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WO2014024939A1 - Résine de polyester de type poly(acide lactique), dispersion aqueuse de résine de polyester de type poly(acide lactique), et procédé pour produire une dispersion aqueuse de résine de polyester de type poly(acide lactique) - Google Patents

Résine de polyester de type poly(acide lactique), dispersion aqueuse de résine de polyester de type poly(acide lactique), et procédé pour produire une dispersion aqueuse de résine de polyester de type poly(acide lactique) Download PDF

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Publication number
WO2014024939A1
WO2014024939A1 PCT/JP2013/071420 JP2013071420W WO2014024939A1 WO 2014024939 A1 WO2014024939 A1 WO 2014024939A1 JP 2013071420 W JP2013071420 W JP 2013071420W WO 2014024939 A1 WO2014024939 A1 WO 2014024939A1
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Prior art keywords
polylactic acid
polyester resin
water
acid
resin
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Ceased
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PCT/JP2013/071420
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English (en)
Japanese (ja)
Inventor
田中　秀樹
奈穂子 小田
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Toyobo Co Ltd
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Toyobo Co Ltd
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Priority to JP2014529541A priority Critical patent/JP6146416B6/ja
Publication of WO2014024939A1 publication Critical patent/WO2014024939A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • 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

Definitions

  • the present invention relates to a polylactic acid-based polyester resin having a self-emulsifying function capable of forming a stable aqueous emulsion without using an emulsifier and an organic solvent, and having a resin skeleton derived from plant raw materials, and a polyester resin containing the same
  • the present invention relates to an aqueous dispersion and a method for producing the aqueous dispersion.
  • the polylactic acid-based resin is a resin mainly composed of plant-derived components that can be produced using lactic acid and / or lactide as raw materials, which can be produced using plants such as corn and potato as raw materials.
  • Polylactic acid-based resins are biodegradable to be decomposed into water and carbon dioxide within several years in soil and seawater, and have a relatively low environmental load when released into the environment. Therefore, if the polylactic acid-based resin can be made into an aqueous dispersion, it is useful as a binder component having biodegradability and using biomass-derived components as raw materials, and paints, inks, coating agents, adhesives, and pressure-sensitive adhesives. It can be expected that it can be used for sealing agents, primers, and various treating agents for textile products and paper products.
  • Patent Documents 1 to 5 Examples of using a resin containing a polylactic acid segment as a binder component after being dispersed in water include Patent Documents 1 to 5.
  • Patent Documents 1 and 2 a polylactic acid aqueous dispersion forcedly emulsified with an emulsifier is used.
  • the water-based polylactic acid shown in Patent Document 3 is also forcibly emulsified using an emulsifier, it is shown that a hydrophilic group may be introduced into the resin.
  • the sodium salt of 5-sulfoisophthalic acid or the sodium salt of dimethyl 5-sulfoisophthalate is preferred.
  • Patent Document 4 discloses a copolymer polyurethane having a polylactic acid segment and a sulfonic acid metal base-containing segment in the molecule, and has a self-emulsifying function capable of forming a stable aqueous emulsion without adding an emulsifier. It has been shown.
  • Patent Document 5 a lactic acid-based polymer having a hydroxyl group is reacted with a polyvalent carboxylic acid or an acid anhydride thereof, the lactic acid-based polymer is dissolved in an organic solvent, a base and water are added, and phase-inversion emulsification is performed, thereby self-water dispersibility. The process for producing the particles is shown.
  • Patent Documents 1, 2, and 3 since an emulsifier is used when preparing a polylactic acid resin aqueous dispersion, when used as a binder component, the emulsifier is attached to the resin. There exists a subject that it remains in the interface of a body and reduces adhesiveness.
  • Patent Document 4 a stable aqueous dispersion is obtained without using an emulsifier, and when used as a binder component, it exhibits high adhesion, but the process for producing an aqueous dispersion There is room for improvement in terms of reducing volatile organic solvent emissions.
  • the solvent removal operation is performed in the production process of the aqueous dispersion, and there is room for improvement from the viewpoint of suppressing emission of volatile organic solvents.
  • the problem to be solved by the present invention is a polylactic acid-based polyester resin having a self-emulsifying function capable of forming an aqueous emulsion without using an emulsifier and an organic solvent, and having a high degree of biomass.
  • this invention consists of the following structures.
  • ⁇ 1> A polylactic acid-based polyester resin characterized by satisfying the formulas (1), (2), and (3). 1 ⁇ Log (MV) ⁇ 4 (1) 300 ⁇ (AV) ⁇ 2,500 (2) Log (MV) ⁇ 0.0028 ⁇ (AV) +1.2 (3)
  • MV is the melt viscosity (Pa ⁇ s) of the polylactic acid-based polyester resin at 80 ° C.
  • AV is the acid value (eq / t) of the polylactic acid-based polyester resin.
  • ⁇ 2> The polylactic acid-based polyester resin according to ⁇ 1>, wherein the lactic acid content is 40% by mass or more.
  • ⁇ 3> The polylactic acid-based polyester resin according to ⁇ 1> or ⁇ 2>, wherein the number average molecular weight is 2,000 or more and 50,000 or less.
  • ⁇ 4> A polylactic acid polyester resin aqueous dispersion comprising the polylactic acid polyester resin according to any one of ⁇ 1> to ⁇ 3>, a basic compound, and water.
  • ⁇ 5> The polylactic acid-based polyester resin aqueous dispersion according to ⁇ 4>, which does not contain a surfactant.
  • ⁇ 6> The polylactic acid-based polyester resin aqueous dispersion described in ⁇ 4> or ⁇ 5>, which does not contain an organic solvent.
  • ⁇ 7> A polylactic acid-based polyester resin dispersed in water by mixing the polylactic acid-based polyester resin according to any one of ⁇ 1> to ⁇ 3>, a basic compound, and water without adding a surfactant and an organic solvent.
  • An aqueous resin composition comprising the polylactic acid-based polyester resin according to any one of ⁇ 1> to ⁇ 3> and a curing agent having reactivity with a carboxyl group.
  • aqueous resin according to ⁇ 8> wherein the curing agent is one or more selected from the group consisting of a polyvalent epoxy compound, a polyvalent oxazoline compound, a carbodiimide compound, and a polyvalent metal salt.
  • Composition. ⁇ 10> An aqueous adhesive comprising the aqueous resin composition according to ⁇ 8> or ⁇ 9>.
  • An aqueous paint comprising the aqueous resin composition according to ⁇ 8> or ⁇ 9>.
  • a water-based ink comprising the water-based resin composition according to ⁇ 8> or ⁇ 9> and a coloring material.
  • a layer (A layer) comprising the polylactic acid-based polyester resin according to any one of ⁇ 1> to ⁇ 3> and a layer (B layer) selected from the group consisting of a film, a sheet, a woven fabric, a nonwoven fabric and paper
  • the laminated body characterized by including.
  • ⁇ 14> The laminate according to ⁇ 13>, wherein the B layer is mainly composed of a biomass-derived substance and / or a chemically modified substance of a biomass-derived substance.
  • a packaging material comprising the laminate according to ⁇ 13> or ⁇ 14> as a constituent element.
  • a sustained-release biodegradable coating agent comprising the aqueous resin composition according to ⁇ 8> or ⁇ 9>.
  • a sustained-release biodegradable coated body wherein the component to be coated is coated with the sustained-release biodegradable coating agent according to ⁇ 16>.
  • the sustained-release biodegradable coating according to ⁇ 17>, wherein the component to be coated has one or more functions of physiological activity, growth promotion, and nutritional supplementation for living organisms. body.
  • the polylactic acid-based polyester resin of the present invention contains a polylactic acid segment at a high concentration, the degree of biomass is high and the biodegradability is excellent.
  • the polylactic acid-based polyester resin of the present invention has a high concentration of carboxyl groups in the molecular chain, it can be easily dispersed in water simply by stirring with an aqueous solution of a basic compound without using an emulsifier and an organic solvent. Exhibits excellent water dispersibility.
  • the polylactic acid-type polyester resin aqueous dispersion of this invention can be prepared without using an emulsifier, it is excellent in adhesiveness.
  • the adhesive layer and ink which are excellent in adhesiveness and water resistance can be obtained easily by mix
  • a laminated body with a high biomass degree can be obtained by combining various biomass materials and the adhesive and / or ink of the present invention.
  • the polylactic acid-type polyester resin of this invention is a polylactic acid-type polyester resin characterized by satisfy
  • MV is the melt viscosity (Pa ⁇ s) of the resin at 80 ° C.
  • AV is the acid value (eq / t) in the resin.
  • the greatest feature of the polylactic acid-based polyester resin of the present invention is that an aqueous dispersion can be easily formed only by stirring with an aqueous solution of a basic compound without using an emulsifier and an organic solvent.
  • an aqueous dispersion can be easily formed only by stirring with an aqueous solution of a basic compound without using an emulsifier and an organic solvent.
  • AV which is the acid value of the resin is an index of the hydrophilic group concentration of the resin.
  • the melt viscosity (unit: Pa ⁇ s) at 80 ° C. of the polylactic acid-based polyester resin of the present invention is MV
  • Log (MV) is 1 or more and 4 or less, preferably 1.7 or more and 3.9 or less, More preferably, it is 2 or more and 3.8 or less, More preferably, it is 2.2 or more and 3.6 or less.
  • Log (MV) is larger than 4, plasticization at the time of dispersion is insufficient, the effect of dispersing the hydrophilic group is not sufficiently exhibited, and the dispersion tends to be poor.
  • Log (MV) is smaller than 1, the cohesive force of the resin is reduced, and the strength of the coating film is reduced. For example, when used as an adhesive, there is a tendency that defects such as poor adhesion occur.
  • the aqueous polylactic acid polyester resin dispersion of the present invention can be obtained by easily dispersing the polylactic acid polyester resin of the present invention with warm water in the presence of a basic compound. If the water temperature in the dispersion process is too high, the evaporation rate of water becomes high, and it becomes difficult to control the blending ratio. Moreover, when the water temperature in a dispersion
  • the temperature of the water to be dissolved is about 80 ° C. Therefore, in the present invention, melt viscosity at 80 ° C. is adopted as an index of plasticization when the polylactic acid-based polyester resin of the present invention is dispersed.
  • the acid value of the polylactic acid-based polyester resin of the present invention is 300 eq / t (meaning ton) to 2,500 eq / t, preferably 400 eq / t to 2,300 eq / t, more preferably 500 eq / t.
  • the above is 2,100 eq / t or less. If the resin acid value is too low, the resin cannot exhibit self-emulsifying properties, and the curability of the coating film using this resin tends to be low. On the other hand, the water dispersibility tends to increase by increasing the resin acid value. However, if the acid value exceeds 2,500 eq / t, the water absorbency of the resin increases and the resin is hydrolyzed even in a solid resin state. The storage stability tends to be poor. Moreover, the water resistance of the cured coating film using this resin also tends to deteriorate.
  • the number average molecular weight of the polylactic acid-based polyester resin of the present invention is preferably 2,000 or more and 50,000 or less, more preferably 3,000 or more and 45,000 or less, and further preferably 4,000 or more and 40,000. It is as follows. If the number average molecular weight is too low, the cohesive force of the resin tends to be small and the adhesiveness tends to be poor. On the other hand, if the number average molecular weight is too high, the cohesive strength of the resin increases, and the water dispersibility tends to be poor.
  • the polylactic acid polyester resin of the present invention preferably has a lactic acid content of 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. If it is less than 40% by mass, it is difficult to say that the degree of biomass is low, the carbon dioxide emission reduction effect is large, and the material has a low environmental load.
  • the resin skeleton for realizing the characteristics of the polylactic acid-based polyester resin of the present invention may be linear or branched, but is more preferably branched.
  • the branched polymer is said to have smaller molecular chain entanglement than the linear polymer in the molten state, and the melt viscosity at the same molecular weight tends to be lower than that of the linear polymer having the same composition.
  • the method of introducing an acid group into the polylactic acid-based polyester resin is not particularly limited, but a method of reacting an acid anhydride with a hydroxyl group at the end of the resin is simple and preferable.
  • a method of reacting an acid anhydride with a hydroxyl group at the end of the resin is simple and preferable.
  • the acid value of the polylactic acid-based polyester resin of the present invention can be easily adjusted by changing the ratio of the polylactic acid-based polyester resin to the raw material and the acid anhydride.
  • Equation (4) Z— (O— (CO—Y—O) q —X) r (4)
  • Z is a residue of a polyol having r hydroxyl groups
  • Y is a group in which —CH (CH 3 ) — or —CH (CH 3 ) — and a linear or branched alkylene group having 2 to 10 carbon atoms are mixed.
  • X is a residue of a polybasic acid having two or more carboxyl groups or hydrogen
  • X, Y, and Z may be a single species or a mixture of plural species.
  • q and r are positive numbers, the average value of q is 5 or more, and the average value of r is 3 or more and 15 or less.
  • the polylactic acid-based polyester resin represented by the formula (4) is, for example, ring-opening addition polymerization of a cyclic compound having lactic acid such as lactide as a constituent, using a polyhydric alcohol having 3 or more hydroxyl groups as an initiator, Subsequently, it can manufacture by making a polybasic acid react with a terminal hydroxyl group and introduce
  • the polylactic acid-based polyester resin represented by the formula (4) is one or two selected from a cyclic compound having a hydroxycarboxylic acid other than lactic acid such as glycolic acid as a constituent and a lactone such as ⁇ -caprolactone.
  • a mixture of two or more species and a cyclic compound having lactic acid such as lactide as a constituent component are subjected to ring-opening addition polymerization using a polyhydric alcohol having three or more hydroxyl groups as an initiator, and then a terminal hydroxyl group is reacted with a polybasic acid to form a molecule. It can also be produced by introducing an acid group at the terminal.
  • polyols having r hydroxyl groups examples include polyhydric alcohols having 3 or more hydroxyl groups and derivatives thereof. Examples of the polyhydric alcohol having three hydroxyl groups include trimethylolpropane and glycerin. Examples of the polyhydric alcohol having 4 or more hydroxyl groups include pentaerythritol, diglycerin, polyglycerin, xylitol, sorbitol, glucose, fructose, mannose and the like. Of these, polyglycerol, xylitol, and sorbitol are preferable because they have a large number of hydroxyl groups.
  • Preferable examples of the derivative of the polyhydric alcohol having 3 or more hydroxyl groups include those in which a part or all of the hydroxyl groups of the polyhydric alcohol are added with alkylene oxide, and ethylene oxide is particularly preferable as the alkylene oxide. .
  • the reactivity of the secondary hydroxyl group as an initiator for ring-opening polymerization of lactide or the like is considerably inferior to the reactivity of the primary hydroxyl group. Therefore, when the polyhydric alcohol has both a secondary hydroxyl group and a primary hydroxyl group, 2 A primary hydroxyl group is unlikely to be the starting point for ring-opening addition polymerization.
  • the derivative of the polyhydric alcohol having 3 or more hydroxyl groups there can be mentioned one obtained by esterifying a part of the hydroxyl groups of the polyhydric alcohol with a fatty acid.
  • Polyglycerin stearates and oleates are examples of such compounds, but they are highly safe compounds that are also used as food additives. It is possible to make the polylactic acid-based resin have a highly branched structure, which is preferable.
  • a polymer polyol having 3 or more hydroxyl groups is also a preferred example of a polyhydric alcohol derivative having 3 or more hydroxyl groups.
  • Specific examples of the polymer polyol having 3 or more hydroxyl groups include polyester polyol, polycarbonate polyol, and polyurethane polyol. Of these, polyester polyols composed of aliphatic components are preferred in view of biodegradability.
  • Y is a group in which —CH (CH 3 ) — or —CH (CH 3 ) — and a linear or branched alkylene group having 2 to 10 carbon atoms are mixed.
  • the — (CO—Y—O) q — can be easily obtained by subjecting lactides or a mixture of lactides and lactones to ring-opening addition polymerization using a polyol as an initiator.
  • lactides for example, lactide (a cyclic dimer of lactic acid), glycolide (a cyclic dimer of glycolic acid) and the like can be used.
  • lactones examples include ⁇ -propionlactone, ⁇ -butyrolactone, pivalolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
  • these compounds do not necessarily need to be used alone, and a plurality of types can be copolymerized.
  • q in — (CO—Y—O) q — is a positive number, and the average value of q is 5 or more, more preferably 7 or more, and still more preferably 10 or more. is there.
  • the average value of q is preferably 50 or less. If the average value of q is too high, the number average molecular weight of the resin is increased, the cohesive force of the resin is increased, the melt viscosity is increased, and water dispersibility may be deteriorated.
  • the average value of r in the — (O— (CO—Y—O) q —X) r is 3 or more and 15 or less, more preferably 3.5 or more and 14 or less, and still more preferably. Is 4 or more and 13 or less. If the average value of r is too low, the number of end groups of the polymer is small and the acid value that can be introduced by acid addition is small. Therefore, when the molecular weight of the resin is high, the water dispersibility is inferior, and the water dispersibility can be secured. If the molecular weight of the resin is lowered, the strength of the resin becomes unusable. On the other hand, if the average value of r exceeds 15, a cross-linking reaction may occur at the time of terminal acid addition and gelation may occur.
  • the — (CO—YO) q — is mainly composed of one or both of a D-lactic acid residue and a 6-hydroxycaproic acid residue and an L-lactic acid residue. It is preferable that it is the random copolymer which becomes.
  • the content of the L-lactic acid residue in — (CO—Y—O) q — is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less. . If the L-lactic acid content is too high, crystallinity appears remarkably, and the water dispersibility tends to be poor. On the other hand, when the L-lactic acid content exceeds 90% by mass, when used as an adhesive, crystallization progresses with time and a significant decrease in adhesive strength may be observed.
  • the — (CO—YO) q — is typically a ring-opening addition polymerization of D-lactide and / or ⁇ -caprolactone and L-lactide.
  • the main component may be a random copolymer obtained by the above process, and other components may be copolymerized.
  • a random copolymer mainly composed of one or both of D-lactide and ⁇ -caprolactone and L-lactide can be prepared, for example, using a polyol as an initiator in the presence or absence of a conventionally known ring-opening polymerization catalyst.
  • D-lactide, ⁇ -caprolactone, or both, and L-lactide can be obtained by heating and stirring.
  • the X is a polybasic acid residue containing two or more carboxyl groups or hydrogen.
  • the polybasic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid and their anhydrides, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, Aliphatic dicarboxylic acids such as dimer acids and acid anhydrides thereof, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and terpene-maleic acid adducts, and acid anhydrides thereof, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, Mention is made of alicyclic dicarboxylic acids such as hexahydroisophthalic acid and 1,2-cyclohexene di
  • trimellitic anhydride can be easily reacted by an addition reaction, and since two carboxyl groups can be introduced per molecule, a large amount of acid groups can be introduced, which is advantageous for water dispersion. This is preferable.
  • succinic anhydride which is a biomass raw material, is preferable because it can easily react and maintain a high degree of biomass.
  • polybasic acid examples include pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′.
  • PMDA pyromellitic anhydride
  • ODPA oxydiphthalic dianhydride
  • BTDA 4,4′-benzophenonetetracarboxylic dianhydride
  • BPDA 4,4'-diphenyltetracarboxylic dianhydride
  • TMEG ethylene glycol bisanhydro trimellitate
  • DSDA 4,4'-diphenylsulfone tetracarboxylic dianhydride
  • 6FDA 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride
  • BSAA 2,2'-bis [(dicarboxyphenoxy) phenyl] propane dianhydride
  • BSAA 2,2'-bis [(dicarboxyphenoxy) phenyl] propane dianhydride
  • Acid dianhydrides such as can also be used.
  • the molecular weight can be increased by the chain extension effect, which is preferable from the viewpoint of improving the resin strength.
  • TMEG ethylene glycol bisanhydro trimellitate
  • TMEG ethylene glycol bisanhydro trimellitate
  • the polylactic acid-based polyester resin of the present invention includes one or a mixture of two or more selected from cyclic compounds having a hydroxycarboxylic acid other than lactic acid such as glycolic acid as a constituent and lactones such as ⁇ -caprolactone, and lactide.
  • a cyclic compound having lactic acid as a constituent component is subjected to ring-opening addition polymerization using a polyhydric alcohol having 3 or more hydroxyl groups and a derivative thereof, and a polymer polyol having 3 or more hydroxyl groups as an initiator, and then a polybasic acid is added to the terminal hydroxyl group. It can also be produced by reacting and introducing an acid group at the molecular end.
  • a polyol, lactide, ⁇ -caprolactone, and catalyst containing 3 or more hydroxyl groups are charged all at once, heated to 150 ° C. or higher, polymerized for 1 to 3 hours, and further added with a polybasic acid anhydride.
  • the polylactic acid-based polyester resin of the present invention can be obtained by reacting for 1 to 2 hours.
  • the polymerization is preferably performed in a vacuum or in an inert gas atmosphere.
  • the polymerization temperature is preferably 180 ° C. or less in consideration of the thermal stability of polylactic acid.
  • the polymerization rate can be increased by using a conventionally known acid addition catalyst.
  • catalysts that can be expected to have such effects include amines such as triethylamine and benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride; imidazoles such as 2-ethyl-4-imidazole Pyridines such as 4-dimethylaminopyridine; phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; sulfonium salts such as sodium p-toluenesulfonate; sulfonic acids such as p-toluenesulfonic acid; octyl And organic metal salts such as zinc acid.
  • amines, pyridines, and phosphines are more preferable as a catalyst for the ring-opening polymerization reaction, and the use of 4-dimethylaminopyr
  • the polylactic acid polyester resin of the present invention When the polylactic acid polyester resin of the present invention is obtained by polymerization, it is effective to add various antioxidants.
  • the polymerization temperature is high or when the polymerization time is long, the polylactic acid segment has low heat resistance and may be oxidized and colored.
  • a segment having low heat resistance such as polyether is copolymerized, it may be more susceptible to oxidative degradation.
  • addition of an antioxidant is particularly effective.
  • the antioxidant include known phenolic antioxidants, phosphorus antioxidants, amine antioxidants, sulfur antioxidants, nitro compound antioxidants, inorganic compound antioxidants, and the like. .
  • a phenolic antioxidant having a relatively high heat resistance is preferable, and addition of 0.05% by mass to 0.5% by mass with respect to the resin is preferable.
  • the polylactic acid polyester resin of the present invention Since the polylactic acid polyester resin of the present invention has good water dispersibility, it can be easily dispersed in warm water in the presence of a basic compound.
  • the liquid temperature during the production of the aqueous dispersion is preferably 40 ° C. or higher and 95 ° C. or lower, more preferably 55 ° C. or higher and 90 ° C. or lower, and further preferably 70 ° C. or higher and 85 ° C. or lower. Even if the water temperature is low, the dispersion proceeds, but it takes time. The higher the water temperature, the faster the dispersion.
  • Examples of the basic compound used in the method for producing the polylactic acid-based polyester resin aqueous dispersion of the present invention include ammonia, an organic amine compound, an inorganic basic compound, and the like.
  • organic amine compound examples include alkylamines such as triethylamine, propylamine, isopropylamine, ethylamine, diethylamine and sec-butylamine, alkoxyamines such as 3-ethoxypropylamine and 3-methoxypropylamine, N , N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine And morpholines such as N-ethylmorpholine.
  • alkylamines such as triethylamine, propylamine, isopropylamine, ethylamine, diethylamine and sec-butylamine
  • alkoxyamines such as 3-ethoxypropylamine and 3-methoxypropylamine
  • N , N-diethylethanolamine N, N-
  • the inorganic basic compound examples include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium bicarbonate and sodium carbonate, bicarbonates, In addition, ammonium carbonate and the like can be used.
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such as sodium bicarbonate and sodium carbonate, bicarbonates
  • ammonium carbonate and the like can be used.
  • a basic compound of a polyvalent metal since it may cause a plurality of carboxyl groups contained in the polylactic acid-based polyester resin of the present invention and a water-insoluble salt to deteriorate the dispersibility. Is preferably limited to a small amount.
  • the basic compound requires an amount capable of neutralizing at least a part of the carboxyl groups of the polylactic acid-based polyester resin of the present invention, specifically, with respect to the acid groups of the polylactic acid-based polyester resin of the present invention. It is desirable to add 0.5 equivalent to 1.0 equivalent.
  • the basic compound is additionally added to form a final base.
  • the addition amount of the functional compound may be 0.5 equivalent to 1.0 equivalent relative to the acid group.
  • the pH of the aqueous dispersion is preferably adjusted to 6.5 to 7.0 from the viewpoint of suppressing hydrolysis of the polylactic acid segment. If the addition ratio of the basic compound is too low, the water dispersibility tends to be low. If it is too high, the pH of the water dispersion becomes high and the polylactic acid polyester resin may be hydrolyzed.
  • aqueous dispersion of the polylactic acid-based polyester resin of the present invention it is not necessary to use an emulsifier or an organic solvent, but the use is not necessarily excluded.
  • the use of various nonionic emulsifiers and anionic emulsifiers may make it possible to further stabilize the aqueous dispersion.
  • a more stable aqueous dispersion may be obtained by previously dissolving the polylactic acid-based polyester resin of the present invention in an appropriate organic solvent and then causing phase transition.
  • the polylactic acid polyester resin aqueous dispersion of the present invention can be used as an aqueous adhesive.
  • curing agent which reacts with a carboxyl group is added, an adhesive agent with higher adhesive force can be obtained.
  • various hardening agents such as amino resins, such as a melamine type and a benzoguanamine type, a polyvalent isocyanate compound, a polyvalent oxazoline compound, a polyvalent epoxy compound, a phenol resin, and a carbodiimide compound, can be used.
  • polyvalent epoxy compounds and polyvalent oxazoline compounds are preferable because they have high reactivity with carboxyl groups, can be cured at low temperatures, and can provide high adhesive strength.
  • Multivalent metal salts can also be used as curing agents.
  • the content thereof is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the polylactic acid-based polyester resin of the present invention.
  • the blending amount of the curing agent is less than 5 parts by mass, the curability tends to be insufficient, and when it exceeds 50 parts by mass, the coating film tends to be too hard.
  • Examples of the polyvalent epoxy compound suitable as the curing agent for the water-based adhesive of the present invention include novolak type epoxy resins, bisphenol type epoxy resins, trisphenol methane type epoxy resins, amino group-containing epoxy resins, and copolymer type epoxy resins. be able to.
  • Examples of novolak-type epoxy resins include those obtained by reacting novolaks obtained by reacting phenols such as phenol, cresol, and alkylphenol with formaldehyde in the presence of an acidic catalyst and epichlorohydrin and / or methyl epichlorohydrin. be able to.
  • bisphenol type epoxy resins include those obtained by reacting bisphenols such as bisphenol A, bisphenol F, and bisphenol S with epichlorohydrin and / or methyl epichlorohydrin, and condensates of bisphenol A diglycidyl ether and the bisphenols. Can be obtained by reacting with epichlorohydrin and / or methyl epichlorohydrin.
  • examples of the trisphenol methane type epoxy resin include those obtained by reacting trisphenol methane, tris-resole methane, etc. with epichlorohydrin and / or methyl epichlorohydrin.
  • amino group-containing epoxy resins examples include glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N, N, N ′, N′-tetraglycidyl-m-xylenediamine and the like. Can be mentioned.
  • copolymer type epoxy resin examples include a copolymer of glycidyl methacrylate and styrene, a copolymer of glycidyl methacrylate and styrene and methyl methacrylate, or a copolymer of glycidyl methacrylate and cyclohexyl maleimide, and the like.
  • the polylactic acid-based polyester resin aqueous dispersion of the present invention has an emulsifying effect
  • an epoxy compound that is not soluble in water can also be used as a curing agent, but a water-soluble epoxy resin is preferred because it is easier to use.
  • the water-soluble epoxy resin include polyethylene glycol, glycerin and derivatives thereof, and water-soluble compounds such as sorbitol in which a part of the hydroxyl group is a glycidyl group.
  • Examples of commercially available water-soluble epoxy resins include SR-EGM, SR-8EG, SR-GLG, SR-SEP manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., Denacol (registered trademark) EX-614 manufactured by Nagase Chemitex Co., Ltd. , EX-512, EX-412, and the like.
  • a polyvalent oxazoline compound suitable as a curing agent for the aqueous adhesive of the present invention a commercially available oxazoline compound can be used, and Nippon Shokubai Epocross (registered trademark) WS-500, WS-700, Epocross (registered trademark) can be used. ) K-2010E, Epocross (registered trademark) K-2020E, etc. can be used.
  • carbodiimide compound suitable as the curing agent for the aqueous adhesive of the present invention a commercially available carbodiimide compound can be used, and Nisshinbo Carbodilite (registered trademark) V-02, V-04, and the like can be used.
  • a polyvalent metal salt suitable as a curing agent for the aqueous adhesive of the present invention calcium salt, zinc salt, aluminum salt and the like can be used, and calcium chloride and ammonium ammonium carbonate are particularly preferable.
  • Examples of the phenol resin suitable as the curing agent for the aqueous adhesive of the present invention include alkylated phenols and / or condensates of cresols and formaldehyde.
  • alkylated phenols alkylated with alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl, p-tert-amylphenol, 4,4'-sec-butylidenephenol, p -tert-butylphenol, o-cresol, m-cresol, p-cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl-o -Condensates of cresol, p-phenylphenol, xylenol and the like with formaldehyde.
  • amino resins suitable as curing agents for the aqueous adhesive of the present invention include, for example, formaldehyde adducts such as urea, melamine, and benzoguanamine, and alkyl ether compounds obtained by alkoxylating these compounds with alcohols having 1 to 6 carbon atoms. Can be mentioned.
  • methoxylated methylol urea methoxylated methylol-N, N-ethylene urea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like.
  • Preferred are methoxylated methylol melamine, butoxylated methylol melamine and methoxylated methylolated benzoguanamine, which can be used alone or in combination.
  • the polyvalent isocyanate compound suitable as the curing agent for the aqueous adhesive of the present invention may be either a low molecular compound or a high molecular compound.
  • the low molecular weight compound include aliphatic isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, aromatic isocyanate compounds such as toluene diisocyanate and diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and isophorone. Mention may be made of alicyclic isocyanates such as diisocyanates.
  • trimers of these isocyanate compounds can be exemplified.
  • the polymer compound include a terminal isocyanate group-containing compound obtained by reacting a compound having a plurality of active hydrogens with an excess of the low-molecular polyisocyanate compound.
  • the compound having a plurality of active hydrogens include polyhydric alcohols such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin and sorbitol, polyhydric amines such as ethylenediamine, hydroxyl groups such as monoethanolamine, diethanolamine and triethanolamine
  • compounds having an amino group polyester polyols, polyether polyols, polyamides, and other active hydrogen-containing polymers.
  • the blocked isocyanate compound may be a blocked isocyanate.
  • the isocyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol, oximes such as acetoxime, methylethyl ketoxime, and cyclohexanone oxime, methanol, ethanol, propanol, Alcohols such as butanol, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol, tertiary alcohols such as t-butanol and t-pentanol, ⁇ -caprolactam, ⁇ -valero Examples include lactams such as lactam, ⁇ -butyrolactam, ⁇ -propyllactam, and other activities such as aromatic amines, imides, acetylacetone, aceto
  • the blocked isocyanate can be obtained by subjecting the above isocyanate compound and an isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.
  • a water-based ink can be obtained by blending a color material with the polylactic acid-based polyester resin aqueous dispersion of the present invention, and the water resistance of the ink can be improved by blending a curing agent having reactivity with a carboxyl group. Can be improved.
  • a curing agent having reactivity with a carboxyl group.
  • the color material a known pigment or dye can be blended. Since the polylactic acid-based polyester resin of the present invention has a high acid value of the polyester resin, the dispersibility of various pigments is large, and a high-concentration aqueous ink can be produced.
  • the curing agent those exemplified in the adhesive application can be used.
  • a water-based paint can be obtained by blending the polylactic acid-based polyester resin aqueous dispersion of the present invention with additives generally used for various pigments and paints, and further having a reactivity with respect to carboxyl groups.
  • the water resistance of a coating film can be improved by mix
  • pigments include known organic / inorganic color pigments, extender pigments such as calcium carbonate and talc, rust preventive pigments such as red lead and lead oxide, aluminum powder, and various functional pigments such as zinc sulfide (fluorescent pigment). Can be blended.
  • Additives include plasticizers, dispersants, anti-settling agents, emulsifiers, thickeners, antifoaming agents, antifungal agents, antiseptics, anti-skinning agents, anti-sagging agents, delustering agents, antistatic agents, A conductive agent, a flame retardant, etc. can be mix
  • the water dispersion, adhesive, ink and paint of the present invention can be adjusted to a viscosity and viscosity suitable for workability by blending various thickeners. From the stability of the system due to the addition of a thickener, nonionic ones such as methylcellulose and polyalkylene glycol derivatives, and anionic ones such as polyacrylates and alginates are preferred.
  • the aqueous dispersion, adhesive, ink and paint of the present invention can further improve applicability by using various surface tension modifiers.
  • the surface tension adjusting agent include acrylic, vinyl, silicone, and fluorine surface tension adjusting agents, and are not particularly limited. Acrylic and vinyl surface tension modifiers are preferred. If the addition amount of the surface tension modifier is excessive, the adhesive strength tends to be impaired. Therefore, the addition amount should preferably be limited to 1% by mass or less, more preferably 0.5% by mass or less based on the resin. is there.
  • the aqueous dispersion obtained by the present invention is known in the manufacture of an aqueous dispersion or a surface smoothing agent, an antifoaming agent, an antioxidant, a dispersing agent, a lubricant, etc. with respect to the produced aqueous dispersion. These additives may be blended.
  • the water dispersion, adhesive, ink and paint of the present invention can be further improved in light resistance and oxidation resistance by adding various ultraviolet absorbers, antioxidants and light stabilizers.
  • Light resistance is greatly improved by introducing a compound having an ultraviolet absorption effect and a light stabilization effect into the polyester skeleton, but an emulsion or an aqueous solution of an ultraviolet absorber, an antioxidant, and a light stabilizer is dispersed in an aqueous polyester resin dispersion.
  • Light resistance is also improved by adding to the above.
  • the ultraviolet absorber various organic types such as benzotriazole, benzophenone, and triazine, and inorganic types such as zinc oxide can be used.
  • As the antioxidant various polymers generally used for polymers such as hindered phenols, phenothiazines and nickel compounds can be used.
  • Various light stabilizers for polymers can be used, but hindered amines are effective.
  • a layer (A layer) made of the polylactic acid-based polyester resin of the present invention and a layer (B layer) selected from the group consisting of a film, a sheet, a woven fabric, a nonwoven fabric and paper can be laminated to form a laminate.
  • the laminate can be easily obtained by, for example, applying the aqueous adhesive and / or aqueous ink of the present invention to a layer (B layer) selected from the group consisting of a film, a sheet, a woven fabric, a non-woven fabric, and paper and drying it. Obtainable.
  • the water-based adhesive and water-based ink of the present invention exhibit strong adhesion to films, sheets, woven fabrics, nonwoven fabrics and papers made of various raw materials, but polylactic acid, polyester, polyurethane, polyamide, cellulose, starch, polyvinyl chloride, It exhibits particularly high adhesion to films and sheets made from polyvinylidene chloride, chlorinated polyolefins and these chemically modified substances.
  • a film, sheet and paper made of biomass raw materials such as polylactic acid, cellulose and starch
  • the biomass degree of the entire laminate can be made extremely high.
  • the layer A / metal vapor-deposited layer / B layer It is also useful to use a laminate having a three-layer structure as described above or a laminate having a three-layer structure of A layer / metal oxide vapor deposition layer / B layer.
  • the metal and B layer used for a metal vapor deposition layer and a metal oxide are not specifically limited, Especially the adhesive force of an aluminum vapor deposition film, and the water-based adhesive and water-based ink of this invention is large.
  • the water-based adhesive and water-based ink of the present invention exhibit high adhesion to various metal vapor-deposited films and various metal oxides because of the effect of the high acid value of the polylactic acid-based polyester resin of the present invention. Seem. Since these laminates have a high degree of biomass, they are suitable for use as materials that are disposable in a relatively short period of time, such as packaging materials, and are particularly suitable as food packaging materials.
  • the polylactic acid polyester resin of the present invention and its aqueous dispersion can be used as a sustained release biodegradable coating agent. Since the polylactic acid-based polyester resin of the present invention has an appropriate biodegradation rate, when it is left in the natural environment, it gradually biodegrades over a long period of time, and gradually releases the components to be coated into the environment. be able to. Therefore, a coated body formed by coating a coating agent such as a fertilizer, agricultural chemical, antifungal agent, bactericidal agent, or biological repellent with the biodegradable coating agent of the present invention is excellent in sustained release of the coating agent. Moreover, the biodegradable coating agent of this invention can form the water dispersion excellent in film forming property in the preferable embodiment, and can be used with the form of a coating film.
  • a coating agent such as a fertilizer, agricultural chemical, antifungal agent, bactericidal agent, or biological repellent
  • the sustained-release biodegradable coating in the present invention is obtained by coating the component to be coated with the sustained-release biodegradable coating in the present invention.
  • the sustained-release biodegradable coating of the present invention may contain components other than the component to be coated and the sustained-release biodegradable coating of the present invention, such as other biodegradable resins, non-degradable resins, and the like. Biodegradable resins, hydrolysis accelerators, hydrolysis inhibitors and the like may be blended.
  • the sustained-release biodegradable coating refers to those in which the component to be coated is coated with a sustained-release biodegradable coating, but only the same component as the component to be coated is present inside the coating. Not only those that also adhere to the outer surface.
  • the sustained-release biodegradable coating in the present invention is gradually decomposed by organisms such as microorganisms in the natural environment such as the surface and the inside of soil, river lakes, and the ocean, and the components to be coated are treated for a long time in the process. It exhibits the effect of continuously releasing over a long period. For this reason, it can be used as a sustained-release agrochemical, slow-acting fertilizer, long-lasting antifouling paint, etc. by selecting an appropriate component to be coated.
  • the component to be coated in the present invention is not particularly limited as long as it is a component that is desired to be gradually released in the natural environment.
  • Specific examples of the component to be coated in the present invention include a component that can be expected to have a biological control action such as insecticidal, herbicidal, sterilizing, antifungal, biological attraction and biological repellent, and a growth promoting action on living organisms such as bioactive substances and fertilizer And / or a component that can be expected to have a nutritional supplement.
  • the component to be coated is not limited to a single component, and may be composed of a plurality of components.
  • the manufacturing method of the sustained release biodegradable coating body of this invention is not specifically limited, It is preferable to manufacture via the aqueous dispersion of the polylactic acid-type polyester resin of this invention.
  • the component to be coated is dissolved or dispersed in an aqueous dispersion, and then the aqueous dispersion itself is sprayed to evaporate the water to form particles, or sprayed in the presence of some carrier to adhere to the carrier surface and / or the inside of the carrier. This is because a biodegradable coating can be easily obtained by applying to some adherend and forming a coating film, which is convenient.
  • the biodegradable polylactic acid-based polyester resin is self-emulsifying, which can form an aqueous dispersion without the addition of a surfactant, the surfactant is released into the environment during the biodegradation process. This is preferable because the environmental load is reduced. Further, if the aqueous dispersion does not contain an organic solvent or uses a small amount of the organic solvent, the organic solvent is not released into the environment in both the manufacturing process of the covering and the use of the covering. Or, since the amount is small, the environmental load is further reduced, which is more preferable.
  • part represents “part by mass”.
  • ⁇ Resin composition> A resin sample was dissolved in deuterated chloroform or deuterated dimethyl sulfoxide and subjected to 1 H-NMR analysis and optionally 13 C-NMR analysis using a VARIAN NMR apparatus 400-MR. The composition was determined and expressed in mass%. The lactic acid content (% by mass) was calculated based on the resin composition shown on the left. The L / D ratio of lactic acid was determined by the following method. A 5 g / 100 mL chloroform solution of the sample was prepared, and the specific rotation was measured at a measurement temperature of 25 ° C. and a measurement light source wavelength of 589 nm to obtain [ ⁇ ] obs.
  • ⁇ Number average molecular weight> A resin sample is dissolved in tetrahydrofuran so that the resin concentration is about 0.5% by mass and filtered through a polytetrafluoroethylene membrane filter having a pore size of 0.5 ⁇ m, and tetrahydrofuran is used as a mobile phase.
  • the molecular weight was measured by gel permeation chromatography (GPC) using a differential refractometer as a detector. The flow rate was 1 mL / min and the column temperature was 30 ° C. KF-802, 804L and 806L manufactured by Showa Denko were used for the column. Monodisperse polystyrene was used as the molecular weight standard.
  • the neutralization point was expressed in terms of equivalents (equivalents / 10 6 g) per 10 6 g of resin.
  • ⁇ Average particle size of water dispersion The arithmetic average diameter based on the volume particle diameter of the water dispersion sample was measured using HORIBA LB-500 and adopted as the average particle diameter of the water dispersion. However, for those having a water dispersibility of ⁇ or ⁇ , the average particle diameter was not measured and indicated as “ ⁇ ”.
  • ⁇ Preparation of adhesive evaluation sample> A water-based adhesive was applied to a corona-treated surface of a 25 ⁇ m thick PET film (manufactured by Toyobo Co., Ltd.) so that the thickness after drying was 5 ⁇ m, and dried at 80 ° C. for 5 minutes.
  • the corona-treated surface of another 25 ⁇ m thick PET film was bonded to the adhesive surface, pressed at 80 ° C. under a pressure of 3 kgf / cm 2 for 30 seconds, cured by heat treatment at 40 ° C. for 8 hours, and peeled off.
  • a sample for strength evaluation was obtained (for initial evaluation). Moreover, after immersing the said sample in 25 degreeC water for 5 hours, the surface water was fully wiped off and it was set as the sample for water resistance evaluation.
  • P-GLY Polyglycerin # 750 (number average molecular weight 750)
  • P-GLY-EO750 Diglycerin ethylene oxide adduct (number average molecular weight 750)
  • P-GLY-MOS Decaglycerin monooleate
  • PEG1000 Polyethylene glycol (number average molecular weight 1000)
  • L-LD L-lactide
  • D-LD D-lactide
  • CL ⁇ -caprolactone
  • TMA trimellitic anhydride
  • SC succinic anhydride MA: maleic anhydride
  • TEA triethylamine
  • TETA triethanolamine
  • Example A-1 Polylactic acid polyester resin No. Production of 1 Into a 500 ml glass flask equipped with a thermometer, stirrer and Liebig condenser, 7.7 parts diglycerin ethylene oxide adduct (number average molecular weight 750), 74.4 parts L-lactide, ⁇ -caprolactone 15 .2 parts and 0.028 part of tin octylate as a catalyst were charged and nitrogen gas was circulated at 60 ° C. for 30 minutes. Subsequently, the pressure was reduced at 60 ° C. for 30 minutes to further dry the contents. The temperature of the polymerization system was raised to 180 ° C. while flowing nitrogen gas again, and the mixture was stirred for 3 hours after reaching 180 ° C.
  • FIG. 1 is a graph plotting the relationship between AV and Log (MV) of the polylactic acid-based polyester resin used in Examples and Comparative Examples.
  • Polylactic acid polyester resin No. No. 9 has a low resin acid value and does not satisfy the formula (3), and is outside the scope of the present invention.
  • Polylactic acid polyester resin No. 10 does not satisfy the formula (3) and is outside the scope of the present invention.
  • Polylactic acid polyester resin No. 11 has a high resin acid value and is outside the scope of the present invention. Resin No. No. 11 is inferior in storage stability, but is presumed to have a high acid value and high water absorption.
  • Polylactic acid polyester resin No. No. 12 has a small Log (MV) and is outside the scope of the present invention.
  • Polylactic acid polyester resin No. No. 13 has a large Log (MV) and does not satisfy the formula (3), and is outside the scope of the present invention.
  • Polylactic acid polyester resin No. 14 does not satisfy Expression (3) and is outside the scope of the present invention.
  • Polylactic acid polyester resin No. 15 also does not satisfy the formula (3) and is outside the scope of the present invention.
  • Example C-1 Production and Evaluation of Polylactic Acid Polyester Resin Aqueous Dispersion and Aqueous Adhesive Polylactic acid polyester resin No. 1 was placed in a 500 ml glass flask equipped with a thermometer, stirrer and Liebig condenser. 25 parts, 1.1 parts of TEA and 75 parts of water were charged, heated to 80 ° C. and stirred for 1 hour, and then the contents were taken out and cooled to produce a polylactic acid-based polyester resin aqueous dispersion 1. The particle size of the obtained water dispersion was measured. Furthermore, the hardening
  • Examples C-2 to C-8 In the same manner as in Example C-1, except that the charged raw materials and the ratio thereof were changed, polylactic acid polyester resin aqueous dispersions were produced, and polylactic acid polyester resin aqueous dispersions 2 to 8 were produced. Further, in the same manner as in Example C-1, a curing agent was blended in the polylactic acid-based polyester resin aqueous dispersions 2 to 8, and the adhesion and water resistance of the obtained coating films were evaluated. The results are shown in Table 3. All showed high water dispersibility, and the cured coating film showed high adhesion and water resistance.
  • Comparative Examples C-9 to C-15 In the same manner as in Example C-1, except that the raw materials and the ratios thereof were changed and production of a polylactic acid-based polyester resin aqueous dispersion was attempted. A curing agent was blended in the same manner as in Example 1, and the adhesion and water resistance of the obtained coating film were evaluated. The results are shown in Table 4.
  • Comparative Examples C-9 and C-10 a large amount of undispersed resin was present even after stirring for 1 hour, and a large amount of undispersed resin remained even after stirring for 1 hour.
  • Polylactic acid-based polyester resin No. 1 used in Comparative Example C-9 and Comparative Example C-10 9 Resin No. 10 does not satisfy the formula (3) and is outside the scope of the present invention. In order to sufficiently plasticize the resin in the water dispersion step, it is presumed that the dispersion of the polylactic acid-based polyester resin hardly progressed because the acid value was too low compared to the melt viscosity.
  • Comparative Examples C-11 and C-12 the water dispersibility of the polylactic acid-based polyester resin was good, but Comparative Example C-11 had poor water resistance, and Comparative Example C-12 had poor adhesion. It was.
  • Resin No. used in Comparative Example C-11 No. 11 has a high acid value of the resin and is outside the scope of the present invention. Although the curing agent equivalent to the acid value is blended, it is presumed that the water resistance is poor because many unreacted carboxyl groups remain.
  • Resin No. used in Comparative Example C-12 No. 12 has a low melt viscosity of the resin and is outside the scope of the present invention. Since the melt viscosity is low, the cohesive force is low and the adhesiveness is estimated to be poor.
  • Resin No. No. 13 has a high melt viscosity of the resin, does not satisfy the formula (3), and is outside the scope of the present invention. In order to sufficiently plasticize the resin in the water dispersion step, it is presumed that the acid value was too low compared with the melt viscosity, so that the dispersion could hardly be performed.
  • Resin No. used in Comparative Example C-14 14 Resin No. used in Comparative Example C-15 No. 15 showed little dispersion of the resin after stirring for 1 hour, and further continued stirring for 1 hour, but could hardly be dispersed.
  • Resin No. 14, Resin No. 15 does not satisfy the formula (3) and is outside the scope of the present invention. In order to sufficiently plasticize the resin at the water dispersion temperature, it is presumed that almost no dispersion was possible because the acid value was too low compared to the melt viscosity.
  • Boiling water test The appearance (blister generation state) of the coating film after the coated steel sheet was immersed in boiling water for 2 hours was evaluated. ⁇ : No blister ⁇ : Blister generation area less than 10% ⁇ : Blister generation area 10-50% ⁇ : Blister generation area over 50%
  • Adhesion In accordance with JIS K-5400 grid-tape method, draw 11 straight vertical and horizontal lines at 1mm intervals to reach the substrate with a cutter knife on the coating surface of the test plate. 100 squares of 1 mm were created. A cellophane pressure-sensitive adhesive tape was adhered to the surface, and the degree of cell peeling when the tape was rapidly peeled was observed and evaluated according to the following criteria.
  • Double-circle Coating film peeling is not seen at all. ⁇ : Although the coating film was slightly peeled, 90 or more squares remained.
  • Laminate (F-1) Polylactic acid-based polyester resin No. 1 was placed in a 500 ml glass flask equipped with a thermometer, a stirrer, and a Liebig condenser. 1 was charged with 100 parts, 4.4 parts of TEA and 233 parts of water, heated to 70 ° C. and stirred for 1 hour, then cooled to 30 ° C. or less, colloidal silica (Snowtex (registered trademark) manufactured by Nissan Chemical Industries, Ltd.) ) 100 parts of C) was added, and the mixture was further stirred for 1 hour, and the filtrate filtered through a 100 mesh filter cloth was added to a 25 ⁇ m thick PLA film (Innovia). Was applied to a corona-treated surface (made by Films) so that the thickness after drying was 5 ⁇ m, and dried at 80 ° C. for 30 minutes to obtain a laminate (F-1).
  • Laminate (F-2) In the laminate (F-1), polylactic acid polyester resin No. 1 instead of polylactic acid-based polyester resin No. 1 A laminate (F-2) was obtained by the same composition and production as the laminate (F-1) except that 7 was used and the TEA amount was 6.8 parts. A performance test was performed using the laminates (F-1) and (F-2). Evaluation followed the following method. The results are shown in Table 7.
  • Laminate 10cm x 10cm is put in a conposter (garbage disposal machine, Mitsui Home Co., Ltd. (MAM)). After 7 days, the sample form is visually observed, and the degree of biodegradability is 4 levels according to the following criteria. It was evaluated with. ⁇ : The sample form is completely absent ⁇ : The sample form is almost absent ⁇ : There is a sample fragment ⁇ : The sample form remains almost
  • ⁇ Slow release biodegradable coating agent> A polylactic acid-based polyester resin No. 1 was added to a 500 ml glass flask equipped with a thermometer, a stirrer, and a Liebig condenser. 7 and 100 parts of TEA, 6.8 parts of TEA, and 233 parts of water were added, heated to 70 ° C. and stirred for 1 hour, then cooled to 30 ° C. or less, and colloidal silica (Snowtex C manufactured by Nissan Chemical Industries, Ltd.) After adding 100 parts and further stirring for 1 hour, the mixture was filtered through a 100 mesh filter cloth.
  • the filtrate is spray-coated on a nitrogen-based granular fertilizer component having an average particle diameter of 4 mm using a jet coating apparatus, and moisture is evaporated and dried with hot hot air to obtain a coated granular sustained-release biodegradable coating G1. It was.
  • the filtrate was applied to a polypropylene sheet, dried in a hot air drier at 60 ° C., and then peeled off from the polypropylene sheet to prepare a sheet made of polylactic acid-based polyester resin H1 having a dry thickness of about 20 ⁇ m. Using this sheet, biodegradability in an aerobic dark place was evaluated.
  • the specific evaluation method was based on ASTM-D5338. The evaluation results are shown in Table 8.
  • the decomposition rate of this sheet was faster than that of a sheet made of polylactic acid-based polyester resin H2 described later, but was found to be slower than that of cellulose.
  • the polylactic acid-based polyester resin H1 is suitable for a coating material and a coated body that exhibit a sustained release property and when it is desired to finish the release of the component to be coated in a relatively short period of time.
  • ⁇ Slow release biodegradable coating agent> A polylactic acid-based polyester resin No. 1 was added to a 500 ml glass flask equipped with a thermometer, a stirrer, and a Liebig condenser. 6 was charged with 100 parts, TEA 11.3 parts, and water 233 parts. After heating to 70 ° C. and stirring for 1 hour, the mixture was cooled to 30 ° C. or lower to obtain colloidal silica (Snowtex C manufactured by Nissan Chemical Industries, Ltd.). After adding 100 parts and further stirring for 1 hour, the mixture was filtered through a 100 mesh filter cloth.
  • the filtrate is spray-coated on a nitrogen-based granular fertilizer component having an average particle diameter of 4 mm using a jet coating apparatus, and moisture is evaporated and dried with hot hot air to obtain a coated granular sustained-release biodegradable coating G2. It was.
  • the filtrate was applied to a polypropylene sheet, dried in a hot air drier at 60 ° C., and then peeled from the polypropylene sheet to prepare a sheet made of polylactic acid-based polyester resin H2 having a dry thickness of about 20 ⁇ m. Using this sheet, biodegradability in an aerobic dark place was evaluated.
  • the specific evaluation method was based on ASTM-D5338. The evaluation results are shown in Table 8.
  • the degradation rate of this sheet is relatively slow and is suitable for coatings and coatings where release of the coated component over a relatively long period is required.
  • the polylactic acid-based polyester resin of the present invention can be easily dispersed with only a basic compound and water, and can provide an environmentally friendly resin and aqueous dispersion. Moreover, a coating film with high water resistance can be provided by mix

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PCT/JP2013/071420 2012-08-09 2013-08-07 Résine de polyester de type poly(acide lactique), dispersion aqueuse de résine de polyester de type poly(acide lactique), et procédé pour produire une dispersion aqueuse de résine de polyester de type poly(acide lactique) Ceased WO2014024939A1 (fr)

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FR3046608A1 (fr) * 2016-01-13 2017-07-14 Saint-Gobain Adfors Composition d'appret pour toile a peindre et produits obtenus.
US10087326B2 (en) 2016-02-29 2018-10-02 Michelman, Inc. Aqueous-based hydrolytically stable dispersion of a biodegradable polymer
WO2022107660A1 (fr) * 2020-11-19 2022-05-27 中京油脂株式会社 Dispersion aqueuse
JP2022533481A (ja) * 2019-05-24 2022-07-22 メレディアン・インコーポレーテッド 種子、肥料および有害生物防除剤用のｐｌａ／ｐｈａ生分解性コーティング

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JP2000007789A (ja) * 1998-04-23 2000-01-11 Dainippon Ink & Chem Inc 生分解性ポリエステルからなる自己水分散性粒子及びその製法
JP2002088334A (ja) * 2000-09-11 2002-03-27 Diabond Industry Co Ltd 生分解性ホットメルト接着剤
WO2010016514A1 (fr) * 2008-08-06 2010-02-11 日東電工株式会社 Polyesters, compositions de polyesters, compositions adhésives, couches adhésives et feuilles adhésives
WO2013042677A1 (fr) * 2011-09-20 2013-03-28 東洋紡株式会社 Résine de polyester à base de poly(acide lactique), dispersion aqueuse de résine de polyester à base de poly(acide lactique), adhésif aqueux, et procédé pour produire une dispersion aqueuse de résine de polyester à base de poly(acide lactique)
WO2013122245A1 (fr) * 2012-02-17 2013-08-22 東洋紡株式会社 Résine en polyester polylactique, dispersion de résine en polyester polylactique aqueux et procédé de production de la dispersion de résine en polyester polylactique aqueux

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JP2000007789A (ja) * 1998-04-23 2000-01-11 Dainippon Ink & Chem Inc 生分解性ポリエステルからなる自己水分散性粒子及びその製法
JP2002088334A (ja) * 2000-09-11 2002-03-27 Diabond Industry Co Ltd 生分解性ホットメルト接着剤
WO2010016514A1 (fr) * 2008-08-06 2010-02-11 日東電工株式会社 Polyesters, compositions de polyesters, compositions adhésives, couches adhésives et feuilles adhésives
WO2013042677A1 (fr) * 2011-09-20 2013-03-28 東洋紡株式会社 Résine de polyester à base de poly(acide lactique), dispersion aqueuse de résine de polyester à base de poly(acide lactique), adhésif aqueux, et procédé pour produire une dispersion aqueuse de résine de polyester à base de poly(acide lactique)
WO2013122245A1 (fr) * 2012-02-17 2013-08-22 東洋紡株式会社 Résine en polyester polylactique, dispersion de résine en polyester polylactique aqueux et procédé de production de la dispersion de résine en polyester polylactique aqueux

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3046608A1 (fr) * 2016-01-13 2017-07-14 Saint-Gobain Adfors Composition d'appret pour toile a peindre et produits obtenus.
WO2017121952A1 (fr) * 2016-01-13 2017-07-20 Saint-Gobain Adfors Composition d'appret pour toile a peindre et produits obtenus
US10458051B2 (en) 2016-01-13 2019-10-29 Saint-Gobain Adfors Finishing composition for paintable cloth and products obtained
US10087326B2 (en) 2016-02-29 2018-10-02 Michelman, Inc. Aqueous-based hydrolytically stable dispersion of a biodegradable polymer
JP2022533481A (ja) * 2019-05-24 2022-07-22 メレディアン・インコーポレーテッド 種子、肥料および有害生物防除剤用のｐｌａ／ｐｈａ生分解性コーティング
JP7638969B2 (ja) 2019-05-24 2025-03-04 ダニマー・アイピーシーオー・エルエルシー 種子、肥料および有害生物防除剤用のｐｌａ／ｐｈａ生分解性コーティング
WO2022107660A1 (fr) * 2020-11-19 2022-05-27 中京油脂株式会社 Dispersion aqueuse

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