WO2013042677A1 - 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) - Google Patents

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) Download PDF

Info

Publication number
WO2013042677A1
WO2013042677A1 PCT/JP2012/073893 JP2012073893W WO2013042677A1 WO 2013042677 A1 WO2013042677 A1 WO 2013042677A1 JP 2012073893 W JP2012073893 W JP 2012073893W WO 2013042677 A1 WO2013042677 A1 WO 2013042677A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester resin
polylactic acid
based polyester
aqueous
resin
Prior art date
Application number
PCT/JP2012/073893
Other languages
English (en)
Japanese (ja)
Inventor
田中　秀樹
菜穂子 小田
Original Assignee
東洋紡株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Publication of WO2013042677A1 publication Critical patent/WO2013042677A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • 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
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • 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 provides 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, an aqueous adhesive, and a method for producing an 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 stable water dispersion is obtained without using an emulsifier, and when used as a binder component, it exhibits high adhesion, but in the production process of the water dispersion.
  • Solvent removal operation is performed, and there is room for improvement from the viewpoint of suppressing 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 present invention has been made against the background of the problems of the prior art. That is, the problem to be solved by the present invention is a polylactic acid polyester resin having a self-emulsifying function capable of forming an aqueous emulsion without using an emulsifier and an organic solvent, and an aqueous dispersion resin composition containing the same. It is in providing the manufacturing method of a water-based adhesive composition and an aqueous dispersion.
  • this invention consists of the following structures.
  • (1) It has a chemical structure represented by the general formula (1), has a resin acid value of 300 to 2,500 eq / 10 6 g, a number average molecular weight of 2,000 to 50,000, and a lactic acid content of 40% by weight or more.
  • a polylactic acid-based polyester resin A polylactic acid-based polyester resin.
  • Y1 is a polyol residue containing a polylactic acid segment
  • Y2 is a polyol residue not containing a polylactic acid segment
  • Y3 is a residue of a compound containing 3 or more hydroxyl groups
  • Y1, Y2, and Y3 are each a single residue. It may be composed of one kind or a mixture of plural kinds.
  • X is a carboxylic acid polyanhydride residue having two or more carboxyl groups, and each X may be a single species or a mixture of plural species.
  • the Y1 is a random copolymer mainly composed of one or both of D-lactide and ⁇ -caprolactone and L-lactide, and the L-lactic acid content is 90% by weight or less.
  • a polylactic acid-based polyester resin aqueous dispersion is obtained by mixing the polylactic acid-based polyester resin according to any one of (1) to (4), a basic compound, and water without adding a surfactant and an organic solvent.
  • the manufacturing method of the polylactic acid-type polyester resin aqueous dispersion which has a process.
  • An aqueous resin composition comprising the polylactic acid-based polyester resin according to any one of (1) to (4) and a curing agent having reactivity with a carboxyl group.
  • An aqueous adhesive comprising the aqueous resin composition according to (9) or (10).
  • An aqueous paint comprising the aqueous resin composition of (9) or (10).
  • a water-based ink comprising the water-based resin composition according to (9) or (10) and a color material.
  • a laminate comprising a layer (A layer) comprising the polylactic acid-based polyester resin and a layer (B layer) selected from the group consisting of a film, sheet, woven fabric, nonwoven fabric and paper body.
  • B layer is mainly composed of a biomass-derived material and / or a chemically modified material of the biomass-derived material.
  • a packaging material having the laminate according to (14) or (15) as a constituent element.
  • a sustained-release biodegradable coating agent comprising the aqueous resin composition according to (9) or (10).
  • the sustained-release biodegradable coating according to (18), wherein the component to be coated has one or more functions of insecticidal, herbicidal, sterilizing, antifungal, biological attraction and biological repellent.
  • the sustained-release biodegradable coating according to (18), wherein the component to be coated has one or more functions of biological activity, growth promotion, and nutritional supplementation for living organisms.
  • the polylactic acid-based polyester resin of the present invention is excellent in biodegradability because it contains a polylactic acid segment at a high concentration.
  • the polylactic acid-based polyester resin of the present invention has a high concentration of carboxyl groups in the molecular chain, an aqueous dispersion can be easily formed by stirring with an aqueous solution of a basic compound without using an emulsifier and an organic solvent. It exhibits excellent water dispersibility that can be formed.
  • the polylactic acid-type polyester resin aqueous dispersion of this invention can be prepared without using an emulsifier, and is excellent in adhesiveness.
  • the adhesive layer excellent in adhesiveness and water resistance can be easily obtained by mix
  • the polylactic acid-based polyester resin of the present invention has a chemical structure represented by the following formula (1), has a resin acid value of 300 eq / 10 6 g to 2,500 eq / 10 6 g, and a number average molecular weight of 2,000 to 35. , A polylactic acid-based polyester resin having a lactic acid content of 40% by weight or more.
  • Y1 is a polyol residue containing a polylactic acid segment
  • Y2 is a polyol residue not containing a polylactic acid segment
  • Y3 is a residue of a compound containing 3 or more hydroxyl groups
  • Y1, Y2, and Y3 are each a single residue. It may be composed of one kind or a mixture of plural kinds.
  • X is a carboxylic acid polyanhydride residue having two or more carboxyl groups, and each X may be a single species or a mixture of plural species.
  • “-ran-” represents a random copolymer. That is,-(Y1-OCO-X-COO) s -segment,-(Y2-OCO-X-COO) t -segment,-(Y3-OCO-X-COO) u -segment are randomly distributed to each other Represents that you are doing.
  • the acid value of the polylactic acid-based polyester resin of the present invention is 300 eq / ton or more and 2500 eq / ton or less, preferably 400 eq / ton or more and 2300 eq / ton or less, more preferably 500 eq / ton or more and 2100 eq / ton or less.
  • the acid value of the polylactic acid-based polyester resin of the present invention is derived from a large number of carboxyl groups contained in the molecular chain, exhibits a self-emulsifying function, and can form small emulsion particles of a particle system. Demonstrate the effect.
  • the resin acid value is too low, the resin cannot exhibit self-emulsifying properties, and the curability of a cured coating film using this resin tends to be low.
  • water dispersibility tends to increase by increasing the resin acid value.
  • the acid value exceeds 2500 eq / ton, the water absorption of the resin increases and the resin is easily hydrolyzed even in a solid resin state. There is a tendency for stability to deteriorate. 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 from 2,000 to 50,000, more preferably from 3,000 to 45,000, still more preferably from 4,000 to 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.
  • the number average molecular weight is too high, the cohesive force of the resin is increased, and the water dispersibility becomes poor.
  • water dispersibility is achieved by a method in which the resin is once dissolved in a solvent and phase-transformed into an aqueous system, Mixing with only a base compound and water leaves a large amount of undispersed material, often resulting in only a very low concentration aqueous dispersion, and the particle size is coarse, and tends to precipitate immediately after production. .
  • the lactic acid content of the polylactic acid-based polyester resin of the present invention is preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 60% by weight or more. If it is less than 40% by weight, it is difficult to say that the degree of biomass is low and the environment has a large effect of reducing carbon dioxide emissions and has a low load on the environment.
  • the polylactic acid-based polyester resin of the present invention is produced by polymerizing a polyol containing a polylactic acid segment, a polyol not containing a polylactic acid segment, and a compound containing 3 or more hydroxyl groups with a carboxylic acid polyanhydride. be able to.
  • an ester bond and a carboxyl group are generated by the reaction of the carboxylic acid anhydride group of the carboxylic acid polyanhydride with the hydroxyl group of the polyol.
  • the polyanhydride is a dianhydride, two ester groups and two carboxyl groups are formed, the two ester groups contribute to the high molecular weight of the resin, and the two carboxyl groups are the water of the resin.
  • the resin skeleton will also exhibit the effect of branching.
  • the water resistance of can be improved.
  • Y1 is a polyol residue containing a polylactic acid segment.
  • the content of the polylactic acid segment in the Y1 is more preferably 70% by weight or more, further preferably 90% by weight or more, from the viewpoint of increasing biodegradability and plant-derived raw material usage. More preferably, the weight is 100% by weight.
  • Y1 is preferably a residue of a polyester polyol having a chemical structure that can be obtained by ring-opening addition polymerization of lactide using a polyol as an initiator from the viewpoint of easy synthesis.
  • Y1 is preferably a residue of a polyester polyol having a chemical structure that can be obtained by ring-opening addition polymerization of lactide and lactone using a polyol as an initiator, from the viewpoint of easy synthesis. Furthermore, Y1 may be a residue of a polyester polyol having a chemical structure that can be obtained by polymerization from lactic acid.
  • the molar fraction p of the segment containing Y1 is 0.25 or more.
  • the ratio of the molar fraction p is low, the lactic acid concentration in the polylactic acid-based polyester resin of the present invention tends to be low and biodegradability tends to be reduced, and plant-derived materials are added to the polylactic acid-based polyester resin of the present invention.
  • the proportion occupied is low.
  • the molar fraction p is more preferably 0.5 or more, further preferably 0.7 or more, and may be 1.0.
  • the L-lactic acid content of Y1 is preferably 90% by weight or less, more preferably 85% by weight or less, and still more preferably 80% by weight 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 weight, when used as an adhesive, crystallization progresses with time and a significant decrease in adhesive strength may be observed.
  • the number average molecular weight of Y1 is preferably 500 or more and 8,000 or less, more preferably 700 or more and 6,500 or less, and still more preferably 900 or more and 5,000 or less.
  • the number average molecular weight of Y1 is too low, the polylactic acid-based polyester resin of the present invention has too many carboxyl groups, and the hydrolysis of the resin is promoted, so that the storage stability tends to deteriorate.
  • the number average molecular weight of Y1 is too high, conversely, the carboxyl group contained in the polylactic acid-based polyester resin of the present invention is too small, and the water dispersibility and curability tend to be poor.
  • Y1 is typically a random copolymer mainly composed of L-lactide and one or both of D-lactide and ⁇ -caprolactone, The component 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 polyol that can be used as the initiator is preferably a diol.
  • glycols having a relatively low molecular weight such as ethylene glycol, 2-methylpentanediol, neopentyl glycol, etc. is preferable because the degree of biomass can be kept relatively high.
  • Tri- or higher functional polyol compounds such as trimethylopropane, glycerin, pentaerythritol, diglycerin and polyglycerin can also be used as an initiator for the ring-opening addition polymerization of lactide.
  • the formed polyester segment becomes a trifunctional or higher functional polyol containing a branched chain, which has an effect of increasing the molecular weight of the polylactic acid-based polyester of the present invention, and can improve adhesiveness.
  • a trifunctional or higher functional polyol compound when used as an initiator for ring-opening addition polymerization, it is preferable to use a diol as an initiator, and the use ratio of the trifunctional or higher functional polyol compound is 10 moles relative to the diol. More preferably, it is suppressed to not more than%.
  • Polymer polyols such as polyester polyols, polycarbonate polyols, and polyurethane polyols can also be used as initiators for lactone ring-opening addition polymerization.
  • the terminal group of the polylactic acid-based polyester resin of the present invention is not particularly limited, but is typically a hydroxyl group derived from Y1, Y2 and / or Y3 and / or a carboxyl group derived from X. Since the polylactic acid-based polyester resin of the present invention has a large number of carboxyl groups in the middle of the polymer chain, part or all of the end groups are blocked with organic groups having poor reactivity with a curing agent such as an alkyl group. However, the polylactic acid-based polyester resin of the present invention can ensure the reactivity with the curing agent and is not particularly harmful.
  • Y2 is a polyol residue that does not contain a polylactic acid segment, and Y2 is not an essential component.
  • Y2 may be a trifunctional or higher functional polyol.
  • Y2 is a diol, there is less concern about causing gelation when the polylactic acid-based polyester of the present invention is polymerized, which is more preferable.
  • a polymer polyol such as a polyester polyol, a polycarbonate polyol, a polyurethane polyol, or a polyether polyol that does not have a polylactic acid segment can be used.
  • aliphatic polyester polyols are preferable, and polycaprolactone diol is particularly preferable.
  • polyethylene glycol is used, the effect of improving water dispersibility may be exhibited.
  • low molecular weight polyols that are not polymer polyols such as aliphatic polyols and alicyclic polyols can also be used.
  • aliphatic polyols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4- Butylene glycol, 2-methyl-1,3-propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,4-diethyl- 1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2 ′, 2′-dimethyl-3′-hydroxypropanate, 2-n-butyl- 2-ethyl-1,3-propanate, 2-n
  • alicyclic polyols examples include 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) cyclohexane, 1,4-bis (hydroxypropyl) ) Cyclohexane, 1,4-bis (hydroxymethoxy) cyclohexane, 1,4-bis (hydroxyethoxy) cyclohexane, 2,2-bis (4-hydroxymethoxycyclohexyl) propane, 2,2-bis (4-hydroxyethoxycyclohexyl) ) Propane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane, 3 (4), 8 (9) -tricyclo [5.2.1.0 2,6 ] decandi Mention may be made of methanol. These polyols can be used alone or in combination of two or more.
  • the molar fraction q of the segment containing Y2 is not particularly limited, and may be 0.
  • the molar fraction q By setting the molar fraction q to 0.05 to 0.5, the effect of alleviating the cohesiveness of the L-lactic acid component contained in Y1 and improving water dispersibility is preferable.
  • the molar fraction q is too high, the effect of lowering the lactic acid content of the polylactic acid-based polyester resin of the present invention is increased.
  • the molar fraction q is more preferably 0.1 to 0.4.
  • Y3 is a residue of a compound containing three or more hydroxyl groups, and examples thereof include residues such as trimethylopropane, glycerin, pentaerythritol, diglycerin, and polyglycerin. .
  • Y3 may be a tetrafunctional or higher functional polyol. It is more preferable that Y3 is triol because the concern of causing gelation is reduced when the polylactic acid-based polyester of the present invention is polymerized.
  • the molar fraction r of the segment containing Y3 is not particularly limited and may be 0, but by setting it to 0.01 to 0.1, This is preferable because the molecular weight of the resin is increased, the adhesion is increased, and the reactivity with the curing agent is increased. However, if the molar fraction r is too large, the possibility of causing gelation at the time of polymerizing the polylactic acid-based polyester of the present invention increases, so it is preferable not to exceed 0.1.
  • the molar fraction r is more preferably 0.02 to 0.07.
  • X is a carboxylic acid polyanhydride residue and has two or more carboxyl groups.
  • a carboxylic acid polyanhydride that can be used as the X component of the present invention, a dianhydride is preferable, and it is also preferable to use a dianhydride in combination with a small amount of a trifunctional or higher functional anhydride.
  • carboxylic acid polyanhydrides examples include pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride (BPDA), ethylene glycol bisanhydro trimellitate (TMEG), 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride Product (DSDA), 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 2,2′-bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA), glycerin trisuan Hydrotrimellitate etc.
  • PMDA pyromellitic anhydride
  • ODPA oxydiphthalic dianhydride
  • BTDA 4,4′-benz
  • TMEG ethylene glycol bisanhydro trimellitate
  • the polylactic acid-based polyester resin of the present invention for example, polymerizes a polyol containing a polylactic acid segment, a polyol not containing a polylactic acid segment, and a compound containing three or more hydroxyl groups with a carboxylic acid polyanhydride.
  • the polylactic acid-based polyester resin of the present invention can be obtained by charging the raw materials shown on the left in a lump, raising the temperature to 120 ° C. or higher and polymerizing for 1 to 3 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.
  • TMEG ethylene glycol bisanhydro trimellitate
  • Polymerization is possible even at a low temperature of about 120 ° C., and it becomes easy to use a polyether polyol having low heat resistance as the Y2 component. Further, the polymerization rate can be increased by using a conventionally known esterification catalyst.
  • 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; organometallic salts such as zinc octylate; However, amines, pyridines, and phosphines are more preferable.
  • the polymerization rate can be increased.
  • the amount of the esterification catalyst used is preferably 0.5 mol% or more and 10 mol% or less, more preferably 1 mol% or more and 8 mol% or less, still more preferably 2 mol% or more with respect to the acid anhydride group charged. 6 mol% or less. If it is 0.5 mol% or less, the effect of adding a catalyst is hardly seen, and if it is 10 mol% or more, the resulting resin tends to be intensely colored and a gel-like product may be generated.
  • the polylactic acid segment When polymerizing the polylactic acid-based polyester resin of the present invention, it is effective to add various antioxidants.
  • the polymerization temperature When 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 0.05 to 0.5% by weight of the resin is preferably added.
  • 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 30 ° C. or higher and 85 ° C. or lower, more preferably 40 ° C. or higher and 80 ° C. or lower, and further preferably 45 ° C. or higher and 75 ° 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. However, when the water temperature is too high, the hydrolysis rate of the polylactic acid segment tends to increase, and the molecular weight of the polyester resin tends to decrease.
  • Examples of basic compounds used in the present invention include ammonia, organic amine compounds, inorganic basic compounds, and the like.
  • organic amine compound examples include triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine.
  • Examples include diethanolamine, triethanolamine, morpholine, N-methylmorpholine, and N-ethylmorpholine.
  • water-dispersibility can be improved by using highly hydrophilic ethanolamines, particularly triethanolamine.
  • 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, And ammonium carbonate etc. 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, And ammonium carbonate etc.
  • 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 value 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 value.
  • 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.
  • An aqueous adhesive can be obtained by adding a curing agent having reactivity with a carboxyl group to the polylactic acid polyester resin aqueous dispersion of the present invention.
  • curing agent various hardening
  • 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 〜 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 epoxy compound suitable as the curing agent for the water-based adhesive of the present invention include novolac type epoxy resins, bisphenol type epoxy resins, trisphenol methane type epoxy resins, amino group-containing epoxy resins, and copolymer type epoxy resins. it can.
  • Examples of novolak-type epoxy resins include those obtained by reacting epichlorohydrin and / or methyl epichlorohydrin with novolaks obtained by reacting phenols such as phenol, cresol and alkylphenol with formaldehyde in the presence of an acidic catalyst. be able to.
  • Examples of 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. And those obtained by reacting epichlorohydrin and / or methyl epichlorohydrin.
  • Examples of the trisphenol methane type epoxy resin include those obtained by reacting trisphenol methane, tris-resole methane and the like with epichlorohydrin and / or methyl epichlorohydrin.
  • amino group-containing epoxy resins include glycidylamine series 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 cyclohexylmaleimide, 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 EX-614, EX-512 manufactured by Nagase Chemitex Co., Ltd. , EX-412 and the like.
  • oxazoline compound suitable as a curing agent for the aqueous adhesive of the present invention a commercially available oxazoline compound can be used, such as Nippon Shokubai Epocross WS-500, WS-700, Epocross K-2010E, Epocross 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 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, 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 Examples include condensates of o-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 alkyls obtained by alkoxylating these compounds with alcohols having 1 〜 6 carbon atoms. Mention may be made of ether compounds.
  • methoxylated methylol urea methoxylated methylol-N, N-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like.
  • methoxylated methylol melamine, butoxylated methylol melamine and methylolated benzoguanamine each of which can be used alone or in combination.
  • the 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.
  • low molecular weight compounds 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 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 aromatic amines, imides, acetylacetone, acetoacetate ester
  • Examples include active methylene compounds such as tellurium, mercaptans, imines, ureas, diaryl compounds and sodium bisulfite.
  • the blocked isocyanate is composed of the above isocyanate compound, isocyanate compound and isocyanate.
  • 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. Also.
  • Additives include plasticizers, dispersants, anti-settling agents, emulsifiers, thickeners, antifoaming agents, antifungal agents, antiseptics, anti-skinning agents, anti-sagging agents, delustering agents, antistatic agents, conductive agents
  • a flame retardant 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 paint can be produced.
  • the curing agent those exemplified in the adhesive application can be used.
  • aqueous 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. 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 weight or less, more preferably 0.5% by weight 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 ultraviolet absorber, an antioxidant, an emulsion of a light stabilizer, and an aqueous solution are dispersed in a polyester resin in water. Addition to the body also improves the weather resistance.
  • 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 show strong adhesion to films, sheets, woven fabrics, non-woven fabrics and papers made of various raw materials, but polylactic acid, polyester, polyurethane, polyamide, cellulose, starch, vinyl chloride, chloride It exhibits particularly high adhesion to films and sheets made from vinylidene, 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 polylactic acid-based polyester resin water-based adhesive and water-based ink of the present invention exhibit high adhesive strength to various metal vapor-deposited films, they are used as a laminate having a three-layer structure of A layer / metal vapor-deposited layer / B layer. It is also useful.
  • the metal and B layer used for a metal vapor deposition layer are not specifically limited, Especially the adhesive force of the aluminum vapor deposition film, the polylactic acid-type polyester resin water-based adhesive of this invention, and water-based ink is large. It seems that the polylactic acid-based polyester resin aqueous adhesive and water-based ink of the present invention exhibit high adhesion to various metal vapor-deposited films due to the high acid value of the polyester resin of the present invention. 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 resin of the present invention has an appropriate biodegradation rate, when it is left in the natural environment, it is gradually biodegraded over a long period of time, and accordingly, the components to be coated can be gradually released into the environment. it can. 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.
  • other biodegradable resins, 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 covering 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, etc. 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 a component that is desired to be released slowly in the natural environment
  • 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 fertilizers. 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. Dissolve or disperse the component to be coated in the aqueous dispersion, and then spray the aqueous dispersion itself to evaporate the moisture to form particles, By spraying in the presence of some carrier and adhering to the surface of the carrier and / or inside the carrier, or applying to some adherend to form a coating film, a biodegradable coating can be easily obtained, Because it is convenient.
  • the polylactic acid-based biodegradable resin is a self-emulsifying agent that can form an aqueous dispersion without the addition of a surfactant
  • the surfactant is released into the environment during the biodegradation process. This is more preferable because the environmental load is less.
  • the organic solvent is not released or released into the environment in both the manufacturing process of the coating and the use of the coating. The environmental load is further reduced, which is more preferable.
  • ⁇ Resin composition> A sample was dissolved in deuterated chloroform or deuterated dimethyl sulfoxide, and 1 H-NMR analysis and 13 C-NMR analysis were performed using an NMR apparatus 400-MR manufactured by VARIAN, and the resin composition was obtained from the integral ratio. Expressed in mol%. The lactic acid content (% by weight), p, q and r were calculated based on the resin composition shown on the left.
  • ⁇ L-lactic acid content> 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. Further, in the sample composition obtained by the above method, a resin having a composition in which all of the lactic acid components are substituted with L-lactic acid components is polymerized, and the specific rotation is measured by the same method as [ ⁇ ] obs, and [ ⁇ ] 100 It was.
  • ⁇ Number average molecular weight> A resin sample was dissolved in tetrahydrofuran so that the resin concentration was about 0.5% by weight and filtered through a polytetrafluoroethylene membrane filter having a pore size of 0.5 ⁇ m, and tetrahydrofuran was used as the 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.
  • ⁇ Acid value> Dissolve 0.2 g of a resin sample in 20 ml of N, N-dimethylformamide and titrate phenolphthalein with 0.1 N potassium hydroxide ethanol solution in the presence of an indicator. The sum was expressed in terms of equivalents per 10 6 g of resin (equivalents / 10 6 g).
  • ⁇ 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.
  • Aqueous adhesive was prepared by blending zinc ammonium carbonate as a curing agent in the ratio described in Table 3 with respect to the aqueous dispersion.
  • zinc ammonium carbonate (16% aqueous solution, zinc concentration 4.5%) was adjusted to pH 9 to 10 by adding about 50 g of 28% ammonia water to 112 g of distilled water, 12 g of zinc oxide and 20 g of ammonium carbonate. I used something.
  • the coating layer of the laminate for adhesion evaluation was carried out in accordance with JIS D0202-2002 4.15 grid adhesion adhesion test method.
  • As cellophane adhesive tape CT24 manufactured by Nichiban Co., Ltd. was used, and it was peeled after being adhered to the film with the finger pad. Judgment is represented by the number of squares that do not peel out of 100 squares. The case where the coating layer does not peel is represented as 100/100, and the case where the coating layer completely peels is represented as 0/100.
  • L-lac L-lactide
  • Gly glycerin
  • TMP trimethylolpropane
  • NPG neopentyl glycol
  • EG ethylene glycol
  • PEG # 1000 polyethylene glycol 1000 (number average molecular weight 1000 )
  • PEG # 400 Polyethylene glycol 400 (number average molecular weight 400)
  • PCL polycaprolactone diol (number average molecular weight 2000)
  • PES Polyester (Adipic acid / 3-methylpentanediol, number average molecular weight 1000)
  • PTMG Polytetramethylene glycol (number average molecular weight 2000)
  • TMEG ethylene glycol bisanhydro trimellitate
  • PMDA pyromellitic dianhydride
  • BTDA 3,3 ′, 4,4′-benzophenone
  • Table 1 shows the charged composition in the polymerization of the polylactic acid-based polyol A, the number average molecular weight, the lactic acid content, the L-lactic acid content, and the number average molecular weight of the obtained polylactic acid-based polyol A.
  • polylactic acid polyols B to G Polylactic acid-based polyols B to G were synthesized in the same manner as polylactic acid-based polyol A, except that the raw materials used and the ratio thereof were changed.
  • Table 1 shows the composition, number average molecular weight, and L-lactic acid content of the polylactic acid-based polyols B to G.
  • the polylactic acid polyol E has an L-lactic acid content outside the range of the Y1 component defined in claim 2 of the present invention.
  • the polylactic acid-based polyols F and G have a number average molecular weight outside the range of the Y1 component defined in claim 3 of the present invention.
  • Example P-1 Polylactic acid-based polyester resin No. 1 Production of Y1 component D83 parts, 4 parts of PEG # 400, 0.2 parts of TMP, 11 parts of TMEG, 0.09 of 4-dimethylaminopyridine as a catalyst in a 500 ml glass flask equipped with a thermometer, stirrer and Liebig condenser 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 120 ° C. with nitrogen gas flowing again, stirred for 2 hours, and then taken out. 1 was obtained. Next, polylactic acid polyester resin No. 1 composition, acid value, number average molecular weight and storage stability were measured, and lactic acid content and p / (p + q + r) were calculated. The results are shown in Table 2.
  • Polylactic acid polyester resin No. No. 7 has a low resin acid value and is outside the scope of the present invention.
  • Polylactic acid polyester resin No. No. 8 has a high resin acid value and is outside the scope of the present invention.
  • Resin No. Y1 used in 8 is F, and since the molecular weight of F is low, the copolymerization ratio of the X component (PMDA) used for chain extension is increased, and as a result, the acid value of the resulting resin is also increased.
  • Resin No. No. 8 is inferior in storage stability, but is presumed to have a high acid value and high water absorption.
  • Polylactic acid polyester resin No. No. 9 has a small number average molecular weight and is outside the scope of the present invention.
  • Polylactic acid polyester resin No. No. 11 has a small lactic acid content and p, and is outside the scope of the present invention. Resin No. No. 11 is not worthy of being called a material having a low biomass degree and a low environmental load. Resin No. No. 11 is slightly inferior in storage stability, but it is presumed that the content of polyethylene glycol having high hydrophilicity is large and hydrolysis is promoted.
  • Example C-1 Production and Evaluation of Polylactic Acid Polyester Resin Aqueous Dispersion and Aqueous Adhesive Polylactic acid polyester resin No. 1 was added to a 500 ml glass flask equipped with a thermometer, stirrer and Liebig condenser. 30 parts of 1, 6.2 parts of TEA and 70 parts of water were charged, heated to 70 ° C. and stirred for 1 hour, 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-6 In the same manner as in Example 1, except that the charged raw materials and the ratios thereof were changed, polylactic acid polyester resin water dispersions were produced, and polylactic acid polyester resin water dispersions 2 to 7 were produced. Further, in the same manner as in Example 1, a curing agent was added to the polylactic acid-based polyester resin aqueous dispersions 2 to 7, and the adhesion and water resistance of the obtained coating film were evaluated. The results are shown in Table 4. All showed high water dispersibility, and the cured coating film showed high adhesion and water resistance.
  • Comparative Examples C-7 to C-11 In the same manner as in Example 1, except that the raw materials and the ratios thereof were changed to try to produce a polylactic acid-based polyester resin aqueous dispersion, and the aqueous dispersion was further obtained in the same manner as in Example 1. A curing agent was blended, and the adhesion and water resistance of the obtained coating film were evaluated. The results are shown in Table 5.
  • Comparative Example C-7 a large amount of undispersed material was present after stirring for 1 hour, and further stirring was continued for 1 hour, but dispersion was not possible.
  • Polylactic acid-based polyester resin No. used in Comparative Example C-7 No. 7 has a small acid value of the resin and is outside the scope of the present invention.
  • the raw material Y1 has a high L-lactic acid content, which is also outside the range of Y1 of the present invention. It is estimated that the water dispersibility was low due to the high crystallinity of Y1 and the low acid value of the resin itself.
  • Polylactic acid-based polyester resin No. used in Comparative Example C-10 No. 10 showed almost no dispersion of resin after stirring for 1 hour, and further stirring was continued for 1 hour, but almost no dispersion was possible.
  • Resin No. No. 10 has a large molecular weight of the resin and is outside the scope of the present invention. Further, the molecular weight of the raw material Y1 is large, which is also outside the range of Y1 of the present invention. When the molecular weight of Y1 is large, the concentration of the carboxyl group introduced into the resin is decreased (the interval at which the carboxyl group is present is increased) and the dispersibility is deteriorated. In addition, since the molecular weight of the resin itself is increased, the cohesiveness of the resin is increased, and it is presumed that the resin could hardly be dispersed.
  • Comparative Example C-9 had poor adhesion, and Comparative Example C-8 had poor water resistance.
  • Resin No. used in Comparative Example C-9 No. 9 has a low molecular weight of the resin and is outside the scope of the present invention. It is presumed that the cohesive force was small and the adhesiveness was poor because the molecular weight was small.
  • Resin No. used in Comparative Example C-8 No. 8 has a large acid value of the resin and is outside the scope of the present invention. Although an equivalent amount of curing agent is blended with respect to the acid value, it is difficult to say that all carboxyl groups have reacted, and a large number of unreacted carboxyl groups remain, resulting in poor water resistance. It is estimated that Comparative Example C-11 has no problem in performance, but is not worthy of being referred to as a material having a low biomass degree and a low environmental load.
  • Example of production of water-based paint (d-2) Polylactic acid polyester resin No. In place of Polylactic acid polyester resin No. 2 4.
  • An aqueous paint (d-2) was obtained by the same composition and production as the aqueous paint (d-1) except that the TEA amount was 4.4 parts.
  • a coating film performance test was conducted using the water-based paints (d-1) and (d-2). In addition, preparation and evaluation of the coated plate followed the following method. The results are shown in Table 6.
  • Boiling water test The coated film appearance (blister occurrence state) after the coated steel sheet was immersed in boiling water for 2 hours was evaluated. ⁇ : No blister ⁇ : Blister generation area within 10% ⁇ : Blister generation area 10-50% ⁇ : Blister generation area 50% or more
  • Solvent resistance 1kg / cm on the coated surface with gauze soaked with methyl ethyl ketone in a room at 20 °C A load of 2 was applied and reciprocated between 5 cm lengths. The number of round trips until the substrate was visible was recorded. If the substrate was not visible after 50 reciprocations,> 50 was displayed. The greater the number of times, the better the curability of the coating film.
  • Adhesion In accordance with JISK-5400 grid-tape method, draw a straight line of 11 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 were made. 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. (Triangle
  • Laminate (f-1) A polylactic acid polyester resin No. 1 was added to a 500 ml glass flask equipped with a thermometer, a stirrer, and a Liebig condenser. 2, 100 parts of TEA, 6.5 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 (Snowtech C, Nissan Chemical Co., Ltd.) was added to 100.
  • colloidal silica Snowtech C, Nissan Chemical Co., Ltd.
  • the filtrate filtered through a 100-mesh filter cloth was applied to a corona-treated surface of a PLA film (manufactured by Innovia Films) having a thickness of 25 ⁇ m so that the thickness after drying would be 5 ⁇ m. And dried at 80 ° C. for 30 minutes to obtain a laminate (f-1).
  • a PLA film manufactured by Innovia Films
  • Laminate (f-2) In the laminate, polylactic acid polyester resin No. In place of Polylactic acid polyester resin No. 2 4. A laminate (f-2) was obtained by the same composition and production as the laminate (f-1) except that the TEA amount was 4.4 parts. A performance test was conducted using the laminates (f-1) and (f-2). Evaluation followed the following method. The results are shown in Table 8.
  • ⁇ Slow release biodegradable coating agent> In a 500 ml glass flask equipped with a thermometer, a stirrer, and a Liebig condenser, a polylactic acid-based polyester resin no. 2, 100 parts of TEA, 6.5 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 (Snowtech C, Nissan Chemical Co., Ltd.) was added to 100. Then, the mixture was further stirred for 1 hour, and then 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 film, dried in a hot air dryer at 60 ° C., and then peeled off from the polypropylene sheet to prepare a sheet made of polylactic acid 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 9.
  • 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> In a 500 ml glass flask equipped with a thermometer, a stirrer, and a Liebig condenser, a polylactic acid-based polyester resin no. 4 and 100 parts of TEA, 4.4 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 lower, and colloidal silica (Snowtech C, Nissan Chemical Co., Ltd.) was added to 100. Then, the mixture was further stirred for 1 hour, and then filtered through a 100 mesh filter cloth.
  • TEA polylactic acid-based polyester resin no. 4 and 100 parts of TEA, 4.4 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 lower, and colloidal silica (Snowtech C, Nissan Chemical Co., Ltd.) was added to 100. Then, the mixture
  • 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 film, dried in a hot air dryer at 60 ° C., and then peeled off 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 9. 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Wrappers (AREA)
  • Epoxy Resins (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

[Problème] Produire une résine polyester à base de poly(acide lactique) qui présente une fonction d'auto-émulsification en ce qu'une émulsion aqueuse stable peut être formée sans utiliser un agent d'émulsification ou un solvant organique ; une composition de dispersion de résine aqueuse contenant celle-ci ; une composition adhésive aqueuse ; et un procédé pour produire une dispersion aqueuse. [Solution] La présente invention concerne une résine polyester à base de poly(acide lactique) qui a une structure chimique représentée par la formule générale (1) et qui a un indice d'acide de résine de 300 à 2 500 eq/106g, un poids moléculaire moyen en nombre de 2 000 à 50 000 et une teneur en acide lactique de 40 % en poids ou plus ; une composition de dispersion de résine aqueuse contenant celle-ci ; une composition adhésive aqueuse ; et un procédé pour produire une dispersion aqueuse. -(Y1-OCO-X-COO)p-ran-(Y2-OCO-X-COO)q-ran-(Y3-OCO-X-COO)r- formule générale (1) Dans la formule générale (1), Y1 est un résidu polyol qui contient un segment de poly(acide lactique), Y2 est un résidu polyol qui ne contient pas un segment de poly(acide lactique), et Y3 est un résidu dérivé d'un composé ayant trois groupes hydroxyle ou plus, Y1, Y2 et Y3 étant chacun une espèce unique ou un mélange d'espèces multiples ; les X sont des résidus qui sont dérivés d'un polyanhydride carboxylique et qui ont chacun deux groupes carboxyle ou plus, chaque X étant une espèce unique ou un mélange d'espèces multiples ; et p, q et r sont des fractions molaires satisfaisant à p+q+r=1, p ≥ 0,25, q ≥ 0, et r ≥ 0.
PCT/JP2012/073893 2011-09-20 2012-09-19 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) WO2013042677A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-204868 2011-09-20
JP2011204868 2011-09-20
JP2012176998 2012-08-09
JP2012-176998 2012-08-09

Publications (1)

Publication Number Publication Date
WO2013042677A1 true WO2013042677A1 (fr) 2013-03-28

Family

ID=47914440

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/073893 WO2013042677A1 (fr) 2011-09-20 2012-09-19 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)

Country Status (2)

Country Link
JP (1) JPWO2013042677A1 (fr)
WO (1) WO2013042677A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014024939A1 (fr) * 2012-08-09 2014-02-13 東洋紡株式会社 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)
US20160031764A1 (en) * 2013-03-14 2016-02-04 Agronutrition Use of acylated carbonic esters of glycerol in agriculture
WO2021233535A1 (fr) * 2020-05-20 2021-11-25 Wacker Chemie Ag Dispersion aqueuse de polyesters biodégradables
CN115746571A (zh) * 2022-11-15 2023-03-07 康辉新材料科技有限公司 一种可降解聚乳酸专用增韧亲水母粒及制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1135655A (ja) * 1997-07-17 1999-02-09 Dainippon Ink & Chem Inc 高分子量乳酸系ポリエーテル共重合体の製造方法
JPH11508640A (ja) * 1996-04-23 1999-07-27 キナートン・リミテッド 酸性ポリ乳酸ポリマー
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
WO2003106539A1 (fr) * 2002-06-17 2003-12-24 日本電気株式会社 Resine biodegradable, composition de resine biodegradable, objet moule biodegradable, et procede de production de resine biodegradable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11508640A (ja) * 1996-04-23 1999-07-27 キナートン・リミテッド 酸性ポリ乳酸ポリマー
JPH1135655A (ja) * 1997-07-17 1999-02-09 Dainippon Ink & Chem Inc 高分子量乳酸系ポリエーテル共重合体の製造方法
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
WO2003106539A1 (fr) * 2002-06-17 2003-12-24 日本電気株式会社 Resine biodegradable, composition de resine biodegradable, objet moule biodegradable, et procede de production de resine biodegradable

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014024939A1 (fr) * 2012-08-09 2014-02-13 東洋紡株式会社 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)
JPWO2014024939A1 (ja) * 2012-08-09 2016-07-25 東洋紡株式会社 ポリ乳酸系ポリエステル樹脂、ポリ乳酸系ポリエステル樹脂水分散体、およびポリ乳酸系ポリエステル樹脂水分散体の製造方法
US20160031764A1 (en) * 2013-03-14 2016-02-04 Agronutrition Use of acylated carbonic esters of glycerol in agriculture
US9790135B2 (en) * 2013-03-14 2017-10-17 Agronutrition Use of acylated carbonic esters of glycerol in agriculture
WO2021233535A1 (fr) * 2020-05-20 2021-11-25 Wacker Chemie Ag Dispersion aqueuse de polyesters biodégradables
CN115746571A (zh) * 2022-11-15 2023-03-07 康辉新材料科技有限公司 一种可降解聚乳酸专用增韧亲水母粒及制备方法

Also Published As

Publication number Publication date
JPWO2013042677A1 (ja) 2015-03-26

Similar Documents

Publication Publication Date Title
JP6020445B2 (ja) ポリ乳酸系ポリエステル樹脂、ポリ乳酸系ポリエステル樹脂水分散体、及びポリ乳酸系ポリエステル樹脂水分散体の製造方法
JP2014139265A (ja) ポリ乳酸系ポリエステル樹脂、ポリ乳酸系ポリエステル樹脂水分散体、及びポリ乳酸系ポリエステル樹脂水分散体の製造方法
JP6579292B1 (ja) ポリエステル樹脂、ポリエステル樹脂水分散体、及びポリエステル樹脂水分散体の製造方法
JP6163766B2 (ja) ポリエステル樹脂、ポリエステル樹脂水分散体、及びポリエステル樹脂水分散体の製造方法
JP6319300B2 (ja) ポリ乳酸系ポリエステル樹脂、ポリ乳酸系ポリエステル樹脂溶液、ポリ乳酸系ポリエステル樹脂水分散体、及びポリ乳酸系ポリエステル樹脂水分散体の製造方法
US20170174829A1 (en) Polyester resins based on fatty acids that have a short oil length, aqueous dispersions and associated coatings
JP3330390B2 (ja) ホットメルト接着剤組成物
JP2004107413A (ja) 可塑剤含有ポリ乳酸系樹脂水分散体
WO2013042677A1 (fr) 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)
WO2017003872A1 (fr) Composition adhésive à base de polyols de polylactide
EP2699613A1 (fr) Composition de résine aqueuse comprenant une résine polyester-polyuréthane et un polyol dendritique
CN103649147A (zh) 包含含枝状多元醇的聚酯-聚氨酯树脂的水性树脂组合物
JP6146416B6 (ja) ポリ乳酸系ポリエステル樹脂、ポリ乳酸系ポリエステル樹脂水分散体、およびポリ乳酸系ポリエステル樹脂水分散体の製造方法
JPWO2014024939A6 (ja) ポリ乳酸系ポリエステル樹脂、ポリ乳酸系ポリエステル樹脂水分散体、およびポリ乳酸系ポリエステル樹脂水分散体の製造方法
JP6340909B2 (ja) ポリ乳酸系ポリエステル樹脂、ポリ乳酸系ポリエステル樹脂水分散体、及びポリ乳酸系ポリエステル樹脂水分散体の製造方法
JP5581609B2 (ja) ポリ乳酸系水性ラミネート用接着剤、エマルジョンおよびそれらを用いた積層体
WO2017003875A1 (fr) Composition adhésive durcissable à l'humidité à base de polylactide polyols
JP2004339419A (ja) ポリ乳酸‐ポリエチレングリコールブロック共重合体の水分散体、該共重合体の粒子及びそれらから形成される被膜
JP2014005369A (ja) ポリ乳酸系ポリエステル樹脂、ポリ乳酸系ポリエステル樹脂水分散体、及びポリ乳酸系ポリエステル樹脂水分散体の製造方法
JP2004018744A (ja) ポリ乳酸系樹脂水分散体
JP2012233023A (ja) 徐放性生分解性被覆剤および徐放性生分解性被覆体
WO2024122240A1 (fr) Composé polymère biodégradable marin, son procédé de production et composition de résine biodégradable marine
CN112852279A (zh) 涂布剂、涂覆有该涂布剂的层叠体、成型体、包装材料
TH97827A (fr)
KR20100078439A (ko) Ｐｃｃｄ 폴리에스테르 조성물, ｐｃｃｄ 폴리에스테르 수지, 이를 포함하는 용제형 코팅제 및 접착제, 및 이의 제조 방법

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2012547371

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12834159

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12834159

Country of ref document: EP

Kind code of ref document: A1