WO2014136746A1 - Mousse de polyester aliphatique et son procédé de fabrication - Google Patents

Mousse de polyester aliphatique et son procédé de fabrication Download PDF

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Publication number
WO2014136746A1
WO2014136746A1 PCT/JP2014/055384 JP2014055384W WO2014136746A1 WO 2014136746 A1 WO2014136746 A1 WO 2014136746A1 JP 2014055384 W JP2014055384 W JP 2014055384W WO 2014136746 A1 WO2014136746 A1 WO 2014136746A1
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Prior art keywords
aliphatic polyester
foam
foaming
polyester foam
porosity
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PCT/JP2014/055384
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English (en)
Japanese (ja)
Inventor
▲高▼橋健夫
山▲崎▼昌博
佐藤浩幸
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株式会社クレハ
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Priority to JP2015504313A priority Critical patent/JPWO2014136746A1/ja
Publication of WO2014136746A1 publication Critical patent/WO2014136746A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/046—Unimodal pore distribution
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/16—Biodegradable polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides

Definitions

  • the present invention relates to an aliphatic polyester foam and a method for producing the same, and further relates to an aliphatic polyester porous particle and a method for producing the same.
  • foams made of resins such as polyurethane, polystyrene, polyolefin, etc. have excellent lightness, heat insulation, buffering properties, etc., and are stable and will not decompose or rot when left as they are. It is widely used as a heat insulating material or a buffer material.
  • porous particles are expected to be used as, for example, a pharmaceutical preparation having sustained release properties, a base material for agricultural chemicals, or a carrier for immobilizing enzymes and catalysts.
  • the foam molded from these general-purpose resins has a property that it is not easily decomposed in a natural environment. For this reason, when these foams are buried in the soil after use, they remain semi-permanently. Problems such as damage and destruction of the living environment of marine and terrestrial organisms occur.
  • thermoplastic biodegradable resins include aliphatic polyesters such as polyglycolic acid, polylactic acid, polybutyrolactone, polycaprolactone, polybutylene succinate, polyhydroxybutyric acid, and polyhydroxyvaleric acid. These aliphatic polyesters are easily decomposed by hydrolysis with acid or alkali.
  • polyglycolic acid resins are known to have excellent heat resistance and strength.
  • the foam formed from the degradable aliphatic polyester can be used as a food packaging container, a disposable container, a heat insulating material, a cushioning material or the like as described above.
  • porous particles formed from degradable aliphatic polyesters can be used as a base for pharmaceutical preparations and an immobilizing carrier, and can also be used as a bioabsorbable carrier for organ cells.
  • well drilling members used in deep underground to produce hydrocarbon resources such as petroleum (including shale oil) or natural gas (including shale gas), such as downhole tools or the like
  • hydrocarbon resources such as petroleum (including shale oil) or natural gas (including shale gas)
  • downhole tools or the like Use as a member or use in a well drilling fluid, for example, anti-sludge agent (LCM), perforated plug agent, temporary plug agent for fracturing (sometimes referred to as “diverting agent”)
  • LCM anti-sludge agent
  • perforated plug agent temporary plug agent for fracturing
  • bridging agent sometimes referred to as a “finishing sealant”.
  • foams formed from degradable aliphatic polyesters, such as porous particles are easily decomposed by biodegradation or hydrolysis after use. Therefore, the volume of waste is reduced, that is, the volume of waste is reduced. It is also attracting attention from the viewpoint of reducing costs and extending the life of landfills and incinerators.
  • a foam formed from a degradable aliphatic polyester that is, an aliphatic polyester foam
  • a foam molding method similar to that for general-purpose resins. For example, thermally induced phase separation or so-called physical foaming / chemical foaming It can be manufactured by the method.
  • Patent Document 1 discloses a foam made of polyglycolic acid having a melt viscosity of 500 to 100,000 Pa ⁇ s, a melting point of 180 ° C. or higher, a melting enthalpy ⁇ Hm of 10 J / g or higher, and a density of 1.50 g / cm 3 or higher.
  • Patent Document 2 discloses expanded particles having a polylactic acid resin as a main component and having an expansion ratio of 45 times or more.
  • Patent Document 3 discloses a biodegradable polyester resin foam molded article having a compression set of 30% or less and a bending stress reduction point displacement of 1.0 cm or more.
  • Patent Document 4 discloses an end-capped polyester resin foam in which two peaks of 10 to 500 ⁇ m and 0.01 to 1 ⁇ m exist in the pore size distribution and the porosity is 80% or more.
  • the cooling and solidification rate of the polyglycolic acid is high, so that the bubble growth in the polyglycolic acid resin by the foaming agent is difficult to proceed and the expansion ratio is difficult to increase There is.
  • the foam obtained is different in foam form between the surface layer part and the inside, the internal pores are enlarged, the surface layer part has no pores or extremely small pores, and has a non-uniform pore structure as a whole. A foam was obtained.
  • the porous particles formed from the foam having such a pore structure were porous particles having a very nonuniform pore structure.
  • an aliphatic polyester foam having a desired expansion ratio, a high porosity, a small variation in pore diameter, and having a degradability, and a method for producing the same have been desired.
  • An object of the present invention is to provide aliphatic polyester foam and aliphatic polyester porous particles having decomposability, having a desired expansion ratio, high porosity, small variation in pore diameter, and production thereof. It is to provide a method.
  • an aliphatic polyester foam having a uniform pore structure is provided.
  • the above-mentioned aliphatic polyester foam having a total porosity in the foam of 10 to 95% and a pore diameter variation coefficient of 35 or less.
  • the said aliphatic polyester foam whose aliphatic polyester is polyglycolic acid resin.
  • the said aliphatic polyester foam whose polyol is polyalkylene glycol.
  • the said aliphatic polyester foam which is a particulate form.
  • the method for producing an aliphatic polyester foam wherein the aliphatic polyester is foamed in the presence of a polyol.
  • the above-mentioned method for producing an aliphatic polyester foam wherein the aliphatic polyester foam is further pulverized to produce an aliphatic polyester foam in the form of particles, that is, aliphatic polyester porous particles.
  • an aliphatic polyester foam or porous particle having a uniform pore structure preferably having a total porosity of 10 to 95% and a pore diameter variation coefficient of 35 or less is desired.
  • an effect of providing an aliphatic polyester foam or porous particles having decomposability, having a high expansion ratio, a high porosity, and a small variation in pore diameter is exhibited.
  • the aliphatic polyester foam is produced by foaming an aliphatic polyester in the presence of a polyol, and the aliphatic polyester foam is further pulverized to form a particulate aliphatic polyester.
  • the aliphatic polyester foam having the uniform pore structure and the aliphatic polyester porous particles can be easily produced by the above-described method for producing an aliphatic polyester foam for producing a foam. An effect is produced.
  • Aliphatic polyester foam having a uniform pore structure Aliphatic polyester foam having a uniform pore structure
  • PGA polyglycolic acid
  • lactic acid Hydroxycarboxylic acid-based aliphatic polyesters such as polylactic acid consisting of repeating units (hereinafter sometimes referred to as “PLA”), lactone-based aliphatic polyesters such as poly- ⁇ -caprolactone, polyethylene succinate, polybutylene succinate, etc.
  • Diol / dicarboxylic acid aliphatic polyesters and copolymers thereof for example, copolymers comprising glycolic acid repeating units and lactic acid repeating units (glycolic acid / lactic acid copolymer), and mixtures thereof. Can be mentioned.
  • the aliphatic polyester forming the aliphatic polyester foam having a uniform pore structure of the present invention is glycolic acid or glycolic acid containing glycolide (GL) which is a bimolecular cyclic ester of glycolic acid; lactic acid or lactic acid 2
  • lactic acids containing lactide which is an intermolecular cyclic ester
  • ethylene oxalate ie, 1,4-dioxane-2,3-dione
  • lactones eg, ⁇ -propiolactone, ⁇ -butyrolactone, Pivalolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone, etc.
  • carbonates eg, trimethylene carbonate
  • ethers eg, 1,3-dioxane
  • ether esters A cyclic monomer such as dioxanone (eg dio
  • Degradable aliphatic polyesters having a repeating unit of glycolic acid or lactic acid represented by 50% by mass or more, polylactone, polyhydroxybutyrate, polyethylene succinate, polybutylene succinate and the like.
  • polyglycolic acid resins having 50% by mass or more of glycolic acid repeating units or polylactic acid resins having 50% by mass or more of lactic acid repeating units are preferred.
  • a glycolic acid homopolymer (PGA) or a glycolic acid repeating unit is 50% by mass or more, preferably 75% by mass or more, more preferably 85% by mass or more, Preferably 90% by weight or more, particularly preferably 95% by weight or more, most preferably 99% by weight or more, particularly preferably 99.5% by weight or more of a copolymer, or a mixture thereof;
  • Poly L-lactic acid or poly D-lactic acid homopolymer (PLA) L-lactic acid or D-lactic acid repeating unit is 50% by mass or more, preferably 75% by mass or more, more preferably 85% by mass or more, and further preferably Is a copolymer having 90% by mass or more, or a mixture thereof; glycolic acid / lactic acid copolymer; a mixture of the above-mentioned polymers, eg If a mixture of PGA and PLA [mixing ratio (mass ratio), 90: 10 to 10: 90. ] I
  • PLA is obtained from L-lactic acid, which is a raw material, at low cost by fermentation from corn, straw, etc., and because it is derived from plant raw materials, it has excellent carbon offset properties.
  • the polymer performance is characterized by high rigidity and good transparency.
  • PGA is characterized by excellent heat resistance, mechanical strength such as tensile strength and bending strength, and wear resistance.
  • aliphatic polyesters can be synthesized, for example, by dehydration polycondensation of ⁇ -hydroxycarboxylic acids such as glycolic acid and lactic acid known per se.
  • a method of synthesizing a bimolecular cyclic ester of ⁇ -hydroxycarboxylic acid and subjecting the cyclic ester to ring-opening polymerization is employed.
  • PLA is obtained by ring-opening polymerization of lactide, which is a bimolecular cyclic ester of lactic acid.
  • PGA is obtained by ring-opening polymerization of glycolide, which is a bimolecular cyclic ester of glycolic acid.
  • the aliphatic polyester can be synthesized by the above method, but a commercially available product may be used.
  • PLA “Lacia” (registered trademark) series (manufactured by Mitsui Chemicals) such as Lacia H-100, H-280, H-400, H-440, 3001D, 3051D, 4032D, 4042D, 6201D, "INGEO” (registered trademark) (made by Nature Works) such as 6251D, 7000D, 7032D, etc.
  • "Ecoplastic U'z series” such as Eco Plastic U'z S-09, S-12, S-17 (Toyota Motor) Manufactured by Toyobo Co., Ltd.
  • Ecoplastic U'z series such as Eco Plastic U'z S-09, S-12, S-17 (Toyota Motor) Manufactured by Toyobo Co., Ltd.
  • melt viscosity As the aliphatic polyester, those having a melt viscosity of usually 100 to 2000 Pa ⁇ s, preferably 200 to 1800 Pa ⁇ s, more preferably 300 to 1500 Pa ⁇ s can be used. The melt viscosity is measured at a temperature of 240 ° C. and a shear rate of 122 sec ⁇ 1 . If the melt viscosity is too small, the resulting aliphatic polyester foam is low in strength and may be brittle, or it may be difficult to retain air bubbles and may not have a uniform pore structure. If the melt viscosity is too high, a high temperature is required for molding the foam, and thus the aliphatic polyester may be thermally deteriorated or foaming of the foaming agent may not be controlled as desired.
  • the aliphatic polyester foam having a uniform pore structure of the present invention may be formed by using only aliphatic polyester as a resin material, but other resins may be used as long as the object of the present invention is not impaired. You may blend and use a material.
  • Examples of other resin materials include cellulose acetate, polyvinyl alcohol, starch, polyglutamic acid ester, natural rubber, polyethylene, polypropylene, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, polymethyl methacrylate, polystyrene, styrene Examples thereof include a butadiene / styrene block copolymer, a styrene / ethylene / butylene / styrene block copolymer, an ABS resin, an MBS resin, and an ethylene / vinyl alcohol copolymer. These other resin materials can be used alone or in combination of two or more.
  • the other resin material is usually used in a proportion of 0 to 100 parts by mass with respect to 100 parts by mass of the aliphatic polyester, but considering the disintegration in soil, it is preferably 50 parts by mass or less, more preferably 30 parts by mass. It is desirable to use at a ratio of less than or equal to parts.
  • the aliphatic polyester foam having a uniform pore structure of the present invention is usually formed by containing a foaming agent and a foaming aid and further does not impair the object of the present invention.
  • Various additives such as a deodorizing agent and a flame retardant may be contained or blended. The content or blending ratio of these additives can be determined as appropriate according to the type of additive.
  • the amount is usually 0 to 100 parts by mass with respect to 100 parts by mass of the aliphatic polyester, but in most cases it is 50 parts by mass or less in consideration of foamability, processability, heat resistance, etc. May be used at a ratio of 5 parts by mass or less, and further 1 part by mass or less.
  • the foaming agent and foaming aid will be described in detail later.
  • ⁇ filler ⁇ Fillers include alumina, silica, silica alumina, zirconia, titanium oxide, iron oxide, boron oxide, calcium carbonate, calcium silicate, calcium phosphate, calcium sulfate, magnesium carbonate, magnesium silicate, magnesium phosphate, magnesium sulfate, kaolin , Talc, mica, ferrite, carbon, silicon nitride, molybdenum disulfide, glass, powders such as potassium titanate, inorganic fillers such as whiskers and fibers, and organic fillers such as resin foam beads. Some agents function as bubble regulators.
  • a filler can be used individually or in combination of 2 types or more, respectively.
  • plasticizer examples include phthalic acid esters such as di (methoxyethyl) phthalate, dioctyl phthalate, diethyl phthalate, and benzyl butyl phthalate; benzoic acid esters such as diethylene glycol dibenzoate and ethylene glycol dibenzoate; dioctyl adipate, dioctyl sebacate, and the like.
  • Aliphatic dibasic acid esters aliphatic tribasic acid esters such as tributyl acetylcitrate
  • polyhydric alcohol esters such as glycerin fatty acid esters, acetylated glycerin fatty acid esters, and propylene glycol fatty acid esters
  • acetylated compounds dioctyl phosphate, phosphorus And phosphoric acid esters such as tricresyl acid
  • epoxy plasticizers such as epoxidized soybean oil; and the like.
  • the plasticizers can be used alone or in combination of two or more.
  • Air conditioner examples include inorganic substances such as talc, calcium carbonate, borax, zinc borate, aluminum hydroxide and calcium stearate.
  • spreading agent examples include liquid paraffin, polybutene, silicone oil, dietary oil, and fatty acid.
  • Foaming method, foaming agent and foaming aid The aliphatic polyester foam having a uniform pore structure of the present invention can be obtained by foaming a material containing the above-mentioned aliphatic polyester.
  • an appropriate foaming method can be employed in consideration of the purpose of use and the like.
  • Specific foaming methods include, for example, (1) a so-called extrusion foaming method in which a material containing an aliphatic polyester is extruded from an extruder and foamed at the same time using a foaming agent, or simultaneously injected from an injection molding machine.
  • So-called injection foaming method for foaming (2) preparing a foamable resin composition by blending a material containing an aliphatic polyester with a pyrolytic foaming agent, and then at a temperature lower than the decomposition temperature of the pyrolytic foaming agent A method of foaming after molding into a desired shape, and (3) molding by blowing air or nitrogen gas into a material containing aliphatic polyester that has been heated and melted into a fluidized state and mechanically mixed or kneaded. (4) A pellet-containing aliphatic polyester-containing material is suspended in a dispersion solution, and a foaming agent that becomes a gas above its melting point is heated and added.
  • the foam obtained by these methods is formed into a desired form at the time of foaming, it can be used after being subjected to secondary processing as necessary and shaped into a desired form.
  • the granular foam, ie, the aliphatic polyester foam which is a porous particle can be obtained by shredding or grind
  • foaming agent one suitable for each foaming method is selected and used. Specifically, (1) physical foaming agent foamed by gas generated by evaporation, for example, hydrocarbon compounds such as butane, pentane, hexane, petroleum ether; halogenated hydrocarbon compounds such as methylene chloride, dichloroethane, dichlorodifluoromethane Carbon dioxide gas, nitrogen gas, etc.
  • hydrocarbon compounds such as butane, pentane, hexane, petroleum ether
  • halogenated hydrocarbon compounds such as methylene chloride, dichloroethane, dichlorodifluoromethane Carbon dioxide gas, nitrogen gas, etc.
  • Pyrolytic foaming agents that generate gas by thermal decomposition
  • inorganic foaming agents such as bicarbonate and carbonate
  • azodicarbonamide, azobisiso Azo compounds such as butyronitrile and barium azodicarboxylate
  • nitroso compounds such as N, N-dinitrosopentamethylenetetramine
  • sulfonyl hydrazide compounds such as p, p'-oxybis (benzenesulfonylhydrazide) and p-toluenesulfonylhydrazide
  • Organic foaming agents such as (3) above
  • the amount of the foaming agent to be used can be appropriately determined according to the type of foaming agent, the foaming method, the desired expansion ratio, etc., but is usually 0.1 to 30 parts by weight with respect to 100 parts by weight of the aliphatic polyester. Preferably it is used in a proportion of 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass.
  • the expansion ratio of the aliphatic polyester foam of the present invention is usually 1.3 to 30 times, preferably 1.5 to 20 times. A foam with an expansion ratio of less than 1.3 cannot exhibit the properties as a foam. Conversely, a foam with an expansion ratio of more than 30 times has a uniform pore structure, in addition to poor mechanical strength. There exists a possibility that manufacture of the foam which has may become difficult.
  • the expansion ratio of the foam varies depending on the end use and is appropriately selected.For example, a relatively low expansion ratio is required for food packaging trays and disposable cups that require mechanical strength, and well drilling applications. In general, a relatively high expansion ratio is selected for a heat insulating material or a cushioning material that requires a heat insulating property and does not require a mechanical strength.
  • foaming aid In order to obtain the aliphatic polyester foam having a uniform pore structure of the present invention, it is desirable to use a foaming aid.
  • the foaming aid is not particularly limited as long as an aliphatic polyester foam having a uniform pore structure can be obtained, but alcohols, ketones, ethers having 1 to 4 carbon atoms, which are conventionally known as foaming aids, Benzene, toluene, etc. can be used, and some of the compounds conventionally known as plasticizers can also be used. From the viewpoint of further improving the uniform structure of the pores, it is preferable to use a polyol, that is, a polyhydric alcohol, more preferably a polyalkylene glycol, as a foaming aid.
  • the working mechanism that can obtain an aliphatic polyester foam having a uniform pore structure is not necessarily clear, but the resin that forms the foam due to the presence of the foaming aid It is assumed that the foaming agent dispersibility in the aliphatic polyester, which is the raw material, is improved, or the cooling rate of the resin raw material is lowered and the solidification is slowed down, so that the foaming time can be secured long enough. Is done. On the other hand, when the foaming aid is not used, the foaming agent may not be sufficiently dispersed in the resin raw material, or it may be difficult to foam particularly near the surface layer due to the high cooling rate. It is presumed that partial bias tends to occur.
  • polyols preferably used as foaming aids include polyhydric alcohols such as glycols, partially substituted polyol compounds such as monoesters of glycerin, polyalkylene glycols, and the like.
  • a polyalkylene glycol derivative such as a partial ester or partial acetylated product of polyalkylene glycol can also be used as long as it is a polyol in which a plurality of free hydroxyl groups remain. Since the low molecular weight polyol may not function as a foaming aid, it is desirable to select a polyol having a molecular weight of 100 or more, preferably 200 or more, more preferably 300 or more.
  • a particularly desirable polyol is polyalkylene glycol.
  • polyalkylene glycol examples include polyethylene glycol, polypropylene glycol, polybutylene glycol and the like, and the weight average molecular weight is preferably in the range of 200 to 50000, more preferably 1000 to 40000, and still more preferably 3000 to 30000. The effect of improving the uniform structure of the pores is high.
  • the amount of the foaming aid may be determined in an optimum amount within a range in which an aliphatic polyester foam having a uniform pore structure can be formed.
  • 0.3 to 22 parts by weight, preferably 0.5 to 19 parts by weight, more preferably 0.7 to 15 parts by weight, and still more preferably 0.9 to 12 parts by weight with respect to 100 parts by weight of the polyester. is there.
  • the use ratio (mass ratio) of the foaming agent and the foaming aid may be set to an optimum amount within a range in which an aliphatic polyester foam having a uniform pore structure can be formed.
  • the foaming agent / foaming aid is 1/10 to 10/1, and depending on the combination of the foaming agent and the foaming aid, 1/5 to 5/1 may be suitable.
  • the uniform pore structure is the total porosity (the sum of the independent pore porosity and the through-hole porosity). It means high and small variation in hole diameter.
  • the aliphatic polyester foam having a uniform pore structure according to the present invention has (1) a total porosity (total of independent pore porosity and through-hole porosity) of usually 10 to 95. %, Preferably 20% or more, more preferably 25% or more, still more preferably 30% or more. Particularly, for aliphatic polyester foams other than porous particles, 40% or more, more preferably 60% or more.
  • a variation coefficient of pore diameter (defined as standard deviation of pore diameter / average pore diameter ⁇ 100) of 35 or less, preferably 34.5 or less, more preferably 34 or less. More preferably, (3) the through-hole porosity is 3% or more, more desirably 5% or more, and even more preferably 10% or more, and (4) the average pore diameter is 50 to 500 ⁇ m, more desirably.
  • the thickness is 60 to 300 ⁇ m, more preferably 80 to 200 ⁇ m.
  • the porosity such as the total porosity of the aliphatic polyester foam can be measured and calculated by the following method.
  • Independent pore porosity (%) [(1 / ⁇ s ) ⁇ (1 / ⁇ )] / (1 / ⁇ s ) ⁇ 100
  • ⁇ s is the density of the foam
  • ⁇ is the density of the aliphatic polyester.
  • ⁇ Porosity of through hole The foam is immersed in a fluorine-based surfactant [GALWICK (surface tension 15.9 dyne / cm, density 1.8 g / cm 3 ) manufactured by Porous Materials, Inc.], and the mass before and after the immersion is measured. To calculate the through-hole porosity (unit:%) of the foam.
  • Through-hole porosity (%) [(W L / ⁇ G ) / (W L / ⁇ G + W / ⁇ )] ⁇ 100
  • W L is the mass of the liquid impregnated in the foam
  • ⁇ G the density of the surfactant
  • W is the mass of the foam
  • ⁇ is the density of the aliphatic polyester.
  • ⁇ Total porosity> The sum of the independent pore porosity and the through-hole porosity is calculated to obtain the total porosity (unit:%) of the foam.
  • the coefficient of variation of the pore diameter of the foam can be measured and calculated by the following method.
  • the foam is cut, and an arbitrary cut surface is observed with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the length of each major axis and minor axis is measured for all recognizable holes in the observation region, and the average value is defined as the hole diameter of the holes.
  • the average pore diameter and standard deviation are calculated from the measured pore diameter values, and the average pore diameter (unit: ⁇ m) and coefficient of variation in pore diameter (standard deviation of pore diameter / average pore diameter ⁇ 100) are calculated. .
  • the aliphatic polyester foam having a uniform pore structure according to the present invention is a foam having a high porosity and a uniform pore diameter, it is a foam having a homogeneous porous structure and reduced after use. Since the capacity (volume reduction rate) is extremely large, it is an aliphatic polyester foam that is easy to use, has low environmental impact, and has the effect of significantly reducing disposal costs.
  • the aliphatic polyester foam having a uniform pore structure according to the present invention may be a particulate aliphatic polyester foam, that is, aliphatic polyester porous particles (hereinafter simply referred to as “porous particles”). .).
  • the aliphatic polyester foam having a uniform pore structure in the form of particles according to the present invention that is, the aliphatic polyester porous particles having a uniform pore structure, can be used alone or in an appropriate solvent by adjusting the particle size. When it is dispersed, the fluidity can be made extremely good, so that it may be very convenient for some applications.
  • the porous particles have a particle size of usually 10 mesh (aperture 1.7 mm) to 100 mesh (aperture 150 ⁇ m), preferably 12 mesh (aperture 1.4 mm) to 80 mesh (aperture 180 ⁇ m), more preferably. Is classified by a sieve or the like so as to be in the range of 16 mesh (aperture 1.0 mm) to 60 mesh (aperture 250 ⁇ m), more preferably 20 mesh (aperture 850 ⁇ m) to 40 mesh (aperture 425 ⁇ m). Is preferred.
  • the use of the aliphatic polyester foam having a uniform pore structure of the present invention is not particularly limited, but it has a high porosity and uniform pore diameter. Since it is a degradable foam, it can be used for applications such as food packaging containers, food containers, various disposable containers (cups, soup dishes, etc.), roses, cushioning materials, heat insulating materials, etc. It can also be used as a well drilling member such as a downhole tool or its member or a temporary sealant.
  • the use of the aliphatic polyester porous particles having a uniform pore structure of the present invention is not particularly limited, but sustained release pharmaceuticals, sustained release agricultural chemicals, immobilization using conventional porous fine particles Carriers for holding pharmaceuticals, agricultural chemicals, enzymes / microorganisms, catalysts, animal cells, etc., or as separation materials in various fields such as enzymes / immobilized microorganisms (bioreactors), chemical reactions, animal cell culture It can be used as a capsule, and can also be used as a temporary sealant blended with a well treatment fluid such as a drilling fluid, a fracturing fluid, a cementing fluid, a temporary plug fluid or a finishing fluid.
  • a well treatment fluid such as a drilling fluid, a fracturing fluid, a cementing fluid, a temporary plug fluid or a finishing fluid.
  • the aliphatic polyester foam having a uniform pore structure according to the present invention obtains a foam having a uniform porosity and a high porosity described above.
  • the production method is not particularly limited, but an aliphatic polyester foam having a more uniform pore structure can be obtained by a method for producing an aliphatic polyester foam in which an aliphatic polyester is foamed in the presence of a polyol. It can be manufactured efficiently.
  • a raw material containing a resin material such as an aliphatic polyester and an additive such as a foaming agent and a polyol as a foaming aid are respectively added to a feeder in advance, and then extruded.
  • An aliphatic polyester extruded foam having a uniform pore structure of a desired shape can be obtained by extrusion molding by supplying to a machine, heat-melting and kneading in a molding machine, and discharging from a die having a predetermined shape. By discharging from the strand die, an aliphatic polyester foamed strand having a uniform pore structure can be obtained.
  • the extruded foam for example, the foamed strand is taken up while being cooled by a cooling roll or the like cooled to a predetermined temperature, but foaming may continue during cooling (that is, during taking-up).
  • the measurement of the hole diameter and porosity of an aliphatic polyester foam is implemented after foaming is complete
  • the aliphatic polyester porous particles having a uniform pore structure can be efficiently produced.
  • a foam in the form of a strand or the like of an aliphatic polyester produced by extrusion molding is cut into a predetermined length (for example, about 10 mm in length) and frozen with liquid nitrogen or the like.
  • aliphatic polyester porous particles can be obtained by pulverization using a pulverizer.
  • the particle size, particle size distribution, and porosity of the porous particles can be adjusted depending on the type of pulverizer and pulverization conditions. Moreover, it classifies as needed and the porous particle which has a desired particle size and particle size distribution can be obtained.
  • ⁇ s is the density of the foam
  • ⁇ is the density of the aliphatic polyester.
  • ⁇ Porosity of through hole The foam is immersed in a fluorine-based surfactant [GALWICK (surface tension 15.9 dyne / cm, density 1.8 g / cm 3 ) manufactured by Porous Materials, Inc.], and the mass before and after the immersion is measured. Thus, the through-hole porosity (unit:%) of the foam was calculated.
  • Through-hole porosity (%) [(W L / ⁇ G ) / (WL / ⁇ G + W / ⁇ )] ⁇ 100
  • W L is the mass of the liquid impregnated in the foam
  • ⁇ G the density of the surfactant
  • W is the mass of the foam
  • ⁇ is the density of the aliphatic polyester.
  • ⁇ Total porosity> The sum of the independent pore porosity and the through-hole porosity was calculated and used as the total porosity (unit:%) of the foam.
  • the variation coefficient of the pore diameter of the foam was measured and calculated by the following method.
  • the foam is cut, and an arbitrary cut surface is observed with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the length of each major axis and minor axis was measured for all recognizable holes in the observation region, and the average value was taken as the hole diameter of the holes.
  • the average value and standard deviation of the pore diameter are calculated from the measured pore diameter values, and the average pore diameter (unit: ⁇ m) and variation coefficient of pore diameter (standard deviation of pore diameter / average pore diameter x 100) are calculated. did.
  • Example 1 As raw materials for forming a foam, the following (1) to (4) (1) Aliphatic polyester: Polyglycolic acid (manufactured by Kureha Co., Ltd., melt viscosity 790 Pa ⁇ s. Hereinafter, simply referred to as “PGA”) 100 parts by mass (2) Foaming agent: Micro made by Kureha Co., Ltd. Sphere (MS-H1100.
  • Foaming aid polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 20000, hereinafter sometimes referred to as “PEG 20000”) Part by mass (4)
  • Spreading agent 0.3 part by mass of liquid paraffin was charged into the hopper of the quantitative feeder. Next, it is supplied from a quantitative feeder to a bi-directional kneading and extruding machine, melted and kneaded at a temperature of 230 to 250 ° C., discharged from a strand die and extruded, and has a diameter of 7 to 8 mm with a cooling roll at a temperature of 25 ° C.
  • the strand was taken up. It was visually confirmed that foaming was progressing even during strand take-up.
  • the polymer was taken up to a position where foaming was completed, and a strand-like polyglycolic acid foam was obtained.
  • the independent pore porosity, the through-hole porosity, the total porosity, the average pore diameter, and the coefficient of variation of the pore diameter (hereinafter sometimes referred to as “particle characteristics”) were measured and calculated. The results are shown in Table 1.
  • Example 2 A strand-like polyglycolic acid foam was obtained in the same manner as in Example 1 except that the blending amount of the foaming aid was changed to 1 part by mass. Table 1 shows the results of measuring and calculating the particle characteristics of the obtained foam.
  • Example 3 A strand-like polyglycolic acid foam was obtained in the same manner as in Example 1 except that the blending amount of the foaming aid was changed to 10 parts by mass. Table 1 shows the results of measuring and calculating the particle characteristics of the obtained foam.
  • Example 4 A strand-like polyglycolic acid foam was obtained in the same manner as in Example 1 except that the blending amount of the foaming aid was changed to 20 parts by mass. Table 1 shows the results of measuring and calculating the particle characteristics of the obtained foam.
  • Example 5 In the same manner as in Example 1 except that the foaming aid was changed to polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 6000, hereinafter sometimes referred to as “PEG6000”). A polyglycolic acid foam was obtained. Table 1 shows the results of measuring and calculating the particle characteristics of the obtained foam.
  • PEG6000 weight average molecular weight 6000
  • Aliphatic polyester is poly-L-lactic acid [INGEO (registered trademark) 4032D from Nature Works. Melt viscosity 560 Pa ⁇ s. Hereinafter, it may be referred to as “PLA”.
  • a strand-like poly-L-lactic acid foam was obtained in the same manner as in Example 1 except that the above was changed. Table 1 shows the results of measuring and calculating the particle characteristics of the obtained foam.
  • Example 1 A strand-like polyglycolic acid foam was obtained in the same manner as in Example 1 except that no foaming aid was blended. Table 1 shows the results of measuring and calculating the particle characteristics of the obtained foam.
  • Example 2 Polyglycolic acid was added in the same manner as in Example 1 except that propylene glycol (molecular weight: 76. Hereinafter, sometimes referred to as “PG”) was blended in place of polyethylene glycol (PEG 20000) as a foaming aid. When extruded in the form of a strand, no foaming was observed in the extruded strand (the porosity is 0%).
  • propylene glycol molecular weight: 76.
  • PEG 20000 polyethylene glycol
  • the aliphatic polyester foams of Examples 1 to 6 produced by foaming an aliphatic polyester in the presence of a polyol as a foaming aid have a porosity (total porosity) of 10 to Since it is as high as 95% and the coefficient of variation in pore diameter is as small as 35% or less, it was found to be an aliphatic polyester foam having a uniform pore structure with a large proportion of pores and small variation in pore diameter. . Moreover, it turned out that the ratio of a hole and the variation in a hole diameter can be adjusted by adjusting the compounding quantity of a foaming adjuvant.
  • Example 7 The strand-like foam obtained in Example 1 was chopped to a length of 10 mm, immersed in liquid nitrogen, pulverized with a pulverizer (manufactured by Kinematica), and then 20 mesh (opening 850 ⁇ m). And collected on the upper surface of a 40 mesh (aperture 425 ⁇ m) sieve to obtain a polyglycolic acid foam (polyglycolic acid porous particles) in the form of particles.
  • Table 2 shows the results obtained by measuring and calculating the particle characteristics of the obtained porous particles.
  • Example 8 Polyglycolic acid porous particles were obtained in the same manner as in Example 7 except that the strand-like foam was changed to the foam obtained in Example 2. Table 2 shows the results obtained by measuring and calculating the particle characteristics of the obtained porous particles.
  • Example 9 Polyglycolic acid porous particles were obtained in the same manner as in Example 7 except that the strand-like foam was changed to the foam obtained in Example 3. Table 2 shows the results obtained by measuring and calculating the particle characteristics of the obtained porous particles.
  • the aliphatic polyester foams (aliphatic polyesters) produced in Example 7 to 9 were produced by pulverizing an aliphatic polyester foam produced by foaming an aliphatic polyester in the presence of a polyol. It was found that the porous particles) are aliphatic polyester porous particles having a uniform pore structure with a large pore ratio and small variation in pore diameter.
  • the aliphatic polyester foam of Comparative Example 3 produced by pulverizing an aliphatic polyester foam produced by foaming without the presence of a polyol as a foaming auxiliary agent has a uniform empty space. It turned out that it cannot be called the aliphatic polyester porous particle which has a pore structure.
  • the aliphatic polyester foam having a uniform pore structure of the present invention preferably having a total porosity of 10 to 95% and a pore diameter variation coefficient of 35 or less, or an aliphatic polyester foam in the form of particles (porous Particles) have a desired expansion ratio, a high porosity, a small variation in pore diameter, and can provide a degradable aliphatic polyester foam or porous particles. High availability.
  • the method for producing an aliphatic polyester foam described above in which the aliphatic polyester of the present invention is foamed in the presence of a polyol and an aliphatic polyester foam in the form of particles by further pulverizing the aliphatic polyester foam. Since the aliphatic polyester foam having the uniform pore structure and the aliphatic polyester porous particles can be easily manufactured, the method for manufacturing the aliphatic polyester foam to be manufactured can be used industrially. High nature.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne : des particules poreuses de polyester aliphatique et une mousse polyester aliphatique telle qu'une résine acide polyglycolique, qui ont une structure uniforme de trous et, de manière idéale, ont un rapport total de trous de 10 %-95 % et un coefficient de variation de diamètre de pore de pas plus de 35 ; un procédé de fabrication de la mousse de polyester aliphatique dans lequel du polyester aliphatique est transformé en mousse en présence de polyol ; et un procédé de fabrication des particules poreuses de polyester aliphatique dans lequel une mousse de polyester aliphatique est pulvérisée.
PCT/JP2014/055384 2013-03-07 2014-03-04 Mousse de polyester aliphatique et son procédé de fabrication WO2014136746A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017088834A (ja) * 2015-11-17 2017-05-25 旭化成株式会社 発泡体
WO2019017773A1 (fr) * 2017-07-19 2019-01-24 Synbra Technology B.V. Récipient pour liquides, procédés de production et d'utilisation de ce dernier
JP2021091225A (ja) * 2015-09-30 2021-06-17 ヒューヴィス コーポレーションＨｕｖｉｓ Ｃｏｒｐｏｒａｔｉｏｎ ポリエステル発泡シートとポリエステル樹脂層を含む複合体、およびそれを含む自動車内外装材

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WO2009078309A1 (fr) * 2007-12-19 2009-06-25 Showa Highpolymer Co., Ltd. Composition de résine moussable et mousse correspondante
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JP2010070631A (ja) * 2008-09-18 2010-04-02 Toray Ind Inc ポリ乳酸系樹脂発泡体
JP2011231286A (ja) * 2010-04-30 2011-11-17 Sekisui Plastics Co Ltd ポリ乳酸系樹脂発泡成形体
JP2012041506A (ja) * 2010-08-23 2012-03-01 Asahi Kasei Chemicals Corp 発泡体
JP2012229416A (ja) * 2011-04-14 2012-11-22 Jsr Corp 発泡成形体の製造方法およびそれにより得られた発泡成形体、ならびに発泡用樹脂組成物

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JP4258758B2 (ja) * 2003-06-06 2009-04-30 株式会社ジェイエスピー 熱成形用ポリ乳酸系樹脂発泡シート
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JPH10114833A (ja) * 1996-08-20 1998-05-06 Kureha Chem Ind Co Ltd ポリグリコール酸発泡体
JP2005060689A (ja) * 2003-07-31 2005-03-10 Toray Ind Inc 発泡体およびその製造方法
JP2009073955A (ja) * 2007-09-21 2009-04-09 Toray Ind Inc ポリ乳酸系樹脂発泡体
WO2009078309A1 (fr) * 2007-12-19 2009-06-25 Showa Highpolymer Co., Ltd. Composition de résine moussable et mousse correspondante
WO2009110587A1 (fr) * 2008-03-07 2009-09-11 東レ株式会社 Matériau d'isolation thermique
JP2010070631A (ja) * 2008-09-18 2010-04-02 Toray Ind Inc ポリ乳酸系樹脂発泡体
JP2011231286A (ja) * 2010-04-30 2011-11-17 Sekisui Plastics Co Ltd ポリ乳酸系樹脂発泡成形体
JP2012041506A (ja) * 2010-08-23 2012-03-01 Asahi Kasei Chemicals Corp 発泡体
JP2012229416A (ja) * 2011-04-14 2012-11-22 Jsr Corp 発泡成形体の製造方法およびそれにより得られた発泡成形体、ならびに発泡用樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021091225A (ja) * 2015-09-30 2021-06-17 ヒューヴィス コーポレーションＨｕｖｉｓ Ｃｏｒｐｏｒａｔｉｏｎ ポリエステル発泡シートとポリエステル樹脂層を含む複合体、およびそれを含む自動車内外装材
JP7280903B2 (ja) 2015-09-30 2023-05-24 ヒューヴィス コーポレーション ポリエステル発泡シートとポリエステル樹脂層を含む複合体、およびそれを含む自動車内外装材
JP2017088834A (ja) * 2015-11-17 2017-05-25 旭化成株式会社 発泡体
WO2019017773A1 (fr) * 2017-07-19 2019-01-24 Synbra Technology B.V. Récipient pour liquides, procédés de production et d'utilisation de ce dernier

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