1 and 2 show the measurement results of tensile strength, magnetic output characteristics, durability, biodegradability, and storage stability.

(Examples 2 to 11) Magnetic cards were obtained in the same manner as in Example 1 except that the lactic acid type polyester sheets obtained in Reference Examples 4 to 13 were used as the support.
Each of the obtained magnetic cards did not have streaks or unevenness on the coated surface caused by the support being invaded by the solvent during the coating of the magnetic coating material, and there was no warpage caused by thermal deformation during drying. The measurement results are shown in Table 1 and Table 2.

Example 12 Example 1 was repeated except that the lactic acid polyester sheet obtained in Reference Example 9 was laminated with the lactic acid polyester sheet obtained in Reference Example 14 as a support. A magnetic card was obtained in the same manner as. The magnetic card thus obtained did not have streaks or unevenness on the coated surface caused by the solvent being applied to the support during the coating of the magnetic paint, and there was no warpage caused by thermal deformation during drying. The measurement results are shown in Table 1 and Table 2.

Example 13 As a support, 100 μm
Example 1 except that the sheet of the lactic acid-based polyester obtained in Reference Example 14 is pasted on both sides of the paper of Example 1
A magnetic card was obtained in the same manner as. The magnetic card thus obtained did not have streaks or unevenness on the coated surface caused by the solvent being applied to the support during the coating of the magnetic paint, and there was no warpage caused by thermal deformation during drying. The measurement results are shown in Table 1 and Table 2.

COMPARATIVE REFERENCE EXAMPLE 1 A blend of ethylenediaminetetraacetic acid, a stretching roll set at 70 ° C., and a tenter set at 65 ° C. were used to biaxially stretch the film vertically and horizontally 2.5 times, and then oven at 90 ° C. A thickness of 200 was obtained in the same manner as in Reference Example 5, except that annealing and crystallization were performed in the chamber.
A sheet of μm was obtained. The weight average molecular weight of the obtained sheet was 119,000. Its appearance was white yellow and had an odor, and the residual lactide was 3.9%. Further, the melting point was 152 ° C., and the weight and molecular weight reduction rates in the thermal stability test were 11% and 9%, respectively, and the stability was considerably poor.

Comparative Reference Example 2 A sheet having a thickness of 200 μm was obtained in the same manner as in Reference Example 5, except that the blend of ethylenediaminetetraacetic acid was omitted. The weight average molecular weight of the obtained sheet was 121,000. Its appearance was white yellow and had an odor, and the residual lactide was 3.8%.
Further, the melting point was 153 ° C., and the weight and molecular weight reduction rates in the thermal stability test were 12% and 10%, respectively, and the stability was considerably poor.

Comparative Reference Example 3 A blend of aluminum isopropoxide and citric acid, a stretching roll set at 70 ° C., and a tenter set at 65 ° C. were used to measure 2.
A sheet having a thickness of 200 μm was obtained in the same manner as in Reference Example 8 except that the film was biaxially stretched 5 times and then annealed and crystallized in an oven at 90 ° C. The weight average molecular weight of the obtained sheet was 98,000. Its appearance was white yellow and had an odor, and the residual lactide was 3.7%. Further, the melting point was 161 ° C., and the reduction rates of weight and molecular weight in the thermal stability test were 11% and 8%, respectively, and the stability was considerably poor.

COMPARATIVE REFERENCE EXAMPLE 4 A blend of monohexadecyl phosphate and a mixture of dihexadecyl phosphate, 70
Vertical with a stretching roll set at ℃ and a tenter set at 65 ℃
Except for annealing and crystallizing in an oven at 90 ° C. after biaxially stretching each laterally 2.5 times,
A sheet having a thickness of 200 μm was obtained in the same manner as in Reference Example 11. The weight average molecular weight of the obtained sheet was 124,000.
Met. Its appearance was white yellow and had an odor, and the residual lactide was 3.8%. Further, the melting point is 159 ° C., and the weight loss and molecular weight reduction rates in the thermal stability test are 12 respectively.
%, 10% was considerably inferior in stability.

Comparative Example 1 As a support, Comparative Reference Example 1
A magnetic card was obtained in the same manner as in Example 1 except that the lactic acid-based polyester sheet obtained in 1 was used. The obtained magnetic card was found to have streaks and unevenness on the coated surface caused by the support being invaded by the solvent during the coating of the magnetic coating material, and the warpage caused by thermal deformation during drying was also remarkable. Tables 1 and 2 show the measurement results of tensile strength, magnetic output characteristics, durability, biodegradability, and storage stability.

(Comparative Examples 2 to 4) Magnetic cards were obtained in the same manner as in Example 1 except that the lactic acid type polyester sheets obtained in Comparative Reference Examples 2 to 4 were used as the support.
Each of the magnetic cards obtained had streaks and unevenness on the coated surface caused by the support being invaded by the solvent during the coating of the magnetic coating, and the warpage caused by thermal deformation during drying was also great. . The measurement results are shown in Table 1 and Table 2.

(Comparative Example 5) A support having a thickness of 200 μm
A magnetic card was obtained in the same manner as in Example 1 except that a commercially available polyethylene terephthalate sheet of m.
Each of the obtained magnetic cards did not have streaks or unevenness on the coated surface caused by the support being invaded by the solvent during the coating of the magnetic coating material, and there was no warpage caused by thermal deformation during drying. The measurement results are shown in Table 1 and Table 2.

[0157]

[Table 1]

[0158]

[Table 2]

[0159]

INDUSTRIAL APPLICABILITY The present invention has solvent resistance, heat resistance, mechanical strength and durability equivalent to those of the current products, yet has a low calorific value when burned, and has thermal stability and processing during molding. And its storage stability during use are good, and even if it is abandoned in the natural world after use, it decomposes naturally, and even if it is incinerated, it does not generate any harmful calorific value and produces no harmful gas. A recording card can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view schematically showing a configuration of a magnetic card according to Examples 1 to 11 of the present invention.

FIG. 2 is a sectional view schematically showing the structure of a magnetic card of Example 12 of the present invention.

FIG. 3 is a sectional view schematically showing the configuration of a magnetic card of Example 13 of the present invention.

[Explanation of symbols]

 1: Protective layer 2: Magnetic layer 3: Support 4: Lactic acid type polyester layer 5: Lactic acid type polyester layer different from 4 6: Paper layer 7: Printing layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G11B 5/80 G11B 5/80 // C08L 67:04

Claims (9)

[Claims] 1. An information recording card, wherein at least a part of the support is composed of crystallized and / or stretched lactic acid-based polyester. 2. The information recording card according to claim 1, wherein the lactic acid-based polyester is crystallized. 3. The information recording card according to claim 1, wherein the lactic acid-based polyester has a polymerization catalyst deactivated. 4. The information recording card according to claim 3, wherein the deactivation treatment of the polymerization catalyst is performed by using a chelating agent and / or an acidic phosphoric acid ester. 5. The information recording card according to any one of claims 1 to 4, wherein the lactic acid-based polyester contains a structural component (A) derived from lactic acid as an essential component. 6. The structural component (A) derived from lactic acid is L-
The information recording card according to claim 5, which contains 70% by weight or more of a structural component derived from lactic acid or D-lactic acid. 7. A lactic acid-based polyester comprises a structural component (A) derived from lactic acid, a structural component (B) derived from a dicarboxylic acid, and a structural component (C) derived from a diol as essential components. The information recording card according to claim 5, wherein the information recording card is present. 8. A structural component (B) derived from a dicarboxylic acid.
8. The information recording card according to claim 7, wherein both the structural component (C) derived from and diol have an aliphatic structure. 9. The information recording card according to claim 1, wherein the information recording card is a magnetic card.