JPWO2013042677A1 - Polylactic acid-based polyester resin, polylactic acid-based polyester resin aqueous dispersion, aqueous adhesive, and method for producing polylactic acid-based polyester resin aqueous dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide 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, an aqueous dispersion resin composition containing the same, and an aqueous adhesive composition And a method for producing an aqueous dispersion. SOLUTION: 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 certain polylactic acid-based polyester resin, an aqueous dispersion resin composition containing the same, an aqueous adhesive composition, and a method for producing an aqueous dispersion. -(Y1-OCO-X-COO) p-ran- (Y2-OCO-X-COO) q-ran- (Y3-OCO-X-COO) r- Formula (1) where Y1 is a polylactic acid segment The polyol residue contained, Y2 is a polyol residue containing no polylactic acid segment, Y3 is a residue of a compound containing 3 or more hydroxyl groups, and Y1, Y2, and Y3 may be composed of a single species, respectively. A mixture of plural kinds may be used. 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. p, q and r are mole fractions, p + q + r = 1, p ≧ 0.25, q ≧ 0, r ≧ 0.

Description

  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.

  In recent years, paints, inks, coating agents, adhesives, pressure-sensitive adhesives, sealants, primers, and various processing agents for textile products and paper products have been changed from conventional organic solvent systems to water-based, high solids from the viewpoint of suppressing emissions of volatile organic solvents. It is progressing in the direction of pulverization and pulverization. In particular, water-based dispersion using an aqueous dispersion is regarded as the most versatile and promising in terms of workability and work environment improvement. In addition, if the binder component forming the aqueous dispersion is mainly composed of a biodegradable resin, it is more preferable from the viewpoint of preventing environmental pollution after disposal. In addition, if the binder component forming the water dispersion is manufactured using biomass-derived components such as animals and plants as raw materials, it is more preferable in terms of reducing carbon dioxide emissions than those using fossil fuels as raw materials.

  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.

  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. In Patent Documents 1 and 2, a polylactic acid aqueous dispersion forcedly emulsified with an emulsifier is used. Although 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-sulfoisophthalic acid 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. In 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.

JP 2008-13657 A JP 2008-13658 A JP 2003-277595 A JP 2010-174170 A JP 2000-7789 A

  When the present inventors examined the background art, it was found that there were the following problems. That is, in the inventions disclosed in 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. In addition, in the invention disclosed in 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. Also in the invention disclosed in Patent Document 5, 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 such prior art problems. 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.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have reached the present invention. That is, 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.
-(Y1-OCO-X-COO) _p -ran- (Y2-OCO-X-COO) _q -ran- (Y3-OCO-X-COO) _r -Formula (1)
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, and 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. p, q and r are mole fractions, p + q + r = 1, p ≧ 0.25, q ≧ 0, r ≧ 0.
(2) The Y1 is a random copolymer mainly composed of either one or both of D-lactide and ε-caprolactone and L-lactide, and the L-lactic acid content is 90% by weight or less. The polylactic acid-based polyester resin according to (1).
(3) The polylactic acid-based polyester resin according to (1) or (2), wherein the number average molecular weight of Y1 is 500 to 8,000.
(4) The polylactic acid-based polyester resin according to any one of (1) to (3), wherein X is a residue of ethylene glycol bisanhydro trimellitate.
(5) A polylactic acid polyester resin aqueous dispersion containing the polylactic acid polyester resin according to any one of (1) to (4), a basic compound, and water.
(6)
The polylactic acid-based polyester resin aqueous dispersion according to (5), which does not contain a surfactant.
(7)
The polylactic acid-based polyester resin aqueous dispersion according to (5) or (6), which does not contain an organic solvent.
(8)
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.
(9)
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.
(10)
The aqueous resin composition according to (9), wherein the curing agent is one or more selected from the group consisting of a polyvalent epoxy compound, an oxazoline resin, a carbodiimide resin, and a polyvalent metal salt.
(11)
An aqueous adhesive comprising the aqueous resin composition according to (9) or (10).
(12)
An aqueous paint comprising the aqueous resin composition according to (9) or (10).
(13)
A water-based ink comprising the water-based resin composition according to (9) or (10) and a color material.
(14)
(1) to (4) A laminate comprising a layer (A layer) made of the polylactic acid-based polyester resin and a layer (B layer) selected from the group consisting of a film, a sheet, a woven fabric, a nonwoven fabric and paper body.
(15)
The layered product according to (14), wherein the B layer is mainly composed of a biomass-derived material and / or a chemically modified material of the biomass-derived material.
(16)
A packaging material having the laminate according to (14) or (15) as a constituent element.
(17)
A sustained-release biodegradable coating agent comprising the aqueous resin composition according to (9) or (10).
(18)
The sustained-release biodegradable coating body which coat | covered the to-be-coated component with the biodegradable coating agent as described in (17).
(19)
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.
(20)
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.

  Since the polylactic acid-based polyester resin of the present invention contains a polylactic acid segment at a high concentration, it is excellent in biodegradability. In addition, since 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. Moreover, the polylactic acid-type polyester resin aqueous dispersion of this invention can be prepared without using an emulsifier, and is excellent in adhesiveness. Furthermore, the adhesive layer excellent in adhesiveness and water resistance can be easily obtained by mix | blending the hardening | curing agent which has reactivity with respect to a carboxyl group in the polylactic acid-type polyester resin aqueous dispersion of this invention.

Polylactic acid-based polyester resin of the present invention consists of a chemical structure represented by the following formula (1), the resin acid value ^{300eq / 10 6 g~2,500eq / 10 6} g, a number average molecular weight of 2,000～35 , A polylactic acid-based polyester resin having a lactic acid content of 40% by weight or more.
-(Y1-OCO-X-COO) _p -ran- (Y2-OCO-X-COO) _q -ran- (Y3-OCO-X-COO) _r -Formula (1)
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, and 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. p, q and r are mole fractions, p + q + r = 1, p ≧ 0.25, q ≧ 0, r ≧ 0.
In the above formula (1), “-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 from 300 eq / ton to 2500 eq / ton, preferably from 400 eq / ton to 2300 eq / ton, more preferably from 500 eq / ton to 2100 eq / ton. 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. If 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. On the other hand, water dispersibility tends to increase by increasing the resin acid value. However, if 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. On the other hand, if the number average molecular weight is too high, the cohesive force of the resin is increased, and the water dispersibility becomes poor.For example, even if 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 polylactic acid-based polyester resin of the present invention preferably has a lactic acid content of 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. In this case, 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. If 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. Contributes to dispersion and also serves as a reaction point with the curing agent. If the polyanhydride has three or more anhydride groups, in addition to increasing the molecular weight of the resin, improving water dispersibility, and improving polymerizability, the resin skeleton will also exhibit the effect of branching. The water resistance of can be improved.

  In the polylactic acid-based polyester resin of the present invention, 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.

  In the polylactic acid-based polyester resin of the present invention, the molar fraction p of the segment containing Y1 is 0.25 or more. When 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. 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. When 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. On the other hand, if 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.

  In the polylactic acid-based polyester resin of the present invention, Y1 is typically a random copolymer mainly composed of L-lactide and either one or both of D-lactide and ε-caprolactone. The component may be copolymerized. A random copolymer mainly composed of either or both of D-lactide and ε-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, ε-caprolactone, or both of them and L-lactide can be obtained by heating and stirring.

The polyol that can be used as the initiator is preferably a diol, such as 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-pentane Diol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2 ', 2'-dimethyl-3'-hydroxypro Panate, 2-n-butyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5- Aliphatic diols such as ntanediol, 3-propyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, 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]} de alicyclic glycols Kanji such as methanol, or ethylene oxide or propylene oxide to hydroxyl groups at both ends of bisphenol-A It is preferably one or more selected from polyethers such as aromatic glycols such as adducts, polyethylene oxide, polypropylene oxide, polytetramethylene oxide and the like. Among these, by using glycols having a relatively low molecular weight such as ethylene glycol, 2-methylpentanediol, neopentyl glycol, etc., the degree of biomass can be kept relatively high, which is more preferable. 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. In this case, 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. However, if it is used in a large amount, it may cause gelation when polymerizing the polylactic acid-based polyester of the present invention. Therefore, when a trifunctional or higher functional polyol compound is 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.

  Although the terminal group of the polylactic acid-type polyester resin of this invention is not specifically limited, Typically, they are the hydroxyl group derived from Y1, Y2, and / or Y3, and / or the 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.

  In the polylactic acid-based polyester resin of the present invention, 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. When 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.

  As Y2, for example, a polymer polyol such as a polyester polyol, a polycarbonate polyol, a polyurethane polyol, or a polyether polyol having no polylactic acid segment can be used. Among these, in view of biodegradability, aliphatic polyester polyols are preferable, and polycaprolactone diol is particularly preferable. When polyethylene glycol is used, the effect of improving water dispersibility may be exhibited.

Further, as Y2, low molecular weight polyols that are not polymer polyols such as aliphatic polyols and alicyclic polyols can also be used. Examples of the aliphatic polyol 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′-hydroxypropanoate, 2-n-butyl- 2-ethyl-1,3-propanediol, 3-ethyl-1,5-pentanediol, 3-propyl-1,5-pen Njioru, 2,2-diethyl-1,3-propanediol, may be mentioned 3-octyl-1,5-pentanediol. Examples of alicyclic polyols 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.

  In the polylactic acid-based polyester resin of the present invention, the molar fraction q of the segment containing Y2 is not particularly limited, and may be 0. By setting the molar fraction q to 0.05 to 0.5, the effect of relaxing the cohesiveness of the L-lactic acid component contained in Y1 and improving water dispersibility tends to be exhibited. When 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.

  In the polylactic acid-based polyester resin of the present invention, 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.

  In the polylactic acid-based polyester resin of the present invention, 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, the branched skeleton 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.

  In the polylactic acid-based polyester resin of the present invention, X is a carboxylic acid polyanhydride residue and has two or more carboxyl groups. As the 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. Examples of carboxylic acid polyanhydrides that can be used 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. can be raised, even if it consists of one kind of carboxylic acid polyanhydride, two or more kinds A mixture may be. It is particularly preferable to use ethylene glycol bisanhydro trimellitate (TMEG), which can be polymerized at a relatively low temperature, has a low cohesive force and good water dispersibility.

  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. Can be obtained at For example, the polylactic acid-based polyester resin of the present invention can be obtained by charging all the raw materials at the same time, raising the temperature to 120 ° C. or higher and polymerizing for 1 to 3 hours. In order to prevent the carboxylic acid polyanhydride from ring-opening due to the reaction with water contained in the polymerization system, it is preferable to use each raw material after reducing the water content by vacuum drying or the like in advance. In order to avoid the influence of moisture during the polymerization, 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. In particular, since ethylene glycol bisanhydro trimellitate (TMEG) has an aliphatic segment derived from ethylene glycol in the molecule, it has higher compatibility with the polylactic acid segment than other carboxylic acid polyanhydride compounds. 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. For example, 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. Particularly, when 4-dimethylaminopyridine is used, 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.

  When polymerizing the polylactic acid-based polyester resin of the present invention, it is effective to add various antioxidants. 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. In addition, when a segment having low heat resistance such as polyether is copolymerized, it may be more susceptible to oxidative degradation. In such a case, addition of an antioxidant is particularly effective. Examples of 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.

  Since the polylactic acid-based 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 the basic compound used in the present invention include ammonia, an organic amine compound, and an inorganic basic compound.

  Specific examples of the organic amine compound include triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine. , Ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, Diethanolamine, triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like can be mentioned. Among these organic amine compounds, water-dispersibility can be improved by using highly hydrophilic ethanolamines, particularly triethanolamine.

  Specific examples of the inorganic basic compound 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. When using 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. In addition, after forming an aqueous dispersion using a basic compound having an acid value of less than 1.0 equivalent with respect to the acid value of the polylactic acid-based polyester resin of the present invention, the basic compound is additionally added to form a final base. It is good also considering the addition amount of an ionic compound as 0.5 equivalent-1.0 equivalent with respect to an acid value. At this time, 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.

  In order to produce the 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. In some cases, 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 to a carboxyl group to the polylactic acid-based polyester resin aqueous dispersion of the present invention. As said hardening | curing agent, various hardening | curing 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, can be used. In particular, 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.

  When these curing agents are used, 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. When 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. Examples of amino group-containing epoxy resins include glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, and the like. Can be mentioned. Examples of the copolymer type epoxy resin 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. .

  Since 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. Examples of 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 Pharmaceutical Co., Ltd., Denacol EX-614, EX-512 manufactured by Nagase Chemitex Co., Ltd. , EX-412 and the like.

  As an oxazoline compound suitable as a curing agent for the aqueous adhesive of the present invention, commercially available oxazoline compounds can be used, such as Nippon Shokubai Epocros WS-500, WS-700, Epocros K-2010E, Epocros K-2020E, etc. Can be used.

  As a carbodiimide compound suitable as a 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.

  As 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 zinc ammonium carbonate are particularly preferable.

  Examples of the phenol resin suitable as the curing agent for the aqueous adhesive of the present invention include a condensate of alkylated phenols and / or cresols with formaldehyde. Specifically, 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. Specific examples include 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. Preferred are 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. Examples of 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. Moreover, trimers of these isocyanate compounds can be exemplified. Examples of 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. Examples of 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 And compounds having an amino group, polyester polyols, polyether polyols, polyamides, and other active hydrogen-containing polymers.

The isocyanate compound may be a blocked isocyanate. Examples of the isocyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol, oximes such as acetoxime, methyl ethyl 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, ε-caprolactam, δ-valero Examples include lactams such as lactam, γ-butyrolactam, β-propyllactam, and other aromatic amines, imides, acetylacetone, acetoacetate ester, ethyl malonate. 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. As 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. As 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 | blending an agent. Examples of 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 etc. can be mix | 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. As the curing agent, those exemplified in the adhesive application can be used.

  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. Examples of 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. As 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) composed 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. Can be obtained. 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. Among these, when combined with 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. Moreover, since 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. Although 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-based 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.

<Slow release biodegradable coating>
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. For example, 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.

<Coated components>
If the component to be coated in the present invention is a component that is desired to be released slowly in the natural environment,
There is no particular limitation. 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 fertilizers. And / or a component that can be expected to have a nutritional supplement. Further, the component to be coated is not limited to a single component, and may be composed of a plurality of components.

<Method for producing sustained-release biodegradable coating>
Although 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. Moreover, if 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. Also,
In the case of an aqueous dispersion that does not contain an organic solvent or uses a small amount of organic solvent, 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.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, but may be implemented with appropriate modifications within a scope that can meet the gist of the present invention. These are all included in the technical scope of the present invention.

  Hereinafter, unless otherwise specified, parts represent parts by weight. The measurement and evaluation methods employed in the present specification are as follows.

<Resin composition>
The 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 determined from the integration 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 [α] obs. Further, in the sample composition obtained by the above-described method, a resin having a composition in which all of the lactic acid component is substituted with the L-lactic acid component is polymerized, and the specific rotation is measured by the same method as [α] obs, and [α] 100 It was.
OP [%] = ABS ([α] obs / [α] 100) * 100
When OP = 100%, the lactic acid contained in the sample is all L-form, and when OP = 0%, the contents of L-form and D-form are equal 50% respectively, and L-lactic acid / (L-lactic acid + D Lactic acid) = 50 + [OP] / 2. From the left, the ratio of L-lactic acid and D-lactic acid was calculated, and the L-lactic acid content was calculated in consideration of the lactic acid content determined separately by the method described above.

<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 μm, 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. Showa Denko KF-802, 804L and 806L 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, titrate phenolphthalein with 0.1 N potassium hydroxide ethanol solution in the presence of an indicator, and check that the solution is colored red. The sum was expressed in terms of equivalents per 10 ⁶ g of resin (equivalents / 10 ⁶ g).

<Storage stability>
After storing the resin sample at 50 ° C. for 10 days, the number average molecular weight was measured and the change in molecular weight was evaluated.
(Judgment) ○: Change in number average molecular weight is less than 5%
Δ: Change in number average molecular weight is 5% or more and less than 10%
×: Change in number average molecular weight is 10% or more

<Evaluation of water dispersibility>
After adding a predetermined amount of resin, basic compound and water, the temperature was kept at 60 ° C., the system was stirred at 400 rpm using a three-one motor BLh600 (manufactured by HEIDON), and water dispersibility was visually determined.
(Judgment) ◯: There is no undispersed material and the resin is completely dispersed.
Δ: Undispersed material exists.
X: Resin is not dispersed at all.

<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.

<Preparation of water-based adhesive>
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. However, ammonium carbonate (16% weight aqueous solution, zinc concentration 4.5%) was adjusted to pH 9-10 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.

<Preparation of laminate for adhesion evaluation>
A water-based adhesive is applied to a 50 μm thick PET film (Toyobo Co., Ltd.) so that the thickness after drying is 5 μm, dried at 80 ° C. for 5 minutes, and then dried at 120 ° C. for 10 minutes. Thus, an adhesive evaluation laminate was prepared.

<Evaluation of adhesiveness>
It performed based on JISD0202-2002 4.15 cross-cut adhesion adhesion test method with respect to the coating layer of the laminated body for adhesive evaluation. 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, and the case where the coating layer does not peel is represented as 100/100, and the case where it completely peels is represented as 0/100.

<Evaluation of water resistance>
The adhesive evaluation laminate was immersed in 25 ° C. water for 5 hours, and then the surface water was sufficiently wiped off. Next, the coating layer was immediately applied to the coating layer in accordance with JIS D0202-2002 4.15 cross-cut adhesion test method.

Hereinafter, the abbreviations of the compounds shown in the text and tables in the examples indicate the following compounds, respectively.
L-lac: L-lactide D-lac: D-lactide ε-CL: ε-caprolactone 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 tetracarboxylic dianhydride TEA: triethylamine TETA: triethanolamine AN: aqueous ammonia ( 28%)
NaOH: Sodium hydroxide NaHCO3: Sodium bicarbonate

Synthesis of polylactic acid polyol A
A 500 ml glass flask equipped with a thermometer, a stirrer, and a Liebig condenser was charged with 1.8 parts of glycerin, 84 parts of L-lactide, 16 parts of D-lactide and 0.066 part of tin octylate as a catalyst at 30 ° C. Divided nitrogen gas was circulated. 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. Subsequently, 0.044 parts of phosphoric acid was added, and after stirring for 20 minutes, the system was depressurized and unreacted residual lactide was distilled off. After about 20 minutes, after the unreacted lactide distills out, the contents were taken out and cooled. Table 1 shows the charged composition at the time of 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.

Synthesis of 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 compositions, number average molecular weights, and L-lactic acid contents of the polylactic acid-based polyols B to G. Among these, the polylactic acid-based polyol E has an L-lactic acid content outside the range of the Y1 component defined in claim 2 of the present invention. In addition, 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. Production of 1 In a 500 ml glass flask equipped with a thermometer, a stirrer, and a Liebig condenser, Y83 component D83 parts, 4 parts PEG # 400, 0.2 parts TMP, 11 parts TMEG, 0.09 4-dimethylaminopyridine as a catalyst 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.

Examples P-2 to P-6, Comparative Examples P-7 to P-11 Polylactic acid polyester resin No. Production of 2 to 11 Polylactic acid polyester resin No. 1 except that polylactic acid-based polyester resin No. 1 2 to 11 were synthesized, and polylactic acid polyester resin No. 1 was synthesized. Evaluation similar to 1 was performed. The evaluation results are shown in Tables 2 to 3.

  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. 10 has a large number average molecular weight and is outside the scope of the present invention. Resin No. Since Y1 used in 10 is G and has a large number average molecular weight, the number average molecular weight of the finished resin is also large. 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 is presumed to have a high content of highly hydrophilic polyethylene glycol and promote hydrolysis.

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 | curing agent was mix | blended with the above-mentioned method, and the adhesiveness and water resistance of the obtained coating film were evaluated. The results are shown in Table 4.

Examples C-2 to C-6
In the same manner as in Example 1, except that the charged raw materials and their ratios were changed to produce polylactic acid polyester resin water dispersions, 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 blended into 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.

  In 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 could not be achieved. 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. Further, 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 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 is not problematic in terms of performance, but is not worthy of being referred to as a material having a low biomass degree and a low environmental load.

<Paint>
Production Example of Water-Based Paint (d-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 the contents were taken out and cooled, and the filtrate was filtered through a 100 mesh filter cloth. 20 parts of Chemical Co., Ltd. (M-40W), 150 parts of ion-exchanged water, 50 parts of titanium oxide (CR-93 produced by Ishihara Sangyo Co., Ltd.), 2.5 parts of 10% benzyl alcohol of sodium dodecylbenzenesulfonate Then, the mixture was shaken for 3 hours using a glass bead type high speed shaker to uniformly disperse to obtain an aqueous paint (d-1).

Production Example of Water-Based Paint (d-2) In the water-based paint, polylactic acid polyester resin No. In place of Polylactic acid polyester resin No. 2 4. A water-based paint (d-2) was obtained by the same formulation and production as the water-based 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.

Preparation of coated plate After applying the water-based paints (d-1) and (d-2) to the hot-dip galvanized steel sheet, the plate was dried at 80 ° C. for 10 minutes, and then baked at 140 ° C. for 30 minutes. The film thickness was 5 μm.

Evaluation method 1. Reflection at 60 degrees was measured using gloss GLOSS METER (manufactured by Tokyo Denka Co., Ltd.).
A: 90 or more O: 80-90 Δ: 50-80
X: 50 or less

2. 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

3. Solvent resistance
1kg / cm on the coated surface with gauze soaked with methyl ethyl ketone in a room at 20 ℃
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.

4). Adhesion
In accordance with JISK-5400 grid-tape method, draw 11 straight vertical and horizontal parallel straight lines at 1mm intervals to reach the substrate with a cutter knife on the coating surface of the test plate 1mm x 1mm
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 | delta): A coating film peels and the remaining number of squares is 50 or more and less than 90 pieces.
X: The coating film was peeled off, and the number of cells remaining was less than 50.

<Ink>
Production Example of Water-based Ink (e-1) Polylactic acid polyester resin No. 1 was added to a 2,000 ml glass flask equipped with a thermometer, stirrer and Liebig condenser. 2 was charged with 100 parts, TEA 6.5 parts and water 233 parts, heated to 70 ° C., stirred for 1 hour, cooled to 30 ° C., and then an iron oxide yellow aqueous dispersion (manufactured by Dainichi Seika Kogyo Co., Ltd.). 19.6 parts of MF-5050 Yellow), 690.2 parts of water and 55 parts of 2-propanol were added, and the mixture was further stirred for 1 hour, then the contents were taken out, filtered through a 100 mesh filter cloth, and water-based ink (e-1 )

Production Example of Water-based Ink (e-2) Polylactic acid polyester resin No. In place of Polylactic acid polyester resin No. 2 4. A water-based ink was sequentially obtained by the same composition and production as the water-based ink (e-1) except that the TEA amount was 4.4 parts.
An ink coating film performance test was performed using the water-based inks (e-1) and (e-2). In addition, preparation and evaluation of the evaluation sample followed the following method. The results are shown in Table 7.

<Evaluation of dispersion stability of water-based ink>
The aqueous inks (e-1) and (e-2) were stored at 20 ° C. and −5 ° C. for 2 weeks, and the change in the appearance of the ink was evaluated.
◎: No change in appearance at all ○: Little change in appearance (occurrence of precipitate that can be redispersed by stirring)
Δ: Slightly sedimented (slightly remaining that cannot be redispersed by stirring)
×: Sediment generation

<Preparation of water resistance evaluation sample>
Water-based inks (e-1) and (e-2) were each applied to a corona-treated surface of a 25 μm-thick PET film (Toyobo Co., Ltd.) so that the thickness after drying was 2 μm. * It dried for 30 minutes and made it the sample for water resistance evaluation.

<Evaluation of water resistance>
The sample for water resistance evaluation was immersed in 25 ° C. water for 5 hours, and then water on the surface was sufficiently wiped off to confirm a change in appearance.
◎: No change in appearance ○: No change in appearance (A trace of water intrusion is observed in a very small part of the interface between the coating film and the substrate)
(Triangle | delta): The swelling by water is seen in a part of coating film.
X: Whole surface peeling / dissolution occurred.

<Laminate>
Production Example of Laminate (f-1) 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. Then, after further stirring for 1 hour, 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 μm so that the thickness after drying would be 5 μm. And dried at 80 ° C. for 30 minutes to obtain a laminate (f-1).

Production Example of 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 performed using the laminates (f-1) and (f-2). Evaluation followed the following method. The results are shown in Table 8.

<Biomass degree>
The weight% of the biomass-derived component contained in the total weight of the laminate was calculated.

<Biodegradability test>
Laminate 1 0 cm × 1 0 cm
The sample was put in a garbage disposal machine, Mitsui Home Co., Ltd. (MAM)), and the form of the sample was visually observed after 7 days, and the degree of biodegradability was evaluated according to the following criteria in four stages.
◎: Sample form is completely absent ○: Sample form is almost absent △: Sample fragment is present ×: Sample form remains almost

<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 lower to obtain colloidal silica (Snowtech C, Nissan Chemical Co., Ltd.) 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 μm. 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. 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 μm. 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 in water only with a basic compound and water, and can provide an environmentally friendly resin and an aqueous dispersion. Moreover, a coating film with high water resistance can be provided by mix | blending a hardening | curing agent.

Claims (20)

Poly having a chemical structure represented by the general formula (1), 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. Lactic acid-based polyester resin.
-(Y1-OCO-X-COO) _p -ran- (Y2-OCO-X-COO) _q -ran- (Y3-OCO-X-COO) _r -Formula (1)
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, and 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. p, q and r are mole fractions, p + q + r = 1, p ≧ 0.25, q ≧ 0, r ≧ 0.   The Y1 is a random copolymer mainly composed of one or both of D-lactide and ε-caprolactone and L-lactide, and the L-lactic acid content is 90% by weight or less. 1. A polylactic acid-based polyester resin according to 1.   The number average molecular weight of said Y1 is 500-8,000, The polylactic acid-type polyester resin of Claim 1 or 2 characterized by the above-mentioned.   The polylactic acid-based polyester resin according to claim 1, wherein X is a residue of ethylene glycol bisanhydro trimellitate.   The polylactic acid-type polyester resin water dispersion containing the polylactic acid-type polyester resin in any one of Claims 1-4, a basic compound, and water.   The polylactic acid-based polyester resin aqueous dispersion according to claim 5, which does not contain a surfactant.   The polylactic acid-based polyester resin aqueous dispersion according to claim 5 or 6, which does not contain an organic solvent.   A step of obtaining a polylactic acid-based polyester resin aqueous dispersion by mixing the polylactic acid-based polyester resin according to any one of claims 1 to 4, a basic compound, and water without adding a surfactant and an organic solvent. A method for producing an aqueous dispersion of a polylactic acid-based polyester resin.   An aqueous resin composition comprising the polylactic acid-based polyester resin according to any one of claims 1 to 4 and a curing agent having reactivity with a carboxyl group.   The aqueous resin composition according to claim 9, wherein the curing agent is one or more selected from the group consisting of a polyvalent epoxy compound, an oxazoline resin, a carbodiimide resin, and a polyvalent metal salt.   An aqueous adhesive comprising the aqueous resin composition according to claim 9 or 10.   An aqueous paint comprising the aqueous resin composition according to claim 9 or 10.   A water-based ink comprising the water-based resin composition according to claim 9 or 10 and a color material.   A laminate comprising a layer (A layer) comprising the polylactic acid-based polyester resin according to claim 1 and a layer (B layer) selected from the group consisting of a film, a sheet, a woven fabric, a nonwoven fabric and paper. The laminate according to claim 14, wherein the B layer is mainly composed of a biomass-derived material and / or a chemical reforming material of the biomass-derived material.   The packaging material which has the laminated body of Claim 14 or Claim 15 as a component.   A sustained-release biodegradable coating agent comprising the aqueous resin composition according to claim 9 or 10.   The sustained-release biodegradable coating body which coat | covered the component to be coated with the biodegradable coating agent of Claim 17.   The sustained-release biodegradable covering according to claim 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 claim 18, wherein the component to be coated has one or more functions of biological activity, growth promotion and nutritional supplementation with respect to a living organism.