JP6163766B2 - Polyester resin, polyester resin water dispersion, and method for producing polyester resin water dispersion - Google Patents

Description

  The present invention relates to a water dispersible polyester resin. More specifically, the present invention relates to a water-dispersible polyester resin having excellent long-term storage stability.

  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.

  In order to meet such a demand, conventionally, a technique in which a water dispersion is obtained by introducing a plurality of carboxylic acid groups into a resin by adding a polyvalent carboxylic acid or the like to a polyester resin has been known ( For example, see Patent Document 1). However, in such a conventional technique, a large amount of unreacted polyvalent carboxylic acid remains after the introduction of the carboxylic acid group, and it is necessary to go through a washing process aimed at removing unreacted substances in the production process.

Conventionally, a technique of improving the storage stability of an aqueous dispersion by adding a polysaccharide has been known (see, for example, Patent Document 2). However, when this conventional technique is used as a binder component, there is a problem that the polysaccharide remains at the interface between the resin and the adherend and reduces the adhesiveness.

JP 2000-7789 A JP 2002-173535 A

  The present invention has been made against the background of such prior art problems. That is, an object of the present invention is to form a polyester resin that has excellent water dispersibility and can be stored for a long period of time, an aqueous dispersion resin composition containing the polyester resin, an aqueous adhesive composition, an aqueous ink, and an aqueous adhesive / aqueous ink. Another object of the present invention is to provide a laminate, a packaging material, and a method for producing an aqueous dispersion.

As a result of intensive studies to achieve the above object, the present inventors have completed the present invention. That is, the present invention
<1> A polyester resin composition containing a polyester resin having an acid value of 300 to 2,500 eq / 10 ⁶ g and a number average molecular weight of 2,000 to 50,000, and a polyvalent carboxylic acid not incorporated in the resin skeleton in things, of the above acid value, the polyester resin composition, wherein the acid value derived from polycarboxylic acids that have not been incorporated into the resin skeleton is 80% to 30%.
<2> The polylactic acid-based polyester resin composition according to <1>, wherein 40% by weight or more of the constituent components of the polyester resin is lactic acid.
<3> The polylactic acid-based polyester resin is a random copolymer mainly composed of either one or both of D-lactic acid and ε-caprolactone acid and L-lactic acid, and the content of L-lactic acid is 90 wt. % Or less, the polylactic acid-based polyester resin composition according to <2>.
<4><1> to <3> The polyester resin composition and a basic compound and the polyester resin composition aqueous dispersion containing water according to any one of.
<5> The polyester resin composition aqueous dispersion according to <4>, which does not contain a surfactant.
<6> The polyester resin composition aqueous dispersion according to <4> or <5>, which does not contain an organic solvent.
<7> A polyester resin composition aqueous dispersion by mixing the polyester resin composition according to any one of <1> to <3>, a basic compound, and water without adding a surfactant and an organic solvent. The manufacturing method of the polyester resin composition aqueous dispersion which has the process of obtaining.
<8> An aqueous resin composition comprising the polyester resin composition according to any one of <1> to <3> and a curing agent having reactivity with a carboxyl group.
<9> The aqueous resin composition according to <8>, wherein the curing agent is at least one selected from the group consisting of a polyvalent epoxy compound, an oxazoline compound, a carbodiimide compound, and a polyvalent metal salt.
<10> An aqueous adhesive comprising the aqueous resin composition according to <8> or <9>.
<11> An aqueous paint comprising the aqueous resin composition of <8> or <9> and a color material.
<12> A water-based ink comprising the water-based resin composition of <8> or <9> and a color material.
<13> A layer (A layer) composed of the polylactic acid-based polyester resin according to any one of <1> to <3> and a layer (B layer) selected from the group consisting of a film, a sheet, a woven fabric, a nonwoven fabric, and paper A laminate consisting of
<14> The laminate according to <13>, wherein the layer A is mainly composed of a biomass-derived material and / or a chemically modified material of the biomass-derived material.
<15> A packaging material having the laminate according to <13> or <14> as a constituent element.
<16> A sustained-release biodegradable coating agent comprising the aqueous resin composition according to <8> or <9>.
<17> A sustained-release biodegradable coated body in which a component to be coated is coated with the biodegradable coating agent according to <16>.
<18> The sustained-release biodegradable coating according to <17>, wherein the component to be coated has one or more functions of insecticidal, herbicidal, sterilizing, antifungal, biological attraction and biological repellent. body.
<19> The sustained release biodegradable coating according to <17>, 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.
It is.

   By this invention, the polyester resin which is excellent in water dispersibility and can be stored for a long period of time is obtained. In addition, since the polyester resin of a more preferable form of the present invention has a high concentration of carboxyl groups in the molecular chain, it can be easily mixed with an aqueous solution of a basic compound without using an emulsifier and an organic solvent. It exhibits excellent water dispersibility that can form a dispersion. Moreover, since the acid value derived from the low molecular weight which is not incorporated in the resin skeleton is small, a polyester water dispersion excellent in water dispersion stability and storage stability can be obtained. Moreover, since the polyester resin aqueous dispersion of this invention can be prepared without using an emulsifier, it is excellent in adhesiveness. Furthermore, the adhesive layer and ink which are excellent in adhesiveness and water resistance can be easily obtained by mix | blending the hardening | curing agent which has the reactivity with respect to a carboxyl group in the polyester resin aqueous dispersion of this invention. Moreover, by using a biomass raw material, a polyester resin having a high degree of biomass and excellent biodegradability can be obtained. By combining various biomass materials and the adhesive and / or ink of the present invention, a laminate having a high degree of biomass can be obtained.

It is a figure which shows an example of the result by the NMR analysis method of this application.

The polyester resin used in the present invention is produced by, for example, reacting a polyhydric carboxylic acid with a terminal hydroxyl group of an acid / glycol polycondensed polyester or a lactone ring-opening polymer and introducing an acid carboxylic acid at the molecular terminal. can do. Among these, a polyester derived from a biomass raw material is more preferable from the viewpoint of reducing environmental burden.

Examples of the acid component used in the acid / glycol polycondensation polyester resin used in the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, diphenic acid, and 5-dihydroxyisophthalic acid. Aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydroisophthalic acid, 1,2-cyclohexene Examples thereof include alicyclic dicarboxylic acids such as dicarboxylic acids, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and terpene-maleic acid adducts, and one or more of these can be used. Among these, sebacic acid, adipic acid, azelaic acid, dimer acid, and succinic acid are more preferable because the degree of biomass can be increased.

  Examples of the glycol component used in the acid / glycol polycondensation polyester resin used in the present invention include ethylene glycol, glycerin, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. 1,9-nonanediol, 1,10-decanediol, aliphatic glycols such as dimer glycol and isosorbide, polyether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, Alicyclic polyalcohols such as 3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecane glycols, water-added bisphenols, propylene glycol (1,2-propane All), 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl -1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1-methyl-1,8-octanediol, 3-methyl-1,6-hexanediol, 4-methyl-1,7 -Heptanediol, 4-methyl-1,8-octanediol, 4-propyl-1,8-octanediol, 1,4-cyclohexanedimethanol, etc., and one or more of these Can be used. Among these, ethylene glycol, glycerin, 1,3-propanediol, 1,4-butanediol, 1,10-decanediol, dimer glycol, and isosorbide are more preferable because the degree of biomass can be increased.

In the acid / glycol polycondensation polyester resin used in the present invention, it is particularly preferable to use a tri- or higher functional acid component or / and a glycol component in the acid component and the glycol component as long as the processability does not deteriorate. Thereby, it becomes easy to form a multi-branched skeleton, and a large amount of acid value can be introduced by acid addition. Therefore, it is easy to have both resin strength and water dispersibility, which is preferable. Examples of the trivalent or higher acid component include trimellitic acid, pyromellitic acid, and benzophenonetetracarboxylic acid. Examples of the trifunctional or higher glycol component include glycerin, trimethylolethane, trimethylolpropane, mannitol, sorbitol, pentaerythritol, Examples include α-methyl glucoside. For hygiene, trimellitic acid, trimethylolethane, trimethylolpropane and glycerin are preferable. These trifunctional or higher functional acid components and glycol components are preferably used in the range of 0.1 to 10 mol% with respect to the total acid component or total glycol component, and when these trifunctional components exceed 10 mol%, The polyester resin gels.
Note that lactones described later may be used as part of the raw material of the acid / glycol polycondensation polyester resin.

An example of a method for producing an acid / glycol polycondensation polyester resin used in the present invention is a mixture of dialkyl ester compounds of various acid components and an excess equivalent of various glycol components, followed by polymerization under high temperature and high vacuum. Examples thereof include a method of reacting, or a method in which various acid components and an excessive amount of glycol component are esterified and then subjected to a polymerization reaction under high temperature and high vacuum. As the polymerization catalyst, commonly used compounds such as titanium, zinc, antimony, magnesium, and germanium can be used.
The acid / glycol polycondensation polyester resin thus obtained can be produced by reacting a polycarboxylic acid with the terminal hydroxyl group and introducing the carboxylic acid into the molecular terminal.

Examples of lactones used in ring-opening polymerization polyester resins of lactones include lactide (cyclic dimer of lactic acid), glycolide (cyclic dimer of glycolic acid), β-propionlactone, β-butyrolactone, and pivalolactone. , Γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone and the like can be used. Moreover, these compounds do not necessarily need to be used alone, and a plurality of types can be copolymerized. Of these, ε-caprolactone and lactide, which are excellent in biodegradability and easy to polymerize, are preferable. In particular, a polylactic acid-based polyester resin using lactide as a raw material is preferable. As the lactide, any of L-lactide, D-lactide, and L, D-lactide can be used.
In addition, polylactic acid-type polyester resin means here that the amount of lactic acid components in a final polyester resin is 40 mass% or more. Furthermore, the amount of lactic acid component is preferably 50% by mass or more, and particularly preferably 60% by mass or more from the viewpoint of increasing the degree of biomass. The amount of lactic acid component is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less. If the amount of lactic acid component exceeds 95% by mass, the amount of polycarboxylic acid to be added decreases, the amount of terminal carboxylic acid groups decreases, and dispersion stability and storage stability may decrease.

  The polylactic acid-based polyester resin preferably contains a specific amount of L-lactic acid and D-lactic acid in order to lower the crystallinity. For example, a polylactic acid-based polyester resin containing a specific amount of L-lactic acid can be obtained by copolymerizing L-lactide and other lactones, or by using L, D-lactide and optionally copolymerizing with other lactones. can get. The lower limit of the larger content of L-lactic acid or D-lactic acid is preferably 10% by weight, more preferably 15% by weight, and still more preferably, based on the total amount of lactone-derived components in the polyester. 20% by weight. If it is less than the above, crystallinity appears remarkably, and the water dispersibility tends to be poor. On the other hand, the upper limit of the larger content of L-lactic acid or D-lactic acid is preferably 90% by weight, more preferably 85% by weight, based on the total amount of lactone-derived components in the polyester. Preferably it is 80 weight%. If it exceeds the above, when used as an adhesive, crystallization progresses over time and the adhesive strength may be significantly reduced.

  The lactone ring-opening polymerization polyester resin of the present invention is obtained by, for example, subjecting lactide or the like to ring-opening addition polymerization using a polyhydric alcohol having 3 or more hydroxyl groups as an initiator, and then reacting the terminal hydroxyl group with a polyvalent carboxylic acid. It can manufacture by introduce | transducing an acid value into a molecule terminal.

The ring-opening polymerization initiator of the lactone ring-opening polymerization polyester resin used in the present invention is a polyhydric alcohol having 3 or more hydroxyl groups, more preferably a polyhydric alcohol having 4 or more hydroxyl groups. When the number of hydroxyl groups contained in the initiator increases, it becomes easier to form a multi-branched skeleton, so the molecular weight can be increased with a small amount of initiator, and a large amount of acid value can be introduced by acid addition. And water dispersibility are easy and preferable. Examples of the polyhydric alcohol having three hydroxyl groups include trimethylolpropane and glycerin. Examples of the polyhydric alcohol having 4 or more hydroxyl groups include pentaerythritol, diglycerin, polyglycerin, xylitol, sorbitol, glucose, fructose, mannose, inositol and the like. Of these, polyglycerol, xylitol, and sorbitol are preferable because they have a large number of hydroxyl groups.
In addition, a polyester oligomer containing a polyhydric alcohol having 3 or more hydroxyl groups and / or a trifunctional or higher functional acid component as a constituent component and containing a large number of hydroxyl groups reacted with dicarboxylic acid or diol as necessary is used as a reaction initiator. May be.

  An example of a specific method for producing a polylactic acid-based polyester resin is as follows. A polyhydric alcohol containing 3 or more hydroxyl groups, lactide, ε-capronlactone, and a catalyst are charged all at once, and the temperature is raised to 150 ° C. or higher for 1 to 3 hours. The polylactic acid-based polyester resin of the present invention can be obtained by polymerizing for a period of time and further reacting for 1 to 2 hours by adding a polycarboxylic acid. In order to prevent ring opening by reaction with water contained in the polymerization system, lactones and polyhydric carboxylic acid anhydrides added to the terminal hydroxyl groups described later are subjected to vacuum drying or the like in advance to reduce the water content. Are preferably used. 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. The polymerization rate can be increased by using a conventionally known acid addition 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, Examples include phosphines such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, sulfonium salts such as sodium p-toluenesulfonate, sulfonic acids such as p-toluenesulfonic acid, and 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.

  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.

  Polycarboxylic acid is added to the terminal hydroxyl group of the polyester resin thus obtained. When the terminal hydroxyl group is a secondary or higher hydroxyl group, the reactivity is low and the polyvalent carboxylic acid is difficult to be incorporated into the resin skeleton. In particular, the terminal where the lactide undergoes ring-opening polymerization becomes a secondary hydroxyl group, and the reactivity with the polyvalent carboxylic acid becomes low.

  The lower limit of the terminal primary hydroxyl group ratio of the polyester resin before addition of the polyvalent carboxylic acid is preferably 10%, more preferably 15%, still more preferably 20% with respect to the total hydroxyl value. If it is less than the above, the reactivity with the polyvalent carboxylic acid is low, and the amount of polyvalent carboxylic acid not incorporated in the resin skeleton increases.

In order to increase the terminal primary hydroxyl group when the terminal primary hydroxyl group ratio of the polyester resin of the present invention is less than the above range, lactones which give a primary hydroxyl group to the terminal of the polyester resin by ring-opening polymerization such as ε-caprolactone It is effective to extend by ring-opening polymerization or the like. The lower limit of the addition amount of lactones for elongation by ring-opening polymerization or the like is preferably 5% by mass, more preferably 10% by mass, and further preferably 15% by mass with respect to the total weight of the final polyester resin. . In particular, in the case of a polylactic acid-based polyester resin, if a method of adding lactones is not employed, since there are many secondary hydroxyl groups having poor reactivity, an acid value sufficient for water dispersion cannot be imparted to the resin, resulting in poor dispersibility. Sometimes. In addition, unreacted polycarboxylic acid may be present and storage stability may deteriorate. On the other hand, the upper limit of the amount of lactone added is preferably 45% by weight, more preferably 40% by weight, and still more preferably 35% by weight. Exceeding the above may increase the crystallinity of the resin and make it difficult to disperse, or the holding stability may deteriorate.

  In the polyester resin of the present invention, examples of the polyvalent carboxylic acid added to the terminal hydroxyl group include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid, and acid anhydrides thereof, succinic acid, glutaric acid, and adipine. Aliphatic dicarboxylic acids such as acids, azelaic acid, sebacic acid, dodecanedioic acid and dimer acids and their anhydrides, unsaturated dicarboxylic acids such as maleic acid, fumaric acid and terpene-maleic acid adducts and their anhydrides, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydroisophthalic acid, 1,2-cyclohexene dicarboxylic acid, and other alicyclic dicarboxylic acids and acid anhydrides thereof, trimellitic acid, methylcyclohexene carboxylic acid, etc. Trivalent or higher carboxylic acids and their anhydrides It can be mentioned. Among these, trimellitic anhydride can be easily reacted by an addition reaction, and two carboxyl groups can be introduced per molecule, so that a large amount of acid value can be introduced, which is advantageous for water dispersion. This is preferable. Further, succinic anhydride, which is a biomass raw material, is preferable because it can easily react and maintain a high degree of biomass.

  The lower limit of the addition amount of the polyvalent carboxylic acid is preferably 30%, more preferably 40%, and further preferably 50% with respect to the hydroxyl value of the polyester resin before addition of the polyvalent carboxylic acid. . If it is less than the above, a sufficient acid value for water dispersion cannot be imparted. On the other hand, the upper limit of the polycarboxylic acid addition amount is preferably 120%, more preferably 100%, and still more preferably 95% with respect to the hydroxyl value. When the above is exceeded, the amount of polyvalent carboxylic acid not incorporated in the resin skeleton may increase.

  The lower limit of the polycarboxylic acid addition temperature is preferably 70 ° C, more preferably 80 ° C. If it is less than the above, the amount of polyvalent carboxylic acid not incorporated in the resin skeleton increases, and the melt viscosity is high and the productivity is poor. On the other hand, the upper limit of the addition temperature of the polyvalent carboxylic acid is preferably 240 ° C, more preferably 235 ° C. When the above is exceeded, an exchange reaction between the terminal end of the polyvalent carboxylic acid and the ester bond of the skeleton portion of the polyester tends to occur, and gelation and foreign matter may occur.

  When the polylactic acid-based polyester resin is used, the upper limit of the addition temperature of the polyvalent carboxylic acid is preferably 200 ° C, more preferably 190 ° C, and further preferably 180 ° C. Exceeding the above may cause gelation and foreign matter generation.

  The lower limit of the degree of biomass of the polyester resin of the present invention is preferably 40% by weight, more preferably 50% by weight, and still more preferably 60% by weight. If it is less than the above, the degree of biomass is low and it is difficult to say that the material has a large effect of reducing carbon dioxide emissions and has a low load on the environment.

  The lower limit of the acid value of the polyester resin of the present invention is preferably 300 eq / ton, more preferably 400 eq / ton, and even more preferably 500 eq / ton. If it is less than the above, it is difficult to disperse, the dispersion is poorly stable, the resin is less likely to exhibit self-emulsifying properties, and the curability of a cured coating film using this resin tends to be low. is there. On the other hand, the upper limit of the acid value is preferably 2500 eq / ton, more preferably 2300 eq / ton, and further preferably 2100 eq / ton. If the above is exceeded, the water absorption of the resin will increase, and even in the state of a solid resin, it tends to be subject to hydrolysis and the storage stability tends to be poor. Moreover, the water resistance of the cured coating film using this resin may tend to deteriorate.

The lower limit of the acid value derived from the polyvalent carboxylic acid not incorporated in the resin skeleton of the polyester resin of the present invention is preferably 30%, more preferably 40%, and still more preferably with respect to the acid value of the entire resin. 50%.
Usually, in the addition reaction, it is difficult to completely react the added polyvalent carboxylic acid, and in order to make it less than the above, a separate removal step or the like is required, resulting in poor productivity. On the other hand, the upper limit of the acid value derived from the polyvalent carboxylic acid not incorporated in the resin skeleton is preferably 80%, more preferably 75%, and still more preferably 70% with respect to the acid value of the entire resin. . Exceeding the above may result in a decrease in dispersion stability and storage stability. The polyvalent carboxylic acid not incorporated in the resin skeleton can be made within the range by optimizing the addition amount, the terminal primary hydroxyl group ratio, and the reaction temperature.

  The lower limit of the number average molecular weight (Mn) of the polyester resin of the present invention is preferably 2000, more preferably 3000, and still more preferably 4000. If it is less than the above, the cohesive strength of the resin tends to be small and the adhesiveness tends to be poor. On the other hand, the upper limit of the number average molecular weight (Mn) is preferably 50000, more preferably 45000, and further preferably 40000. When the above is exceeded, conversely, the cohesive strength of the resin increases and the water dispersibility tends to be poor. For this reason, even if it is possible to prepare an aqueous dispersion with a high concentration by the method of once dissolving in a solvent and performing phase transition to an aqueous system, it is extremely low when an aqueous dispersion is prepared by mixing with only a base compound and water. Often only aqueous dispersions of concentration can be obtained. Further, when the aqueous dispersion is adjusted by mixing only with the base compound and water, the particle diameter tends to be coarse and tends to precipitate immediately after production.

  The lower limit of the melt viscosity (Log (MV)) at 80 ° C. of the polyester resin of the present invention is preferably 1 Pa · s, more preferably 1.7 Pa · s, still more preferably 2 Pa · s, particularly Preferably, it is 2.2 Pa · s. If it is less than the above, the cohesive force of the resin is reduced, and the strength of the coating film is reduced. For example, when used as an adhesive, there is a tendency to cause defects such as poor adhesion. On the other hand, the upper limit of Log (MV) is preferably 4 Pa · s, more preferably 3.9 Pa · s, still more preferably 3.8 Pa · s, and particularly preferably 3.6 Pa · s. When the above is exceeded, plasticization at the time of dispersion is insufficient, the effect of dispersing the hydrophilic group is not sufficiently exhibited, and there is a tendency to cause poor dispersion.

  Since the 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 polylactic acid-based polyester resin of the present invention tends to decrease.

  Examples of the basic compound used in the method for producing a polyester resin aqueous dispersion of the present invention include ammonia, an organic amine compound, and an inorganic basic compound.

  Specific examples of the organic amine compound include alkylamines such as triethylamine, isopropylamine, ethylamine, diethylamine and sec-butylamine, alkoxyamines such as 3-ethoxypropylamine, propylamine and 3-methoxypropylamine, N , N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, monoethanolamine, diethanolamine, triethanolamine and other alkanolamines, morpholine, N-methylmorpholine , Morpholines such as N-ethylmorpholine. Of these organic amine compounds, the use of highly hydrophilic alkanolamines, particularly triethanolamine, can improve water dispersibility.

  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 polyester resin of the present invention, specifically 0.5% relative to the acid value of the polylactic acid-based polyester resin of the present invention. It is desirable to add 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 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. Examples of the organic solvent include methanol, ethanol, propanol, acetone, butyl cellosolve, ethyl cellosolve, carbitol and the like. The amount of the organic solvent is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less based on the total amount of the solvent. The most preferable form is one that does not contain an organic solvent. The emulsifier is also preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less, based on the polyester resin. The most preferred form is one that does not contain an emulsifier.

  The polyester resin aqueous dispersion of the present invention can be used as an adhesive. Under the present circumstances, if the hardening | curing agent which reacts with a carboxyl group is added, an adhesive agent with higher adhesive force can be obtained. 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 using these hardening | curing agents, it is preferable that the content is 5-50 mass parts with respect to 100 mass parts of polyester resins of this 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 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 Yakuhin Kogyo 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.

  Examples of amino resins suitable as curing agents for the aqueous adhesive of the present invention include formaldehyde adducts such as urea, melamine, and benzoguanamine, and alkyl ether compounds obtained by alkoxylating these compounds with alcohols having 1 to 6 carbon atoms. Can be mentioned. 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 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. 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 obtained by subjecting the above isocyanate compound, isocyanate compound and isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.

  A water-based ink can be obtained by blending a color material with the polyester resin aqueous dispersion of the present invention, and further, the water resistance of the ink can be improved by blending a curing agent having reactivity with a carboxyl group. Can do. As the color material, a known pigment or dye can be blended. Since the 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, paint and ink 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, paint, and ink 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, paint and ink 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) made of the 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 polyester resin water-based adhesive and water-based ink of the present invention exhibit high adhesive force to various metal vapor-deposited films, it is also useful to use as a laminate having a three-layer structure of A layer / metal vapor-deposited layer / B layer. It is. 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 polyester resin water-based adhesive of this invention, and water-based ink is large. The polyester resin water-based adhesive and water-based ink of the present invention exhibit high adhesion to various metal vapor-deposited films because of 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 fertilizer 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. The component to be coated is dissolved or dispersed in an aqueous dispersion, and then the aqueous dispersion itself is sprayed to evaporate the water to form particles, or sprayed in the presence of some carrier to adhere to the carrier surface and / or the inside of the carrier. This is because a biodegradable coating can be easily obtained by applying to some adherend and forming a coating film, which is convenient. 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. Further, if the aqueous dispersion does not contain an organic solvent or uses a small amount of the organic solvent, the organic solvent will not be released into the environment in both the manufacturing process of the covering and the use of the covering, or Less, more less environmental impact, 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>
A resin sample was dissolved in deuterated chloroform or deuterated dimethyl sulfoxide, and a ¹ H-NMR analysis and a ¹³ C-NMR analysis were performed using an NMR apparatus 400-MR manufactured by VARIAN. Expressed in weight percent. The lactic acid content (% by weight) was calculated based on the resin composition on the left. ^{By 1} H-NMR analysis, an acid value (%) derived from a polyvalent carboxylic acid not incorporated in the resin skeleton and a terminal primary hydroxyl group ratio (%) were calculated.

<L-lactic acid content>
A 5 g / 100 mL chloroform solution of a resin 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 0.8 g of resin sample in 20 ml of N, N-dimethylformamide and titrate phenolphthalein with 0.1N sodium methoxide in methanol in the presence of an indicator. The neutralization point was expressed in terms of equivalents (equivalents / 10 ⁶ g) per 10 ⁶ g of resin.

<Melt viscosity>
Using a flow tester (CFT-500C type) manufactured by Shimadzu Corporation, a resin sample dried to a moisture content of 0.1% or less is filled into a cylinder at the center of a heating body set at 80 ° C. A pressure (4.9 MPa) was applied to the sample through a jar, and the molten sample was extruded from a die (hole diameter: 0.5 mm, thickness: 20 mm) at the bottom of the cylinder, and the plunger descending distance and descent time were recorded. The melt viscosity was calculated.

<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, and water dispersibility was judged visually.
(Judgment) ◯: There is no undispersed material and the resin is completely dispersed.
Δ: Undispersed material exists.
X: Resin is not dispersed at all.

Hereinafter, the abbreviations of the compounds shown in the text and tables in the examples indicate the following compounds, respectively.
L-LD: L-lactide D-LD: D-lactide ε-CL: ε-caprolactone TMA: trimellitic anhydride SC: succinic anhydride TEA: triethylamine TETA: triethanolamine AN: aqueous ammonia (28%)
NaHCO3: Sodium bicarbonate TMP: Trimethylolpropane

Example A-1
Acid / glycol copolymer polyester resin No. Preparation of No. 1 187.9 parts of sebacic acid, 13.4 parts of trimellitic anhydride, 114.0 parts of 1,3-propanediol and 0.1 part of titanium tetrabutoxide were charged into a 0.5 L autoclave, 3.5 kg / cm. Esterification was performed by gradually raising the temperature to 235 ° C. over 3 hours under nitrogen pressure of G. Next, the polymerization was carried out under reduced pressure to 10 mmHg over 1 hour, the temperature was raised to 250 ° C., and the latter polymerization was carried out for 10 minutes at 1 mmHg or less. Subsequently, the resin at one end was cooled to 230 ° C. under a nitrogen stream, 27.9 parts of trimellitic anhydride was added thereto, and the mixture was stirred for 2 hours to obtain the polyester resin A of the present invention. There was no difference in the performance of the resin A obtained by the transesterification method and the direct polymerization method, respectively. The composition and characteristic values are shown in Table 1.

Example A-2
Polylactic acid polyester resin No. Production of 2 In a 500 ml glass flask equipped with a thermometer, stirrer and Liebig condenser, 1.7 parts sorbitol, 54.3 parts L-lactide, 18.4 parts ε-caprolactone and 0.021 parts tin octylate as a catalyst And nitrogen gas was circulated at 60 ° C. for 30 minutes. Subsequently, the pressure was reduced at 60 ° C. for 30 minutes to further dry the contents. The temperature of the polymerization system was raised to 180 ° C. while flowing nitrogen gas again, and the mixture was stirred for 2-3 hours after reaching 180 ° C. Next, 27.3 parts of ε-caprolactone was charged and further stirred at 180 ° C. for 1 to 2 hours. Thereafter, 0.05 part of phosphoric acid was added, and after stirring for 20 minutes, the system was decompressed to distill off unreacted lactide and caprolactone. About 20 minutes later, after distilling of unreacted substances was settled, 8.8 parts of trimellitic anhydride was charged and stirred at 150 ° C. for 2 hours to obtain a polylactic acid-based polyester resin A of the present invention. The composition and characteristic values are shown in Table 2.

Examples A-1 to A-7, Comparative Examples A-8 to A-13
Polyester resin No. Production of 3 to 13 Acid / glycol copolymer polyester resin No. No. 8 is an acid / glycol copolymer polyester resin no. The synthesis was carried out in the same manner as 1, except that the raw materials used and the ratio thereof were changed. Polylactic acid polyester resin No. 3-7, 9-13 are polyester resin No.3. In the same manner as in Example 2, except that the charged raw materials and their ratios were changed. These are polyester resin no. Evaluation similar to 1 was performed. The evaluation results are shown in Tables 1 and 2.

  Polyester resin No. No. 8 has a high acid value and is outside the scope of the present invention. Polyester resin No. 9 has a high acid value derived from a polyvalent carboxylic acid not incorporated in the resin skeleton relative to the acid value, and is outside the scope of the present invention. Polyester resin No. No. 10 has a large number average molecular weight and is outside the scope of the present invention. Polyester resin No. No. 11 has a small number average molecular weight and is outside the scope of the present invention. Polyester resin No. No. 12 has a small acid value and is outside the scope of the present invention. Polyester resin No. No. 13 has a large amount of polyvalent carboxylic acid and is outside the scope of the present invention.

Example C-1
Production and Evaluation of 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, a stirrer and a Liebig condenser. 25 parts of TEA, 1.7 parts of TEA, and 75 parts of water were charged, heated to 70 ° C. and stirred for 1 hour, and then the contents were taken out and cooled to produce polyester resin aqueous dispersion 1. The results are shown in Table 1.

Examples C-2 to C-7, Comparative Example C-8
Polyester resin water dispersions 2 to 8 were produced in the same manner as in Example 1, except that the polyester resin water dispersions were produced by changing the charged raw materials and the ratios thereof. The results are shown in Tables 1 and 2. All showed high water dispersibility and storage stability.

Comparative Examples C-9 to C-12
In the same manner as in Example 1, except that the raw materials and the ratios thereof were changed and the production of the polyester resin aqueous dispersion was attempted, and the aqueous dispersion obtained was further stored in the same manner as in Example 1. Evaluated. The results are shown in Table 1.

  Polylactic acid-based polyester resin No. used in Comparative Example C-8 8 was dispersed after stirring for 1 hour, but when stored at 50 ° C., a precipitate was generated after 10 days. Acid / glycol copolymer polyester resin No. 1 used in Comparative Example C-8 No. 8 is outside the scope of the present invention because the acid value is 2500 eq / ton or more. Acid / glycol copolymer polyester resin No. No. 7 is presumed to have poor storage stability because of its high acid value.

  Polylactic acid-based polyester resin No. used in Comparative Example C-9 No. 9 was dispersed after stirring for 1 hour, but when stored at 50 ° C., a precipitate was generated after 10 days. Polylactic acid polyester resin No. 9 is outside the scope of the present invention because the acid value not contained in the resin skeleton is 80% or more of the acid value of the entire resin. Since the terminal primary hydroxyl group ratio is low and it is difficult to add polyvalent carboxylic acid, it is presumed that there are many acid values not included in the resin skeleton in the system, and the storage stability is poor.

  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. Polylactic acid polyester resin No. No. 10 has a large molecular weight and is outside the scope of the present invention. It is presumed that since the molecular weight is large, the cohesive force of the resin is large and dispersion is hardly possible.

  Polylactic acid-based polyester resin No. used in Comparative Example C-11 11 was dispersed after stirring for 1 hour, but when stored at 50 ° C., a precipitate was generated after 10 days. Polylactic acid polyester resin No. 11 is small in the molecular weight of the resin and is outside the scope of the present invention. It is presumed that the molecular weight was low, the cohesive force was small, and the emulsion state could not be maintained.

  Polylactic acid-based polyester resin No. used in Comparative Example C-12 No. 12 was stirred for 1 hour but could not be dispersed in water. Polylactic acid polyester resin No. No. 12 has an acid value of 300 eq / ton or less, which is outside the scope of the present invention. Further, since the amount of lactone added to extend to the terminal chain is 45% or more, this is also outside the scope of the present invention. It is presumed that the crystallization of the resin occurred and the acid value was too low, so that the polyester resin was hardly dispersed.

<Paint>
Production Example of Water-Based Paint (D-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. 100 parts of TEA, 4.0 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 It was added and uniformly dispersed by shaking for 3 hours using a glass bead type high speed shaker 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. 1 instead of polylactic acid-based polyester resin No. 1 5. 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 8.3 parts.
A coating film performance test was performed 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 3.

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.).
◎: 90 or more ○: 80 to 90 Δ: 50 to 80 ×: 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
In a room at 20 ° C., a load of 1 kg / cm 2 was applied to the coated surface with gauze soaked with methyl ethyl ketone, 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, 11 mm vertical and horizontal parallel straight lines are drawn at 1 mm intervals so as to reach the substrate with a cutter knife on the coating surface of the test plate. 100 eyes were created. A cellophane pressure-sensitive adhesive tape was adhered to the surface, and the degree of cell peeling when the tape was rapidly peeled was observed and evaluated according to the following criteria.
(Double-circle): Coating film peeling is not seen at all.
○: Although the coating film was slightly peeled, 90 or more squares remained.
(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, a stirrer, and a Liebig condenser. 100 parts of TEA, 4.0 parts of TEA and 233 parts of water were added, 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. The contents were taken out and filtered through a 100-mesh filter cloth. )

Production Example of Water-based Ink (E-2) Polylactic acid polyester resin No. 1 instead of polylactic acid-based polyester resin No. 1 5. A water-based ink was obtained in the same manner as in the water-based ink (e-1) except that the TEA amount was 8.3 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 4.

<Evaluation of dispersion stability of water-based ink>
The water-based inks (E-1) and (E-2) were stored at 20 ° C. and −5 ° C. for 2 weeks, and the appearance change 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 applied to a corona-treated surface of a 25 μm-thick PET film (manufactured by 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.

<Laminated body>
Production Example of 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. 1 was charged with 100 parts, TEA 4.0 parts, and water 233 parts. After heating to 70 ° C. and stirring for 1 hour, the mixture was cooled to 30 ° C. or lower to obtain colloidal silica (Snowtech C, Nissan Chemical Co., Ltd.) 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. 1 instead of polylactic acid-based polyester resin No. 1 5. A laminate (F-2) was obtained by the same composition and production as the laminate (F-1) except that the TEA amount was 8.3 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 5.

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

<Biodegradability test>
Laminate body 10 cm × 10 cm is placed in a conposter (garbage disposal machine, Mitsui Home Co., Ltd. (MAM)), and after 7 days, the sample form is visually observed and biodegradable. The degree was evaluated in four stages according to the following criteria.
◎: 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 and 100 parts of TEA, 3.5 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 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 6.
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, 21.1 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 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 6.
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 (19)

An acid value of 300-2,500 eq / 10 ⁶ g,
In the polyester resin composition containing a polyester resin having a number average molecular weight of 2,000 to 50,000 and a polyvalent carboxylic acid not incorporated in the resin skeleton, the acid value is not incorporated in the resin skeleton. A polyester resin composition having an acid value derived from polyvalent carboxylic acids of 30% to 80%. The polylactic acid-based polyester resin composition according to claim 1, wherein 40% by weight or more of the constituent components of the polyester resin is composed of lactic acid. The polylactic acid-based polyester resin is a random copolymer mainly composed of either or both of D-lactic acid and ε-caprolactone acid and L-lactic acid, and the content of L-lactic acid is 90% by weight or less. The polylactic acid-based polyester resin composition according to claim 2, wherein the polylactic acid-based polyester resin composition is present . Polyester resin composition and a basic compound and the polyester resin composition aqueous dispersion containing water according to any one of claims 1 to 3. The polyester resin composition aqueous dispersion according to claim 4, which does not contain a surfactant. The polyester resin composition aqueous dispersion according to claim 4 or 5, which does not contain an organic solvent. It has the process of obtaining the polyester resin composition aqueous dispersion by mixing the polyester resin composition in any one of Claims 1-3, a basic compound, and water, without adding surfactant and an organic solvent. The manufacturing method of the polyester resin composition water dispersion. The aqueous resin composition containing the polyester resin composition in any one of Claims 1-3, and the hardening | curing agent which has reactivity with respect to a carboxyl group.   The aqueous resin composition according to claim 8, wherein the curing agent is at least one selected from the group consisting of a polyvalent epoxy compound, an oxazoline compound, a carbodiimide compound, and a polyvalent metal salt.   An aqueous adhesive comprising the aqueous resin composition according to claim 8 or 9.   An aqueous paint comprising the aqueous resin composition according to claim 8 or 9.   A water-based ink comprising the water-based resin composition according to claim 8 or 9 and a color material. It consists of a layer (A layer) which consists of a polylactic acid-type polyester resin composition in any one of Claims 1-3, and a layer (B layer) chosen from the group which consists of a film, a sheet | seat, a woven fabric, a nonwoven fabric, and paper. Laminated body.   The layered product according to claim 13, wherein the layer A 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 13 or Claim 14 as a component.   A sustained-release biodegradable coating agent comprising the aqueous resin composition according to claim 8 or 9.   The sustained-release biodegradable coating body which coat | covered the to-be-coated component with the biodegradable coating agent of Claim 16.   The sustained-release biodegradable coating according to claim 17, 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 17, wherein the component to be coated has one or more functions of biological activity, growth promotion and nutritional supplementation for living organisms.