JP2008024850A - Biodegradable composition, molded product thereof, and application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition containing a new biodegradable polymer which has no water solubility (hygroscopicity), can be molded, and has excellent water disintegration properties and biodegradability, and to provide a molded product thereof. <P>SOLUTION: The biodegradable polymer contained in the biodegradable composition of the present invention is a polymer having one or more imine linkages in the molecule, wherein the imine linkages form part of the main chain structure of the biodegradable polymer. The biodegradable polymer preferably contains a biodegradable part and an imine part having one or more imine linkages, wherein the polymer has a chemical structure in the form of coupling the biodegradable parts with the imine parts. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a biodegradable composition comprising a novel biodegradable polymer. Specifically, it can be used stably without collapsing against moisture in the air or a small amount of water, and the water-disintegrating biodegradation has the property that its shape collapses when it comes into contact with a large amount of water. The present invention relates to a biodegradable composition containing a functional polymer, a molded article thereof, and an application.

  Currently, thermoplastic resins such as polyethylene (hereinafter abbreviated as “PE”) and polypropylene (hereinafter abbreviated as “PP”) are used in various applications. Thermoplastic resins such as PE and PP are widely used in various applications because they have a high degree of freedom in molding processability, but there are various uses such as fibers, nonwoven fabrics, and films.

  However, a molded body made of such a resin does not easily collapse due to contact with water, and since it does not have biodegradability, it is given to the environment when it is discarded or discharged to the natural world after use. There is concern about the load. Therefore, as a molded body that may diffuse into the natural world, a biodegradable material is preferable from the viewpoint of reducing environmental load, and its development is desired.

  From such a background, as a molded body that may diffuse into the natural world, it does not disintegrate by a small amount of water during use, but collapses by contact with a large amount of water after use (water disintegrating) Development of is strongly desired.

  In addition, paper that has been used as a biodegradable material has advantages such as being highly water-absorbing and being able to flow to the toilet because it is a natural material. In other words, applications that can be used are limited because they do not have a high degree of freedom in molding processability.

From the above, in materials used for molded bodies that may diffuse into the natural world, it is required to create materials that satisfy the following three characteristics.
1. Water disintegration that is stable to moisture in the air and a small amount of water without deterioration in strength, and easily collapses when contacted with a large amount of water, especially under neutral conditions.
2. Biodegradability without impacting the global environment,
3. Molding processability to maintain a good feel and appearance such as touch.

  As a method for solving the above problems, Patent Document 1 discloses poly (3-hydroxybutyric acid). In this example, the use of thermoplastic biodegradable plastics has solved the problems of biodegradability and moldability, but poly (3-hydroxybutyric acid) does not have water disintegration, The water disintegration problem has not been solved.

  As an example of improving this problem, Patent Document 2 discloses a method of hydrolyzing poly (3-hydroxybutyric acid) under basic conditions. This method hydrolyzes the ester bond by hydrolyzing the ester bond under strongly basic conditions (pH 12 or more). However, since the reaction rate of hydrolysis of the ester bond is slow, sufficient water disintegrability has not been obtained, and the problem of water disintegration has not been sufficiently solved.

In addition, as an example of improving water disintegration property under basic conditions, Patent Document 3 discloses weak basic conditions (pH
In 10), an acrylic polymer having a carboxyl group exhibiting water disintegration is disclosed. This acrylic polymer having a carboxyl group shows water resistance under neutral conditions and exhibits water disintegration by adding a base to water such as toilets to make it weakly basic, but this polymer is not biodegradable, The problem of environmental impact remains.

  Next, Patent Document 4 and Patent Document 5 using water-soluble resins such as polyvinyl alcohol and polyethylene glycol are disclosed as examples of water disintegration under neutral conditions. However, in this example, since the material contains a water-soluble resin, there is a problem in use in which moisture is absorbed over time and wetted before use, and the surface becomes sticky or mold is generated.

  Patent Document 6 discloses a biodegradable resin composition obtained by mixing 20 to 80% by weight of a biodegradable plastic and 80 to 20% of a water-soluble thermoplastic resin. This biodegradable resin composition is one in which the shape of the molded body of the biodegradable resin composition is broken or sometimes collapsed when the water-soluble thermoplastic resin is dissolved or swollen in water. Since the biodegradable plastic itself has no water disintegration property, sufficient water disintegration property cannot be obtained. In addition, since a water-soluble thermoplastic resin is used, there is a problem in use in that it absorbs moisture over time and becomes wet before use and the surface becomes sticky or mold is generated.

  In addition to the above, as a measure for improving water disintegration, a method using a chemical bond such as an imine bond or an acetal bond that is easily hydrolyzed can be considered, but the above three required characteristics have been satisfied so far. No material has been found.

  For example, as a polymer having an imine bond (also referred to as an azomethine bond), polyphenylazomethine having high heat resistance and easily decomposable only in an acidic aqueous solution or cyclic not decomposing at all in a neutral aqueous solution A polymer having an imine structure (Patent Document 7) is known.

  Furthermore, Patent Document 8, Non-Patent Document 1, and Non-Patent Document 2 disclose various azomethine polymers. These documents do not specifically mention degradability to water, but all of the disclosed azomethine polymers are not biodegradable. An example of the polymer having an acetal bond is polyoxymethylene, which is one of typical engineering plastics. This polymer has excellent heat resistance, water resistance, and durability, which cannot be predicted from the unstable chemical structure of acetal bonds constituting the polymer, and is used as a material for plastic water pipes and the like.

It is extremely difficult to predict or discuss the water disintegration property of such a polymer that is composed of chemical bonds that are easily hydrolyzed. In addition, there is no known practical material having both water-disintegrating property and biodegradable property that disintegrates by contact with a large amount of water without being disintegrated under normal use.
JP-A 63-302845 European Patent No. 0142950 Japanese Patent Publication No. 7-57230 JP-A-5-29211 JP-A-6-134910 JP-A-6-299077 JP 2003-73470 A WO2004 / 003044 J.MACROMOL.SCI.-CHEM., A1 (7), 1161-1249 (1967) CHEM. COMMUN., 1522-1524 (2005)

The following four problems are listed as materials that may diffuse into the natural world.
1. It must not be water-soluble (hygroscopic) that absorbs moisture in the air during storage and causes stickiness.
2. It can be used in the same way as usual without collapsing with a small amount of water, and after use it must have water disintegrating properties that collapse its shape after coming into contact with a large amount of water.
3. Biodegradability that can be decomposed by microorganisms to minimize the impact on the natural environment.
4). It must have moldability to maintain the feel and appearance such as touch.

None of the conventional techniques satisfy the above four problems.
Accordingly, an object of the present invention is to provide a biodegradable composition containing a novel biodegradable polymer that has no water solubility (hygroscopicity), can be molded, and has excellent water disintegration and biodegradability, and a molded product thereof As well as providing uses.

  The present inventors diligently studied in order to achieve the above problems. As a result, a polymer material having both an imine moiety having a specific imine bond and a specific biodegradable moiety is not water-soluble (hygroscopic) such as stickiness or shape collapse in a normal state, and a large amount of water It was found that the shape collapses easily only after contact, and that the shape collapses faster when contacted with acidic water. Furthermore, surprisingly, it has been found that biodegradability is also improved, and the present invention has been completed.

That is, the present invention provides the following [1] to [20].
[1]
A biodegradable polymer having one or more imine bonds in the molecule, wherein the imine bond forms part of the main chain structure of the biodegradable polymer. Biodegradable composition.
[2]
[1] A biodegradable molded article using the biodegradable composition according to [1].
[3]
[1] A hot melt adhesive using the biodegradable composition according to [1].
[4]
[1] An aqueous paper coating composition using the biodegradable composition according to [1].
[5]
[1] An easily peelable adhesive material using the biodegradable composition according to [1].
[6]
[1] A thermal transfer medium using the biodegradable composition according to [1].
[7]
[2] The biodegradable molded product according to [2], wherein the biodegradable molded product is a fiber.
[8]
[2] The biodegradable molded product according to [2], wherein the biodegradable molded product is a nonwoven fabric.
[9]
[2] A biodegradable molded article, wherein the biodegradable molded article is a film.
[10]
[2] The biodegradable molded product according to [2], wherein the biodegradable molded product is a protective film. [11]
[2] The biodegradable molded product according to [2], wherein the biodegradable molded product is a porous film. [12]
[2] The biodegradable molded product according to claim 2, wherein the biodegradable molded product is an agricultural and horticultural material.
[13]
The biodegradable molded product according to [2], wherein the biodegradable molded product is a pet waste disposal agent.
[14]
[2] A biodegradable molded product according to the above, wherein the biodegradable molded product is a sustained-release drug.
[15]
[2] The biodegradable molded product according to [2], which is a casing of an electronic device.
[16]
[2] A biodegradable molded article, wherein the biodegradable molded article is a processing aid.
[17]
[2] The biodegradable molded product according to claim 2, wherein the biodegradable molded product is a civil engineering and building material. [18]
The biodegradable molded product according to [2], wherein the biodegradable molded product is a cleaning article.
[19]
[2] The biodegradable molded product according to [2], wherein the biodegradable molded product is an acid absorbent.
[20]
[2] The biodegradable molded product according to [2], wherein the biodegradable molded product is an alkali absorbent.

  The biodegradable composition using the novel biodegradable polymer provided by the present invention exhibits excellent water disintegration and biodegradability. In addition, since the biodegradable composition of the present invention does not have water solubility (hygroscopicity), the molded body is not deteriorated in surface condition or collapsed due to moisture or body fluid in the air. . Therefore, the molded product obtained from the biodegradable composition of the present invention has no problem at the time of storage or use, and after being used, it is discharged into a toilet or kitchen sink, and its shape is not contacted with a large amount of water. Collapses. Moreover, this water disintegration is also exhibited under neutral conditions (about pH 7). And after a discharge process, it is biodegraded by microorganisms etc. in a sewage treatment process and nature, and does not pollute the natural environment. Moreover, since the biodegradable composition of this invention has the outstanding moldability, the molded object with favorable tactile sensations, such as an external appearance and the touch, can be obtained.

  The water-disintegrating property in the present invention refers to a material whose form is disintegrated when contacted with a large amount of water. More preferably, according to the ease of loosening test of toilet paper of JIS P 4501, an 11 cm square film becomes 4 cm square or less in distilled water (about pH 7) in 520 hours or less. The biodegradability in the present invention means that polymer molecules are decomposed into low molecular weight compounds by microorganisms or the like in a sewage treatment process or in nature, and further decomposed into carbon dioxide gas or water. More preferably, the film has a biodegradability of 60% or more in the biodegradability test of the film in accordance with ISO14855.

The biodegradable composition concerning this invention contains the biodegradable polymer mentioned later.
[Biodegradable polymer]
The biodegradable polymer used in the present invention is a biodegradable polymer having one or more imine bonds in the molecule, and the imine bond forms part of the main chain structure of the biodegradable polymer. Preferably, it contains at least a biodegradable site having biodegradability and an imine site having one or more imine bonds. More preferably, it contains a chemical structure in which the biodegradable sites are linked by the imine sites. The biodegradable site is composed of a biodegradable low molecular compound, oligomer or polymer, and the imine site is composed of a low molecular compound, oligomer or polymer having one or more imine bonds in the molecule.

<Biodegradable site>
The biodegradable moiety may have any chemical structure as long as it does not inhibit the object of the present invention and is derived from a molecule having biodegradability, and any of low molecular compounds, oligomers or polymers. But you can. Examples of molecules constituting such biodegradable sites include low molecular weight compounds, polyesters, oligoesters, polyamides, oligoamides, poly (amide-esters), oligo (amide-esters), poly Peptides, oligopeptides, polyethers or oligoethers can be mentioned. These may be used alone or in combination of two or more as the biodegradable portion of the biodegradable polymer used in the present invention.

The low molecular weight compound constituting the biodegradable site is a compound having 1 to 100 carbon atoms, preferably 2 to 50 carbon atoms, and having two or more functional groups such as a hydroxyl group, an amino group or a carboxyl group in the molecule. For example, divalent aliphatic alcohols, dibasic acids, hydroxycarboxylic acids, divalent aliphatic amines, and amino acids. As a low molecular weight compound constituting such a biodegradable site, for example,
Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentane Divalent aliphatic alcohols such as diol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol and 1,4-cyclohexanediol;
Dibasic acids such as succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and terephthalic acid;
Hydroxycarboxylic acids such as glycolic acid, lactic acid, 2-hydroxybutyric acid, 2-hydroxyvaleric acid, 2-hydroxycaproic acid, 2-hydroxycapric acid, malic acid and citric acid;
Ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 2,2 ′-(ethylenedioxy) bis (ethylamine), 3,3 ′ Divalent aliphatic amines such as iminobis (propylamine) and N-methyl-3,3′-iminobis (propylamine);
Examples thereof include amino acids such as valine, leucine, isoleucine, methionine, phenylalanine, aspartic acid, glutamic acid and lysine.

  Examples of the polyesters or oligoesters constituting the biodegradable site include polyesters or oligoesters having a chemical structure that can be produced by a dehydration reaction between a divalent aliphatic alcohol and a dibasic acid. It is done.

  Examples of the divalent aliphatic alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, oligoethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, oligopropylene glycol, polypropylene glycol, 1, 3 -Propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene Examples include glycol and 1,4-cyclohexanediol. Examples of the dibasic acids include succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and terephthalic acid. . These constituent monomers may be used alone or in combination of two or more.

The polyesters or oligoesters include polyesters or oligoesters having a chemical structure that can be produced by dehydration reaction of hydroxycarboxylic acids, and chemistry that can be produced by ring-opening polymerization reaction of lactones. Also included are polyesters or oligoesters having a structure.

  Examples of the hydroxycarboxylic acids include glycolic acid, lactic acid, 2-hydroxybutyric acid, 2-hydroxyvaleric acid, 2-hydroxycaproic acid, 2-hydroxycapric acid, malic acid, and citric acid. Examples of the lactone include benzyl malolactonate, malite benzyl ester, 3-[(benzyloxycarbonyl) methyl] -1,4-dioxane-2,5-dione, β-propiolactone, δ-valero Examples include lactone, ε-caprolactone, N-benzyloxycarbonyl-L-serine-β-lactone, β-butyrolactone, pivalolactone, β-benzylmalolactonate, γ-butyrolactone, and γ-valerolactone. These constituent monomers may be used alone or in combination of two or more.

  Furthermore, as the polyesters or oligoesters, polyesters having a chemical structure that can be produced by a dehydration reaction using one or more of the dibasic acids, the divalent aliphatic alcohols, and the hydroxycarboxylic acids. Or oligoesters.

  Examples of the polyamides or oligoamides constituting the biodegradable site include polyamides or oligoamides having a chemical structure that can be produced by a dehydration reaction between a divalent aliphatic amine and a dibasic acid.

  Examples of the divalent aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 2,2 ′-( Ethylenedioxy) bis (ethylamine), 3,3′-iminobis (propylamine), N-methyl-3,3′-iminobis (propylamine) and the like. Examples of the dibasic acids include succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and terephthalic acid. . These constituent monomers may be used alone or in combination of two or more.

  Examples of the polyamides or oligoamides include polyamides or oligoamides having a chemical structure in a form produced by a ring-opening polymerization reaction of lactams such as pyrrolidone or ε-caprolactam. These constituent monomers may be used alone or in combination of two or more.

The poly (amide-esters) or oligo (amide-esters) constituting the biodegradable site are obtained by dehydration reaction of dibasic acids, divalent aliphatic amines and divalent aliphatic alcohols. Mention may be made of poly (amide-esters) or oligo (amide-esters) having the form of chemical structure produced.

Examples of the dibasic acids include succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and terephthalic acid. . Examples of the divalent aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 2,2 ′-( Ethylenedioxy) bis (ethylamine), 3,3′-iminobis (propylamine), N-methyl-3,3′-iminobis (propylamine) and the like. Examples of the divalent aliphatic alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, oligoethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, oligopropylene glycol, polypropylene glycol, 1, 3 -Propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene Examples include glycol or 1,4-cyclohexanediol. These constituent monomers may be used alone or in combination of two or more.

  The poly (amide-ester) or oligo (amide-ester) is a poly (amide-ester) having a chemical structure that can be produced by a ring-opening polymerization reaction between a lactam and a lactone. Also included are oligo (amide-esters).

  Examples of the lactams include pyrrolidone and ε-caprolactam. Examples of the lactone include benzyl malolactonate, malite benzyl ester, 3-[(benzyloxycarbonyl) methyl] -1,4-dioxane-2,5-dione, β-propiolactone, δ-valero Examples include lactone, ε-caprolactone, N-benzyloxycarbonyl-L-serine-β-lactone, β-butyrolactone, pivalolactone, β-benzylmalolactonate, γ-butyrolactone, and γ-valerolactone. These constituent monomers may be used alone or in combination of two or more.

  Furthermore, the poly (amide-ester) s or oligo (amide-esters) mentioned above are poly (amides) having a chemical structure produced by ring-opening polymerization reaction of depsipeptides such as morpholine-2,5-dione. -Esters) or oligo (amide-esters). These constituent monomers may be used alone or in combination of two or more.

  Examples of the polypeptides or oligopeptides constituting the biodegradable site are produced by dehydration reaction of amino acids such as alanine, valine, leucine, isoleucine, methionine, phenylalanine, glycine, aspartic acid, glutamic acid and lysine. These constituent monomers such as polypeptides or oligopeptides having a chemical structure of the following form may be used singly or in combination of two or more.

  Examples of the polyethers or oligoethers constituting the biodegradable site include polyethers such as polyethylene glycol and polypropylene glycol, or oligoethers such as oligoethylene glycol and oligopropylene glycol.

The biodegradable portion is preferably polyesters, oligoesters, poly (amide-esters), oligo (amide-esters) from the viewpoint of improving the biodegradability and mechanical properties such as molded articles. Or polyethers, more preferably polyesters, oligoesters, poly (amide-esters) or oligo (amide-esters), and still more preferably polyesters or oligoesters. Particularly preferably, polyesters or oligoesters composed of one or more divalent alcohols having 1 to 48 carbon atoms and one or more dibasic acids having 2 to 10 carbon atoms, or one or more carbons Polyesters or oligoesters composed of hydroxycarboxylic acids of several 2 to 10 are used.

  The molecular weight of the biodegradable site is preferably in the range of 100 to 100,000, more preferably 400 to 30,000, and even more preferably 1000 to 10,000 in order to improve water disintegration and biodegradability.

<Imine site>
The imine moiety constituting the biodegradable polymer used in the present invention may have any chemical structure as long as it does not inhibit the object of the present invention and has one or more imine bonds. Any of a compound, an oligomer or a polymer may be used. The structure of such an imine moiety is not particularly limited, and examples thereof include organic groups represented by the following general formula (1) or general formula (1 ′). These may be used alone or in combination of two or more as the imine moiety of the biodegradable polymer used in the present invention.

In the above formulas (1) and (1 ′), R _{1 to} R ₈ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and Y _{1 to} Y ₆ each independently represent —CR═N— or -N = CR-, R represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and k represents an integer of 0 to 1000. Of the above formula (1) or (1 ′), formula (1) is preferred.

R _{1 to} R ₈ in the above formulas (1) and (1 ′) represent a group constituting an imine moiety, and a group having any chemical structure may be used as long as the object of the present invention is not impaired. . The hydrocarbon group having 1 to 20 carbon atoms represented by R _{1 to} R ₈ includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and more specifically, the same or different types. An aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms having one or more ester bonds, and an aliphatic group having 1 to 20 carbon atoms having one or more ether bonds A hydrocarbon group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms having one or more amide bonds, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or Examples thereof include an aliphatic hydrocarbon group having 7 to 20 carbon atoms having an aromatic hydrocarbon group. Furthermore, these organic groups may have any substituent as long as the object of the present invention is not impaired.

  Among these, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms having one or more ester bonds, and 1 to 20 carbon atoms having one or more ether bonds. Are preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, one or more An aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms having an ether bond are more preferable.

Y ₁ to Y ₆ in the above formulas (1) and (1 ′) each independently represent —CR═N— or —N═CR—, which may be the same or different. In the above formula (1), Y ₁ and Y ₂ are simultaneously -N = CR- or -CR = N-, Y ₁ is -CR = N- and Y ₂ is -N = CR-, Alternatively, it is preferred that Y ₁ is -N = CR- and Y ₂ is -CR = a N-. In the above formula (1 ′), Y ₃ and Y ₅ are simultaneously —N═CR— and Y ₄ and Y ₆ are simultaneously —CR═N—, or Y ₃ and Y ₅ are simultaneously —CR═N—. And Y ₄
And Y ₆ are preferably -N = CR- at the same time.

R in Y _{1 to} Y ₆ may be the same or different, and represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. From the viewpoint of the water-disintegrating property of the biodegradable polymer, it is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Particularly preferred are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.

K in the above formulas (1) and (1 ′) represents an integer of 0 to 1000, preferably in the range of 0 to 100, more preferably in the range of 0 to 50, and still more preferably in the range of 0 to 20.
The molecular weight of the imine moiety is not particularly limited, but is preferably 50,000 or less, more preferably 10,000 or less, and even more preferably 2000 or less in order to exhibit excellent water disintegration and biodegradability.

<Connection site>
The connecting part for connecting the biodegradable part and the imine part may have any chemical structure as long as the object of the present invention is not inhibited. Examples of the chemical bond that enables such a connection include an ester bond, an amide bond, a urethane bond, a urea bond, a carbonate bond, and a bond represented by the following general formula (2) (hereinafter referred to as “bond (2)”). For example).

In the formula (2), R ′ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and X ₁ and X ₂ each independently represent an ester bond, an amide bond, a urethane bond, a urea bond, or a carbonate bond. .

  The divalent hydrocarbon group having 1 to 20 carbon atoms represented by R ′ includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. More specifically, the carbon number is 1 2 to 20 divalent aliphatic hydrocarbon groups, 1 to 20 carbon divalent aliphatic hydrocarbon groups having one or more ether bonds, and 1 to 2 carbon atoms having 1 or more ester bonds A monovalent aliphatic hydrocarbon group, a C1-C20 divalent aliphatic hydrocarbon group having one or more amide bonds, a C3-C20 divalent alicyclic hydrocarbon group, a carbon number of 6 -20 divalent aromatic hydrocarbon group or a C7-20 divalent aliphatic hydrocarbon group having an aromatic hydrocarbon group.

  Among these, from the viewpoint of improving biodegradability and water disintegration, preferably a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms and 1 to 20 carbon atoms having one or more ether bonds. A divalent aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms having one or more ester bonds, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and more Preferably, it is a C1-C20 divalent aliphatic hydrocarbon group, a C1-C20 divalent aliphatic hydrocarbon group having one or more ether bonds, or a carbon number having one or more ester bonds. A divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms having one or more ether bonds. It is an aliphatic hydrocarbon group.

X ₁ and X ₂ represent an ester bond, an amide bond, a urethane bond, a urea bond, or a carbonate bond, and may be the same or different. Among these, from the viewpoint of improving biodegradability and water disintegration, preferably an ester bond, a urethane bond, a urea bond, or a carbonate bond, more preferably an ester bond, a urethane bond, or a carbonate bond, More preferably, they are an ester bond or a urethane bond.

  The chemical bond used as the linking site may be used singly or in combination of two or more in order to link the biodegradable site and the imine site. From the viewpoint of improving biodegradability and water disintegration, the chemical bond used as the linking site is preferably an ester bond, a urethane bond, a carbonate bond or a bond (2), more preferably an ester bond or a urethane. It is a bond or bond (2), more preferably an ester bond or bond (2).

  As described above, the biodegradable polymer used in the present invention has a chemical structure in which a biodegradable moiety and an imine moiety are linked, and the ratio of the biodegradable moiety and the imine moiety is preferably It is in the range of 1: 9 to 9: 1, more preferably in the range of 1: 7 to 7: 1, still more preferably in the range of 1: 5 to 5: 1, particularly preferably in the range of 1: 3 to 3. : 1 range.

  The preferred biodegradable polymer used in the present invention is such that the biodegradable site is a polyester, oligoester, poly (amide-ester), oligo (amide-ester) or polyether, and the imine site is the above formula. The chemical bond that is an imine moiety represented by (1) and connects the biodegradable moiety and the imine moiety is an ester bond, an amide bond, a urethane bond, a urea bond, a carbonate bond, or a bond (2).

  A more preferred biodegradable polymer used in the present invention is that the biodegradable site is polyesters, oligoesters, poly (amide-esters) or oligo (amide-esters), and the imine site is represented by the formula (1). The chemical bond that links the biodegradable site and the imine site is an ester bond, an amide bond, a urethane bond, a urea bond, a carbonate bond, or a bond (2).

Particularly preferred biodegradable polymers used in the present invention are those in which the biodegradable site is polyesters, oligoesters, poly (amide-esters) or oligo (amide-esters), and the imine site is represented by the formula (1). R _{1 to} R ₃ are a C 1-20 aliphatic hydrocarbon group, a C 1-20 aliphatic hydrocarbon group having one or more ester bonds, and a carbon having one or more ether bonds. An aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and Y ₁ and Y ₂ are each independently —N═ A chemical bond that is an imine moiety in which CR- or -CR = N- and links the biodegradable moiety and the imine moiety is an ester bond, an amide bond, a urethane bond, a carbonate bond, or a bond (2).

In the most preferred biodegradable polymer used in the present invention, the biodegradable moiety is a polyester, oligoester, poly (amide-ester) or oligo (amide-ester), and the imine moiety is represented by the above formula (1). R _{1 to} R ₃ are a C 1-20 aliphatic hydrocarbon group, a C 1-20 aliphatic hydrocarbon group having one or more ester bonds, and a carbon having one or more ether bonds. An aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, Y ₁ and Y ₂ are each independently —N═CR— or —CR═N—, and R is It is an imine moiety that is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and a chemical bond that links the biodegradable moiety and the imine moiety is an ester bond, a urethane bond, a carbonate bond, or a bond (2). is there.

  The molecular weight of the biodegradable polymer used in the present invention is not particularly limited, but is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 20,000 to 500,000 considering the strength as a molded article.

  Although the glass transition temperature (Tg) of the biodegradable polymer used for this invention is not specifically limited, -120-80 degreeC, Preferably it is -80-70 degreeC, More preferably, it is the range of -50-60 degreeC. When the Tg of the biodegradable polymer is in the above range, the biodegradable polymer exhibits excellent biodegradability and water disintegration.

[Method for producing biodegradable polymer]
Next, the manufacturing method of the biodegradable polymer used for this invention is demonstrated in detail below. The biodegradable site and the imine site described here are the same as the biodegradable site and the imine site defined in the biodegradable polymer used in the present invention.

  The method for producing the biodegradable polymer used in the present invention differs depending on the type of chemical bond connecting the biodegradable site and the imine site, and is not uniform. In order to link the biodegradable site and the imine site, the compound containing each site needs to have two or more specific functional groups that enable the connection between the two, and two are preferable. Further, such a functional group is preferably located at both ends of the molecular chain of the molecule constituting the biodegradable site and the imine site. The functional group is determined depending on the chemical bond between the two sites.

  The chemical bond for linking the biodegradable site and the imine site in the present invention may have any chemical structure as long as the object of the present invention is not inhibited. For example, ester bond, amide bond, urethane Examples thereof include a bond, a urea bond, a carbonate bond, and the above bond (2).

  In order to enable such chemical bonding, the functional group that a compound containing a biodegradable site and a compound containing an imine site must have include a carboxyl group, a hydroxyl group, and an amino group. There are various combinations of these functional groups.

<Specific examples of combinations of functional groups>
Specifically, the combination of the functional groups depending on the type of bond will be described. When producing a biodegradable polymer in which a biodegradable site and an imine site are linked by an ester bond, the functional groups used at both sites are two types, a carboxyl group and a hydroxyl group. And as a combination thereof, a combination of a compound containing a biodegradable moiety having two carboxyl groups and a compound containing an imine moiety having two hydroxyl groups, a compound containing a biodegradable moiety having two hydroxyl groups And a compound containing an imine moiety having two carboxyl groups, or a combination of a compound containing a biodegradable moiety each having one carboxyl group and one hydroxyl group and a compound containing an imine moiety . Furthermore, in the case of producing a biodegradable polymer in which X ₁ and X ₂ are linked by a bond (2) which is an ester bond, a compound represented by the following general formula (2′-1) is used as a compound that leads the bond. (Hereinafter also referred to as “compound (2′-1)”) is newly used. Therefore, a new combination occurs. The combinations are shown in Table 1.

In formula (2′-1), R ′ has the same meaning as R ′ in formula (2), and Z ₁ and Z ₂ each independently represent a carboxyl group or a hydroxyl group.

Next, a combination in the case of producing a biodegradable polymer linked by an amide bond or a bond (2) in which X ₁ and X ₂ are amide bonds will be described.
When producing a biodegradable polymer linked by an amide bond, a combination of a compound containing a biodegradable moiety having two carboxyl groups and a compound containing an imine moiety having two amino groups, A combination of a compound containing a biodegradable moiety having an amino group and a compound containing an imine moiety having two carboxyl groups, or a compound having a biodegradable moiety each having one carboxyl group and one amino group And a compound containing an imine moiety. Furthermore, when producing a biodegradable polymer in which X ₁ and X ₂ are linked by a bond (2) in which an amide bond is formed, a compound represented by the general formula (2′-2) (hereinafter referred to as a compound that leads to the bond) "Compound (2'-2)") is also used. The combinations are shown in Table 2.

In formula (2′-2), R ′ has the same meaning as R ′ in formula (2), and Z ₃ and Z ₄ each independently represent a carboxyl group or an amino group.

Next, a combination in the case of producing a biodegradable polymer linked by a urethane bond or a bond (2) in which X ₁ and X ₂ are urethane bonds will be described.
When producing a biodegradable polymer linked by a urethane bond, a combination of a compound containing a biodegradable moiety having two hydroxyl groups and a compound containing an imine moiety having two amino groups, two amino groups A combination of a compound having a biodegradable moiety having a group and a compound having an imine moiety having two hydroxyl groups, or a compound having a biodegradable moiety having one hydroxyl group and one amino group, respectively, and an imine moiety And a combination with a compound containing. Furthermore, when producing a biodegradable polymer in which X ₁ and X ₂ are linked by a bond (2) which is a urethane bond, a compound represented by the general formula (2′-3) (hereinafter referred to as a compound that induces the bond) "Compound (2'-3)") is also used. The combinations are shown in Table 3.

In formula (2′-3), R ′ has the same meaning as R ′ in formula (2), and Z ₅ and Z ₆ each independently represent a hydroxyl group or an amino group.

Next, a combination in the case of producing a biodegradable polymer linked by a urea bond or a bond (2) in which X ₁ and X ₂ are urea bonds will be described.
When producing a biodegradable polymer linked by a urea bond, a combination of a compound containing a biodegradable moiety having two amino groups and a compound containing an imine moiety having two amino groups can be mentioned. Furthermore, in the case of producing a biodegradable polymer in which X ₁ and X ₂ are linked by a bond (2) in which a urea bond is present, a compound represented by the general formula (2′-4) (hereinafter referred to as a compound that induces the bond) "Compound (2'-4)") is also used. The combinations are shown in Table 4.

In formula (2′-4), R ′ has the same meaning as R ′ in formula (2), and Z ₇ and Z ₈ represent an amino group.

Next, a combination in the case of producing a biodegradable polymer linked by a carbonate bond or a bond (2) in which X ₁ and X ₂ are carbonate bonds will be described.
In the case of producing a biodegradable polymer linked by a carbonate bond, a combination of a compound containing a biodegradable moiety having two hydroxyl groups and a compound containing an imine moiety having two hydroxyl groups can be mentioned. Furthermore, when producing a biodegradable polymer in which X ₁ and X ₂ are linked by a bond (2) in which a carbonate bond is formed, a compound represented by the general formula (2′-5) (hereinafter referred to as a compound that leads to the bond) "Compound (2'-5)") is also used. The combinations are shown in Table 5.

In the formula (2′-5), R ′ has the same meaning as R ′ in the formula (2), and Z ₉ and Z ₁₀ each represent a hydroxyl group.

  As described above, it has been described that the functional group to be possessed by a compound containing a biodegradable site and a compound containing an imine site are different depending on the type of bond to be linked, and the combination thereof is also different. Here, it is as follows when the compound containing the biodegradable site | part used when manufacturing the biodegradable polymer used for this invention and the compound containing an imine site | part are put together.

First, a compound containing a biodegradable site and a production method thereof will be described.
Examples of the compound containing a biodegradable site having two functional groups include a compound containing a biodegradable site having two carboxyl groups, a compound containing a biodegradable site having two hydroxyl groups, A compound containing a biodegradable moiety having a carboxyl group and one hydroxyl group, a compound containing a biodegradable moiety having two amino groups, a biodegradable moiety having one carboxyl group and one amino group And a compound containing a biodegradable moiety having one hydroxyl group and one amino group.

As a method for producing a compound containing a biodegradable moiety having two functional groups, for example, in the case of a compound containing a biodegradable moiety having two carboxyl groups, the molar ratio of carboxyl group / hydroxyl group is 1. A method of producing by dehydration reaction from a dibasic acid and a divalent aliphatic alcohol under larger conditions, or a dibasic acid and a divalent aliphatic amine under a condition where the molar ratio of carboxyl group / amino group is greater than 1. And a method of producing it by dehydration reaction. In the case of a compound containing a biodegradable moiety having two hydroxyl groups, the compound is produced by a dehydration reaction from a dibasic acid and a divalent aliphatic alcohol under the condition that the molar ratio of carboxyl group / hydroxyl group is smaller than 1. The method etc. are mentioned. Further, in the case of a compound containing a biodegradable site having one carboxyl group and one hydroxyl group, a method of producing by a dehydration reaction of hydroxycarboxylic acids can be mentioned. In the case of a compound containing a biodegradable moiety having two amino groups, a dehydration reaction can be carried out from dibasic acids and divalent aliphatic amines under the condition that the molar ratio of carboxyl group / amino group is less than 1. The manufacturing method etc. are mentioned. Furthermore, in the case of a compound containing a biodegradable site having one carboxyl group and one amino group, a method of producing it from amino acids by a dehydration reaction may be mentioned. In the case of a compound containing a biodegradable site having one hydroxyl group and one amino group, dibasic acids, 2 and 2 under the condition that the molar ratio of carboxyl group / (sum of hydroxyl group and amino group) is less than 1. And a method of producing it from a divalent aliphatic alcohol and a divalent aliphatic amine by a dehydration reaction.

  Next, the compound containing an imine moiety having the two functional groups is represented by the following general formula (3) or (3 ').

R _{1 to} R ₈ , Y _{1 to} Y ₆ and k in the above formulas (3) and (3 ′) are the same as those of the imine moiety defined in the biodegradable polymer used in the present invention, and X ₃ and X ₄ represents a carboxyl group, a hydroxyl group or an amino group, and may be the same or different.

Such a compound containing an imine moiety having two functional groups can be produced by a known method. In the case of a compound containing an imine moiety having two functional groups in which R of Y _{1 to} Y ₆ is hydrogen, for example, two functional groups are obtained by dehydration reaction between an aldehyde compound having a desired functional group and an amine compound. A compound containing an imine moiety having a group is obtained. In the case of a compound containing an imine moiety having two functional groups in which R in Y _{1 to} Y ₆ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, for example, a ketone compound and an amine each having a desired functional group A compound containing an imine moiety having two functional groups is obtained by reaction with the compound.
<Specific Embodiment of Method for Producing Biodegradable Polymer>
A biodegradable polymer used in the present invention can be produced by linking a compound containing a biodegradable moiety having two functional groups and a compound containing an imine moiety having two functional groups. . The production method differs depending on the type of chemical bond for linking the two, and is roughly divided into a method using a condensing agent and a method using a linking agent. The former is a case where the chemical bond to be linked is an ester bond, an amide bond, or a bond (2) in which X ₁ and / or X ₂ is an ester bond or an amide bond, and the latter is a urethane bond, urea bond, carbonate bond or X _1. And / or the bond (2) in which X ₂ is a urethane bond, a urea bond or a carbonate bond.

  In the production of a biodegradable polymer, after carrying out a production method using a condensing agent, a production method using a linking agent may be carried out, or after carrying out a production method using a linking agent, a production method using a condensing agent May be implemented.

First, the manufacturing method using a condensing agent is demonstrated. By reacting a compound containing a biodegradable moiety having two functional groups with a compound containing an imine moiety having two functional groups and a condensing agent, an ester bond, an amide bond or X ₁ and / or A biodegradable polymer linked by a bond (2) in which X ₂ is an ester bond or an amide bond can be produced.

Here, as a combination of constituent parts in this production method, when the connecting part is an ester bond, a combination of constituent parts exemplified for the biodegradable polymer connected by the ester bond is used. Moreover, when a connection site | part is an amide bond, the combination etc. of the structural site illustrated with the biodegradable polymer connected with the said amide bond are used. Next, when the linking site is a bond (2) in which X ₁ and X ₂ are ester bonds, combinations of constituent sites exemplified in Table 1 are used. When the linking site is a bond (2) in which X ₁ and X ₂ are amide bonds, combinations of constituent sites exemplified in Table 2 are used. Furthermore, two or more of these combinations may be used in combination, and the combinations exemplified in the case of an ester bond, the combinations exemplified in the case of an amide bond, and X ₁ and X ₂ are ester bonds or amide bonds. Two or more combinations exemplified in the bond (2) may be used together.

  Examples of the condensing agent used in this production method include 2-chloro-1-methylpyridinium iodide, 2-bromo-1-methylpyridinium iodide, 2-chloro-1-ethylpyridinium tetrafluoroborate, 2- Examples include bromo-1-ethylpyridinium tetrafluoroborate. Preferred are 2-chloro-1-methylpyridinium iodide, 2-chloro-1-ethylpyridinium tetrafluoroborate, and 2-bromo-1-ethylpyridinium tetrafluoroborate. More preferred are 2-chloro-1-methylpyridinium iodide and 2-bromo-1-ethylpyridinium tetrafluoroborate.

  The condensing agent may be used alone or in combination of two or more. The amount of the condensing agent used is usually 1. with respect to the total number of moles of carboxyl groups contained in the compound containing a biodegradable site and the compound containing an imine site, which are constituent materials of the biodegradable polymer. The range is 0 to 3.0 times mol, preferably 1.1 to 2.5 times mol, more preferably 1.2 to 2.0 times mol.

When a biodegradable polymer is produced by this method, hydrogen halide is by-produced, and thus a base is usually used to neutralize the hydrogen halide. Examples of the base include triethylamine, tripropylamine, triisopropylamine, tributylamine, tripentylamine, trioctylamine, triisooctylamine, N, N′-diisopropylethylamine, N, N-dimethyl-n-octylamine, N, N-dimethylisopropylamine, tris (2-ethylhexyl) amine, N, N-dimethylethylamine, N, N-diethylmethylamine, N, N-dicyclohexylmethylamine, N, N-dimethylcyclohexylamine, tribenzylamine , Triphenylamine, N-benzyldiethylamine, triethylenediamine, hexamethylenetetramine, N, N, N ′, N′-tetramethylethylenediamine, bis (2-dimethylaminoethyl) ether, pyridine, 4-di Chill aminopyridine, picoline, N, N- dimethylaniline, N, N- diethylaniline, N- ethyl -N- methyl aniline, 2,6 Ruichijin the like. Among these, triethylamine, tripropylamine, triisopropylamine, tributylamine, tripentylamine, trioctylamine, triisooctylamine, N, N′-diisopropylethylamine, N, N-dimethyl-n-octylamine, N, N-dimethylisopropylamine and tris (2-ethylhexyl) amine are preferable, and triethylamine, tripropylamine, triisopropylamine, and tributylamine are more preferable.

  The said base may be used individually by 1 type, or may use 2 or more types together. Moreover, the usage-amount of the said base is 1.0-6.0 times mole normally with respect to the usage mole number of a condensing agent, Preferably it is 2.2-5.0 times mole, More preferably, it is 2.4- The range is 4.0 moles.

  In this production method, the molar ratio of the compound containing the biodegradable moiety and the compound containing the imine moiety is usually in the range of 0.5 to 2.0, preferably in the range of 0.8 to 1.5. More preferably, it is the range of 0.9-1.1.

  In the production method using the condensing agent, it is preferable to use an organic solvent such as dichloromethane or chloroform. Although reaction temperature is based also on the boiling point of the organic solvent used, the range of 10-100 degreeC is preferable and the range of 20-50 degreeC is more preferable. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon in order to prevent deactivation of the condensing agent due to moisture.

  When the biodegradable polymer reaches the desired molecular weight, organic solvents such as methanol, ethanol, isopropyl alcohol, etc., in which the impurities are soluble and the polymer is insoluble, in order to remove impurities such as salts of hydrogen halide and base The biodegradable polymer is purified by reprecipitation and washing using After the purification, the organic solvent used during the purification is removed by drying under reduced pressure, drying by heating, or the like.

While there has been described a manufacturing method using a condensing agent, if X ₁ and X ₂ to produce a biodegradable polymer linked by bond (2) an ester bond or an amide bond, as other means, the following general It can also be produced using an acid chloride represented by the formula (4) (hereinafter simply referred to as “acid chloride”).

In formula (4), R ′ has the same meaning as R ′ in formula (2).
Specifically, a compound containing a biodegradable moiety having two hydroxyl groups, a combination of a compound containing an imine moiety having two hydroxyl groups and an acid chloride, or a biodegradable moiety having two amino groups Biodegradation in which X ₁ and X ₂ are linked by a bond (2) wherein each of X ₁ and X ₂ is an ester bond or an amide bond by using a combination of a compound containing, a compound containing an imine moiety having two amino groups, and an acid chloride A soluble polymer is obtained. The amount of acid chloride used in this production method is usually 0.25 to 4.0 times moles, preferably 0.3 to 3.0 times the total number of moles of hydroxyl groups contained in the constituent parts. More preferably, it is in the range of 0.4 to 1.0 times mole, more preferably 0.45 to 0.6 times mole.

  When producing a biodegradable polymer by the production method using the above acid chloride, the base exemplified in the production method using a condensing agent is usually used to neutralize the by-produced hydrogen halide. This base may be used individually by 1 type, or may use 2 or more types together. The amount of base used in this production method is usually 1.5 to 6.0 times mol, preferably 2.2 to 5.0 times mol, more preferably 2 with respect to the number of mols of acid chlorides used. The range is from 4 to 4.0 moles.

  In the production method using the acid chloride, the molar ratio of the compound containing the biodegradable moiety and the compound containing the imine moiety is usually in the range of 0.5 to 2.0, preferably 0.8 to 1. .5, more preferably 0.9 to 1.1.

  In the production method using the acid chloride, an organic solvent such as dichloromethane or chloroform is preferably used. Although it depends on the boiling point of the solvent used, the reaction temperature is preferably in the range of -30 to 100 ° C, more preferably in the range of -10 to 50 ° C. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon in order to prevent acid chloride from being deactivated by moisture.

  When the biodegradable polymer reaches the desired molecular weight, organic solvents such as methanol, ethanol, isopropyl alcohol, etc., in which the impurities are soluble and the polymer is insoluble, in order to remove impurities such as salts of hydrogen halide and base The biodegradable polymer is purified by reprecipitation and washing using After the purification, the organic solvent used in the purification is removed by drying under reduced pressure or drying by heating.

Next, the manufacturing method using a coupling agent is demonstrated. By reacting a compound containing a biodegradable moiety having two functional groups with a compound containing an imine moiety having two functional groups and a linking agent, a urethane bond, urea bond, carbonate bond or X ₁ In addition, a biodegradable polymer in which X ₂ is linked by a bond (2) in which X ₂ is a urethane bond, a urea bond, or a carbonate bond can be produced.

Here, as a combination of constituent parts in this production method, when the connecting part is a urethane bond, a combination of constituent parts exemplified for the biodegradable polymer connected by the urethane bond is used. Moreover, when a connection site | part is a urea bond, the combination etc. of the structure part illustrated with the biodegradable polymer connected with the said urea bond are used. Moreover, when a connection site | part is a carbonate bond, the combination of the structural part illustrated with the biodegradable polymer connected by the said carbonate bond, etc. are used. Further, when the linking site is a bond (2) in which X ₁ and X ₂ are urethane bonds, combinations of constituent parts exemplified in Table 3 are used. When the linking site is a bond (2) in which X ₁ and X ₂ are urea bonds, combinations of constituent sites exemplified in Table 4 are used. When the linking site is a bond (2) in which X ₁ and X ₂ are carbonate bonds, combinations of constituent parts exemplified in Table 5 are used. Further, two or more of these combinations may be used in combination, and combinations exemplified in the case of urethane bonds, combinations exemplified in the case of urea bonds, combinations exemplified in carbonate bonds, and X ₁ and / or X You may use together 2 or more types from the combination illustrated by the coupling | bonding (2) whose ₂ is a urethane bond, a urea bond, or a carbonate bond.

Examples of the linking agent used in this production method include phosgene, carbonates, or chloroformates. Examples of chloroformates include methyl chloroformate, ethyl chloroformate, propyl chloroformate, butyl chloroformate, phenyl chloroformate, and the like. Examples of carbonate esters include dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. , Diphenyl carbonate, dipropyl carbonate, dibutyl carbonate or dibenzyl carbonate. Among these, ethyl chloroformates or carbonates are preferable, carbonates are more preferable, and dimethyl carbonate or diethyl carbonate is more preferable.

  The amount of the above-mentioned linking agent is usually 0. 0 to the total number of moles of hydroxyl groups or amino groups contained in the compound containing a biodegradable site and the compound containing an imine site, which are constituent materials of the biodegradable polymer. It is 25-4.0 times mole, Preferably it is 0.3-3.0 times mole, More preferably, it is 0.4-1.0 times mole, More preferably, it is the range of 0.45-0.6 times mole.

  When carbonates are used as the linking agent, it is preferable to add a catalyst in order to promote the reaction between the compound containing the biodegradation site, the compound containing the imine site, and the linking agent. Catalysts include dibutyltin diacetate, dibutyltin dilaurate, sodium methoxide or titanyl (IV) acetylacetonate.

  The said catalyst may be used individually by 1 type, or may use 2 or more types together. The amount of the catalyst used is usually 10 to 1000 ppm, preferably 30 to 800 ppm, based on the total weight of the compound containing a biodegradation site having two functional groups, the compound containing an imine site, and the linking agent. More preferably, it is the range of 80-500 ppm.

  When phosgene and chloroformate are used as a linking agent, the base exemplified in the production method using a condensing agent is usually used to neutralize by-produced hydrogen halide. A base may be used individually by 1 type, or may use 2 or more types together. The amount of base used in this production method is usually 1.5 to 6.0 times mol, preferably 2.2 to 5.0 times mol, more preferably 2 with respect to the number of mols of acid chlorides used. The range is from 4 to 4.0 moles.

  In this production method, the molar ratio of the compound containing the biodegradable moiety and the compound containing the imine moiety is usually in the range of 0.5 to 2.0, preferably 0.8 to 1.5. More preferably, it is the range of 0.9-1.1.

  In the production method using the above-mentioned linking agent, when carbonates are used, they may be produced using an organic solvent such as methylene chloride, chloroform, tetrahydrofuran or dimethylformamide, if necessary. Alternatively, it may be produced under conditions where the raw material or product melts. Moreover, when using phosgene or chloroformate, it is preferable to use said organic solvent.

  Although reaction temperature is based also on the boiling point of the organic solvent used as needed, when using carbonate ester as a coupling agent, the range of 50-300 degreeC is preferable, and the range of 60-220 degreeC is more preferable. Moreover, when using phosgene or chloroformate as a coupling agent, the range of -78-60 degreeC is preferable, and the range of -10-40 degreeC is more preferable.

  When the linking agent is a carbonate, the reaction is preferably carried out under a flow of an inert gas such as nitrogen or argon or under reduced pressure in order to remove the by-produced alcohol. Further, when the linking agent is phosgene or chloroformate, it is preferable to carry out in an inert gas atmosphere such as nitrogen or argon in order to prevent deactivation of the linking agent by water in the atmosphere.

Once the biodegradable polymer has reached the desired molecular weight, if an organic solvent is used during production, reprecipitate using an organic solvent such as methanol, ethanol, isopropyl alcohol, or hexane that does not dissolve the biodegradable polymer. The biodegradable polymer may be purified by washing, or the organic solvent used may be removed to dry the biodegradable polymer. On the other hand, when no organic solvent is used during production, it is preferable to discharge the biodegradable polymer in a molten state as it is, and after discharge, the biodegradable polymer is dissolved in an organic solvent such as methylene chloride, chloroform or dimethylformamide. However, the same purification as in the case of using an organic solvent at the time of production may be performed. After purification or discharge, the biodegradable polymer is dried under reduced pressure or heat.

As mentioned above, although the manufacturing method using a coupling agent was demonstrated, when manufacturing the biodegradable polymer connected with the coupling | bonding (2) whose X < ₁ > and X < ₂ > are urethane bonds or urea bonds, as the other means, the following general It can also be produced using a diisocyanate compound represented by the formula (5) (hereinafter also simply referred to as “diisocyanates”) as a linking agent.

In formula (5), R ′ has the same meaning as R ′ in formula (2).
Specifically, by using a combination of a compound containing a biodegradable moiety having two hydroxyl groups, a compound containing an imine moiety having two hydroxyl groups and a diisocyanate, X ₁ and X ₂ are urethane bonds. A biodegradable polymer linked by a bond (2) is obtained. Also, by using a combination of a compound containing a biodegradable moiety having two amino groups, a compound containing an imine moiety having two amino groups, and a diisocyanate, X ₁ and X ₂ are urea bonds A biodegradable polymer linked by the bond (2) is obtained. Two or more of the combinations exemplified for the bond (2) in which X ₁ and / or X ₂ are a urethane bond or a urea bond may be used together.

  The amount of the diisocyanates used is generally 0. 0 relative to the total number of moles of hydroxyl groups or amino groups contained in the compound containing a biodegradable site and the compound containing an imine site, which are constituent materials of the biodegradable polymer. It is 25-4.0 times mole, Preferably it is 0.3-3.0 times mole, More preferably, it is 0.4-1.0 times mole, More preferably, it is the range of 0.45-0.6 times mole.

When the linking site is a bond (2) in which X ₁ and X ₂ are urethane bonds, in order to promote the reaction between the compound containing the biodegradation site, the compound containing the imine site, and the linking agent It is preferable to add a catalyst.

  Examples of the catalyst include stannous octate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin dilaurate, sodium o-phenylphenate, tetra (2-ethylhexyl) titanate, stannic chloride, and chloride. Examples thereof include ferric iron, ferric octate iron, cobalt octate, zinc naphthenate, triethylamine, and triethylenediamine. Preferred are dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, sodium o-phenylphenate, tetra (2-ethylhexyl) titanate, stannic chloride or ferric chloride.

  The said catalyst may be used individually by 1 type, or may use 2 or more types together. The amount of the catalyst used is usually 10 to 1000 ppm, preferably 30 to 800 ppm, based on the total weight of the compound containing a biodegradation site having two functional groups, the compound containing an imine site and diisocyanates. More preferably, it is the range of 80-500 ppm.

  In this production method, the molar ratio of the compound containing the biodegradable moiety and the compound containing the imine moiety is usually in the range of 0.5 to 2.0, preferably 0.8 to 1.5. More preferably, it is the range of 0.9-1.1.

  In the production method using the above linking agent, it may be produced using an organic solvent such as methylene chloride, chloroform, tetrahydrofuran or dimethylformamide, if necessary, and the raw material or product is melted without using a solvent. You may manufacture on condition.

  The reaction temperature depends on the boiling point of the organic solvent used as necessary and the melting point of the compound containing a biodegradable site and / or the compound containing an imine site, but is preferably in the range of 10 to 200 ° C. The range of is more preferable. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon in order to prevent the reaction between water in the atmosphere and the isocyanate group of the linking agent.

  The reaction order of the compound containing the biodegradable site, the compound containing the imine site, and the diisocyanate may be the same as the compound containing the biodegradable site, the compound containing the imine site, and the diisocyanate. Alternatively, after reacting either one of the compound containing a biodegradable site or the compound containing an imine site with the diisocyanate first, the compound containing the other site may be reacted. Also, after reacting either a compound containing a biodegradable site or a compound containing an imine site with a large excess of diisocyanate in advance and removing the unreacted binder with a high vacuum thin film evaporator, etc. A compound containing one site may be reacted.

  Once the biodegradable polymer has reached the desired molecular weight, if an organic solvent is used during production, reprecipitate using an organic solvent such as methanol, ethanol, isopropyl alcohol, or hexane that does not dissolve the biodegradable polymer. The biodegradable polymer may be purified by washing, or the organic solvent used may be removed to dry the biodegradable polymer. On the other hand, when no organic solvent is used during production, it is preferable to discharge the biodegradable polymer in a molten state as it is, and after discharge, the biodegradable polymer is dissolved in an organic solvent such as methylene chloride, chloroform or dimethylformamide. However, the same purification as in the case of using an organic solvent at the time of production may be performed. After purification or discharge, the biodegradable polymer is dried under reduced pressure or heat. In the production method using diisocyanates, a biodegradable polymer may be produced using an extruder such as a single-screw or twin-screw extruder or a kneader such as a kneader. Further, by adding diisocyanates after completion of the reaction or after purification, the unreacted hydroxyl group or amino group may react with the isocyanate group to increase the molecular weight of the biodegradable polymer.

[Biodegradable composition containing biodegradable polymer]
The biodegradable composition of the present invention contains the biodegradable polymer, and may contain a normal biodegradable polymer such as polyethylene glycol, vinyl alcohol, polylactic acid, and polybutylene succinate as other components. The biodegradable composition of the present invention may further contain various additives depending on the purpose. Examples of additives include plasticizers, fillers, antioxidants, ultraviolet absorbers, heat stabilizers, flame retardants, mold release agents, inorganic additives, crystal nucleating agents, antistatic agents, pigments, antiblocking agents, etc. Is mentioned.

As the plasticizer, those having biodegradability and excellent compatibility with the biodegradable polymer used in the present invention are preferably used. For example, a monovalent or polyvalent fatty acid ester plasticizer, a monovalent or polyvalent aliphatic alcohol ester plasticizer, a polyalkylene glycol plasticizer, an aliphatic polyester plasticizer, and the like can be given. Specifically, phthalic acid derivatives such as di-n-octyl phthalate, di-2-ethylhexyl phthalate and dibenzyl phthalate, isophthalic acid derivatives such as diisooctyl phthalate, adipine such as di-n-butyl adipate and dioctyl adipate Acid derivatives, maleic acid derivatives such as di-n-butyl malate, citric acid derivatives such as tri-n-butyl citrate, itaconic acid derivatives such as monobutyl itaconate, oleic acid derivatives such as butyl oleate, glycerin monoricinolate, etc. Illustrative of ricinoleic acid derivatives, phosphate esters such as tricresyl phosphate, trixylenyl phosphate, triethyl acetyl citrate, tributyl acetyl citrate, lactic acid, linear lactic acid oligomer, cyclic lactic acid oligomer and lactide . In particular, at least one selected from citric acid ester, glycerin ester, phthalic acid ester, adipic acid ester, sebacic acid ester, azelaic acid ester and triethylene glycol ester having two or more carboxylic acid ester groups in the molecule The ester compound is preferably. These plasticizers may be used alone or in combination of two or more.

  The biodegradable composition of the present invention can contain an inorganic additive. By containing a specific inorganic additive, the water degradability of the biodegradable polymer used in the present invention can be increased. it can. Such inorganic additives are not particularly limited, but inorganic oxides and zeolites are preferable, and inorganic oxides are more preferable.

  Examples of the inorganic oxides include silica, alumina, titanium oxide, silicate clay, diatomaceous earth, and acid clay. Examples of zeolites include Philipsite, mordenite, clinoptilolite, harmotome, merlinite, shabasite, and erio. Night, natrolite, heurlandite, faujasite and so on.

  The said inorganic additive may be used individually by 1 type, and may use 2 or more types together. The blending condition of the biodegradable composition containing the biodegradable polymer and the inorganic additive used in the present invention is usually 0.01 to 50 parts by weight of the inorganic additive with respect to 100 parts by weight of the biodegradable polymer. Preferably, the inorganic additive is in the range of 0.1 to 40 parts by weight, more preferably the inorganic additive is in the range of 0.5 to 30 parts by weight, and more preferably 1 to 20 parts by weight. Range.

  The average particle size of the inorganic additive is preferably 30 μm or less, more preferably 10 μm or less, and particularly preferably in the range of 0.7 to 5 μm. If the particle size is too large, the fineness of the pores of the film will deteriorate, and if it is too small, the dispersibility in the resin will deteriorate. Moreover, you may add these inorganic additives in order to improve the air permeability, for example, when a molded object is a film.

  In order to add various additives such as a plasticizer, an inorganic filler, a dispersant, and a stabilizer as the biodegradable composition of the present invention, for example, a Henschel mixer, a super mixer, a tumbler mixer, and the like are mixed. Then, it can carry out by carrying out continuous kneading using a single screw or twin screw type extruder. Here, in order to further improve the dispersibility of the biodegradable polymer and filler, a twin screw extruder is preferred.

  The biodegradable composition of the present invention may be used as a hot-melt adhesive, an aqueous paper coating composition, an easily peelable adhesive, a thermal transfer medium, and a molded body. Even when the biodegradable composition of the present invention diffuses into nature, the biodegradable composition is preferable because of its water disintegrating property and biodegradability, and has a low environmental impact.

  The hot melt adhesive using the biodegradable composition of the present invention can be used in various applications such as sanitary materials, packaging, heat insulating materials, and woodworking. In addition, the product using the hot melt adhesive of the present invention has water disintegration and biodegradability, so after use as a product, the adhesive part is dissociated by washing with water. can do.

  The aqueous paper coating composition using the biodegradable composition of the present invention can be applied to a substrate such as paper, metal, plastic, etc., thereby improving printability and protecting the base. Further, when the base of paper or the like coated with the aqueous paper coating composition of the present invention is collected and reused, the aqueous paper coating composition can be removed by washing with water or warm water. Therefore, it is possible to easily collect the base such as paper.

  The easily peelable pressure-sensitive adhesive material using the biodegradable composition of the present invention preferably contains a peelability adjusting agent in addition to the above-described biodegradable polymer. As the peelability adjusting agent, components having an action as a slip agent, an antistatic agent and a water repellent agent can be used. The easily peelable pressure-sensitive adhesive material of the present invention can be applied and used, for example, on a sanitary material protective sheet, and can be easily peeled because it contains a peelability adjusting agent at the time of peeling. In addition, when a complicated shape is protected, the easily peelable adhesive material may remain on a member intended to protect hygiene materials or the like, but the easily peelable adhesive material of the present invention can be easily removed by washing. This is preferable because the protective surface is not damaged.

  The thermal transfer medium using the biodegradable composition of the present invention contains a dye and / or pigment in addition to the biodegradable polymer as the biodegradable composition, and preferably further contains a plasticizer. Since the thermal transfer medium of the present invention has water disintegration property, the transferred image can be easily deleted after being transferred to a film or the like.

[Biodegradable molded product]
The biodegradable molded article of the present invention is composed of a biodegradable composition containing the above-described biodegradable polymer, and does not disintegrate with a small amount of water and exhibits disintegrability in a large amount of water.

  The biodegradable molded product of the present invention may be a fiber. The biodegradable fiber of the present invention having both water-disintegrating property and biodegradability may be used as a non-woven fabric or medical clothing obtained by further processing the fiber.

  As a method for obtaining the biodegradable fiber, a known spinning method may be applied, and single spinning or composite spinning may be used. Particularly, examples of the composite spinning include core-sheath type and parallel type composite spinning. As a specific spinning method, a melt spinning method in which the biodegradable composition is melt-spun using an extruder; the biodegradable composition is dissolved in a solvent to form a solution; Examples thereof include a wet spinning method in which the solution is discharged into a poor solvent; a dry spinning method in which the solution is discharged into a dry gas from a nozzle. In the melt spinning method, a known extruder such as a single screw extruder or a twin screw extruder can be used.

  The fiber of the present invention has a heat shrinkage rate at 130 ° C. of preferably 10% or less, more preferably 8% or less, and further preferably 5% or less. When the heat shrinkage rate is 10% or less, there is almost no shrinkage due to thermoforming, etc., and it is easy to produce a product. Excellent.

The biodegradable molded product of the present invention may be a nonwoven fabric.
There is no restriction | limiting in particular as a method of obtaining the nonwoven fabric of this invention, For example, it manufactures by a well-known method, for example, a dry method, a spun bond method, a melt blow method, a wet method. That is, it is obtained by spinning the biodegradable composition of the present invention, forming a web, and bonding the web by a conventionally known method.

A known spinning method is applied to the spinning method of the raw fiber. Single spinning or composite spinning may be used. Particularly, the form of composite spinning includes core-sheath type or parallel type composite spinning. Examples of the spinning method include a melt spinning method in which melt spinning is performed using an extruder, and a wet spinning method in which the biodegradable composition is dissolved in a solvent to form a solution, and then the solution is discharged from a nozzle into a poor solvent. , Dry spinning or the like in which the solution is discharged from a nozzle into a dry gas is applied. In the melt spinning method, a known extruder such as a single screw extruder or a twin screw extruder can be used.

  The diameter of the die (nozzle) of the extruder is appropriately determined according to the relationship between the required fiber diameter (yarn diameter) and the discharge speed and take-off speed of the extruder, but preferably 0.1 to 3.0 mm. Degree. In any spinning method, it is not always necessary to stretch the fiber after spinning, but when stretching is performed, the fiber is stretched 1.1 to 10 times, preferably 2 to 8 times. A preferable yarn diameter of the fiber is 0.5 to 40 denier. Moreover, the single fiber or the composite fiber constituting the nonwoven fabric of the present invention may be either a long fiber or a short fiber, and can be appropriately selected depending on the purpose of use.

  From the obtained fiber, a fiber lump called a web is formed. A known method can be used as a method for producing the web, and is not particularly limited. For example, a card type using a flat card machine, a roller card machine, a garnet machine, etc., and a melt blow type can be mentioned. Further, when the resin is spun, a spunbond type in which high-speed air is blown when fibers come out from the nozzle of the spinning machine and collected on a perforated conveyor perpendicular to the airflow to form a web may be used.

A known method can be used to obtain the nonwoven fabric of the present invention from the web thus obtained. For example, a needle punch method for entanglement with a needle, a stitch bond method for entanglement with a yarn, a thermal bond method for adhesion by heat, a chemical bond method using an adhesive, and a resin bond method may be mentioned. Nonwoven basis weight of the present invention is preferably 1 to 50 g / m ^2, more preferably from 5 to 20 g / m ^2.
Further, the biodegradable molded product of the present invention may be a draining bag, medical clothing, or sheet obtained by further processing the nonwoven fabric.

  The biodegradable molded product of the present invention may be a film. There is no restriction | limiting in particular as a method of obtaining the film which consists of a biodegradable composition of this invention, It shape | molds in a film form or a sheet form with a well-known shaping | molding method. Examples of the method include forming a film or a sheet by a T-die molding method, an inflation molding method, a calendar molding method, a hot press molding method, or the like. Further, these films and sheets may be stretched in at least one direction. The stretching method is not particularly limited, and examples thereof include a roll stretching method, a tenter method, and an inflation method.

  The method for obtaining a film having a shape suitable for the application from the biodegradable composition of the present invention is not particularly limited and can be produced by a known method. For example, a method of performing extrusion molding or injection molding on a mold, etc. Is mentioned.

The thickness of the film of the present invention is preferably thinly formed in order to enhance its water disintegration property and biodegradability, but can be freely adjusted so as to satisfy strength and flexibility. The preferred thickness of the film is 5 to 300 μm, and more preferably 10 to 100 μm. Further, the value of the tensile elastic modulus is not particularly limited, but is usually preferably 1200 MPa or less, and more preferably 600 MPa or less. The tensile strength is not particularly limited, but is preferably in the range of 10 to 100 MPa, more preferably in the range of 15 to 70 MPa, and still more preferably in the range of 20 to 50 MPa.
The biodegradable molded article of the present invention may be a packaging film, a packaging bag, a compost bag, a shopping bag, a garbage bag, and a shrink film obtained by further processing the film.

  It is particularly preferable to use as a garbage bag for garbage. The garbage bag of the present invention is preferable because it does not collapse with moisture enough to throw away the garbage into the garbage bag, and can be recycled as a resource for garbage together with the garbage after being collected.

  Currently, from the viewpoint of environmental protection, the recycling of raw garbage (for example, biogas, recycling as liquid fertilizer) is being considered, but usually each household collects raw garbage in a separate container from other garbage, It is transferred to a large container installed at a collection location used by several to several tens of households for collection and resource recovery. However, when moving to a large container, the odor of raw garbage becomes a problem. ing. When a garbage bag made using the film of the present invention is used, it has water disintegration property and biodegradability, so that it is possible to collect the garbage bag at the same time and to recycle it. For this reason, since it can collect | recover without feeling odor etc., the improvement of a collection rate is anticipated.

  The biodegradable molded article of the present invention may be a protective film. The protective film of the present invention is attached to or attached to the shield part of a helmet or the lens part of sports goggles used for skiing, etc., and is peeled off when water, mud, oil, etc. adheres and obstructs the field of view. It is used for the purpose of securing the field of view. Since the protective film of the present invention has water disintegration property and biodegradability, it is preferable because it disintegrates in water in soil even if it is scattered in the natural environment.

The biodegradable molded article of the present invention may be a porous film having air permeability. A porous film can be obtained by forming the biodegradable composition described above into a film using an extrusion method or the like, preferably using a T-die method, and then stretching. In order to obtain a porous film, a filler (inorganic filler and / or organic filler) is usually contained as a part of the biodegradable composition. Inorganic fillers include calcium carbonate, talc, clay, kaolin, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, calcium oxide, magnesium oxide, mica, etc. Is mentioned. Among these, calcium carbonate, magnesium oxide, barium sulfate, talc, and clay are preferable. Examples of the organic filler include cellulose powder such as wood powder and pulp powder. These fillers may be used alone or in combination of two or more.

  The average particle size of the filler is preferably 30 μm or less, more preferably 10 μm or less, and particularly preferably in the range of 0.7 to 5 μm. If the particle size is too large, the fineness of the pores of the film will deteriorate, and if it is too small, the dispersibility in the resin will deteriorate. In addition, after making a planar unstretched sheet, the film becomes porous and becomes air permeable by uniaxially stretching in the longitudinal direction or biaxially stretching in the longitudinal and lateral directions.

  The biodegradable molded product of the present invention may be an agricultural or horticultural material. Examples of agricultural and horticultural materials include multi-films, seedling pots, agricultural and horticultural tapes, fruit cultivation bags, piles, fumigation sheets, and greenhouse films. For example, when used as a seedling pot, it has sufficient strength at the stage of growing seedlings and distribution stage by adjusting its water disintegration and biodegradability, and it can be decomposed after being embedded in soil. It is possible to eliminate the trouble of removing the seedling pot after raising the seedling and before burying the soil.

  The biodegradable molded product of the present invention may be a pet waste disposal material. Examples of the pet filth treatment agent include non-woven fabrics, films and sheets used in pet filth collection bags and pet sheets. For example, when it is used as a pet waste collection bag, it is preferable that water that is contained in the waste does not collapse with water, and can be poured into the toilet as it is due to water disintegration and biodegradability after putting pet waste.

The biodegradable molded article of the present invention may be a sustained-release drug, specifically, a sustained-release drug, agricultural chemical, veterinary drug, or fertilizer. When the biodegradable molded product of the present invention is used as a sustained-release drug in medicines or veterinary drugs, it is generally gradually degraded by water in the body, and accordingly, a stable amount of a medicinal component is released for a long time. be able to. In addition, when the biodegradable molded article of the present invention is used for agricultural chemicals, fertilizers, etc., it is possible to release the drug at an arbitrary time by decomposing the water-disintegrating molded article at an arbitrary time with moisture in the ground. Is possible.

  The biodegradable molded article of the present invention may be a casing of an electric device. Specifically, it can be used as a housing of a personal computer or a home appliance. Since normal electric equipment is not used outdoors, there is no danger of water collapse due to a large amount of water, so that it can be used as a casing. Further, after use, it is water disintegrating and biodegradable, so that it is easy to process and is easy to separate from other materials (metal, semiconductor, etc.), which is preferable.

  The biodegradable molded product of the present invention may be a processing aid, specifically a core during resin molding. When the biodegradable molded article of the present invention is used as a core at the time of resin molding, the biodegradable molded article has water-disintegrating property. Since it can be removed, resin molded bodies having various shapes can be easily produced.

  The biodegradable molded article of the present invention may be a civil engineering and building material. As a civil engineering construction material, it can be suitably used as a vegetation net, a vegetation bag, a vegetation pot, a three-dimensional net, a civil engineering fiber, a pile, and a heat insulating material.

  When the biodegradable molded article of the present invention is used as a vegetation net, it can be used as a vegetation net by forming the biodegradable composition into a fiber and braiding it. The vegetation net may be used as a vegetation bag by knitting it into a bag shape. By using the vegetation net and / or vegetation bag of the present invention, the slope is protected by the vegetation net and / or the vegetation bag until the plant is sufficiently rooted during the protection of the slope and the greening work, and thereafter the vegetation is protected. Nets and / or vegetation bags collapse and biodegrade.

  When the biodegradable molded article of the present invention is used as a vegetation pot, it can be used as a normal flower pot while the seedlings grow, and water transplantability and biodegradability are utilized for transplantation. The vegetation pot can be buried in the soil. As a result, it is useful from the viewpoint of environmental conservation because it saves the trouble of collecting the vegetation pot and does not incinerate. In addition, the transplant yield rate can be improved without damaging the roots of seedlings and the like during transplantation. In this case, it is especially effective for reforestation of bushes and cedars in the mountains, and transplanting of seedlings that tend to damage the roots, and after the vegetation pot is buried in the soil, it biodegrades as soon as possible. Does not hinder root growth such as seedlings.

  The biodegradable molded article of the present invention may be a cleaning article. As a cleaning article, it can be suitably used as a wet wiper or a brush. Since the cleaning article of the present invention has water disintegration and biodegradability, it is preferable because it disintegrates in water in soil even if it is scattered in the natural environment.

  The biodegradable molded article of the present invention may be an acid absorbent. The acid absorbent is obtained by molding a biodegradable composition in which a salt showing alkalinity in water is mixed. By loading the acid absorbent into a drain pipe or the like, the acid can be absorbed and neutralized, so that it can be used for wastewater treatment. The biodegradable molded article of the present invention is preferable because it has a biodegradability even when it is diffused to the natural world and has a low environmental impact. As the salt exhibiting alkalinity in water, calcium carbonate, sodium carbonate, calcium acetate, sodium acetate and the like are preferable. These salts may be used alone or in combination of two or more. When the total biodegradable composition is 100 parts by weight, the ratio of the salt to be mixed is preferably 0.1 to 30 parts by weight, and more preferably 0.5 to 20 parts by weight. As a method for obtaining a biodegradable composition in which a salt exhibiting alkalinity in water is mixed, a known method such as a melt-kneading method can be used.

  The biodegradable molded article of the present invention may be an alkali absorbent. The alkaline absorbent is obtained by molding a biodegradable composition in which a salt that exhibits acidity in water is mixed. By loading the alkali absorbent into a drain pipe or the like, the alkali can be absorbed and neutralized, so that it can be used for wastewater treatment. The biodegradable molded article of the present invention is preferable because it has a biodegradability even when it is diffused to the natural world and has a low environmental impact. As the salt showing acidity in water, ammonium chloride, ammonium sulfate and the like are preferable. These salts may be used alone or in combination of two or more. When the total biodegradable composition is 100 parts by weight, the ratio of the salt to be mixed is preferably 0.1 to 30 parts by weight, and more preferably 0.5 to 20 parts by weight. As a method for obtaining a biodegradable composition in which a salt that exhibits acidity in water is mixed, a known method such as a melt-kneading method can be used.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these. In addition, the evaluation method in the following Example is as follows.

[1] Molecular Weight of Polymer The molecular weight of the polymer was determined by gel permeation chromatography (hereinafter referred to as “GPC”). Polystyrene was used as a standard substance.

[2] Tensile strength and tensile modulus of film Tensile strength at break and tensile modulus were measured by pulling a film test piece punched into a dumbbell mold at a tensile rate of 50 mm / min and measuring stress. Asked.

[3] Water-soluble test The film was immersed in distilled water at 35 ° C. for 24 hours, the taken-out film was dried, and the weight of the film was measured. A film having a weight retention of 98% or more after being immersed in distilled water at 35 ° C. for 24 hours was judged not to be water-soluble.

[4] Water disintegration test According to JIS P 4501 toilet paper ease test, the water disintegration property of distilled film (about pH 7) was tested. It was judged that an 11 cm square film or non-woven fabric became 4 cm square or less in 520 hours or less and showed water disintegration.

[5] Biodegradability test The biodegradability test of the film was performed according to ISO14855. A film having a biodegradability of 60% or more was judged to be biodegradable.

[6] Fineness Measured according to JIS L 1015.
[7] Fabric weight A test piece of 10 cm square is prepared from a sample in a standard state, and after making the equilibrium moisture, the weight of the test piece [
g] was weighed, and the obtained value was converted to a unit area [g / m ² ] per unit area.

[8] Strength of KGSM In accordance with the strip method of JIS L 1096, a test piece having a length of 10 cm and a width of 5 cm was prepared and stretched in the warp direction (MD) and the weft direction (CD), and the resulting load at break [kg / 5
cm] was converted to a unit weight per unit weight to make KGSM strong.

[Production of imine moiety-containing compound]
The production example of the compound containing an imine moiety constituting the biodegradable polymer is specifically shown below.

<Production Example 1>
To a 300 mL separable flask equipped with a Dean Stark with condenser, thermometer, glass stirring blade and dropping funnel was added 13.4 g of terephthalaldehyde (0.1 mol, Aldrich, purity 99.0%) and 120 mL of toluene. The mixture was stirred with a glass stirring blade and cooled to 3 to 5 ° C. with ice water. 12.2 g of 2-ethanolamine (0.2 mol, manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0%) was placed in the dropping funnel and dropped into the flask in 30 minutes. After dropping, the mixture was heated in an oil bath and heated to reflux until the by-product of water was completed. After cooling to room temperature, the precipitate was filtered off and washed on a filter with 120 mL of toluene. The obtained crystals were dried overnight at 50 ° C. under a nitrogen atmosphere, and N, N ′-(1,4-phenylenedimethylidene) bis (ethanolamine) (hereinafter referred to as “imine compound 1”) as a pale yellow solid. 21.2 g was obtained. From the proton nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) measured by dissolving the imine compound 1 in deuterated DMSO, the production of the imine compound 1 was confirmed.

¹ H-NMR spectrum: δH 4.61 (s, 2H), δH 3.67 (s, 8H), δH 8.31 (s, 2H), δH 7.71 (s, 4H).
<Production Example 2>
Except for using 21.46 g (0.2 mol, manufactured by Tokyo Chemical Industry Co., Ltd., purity 98.0%) instead of 2-ethanolamine and drying under reduced pressure for 3 days at room temperature. The same reaction operation as in Production Example 1 was carried out, and a pale yellow solid N, N ′-(1,4-phenylenedimethylidene) bis (2- (2-aminoethoxy) ethanol) (hereinafter referred to as “imine compound 2”) ) 28.3 g was obtained. From the proton nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) measured by dissolving the imine compound 2 in deuterated DMSO, the production of the imine compound 2 was confirmed.

¹ H-NMR spectrum: δH 4.58 (t, 2H), δH 3.44 (m, 8H), 3.68 (m, 8H), δH 8.37 (s, 2H), δH 7.79 (s, 4H) .
<Production Example 3>
The reaction operation was the same as in Production Example 1 except that 18.5 g of hydroxyacetone (0.2 mol, Tokyo Chemical Industry Co., Ltd., purity 80.0%) was used instead of terephthalaldehyde, and 2- (2-hydroxyethyl) was obtained. 28.2 g of imino) propan-1-ol (hereinafter referred to as “imine compound 3”) was obtained. From the result of dissolving the imine compound 3 in deuterated DMSO and measuring the proton nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum), it is confirmed that the imine compound 3 has the chemical structure of the following formula (6). did.

<Production Example 4>
Except for using 26.0 g (0.2 mol) of 2-hydroxyethyl pyruvate instead of terephthalaldehyde, the same reaction operation as in Production Example 1 was carried out to give 2-hydroxyethyl 2- (2-hydroxyethylimino) propanoate ( Hereinafter referred to as “imine compound 4”) 35
. 6 g was obtained. From the result of dissolving the imine compound 4 in deuterated DMSO and measuring the proton nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum), it was confirmed that the imine compound 4 has the chemical structure of the following formula (7). did.

[Production of biodegradable moiety-containing compound]
<Production of biodegradable moiety-containing compound having COOH groups at both ends>
The production example of a compound containing a biodegradable site constituting the biodegradable polymer is specifically shown below. In addition, in order to confirm the end point when producing a biodegradable moiety-containing compound from a dibasic acid and a divalent aliphatic alcohol, and to measure the carboxyl group content of the produced biodegradable moiety-containing compound, biodegradable The acid value of the site-containing compound was measured. The measuring method is shown below.

<Method for measuring acid value>
A biodegradable site-containing compound having COOH groups at both ends is dissolved in chloroform, a few drops of an indicator (bromothymol blue methanol solution) is added, and titrated with 0.05N alcoholic KOH solution. Asked.

Acid value [mg-KOH / g] = 2.805 × f × V / S
f: Factor of 0.05N alcoholic KOH solution V; Titration volume of 0.05N alcoholic KOH solution [mL]
S: Amount of sample collected from biodegradable sites having COOH groups at both ends [g]
<Production Example 5>
In a SUS 1L separable flask equipped with a moisture meter with condenser, thermometer, bent tube and SUS stirring blade, 202.5 g of oxalic acid (1.71 mol, manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5) %) And 143.6 g of 1,4-butanediol (1.56 mol, manufactured by Wako Pure Chemical Industries, Ltd., purity 98.0%), heated to 60 ° C. in an oil bath, and degassed for 30 minutes under reduced pressure did. After the deaeration, the reaction temperature was increased stepwise to 160 ° C. by switching to nitrogen blowing. The reaction was continued at 160 ° C. until the acid value of the reaction product reached 45.7 mg-KOH / g, and the melt was discharged into a SUS vat at the end of the reaction. 278.3 g of polybutylene succinate (hereinafter referred to as “PBS1”) having COOH groups at both ends was obtained. As a result of measuring the acid value of PBS1, it was 45.2 mg-KOH / g. Further, the molecular weight of PBS1 was measured by GPC, and as a result, the number average molecular weight was 3169.

<Production Example 6>
The amount of succinic acid used was changed to 351.1 g (2.96 mol), the amount of 1,4-butanediol used was changed to 262.8 g (2.86 mol), and the reaction temperature was increased stepwise to 180 ° C. Production Example 5 except that the reaction was continued at 0 ° C. until the acid value reached 19.0 mg-KOH / g.
The same reaction operation was carried out to obtain 485.4 g of polybutylene succinate (hereinafter referred to as “PBS2”) having COOH groups at both ends. The acid value of PBS2 is 18.4 mg-KOH / g
The number average molecular weight of PBS2 was 10312.

<Production Example 7>
The amount of succinic acid used was changed to 291.0 g (2.45 mol), the amount of 1,4-butanediol used was changed to 188.5 g (2.05 mol), and the acid value was 110.3 mg-K at 160 ° C.
Except for continuing the reaction until reaching OH / g, the same reaction operation as in Production Example 5 was performed to obtain 395.3 g of polybutylene succinate (hereinafter referred to as “PBS3”) having COOH groups at both ends. The acid value of PBS3 is 108.6 mg-KOH / g, and the number average molecular weight of PBS3 is 142.
0.

<Production Example 8>
The amount of succinic acid used was changed to 305.9 g (2.58 mol), the amount of 1,4-butanediol used was changed to 163.5 g (1.78 mol), and the acid value at 160 ° C. was 224.5 mg-K.
Except for continuing the reaction until reaching OH / g, the same reaction operation as in Production Example 5 was performed to obtain 385.1 g of polybutylene succinate (hereinafter referred to as “PBS4”) having COOH groups at both ends. The acid value of PBS4 is 221.7 mg-KOH / g, and the number average molecular weight of PBS4 is 653
Met.

<Production Example 9>
The amount of succinic acid used was changed to 305.9 g (2.58 mol), the amount of 1,4-butanediol used was changed to 233.3 g (2.54 mol), and the reaction temperature was increased stepwise to 180 ° C. A polybutylene succinate having a COOH group at both ends (hereinafter referred to as “PBS5”) was carried out in the same manner as in Production Example 5 except that the reaction was continued at 0 ° C. until the acid value reached 11.2 mg-KOH / g. ) 428.8 g was obtained. The acid value of PBS5 is 10.9 mg-KOH /
g, The number average molecular weight of PBS5 was 17400.

<Production Example 10>
The amount of succinic acid used was changed to 206.9 g (1.74 mol), the amount of 1,4-butanediol used was changed to 106.5 g (1.12 mol), and diethylene glycol 51.2 g (0.48 mol, Pure Chemical) Kogyo Co., Ltd., purity 99.0%) was used, and the reaction was continued until the acid value reached 46.6 mg-KOH / g. 282.6 g of oxalic acid / 1,4-butanediol / diethylene glycol copolymer (hereinafter referred to as “PBDEGS”) having a group was obtained. The acid value of PBDEGS was 45.5 mg-KOH / g, and the number average molecular weight of PBDEGS was 2858.

<Production of biodegradable moiety-containing compound having OH groups at both ends>
The production example of a compound containing a biodegradable site constituting the biodegradable polymer is specifically shown below. In addition, in order to confirm the end point when producing a biodegradable moiety-containing compound from a dibasic acid and a divalent aliphatic alcohol, and to measure the amount of hydroxyl groups of the produced biodegradable moiety-containing compound, the biodegradable moiety The hydroxyl value of the contained compound was measured. The measuring method is shown below.

<Acetyl value measuring method>
Chloroform (Wako Pure Chemical Industries, Ltd., first grade reagent) 400 mL, 70% perchloric acid (Wako Pure Chemical Industries, Ltd., special grade reagent) 4 g and acetic anhydride (Wako Pure Chemical Industries, Ltd., special grade reagent) 50 mL From this, an acetylating reagent was prepared.

A biodegradable site-containing compound having an OH group at both ends was acetylated with this acetylating reagent, tens of drops of cresol red-thymol blue mixed indicator were added, and titrated with 0.5N alcoholic sodium hydroxide solution. At the same time, a blank test was also conducted. From these titration results, the acetyl value was determined from the following formula.

Acetyl value [mg-KOH / g] = (V ₀ −V ₁ ) × f × 28.05 / S
f: Factor of 0.5N alcoholic sodium hydroxide solution V ₀ ; Titration amount of 0.5N alcoholic sodium hydroxide solution required for the blank test [mL]
V ₁ ; titration amount of 0.5N alcoholic sodium hydroxide solution required for testing a sample of a biodegradable site having OH groups at both ends [mL]
S: Sample collection amount of biodegradable site compound having OH groups at both ends [g]
<Method for measuring acid value>
A biodegradable moiety-containing compound having an OH group at both ends was dissolved in a chloroform-methanol mixed solvent, a few drops of bromothymol blue-phenol red mixed indicator were added, and titrated with a 0.1N alcoholic potassium hydroxide solution. At the same time, a blank test was also conducted. From these titration results, the acid value was determined by the following formula.

Acid value [mg-KOH / g] = (V ₁ −V ₀ ) × f × 5.61 / S
f: Factor of 0.1N alcoholic potassium hydroxide solution V ₀ ; Titration amount of 0.1N alcoholic potassium hydroxide solution required for the blank test [mL]
V ₁ ; titration amount of 0.1N alcoholic potassium hydroxide solution required for testing a sample of a biodegradable site having OH groups at both ends [mL]
S: Sample collection amount of biodegradable site compound having OH groups at both ends [g]
<Method for obtaining hydroxyl value>
The hydroxyl value was determined from the following formula.

Hydroxyl value [mg-KOH / g] = acetyl value + acid value <Production Example 11>
In a 1 L separable flask made of glass with a moisture quantification receiver with a condenser, a thermometer, a curved tube and a stirring blade made of SUS, 320.4 g (2.70 mol) of oxalic acid and 303.5 g of 1,4-butanediol (3 .30 mol) was added and the reaction temperature was raised stepwise to 180 ° C. under a nitrogen stream. When almost no water was observed at 180 ° C., 1.32 g of 1% 2-ethylhexanoic acid (II) toluene solution (2-ethylhexanoic acid (II): 0.033 mmol, Wako Pure Chemical Industries, Ltd.) The reaction was continued. Furthermore, the reaction temperature was raised to 200 ° C., and the hydroxyl value and acid value of the reaction product were 57.6 mg-KO, respectively.
The reaction is continued until H / g and 0.3 mg-KOH / g.
The product was discharged into a US bat. 434.4 g of polybutylene succinate (hereinafter referred to as “PBS6”) having OH groups at both ends was obtained. As a result of measuring the hydroxyl value and acid value of PBS6,
The hydroxyl value was 57.5 mg-KOH / g, and the acid value was 0.2 mg-KOH / g. Further, the molecular weight of PBS6 was measured by GPC, and as a result, the number average molecular weight was 1951.

<Production Example 12>
The amount of oxalic acid used was changed to 288.4 g (2.43 mol), and 39.7 g of adipic acid (0.27 mol, manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%) was used. A polybutylene succinate adipate having OH groups at both ends was carried out in the same manner as in Production Example 11 except that the reaction was continued until 57.7 mg-KOH / g and the acid value reached 0.4 mg-KOH / g. 480.7 g (hereinafter referred to as “PBSA diol”) was obtained. As a result of measuring the hydroxyl value and acid value of PBSA diol, the hydroxyl value was 57.6 mg-KOH / g and the acid value was 0.3 mg-KOH / g. In addition, the molecular weight of PBSA diol
As a result of measurement by C, the number average molecular weight was 1947.

[Example 1]
In a 500 mL four-necked flask equipped with a condenser, thermometer and stirring blade,
10.0 50.0 g (COOH group; 40.3 mmol), tributylamine 22.9 g (120.9 mmol, manufactured by Wako Pure Chemical Industries, Ltd., purity 98.0%), dry dichloromethane 350 mL, put under nitrogen atmosphere Stir and dissolve. Next, 15.76 g of 2-chloro-1-methylpyridinium iodide (60.5 mmol, manufactured by Tokyo Chemical Industry Co., Ltd., purity 98.0)
%) Was allowed to stand for 15 minutes, and 4.44 g (20.2 mmol) of imine compound 1 was added. The reaction was performed at 40 to 42 ° C. for 12 hours under a nitrogen atmosphere. After the reaction, the reaction solution was cooled to room temperature, and the reaction solution was added dropwise to 1400 mL of dry methanol under a nitrogen atmosphere to precipitate a cottony polymer. This suspension was pressure-filtered with nitrogen, and the obtained polymer was dried overnight at 30 ° C. under a nitrogen atmosphere. The dried polymer was added to 1400 mL of dry methanol, stirred under a nitrogen atmosphere, washed, and filtered under pressure. The same cleaning operation was performed again, and the film was dried overnight at 50 ° C. in a nitrogen atmosphere. 51.5 g of polybutylene succinate having an imine bond (hereinafter referred to as “imine-containing PBS”) was obtained. As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 26984. Further, ¹ H-NMR spectrum was measured, and it was confirmed that an imine bond was present in the imine-containing PBS from a methine peak of 8.29 ppm imine bond. As a result of analyzing the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (8).

  The obtained imine-containing PBS was hot-pressed at 115 ° C. for 3 minutes to produce films having thicknesses of 15 μm, 30 μm, and 100 μm. The film having a thickness of 100 μm had a tensile strength of 25.5 MPa and a tensile modulus of 687 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.7%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 to 2 cm square in 119 hours, and the number average molecular weight at that time was reduced to 12700. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 32.5% after 1 week, 66.4% after 2 weeks, 81.0% after 3 weeks, 4 It was 92.3% after a week.

[Example 2]
The same procedure as in Example 1 was performed except that the amount of tributylamine used was changed to 18.3 g (96.7 mmol) and the amount of 2-chloro-1-methylpyridinium iodide was changed to 12.6 g (48.4 mmol). 51.4 g of cotton-like imine-containing PBS was obtained. As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 26035. Further, the structure of the imine-containing PBS was confirmed in the same manner as in Example 1, and it was confirmed that it had the same chemical structure as in Example 1.

  A film was produced in the same manner as in Example 1 using the obtained imine-containing PBS. The film having a thickness of 100 μm had a tensile strength of 24.5 MPa and a tensile elastic modulus of 678 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 to 2 cm square in 118.9 hours, and the number average molecular weight at that time was reduced to 11566. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 32.7% after 1 week, 66.8% after 2 weeks, 81.2% after 3 weeks, 4 It was 92.5% after a week.

Example 3
The same procedure as in Example 1 was conducted except that the amount of tributylamine used was changed to 38.1 g (201.5 mmol) and the amount of 2-chloro-1-methylpyridinium iodide used was changed to 26.3 g (100.8 mmol). 51.6 g of cotton-like imine-containing PBS was obtained. As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 31391. Further, the structure of the imine-containing PBS was confirmed in the same manner as in Example 1, and it was confirmed that it had the same chemical structure as in Example 1.

  A film was produced in the same manner as in Example 1 using the obtained imine-containing PBS. The film having a thickness of 100 μm had a tensile strength of 25.6 MPa and a tensile modulus of 680 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.6%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 to 2 cm square in 118.7 hours, and the number average molecular weight at that time was reduced to 11077. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 32.4% after 1 week, 66.3% after 2 weeks, 80.9% after 3 weeks, 4 It was 91.8% after a week.

Example 4
Instead of PBS1, 50.0 g (COOH group; 16.4 mmol) of PBS2 was used, the amount of tributylamine used was changed to 9.31 g (49.2 mmol), and the amount of 2-chloro-1-methylpyridinium iodide used Was changed to 6.41 g (24.6 mmol) and the amount of imine compound 1 used was changed to 1.80 g (8.20 mmol), in the same manner as in Example 1, 49.5 g of cotton-like imine-containing PBS Got. As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 30686. Further, the structure of the imine-containing PBS was confirmed in the same manner as in Example 1, and it was confirmed that it had the same chemical structure as in Example 1.

  A film was produced in the same manner as in Example 1 using the obtained imine-containing PBS. The film having a thickness of 100 μm had a tensile strength of 37.7 MPa and a tensile elastic modulus of 779 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 2 to 3 cm square in 240 hours, and the number average molecular weight at that time was reduced to 14400. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 28.5% after 1 week, 58.6% after 2 weeks, 77.3% after 3 weeks, 4 It was 89.7% after a week.

Example 5
Instead of PBS1, 50.0 g (COOH group; 96.8 mmol) of PBS3 was used, the amount of tributylamine used was changed to 54.9 g (290.4 mmol), and the amount of 2-chloro-1-methylpyridinium iodide used Was changed to 35.9 g (145.2 mmol) and the amount of imine compound 1 used was changed to 10.6 g (48.4 mmol), in the same manner as in Example 1, 57.1 g of cotton-like imine-containing PBS Got. As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 31391. Further, the structure of the imine-containing PBS was confirmed in the same manner as in Example 1, and it was confirmed that it had the same chemical structure as in Example 1.

  A film was produced in the same manner as in Example 1 using the obtained imine-containing PBS. The film having a thickness of 100 μm had a tensile strength of 20.7 MPa and a tensile modulus of 677 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 98.7%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed into 1 to 2 cm square in 8 hours, and the number average molecular weight at that time was 7245. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the biodegradation degree was 40.5% after 1 week, 77.5% after 2 weeks, 87.6% after 3 weeks, 4 It was 95.3% after a week.

Example 6
Instead of PBS1, 50.0 g (COOH group; 197.6 mmol) of PBS4 was used, the amount of tributylamine used was changed to 112.1 g (592.8 mmol), and the amount of 2-chloro-1-methylpyridinium iodide used Was changed to 77.3 g (296.4 mmol) and the amount of imine compound 1 was changed to 21.7 g (98.8 mmol), and in the same manner as in Example 1, 68.2 g of cotton-like imine-containing PBS Got. As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 32501. Further, the structure of the imine-containing PBS was confirmed in the same manner as in Example 1, and it was confirmed that it had the same chemical structure as in Example 1.

  A film was produced in the same manner as in Example 1 using the obtained imine-containing PBS. The film having a thickness of 100 μm had a tensile strength of 20.1 MPa and a tensile elastic modulus of 595 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 98.6%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 to 2 cm square in 2 hours, and the number average molecular weight at that time was reduced to 5490. Moreover, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 46.3% after 1 week, 80.0% after 2 weeks, 90.0% after 3 weeks, 4 It was 96.0% after a week.

Example 7
Instead of PBS1, 50.0 g of PBS5 (COOH group; 9.71 mmol) was used, the amount of tributylamine used was changed to 5.50 g (29.1 mmol), and the amount of 2-chloro-1-methylpyridinium iodide used Was changed to 3.81 g (14.6 mmol) and the amount of imine compound 1 used was changed to 1.07 g (4.86 mmol) in the same manner as in Example 1 to obtain 49.4 g of imine-containing PBS. . As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 27443. Further, the structure of the imine-containing PBS was confirmed in the same manner as in Example 1, and it was confirmed that it had the same chemical structure as in Example 1.

  A film was produced in the same manner as in Example 1 using the obtained imine-containing PBS. The film having a thickness of 100 μm had a tensile strength of 38.9 MPa and a tensile elastic modulus of 790 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 3 to 4 cm square in 520 hours, and the number average molecular weight at that time was reduced to 15460. Moreover, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 28.0 after 1 week, 53.6% after 2 weeks, 72.5% after 3 weeks, and 4 weeks. Later it was 85.5%.

Example 8
Instead of PBS1, 50.0 g (COOH group; 40.6 mmol) of PBDEGS was used, the amount of tributylamine used was changed to 16.8 g (121.8 mmol), and the amount of 2-chloro-1-methylpyridinium iodide used Was changed to 15.9 g (60.9 mmol) and the amount of imine compound 1 used was changed to 4.5 g (20.3 mmol), to obtain 50.1 g of imine-containing PBDEGS in the same manner as in Example 1. . As a result of measuring the molecular weight of the obtained imine-containing PBDEGS by GPC, the number average molecular weight was 36700. Further, the structure of the imine-containing PBDEGS was analyzed in the same manner as in Example 1, and it was estimated that it had a chemical structure of the following formula (9).

  A film was produced in the same manner as in Example 1 using the obtained imine-containing PBDEGS. The 100 μm film had a tensile strength of 30.9 MPa and a tensile modulus of 520 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 mm to 1 cm square in 206 hours, and the number average molecular weight at that time was reduced to 12800. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 30.2% after 1 week, 64.5% after 2 weeks, 79.0% after 3 weeks, 4 It was 89.7% after a week.

[Comparative Example 1]
49.7 g of cotton-like polybutylene succinate was obtained in the same manner as in Example 4 except that 0.753 g (8.20 mmol) of 1,4-butanediol was used in place of the imine compound 1. As a result of measuring the molecular weight of the obtained polybutylene succinate by GPC, the number average molecular weight was 34465.

  A film was produced in the same manner as in Example 1 using the obtained polybutylene succinate. The film having a thickness of 100 μm had a tensile strength of 39.3 MPa and a tensile modulus of 371 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. As a result of conducting a water disintegration test using the above film, the film did not disintegrate even after 520 hours. Further, the number average molecular weight of the film at this time is 33531 and no change in molecular weight is observed. Moreover, as a result of conducting a biodegradability test using the same film, the degree of biodegradation was 27.0% after 1 week, 52.5% after 2 weeks, 69.0% after 3 weeks, and 4 weeks. It was 79.0% later, which was inferior to the biodegradability of imine-containing PBS.

Example 9
In a 200 mL glass separable flask equipped with a condenser, a thermometer and a stirring blade, 100.0 g (OH group; 0.102 mol) of PBS6 and 11.3 g (OH group; 0.102 mol) of imine compound 1 were placed. . After melting at 130 ° C. in a nitrogen atmosphere, 0.89 g of 1% dibutyltin dilaurate (IV) toluene solution (dibutyltin dilaurate (IV): 0.014 mmol, manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0) %) Was added. Next, 16.5 g of hexamethylene diisocyanate (hereinafter referred to as “HDI”) (NCO group; 0.195 mol, “Takenate 700” manufactured by Mitsui Chemicals Polyurethane Co., Ltd., NCO content 49.6% by weight) was added dropwise over 10 minutes. The HDI remaining in the dropping funnel was washed away with 1.3 g of toluene. Subsequently, after reacting at 130 ° C. for 3 hours in a nitrogen atmosphere, the molten polymer was discharged into a stainless steel vat to obtain 101.0 g of imine-containing PBS. As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 26984. Further, ¹ H-NMR spectrum was measured, and it was confirmed that an imine bond was present in the imine-containing PBS from a methine peak of 8.29 ppm imine bond. As a result of analyzing the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (10).

The obtained imine-containing PBS was hot-pressed at 130 ° C. for 5 minutes to produce films having thicknesses of 15 μm, 30 μm, and 100 μm. The tensile strength of a 100 μm thick film is 31.
The tensile modulus was 932 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 to 2 cm square in 259 hours, and the number average molecular weight at that time was reduced to 15800. Moreover, as a result of measuring the time-dependent change in tensile strength after immersion in water using a 100 μm-thick film, the tensile strength decreased to 12.2 MPa after 2 hours of immersion in water. The results of measuring the temporal change in tensile strength after immersion in water are shown in FIG. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 15.3% after 1 week, 27.5% after 2 weeks, 40.8% after 3 weeks, 40.8%, It was 52.3% after 5 weeks and 60.0% after 5 weeks.

Example 10
100.0 g of polybutylene adipate diol (hereinafter referred to as “PBA diol”) instead of PBS 6 (OH group: 0.100 mol, “Takelac U-2420” manufactured by Mitsui Chemicals Polyurethanes, Inc., hydroxyl value 56.1 mg-KOH / g) And Example 9 except that the amount of imine compound 1 used was changed to 11.0 g (OH group; 0.100 mol) and the amount of HDI used was changed to 16.1 g (NCO group; 0.190 mol). Similarly, 115.1 g of polybutylene adipate (hereinafter referred to as “imine-containing PBA”) having an imine bond was obtained. As a result of measuring the molecular weight of the obtained imine-containing PBA by GPC, the number average molecular weight was 34850. Further, ¹ H-NMR spectrum was measured, and it was confirmed that an imine bond was present in the imine-containing PBA from a methine peak having an imine bond of 8.29 ppm. As a result of analyzing the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (11).

  A film was produced in the same manner as in Example 9 using the obtained imine-containing PBA. The film having a thickness of 100 μm had a tensile strength of 30.9 MPa and a tensile modulus of 520 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 to 2 cm square in 3 hours, and the number average molecular weight at that time was reduced to 12930. Moreover, as a result of measuring the temporal change in tensile strength after immersion in water using a 100 μm thick film, the tensile strength decreased to 7.1 MPa in 2 hours of immersion in water. The results of measuring the temporal change in tensile strength after immersion in water are shown in FIG. Moreover, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 20.0% after 1 week, 31.5% after 2 weeks, 48.3% after 3 weeks, 4 It was 61.2% after a week.

Example 11
95.3 g of imine-containing PBS was obtained in the same manner as in Example 9, except that 15.8 g (OH; 0.102 mol) of imine compound 2 was used instead of imine compound 1. As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 30240. Further, ¹ H-NMR spectrum was measured, and it was confirmed that an imine bond was present in the imine-containing PBS from a methine peak of 8.29 ppm imine bond. As a result of analyzing the ¹ H-NMR spectrum, it was presumed to have a chemical structure of the following formula (12).

  A film was produced in the same manner as in Example 9 using the obtained imine-containing PBS. The film having a thickness of 100 μm had a tensile strength of 29.9 MPa and a tensile elastic modulus of 785 MPa. This film was good in appearance and touch, flexible and high in strength.

A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.7%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 to 2 cm square in 86 hours, and the number average molecular weight at that time was reduced to 15870. As a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 17.4% after 1 week, 30.6% after 2 weeks, 45.5% after 3 weeks, 4 It was 58.3% after 5 weeks and 63.9% after 5 weeks.

Example 12
102.3 g of imine-containing PBA was obtained in the same manner as in Example 10 except that 15.4 g (OH group; 0.100 mol) of imine compound 2 was used instead of imine compound 1. As a result of measuring the molecular weight of the obtained imine-containing PBA by GPC, the number average molecular weight was 34200. Further, ¹ H-NMR spectrum was measured, and it was confirmed that an imine bond was present in the imine-containing PBA from a methine peak having an imine bond of 8.29 ppm. As a result of analyzing the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (13).

  A film was produced in the same manner as in Example 9 using the obtained imine-containing PBA. The film having a thickness of 100 μm had a tensile strength of 29.3 MPa and a tensile modulus of 480 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 to 2 cm square in 2 hours, and the number average molecular weight at that time was reduced to 11950. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 33.0% after 1 week, 45.5% after 2 weeks, 59.3% after 3 weeks, 4 It was 75.6% after a week.

[Comparative Example 2]
80.5 g of PBS was obtained in the same manner as in Example 9, except that imine compound 1 was not used and the amount of HDI used was changed to 8.2 g (NCO group; 0.097 mol). As a result of measuring the molecular weight of the obtained PBS by GPC, the number average molecular weight was 24150.

  A film was produced in the same manner as in Example 9 using the obtained PBS. The film having a thickness of 100 μm had a tensile strength of 67.4 MPa and a tensile modulus of 455 MPa. This film was good in appearance and touch, flexible and high in strength.

A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.6%, and it was confirmed that this film was not water-soluble. 15 μm
A water disintegration test was performed using a thick film, but no water disintegration was observed. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 5.2% after 1 week, 15.7% after 2 weeks, 23.6% after 3 weeks, 4 It was 37.7% after 5 weeks and 46.8% after 5 weeks, which was inferior in biodegradability to PBS containing imine.

[Comparative Example 3]
Implementation was carried out except that 100.0 g of PBA diol (OH group; 0.100 mol) was used instead of PBS6, and the amount of HDI used was changed to 8.0 g (NCO group; 0.095 mol) without using imine compound 1. In the same manner as in Example 9, 91.6 g of polybutylene adipate (hereinafter referred to as “PBA”) was obtained. As a result of measuring the molecular weight of the obtained PBA by GPC, the number average molecular weight was 45450.

  A film was produced in the same manner as in Example 9 using the obtained PBA. The film having a thickness of 100 μm had a tensile strength of 72.5 MPa and a tensile elastic modulus of 250 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.7%, and it was confirmed that this film was not water-soluble. Moreover, although the water disintegration test was done using the film of 15 micrometers thickness, water disintegration was not recognized. Moreover, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 10.1% after 1 week, 16.0% after 2 weeks, 25.2% after 3 weeks, 4 After 40 weeks, it was 40.3%, which was inferior in biodegradability to imine-containing PBA.

Example 13
Instead of PBS6, 50.0 g (OH group; 0.051 mol) of PBS6 and 50.0 g (OH group; 0.050 mol) of PBA diol were used, and the amount of imine compound 1 used was 11.1 g (OH group; 0 The amount of HDI used was changed to 16.3 g (NCO
112.5 g of a polybutylene adipate-polybutylene succinate copolymer (hereinafter referred to as “imine-containing PBA-PBS”) having an imine bond was obtained in the same manner as in Example 9 except that the group was changed to 0.192 mol). It was. As a result of measuring the molecular weight of the obtained imine-containing PBA-PBS by GPC, the number average molecular weight was 41200. Further, ¹ H-NMR spectrum was measured, and it was confirmed that an imine bond was present in the imine-containing PBA-PBS from a methine peak having an imine bond of 8.29 ppm. As a result of analyzing the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (14).

A film was produced in the same manner as in Example 9 using the obtained imine-containing PBA-PBS. The film having a thickness of 100 μm had a tensile strength of 20.9 MPa and a tensile elastic modulus of 630 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 to 2 cm square in 200 hours, and the number average molecular weight at that time was reduced to 12930. Further, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 25.3% after 1 week, 38.5% after 2 weeks, 50.7% after 3 weeks, 4 It was 61.3% after a week.

[Comparative Example 4]
Polybutylene adipate-polybutylene succinate copolymer (hereinafter “ 81.6 g) (referred to as “PBA-PBS”). As a result of measuring the molecular weight of the obtained PBA-PBS by GPC, the number average molecular weight was 30650.

  A film was produced in the same manner as in Example 9 using the obtained PBA-PBS. The film having a thickness of 100 μm had a tensile strength of 69.1 MPa and a tensile modulus of 389 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.7%, and it was confirmed that this film was not water-soluble. Moreover, although the water disintegration test was done using the film of 15 micrometers thickness, water disintegration was not recognized. Moreover, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 8.3% after 1 week, 16.3% after 2 weeks, 30.9% after 3 weeks, 4 The biodegradability was inferior to the imine-containing PBA-PBS after 5 weeks.

Example 14
Instead of PBS6, 100.0 g of PBA diol (OH group; 0.100 mol) and 4.6 g of 1,4-butanediol (OH group; 0.100 mol) were used, and the amount of imine compound 1 used was 22.0 g. (OH group; 0.200 mol) and polybutylene adipate-butanediol having an imine bond in the same manner as in Example 9 except that the amount of HDI used was changed to 32.2 g (NCO group; 0.380 mol). 90.5 g of a copolymer (hereinafter referred to as “imine-containing PBA-BD”) was obtained. As a result of measuring the molecular weight of the obtained imine-containing PBA-BD by GPC, the number average molecular weight was 20,530. Moreover, the < ¹ > H-NMR spectrum was measured and it confirmed that the imine bond exists in imine containing PBA-BD from the methine peak of 8.29 ppm imine bond. As a result of analyzing the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (15).

  A film was produced in the same manner as in Example 9 using the obtained imine-containing PBA-BD. The film having a thickness of 100 μm had a tensile strength of 40.9 MPa and a tensile modulus of 753 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.9%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed into a 4 cm square in 520 hours, and the number average molecular weight at that time was reduced to 11050. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the biodegradation degree was 10.7% after 1 week, 21.8% after 2 weeks, 35.7% after 3 weeks, 4 It was 49.3% after 5 weeks, 55.8% after 5 weeks, and 62.3% after 6 weeks.

[Comparative Example 5]
A polybutylene adipate-butanediol copolymer (hereinafter referred to as “PBA-”) was used in the same manner as in Example 14 except that the imine compound 1 was not used and the amount of HDI used was changed to 16.1 g (NCO group; 0.190 mol). 81.6 g) (referred to as “BD”). As a result of measuring the molecular weight of the obtained PBA-BD by GPC, the number average molecular weight was 31450.

  A film was produced in the same manner as Example 9 using the obtained PBA-BD. The film having a thickness of 100 μm had a tensile strength of 75.3 MPa and a tensile modulus of elasticity of 544 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.7%, and it was confirmed that this film was not water-soluble. Moreover, although the water disintegration test was done using the film of 15 micrometers thickness, water disintegration was not recognized. Further, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 3.4%, 7.1% after 2 weeks, 18.4% after 3 weeks, and 26 after 4 weeks. The biodegradability was lower than that of the imine-containing PBA-BD, which was 0.8%, 58.5 after 3 weeks, and 45.8% after 6 weeks.

Example 15
Instead of PBS6, 100.0 g of PBS6 (OH group; 0.102 mol) and 10.1 g of polyethylene glycol (OH group; 0.010 mol, “PEG-2000” manufactured by Toho Chemical Industry Co., Ltd., hydroxyl value 57.1 mg- KOH / g), except that the amount of imine compound 1 used was changed to 12.4 g (OH group; 0.112 mol) and the amount of HDI used was changed to 18.2 g (NCO group; 0.214 mol) In the same manner as in Example 9, 90.5 g of a polybutylene succinate-polyethylene glycol copolymer (hereinafter referred to as “imine-containing PBS-PEG”) having an imine bond was obtained. As a result of measuring the molecular weight of the obtained imine-containing PBS-PEG by GPC, the number average molecular weight was 35705. Moreover, the < ¹ > H-NMR spectrum was measured and it confirmed that the imine bond exists in imine containing PBS-PEG from the methine peak of 8.29 ppm imine bond. As a result of analyzing the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (16).

A film was produced in the same manner as in Example 9 using the obtained imine-containing PBS-PEG. The film having a thickness of 100 μm had a tensile strength of 25.0 MPa and a tensile modulus of 685 MPa. This film was good in appearance and touch, flexible and high in strength.

A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.5%, and it was confirmed that this film was not water-soluble. 15 μm
As a result of conducting a water disintegration test using a thick film, an 11 cm square film collapsed to 1 to 2 cm square in 180 hours, and the number average molecular weight at that time was reduced to 15852. Further, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 17.3% after 1 week, 30.5% after 2 weeks, 45.2% after 3 weeks, 4 It was 55.5% after 5 weeks and 64.2% after 5 weeks.

[Comparative Example 6]
A polybutylene succinate-polyethylene glycol copolymer (hereinafter referred to as “PBS”) was used in the same manner as in Example 15 except that the imine compound 1 was not used and the amount of HDI used was changed to 9.1 g (NCO group; 0.106 mol). 80.6 g) (referred to as “-PEG”). As a result of measuring the molecular weight of the obtained PBS-PEG by GPC, the number average molecular weight was 42521.

  A film was produced in the same manner as Example 9 using the obtained PBS-PEG. The film having a thickness of 100 μm had a tensile strength of 65.3 MPa and a tensile modulus of 498 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.5%, and it was confirmed that this film was not water-soluble. Moreover, although the water disintegration test was done using the film of 15 micrometers thickness, water disintegration was not recognized. Moreover, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 8.7% after 1 week, 17.3% after 2 weeks, 25.8% after 3 weeks, 4 The biodegradability was inferior to imine-containing PBS-PEG, 33.4% after 5 weeks and 45.6% after 5 weeks.

Example 16
100.0 g of PBS6 (OH group; 0.102 mol) and 11.3 g of imine compound 1 in a SUS 200 mL separable flask equipped with a moisture meter with condenser, thermometer, bent tube and SUS stirring blade OH group; 0.102 mol), diethyl carbonate 12.3 g (0.102 mol, manufactured by Wako Pure Chemical Industries, Ltd., purity 98%), sodium methoxide 0.03 g (0.528 mmol, Wako Pure Chemical Industries, Ltd.) Manufactured, purity 95%). The temperature was raised slowly to 120 ° C., and the reaction was continued at 120 ° C. until the produced ethanol was no longer distilled off. Furthermore, it was made to react at 180 degreeC under pressure reduction for 24 hours, and the polycarbonate (henceforth "imine containing PC") which has an imine bond was obtained.

As a result of measuring the molecular weight of the obtained imine-containing PC by GPC, the number average molecular weight was 25200. Further, ¹ H-NMR spectrum was measured, and it was confirmed that an imine bond was present in the imine-containing PC from a methine peak of 8.29 ppm imine bond. As a result of analyzing the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (17).

  A film was produced in the same manner as in Example 9 using the obtained imine-containing PC. The film having a thickness of 100 μm had a tensile strength of 21.0 MPa and a tensile elastic modulus of 578 MPa. This film was good in appearance and touch, flexible and high in strength.

A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.5%, and it was confirmed that this film was not water-soluble. 15 μm
As a result of conducting a water disintegration test using a thick film, an 11 cm square film collapsed to 1 to 2 cm square in 270 hours, and the number average molecular weight at that time was reduced to 13600. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 40.3% after 1 week, 60.5% after 2 weeks, 75.3% after 3 weeks, 4 It was 86.4% after a week.

[Comparative Example 7]
90.6 g of polycarbonate (hereinafter referred to as “PC”) was obtained in the same manner as in Example 16 except that the amount of diethyl carbonate used was changed to 6.2 g (0.050 mol) without using imine compound 1. As a result of measuring the molecular weight of the obtained PC by GPC, the number average molecular weight was 26528.

  A film was produced in the same manner as in Example 9 using the obtained PC. The film having a thickness of 100 μm had a tensile strength of 22.0 MPa and a tensile elastic modulus of 530 MPa. This film was good in appearance and touch, flexible and high in strength.

A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. 15 μm
A water disintegration test was performed using a thick film, but no water disintegration was observed. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 21.3% after 1 week, 32.1% after 2 weeks, 40.6% after 3 weeks, 4 It was 58.2% after a week, and biodegradability was inferior to imine containing PC.

Example 17
A polybutylene succinate adipate (hereinafter referred to as “imine-containing PBSA”) having 100.3 g of imine bond was used in the same manner as in Example 9 except that 100.0 g of PBSA diol (OH; 0.102 mol) was used instead of PBS6. ) As a result of measuring the molecular weight of the resulting imine-containing PBSA by GPC, the number average molecular weight was 31,000. Also ¹
An H-NMR spectrum was measured, and it was confirmed that an imine bond was present in imine-containing PBSA from a methine peak having an imine bond of 8.29 ppm. As a result of analyzing the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (18).

  The obtained imine-containing PBSA was hot-pressed at 130 ° C. for 5 minutes to produce films having thicknesses of 15 μm, 30 μm, and 100 μm. The film having a thickness of 100 μm had a tensile strength of 28.5 MPa and a tensile modulus of 632 MPa. This film was good in appearance and touch, flexible and high in strength.

A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.7%, and it was confirmed that this film was not water-soluble. 15 μm
As a result of conducting a water disintegration test using a thick film, an 11 cm square film collapsed to 1 to 2 cm square in 249 hours, and the number average molecular weight at that time was reduced to 16000. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 16.8% after 1 week, 30.3% after 2 weeks, 45.0% after 3 weeks, 45.0%, It was 58.2% after 6 weeks and 66.5% after 5 weeks.

Example 18
Example 10 except that 100.0 g of PBSA diol (OH; 0.102 mol) was used instead of PBS6, and 15.8 g (OH; 0.102 mol) of imine compound 2 was used instead of imine compound 1. 95.3 g of imine-containing PBSA was obtained. As a result of measuring the molecular weight of the resulting imine-containing PBSA by GPC, the number average molecular weight was 30,450. Further, ¹ H-NMR spectrum was measured, and it was confirmed that an imine bond was present in imine-containing PBSA from a methine peak having an imine bond of 8.29 ppm. As a result of analyzing the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (19).

The obtained imine-containing PBSA was hot-pressed at 130 ° C. for 5 minutes to produce films having thicknesses of 15 μm, 30 μm, and 100 μm. The film having a thickness of 100 μm had a tensile strength of 27.9 MPa and a tensile modulus of elasticity of 530 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.6%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 1 to 2 cm square in 75 hours, and the number average molecular weight at that time was reduced to 15240. Moreover, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the biodegradability was 19.1% after 1 week, 33.5% after 2 weeks, 49.7% after 3 weeks, 4 It was 63.9% after a week.

[Comparative Example 8]
80.5 g of PBSA was obtained in the same manner as in Example 17 except that the imine compound 1 was not used and the amount of HDI used was changed to 8.2 g (NCO group; 0.097 mol). As a result of measuring the molecular weight of the obtained PBSA by GPC, the number average molecular weight was 24150.

  A film was produced in the same manner as in Example 9 using the obtained PBS. The film having a thickness of 100 μm had a tensile strength of 65.2 MPa and a tensile modulus of 436 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. Moreover, although the water disintegration test was done using the film of 15 micrometers thickness, water disintegration was not recognized. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 5.7% after 1 week, 16.9% after 2 weeks, 25.0% after 3 weeks, 4 The biodegradability was inferior to imine-containing PBSA, 38.9% after 5 weeks and 50.8% after 5 weeks.

Example 19
97.7 g of imine-containing PBS was obtained in the same manner as in Example 9, except that 8.2 g (OH; 0.102 mol) of imine compound 3 was used instead of imine compound 1. As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 29544. Moreover, as a result of analyzing the result of measuring the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (20).

The obtained imine-containing PBS was hot-pressed at 130 ° C. for 5 minutes to produce films having thicknesses of 15 μm, 30 μm, and 100 μm. The tensile strength of a 100 μm thick film is 29.0
MPa and tensile modulus were 577 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.9%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to 2 to 3 cm square in 433 hours, and the number average molecular weight at that time was reduced to 19421. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 14.4% after 1 week, 25.6% after 2 weeks, 38.7% after 3 weeks, 4 It was 50.8% after 5 weeks and 60.0% after 5 weeks.

Example 20
98.3 g of imine-containing PBS was obtained in the same manner as in Example 9 except that 11.1 g (OH; 0.102 mol) of imine compound 4 was used instead of imine compound 1. As a result of measuring the molecular weight of the obtained imine-containing PBS by GPC, the number average molecular weight was 31,000. Moreover, as a result of analyzing the result of measuring the ¹ H-NMR spectrum, it was estimated that it had a chemical structure of the following formula (21).

  The obtained imine-containing PBS was hot-pressed at 130 ° C. for 5 minutes to produce films having thicknesses of 15 μm, 30 μm, and 100 μm. The film having a thickness of 100 μm had a tensile strength of 28.7 MPa and a tensile elastic modulus of 598 MPa. This film was good in appearance and touch, flexible and high in strength.

  A water solubility test was performed using a film having a thickness of 100 μm. As a result, the weight retention of the film was 99.8%, and it was confirmed that this film was not water-soluble. Moreover, as a result of conducting a water disintegration test using a film having a thickness of 15 μm, an 11 cm square film collapsed to a 2-3 cm square in 445 hours, and the number average molecular weight at that time was reduced to 19540. In addition, as a result of conducting a biodegradability test using a film having a thickness of 30 μm, the degree of biodegradation was 14.7% after 1 week, 25.9% after 2 weeks, 39.0% after 3 weeks, 4 It was 51.4% after 5 weeks and 60.0% after 5 weeks.

<Inorganic additive-containing film>
[Examples 21 to 29 and Reference Examples 1 to 4]
The biodegradable polymer and the inorganic additive were mixed under the blending conditions shown in Table 6, and melt-mixed at 130 ° C. for 5 minutes using a plastmill, and the discharged biodegradable resin composition was used in the same manner as in Example 9. A film having a thickness of 15 μm was prepared and a water disintegration test was performed. The water disintegration time is shown in Table 6.

  From the results of the water disintegration test, the water disintegration of the inorganic additive-containing film in which the inorganic additive is blended in the range of 0.01 to 50 parts by weight with respect to 100 parts by weight of the biodegradable polymer is improved as compared with the additive-free film To do. On the other hand, the inorganic additive-containing film containing more than 50 parts by weight of the inorganic additive was not improved in water disintegration.

<Manufacture of biodegradable polymer nonwoven fabric>
[Examples 30 to 35 and Comparative Examples 9 to 13]
Biodegradable polymers shown in Table 7 were used. The spinning temperature was 210 ° C., and melt spinning was performed using a nozzle having 72 holes. The spun yarn was cooled with a cooling air flow of 20 ° C., and subsequently drawn using an air football at a take-up speed of 3500 m / min, and collected and deposited on a net conveyor to produce a web. Thereafter, the web was partially thermally bonded with an embossing roll and a flat roll under the conditions of a roll temperature of 105 ° C., a pressure contact area ratio of 17%, and a linear pressure of 30 kg / cm. Then, a nonwoven fabric of biodegradable polymer having a fineness of 3.0 denier and a basis weight of 50 g / m ² was obtained by a spunbond method. About the obtained nonwoven fabric, while measuring KGSM strength (MD / CD), the water disintegration test was done. The results are shown in Table 7.

Nonwoven fabrics (Examples 30 to 35) produced with biodegradable polymers have good appearance and feel, are flexible and have sufficient strength. It also showed excellent water disintegration. On the other hand, the nonwoven fabrics (Comparative Examples 9 to 13) manufactured with biodegradable polymers having no imine bond were good in appearance, touch and strength, but did not show water disintegration.

The biodegradable polymer used for this invention from the said Example has the water disintegration property (flashable property) and biodegradability which disintegrate in a lot of water.

  Therefore, the biodegradable composition containing the biodegradable polymer is a hot melt adhesive, an aqueous paper coating composition, an easily peelable adhesive, a thermal transfer medium, a fiber, a nonwoven fabric, a film, a protective film, a porous film, It can be used as agricultural and horticultural materials, pet filth treatment materials, sustained-release drugs, electrical equipment casings, processing aids, civil engineering and construction materials, cleaning articles, acid absorbents, and alkaline absorbents.

FIG. 1 is a graph showing the results of measuring the change in tensile strength with time after immersion in water of films made of biodegradable polymers performed in Example 9 and Example 10.

Claims (20)

  A biodegradable polymer having one or more imine bonds in the molecule, wherein the imine bond forms part of the main chain structure of the biodegradable polymer. Biodegradable composition.   A biodegradable molded article using the biodegradable composition according to claim 1.   A hot melt adhesive using the biodegradable composition according to claim 1.   An aqueous paper coating composition using the biodegradable composition according to claim 1.   An easily peelable adhesive material using the biodegradable composition according to claim 1.   A thermal transfer medium using the biodegradable composition according to claim 1.   A biodegradable molded article according to claim 2, wherein the biodegradable molded article is a fiber.   A biodegradable molded article according to claim 2, wherein the biodegradable molded article is a non-woven fabric.   The biodegradable molded product according to claim 2, wherein the biodegradable molded product is a film.   A biodegradable molded article according to claim 2, wherein the biodegradable molded article is a protective film.   The biodegradable molded article according to claim 2, wherein the biodegradable molded article is a porous film.   A biodegradable molded article according to claim 2, wherein the biodegradable molded article is an agricultural and horticultural material.   A biodegradable molded article according to claim 2, wherein the biodegradable molded article is a pet waste disposal agent.   A biodegradable molded article according to claim 2, wherein the biodegradable molded article is a sustained-release drug.   A biodegradable molded article according to claim 2, which is a casing of an electronic device.   A biodegradable molded article according to claim 2, wherein the biodegradable molded article is a processing aid.   A biodegradable molded article according to claim 2, which is a civil engineering and building material.   A biodegradable molded article according to claim 2, wherein the biodegradable molded article is a cleaning article.   A biodegradable molded article according to claim 2, wherein the biodegradable molded article is an acid absorbent.   A biodegradable molded article according to claim 2, wherein the biodegradable molded article is an alkali absorbent.

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