WO2005003450A1 - Procede de production d'une composition polyester aliphatique, pate de cellulose et fibres cellulosiques a utiliser dans procede, et procede de microfibrillation correspondant - Google Patents

Procede de production d'une composition polyester aliphatique, pate de cellulose et fibres cellulosiques a utiliser dans procede, et procede de microfibrillation correspondant Download PDF

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Publication number
WO2005003450A1
WO2005003450A1 PCT/JP2004/009720 JP2004009720W WO2005003450A1 WO 2005003450 A1 WO2005003450 A1 WO 2005003450A1 JP 2004009720 W JP2004009720 W JP 2004009720W WO 2005003450 A1 WO2005003450 A1 WO 2005003450A1
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Prior art keywords
aliphatic
acid
aliphatic polyester
polyester composition
producing
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PCT/JP2004/009720
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English (en)
Japanese (ja)
Inventor
Hiroyuki Yano
Kazunori Yano
Yuko Motegi
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Kansai Technology Licensing Organization Co., Ltd.
Kimura Chemical Plants Co., Ltd.
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Application filed by Kansai Technology Licensing Organization Co., Ltd., Kimura Chemical Plants Co., Ltd. filed Critical Kansai Technology Licensing Organization Co., Ltd.
Publication of WO2005003450A1 publication Critical patent/WO2005003450A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/728—Measuring data of the driving system, e.g. torque, speed, power, vibration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/823—Temperature control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/826—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B29B7/92—Wood chips or wood fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers

Definitions

  • the present invention is used in the field of household goods and packaging materials, and after being disposed of, is biologically decomposed by microorganisms in a natural environment such as in soil, and finally is completely dissolved in carbon dioxide gas and water.
  • a method for industrially producing a high-strength, high-rigidity aliphatic polyester composition, which is an environmentally friendly, biodegradable aliphatic polyester composition which is degraded The present invention relates to a treated pulp and / or a cellulosic fiber and a microfibrillating method thereof.
  • JP-A-06-345944 and JP-A-2002-292608 disclose that a pulp or a cellulosic fiber is dispersed in a biodegradable resin to obtain a biodegradable composite material having excellent rigidity. It states that it can.
  • a composite material composed of a thermoplastic resin and a fiber is controlled by an aspect ratio of a fiber dispersed in the material such as mechanical strength.
  • a method of forming microfibrils utilizing the hydrophilicity characteristic of pulp or cellulosic fibers is disclosed in Japanese Patent Publication Nos. 48-6641 and 50-38720. It is described in the gazette, where the pulp is highly and repeatedly ground or beaten with a refiner or a homogenizer to obtain microfibrillated cellulose fibers.
  • the present invention does not require complicated pretreatment of a biodegradable resin or fine fibers of pulp, and employs a general-purpose kneading means to uniformly and finely disperse a fiber component in a resin component.
  • a general-purpose kneading means to uniformly and finely disperse a fiber component in a resin component.
  • Another object of the present invention is to provide a pulp and a cellulosic fiber used in this method and a method for microfibrillating the same.
  • an aliphatic polyester composition of the present invention (a) an aliphatic polyester obtained by reacting (b) an aliphatic dicarboxylic acid and / or a derivative thereof with an aliphatic diol (A) l-99% by weight of a resin component consisting of 100% by weight and 99-0% by weight of polylactic acid (B), and a pre-treated pulp and / or cell opening having damaged outer layers of primary and secondary walls. 99-0.1 part by weight of the fiber component comprising the staple fiber (C) is melt-kneaded in the presence of the cellulose amorphous region swelling agent (D). However, the total amount of the resin component and the fiber component shall be 100 parts by weight.
  • aliphatic means “aliphatic” in a broad sense including “alicyclic”.
  • the aliphatic polyester (A) is obtained by reacting (a) an aliphatic diol, (b) an aliphatic dicarboxylic acid and / or a derivative thereof, and ( c ) a bifunctional aliphatic hydroxycarboxylic acid and Z or a derivative thereof. It may be obtained by performing the above.
  • the present inventors have found that a pulp and / or a cellulosic fiber in which a primary wall and a secondary wall outer layer have been damaged by pretreatment are subjected to a general-purpose melt-kneading method which does not require pretreatment of a resin component. Microfine fibril-like cellulose fibers are uniformly and finely dispersed in the resin component; thus, a high-rigidity and high-strength composite material can be obtained by a general-purpose molding method. [0010] In the conventional plant fiber / biodegradable resin composite member as described above, the biodegradable resin is preliminarily pulverized or fine fiber in order to uniformly disperse the fiber component in the biodegradable resin. And a great deal of labor was required for the pretreatment for this purpose. In addition, complicated operations were necessary for kneading, molding, and subsequent drying.
  • microfibrillation has been performed by repeatedly grinding or beating the fiber component.
  • the microfibrillation of the fiber component requires complicated operations and a great deal of labor in the presence of moisture.
  • the microfibrillated fiber since the microfibrillated fiber is in a slurry state, it must be handled. It is difficult and the supply to the kneader is not always easy.
  • Pre-microfibrillated fibers are less likely to form frogs (agglomerates) during kneading with the resin and to quickly become high aspect ratio fibers.
  • Such a simple pretreatment that does not require a great deal of labor for the pretreatment operation, or a general-purpose kneading means that does not require a special kneading means, enables the fiber component to be contained in the resin component.
  • the present inventors have studied a method of uniformly and finely dispersing the particles. Pulp and / or cellulosic fibers that have been subjected to a simple pretreatment of damaging the outer layers of the primary and secondary walls are melt-kneaded with the resin component in the presence of a cellulose amorphous region swelling agent. It was found that the fiber component was disintegrated into microfibrils, and was uniformly and finely dispersed in the resin component.
  • pulp and / or cellulosic fibers whose primary and secondary wall outer layers have been damaged by pretreatment are easily defibrated during melt-kneading and are finely dispersed uniformly in the molten resin. Is done.
  • the pulp and / or cellulosic fiber which only damage the outer layers of the primary wall and the secondary wall are easy to handle and kneaded smoothly with the resin.
  • the pulp and the cellulosic fiber of the present invention have damaged primary and secondary wall outer layers, and are used in a method for producing such an aliphatic polyester composition.
  • the pulp formed by damaging the outer layers of the primary wall and the secondary wall is kneaded in the presence of a swelling agent for the amorphous cellulose region to dissolve the fiber component.
  • a swelling agent for the amorphous cellulose region to dissolve the fiber component.
  • the primary wall and the secondary wall outer layer The fiber component is fibrillated by kneading the cellulosic fiber formed by scratching in the presence of the cellulose amorphous region swelling agent.
  • the fiber component is simply subjected to a simple pretreatment, which does not require a complicated pretreatment step of the resin component.
  • a simple pretreatment which does not require a complicated pretreatment step of the resin component.
  • a high-strength, high-rigidity fiber / biodegradable resin composite molded article can be manufactured using a general-purpose thermoplastic resin kneading means and molding means.
  • INDUSTRIAL APPLICABILITY The present invention can be applied to injection molding equipment for general-purpose thermoplastic resin, extrusion molding of films, sheets, and the like, thereby improving production efficiency and reducing production costs.
  • FIG. 1 is a schematic perspective view showing a laminated structure of pulp and cellulosic fibers.
  • FIG. 2a is an electron micrograph showing the morphology of the pretreated pulp used in the examples
  • FIG. 2b is an electron micrograph showing the morphology of the pulp without pretreatment used in the comparative example.
  • FIG. 3a is an electron micrograph showing the morphology of the fiber component in the composition obtained in Example 2
  • FIG. 3b is the morphology of the fiber component in the composition obtained in Comparative Example 2. It is an electron microscope photograph shown.
  • the aliphatic polyester (A) used in the present invention comprises, under polyester production conditions, (a) an aliphatic diol, (b) an aliphatic dicarboxylic acid and / or a functional derivative thereof, and (c) It is obtained by reacting a bifunctional aliphatic hydroxycarboxylic acid and / or a derivative thereof, and is preferably obtained by performing this reaction in the presence of a germanium catalyst.
  • the (a) aliphatic diol (including alicyclic diol) used in the present invention has two hydroxyl groups.
  • the preferred specific examples thereof are those represented by the following general formula (I): [0022] HO-R-OH (I)
  • R 1 is a divalent aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group having 211 carbon atoms, particularly preferably an aliphatic hydrocarbon group having 2 to 6 carbon atoms.
  • R 1 may have a branched chain and may be a cycloalkylene group.
  • R 1 is preferably — (CH 2) n — (only
  • n represents an integer of 2-11, preferably an integer of 26. ).
  • the aliphatic diol is preferably 1,4-butanediol.
  • aliphatic dicarboxylic acids including alicyclic dicarboxylic acids
  • / or derivatives thereof used in the present invention are those represented by the following general formula (II), or those having a lower carbon number of 114. Forces such as alkyl esters or their anhydrides are not limited thereto.
  • R 2 is a direct bond or a divalent aliphatic hydrocarbon group, preferably a divalent aliphatic hydrocarbon having 211 to 11 carbon atoms, and particularly preferably a divalent aliphatic hydrocarbon having 2 to 6 carbon atoms.
  • Group. R 2 may have a branched chain or may be a cycloalkylene group.
  • R 2 is preferably — (CH 2) m — (where m represents an integer of 0 or 11-11, preferably an integer of 0 or 116)
  • aliphatic dicarboxylic acid examples include oxalic acid, succinic acid, dataric acid, adipic acid, sebacic acid, suberic acid, dodecane diacid, and the like.
  • Anhydrides but are not limited thereto.
  • aliphatic dicarboxylic acid and / or its derivative may be succinic acid or succinic anhydride, or a mixture of these with adipic acid. Preferably, there is.
  • the (c) bifunctional aliphatic hydroxycarboxylic acid (including alicyclic hydroxycarboxylic acid) and / or a derivative thereof which can be used in the present invention includes one hydroxyl group in the molecule.
  • an aliphatic hydroxycarboxylic acid corresponding to an aliphatic hydroxycarboxylic acid unit of the following general formula (II) is preferable, and Preferable are lower alkyl esters having 14 to 14 carbon atoms or intramolecular esters thereof.
  • R 3 is a divalent aliphatic hydrocarbon group, preferably a divalent aliphatic hydrocarbon group having 1 to 11 carbon atoms, more preferably a divalent aliphatic hydrocarbon group having 16 carbon atoms. is there.
  • R 3 may be a cycloalkylene group, but is preferably a chain hydrocarbon group.
  • the term “chain” includes not only “linear” but also “branched”.
  • the bifunctional aliphatic hydroxycarboxylic acid and / or a derivative thereof is more preferably one in which a hydroxyl group and a carboxy group are bonded to one carbon atom, and represented by the following general formula (IV) Those represented are preferred.
  • the use of a bifunctional aliphatic hydroxycarboxylic acid represented by the following general formula (IV) or a derivative thereof is particularly preferable because the polymerization rate increases.
  • a is 0 or an integer of 1 or more, preferably 0 or 110, more preferably 0 or 115.
  • the bifunctional aliphatic hydroxycarboxylic acid include lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy_n_butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, Ratantones such as 2-hydroxy-3-methylbutyric acid, 2-methyllactic acid, 2-hydroxycaproic acid, or ryprotonate may be used. These may be used alone or as a mixture of two or more.
  • any of the D-form, L-form, and racemic form may be a solid, liquid, or aqueous solution.
  • lactic acid and an aqueous solution thereof which are particularly remarkable in increasing the polymerization rate during use and are easily available are preferred.
  • Lactic acid is generally commercially available in 50%, 70%, and 90% aqueous solutions, and is easily available. By using lactic acid, the compatibility between the aliphatic polyester (A) and the polylactic acid (B) can be enhanced.
  • the aliphatic polyester (A) used in the present invention comprises the above components (a) and (b) and, if necessary, further the component (c), under the polyester formation conditions, preferably in the presence of a catalyst comprising a germanium compound. It is produced by the following reaction method.
  • the amount of (a) the aliphatic diol used is (b) a force that is substantially equimolar to the aliphatic dicarboxylic acid and / or a derivative thereof.
  • the aliphatic diol (a) is used in an excess of 1 to 50 mol, preferably 5 to 30 mol per 100 mol of the aliphatic dicarboxylic acid and / or a derivative thereof (b).
  • the amount of the (c) bifunctional aliphatic hydroxycarboxylic acid and / or the derivative thereof is determined based on (b) 100 mol of the aliphatic dicarboxylic acid and / or a derivative thereof. It is preferably 0.04 to 60 monoles, preferably f to 1 to 20 monoles, and more preferably f to 3 to 10 monoles. (c) If the amount of the bifunctional aliphatic oxycarboxylic acid and Z or a polymer thereof is less than this range, it is difficult to obtain a high molecular weight aliphatic polyester which is less likely to exhibit the effect of improving the polymerization reactivity by using this. If it exceeds this range, the heat resistance and strength become insufficient.
  • the timing of adding the bifunctional aliphatic hydroxycarboxylic acid and Z or a derivative thereof is not particularly limited as long as it is before the ester formation reaction.
  • Raw material preparation in the state of being dissolved in acid and / or derivative solution Preferred is a method in which the catalyst is added during the reaction or during the esterification reaction, or a method in which the catalyst is added at the same time as the catalyst is added at the time of charging the raw materials.
  • the production of the aliphatic polyester (A) used in the present invention is preferably carried out in the presence of a germanium compound-based catalyst using the above raw materials.
  • the germanium compound-based catalyst used may be one composed of only one kind of germanium compound or may be one composed of two or more kinds. Also, one or more kinds of germanium compound may be used. Any known catalyst that can be used for the production of polyester, for example, a metal compound catalyst that is soluble in a reaction system such as titanium, antimony, tin, magnesium, zinc, and calcium can be used.
  • a metal compound catalyst that is soluble in a reaction system such as titanium, antimony, tin, magnesium, zinc, and calcium
  • the germanium compound for example, an organic germanium compound such as tetraalkoxygermanium, or an inorganic germanium compound such as germanium oxide or germanium chloride is particularly preferable. From the viewpoint of price and availability, germanium oxide, tetraethoxygermanium, tetrabutoxygermanium and the like are preferable.
  • the amount of these catalysts used is generally 0.001 to 3% by weight, more preferably 0.005 to 1.5% by weight, based on the amount of monomer used, that is, the total amount of components (a) to (c). %.
  • the timing of adding the catalyst is not particularly limited as long as it is before the production of the polyester, but may be added at the time of charging the raw materials or may be added at the start of reduced pressure.
  • the conditions such as temperature, time, and pressure for producing the aliphatic polyester (A) are not particularly limited as long as the aliphatic polyester (A) as a target product can be obtained.
  • polymerization time is 1 hour or more, preferably 215 hours
  • the degree of vacuum during the polycondensation reaction is 1.33 ⁇ 10 3 Pa or less, more preferably 0.27. Les, Shi preferable be selected from X 10 3 Pa follows ranges.
  • the aliphatic polyester (A) obtained in this manner has the (a) component and the (b) component as main polyester members.
  • (a) an aliphatic diol unit and (b) an aliphatic dicarboxylic acid When the molar ratio of the (functional derivative) units is substantially equal and the number of moles of all the constituent components of the aliphatic polyester copolymer is 100 moles, (c) the bifunctional aliphatic hydroxycarboxylic acid unit is as follows: Preferably it is 0.02-30 mol.
  • the bifunctional aliphatic hydroxycarboxylic acid component (c) is lactic acid
  • the compatibility between the aliphatic polyester (A) and the polylactic acid (B) can be obtained by introducing the component (c) in such a range. Is very high.
  • the number average molecular weight Mn of the aliphatic polyester (A) used in the present invention is generally from 10,000 to 300,000, usually from 30,000 to 300,000.
  • the polylactic acid ( ⁇ ) used in the present invention is not particularly limited, but the number average molecular weight required for having sufficient strength is 30,000 or more, preferably 100,000 or more.
  • the upper limit of the number average molecular weight of the polylactic acid (II) is not particularly limited, but is usually 1,000,000 or less, preferably 500,000 or less.
  • the molar ratio of L-form and D-form constituting polylactic acid ( ⁇ ) is L / D is 100 / 0—the force that can be used in all compositions of OZlOO High elastic modulus In order to obtain the above, it is preferable that the L-form is 95 mol% or more.
  • the method for producing polylactic acid (B) is not particularly limited, and examples thereof include a ring-opening polymerization method via lactide and a direct polycondensation method of lactic acid.
  • pulp and / or cellulosic fiber used in the present invention kraft pulp, chemically treated pulp of wood such as sulfite pulp, recycled pulp recycled from waste paper, artificial cellulose fiber, bacterial cellulose fiber by acetic acid bacteria, Examples thereof include cellulose fibers derived from animals such as sea squirts and those obtained by chemically modifying them. These may be used alone or in combination of two or more. Of these, pulp obtained from plant-derived wood, waste paper, and the like is preferable in terms of cost and the global environment. Representative chemical modification methods for pulp and / or cellulosic fibers include acetylation and cyanoethylation.
  • the pulp and the cellulosic fiber have a laminated structure including a primary wall 1, a secondary wall outer layer 2, a secondary wall middle layer 3, and a secondary wall inner layer 4.
  • the thin line in each layer indicates the orientation direction of the microfibrils in the cell opening.
  • the primary wall 1 of the pulp and the outer layer 2 of the secondary wall function as sheaths of the inner layers 3 and 4 in the secondary wall occupying 70-90% of the laminated structure, and the inner layer 3 in the secondary wall 3 4 is tightly united.
  • thermoplastic resin-based composite material in order to completely unravel the sheath-like hulls and microfibrillate the cellulose fibers of the aggregate, it is repeatedly milled several tens of times using a refiner and a high-pressure homogenizer. , Beating.
  • the above-mentioned pulp and / or cellulosic fiber is subjected to a mild pretreatment of damaging the outer layers of the primary and secondary walls, so that the sheath of the outermost layer is easily broken.
  • Examples of the pretreatment method include well-known refiner treatment, medium stirring mill treatment, vibration mill treatment, stone mill treatment, and the like. Refiner treatment is preferred.
  • Semi-chemical pulp obtained by mechanically processing pulp with a refiner, a grinder, or the like is also generally provided. If the pulp satisfies the water retention described below, this semi-chemical pulp can be used as pre-treated pulp. .
  • the state of damage to the outer layers of the primary wall and the secondary wall due to such pretreatment is determined by observing the morphology of the pretreated pulp and / or the cellulosic fiber using a microscope, and the water retention of the pretreated pulp and the Z or cellulosic fiber. Can be grasped.
  • the water retention is defined as the water content of a 2% by weight slurry after centrifugation at 1000 G for 15 minutes using a centrifuge.
  • X) 100% by weight, and the water retention of pulp and cellulosic fiber without pretreatment is usually 100-120%.
  • the pretreated pulp and the Z or cellulosic fibers (C) are aggregates of cellulose fibers having an average diameter of tens of ⁇ m to tens of ⁇ m.
  • the melt-kneading with the resin component by a twin-screw extruder described later results in a microfibrillated cellulose having an average diameter of several zm—0.005 xm and a length / diameter ratio (aspect ratio) of 10 or more, for example, 20-200. Is obtained.
  • This microfibrillated cellulose is branched (fibrillated) from the aggregate of the cellulose fibers and uniformly and finely dispersed in the resin component as if it were a spider web.
  • the pulp and the Z or cellulosic fibers that damage the outer layers of the primary wall and the secondary wall may be kneaded without a resin component in the presence of a cellulose amorphous region swelling agent (D) described later.
  • the fibrous component is defibrated and microfibrillated.
  • the pulp and / or cellulosic fiber thus obtained can be effectively used not only for the aliphatic polyester composition but also for various uses.
  • the cellulose amorphous region swelling agent (D) used in the present invention is a low molecular weight compound having a hydrogen bonding ability with cellulose fibers, and is a cellulose fiber aggregate or a pretreated pulp and / or a cellulosic fiber (C). It is a compound that can be impregnated and diffused into the amorphous region of cellulose fibers.
  • Specific compounds of the cellulose amorphous region swelling agent (D) include water, ethylene glycol, butylene glycol, methyl alcohol, and ethyl alcohol, and preferred are water, ethylene glycol, and methyl alcohol. . These cellulose amorphous region swelling agents (D) may be used alone or as a mixture of two or more.
  • the blending ratio of the aliphatic polyester (A), the polylactic acid (B) optionally blended, the pretreated pulp and / or the cellulose fiber (C) is determined by the proportion of the aliphatic polyester ( A): Resin component consisting of a mixture of 100-1% by weight and polylactic acid (B): 0-99% by weight per 119.9 parts by weight of pretreated pulp and / or cellulosic fiber (D) 99-0.1 parts by weight.
  • the aliphatic polyester (A) is inferior in rigidity and heat resistance to the polylactic acid (B), but is preferably a resin component because of its excellent fine dispersibility of the pretreated pulp and / or the cellulosic fiber (C).
  • the content of polylactic acid (B) is 60% by weight based on 40% by weight of the aliphatic polyester (A), and more preferably, 100% to 60% by weight of the aliphatic polyester (A) is 40% by weight of the polylactic acid (). In% by weight.
  • the form of the aliphatic polyester (A) and polylactic acid (B) may be any of granular, powdery, and fibrous, but is preferably granular.
  • Resin component total of aliphatic polyester (A) and polylactic acid (B)
  • the ratio of fiber component (pretreated pulp and Z or cellulosic fiber (C)) to 99.9 parts by weight is as follows. , 99-0.1 parts by weight.
  • the preferred compounding ratio is 95 to 3 parts by weight of the fiber component to 5 to 97 parts by weight of the resin component, and more preferably 65 to 5 parts by weight of the fiber component to 35 to 95 parts by weight of the resin component.
  • the total of the resin component and the fiber component shall be 100 parts by weight.
  • the aliphatic polyester composition according to the production method of the present invention may contain an aliphatic polyester (A), a polylactic acid (B), a pre-treated pulp and / or a polylactic acid, if necessary, as long as the effects of the present invention are not impaired.
  • Components other than the cellulosic fiber (C) for example, a lubricant, a wax, a colorant, a stabilizer, and other various additives may be blended.
  • the amount of the cellulose amorphous region swelling agent (D) used in the melt kneading with respect to the fiber component, that is, the pretreated pulp and / or the cellulosic fiber (C) may be any amount as long as it is equal to or more than the water retention of the fiber component. From the refining effect in the dispersing step described later and the separability thereafter, it is preferable that the content of the pretreated pulp and / or the cellulosic fiber (C) is 100 to 600% by weight, particularly 200,500% by weight. .
  • the resin component and the fiber component are melted and kneaded in the presence of the cellulose amorphous region swelling agent (D) using a twin-screw extruder, so that the fiber component is defibrated and the tree is extruded.
  • the aliphatic polyester composition may be produced by uniformly and finely dispersing the fiber component in the fat component.
  • twin-screw extruder used is a device used for mixing, plasticizing, and extruding a general-purpose thermoplastic resin, and the two screws can be rotated in different directions or in the same direction. Is good. Screws can be completely meshed, incompletely meshed, or non-engaged, but the completely meshed type is preferred from the viewpoint of dispersibility of fiber components. If the screw length / screw diameter ratio is 20 70, it is good. Specific twin screw extruders such as “TEX” manufactured by Nippon Steel Works, “TEM” manufactured by Toshiba Machine Co., Ltd., and rzSKj manufactured by Krupp “Werner” can be used.
  • the melt-kneading according to the present invention is preferably performed by using such a twin-screw extruder, for example, through the following step (1) or (2) by a combination of screw constitutions.
  • a resin component, a fiber component and a cellulose amorphous region swelling agent are supplied to a twin-screw extruder, and the fiber component is added to the resin component in the twin-screw extruder in the presence of the cellulose amorphous region swelling agent.
  • Defibration and dispersing ⁇ Dispersion process '' followed by melting and dispersing the fiber component in the molten resin component while further melting and finely dispersing the resin component, and then swelling the cellulose amorphous region Separation agent for cellulose amorphous region swelling agent that extrudes kneaded material while separating agent.
  • the defibrating and dispersing steps are preferably performed at a temperature of 30 to 90 ° C. Melting.
  • the dispersing step is preferably performed at a temperature of 120 to 200 ° C.
  • the temperature of the cellulose amorphous region swelling agent separation / extrusion step is preferably 120 to 200 ° C.
  • the screw rotation speed is preferably in the range of 50 to 400 rpm in all steps.
  • the screw length / screw length is required. The smaller the diameter ratio, the more preferable it is 2550.
  • a melting step in which the resin component is supplied to the twin-screw extruder and the resin component is melted in the twin-screw extruder, and thereafter, the mixture of the fiber component and the cellulose amorphous region swelling agent is biaxially extruded.
  • a fiber 'fibrillation' dispersion process in which the fiber component is fibrillated and finely dispersed in the resin component in the presence of the cellulose amorphous region swelling agent by pressure injection into the machine, and then the cellulose amorphous region swelling agent is separated And swelling agent for cellulose amorphous region extruding the kneaded material.
  • the melting step is preferably performed at a temperature of 120 to 200 ° C, and the melting 'fibrillation' dispersion step is preferably performed at a temperature of 120 to 180 ° C.
  • the swelling agent separation / extrusion step is preferably performed at a temperature of 120 to 200 ° C. and a pressure of atmospheric pressure and vacuum.
  • the screw rotation speed is preferably in the range of 50 to 400 rpm in all the steps.
  • a mixture of the cellulose amorphous region swelling agent (D) and the fiber component is injected under pressure into a molten resin component at atmospheric pressure of a few MPa using a pump. It is preferable to further perform melting, defibration, and fine dispersion without separating the cellulose amorphous region swelling agent (D).
  • the ratio of the screw length Z to the screw diameter is preferably 30 to 70.
  • the injection of the cellulose amorphous region swelling agent (D) into the twin-screw extruder is premixed with the fiber component and supplied in a liquid state by a pump.
  • the cellulose amorphous region swelling agent (D) may be supplied alone in a liquid form.
  • the melt-kneading step may be performed under pressure to prevent evaporation of the cellulose amorphous region swelling agent (D).
  • a cellulose amorphous region swelling agent (D) can be added by a pressure pump during the melting step of the resin component. After the melt-kneading, the pressure is released, and the pressure is further reduced, whereby the cellulose amorphous region swelling agent (D) can be separated.
  • the aliphatic polyester composition extruded and granulated in this way does not require a drying step, and only has a preliminary drying for separating water adhering to the surface before molding, which is essential for the polyester resin. Can be used for molding power.
  • the properties of the obtained aliphatic polyester composition that is, the composite material in which the fiber component is uniformly and finely dispersed in the resin component, largely depends on the form of the fiber component dispersed in the resin component. It is preferable that microfibrils are formed, rather than the aggregates.
  • the resin component and the fiber component are melt-kneaded, preferably using a twin-screw extruder, in the presence of the cellulose amorphous region swelling agent (D), the resin component becomes As a mixing and kneading medium for aliphatic polyester (A) and polylactic acid (B), fiber components can be defibrated and uniformly finely dispersed in resin components with good mixing and kneading properties. .
  • the cellulose amorphous region swelling agent (D) reduces the cohesive force between cellulose microfibrils in such a melt-kneading step, and causes the aggregate of cellulose fibers to become microscopic.
  • any method similar to the method for molding a usual thermoplastic resin composition can be applied. Specifically, injection molding, extrusion molding, hollow molding, foam molding and the like can be employed.
  • the aliphatic polyester composition according to the present invention has sufficient rigidity and mechanical strength and can be subjected to various molding processes such as extrusion molding and injection molding, so that it can be used for household goods, various packaging materials, and the like. It can be suitably used for molded articles for a wide range of uses. After use and disposal, it is biodegraded, which is effective in reducing waste and protecting the environment.
  • Injection molded product is conditioned at 23 ° C, 50% relative humidity, 24 hours, and complies with JIS K 7203 Then, the three-point bending rigidity and the breaking strength were measured.
  • the injection molded product was visually observed, and the uniformity was evaluated depending on the presence or absence of fiber aggregates.
  • composition Dissolve the composition in black-mouthed form, add distilled water to extract the pulp or fiber into the aqueous layer side, freeze-dry part of the extract, and use a scanning electron microscope. I took a picture.
  • Production Example 1 Production of aliphatic polyester (A)
  • succinic acid (b) 118 ⁇ lg, 1,4-butanediol (a) 99 ⁇ lg, 6.3 g (6.3 mol per 100 mol of succinic acid) of a 90% aqueous lactic acid (c) solution in which 1% by weight of germanium oxide was previously dissolved, and 0.2 g of malic acid (d) (100 mol of conodic acid) 0.15 mol) was added to the mixture, and the mixture was reacted in a nitrogen atmosphere at 180 ° C for 0.5 hours, and then heated to 220 ° C and reacted for 0.5 hours.
  • succinic acid (b) 118 ⁇ lg, 1,4-butanediol (a) 99 ⁇ lg, 6.3 g (6.3 mol per 100 mol of succinic acid) of a 90% aqueous lactic acid (c) solution in which 1% by weight of germanium oxide was previously dissolved, and 0.2 g of malic acid (d) (
  • the obtained polyester was milky white, had a number average molecular weight Mn of 75,300 and a melting point of 110 ° C.
  • the lactic acid introduction rate by 1 H-NMR was 6.3 mol per 100 mol of succinic acid.
  • Aliphatic polyester (A), polylactic acid (B), pulp, and water as a swelling agent for the amorphous region of cellulose were kneaded with the composition shown in Table 1 using a twin-screw extruder.
  • the specifications of the twin-screw extruder used are as follows.
  • the particles of the aliphatic polyester (A) and the polylactic acid (B) were blended and supplied to a twin-screw extruder by a weight feeder.
  • a melting step In the twin-screw extruder, three steps, a melting step, a melting 'fibrillation' dispersion step, and a water separation / extrusion step, were set in the extrusion direction according to the screw configuration.
  • the set temperatures for each step are as follows.
  • Pulp is preliminarily mixed with water as a cellulose amorphous region swelling agent at a predetermined ratio to form a mixture, and this mixture is mixed by a high-pressure pump at the boundary between the melting step and the melting, defibration, and dispersion steps. It was injected into a twin screw extruder.
  • the melting / fibrillation 'dispersion step' was a 1.5MPa pressurized section by a screw configuration, and the water separation 'extrusion step pressure was 53.2kPa by a vacuum pump.
  • the obtained composition was injection-molded with an injection molding machine having the following specifications, and the obtained molded product was evaluated. The results are shown in Table 1.
  • Fig. 3a shows a photograph of the morphology of the fiber in the composition obtained in Example 2.
  • An aliphatic polyester composition was obtained in the same manner as in Example 1, except that the polylactic acid (B) was not used and the composition shown in Table 1 was used, and injection molding was performed in the same manner. Are shown in Table 1.
  • An aliphatic polyester composition was obtained in the same manner as in Example 1 except that pulp and water were not used, and injection molding was performed in the same manner.
  • the evaluation results of the injection-molded product were shown in Table 1.
  • An aliphatic polyester composition was obtained in the same manner as in Example 2 except that panolep without pretreatment was used instead of the pretreated pulp (C), and injection molding was performed in the same manner. It is shown in Table 1.
  • Fig. 3b shows a morphological photograph of the fibers in the composition obtained in Comparative Example 2.
  • An aliphatic polyester composition was obtained in the same manner as in Example 3 except that water was not used and water was not separated in a twin-screw extruder, and injection molding was performed in the same manner to evaluate an injection molded product. The results are shown in Table 1.
  • Comparative Example 4 In Comparative Example 3, an aliphatic polyester composition was obtained in the same manner except that the pretreated pulp (C) was not used, and injection molding was performed in the same manner. The evaluation results of the injection molded product are shown in Table 1.

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Abstract

Un matériau composite de fibres/résine biodégradable d'une haute rigidité et d'une haute résistance peut être produit en dispersant finement et uniformément un composant fibreux par des moyens de malaxage d'usage général, sans prétraitement du composant résine. Plus particulièrement, un tel matériau composite peut être produit en malaxant à fusion 1 à 99,9 parties en poids d'un composant résine comprenant 1 à 100 % en poids (A) d'un polyester aliphatique et 99 à 0 % en poids (B) d'un acide polylactique, et 99 à 0,1 parties en poids d'un composant fibreux comprenant (C) de la pâte de cellulose prétraitée et/ou des fibres cellulosiques avec des rayures sur les couches extérieures des parois primaires et secondaires, en présence de (D) un agent de gonflement capable de gonfler la région non cristalline de la cellulose. Durant le malaxage à fusion, le composant fibreux est microfibrillé à travers l'orifice et dispersé uniformément et finement dans le composant résine.
PCT/JP2004/009720 2003-07-08 2004-07-08 Procede de production d'une composition polyester aliphatique, pate de cellulose et fibres cellulosiques a utiliser dans procede, et procede de microfibrillation correspondant WO2005003450A1 (fr)

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