JPH1129627A - Decomposable polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer having excellent heat resistance, decomposability and toughness by performing a reaction in a reaction system containing a specific hydroxycarboxylic acid and/or lactones, a polyfunctional carboxylic acid compound and/or its acid anhydride, a polyhydric alcohol and a catalyst. SOLUTION: This polymer is obtained by performing a polymerization in a reaction system containing (A) a cyclic dimer of a hydroxycarboxylic acid and/or lactones (preferably L-lactide), (B) a polyfunctional carboxylic acid compound having more than three carboxyl groups and/or its acid anhydride (e.g. 1,2,3,4-cyclopentanetetracarboxylic acid), (C) a polyhydric alcohol having more than two hydroxyl groups (e.g. ethylene glycol) and (D) a metal of I to V group in the periodic table, its oxide or its salt, etc., (e.g. zinc dust) as a catalyst. Preferably, the component B is 0.01-0.5 wt.% based on the polymer and an equivalent ratio of carboxyl group in the component B to hydroxyl group in the component C is (100/90)-(100/110).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a compound (A) comprising a cyclic dimer and / or lactone of hydroxycarboxylic acid, and a component (B) comprising a polycarboxylic acid compound having three or more carboxyl groups. And / or its anhydride,
The present invention relates to a decomposable polymer characterized by reacting in a reaction system containing a polyhydric alcohol having two or more hydroxyl groups as the component (C) and a catalyst as the component (D), and a method for producing the same. The decomposable polymer produced according to the present invention may be a conventional aliphatic polyester (for example, an aliphatic polyester obtained by polycondensation of an aliphatic polycarboxylic acid and an aliphatic polyhydric alcohol, or a hydroxycarboxylic acid). Compared to condensed aliphatic polyesters, etc., while maintaining high transparency equal to or higher, and also have a remarkably high and excellent melt tension. , Etc. The decomposable polymer according to the present invention includes a polysaccharide and an aliphatic polyester (for example, an aliphatic polyester obtained by polycondensation of an aliphatic polycarboxylic acid and an aliphatic polyhydric alcohol, an aliphatic polyester obtained by polycondensation of a hydroxycarboxylic acid, and the like. ), And has a characteristic that coloring is remarkably small as compared with a copolymer or a polymer blend. The degradable polymer according to the present invention is useful as a substitute for a medical material or a general-purpose resin. The decomposable polymer according to the present invention is useful as a molded product or processed product utilizing its advantageous features.

[0002]

[Prior art]

[Technical Background] In recent years, waste disposal has become a problem in connection with environmental protection. Particularly, molded products and processed products of general-purpose general-purpose polymer materials do not decompose or disintegrate by microorganisms when buried as waste, so they remain semi-permanently as foreign substances, and furthermore, plasticizers, etc. There is a problem that the additives are eluted and pollute the environment. Also, when incinerated as waste, the high heat generated by combustion can damage the furnace, and the smoke and exhaust gases generated by combustion can cause air pollution, ozone depletion, global warming,
What could be the cause of acid rain etc. has been highlighted. Against this background, despite the increasing demand for polymer materials having excellent heat resistance, decomposability and toughness, polymer materials that can meet such demands are not necessarily supplied. I can't say that. Conventionally,
Polyhydroxycarboxylic acids and polysaccharides each have the property of easily hydrolyzing in the presence of water, and when used as a general-purpose resin, decompose without contaminating the environment after disposal, so they are environmentally friendly and medical When placed in a living body as a material for use, the excellent property that it is decomposed and absorbed in the living body without causing toxicity to the living body after achieving the purpose, and is thus easy on the living body, has already attracted attention before the present application. For example, polylactic acid and cellulose acetate each have the property of being easily hydrolyzed in the presence of water, and when used as a general-purpose resin, decompose without contaminating the environment after disposal, so they are environmentally friendly, When placed in a living body as a material for use, the excellent property that it is degraded and absorbed in the living body without causing toxicity to the living body after achieving the object, and is easy on the living body, has already attracted attention before the present application. However, when trying to mold and process into molded products or processed products such as films and filaments, polylactic acid is transparent, but has a problem that it is brittle, hard, lacks flexibility, and has a low melt viscosity. In the case of cellulose, there is a use as a cigarette filter or a photographic base film, but there is a problem in that a plasticizer of tens of weight% is required for molding.

[Prior Art of Adding Degradable High Molecular Weight Side Chain to Multifunctional Central Compound] In view of the above technical background, for example, as shown in the following, lactide (ie, , A cyclic dimer of lactic acid) or a cyclic monomer such as a lactone (eg, ε-caprolactone) is subjected to a ring-opening polymerization reaction, and a plurality of degradable high molecular weight side chains are radially added to the central compound. As a result, techniques for solving the problems have been developed. UK Patent No. 2,145,422 and JP-A-60-
No. 76531, UK Patent No. 2,145,422 (inventor; Brich
And Kissel, applicant; Sandoz AG) and JP-A-60-76531 (inventor; Brich and K)
issel, applicant; Sandoz AG) include, for example, polylactic acid and polyhydroxycarboxylic acid in the hydroxyl groups of polyhydric alcohols (hydrocarbon compounds having a plurality of hydroxyl groups (hydroxyl groups) in the molecule) such as sugars and sugar alcohols. A technique relating to a polymer having an acid or the like provided as a side chain is disclosed. More specifically, a polyhydric alcohol having a molecular weight of 20,000 or less, such as glucose, or a derivative thereof is converted to a polylactic acid or a derivative thereof (polylactic acids) having a molecular weight of 5,000 or more, or copolylactic acid or a derivative thereof (copoly There is disclosed a technique relating to an ester of a polyhydric alcohol obtained by esterification with a polyhydric alcohol obtained by esterification with a polylactic acid or a copolylactic acid. That is, (A) 2
(B) lactic acid or a derivative thereof, and if necessary, one or more secondary hydroxycarboxylic acids or a derivative thereof. A technique relating to an ester of a polyhydric alcohol obtained by esterification with a derivative, in which at least one hydroxyl group of the polyhydric alcohol is ester-bonded to polylactic acid or copolylactic acid having a molecular weight of 5,000 or more, is disclosed.

The above-mentioned esters of polyhydric alcohols have relatively low molecular weights, and are used as DDs for sustained release of physiologically active substances.
It is suitable for application to S.

US Pat. No. 5,225,521 US Pat. No. 5,225,521 (inventor; Spin
u, Applicant; Du Pont De Nemours
& Co EI) includes, as a central compound, a polyfunctional compound having at least 5 or more amino groups or hydroxyl groups and 5 to 100 carbon atoms, and the central compound has a plurality of high molecular weight arms (side chains). A technology relating to a star-shaped polymer having radially added is disclosed. The high-molecular-weight side chain is a block such as polyhydroxycarboxylic acid such as polylactic acid, polyglycolide, or polycaprolactone.A portion close to the central compound is an amorphous block, and a portion far from the central compound is a semicrystalline block. Has a special structure. The star-shaped polymer described above.
Can be applied to a three-dimensional network structure.

US Pat. No. 5,210,108 US Pat. No. 5,210,108 (Inventor; Ford and Spinu, Applicant: Du Pont De Nem)
ours & Co EI) has 3 to 100 amino groups and / or hydroxyl groups and has 5 to 10 carbon atoms.
000 polyfunctional compounds as a central compound, and a plurality of high molecular weight arms (side chains) are radially added to the central compound to form a star-shaped polymer.
(Japanese Patent Application Laid-Open No. H11-163873). The high-molecular-weight side chain is a segment of polyhydroxycarboxylic acid such as polylactic acid, polyglycolide, a segment of polycaprolactone or the like, a portion near the central compound is an amorphous segment, and a portion far from the central compound is a semicrystalline segment. Has a special structure. The hard resin foam is degradable and has a density of 320 mg / cm ³
The following is preferred as an environmentally friendly heat insulating agent.

JP-A-59-86621 JP-A-59-86621 (Japanese Patent Publication No. 3-76321,
Registration No. 172368) (Inventors; Masahiro Asami, Okitsu)
Kiyo, Yoshiaki Okumura, Hajime Namikoshi, Masatoshi Mikumo and Masaharu Watanabe (Applicant; Daicel Chemical Industries, Ltd.) to conduct ring-opening polymerization of a cyclic ester by adding a ring-opening polymerization catalyst in the presence of a cellulose derivative. Discloses a technique for obtaining a graft polymer having excellent transparency and film forming properties. Here, the cellulose derivative has good solubility in an organic solvent,
Cellulose esters are preferred from the viewpoint of being relatively inexpensive and easily available industrially, and among these, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are more preferred from the viewpoint of operability. As the cyclic ester, it is advantageous to use ε-caprolactone, which is easily available industrially, is relatively inexpensive, and has excellent compatibility with cellulose derivatives.

As described above, JP-A-59-86621 discloses a technique relating to a method for producing a graft copolymer in which ε-caprolactone is graft-copolymerized with a cellulose ester. However, JP-A-59-86
In the production method disclosed in No. 621, the produced graft copolymer becomes cloudy due to the graph of ε-caprolactone and the properties of the chain, and a highly transparent graft copolymer cannot be obtained. However, there is a problem that the glass transition temperature is low and the thermal properties are not sufficient.

JP-A-58-225101 JP-A-58-225101 (Japanese Patent Publication No. 1-38402)
No. 1555484) (Inventors: Hajime Namakoshi, Yoshiaki Okumura and Tsuyoshi Seiki, Applicant: Daicel Chemical Industries, Ltd.)
By reacting cellulose with a specific esterifying agent such as glycolide or ε-caprolactone in an organic solvent such as N, N-dimethylacetamide in the presence of an esterification promoting catalyst such as sodium hydroxide. A technique for efficiently obtaining a cellulose ester derivative having a novel specific chemical structure which is solvent-soluble and has a thickening effect is disclosed. The cellulose ester derivative is prepared from water or D
It has solubility in MF and the like, is useful as a coating agent, a thickener, and a protective colloid, and can be applied to a dye field by reacting with isocyanate. As described above, JP-A-58-225101 discloses a technique relating to a method for producing a lactide-based graft copolymer in which lactide is graft-copolymerized to cellulose.
However, in the production method disclosed in JP-A-58-225101, since cellulose is insoluble in lactide or an organic solvent, ring-opening graft copolymerization initially starts with a heterogeneous reaction, and the progress of the reaction is slow. The copolymer obtained is not transparent. In addition, the reaction temperature is high and the cellulose is sometimes colored, so that a copolymer having excellent transparency cannot be obtained.

JP-A-6-287279 JP-A-6-287279 (inventor: Hiroshi Ebato and Yoichi Murakami, applicant: Dainippon Ink and Chemicals, Inc.) reacts a lactide with a cellulose ester or cellulose ether. A method for producing a lactide-based graft copolymer is disclosed. This technique is disclosed in JP-A-59-86621 and JP-A-58-225101.
In view of the above problems, lactide, which has sufficient transparency, melting point required for molding and appropriate glass transition temperature when ring-opening graft copolymerization of lactide, which is a dimer of lactic acid, and cellulose ester or cellulose ether, is required. It is based on the finding that a graft copolymer can be obtained.
That is, this technique is characterized in that a lactide (A) and a cellulose ester or a cellulose ether (B) are subjected to ring-opening graft copolymerization in the presence of an esterification catalyst (C). To provide a method for producing a lactide-based graft copolymer having excellent thermoplasticity and lamination properties.

Here, for example, (A) contains 90% or more of L-lactide in total lactide, and (B) has a degree of esterification in the range of 50% to 60% and a degree of polymerization of Is preferably 100 or more (for example, cellulose acetate), and as (C), tin octoate or the like can be suitably used.

[Problems of the prior art for adding a decomposable high molecular weight side chain to a polyfunctional center compound] The prior art for radially adding a polyfunctional center compound as described in (1) to (4) is disclosed in the present application. A ring-opening polymerization method of lactide using a polyhydric alcohol as an initiator, which has been known for a long time, is also included in the above prior art. In this method, when the addition amount of the polyhydric alcohol is increased, the molecular weight of the polymer does not increase, and there is a disadvantage that a polymer having practical strength is hardly obtained. On the other hand, it has been a major problem to obtain a polymer having a high molecular weight enough to add a polyhydric alcohol only to increase the melt tension and to give practical strength. Further, when a degradable high molecular weight side chain is added to a polysaccharide as a polyfunctional central compound, there is a problem that coloring is easy. Further, while the prior art is a star polymer or a graft polymer in which a high molecular weight side chain is introduced into a polyfunctional center compound, the degradable polymer of the present invention has a structure in which star polymers are further linked. In that it has the following.

[0013]

[Problems to be solved by the invention]

[Technical Thought of the Invention] The technique of imparting a decomposable high molecular weight side chain by ring-opening polymerization of lactide or lactone to a polyfunctional center compound is based on the fact that the equivalent ratio of a hydroxyl group or an amino group to a carboxyl group to react is from 1 In general, it is difficult to obtain a degradable polymer having a high molecular weight enough to show a high melt tension. In particular, the tendency increases as the amount of the multifunctional center compound increases. However, the decomposable polymer of the present invention contains a polyhydric alcohol having two or more hydroxyl groups as the third component in order to make the equivalent ratio of the hydroxyl group and the carboxyl group to react close to one, so that three or more A high molecular weight degradable polymer can be obtained regardless of the amount of the polycarboxylic acid compound having a carboxyl group and / or an acid anhydride thereof.

Further, by connecting star polymers having a decomposable high molecular weight side chain at the terminal of a carboxyl group with a polyhydric alcohol having two or more hydroxyl groups, the molecular weight can be easily increased, and high melt tension can be obtained. It has become possible to obtain a degradable polymer having the following formula:

[0015] The present invention relates to a method for preparing a polyfunctional central compound known in the prior art by adding a cyclic monomer such as lactide (ie, a cyclic dimer of lactic acid) or a lactone (eg, ε-caprolactone). An object of the present invention is to obtain the following degradable polymer by further developing the technology of ring-opening polymerization. Significantly less coloring than when polysaccharides are used for the polyfunctional center compound. Higher melt tension than ordinary aliphatic polyester. It is excellent in molding process (foam molding etc.) as compared with ordinary aliphatic polyester. It has the same or higher transparency than ordinary aliphatic polyesters.

[0016]

Means for Solving the Problems In view of the above-mentioned problem to be solved by the present inventors, the present inventors have conducted intensive studies and as a result, as a component (A), a cyclic dimer of hydroxycarboxylic acid And / or lactones, as a component (B), a polyvalent carboxylic acid compound having three or more carboxyl groups and / or an acid anhydride thereof, and as a component (C), 2
By reacting in a reaction system containing a polyhydric alcohol having at least two hydroxyl groups and a catalyst as component (D), the color is significantly colored as compared with the case where a polysaccharide is used as a polyfunctional center compound. Less is. Higher melt tension than ordinary aliphatic polyester. It is excellent in molding process (foam molding etc.) as compared with ordinary aliphatic polyester. It has the same or higher transparency than ordinary aliphatic polyesters. It has been found that a decomposable polymer having the following characteristics can be obtained, and the present invention has been completed. The present invention is specified by the following items [1] to [10].

[1] As the component (A), a cyclic dimer and / or lactone of a hydroxycarboxylic acid, and as the component (B), a polycarboxylic acid compound having three or more carboxyl groups and / or an anhydride thereof. A method for producing a decomposable polymer, comprising reacting in a reaction system comprising a product, a polyhydric alcohol having two or more hydroxyl groups as component (C), and a catalyst as component (D).

[2] The weight of the component (B) is
Is equivalent to 0.005 to 1%, based on the weight of the polymer assuming that the polymer has completely polymerized alone, and the carboxyl group of component (B) and the hydroxyl group of component (C) The method for producing a degradable polymer according to [1], wherein the equivalent ratio is 100: 50 to 200.

[3] The component (B) according to [1] or [2], wherein the “polycarboxylic acid compound having three or more carboxyl groups and / or an anhydride thereof” includes a linear compound. A method for producing a degradable polymer.

[4] The component according to any one of [1] to [3], wherein the "polycarboxylic acid compound having three or more carboxyl groups and / or an anhydride thereof" of the component (B) contains a cyclic compound. A method for producing the described degradable polymer.

[5] The “catalyst” of the component (D) is (d-
1) Tin catalyst, (d-2) zinc-based catalyst, and (d-
3) The method for producing a decomposable polymer according to any one of [1] to [4], wherein the method includes at least one selected from the group consisting of titanium-based catalysts.

[6] The degradable polymer according to any one of [1] to [5], wherein the cyclic dimer of hydroxycarboxylic acid of the component (A) contains lactide which is a cyclic dimer of lactic acid. Manufacturing method of coalescence.

[7] A degradable polymer obtained by the production method according to any one of [1] to [6].

[8] A degradable polymer having a melt tension of 0.7 g or more at a melt flow index of 10 g / 10 minutes, obtained by the production method according to any one of [1] to [6].

[9] A degradable polymer having a structure in which a star-shaped polymer comprising a hydroxycarboxylic acid and a polyvalent carboxylic acid compound having three or more carboxyl groups is linked by a polyhydric alcohol having two or more hydroxyl groups. Coalescing.

[10] A foam comprising the degradable polymer according to any one of [7] to [9].

[0027]

DETAILED DESCRIPTION OF THE INVENTION For example, a high molecular weight decomposable polymer is obtained by reacting lactide, butanetetracarboxylic acid and 1,4-butanediol in the presence of a catalyst. Since the united product has a high melt tension, it is suitable for obtaining a processed product such as a foam or a molded product obtained by blow molding. In the present application, when the cited documents and the cited ranges are explicitly indicated, all of the descriptions are part of the disclosure of the specification of the present application and refer to the explicitly cited ranges, unless otherwise specified. In view of the matters or disclosures described in the application specification, those matters or disclosures can be directly and uniquely derived by those skilled in the art.

[Concept of word used in claims and specification of this application] (1) Concept of word "decomposability" Concept of word "decomposable" used in claims and specification of this application For organic materials, the characteristics of the organic materials shall be maintained during the period of use for the specified purpose, and after the end of the purpose or after disposal, the materials will be weakened and detoxified in the natural environment or in vivo environment. It also includes functions that perform The concept of the term “degradable” used in the claims and the specification of the present application includes, for example, “New Edition Polymer Dictionary (edited by The Society of Polymer Science, Asakura Shoten, Tokyo, 1988).
Year) ”, page 424, right column to page 425, left column,“ disintegrable polymer ”. The concept of the term “degradable” used in the claims and the specification of the present application includes, for example, “New Edition Polymer Dictionary (edited by the Society of Polymer Science, Asakura Shoten, Tokyo, 1988)”.
The concept of “photodegradability” described in the section of “photodegradability” on the left column on page 369 is also included. The concept of the term “degradable” used in the claims and the specification of the present application includes, for example, “MARUZEN High Polymer Dictionary-Conc”.
is Encyclopedia of Polym
er Science and Engineerine
g (edited by Kroschwitz, edited by Tatsuta Mita, Maruzen, Tokyo, 1994) ”. The concept of“ biodegradable ”described in the section“ Biodegradable polymer ”in the left column on page 539 to the right column on page 540 is also used. Include. The concept of the term "degradable" as used in the claims and specification of the present application includes:
It also encompasses the concept of "composable". `` Evaluation of degradability includes, for example, an embedding test in soil, a decomposition test by a cultured microorganism, a decomposition test by an enzyme preparation, an in-vitro decomposition test in serum, an in-vivo decomposition test by in vivo implantation, It can be evaluated by a light irradiation test or the like, and more specifically, for example, by ASTM D5209-91 (biodegradability test) or ASTM D5338-92 (compostability (soil regression performance) test). Can be.

(2) Concept of the term "aliphatic" The concept of the term "aliphatic" used in the claims and the specification of the present application includes not only aliphatic in a narrow sense but also substantially aromaticity. But also low aliphatics. The term "aliphatic" compound as used in the claims and specification of the present application includes the concept of "substantially aromatic" having a divalent hydrocarbon group containing at least one carbon atom in the molecule. And specifically includes not only an aliphatic group in a narrow sense, but also an alicyclic group having a substantially low degree of aromaticity, a group obtained by combining them, or a group having a hydroxyl group or a nitrogen group. , Sulfur, silicon, phosphorus and the like, and also includes a group consisting of compounds having a divalent residue in a molecule. , A cycloalkyl group, an allyl group, an alkoxyl group, a cycloalkoxyl group, an allyloxyl group, and a compound having a group substituted with a halogen (F, Cl, Br, etc.) group in the molecule. By appropriately selecting these substituents, various properties (heat resistance, toughness, degradability, strength properties, elongation properties, etc.) of the decomposable polymer according to the present invention can be controlled. The term "aliphatic" compound as used in the claims and specification of the present application includes not only one compound but also a combination of two or more compounds.

(3) Concept of the word “foam” The concept of the term “foam” used in the claims and the specification of the present application includes many voids (bubbles, voids, microvoids) inside a resin. , Cavity, etc.)
Is present, in the apparent density of the resin, in the continuous phase of the resin,
Includes a resin structure having a two-phase structure or a multi-phase structure in which a void phase (including continuous or independent air) is mixed. For example, a polymer having a cellular structure, a foamed polymer, It also includes those generally recognized as structures such as molecules, polymer foams, and polymer foams, and also includes soft and hard structures. The foam containing the decomposable polymer according to the present invention can be produced by a known / public method. For example, "MARUZEN High Polymer Dictionary-Concise
Encyclopedia of Polymer
Science and Engineering (K
Roschwitz, translated by Tatsuta Mita, Maruzen, Tokyo, 1
994) ", pp. 811 to 815, and a foaming agent and a foaming technique can be suitably used.

(4) Concept of the word "yarn" The concept of the word "yarn" used in the claims and specification of the present application is described in Textile Handbook, edited by Textile Society, edited by Maruzen, Tokyo, 1969. -It also includes the concept of "raw yarn" described on pages 393 to 421, and includes, for example, monofilament, multifilament, staple fiber (swoof), tow, high bulk swoof, high bulk tow, spun yarn, blended yarn, processed yarn, temporary yarn. Twisted yarn, irregularly shaped yarn, hollow yarn, conjugate yarn, POY (partially oriented yarn), DR
Y (stretched yarn), POY-DTY, sliver, and the like are also included.

(5) Concept of the word “textile” The concept of the word “textile” used in the claims and the specification of the present application includes woven fabric, knitted fabric, nonwoven fabric, and the like.
Braids including strings and ropes, cottony high bark swoosh, slivers,
It includes those generally recognized as fibrous structures such as porous sponges, felts, papers, nets and the like.

(6) The term “star-shaped polymer (star-sh)
The concept of the word "apped polymer" is described in, for example, "Star Polymer" on the right column on page 432 of "New Edition Polymer Dictionary (edited by the Society of Polymer Science, Asakura Shoten, Tokyo, 1988)" Embrace the concept being In general, it means a branched polymer in which three or more linear polymers having substantially the same length (same molecular weight) are bonded to the central compound. Generally, the primary structure of a star-shaped polymer compound can be evaluated by the degree of branching and the molecular weight.

[Component (A) cyclic dimer and / or lactone of hydroxycarboxylic acid] The cyclic dimer and / or lactone of hydroxycarboxylic acid of the component (A) is not particularly limited. Preferred examples include lactide, which is a cyclic dimer of lactic acid, glycolide, which is a cyclic dimer of glycolic acid, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and the like. Lactide is preferred from the viewpoint of transparency of the decomposable polymer obtained. These hydroxycarboxylic acid cyclic dimers and / or lactones may be used alone or in combination of two or more. However, two or more kinds of hydroxycarboxylic acid cyclic dimers and / or lactones may be used. When used in combination, it is preferable that the polymer contains lactide (combination of lactide and other cyclic dimer of hydroxycarboxylic acid and / or lactone) from the viewpoint of transparency of the obtained degradable polymer.

When the molecule has an asymmetric carbon such as lactide, there are D-form, L-form and meso-form, and any of them can be used. Among them, L-lactide is particularly preferred.

[Component (B) a polyvalent carboxylic acid compound having three or more carboxyl groups and / or an anhydride thereof] The polyvalent carboxylic acid compound having three or more carboxyl groups and / or the component (B) The acid anhydride is not particularly limited, but specific examples include a linear compound and a cyclic compound. The acid anhydride of the polycarboxylic acid compound having three or more carboxyl groups of the component (B) is:
It may have an anhydride bond in the molecule, or may have an anhydride bond between the molecules to be cyclic or linear. When it has an anhydride bond between molecules, it may be a dimer or higher oligomer or a polymer. Specific examples of cyclic compounds Specific examples of cyclic compounds include, for example, 1, 2, 3, 4
-Cyclopentanetetracarboxylic acid, 1,2,3,4
5,6-cyclohexanehexacarboxylic acid, tetrahydrofuran-2R, 3T, 4T, 5C-tetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid,
1,3,5-cyclohexanetricarboxylic acid, 2,3
4,5-furantetracarboxylic acid, 2-methyl-3,
Aliphatic polycarboxylic acids having three or more carboxyl groups such as 4,6-pyridinetricarboxylic acid, aromatic polycarboxylic acids having three or more carboxyl groups such as trimellitic acid and pyromellitic acid, and These acid anhydrides are mentioned. These can be used alone or in combination of two or more. In the case where the molecule has an asymmetric carbon in the molecule, there are D-form, L-form and an equivalent mixture thereof (racemic form), and any of them can be used. Specific examples of the linear compound Specific examples of the linear compound include, for example, butane-1,
2,3,4-tetracarboxylic acid, meso-butane-
1,2,3,4-tetracarboxylic acid, 1,3,5-pentanetricarboxylic acid, 2-methylpropanetricarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,1,2
Aliphatic polycarboxylic acids having three or more carboxyl groups, such as ethanetricarboxylic acid and 1,2,4-butanetricarboxylic acid, and acid anhydrides thereof.
These can be used alone or in combination of two or more. When the compound has an asymmetric carbon in the molecule, D-form, L-form and an equivalent mixture thereof (racemic form)
Exist, but any of them can be used.

[Linear Oligo or Poly Acid Anhydrides (Anhydrides)] In the present specification, the term "linear" includes not only linear but also three or more components (B). Oligo or poly acid anhydrides (anhydrides) of a dimer or more on the line of a polycarboxylic acid compound having a carboxyl group
Form a macrocycle. Further, a copolymerized linear condensate of a polyvalent carboxylic acid compound having three or more carboxyl groups of two or more components (B) can also be used. Here, “linear” has the opposite concept of “small ring”, but does not have the opposite concept of “branched”. Therefore, in the specification of the present application, the concept of "linear" is a concept that is not "small ring" to the last, that is, "linear", linear, macrocyclic, branched It includes any primary or higher-order structure such as a shape, a branch, a star, a three-dimensional network, and an IPN (inter penetrated network). The concept of the term "linear anhydride of a polycarboxylic acid compound" includes "polymeric polyanhydride",
“Polymeric anhydride containing a polymer skeleton containing an acid anhydride group and a plurality of acid functional groups”, “polyanhydride of carboxylic acid”, “polymeric po”
lyanhydride "," polymeric p
olyanhydride containing s
nhydride links in the the
polymeric backbone "," poly
meric polycarboxylic acid
s containing anhydride li
nkages in the polymeric b
ackbone "and" polyanhydride "
of carboxylic acids "and the like.

As used herein, “anhydride”,
The concepts of the terms "anhydride group", "anhydride bond" and "polyanhydride" include "MARUZEN Polymer Encyclopedia-Concise Encyclopedia".
a of PolymerScience and E
Nginering (edited by Kroschwitz, translated by Tatsuta Mita, Maruzen, Tokyo, 1994) ", 996-99
The concept for each word described in the section “Polyanhydride” on page 8 is also included. Polyanhydride has been studied vigorously by MIT researchers in the early 1980s, when research and development on biodegradable bio (medical) polymer materials and application of the materials to drug delivery systems was vigorous. It became so. An acid anhydride (anhydride) of a linear oligo or poly polycarboxylic acid compound can be synthesized by, for example, a method such as melt polycondensation, solution polycondensation, and interfacial polycondensation.

[Component (C) Polyhydric alcohol having two or more hydroxyl groups] The polyhydric alcohol having two or more hydroxyl groups of the component (C) is not particularly limited. Specific examples of the polyhydric alcohol having two or more hydroxyl groups of the component (C) include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4- Butanediol, 3-methyl-1,5
-Pentanediol, 1,6-hexanediol, 1,
7-heptanediol, 1,8-octanediol,
1,9-nonanediol, neopentyl glycol,
Examples thereof include 1,4-cyclohexanedimethanol, glycerin, pentaerythritol, dipentaerythritol, trimethylolpropane, trimethylolethane, and inositol. These can be used alone or in combination of two or more. When the molecule has an asymmetric carbon in the molecule, there are D-form, L-form and an equivalent mixture thereof (racemic form), and any of them can be used.

[Component (D) Catalyst] In the method for producing a decomposable polymer according to the present invention, the catalyst of component (D) is not particularly limited as long as it substantially accelerates the progress of the reaction.

Specific Examples of the Catalyst of Component (D) Specific examples of the catalyst of Component (D) include, for example, Periodic Table I
Examples include metals of Group I, III, IV, and V, oxides thereof, and salts thereof. More specifically, metals such as zinc powder, tin powder, aluminum and magnesium, stannous oxide, antimony oxide, zinc oxide, aluminum oxide, magnesium oxide, metal oxides such as titanium oxide, stannous chloride, chloride Stannic, stannous bromide, stannic bromide, antimony fluoride, zinc chloride, magnesium chloride, metal halides such as aluminum chloride, tin sulfate, zinc sulfate, sulfates such as aluminum sulfate, magnesium carbonate, Carbonates such as zinc carbonate, organic carboxylate such as tin acetate, tin octoate, tin lactate, zinc acetate, aluminum acetate, tin trifluoromethanesulfonate, zinc trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, methanesulfonic acid ,
organic sulfonates such as tin p-toluenesulfonate;
Examples include sulfonic acids such as toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, and acids, and zinc borate. Other examples include an organic metal oxide of the above metal such as dibutyltin oxide, a metal alkoxide of the above metal such as titanium isopropoxide, or an alkyl metal of the above metal such as diethyl zinc. These can be used alone or in combination of two or more. Use Amount of Catalyst of Component (D) The use amount of the catalyst of component (D) is not particularly limited as long as it substantially accelerates the reaction rate. The amount of the catalyst used is generally 0.000% of the cyclic dimer of hydroxycarboxylic acid and / or the lactone of component (A).
The content is preferably in the range of 1 to 5% by weight.
The range is more preferably from 0.001 to 1% by weight.

[Reaction and Reaction Method] In the method for producing a decomposable polymer according to the present invention, as the component (A), a cyclic dimer and / or lactone of hydroxycarboxylic acid, and as the component (B), three Reaction in a reaction system containing the above polycarboxylic acid compound having a carboxyl group and / or an acid anhydride thereof, a polyhydric alcohol having two or more hydroxyl groups as a component (C), and a catalyst as a component (D). This method may be performed by any method. Usually component (A),
(B), (C), and (D) are charged at once and polymerization is carried out by a ring-opening polymerization method. Two types of cyclic dimer and / or lactone of hydroxycarboxylic acid of component (A) are used. When used in combination, the component (A) may be dividedly charged during the reaction for the purpose of controlling the physical properties of the obtained degradable polymer.

[Composition of Component (B) and Component (C)] The composition of the degradable polymer according to the present invention is such that the weight of the component (B) is
It is equivalent to 0.005 to 1%, preferably 0.01 to 0.5%, based on the weight of the weight assuming that the component (A) is completely polymerized alone, and The equivalent ratio of the carboxyl group of the component (B) to the hydroxyl group of the component (C) is 100: 50 to 200, preferably 100: 80.
~ 120, more preferably 100: 90 ~ 110. When the weight of the component (B) is 0.
If the content is less than 005%, the resulting decomposable polymer tends to have insufficient melt tension. When the weight of the component (B) exceeds 1%, the attained molecular weight tends to be low due to the effect of water produced as a result of the reaction, and it tends to be difficult to obtain a degradable polymer having practical strength. When the equivalent ratio of the carboxyl group of the component (B) to the hydroxyl group of the component (C) is out of the above range, the resulting decomposable polymer does not have sufficient melt tension or the molecular weight of the polymer does not increase, There is a tendency that it becomes difficult to obtain a degradable polymer having practical strength.

[Operation in Reaction] In the method for producing a decomposable polymer according to the present invention, the reaction is preferably carried out in a vacuum or in an atmosphere of an inert gas such as nitrogen or argon so that moisture does not enter from outside the system. Alternatively, the reaction may be performed while replacing with an inert gas or while bubbling with an inert gas. The method for producing a decomposable polymer according to the present invention includes the step of subjecting component (A) to ring-opening polymerization in the presence of catalyst (D),
It can be produced by simultaneously polymerizing the component (B) and the component (C). The reaction is usually performed in a molten state,
The reaction can be carried out by solid-phase polymerization. In the method for producing a degradable polymer according to the present invention, the reaction is:
It can be performed in either a continuous operation or a batch operation.

[Reaction temperature] In the present invention, when solid phase polymerization is carried out, the reaction temperature is set so that the degradable polymer which may be present in the reaction system substantially proceeds in the solid state while maintaining the progress of the reaction. There is no particular limitation as long as it can be maintained. Specifically, the reaction is performed at a temperature not higher than the melting point of the decomposable polymer present in the reaction system, but it is preferable that the reaction is performed at a temperature in the range from 100 ° C. to the melting point. In the present invention, when performing the melt polymerization, the reaction temperature is not particularly limited as long as the progress of the reaction can be maintained while the decomposable polymer which may be present in the reaction system is maintained in a substantially molten state. Specifically, the reaction is performed at a temperature equal to or higher than the melting point of the degradable polymer present in the reaction system,
The reaction is preferably performed in a temperature range from the melting point to 250 ° C.

[Recovery Method of Reaction Product (Degradable Polymer)] The method employed in the present invention for recovering the degradable polymer as a reaction product after the completion of the reaction substantially removes the reaction product to a desired purity. There is no particular limitation as long as it can be recovered at The method for recovering the reaction product may be any of known and public methods. As a specific example of the recovery method, for example, a method of obtaining a decomposable polymer by removing unreacted raw materials and components having a low boiling point from a reaction product in a molten state under reduced pressure, extracting the same, and cooling it. Alternatively, the reaction product is heated and dissolved in a solvent to precipitate by cooling, or the reaction product is dissolved in a good solvent and precipitated in a poor solvent, and then further dried under reduced pressure while heating. Can be

[Control of Molecular Weight and Molecular Weight Distribution of Degradable Polymer] The weight average molecular weight and molecular weight distribution of the degradable polymer according to the present invention are determined by the type and amount of the catalyst, the reaction temperature, the reaction time, and the component (B). Reaction conditions such as the addition amount of “a polycarboxylic acid compound having three or more carboxyl groups and / or an anhydride thereof” and the addition amount of “polyhydric alcohol having two or more hydroxyl groups” of component (C) are set. By appropriate selection, it can be controlled to a desired one. The weight average molecular weight of the degradable polymer according to the present invention is generally about 5
It is preferably in the range of from 000 to 1,000,000, more preferably in the range of from 100,000 to 1,000,000, and more preferably from 200,000 to 1,000,000
Those in the range are particularly preferred.

[Degradable Polymer] The degradable polymer according to the present invention is characterized in that it is less likely to be colored than a polymer obtained by adding a degradable high molecular weight side chain to a polysaccharide. The degradable polymer according to the present invention is characterized in that it has high transparency equal to or higher than that of a normal aliphatic polyester. The decomposable polymer according to the present invention is characterized by a remarkably high melt tension as compared with a normal aliphatic polyester. As a result, the moldability has been greatly improved, and it has become possible to produce various types of molded products. The degradable polymer of the present invention can obtain a degradable polymer having desired physical properties depending on the type and composition of hydroxycarboxylic acid as a constituent component of the side chain. At this time, the polyhydroxycarboxylic acid component constituting the side chain may be a homopolymer (homopolymer) or a copolymer (copolymer). In the case of a copolymer, the arrangement mode is random copolymer , Cross-copolymer,
Either a block copolymer or a graft copolymer may be used.
The structure of the polyhydroxycarboxylic acid constituting the side chain is not particularly limited. The decomposable polymer of the present invention includes a polyfunctional central compound (a polycarboxylic acid compound having three or more carboxyl groups and / or an anhydride thereof).
Has a structure in which star polymers formed by adding degradable high molecular weight side chains (polyhydroxycarboxylic acid) to each other are connected by an aliphatic polyhydric alcohol having two or more hydroxyl groups. It is considered that the high melt tension described above was developed.

[Melt Tension] For the evaluation method of the melt tension, see, for example, “Plastic Processing Technology Handbook”.
(Edited by The Society of Polymer Science, published by Nikkan Kogyo Shimbun, 19
This is described in detail in the section “(2) Melt tension” on pages 1414 to 1416. The melt tension is a tension necessary for stretching a strand extruded from a melt indexer at a constant speed to a constant yarn diameter by a melt tension measuring device, and is measured at a test temperature corresponding to an actual molding temperature. In general, when the melt tension is large, bubble stability in inflation molding is good, and drawdown in blow molding is small. In addition, there is a neck-in phenomenon in which the width of a film formed as a product in sheet and cast film molding is narrower than the exit width of the die. The amount of neck-in also has a close relationship with the melt tension. The melt tension of the decomposable polymer according to the present invention is as follows: the "polyvalent carboxylic acid compound having three or more carboxyl groups and / or an anhydride thereof" of the component (B), and the "two or more polycarboxylic acid compounds of the component (C)". It can be controlled to a desired one by the kind and amount of the “aliphatic polyhydric alcohol having a hydroxyl group”. As for the melt tension of the decomposable polymer according to the present invention, the melt flow index is measured at two appropriate temperatures using a load of 2160 g. Find the temperature,
When the melt tension is measured at that temperature, the value is preferably 0.7 g or more.

[Uses of Degradable Polymer] The degradable polymer according to the present invention may be used in medical applications known and used before the present application,
It can be suitably used as a substitute for a resin used for food packaging or for general use.

[Method for Forming Degradable Polymer According to the Present Invention] The method for forming the degradable polymer according to the present invention is not particularly limited, but specific examples include injection molding, extrusion molding, inflation molding, and extrusion. Hollow molding, foam molding, calender molding, blow molding, balloon molding, vacuum molding, spinning, and the like are preferred, and inflation molding, blow molding, extrusion hollow molding, foam molding, vacuum molding, and spinning are particularly preferred. In addition, the degradable polymer can be formed by an appropriate molding method, for example, a member of a writing implement such as a ball-point pen, a mechanical pen, a pencil, a member of a stationery, a golf tee, a member of a smoking ball for a starting ball, and a drug for oral medicine. Capsules, carrier for anal / vaginal suppositories, carrier for skin and mucous membrane patch, pesticide capsule, fertilizer capsule, seedling capsule, compost, fishing line spool, fishing float, fishing bait, lure, fishing buoy It can also be suitably used as a hunting decoy, a hunting shot capsule, camping equipment such as tableware, nails, piles, binding materials, non-slip materials for muddy and snowy roads, blocks and the like. Degradable polymer according to the present invention,
Appropriate forming methods include, for example, lunch boxes, tableware, containers for lunch boxes and prepared dishes, chopsticks, split chopsticks, forks, spoons, skewers, toothpicks, cups for ramen, drink vending machines Containers and trays for foods such as cups, fresh fish, meat, fruits and vegetables, tofu, prepared foods, etc., bottles for torobaco used in the fresh fish market, dairy products such as milk, yogurt, lactic acid bacteria drinks etc. , Bottles for soft drinks such as carbonated drinks and soft drinks, bottles for alcoholic drinks such as beer and whiskey, bottles with or without pumps for shampoo and liquid soap, tubes for toothpaste, cosmetic containers, detergent containers, bleaching Agent container, cool box, flowerpot, casing of water purifier cartridge, casing of artificial kidney and artificial liver, etc.
Syringe parts, cushioning materials for transporting home appliances such as televisions and stereos, cushioning materials for transportation of precision occasions such as computers, printers and clocks, and ceramic products such as glass and ceramics. It can also be suitably used as a buffer for transportation.

[Production and Film Production of Films and Sheets] The decomposable polymer according to the present invention is suitable for processes requiring the strength of a molten polymer such as blow molding, foam molding and extrusion molding. For example, in the case of a sheet formed by extrusion molding, there is a feature that the decrease in the sheet width due to the dripping of the molten sheet and neck-in is small.

Production Technology Films and sheets containing the degradable polymer according to the present invention are:
It can be manufactured by a known or publicly used extrusion method, coextrusion method, calender method, hot press method, solvent casting method, inflation method, balloon method, tenter method and the like. Thermal properties, molecular structure,
Manufacturing conditions are set in consideration of crystallinity and the like.

Additives Additives (antioxidants, heat stabilizers, UV stabilizers, lubricants,
Fillers, anti-adhesives, anti-statics, surface wetting improvers, incineration aids, anti-slip agents, pigments, etc.), extrusion conditions, stretching conditions, etc., can be selected appropriately according to the purpose to obtain desired physical properties. A film or sheet containing the decomposable polymer according to the present invention, having properties such as gas barrier properties, optical properties, transmitted light wavelength spectrum, light blocking properties, and oil resistance, can be produced.

Process Design In the manufacturing process, the uniaxial stretching ratio, the biaxial stretching ratio, the number of stretching steps, the heat treatment temperature, the rate of change of the heat treatment temperature, the number of cooling rollers, the arrangement of the cooling rollers, the winding type around the cooling rollers, the cooling Conditions such as the roller temperature and the degree of mirror finish of the cooling roller surface can be appropriately set according to the purpose.

Method of Quality Control In the manufacturing process, by using known and publicly-known measuring optical methods using radiation, electromagnetic waves, light, ultrasonic waves, etc., the data of the thickness of the product is detected and the data is detected. Is fed back to the manufacturing process, so that the thickness variation of the product can be quality controlled manually or automatically. The measurement optical method using radiation includes, for example, a method using a transmission (absorption) or scattering type alpha-ray thickness meter, beta-ray thickness meter, or gamma-ray thickness meter. Known and publicly used radioisotopes are used.

Methodology of Post-Processing Step and Finishing Step In the post-processing step or finishing step, welding,
Heat sealing, perforation, primer application, adhesive application, chemical application, parkerizing, vapor deposition, sputtering, CVD, coating, etching, spraying,
Dyeing, painting, electrostatic painting, air brushing, laminating, sandwiching, embossing, embossing, embossing, corrugating, printing, transfer, sanding, sandplast, shearing, punching, punching, honeycomb structure, corrugated cardboard structure Post-processing and finishing such as formation and formation of a laminate can also be performed. In the post-treatment process or finishing process, depending on the purpose, calendering method, extrusion method, screen printing method, gravure printing method, letterpress method, intaglio method, doctor blade method, immersion method, spray method, air brush method, electrostatic coating A publicly known / public method such as a law can be adopted. The film or sheet containing the degradable polymer according to the present invention,
A laminate having a multilayer structure can also be formed by laminating or laminating a sheet of another material such as paper or another polymer.

Methodology of Extrusion Method or Coextrusion Method In the extrusion method or coextrusion method, a T die, an inflation die (circular die), a flat die, a feed block / single manifold die or a single manifold die combining several feed blocks. Known or public dies can be used. In the coextrusion method, a multilayer film can be produced by using a plurality of the polymers having different properties and / or other polymers. When the inflation method or the balloon method is adopted, biaxial simultaneous stretching can be performed, so that a durable product having low elongation, high elastic modulus, and high toughness can be manufactured with high productivity and relatively low cost. It can be made and has a bag-like (seamless) shape, so it can be used in supermarket take-out bags, bags to prevent water condensed in low-temperature food packs such as frozen foods and meat, and compost bags. Suitable for production of bags and bags. By combining with a coextrusion method, a multilayer film can be manufactured with high productivity using a plurality of degradable polymers and / or other types of polymers according to the present invention having different properties. It is also possible to combine the inflation method or the balloon method with the coextrusion method. The film or sheet containing the degradable polymer according to the present invention,
By setting the process conditions according to the purpose, it can be manufactured in a roll shape, tape shape, cut sheet shape, plate shape, bag shape (seamless shape).

Secondary Processing The film or sheet containing the degradable polymer according to the present invention can exhibit characteristics that are difficult to be satisfied with polyhydroxycarboxylic acid alone. For example, in the case of polyhydroxycarboxylic acid alone, since the drawdown property is large, the range of selection of molding processing conditions such as a processing temperature and a molding cycle is relatively narrow. In contrast, in the case of the degradable polymer according to the present invention, since the drawdown property is small, the range of selection of molding processing conditions such as a processing temperature and a molding cycle is relatively wide. Therefore, the film or sheet containing the decomposable polymer according to the present invention is a so-called secondary processing, which imparts a secondary, tertiary or higher-order shape such as stretching, blow processing, and vacuum forming. It is a suitable material.

Specific Examples of Use The film or sheet containing the degradable polymer according to the present invention can be used for shopping bags, garbage bags, compost bags,
Cement bags, fertilizer bags, food and confectionery packaging films, food wrap films, agricultural and horticultural films, greenhouse films, films for magnetic tape cassette products such as video and audio, films for floppy disk packaging, fences, Marine, river and lake oil fences, adhesive tapes, tapes, binding materials, waterproof sheets, bulks,
It can be suitably used as a tent, a sandbag bag or the like. In addition, a film formed by extruding a polymer containing an inorganic substance such as calcium carbonate, barium sulfate, or titanium oxide can be further stretched to obtain a porous film having air permeability. It can be used for various packaging materials.

[Production of Seamless Pipe] A seamless pipe containing the degradable polymer according to the present invention can be produced by extrusion with a circular die. By combining with a co-extrusion method, a multilayer seamless pipe can be produced using a plurality of degradable polymers and / or other kinds of polymers according to the present invention having different properties.

[Manufacture of squares and rounds] Squares and rounds containing the degradable polymer according to the present invention can be manufactured by extrusion with a die. By combining with the coextrusion method, it is also possible to produce a square or round material having a multilayer structure cross section by using a plurality of degradable polymers and / or other kinds of polymers according to the present invention having different properties. By combining with such a coextrusion method, for example, square or round materials having a specific cross-sectional structure and cross-sectional contour, such as Kintaro candy, Naruto winding, and Date winding, can also be manufactured.

[Foam] The concept of the word "foam" As already mentioned, the concept of the word "foam" used in the claims and specification of the present application includes many parts inside the resin. Voids (including air bubbles, voids, microvoids, and cavities), low apparent density, and a continuous phase of resin mixed with void phases (including voids that are continuous and independent) Includes a resin structure having a two-phase structure or a multi-phase structure, and is recognized as a structure such as a polymer having a cellular structure, a foamed polymer, an expanded polymer, a polymer foam, or a polymer foam. It includes general and also includes soft and hard materials.

Production of Foam The foam containing the degradable polymer according to the present invention can be produced by a known and publicly used method. For example, "MAR
UZEN High Polymer Dictionary-Concense Encycl
opedia of Polymer Science
and Engineering (Kroschwi
tz, translated by Tatsuta Mita, Maruzen, Tokyo, 1994) ”
Foaming agents and foaming techniques described on pages 811 to 815 can be suitably used. In addition, according to the regulations of the Montreal Protocol concerning the regulation of chlorofluorocarbons for protecting the ozone layer, a new or publicly-known or publicly-known foaming agent or foaming technology that meets the environmental regulation standards can be suitably used. Characteristics such as continuity, independence, size, shape, distribution, and size uniformity of the voids (including bubbles, voids, microvoids, and cavities) of the foam are appropriately adjusted according to the purpose. Can be controlled by setting.

Blowing agents Blowing agents include inert gases, chemical blowing agents that generate an inert gas when decomposed, hydrocarbons having 3 to 5 carbon atoms or chlorinated hydrocarbons, fluorocarbons, fluorocarbons, water, Includes nitrogen, LPG, LNG, low-boiling organic liquids, carbon dioxide, inert gases and the like. Examples of chemical blowing agents include sodium bicarbonate, dinitrosopentamethylenetetramine, sulfonyl hydrazide, azodicarbonamide, p
-Toluenesulfonyl semicarbazide, 5-phenyltetrazole, diisopropylhydrazodicarboxylase, 5-phenyl-3,6-dihydro-1,3,4-oxadiazin-2-one, sodium borohydride and the like. Examples of physical blowing agents include pentanes such as n-pentane, 2,2-dimethylpropane, 1-pentene, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, cyclohexane Hexanes, n-heptane, 2,2-dimethylpentane, 2,4-dimethylpentane, 3-ethylpentane, heptane such as 1-heptene, toluene, trichloromethane, tetrachloromethane, trichlorofluoromethane, methanol , 2-propanol, isopropyl ether, methyl ethyl ketone and the like. Examples of fluorocarbons include CFC-11, CFC-1
2, CFC series fluorocarbons such as CFC-113 and CFC-114.

General-purpose use The foam containing the degradable polymer according to the present invention may be, for example, a lunch box, tableware, a container for lunches and prepared foods, a cup for cup ramen, and a vending machine for beverages, which are sold at convenience stores. Containers and trays for foods such as cups, fresh fish, meat, fruits and vegetables, tofu, prepared foods, etc., containers for dairy products such as torobaco, milk, yogurt, lactic acid bacteria drinks used in the fresh fish market Used for transporting home appliances such as containers for carbonated drinks and soft drinks, containers for liquor drinks such as beer and whiskey, cosmetic containers, detergent containers, bleach containers, cool boxes, flower pots, tapes, televisions and stereos For transporting precision machinery such as computers, printers and watches, and for transporting optical machinery such as cameras, glasses, microscopes, and telescopes. Buffer material for use, glass, cushioning material for use in transportation of ceramic products such as ceramic, the light-shielding material, heat insulating material, can be suitably used as a soundproofing material.

Medical Use and Hygiene Use The foam containing the degradable polymer according to the present invention can be suitably used for medical or hygiene use. For example, bandage, carrier for patches for skin and mucous membranes, triangle bandage, plaster, towel, disposable towel, disposable wet towel, towel, rag,
Tissues, Wet tissues for cleaning and disinfection, Wet tissues for baby wipes of Akachan, Disposable diapers, Napkins for sanitary and vaginal use, Sanitary tampons, Tampons for blood absorption for surgery and birth, Sanitary cover stocks, Sterilization bags And the like. These medical or hygiene products are sterilized by heating or steam,
Sterilization with ethylene oxide gas, sterilization with hydrogen peroxide water or ozone, sterilization by irradiation of ultraviolet rays or electromagnetic waves, sterilization by irradiation of radiation such as gamma rays, and publicly and publicly used sterilization materials such as ethanol and benzalkonium chloride Depending on the method, it can be sterilized, sterilized or disinfected and then sterilely packaged. Further, by installing the process in a clean bench or a clean room where the HEPA filter can supply ultra-clean air in a laminar flow, the product can be manufactured and packaged in a sterile state and / or in an endotoxin-free state.

General Industrial Use and Recreational Use The foam containing the degradable polymer according to the present invention includes general industrial use including agriculture, fishing, forestry, industry, construction and civil engineering, transportation and transportation, and leisure and sports. It can be suitably used for recreational purposes. For example, agricultural cold gauze, oil absorbing material, soft ground reinforcement, artificial leather, floppy disk lining, sandbag bag, heat insulating material, soundproofing material, cushioning material, cushioning material for furniture such as bed and chair, cushioning material for floor , Packaging materials, binding materials, muddy
It can be suitably used as a non-slip material for snowy roads and the like.

[Spinning] Concept of "Yarn" As described above, the concept of the word "yarn" used in the claims and specification of the present application is based on the Textile Handbook / Processing Edition (edited by The Society of Textile Engineers, Maruzen, Tokyo, 1969) 393-
The concept of "raw yarn" described on page 421 is also included,
For example, monofilament, multifilament, staple fiber (staple), tow, high bulk staple, high bulk tow, spun yarn, blended yarn, processed yarn, false twisted yarn, irregular cross section yarn, hollow yarn, conjugate yarn, POY (partially oriented yarn), DTY (Drawn yarn), POY-DTY, sliver, and the like.

Production of Yarn (Spinning, Spinning) The degradable polymer according to the present invention is a material suitable for melt spinning and dry spinning. The degradable polymer according to the present invention is a yarn-forming condition, a spinning condition, a knitting condition, a post-treatment condition, a dyeing condition, and a processing condition, depending on the purpose, by appropriately setting a desired thickness, a cross-sectional shape, Fineness (tex, denier, count, etc.), physical properties and properties such as tensile strength and elongation, binding strength, heat resistance, degree of crimp, water absorption, oil absorption, bulkiness, waist strength, texture Can be processed into yarn or textile having

Production of Deformed Cross-Section Yarn, Multi-Layer Structure Yarn, and Hollow Fiber The degradable polymer according to the present invention has a hollow structure similar to the lumen structure of cotton by appropriately designing a spinneret. Fibers having a core-shell structure similar to the cuticle / cortex / medula coaxial three-layer structure of wool, fibers having a conjugate structure similar to the bilateral structure of wool, and triangular cross-sectional structure of silk Can be suitably spun into fibers having an irregular or polygonal cross section as represented by

Manufacturing a yarn having a multilayer structure cross section by using a plurality of degradable polymers and / or other types of polymers according to the present invention having different properties by spinning with a multilayer die (nozzle, orifice). Can also. With such a co-spun yarn, for example, a yarn having a specific cross-sectional layer structure and cross-sectional contour, such as Kintaro candy, Naruto winding, Date winding, Baum Kuchen, and the like can also be produced. By spinning with a hollow die (nozzle, orifice), a hollow fiber containing the degradable polymer according to the present invention can be manufactured. By combining with the co-spinning, a multilayer hollow fiber can be produced using a plurality of degradable polymers and / or other kinds of polymers according to the present invention having different properties. For example, hollow fibers filled with pigments in the voids can be applied to textiles that are impermeable even when wet with water, hollow fibers filled with liquid crystal in voids can be applied to textiles that change color depending on temperature, and ceramics or carbon can be used in the voids. The hollow fiber filled with black can be applied to a far-infrared absorbing endothermic textile, and the hollow fiber filled with lead in the void can be applied to a fishing net sinking in water.

Process Design In the spinning process, the conditions such as the shape and style of the spinneret, the draw ratio, the number of drawing steps, the heat treatment temperature, the rate of change of the heat treatment temperature, the application of crimping, and the treatment with an oil agent are appropriately set according to the purpose. can do.

Products From ultrafine fibers comparable to fibers constituting Exaine (registered trademark, Toray) or finer fibers, to ultrathick fibers or thicker fibers comparable to the thickness of woven fibers for fasteners Until then, a filament containing the degradable polymer according to the present invention having a desired fineness can be suitably produced.

[Manufacture of Textiles] Concept of “Textile” As described above, the concept of the term “textile” used in the claims and specification of the present application includes woven fabric, knitted fabric, non-woven fabric, and the like. It includes general braids including cords and ropes, fibrous structures such as cottony high bark slivers, slivers, porous sponges, felts, papers, and nets.

Production of Woven Fabrics By using known and public looms and shuttleless looms (water jet loom, air jet loom), filament yarn woven fabric, spun yarn woven fabric, stretch woven fabric, and industrial material woven fabric can be manufactured.

Manufacture of knits, braids, nets, etc. Using known and public knitting machines, knitting, weft knitting, circular knitting, vertical knitting, tricot, circular knit socks, seamless socks, tricot socks, lace, braids , Can manufacture netting.

Production of staple (staple fiber) The staple containing the degradable polymer according to the present invention can be mixed with other natural fiber, synthetic fiber and / or semi-synthetic fiber staple at any mixing ratio and at any staple diagram. It can be blended. The swoof containing the decomposable polymer according to the present invention can also be suitably used as a raw material for paper, a filler for composite materials, whiskers (cat whiskers) for composite materials, and fibers for FRP filling.

Production of Nonwoven Fabric The nonwoven fabric containing the degradable polymer according to the present invention can be produced by a known and publicly-known method. In the production of the nonwoven fabric containing the degradable polymer according to the present invention, for example, “MARU
ZEN High Polymer Dictionary-Concise Encyclopedia
pedia of Polymer Science
and Engineering (Kroschwit
z, translated by Tatsuta Mita, Maruzen, Tokyo, 1994) "・ 9
The production method described on pages 06 to 910 can be suitably employed. The production of the nonwoven fabric containing the degradable polymer according to the present invention includes, for example, a dry-card method, a thermal bonding method, an air array method, a wet method, a spun bond method, a melt blow method, a microfiber method, a running water entanglement method, and a needle punch. Method, a laminating method, a stitch bonding method, a paper making method and the like can be suitably employed. The nonwoven fabric containing the degradable polymer according to the present invention is similar to non-woven fabrics on the market such as Thinsulate (registered trademark, 3M) and Isaac (registered trademark, Teijin), as well as Gore-Tex (registered trademark, Junkosha, stretched fine Porous polytetrafluoroethylene (PTFE))
Combined with a waterproof sheet that allows marketed vapors to permeate but does not allow water to pass through, such as espoir (registered trademark, Mitsui Toatsu Chemicals), it can be used in winter and waterproof clothing (for mountain climbing, skiing, etc.). Can be applied.

Uses of Textiles Textiles containing the degradable polymer according to the present invention can be used as outer garments for general clothing or medical clothing, work clothing, surgical gowns, sleepwear, underwear, underwear, linings, hats, masks, bandages. , Triangle cloth,
Socks, women's stockings, women's foundations (bras, shorts, etc.), pantyhose, tights,
Socks, gloves, gloves, gloves, towels, gauze, towels, carpets, mats, curtains, wallpapers, clothing cores, car interior materials, mattresses, bags, furoshiki, bedding, futon cotton, pillowcases, blankets, sheets, It can be suitably used as a heat insulating material for winter wear, lace, tape, synthetic or artificial artificial leather, synthetic or artificial artificial fur, synthetic or artificial artificial suede, synthetic or artificial artificial leather, mesh pipe, and the like.
The textile containing the degradable polymer according to the present invention can be suitably used for medical or hygienic purposes. For example, surgical sutures, bandages, triangles, bandages, towels, disposable towels, disposable wet towels, commercial roll towels, towels, rags, tissues, cleaning and disinfecting wet tissues, Aka-chan wet wipes, disposables Diapers, disinfectant cotton, sanitary and vaginal napkins, sanitary tampons, underpads, surgical
Tampon for blood absorption for childbirth, cover stock for hygiene,
It can be suitably used for sterilization bags, garbage nets, garbage bags, and the like.

These medical or sanitary products can be sterilized, sterilized or disinfected and then aseptically packaged in the same manner as in the foam. Further, the product can be manufactured and packaged in a sterile state and / or in an endotoxin-free state by the same method as in the case of the foam.

The textile containing the degradable polymer according to the present invention is suitably used for general industrial applications including agriculture, fishing, forestry, industry, construction and civil engineering, transportation and transportation, and recreational applications including leisure and sports. be able to. For example, agricultural cold gauze, insect repellent and bird net, sieve, fishing line, fishing net, cast net, longline, oil absorbent, net, rope,
Zail, sail (canvas), hood, tarpaulin, tycon,
Container bags, industrial return bags, cement bags, fertilizer bags,
Filter materials, water-permeable cloth for landfill construction, cloth for soft ground reinforcement, artificial leather, felt for papermaking, lining for floppy disks, tents, sandbag bags, nets for tree planting, thermal insulation, soundproofing materials, light shielding materials, shock absorbing materials, It can be suitably used as a cushion material, a binding material, a non-slip material for muddy or snowy roads, a net-like pipe, a drainage pipe for civil engineering and construction, and the like. The shock-absorbing material includes, for example, a shock-absorbing material for use in transporting home appliances such as a television and a stereo, a shock-absorbing material for use in transporting a precision machine such as a computer, a printer and a clock, and a camera, glasses, and the like. It also includes cushioning materials for use when transporting optical machines such as microscopes and telescopes, and cushioning materials for use when transporting ceramic products such as glass and ceramics.

[0083]

【Example】

[Synthesis Examples, Embodiments, and Examples] Hereinafter, the present invention will be described in detail with reference to Synthesis Examples, Embodiments, and Examples. It should be noted that the descriptions of synthesis examples, aspects, and examples in the specification of the present application are explanations that assist understanding of the contents of the present invention, and that the descriptions serve as a basis for interpreting the technical scope of the present invention narrowly. Not a thing. [Methodology for Measurement of Physical Properties in Examples] The evaluation methods used in the examples are as follows. (1) Weight average molecular weight The weight average molecular weight (Mw) of the obtained degradable polymer was measured by gel permeation chromatography (column temperature 4).
(0 ° C., chloroform solvent) in comparison with a polystyrene standard sample. (2) Differential thermal analysis It analyzed with the scanning calorimeter (DSC-3100, the product made by Mac Science) in the temperature range of -20 degreeC-230 degreeC. (3) Tensile strength The tensile strength was 180 ° C according to JIS K-6372.
The measurement was performed using a film sample prepared by hot pressing in the above. (4) Bending strength The bending strength is from 180 to 180 in accordance with JIS K-7113.
The measurement was performed using a molded article having a predetermined shape which was injection molded at 200 ° C. (5) Haze (Haze) A 100 μm-thick film sample hot-pressed at 180 ° C. was formed according to JIS K-6714.
It was measured using a ze meter TC-HIII (Tokyo Denshoku Co., Ltd.). (6) Yellowness (YI value) A plate sample having a thickness of 2 mm was prepared.
The yellowness was measured using an SM color computer (model: SM-6-IS-2B, Suga Test Instruments Co., Ltd.) according to JIS K-7103. (7) Melt tension (MT value) After measuring the melt flow index at two appropriate temperatures using a load of 2160 g, the temperature-melt flow index-plot was used to determine the temperature at which the melt flow index was 10 g / 10 min. At that temperature, the melt tension was measured. (8) Degradability A film hot-pressed at 180 ° C. was placed in a compost at room temperature.
Buried for 30 days, measure the tensile strength before and after burying,
Degradability was evaluated.

Example 1 72.0 g of L-lactide,
Butane-1,2,3,4-tetracarboxylic acid 93.7 m
g, 72.1 mg of 1,4-butanediol and 1.08 g of tin octoate were dissolved in toluene and adjusted to 100 ml, and 1 ml of a catalyst solution was charged into a 300 ml stainless steel reactor. The toluene was distilled off at 40 ° C. and 2 mmHg, and the temperature was raised to 170 ° C. over 1.5 hours in a dry nitrogen atmosphere, followed by a reaction at 210 ° C. for 2 hours. Next, unreacted monomers were distilled out of the system at 200 ° C. and 2 mmHg for 1 hour, and then the polymer was extracted in a strand form from the bottom of the reactor to obtain 68.0 g of a decomposable polymer (94% yield). Was.

The physical properties are shown below. Weight average molecular weight: 320,000 Differential thermal analysis: glass transition temperature is 60.0 ° C., melting point is 16.
7.0 ° C. Tensile strength: 550 kg / cm ² Tensile elongation: 8% Flexural strength: 820 kg / cm ² Haze: <1% Yellowness (YI value): 2.2 In addition, the melt flow index (MI value) 10g
/ 10 min and the melt tension at that temperature (M
T value) and evaluation of degradability are shown below. Temperature (MI: 10 g / 10 min): 187 ° C. Melt tension (MT value): 3.5 g Degradability: The film was so deteriorated that its strength could not be measured.

Example 2 72.0 g of L-lactide,
101.4 mg of trimellitic anhydride, 72.1 mg of 1,4-butanediol, and 1.08 g of tin octoate were dissolved in toluene to make 1 ml of a catalyst solution.
It was charged to a 00 ml stainless steel reactor. 40 ° C, 2
The toluene was distilled off at a pressure of mmHg.
After raising the temperature to 170 ° C. over 5 hours, the reaction was carried out at 210 ° C. for 2 hours. Then, the unreacted monomer was heated at 200 ° C. for 2 mm.
After distilling out of the system over 1 hour with Hg, the polymer was taken out in a strand form from the bottom of the reactor, and the decomposable polymer 67.
5 g (94% yield) was obtained.

The physical properties are shown below. Weight average molecular weight: 300,000 Differential thermal analysis: glass transition temperature is 59.0 ° C., melting point is 16.
5 ° C. Tensile strength: 560 kg / cm ² Tensile elongation: 7% Flexural strength: 830 kg / cm ² Haze: <1% Yellowness (YI value): 1.8 Also, melt flow index (MI value) is 10 g /
And the melt tension at that temperature (MT
Values) and the evaluation of degradability are shown below. Temperature (MI: 10 g / 10 min): 184 ° C. Melt tension (MT value): 2.2 Degradability: The film was deteriorated so that the strength could not be measured.

Example 3 72.0 g of L-lactide
38.0 mg of trimellitic anhydride, 20.4 mg of pentaerythritol, and 1.08 g of tin octoate were dissolved in toluene to make 100 ml of a 1 ml catalyst solution.
It was charged to a ml stainless steel reactor. 40 ° C, 2mm
The toluene was distilled off with Hg, and the temperature was raised to 170 ° C. over 1.5 hours in a dry nitrogen atmosphere, followed by a reaction at 210 ° C. for 2 hours. Next, the unreacted monomer was heated at 200 ° C. and 2 mmHg.
After distilling out of the system over 1 hour, the polymer was taken out in a strand form from the bottom of the reactor, and 67.0 g of decomposable polymer was obtained.
(93% yield).

The various physical properties are shown below. Weight average molecular weight: 360,000 Differential thermal analysis: glass transition temperature is 58.5 ° C., melting point is 16.
4 ° C. Tensile strength: 530 kg / cm ² Tensile elongation: 8% Flexural strength: 810 kg / cm ² Haze: <1% Yellowness (YI value): 1.5 Further, the melt flow index (MI value) is 10 g.
/ 10 min and the melt tension at that temperature (M
T value) and evaluation of degradability are shown below. Temperature (MI: 10 g / 10 min): 188 ° C. Melt tension (MT value): 4.5 g Degradability: The film was deteriorated to such an extent that the strength could not be measured.

Comparative Example 1 Weight average molecular weight 220,00
The differential thermal analysis of L-polylactic acid of 0 showed a glass transition temperature of 60.0 ° C and a melting point of 168.5 ° C.
The polylactic acid was hot-pressed at a temperature of 180 ° C. to produce a press film. The physical properties of the obtained film are shown below. Tensile strength: 570 kg / cm ² Tensile elongation: 7% Haze: <1% Flexural strength: 900 kg / cm ² Also, the melt flow index (MI value) is 10 g /
And the melt tension at that temperature (MT
Values), yellowness (YI value) and degradability are shown below. Temperature (MI: 10 g / 10 min): 185 ° C. Melt tension (MT value): 0.6 g, which is lower than that of the examples. Yellowness (YI value): 1.8 Degradability: The film was deteriorated so that the strength could not be measured.

[0091]

According to the present invention, the decomposable polymer produced by the present invention is a conventional aliphatic polyester (for example, an aliphatic polyester obtained by polycondensation of an aliphatic polycarboxylic acid and an aliphatic polyhydric alcohol, Compared to aliphatic polyesters obtained by polycondensation of hydroxycarboxylic acid, etc.), while maintaining high transparency equal to or higher, and having a remarkably high and excellent melt tension. Molding, etc.). The decomposable polymer according to the present invention includes a polysaccharide and an aliphatic polyester (for example, an aliphatic polyester obtained by polycondensation of an aliphatic polycarboxylic acid and an aliphatic polyhydric alcohol, an aliphatic polyester obtained by polycondensation of a hydroxycarboxylic acid, and the like. ), And has a characteristic that coloring is remarkably small as compared with a copolymer or a polymer blend.

The degradable polymer according to the present invention is useful as a substitute for medical materials and general-purpose resins. The degradable polymer according to the present invention is useful as a molded product or processed product utilizing its advantageous properties.

For applications requiring safety, such as the medical field and the food field, it can be suitably used without adding additives. Molding method of the degradable polymer according to the present invention, injection molding, extrusion molding, inflation molding,
Extrusion hollow molding, foam molding, calender molding, blow molding, balloon molding, vacuum molding, spinning, and the like are preferred, and inflation molding, blow molding, extrusion hollow molding, foam molding, vacuum molding, and spinning are particularly preferred. The decomposable polymer according to the present invention includes films, sheets, textiles, monofilaments, multifilaments, yarns, nonwoven fabrics, flat yarns, staples, crimped fibers, side-by-side fibers, tapes with split lines, split yarns, composite fibers, laminates, and blows. It can be suitably used for processed products such as bottles, plates, stretched sheets, foams, and nets. At that time, a lubricant, a coloring agent, another polymer, a release agent, a filler, a reinforcing agent, and the like can be used as necessary. After molding or processing, high heat resistance can be imparted by further heat-treating the molded product or the processed product.

The decomposable polymer according to the present invention can also be used as a substitute for a medical material or a general-purpose resin known and used before the present application. The molded product or processed product of the degradable polymer may be subjected to heat treatment without or with heat treatment, depending on the purpose, to replace a molded product or processed product of another resin known and used before the present application. It can be used as an object. Furthermore, the degradable polymer according to the present invention has an excellent biodegradability that is completely degraded in a living body or soil, so as a bio-friendly polymer, as a global environment-friendly polymer, It is useful. Therefore, surgical sutures, shopping bags, garbage bags, agricultural films, cosmetic containers, detergent containers, bleach containers, fishing lines, fishing nets, ropes, ties, surgical threads, hygienic coverstocks, cool boxes, cushions It is highly expected for uses such as materials. In particular, since it has high performance without adding a plasticizer, it is suitable for food packaging materials and medical applications.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Masanobu Amioka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Toatsu Chemicals Co., Ltd.

Claims (10)

[Claims] 1. A cyclic dimer and / or lactone of a hydroxycarboxylic acid as the component (A), and a polycarboxylic acid compound having three or more carboxyl groups and / or an anhydride thereof as the component (B). A method for producing a decomposable polymer, comprising reacting in a reaction system containing, as a component (C), a polyhydric alcohol having two or more hydroxyl groups, and a catalyst as a component (D). 2. The weight of component (B) is equivalent to 0.005 to 1%, based on the weight of the polymer assuming that component (A) is completely polymerized alone, The method for producing a degradable polymer according to claim 1, wherein the equivalent ratio of the carboxyl group of the component (B) to the hydroxyl group of the component (C) is 100: 50 to 200. 3. The decomposable polymer according to claim 1, wherein the “polyhydric carboxylic acid compound having three or more carboxyl groups and / or an anhydride thereof” of the component (B) contains a linear compound. Manufacturing method of coalescence. 4. The decomposition according to claim 1, wherein the “polycarboxylic acid compound having three or more carboxyl groups and / or an anhydride thereof” of the component (B) contains a cyclic compound. Method for producing functional polymer. 5. The catalyst of component (D) is (d-1)
Tin catalyst, (d-2) zinc-based catalyst, and (d-3)
The method for producing a decomposable polymer according to any one of claims 1 to 4, wherein the method comprises at least one selected from the group consisting of titanium-based catalysts. 6. The production of the degradable polymer according to claim 1, wherein the cyclic dimer of hydroxycarboxylic acid of the component (A) contains lactide which is a cyclic dimer of lactic acid. Method. 7. A degradable polymer obtained by the production method according to claim 1. 8. A degradable polymer having a melt tension of 0.7 g or more at a melt flow index of 10 g / 10 minutes obtained by the production method according to claim 1. 9. A degradable polymer having a structure in which a star polymer comprising a hydroxycarboxylic acid and a polyvalent carboxylic acid compound having three or more carboxyl groups is linked by a polyhydric alcohol having two or more hydroxyl groups. . 10. A foam comprising the degradable polymer according to any one of claims 7 to 9.