WO2004037924A1 - ポリエステル樹脂水性分散体およびその製造方法 - Google Patents
ポリエステル樹脂水性分散体およびその製造方法 Download PDFInfo
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- WO2004037924A1 WO2004037924A1 PCT/JP2003/013418 JP0313418W WO2004037924A1 WO 2004037924 A1 WO2004037924 A1 WO 2004037924A1 JP 0313418 W JP0313418 W JP 0313418W WO 2004037924 A1 WO2004037924 A1 WO 2004037924A1
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- polyester resin
- aqueous
- aqueous dispersion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
Definitions
- the present invention relates to an aqueous polyester resin dispersion which has excellent storage stability and can be applied to various substrates to form a resin film having excellent film performance.
- Polyester resin is used as a film-forming resin because of its excellent processability, resistance to organic solvents (solvent resistance), weather resistance, adhesion to various substrates, etc. for coatings, inks, adhesives, It is used in large quantities as a binder component in fields such as coating agents.
- Patent Documents 1 to 4 propose a polyester resin aqueous dispersion in which an acid value is small and a high-molecular weight polyester resin is dispersed in an aqueous medium, and when such an aqueous dispersion is used, processability, water resistance, It describes that a film having excellent performance such as solvent resistance can be formed.
- the aqueous dispersions of the polyester resins described in these documents are all dispersed in an aqueous medium by neutralizing the carboxyl groups of the polyester resin with a basic compound.
- Emulsion type polyester resin A water dispersion of polyester resin.
- the polyester resin used has a carboxyl group corresponding to an acid value of 8 mg KOH / g or more in order to stably disperse the polyester resin in an aqueous medium. I had to be. As a result, there have been problems that the molecular weight of the polyester resin is limited and that the water resistance may be insufficient.
- Patent Documents 5 and 6 propose a method for producing an aqueous dispersion of a polyester resin using a basic compound and a nonionic surfactant.
- any of the polyester resin aqueous dispersions described in these documents is a polyester resin.
- the resin film is formed using such a polyester resin aqueous dispersion, a large amount of surfactant remains in the resin film, and the resin content is high. There is a problem that the water resistance of the coating film is deteriorated.
- Patent Document 6 is essentially a W / O type emulsion, and has a problem that, depending on the type of material to be coated (substrate), it is damaged by the organic solvent contained in the aqueous polyester resin dispersion. Was.
- Patent Document 7 proposes an aqueous polyester resin dispersion in which a polyester resin containing a monomer having a specific chemical structure as a copolymer component is dispersed in an aqueous medium. Although it is described that an excellent resin film is formed, there was a problem that the workability of the formed resin film was poor due to its low molecular weight.
- Patent Document 1 JP-A-9-1296100
- Patent Document 2 JP-A-2000-26709
- Patent Document 3 Japanese Patent Application Laid-Open No. 2000-313793
- Patent Document 4 JP 2002-173582A
- Patent Document 5 Japanese Patent Publication No. 51-24375
- Patent Document 6 Japanese Patent Publication No. 53-14101
- Patent Document 7 Patent No. 3162477
- an object of the present invention is to provide a resin film which is excellent in storage stability and excellent in film performance such as adhesion to a substrate, water resistance, solvent resistance and workability. It is an object of the present invention to provide an aqueous polyester resin dispersion having a high acid value and a high molecular weight and a method for producing the same.
- the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by controlling the temperature during phase inversion emulsification, a polyester having a low acid value and a high molecular weight can be obtained without using a surfactant.
- the present inventors have found that a resin can be stably dispersed in an aqueous medium, and that a resin coating formed from the aqueous dispersion thus obtained has good coating performance. We have completed Ming.
- the gist of the present invention is:
- a method of producing an aqueous polyester resin dispersion by dispersing an organic solvent solution of the polyester resin (A) together with the basic conjugate (B) in water by phase inversion emulsification, Is carried out at a temperature of 40 ° C. or lower.
- a method for producing an aqueous dispersion of a polyester resin which comprises a step of removing an organic solvent after phase inversion emulsification.
- the aqueous polyester resin dispersion of the present invention can form a resin film having excellent film properties such as adhesion to a substrate, water resistance, and solvent resistance, it can be used alone as a paint, a coating agent, or an adhesive. Alternatively, it can be used as a binder component by mixing other components, such as PET film, polyolefin film, vapor-deposited film, etc., an anchor coat agent for various films and an adhesion-imparting agent (easy adhesion), aluminum plate, steel plate and plating steel plate, etc.
- Anchor coating agent and adhesion-imparting agent for various metal plates Easy adhesion
- pre-coated metal paint paper coating agent
- fiber treatment agent adhesive for bonding substrates such as paper, metal plate, resin sheet
- adhesive for bonding substrates such as paper, metal plate, resin sheet
- It can be used for applications such as ink binders to improve their performance. It is also excellent in dispersion stability during storage and during production.
- FIG. 1 is a diagram showing the relationship between the acid value of the polyester resin in the phase inversion emulsification step and the preferred amount of the basic conjugate used at that time.
- the amount of the basic compound is shown as an equivalent ratio to the total molar amount of the carboxyl groups of the polyester resin (the range of the formula (1)).
- aqueous dispersion The aqueous polyester resin dispersion of the present invention (hereinafter referred to as “aqueous dispersion”)
- polyester resin (A) dispersed in an aqueous medium containing water (C) without using a surfactant.
- polyester resin (A) First, the polyester resin (A) will be described.
- the polyester resin has an acid value of 2 mgKOHZg or more and less than 8 mgKOHZg, preferably 3 mgKOH / g or more and less than 8 mgKOH / g, and more preferably 4.1 mgKOH / g or more and less than 8 mgKOHZg. More preferably, it is more than 4.6 mgKOH / g and less than 8 mgKOH / g.
- the acid value is 8 mgKOH / g or more, the molecular weight of the polyester resin tends to be small, the workability of the resin film tends to be poor, and the water resistance may be insufficient.
- the acid value is less than SmgKOHZg, it tends to be difficult to obtain a uniform aqueous dispersion.
- the polyester resin may contain a hydroxyl group as long as the water resistance of the resin film is not impaired, and the hydroxyl value is preferably 3 OmgKOHZg or less, more preferably 2 OmgKOHZg or less, and 10 mgKOH / g or less. More preferably,
- the number average molecular weight of the polyester resin is 5,000 or more, preferably 7,000 or more, more preferably 9,000 or more, still more preferably 11,000 or more, Particularly preferred is at least 000, most preferably at least 15,000. If the number average molecular weight is less than 5,000, the processability of the resin film tends to be insufficient.
- the upper limit of the number average molecular weight is not particularly limited, but the number average molecular weight of the polyester resin is preferably 50,000 or less from the viewpoint that an aqueous dispersion having good storage stability is easily obtained. It is more preferably 40,000 or less, particularly preferably 30,000 or less.
- the degree of dispersion of the molecular weight distribution of the polyester resin is not particularly limited, but the dispersion degree of the molecular weight distribution is preferably 8 or less, more preferably 5 or less, in view of the fact that the storage stability of the aqueous dispersion tends to be excellent.
- the degree of dispersion of the molecular weight distribution is a value obtained by dividing the weight average molecular weight by the number average molecular weight.
- the glass transition temperature (hereinafter, referred to as Tg) of the polyester resin is not particularly limited, but is preferably from 150 to 120 ° C because the storage stability of the aqueous dispersion tends to be excellent. 0 to 85 ° C is more preferable.
- the polyester resin is not originally dispersed or dissolved in water by itself, and is substantially synthesized from a polybasic acid and a polyhydric alcohol.
- the components of these polyester resins will be described.
- polybasic acid component constituting the polyester resin examples include aromatic polybasic acids, aliphatic polybasic acids, and alicyclic polybasic acids.
- aromatic polybasic acids examples include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and the like.
- aromatic dicarboxylic acids examples include saturated aliphatic dicarboxylic acids such as oxalic acid, conodic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dodecane diacid, eicosane diacid, hydrogenated dimer monoacid, and the like.
- unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and dimer acid.
- alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 2,5-cyclohexanedicarboxylic acid.
- 1,4-cyclohexanedicarboxylic acid 1,3-cyclohexanedicarboxylic acid
- 1,2-cyclohexanedicarboxylic acid 1,2-cyclohexanedicarboxylic acid
- 2,5-cyclohexanedicarboxylic acid 2,5-cyclohexanedicarboxylic acid.
- tribasic or higher polybasic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride Acid, trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydride (Drotrimellitate), 1,2,3,4-butanetetracarboxylic acid, etc. may be contained, but in order to suppress gelation during the production of polyester resin, it is added to the polybasic acid component of polyester resin.
- the proportion of the tribasic or higher polybasic acid occupying is preferably 5 mol% or less.
- a polybasic acid component having a hydrophilic group other than a carboxyl group or a hydroxyl group such as 5-sodium sulfoisophthalic acid, can be used as the polybasic acid component.
- Water resistance of the resin film formed from the aqueous dispersion It is preferable not to use such a polybasic acid component because the acidity tends to deteriorate.
- aromatic polybasic acids are preferable, and the proportion of the aromatic polybasic acid in the polybasic acid component of the polyester resin is preferably 50% by weight or more, and 60% or more. More preferably, it is at least 70 mol%, more preferably at least 70 mol%.
- the proportion of aromatic polybasic acid By increasing the proportion of aromatic polybasic acid, the proportion of aromatic ester bonds, which are less likely to be hydrolyzed than aliphatic or alicyclic ester bonds, occupying the resin skeleton increases. However, a decrease in the molecular weight of the polyester resin can be reduced.
- the proportion of the aromatic polybasic acid the hardness, water resistance, solvent resistance, workability, and the like of the resin film formed from the aqueous dispersion are improved.
- the aromatic polybasic acid it is inexpensive because it is produced in large quantities on an industrial scale.Terephthalic acid and isophthalic acid are preferable because they are inexpensive.
- the total ratio of terephthalic acid and isophthalic acid in the polybasic acid component of the polyester resin Is preferably at least 49 mol%, more preferably at least 59 mol%, even more preferably at least 69 mol%.
- the proportion of terephthalic acid in the polybasic acid component of the polyester resin is preferably at least 25 mol%, more preferably at least 45 mol%, even more preferably at least 65 mol%. , 85 mol% or more is particularly preferred. Increasing the proportion of terephthalic acid tends to improve the hardness of the resin film and the solvent resistance.
- Polyhydric alcohol components constituting the polyester resin include aliphatic glycols having 2 to 10 carbon atoms, alicyclic glycols having 6 to 12 carbon atoms, and ether bond-containing glycols. Call and the like.
- Aliphatic glycols having 2 to 10 carbon atoms include ethylene dalicol, 1,2-propanediole, 1,3-propanediole, 1,4-butanediol, and 2-methinole-1,3 —Propanediole, 1,5-Pentanediol, Neopentyl glycol, 1,6-Hexanediamine, 3-Methylenole 1,5-pentanediol, 1,9-Nonanediol, 2-Ethyl_2-butylpropane
- Examples of the alicyclic dalicol having 6 to 12 carbon atoms include 1,4-cyclohexane dimethanol, and examples of the dalicol containing an ether bond include
- dipropylene glycol polytetramethylene glycol, polyethylene glycol, polypropylene glycol, and the like.
- the proportion of glycol-containing daricol containing an ether bond in the polyhydric alcohol component of the polyester resin is 10%. It is preferably at most 5 mol%, more preferably at most 5 mol%.
- ethylene oxide or propylene oxide of bisphenols such as bisphenol A and bisphenol S
- bisphenols such as bisphenol A and bisphenol S
- 2,2-bis (4-hydroxyoxenylphenyl) propane Adducts can also be used.
- ethylene glycol and neopentyl glycol are preferred because they are inexpensive because they are produced in large quantities on an industrial scale.
- the total of ethylene glycol and neopentyl glycol in the polyhydric alcohol component of the polyester resin is preferred. Is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, and particularly preferably 80 mol% or more.
- Ethylene glycol is particularly preferred as a polyhydric alcohol component of a polyester resin because it has the advantage of improving the chemical resistance of a resin film, and neopentyl glycol has the advantage of improving the weather resistance of a resin film.
- tri- or higher functional polyalcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like may be contained, but in order to suppress gelling during production of the polyester resin, Polyvalent It is preferable that the proportion of trifunctional or higher polyhydric alcohol in the alcohol be 5 mol% or less.
- the polyester resin may be copolymerized with monocarboxylic acid, monoalcohol, or hydroxycarponic acid.
- monocarboxylic acid monoalcohol, or hydroxycarponic acid.
- lauric acid myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, Benzoic acid, mono-tert-butylbenzoic acid, cyclohexanoic acid, 4-hydroxyphenylstearic acid, stearyl alcohol, 2-phenoxyethanol, ⁇ -force prolatatone, lactic acid, ⁇ -hydroxybutyric acid, ⁇ -hydroxy Benzoic acid or the like can be used.
- the polyester resin can be produced by polycondensing one or more of the above-mentioned polybasic acid components and one or more of the polyhydric alcohol components by a known method.
- the polymer is reacted under an inert atmosphere at 180 to 260 ° C. for about 2.5 to 10 hours to carry out the esterification reaction, and subsequently, in the presence of an ester exchange catalyst, 130 P a)
- a method of obtaining a polyester resin by advancing a polycondensation reaction at a temperature of 220 to 280 ° C. under a reduced pressure of not more than a until a desired molecular weight is reached.
- a polybasic acid component or a polyhydric alcohol component is further added after the above-mentioned polycondensation reaction, and depolymerization is performed under an inert atmosphere. And the like.
- the degree of decompression at the time of re-decompression is preferably 67,000 Pa or less, more preferably 100,000 Pa. If the degree of decompression is higher than 67,000 Pa, the time required for defoaming becomes longer even if the pressure is reduced again, which is not preferable.
- a method for imparting a desired acid value to the polyester resin a method in which a polybasic anhydride is further added following the above-mentioned polycondensation reaction and an addition reaction is performed with a hydroxyl group of the polyester resin under an inert atmosphere.
- the polyester resin of the present invention is preferably a polyester resin in which a carboxyl group has been introduced by the above-mentioned depolymerization and / or addition reaction using a polybasic acid.
- a carboxyl group By introducing a carboxyl group by depolymerization and / or addition reaction, The molecular weight and the acid value of the polyester resin can be easily controlled.
- the polybasic acid used at this time is preferably a tribasic or higher polybasic acid.
- a tribasic or higher polybasic acid By using a tribasic or higher polybasic acid, a desired acid value can be imparted while suppressing a decrease in the molecular weight of the polyester resin due to depolymerization.
- a polybasic acid having three or more functions an aqueous dispersion having more excellent storage stability can be obtained, although details are unknown.
- polybasic acid used in the depolymerization and the Z or addition reaction examples include the polybasic acid components described for the constituent components of the polyester resin.
- aromatic polybasic acids are preferable, and among the aromatic polybasic acids, Preferred are terephthalic acid, isophthalic acid, and phthalic anhydride, which are aromatic dicarboxylic acids.
- Trimellitic acid which is a trifunctional polybasic acid, and anhydrous trimellitic acid are preferred.
- trimellitic anhydride it is considered that the depolymerization and the addition reaction occur in parallel.Therefore, it is necessary to impart a desired acid value while minimizing the decrease in the molecular weight of the polyester resin due to the depolymerization. It is particularly preferable to use trimellitic anhydride since it is possible.
- the polyester resin may be used alone or in combination of two or more.
- the content of the polyester resin (A) contained in the aqueous dispersion of the present invention is 1 to 70% by mass, preferably 5 to 60% by mass, based on the total amount of the dispersion.
- the content is more preferably from 50 to 50% by mass, and most preferably from 15 to 40% by mass.
- the content of the polyester resin (A) exceeds 70% by mass, the viscosity of the aqueous dispersion becomes extremely high, and it tends to be difficult to substantially form a resin film. Less than 1% by mass is not practical.
- the aqueous dispersion of the present invention needs to contain a basic compound.
- the basic compound neutralizes the propyloxyl group of the polyester resin to form carboxyladione, and due to the electric repulsion between the aions, the polyester resin fine particles are stably dispersed without aggregation.
- Organic amines having a boiling point of 250 ° C. or less, preferably 160 ° C. or less, or ammonia are preferred because they are easy to volatilize when forming a resin film as a basic conjugate.
- preferably used organic amines include triethylamine, N, N-getylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, Iminobispropylamine, ethylamine, cetylamine, 3-ethoxypropylamine, 3-ethylethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobis Propylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, monorephorin, N-methylmorpholine, N-ethylmorpholine and the like.
- the content of the basic compound (B) is not particularly limited as long as the aqueous dispersion of the present invention can achieve the desired dispersion stability, particularly storage stability, but the basic compound is a polyester resin.
- the acid value of (A) is E (mgKOH / g) and the equivalent ratio of the basic compound (B) used to the total molar amount of carboxyl groups of the polyester resin (A) is F, It is preferably used in the range of the formula (1), more preferably in the range of the following formula (2), and still more preferably in the range of the following formula (3).
- Figure 1 shows the range of equation (1).
- Figure 1 shows the acid value of the polyester resin (A) in the phase inversion emulsification step represented by the above formula (1) and the equivalent of the required basic compound (B) to the total molar amount of the carboxy groups of the polyester resin.
- 6 illustrates the relationship between the ratios. From Fig. 1, it can be seen that the lower the acid value of the polyester resin used, the lower the lower limit of the equivalent ratio of the basic compound (B) used to the total molar amount of lipoxyl groups in the polyester resin (A). You can see that. Specifically, if the acid value of the polyester resin is 2 mg KOH, use a basic compound (B) that is at least twice equivalent to the total molar amount of the carboxyl groups of the polyester resin (A).
- the hydroxyl group of the polyester resin (A) is preferably used.
- the aqueous dispersion of the present invention can be obtained by using about 0.5 equivalent of the basic compound (B) to the total molar amount of
- the equivalent ratio of the basic compound (B) to the total molar amount of the carboxyl groups of the polyester resin (A) refers to the molar amount of the basic compound (B) used. It is a value obtained by dividing by the total molar amount of free lipoxyl groups.
- the free force of the polyester resin (II) The total molar amount of ropoxyl groups can be calculated from the acid value of the resin.
- the obtained aqueous dispersion tends to have a large volume average particle size, and thus may have poor storage stability.
- F exceeds “15 + 50” a large amount of the basic compound remains in the obtained aqueous dispersion, which is not preferable. Further, in the solvent removal step described later, the polyester resin tends to aggregate and precipitate, which is not preferable.
- the content in the aqueous dispersion is usually 0.005 to 10 % by mass / 0 . , In particular from 0.01 to 8 mass 0/0, preferably 0.015
- the water (C) contained in the aqueous dispersion is not particularly limited, and distilled water, ion-exchanged water, purified water, industrial water, and the like can be used. Preferably, distilled water or ion-exchanged water is used.
- the content of water (C) is at least 10% by mass, preferably at least 20% by mass, more preferably at least 30% by mass, based on the total amount of the dispersion. If the water (C) content is less than 10% by mass, it is no longer an aqueous dispersion.
- the upper limit of the water (C) content is appropriately determined according to the amounts of the components (A), (II) and (D).
- the aqueous dispersion of the present invention may further contain an organic solvent (D). Since the organic solvent may deteriorate the working environment or cause damage depending on the type of the material to be coated, the content of the organic solvent (D) is preferably small, and in the present invention, the aqueous dispersion is preferably used.
- the content of the organic solvent (D) ′ contained in the dispersion is 0 to 85% by mass, preferably 0 to 50% by mass, and 0 to 30% by mass based on the total amount of the dispersion. %, More preferably 0 to 10% by mass, particularly preferably 0 to 1% by mass, and most preferably 0 to 0.5% by mass.
- the content of the organic solvent (D) As the content of the organic solvent (D) is smaller, the molecular weight of the polyester resin tends to be less likely to decrease when the aqueous dispersion is stored for a long period of time. Specifically, when the content of the organic solvent (D) is 0 to 30% by mass, the retention of the molecular weight of the aqueous dispersion is reduced.
- the aqueous dispersion has an excellent advantage that the molecular weight retention is 95% or more.
- the content of the organic solvent (D) is 0 to 10% by mass
- the difference between the viscosity at 10 ° C and the viscosity at 40 ° C is 1 OmPa ⁇ S or less.
- the mass ratio (D) / (C) of water (C) to the organic solvent (D) contained in the aqueous dispersion may be in the range of OZl 100 to 100/100. preferable.
- the mass ratio “(D) / (C)” of water (C) and the organic solvent (D) is more preferably in the range of 0/100 to 40/100, and 0/100 to 15 More preferably, it is in the range of 0/100 to 0/100 to 1.5 / 100.
- Examples of the organic solvent (D) include an organic solvent used in a dissolving step in a method for producing an aqueous dispersion described below.
- the volume average particle size of the aqueous dispersion of the present invention is preferably 400 nm or less, and is preferably 30 Onm or less. More preferably, it is more preferably 200 nm or less, particularly preferably 150 nm or less. If the volume average particle size exceeds 400 nm, the polyester resin in the obtained aqueous dispersion tends to settle, and storage stability tends to be impaired.
- the aqueous dispersion of the present invention does not contain a surfactant, and since it does not contain a surfactant, the resulting resin film has excellent film performance such as water resistance.
- the production of the aqueous dispersion of the present invention essentially comprises two steps, a dissolution step and a phase inversion emulsification step, and, if necessary, a desolvation step.
- the dissolving step is a step of dissolving the polyester resin in an organic solvent
- the phase inversion step is a step of dispersing the polyester resin solution dissolved in the organic solvent in water together with a basic compound.
- the solvent removing step is a step of removing a part or all of the organic solvent used in the polyester resin dissolving step from the obtained aqueous dispersion to the outside of the system.
- the polyester resin is dissolved in an organic solvent.
- the concentration of the polyester resin in the obtained solution is preferably in the range of 10 to 70% by mass, more preferably in the range of 20 to 60% by mass, and more preferably in the range of 30 to 50% by mass. Is particularly preferred. If the concentration of the polyester resin in the solution exceeds 70% by mass, the next phase inversion? In the L-formation step, the viscosity increases when mixed with water, and the aqueous dispersion obtained from such a state tends to have a large volume average particle size, which is not preferable in terms of storage stability.
- the concentration of the polyester resin is less than 10% by mass, the concentration of the polyester resin is further reduced by the following phase inversion step, and a large amount of the organic solvent is removed in the desolvation step. This is uneconomical.
- the apparatus for dissolving the polyester resin in the organic solvent is not particularly limited as long as it is provided with a tank into which a liquid can be charged and capable of appropriately stirring. If the polyester resin is difficult to dissolve, heating may be performed.
- organic solvents can be used, for example, ketone-based organic solvents, aromatic hydrocarbon-based organic solvents, ether-based organic solvents, halogen-containing organic solvents, alcohol-based organic solvents, and ester-based solvents.
- Organic solvents, glycol-based organic solvents and the like are listed.
- Specific examples of the ketone-based organic solvent include, for example, methyl ethyl ketone (2-butanone) (hereinafter referred to as MEK), acetone, and getyl ketone (3-pen).
- MIBK (4-Methyl-1-pentanone) (hereinafter referred to as MIBK), 2-hexanone, 5-methyl-2_hexanone, 2-heptanone, 3-heptanone, 4-heptanone cyclopentanone, cyclohexanone, etc.
- Aromatic hydrocarbon organic Specific examples of the solvent include, for example, toluene, xylene, benzene and the like.
- ether organic solvent include, for example, dioxane and tetrahydrofuran.
- Specific examples of the nodogen-containing organic solvent include, for example, carbon tetrachloride, trichloromethane, dichloromethane and the like.
- alcoholic organic solvents include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec —Amyl alcohol, tert-amyl alcohol, 1-ethyl-11-propanol, 2-methyl-11-butanol, n-hexanol, cyclohexanol, and the like.
- ester organic solvents include, for example, ethyl acetate, _n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, monobutyl acetate, butyl acetate, and propionic acid. Examples thereof include methyl, ethyl propionate, getyl carbonate, and dimethyl carbonate.
- glycol-based organic solvent include, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycolone monopropynoleate, ethylene glycolone monopropynoleate, ethylene glycol monoleptinolateate, and the like.
- organic solvents such as 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylinoacetamide, diacetone alcohol, and ethyl acetate are exemplified.
- the above-mentioned solvents can be used alone or in combination of two or more, but in order to obtain the aqueous dispersion of the present invention, the polyester resin is dissolved in 10% by mass or more. It is preferable to select an organic solvent so that the solvent can be dissolved, more preferably an organic solvent that can dissolve at least 20% by mass, and even more preferably an organic solvent that can dissolve at least 30% by mass.
- Organic solvents include acetone, MEK, MIBK, dioxane, tetrahydrofuran, and hexahexanone alone, acetone / ethylene glycol / remonobutynol ether mixed solution, MEK / ethylene glycol monobutyl ether mixed solution, and MlBK / Ethylene glycol monobutyl ether mixed solution, dioxane / ethylene glycol monobutyl ether mixed solution, tetrahydrofuran / ethylene glycol monobutyl ether mixed solution, cyclohexanone Z-ethylene glycol
- the polyester resin solution obtained in the dissolution step is mixed with water and a basic compound to perform phase inversion emulsification.
- a basic compound it is preferable to add a basic compound to a polyester resin solution, and gradually add water to the solution to perform phase inversion emulsification. If the rate of addition of water is high, polyester resin lumps are formed, which tend to no longer disperse in the aqueous medium, resulting in a poor yield of the final aqueous dispersion and economical is not.
- phase inversion emulsification refers to adding an amount of water that exceeds the amount of the organic solvent contained in an organic solvent solution of a polyester resin to an O / w emulsion dispersion system from the organic solvent phase. Means to change.
- the phase inversion process is performed at 40 ° C or lower, preferably at 30 ° C or lower, more preferably at 20 ° C or lower, particularly preferably at 15 ° C or lower. .
- the phase inversion emulsification step By performing the phase inversion emulsification step at 0 ° C. or lower, the volume average particle diameter of the obtained aqueous dispersion becomes small, and an aqueous dispersion having excellent storage stability can be obtained. Further, during the desolvation step described below, it is possible to suppress the generation of precipitation of the polyester resin, which is caused by the aggregation of the aqueous dispersion, and as a result, the yield is improved and economical.
- the details of the mechanism by which the aqueous dispersion having a small volume average particle size is obtained when the phase inversion emulsification step is performed at a relatively low temperature as described above are not clear. If the phase inversion emulsification step is carried out at more than 40 ° C., the volume average particle size of the obtained aqueous dispersion becomes large, and the storage stability deteriorates.
- the temperature of the above-mentioned phase inversion emulsification step is preferably maintained at 40 ° C or lower throughout this step, but when the liquid temperature tends to rise due to shear heat insulation by stirring, etc., it is difficult to maintain the system temperature. There is. Even in such a case, it is preferable to control the temperature to 40 ° C or lower (not to exceed 40 ° C) until the addition of 0.8 times the amount of water of the organic solvent contained in the polyester resin solution is completed. More preferably, the temperature is controlled until the addition of 1 volume of water is completed, more preferably until the addition of 1.1 volume of water is completed.
- the apparatus for performing the phase inversion emulsification step is not particularly limited as long as it has a tank into which a liquid can be charged and can perform appropriate stirring.
- Examples of such an apparatus include those widely known to those skilled in the art as a solid Z liquid stirring apparatus and an emulsifier (eg, a homomixer).
- an emulsifier eg, a homomixer
- the liquid temperature may rise due to shear heat insulation.
- the phase inversion emulsification step may be performed under any conditions of normal pressure, reduced pressure, and increased pressure.
- the solvent removal step is a step of distilling the organic solvent contained in the aqueous dispersion obtained in the phase inversion step and removing part or all of the organic solvent from the aqueous dispersion.
- This step can be performed under reduced pressure or normal pressure. If the solvent is removed under normal pressure, agglomerates may be easily generated.In such a case, the reaction is performed under reduced pressure, and the internal temperature is 70 ° C or lower, preferably 60 ° C or lower, more preferably The temperature should be adjusted to 50 ° C or less.
- the apparatus for performing the solvent removing step may be any apparatus provided with a tank into which a liquid can be charged and capable of appropriately stirring.
- phase inversion emulsification step After the phase inversion emulsification step, a part of or all of the basic compounds contained in the aqueous dispersion after the phase inversion emulsification step and not contributing to the neutralization of the polyester resin are removed by performing the solvent removal step. There is also.
- the aqueous dispersion of the present invention has a uniform and uniform appearance in which a portion having a solid concentration locally different from other portions, such as precipitation and phase separation, in an aqueous medium is not found. Obtained in a stable state.
- a filtration step may be provided during the step for the purpose of removing foreign substances and the like.
- a stainless steel filter wire diameter: 0.035 mm, plain weave
- pressure filtration air pressure: 0.2 MPa
- the aqueous dispersion of the present invention is excellent in film-forming ability, it can be uniformly coated on various substrate surfaces by a known film forming method, for example, a dive method, a brushing method, a spray coating method, a curtain flow coating method, or the like. After coating, setting as needed at around room temperature, and subjecting it to heat treatment for drying and baking, a uniform resin film can be formed in close contact with various substrate surfaces.
- a heating device at this time an ordinary hot air circulation type open or infrared heater may be used. The heating temperature and the heating time are appropriately selected depending on the type of the substrate to be coated, and the like.
- the heating temperature is 60 to 250 ° C is preferred, 70 to 230 ° C is more preferred, and 80 to 200. C is particularly preferred, and the heating time is preferably from 1 second to 30 minutes, more preferably from 5 seconds to 20 minutes, and particularly preferably from 10 seconds to 10 minutes! /.
- the thickness of the resin film formed using the aqueous dispersion of the present invention is appropriately selected depending on the purpose and application, but is preferably from 0.11 to 40 ⁇ , and from 0.1 to 40 ⁇ . 3 O ⁇ m is more preferable, and 0.5 to 20 ⁇ m is particularly preferable.
- the aqueous dispersion of the present invention includes, as necessary, a curing agent, various additives, a compound having a protective colloid function, water, an organic solvent, a surfactant, a pigment such as titanium oxide, zinc white, and carbon black.
- An aqueous resin such as a dye, another aqueous polyester resin, an aqueous urethane resin, an aqueous olefin resin, an aqueous acrylic resin, or the like can be blended.
- the curing agent is not particularly limited as long as it is a curing agent having reactivity with a functional group of the polyester resin, for example, a carboxyl group, an anhydride thereof, and a hydroxyl group.
- urea resin ⁇ melamine resin or benzoguanamine resin And the like polyfunctional epoxy compounds, polyfunctional isocyanate compounds and their various block isocyanate compounds, polyfunctional aziridine compounds, carbodiimide group-containing compounds, oxazoline group-containing polymers, phenolic resins, and the like. 1 type Or two or more of them may be used in combination.
- Additives include repelling agents, leveling agents, antifoaming agents, anti-glazing agents, rheology control agents, pigment dispersants, ultraviolet absorbers, lubricants and the like.
- Compounds having a protective colloidal action include polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, modified starch, polybutylpyrrolidone, polyacrylic acid, acrylic acid and / or methacrylic acid.
- organic solvent which can be exemplified by a polymer of a vinyl monomer as a component, polyitaconic acid, gelatin, gum arabic, casein, swellable mica, and the like are used in the dissolving step in the above-described method for producing an aqueous dispersion.
- Organic solvents can be mentioned.
- Surfactants include all surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.
- the nonionic surfactant include alkylene oxide adducts of alkyl phenols such as noel phenol and otatyl phenol and alkylene oxide adducts of higher alcohols.
- examples of such nonionic surfactants include Igepa 1 series manufactured by A1drich, Naroacty N_100, Narrowacty N—120, and Narrowacty N—140 manufactured by Sanyo Kasei Corporation. Etc., Sannonic SS—120, Sannonic SS—90, Sannonic SS—70, etc. Sannonic SS series, Sannonic FD—140, Sannonic FD—100, Sannonic FD—80, etc. Sannonic FD series, Cedran F
- Cedran FF series such as F-220, Cedran FF — 210, Cedran FF—200, Cedran FF—180, Cedran SNP series, such as Cedran SNP—112, New Ponole PE—64, Newpole PE series such as New Ponole PE-74 and New Ponole PE_75, and Sanmorin 11 etc.
- the difference (W0-W1) is calculated in mg of KOH from the amount of KOH required for neutralization (calculated value: W 0) when all of the acetic acid is converted to acetic acid without reacting with it.
- W 0 The value obtained by dividing by the number of grams of the resin was defined as the hydroxyl value.
- the number average molecular weight is determined by GPC analysis (using a liquid sending unit LC-I OADv P type and an ultraviolet-visible spectrophotometer SPD-6AV type manufactured by Shimadzu Corporation, detection wavelength: 254 nm, solvent: tetrahydrofuran, converted to polystyrene).
- the weight average molecular weight of the polyester resin can also be determined by the GPC analysis, and the degree of dispersion of the molecular weight distribution can be determined as a value obtained by dividing the weight average molecular weight by the number average molecular weight.
- Glass transition temperature of polyester resin Using a sample of 1 Omg of polyester resin as a sample, measurement was performed using a DSC (differential scanning calorimetry) device (Perkin Elmer Co., Ltd., DSC 7) under the condition of a heating rate of 10 ° CZ. The intermediate value between the two bending temperatures derived from the glass transition was calculated, and this was defined as the glass transition temperature (Tg).
- DSC differential scanning calorimetry
- the aqueous dispersion was weighed to about lg (Xg), dried at 150 ° C for 2 hours, weighed (Yg), and the solid content was determined by the following formula. I asked.
- Gas chromatograph GC-8A manufactured by Shimadzu Corporation [Using FID detector, carrier gas: nitrogen, column packing material (manufactured by GL Sciences): PEG-HT (5%)-UNIPORT HP (60 80 mesh), Column size: diameter 3 mm x 3 m, sample injection temperature (injection temperature): 150 ° C, column temperature: 60 ° C, internal standard substance: n-butanol], dilute the aqueous dispersion with water. was directly charged into the apparatus to determine the content of the organic solvent. The detection limit was 0.01% by mass.
- the ZK dispersion was diluted to 0.1% with water, and the volume average particle diameter was measured using MICROTRAC UP A (Model 9340-UPA) manufactured by Nikkiso Co., Ltd. .
- the thickness of the base material is measured in advance using a thickness gauge (manufactured by Union Tool Co., Ltd., MICROF INE II), and a resin coating is formed on the base material using an aqueous dispersion.
- the thickness of the substrate having was measured by the same method, and the difference was defined as the thickness of the resin film.
- the peeled adhesive tape surface was analyzed with a surface infrared spectrometer (SY STEM 2000, Ge 60, manufactured by PerkinElmer Inc., using a 50x20x2 mm prism), and the resin film was adhered to the adhesive tape surface.
- the adhesiveness of the resin film to the substrate was evaluated according to the following criteria.
- a biaxially stretched PET film (12 ⁇ in thickness, manufactured by Unitika Ltd.) was used.
- the above-mentioned biaxially stretched PET film was coated with the aqueous dispersion using a tabletop coating device, and heated for 1 minute in an oven set at 130 ° C to form a resin coating with a thickness of about 1 m.
- the PET film on which the resin film was formed was immersed in hot water at 80 ° C, gently pulled up after 10 minutes, air-dried, and the appearance of the resin film was visually observed.
- the evaluation was performed according to the following criteria.
- the above-mentioned biaxially stretched PET film was coated with the aqueous dispersion using a tabletop coating device, and heated in an oven set at 130 ° C for 1 minute to form a resin coating with a thickness of about 1 ⁇ .
- the film with the resin film formed was immersed in ethanol at 25 ° C, gently pulled up after 10 minutes, air-dried, and the appearance of the resin film was visually observed.
- the evaluation was based on the following criteria. ⁇ : ⁇ No change is observed.
- the rotational viscosity of the aqueous dispersion was measured at 10 ° C and 40 ° C, respectively, using a DVL-B I type digital viscometer (B type viscometer) manufactured by Tokimec Co., Ltd.
- a 0.19 mm thick metal plate (tin-free steel plate) is coated with the aqueous dispersion using a tabletop coating machine, and heated in an oven set at 200 ° C for 3 minutes to obtain a thickness of 3 ⁇ .
- the metal plate having the same thickness as described above was bent between the inside bent portions by a press machine with several sheets of force sandwiched therebetween.
- the occurrence of cracks in the resin film at the bent portion was visually observed and determined.
- the number of metal plates sandwiched between the bent portions was changed, and the minimum number ⁇ at which the above cracks did not occur was used as an index of workability, and was marked as ⁇ . At this time, the smaller ⁇ , the better the workability.
- Polyester resins used in Examples and Comparative Examples were obtained as follows.
- a mixture consisting of 2492 g of terephthalic acid, 415 g of isophthalic acid, 1516 g of sebacic acid, 1210 g of ethylene glycol, and 1484 g of neopentyl glycol was heated in an autoclave at 250 ° C for 4 hours to perform an esterification reaction. . Then, after adding 3.3 g of zinc acetate dihydrate as a catalyst, the temperature of the system was raised to 270 ° C, and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. . Under these conditions, the polycondensation reaction is continued for another 4 hours, the system is brought to normal pressure with nitrogen gas, and the temperature of the system is lowered.
- a mixture of 2077 g of terephthalic acid, 2077 g of isophthalic acid, 1125 g of polytetrahydrofuran 1000, 1510 g of neopentyl glycol, and 1358 g of ethylene glycol is heated in an autoclave at 240 ° C for 4 hours to carry out the esterification reaction. went.
- 12.8 g of tetra-n-butyl titanate was added as a catalyst, the temperature of the system was raised to 255 ° C, and the pressure of the system was gradually reduced to 1.
- a mixture consisting of 2077 g of terephthalic acid, 2077 g of isophthalic acid, 1102 g of ethylene glycol and 1666 g of neopentyl glycol was heated in an autoclave at 240 ° C. for 4 hours to carry out an esterification reaction.
- 3.3 g of zinc acetate was added as a catalyst, the temperature of the system was raised to 265 ° C, and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under these conditions, the polycondensation reaction was continued.After 4 hours, the system was brought to normal pressure with nitrogen gas, the temperature of the system was lowered, and when it reached 260 ° C, 29 g of anhydrous trimellitic acid was added.
- a mixture consisting of 2907 g of terephthalic acid, 1246 g of isophthalic acid, 1133 g of ethylene glycol, and 1614 g of neopentyl glycol was heated in an autoclave at 260 ° C. for 4 hours to perform an esterification reaction.
- 1.8 g of antimony triacid value was added as a catalyst, the temperature of the system was raised to 280 ° C, and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours.
- the polycondensation reaction was continued under these conditions.After 4 hours, the system was brought to normal pressure with nitrogen gas, the temperature of the system was lowered, and when the temperature reached 250 ° C, 53 g of trimellitic acid was added, followed by stirring at 250 for 2 hours. Then, a depolymerization reaction was performed. Thereafter, the pressure of the system was gradually reduced to 13 Pa after 0.5 hour, and then degassing was performed for 1 hour. Next, the system was pressurized with nitrogen gas, and the resin was discharged in a strand shape, cooled with water, cut, and pelletized (about 3 mm in diameter, Polyester resin P-6 having a length of about 3 mm) was obtained.
- a mixture comprising 4153 g of terephthalic acid, 388 g of ethylene glycol, and 2568 g of 1,2-propanediol was heated in an autoclave at 240 for 3 hours to carry out an esterification reaction. Next, 5. 1 g of tetra-n-butyl titanate was added as a catalyst, and while maintaining the temperature at 240 ° C, the pressure of the system was gradually reduced to 13 Pa after 1.5 hours.
- a mixture consisting of 2907 g of terephthalic acid, 1246 g of isophthalic acid, 1133 g of ethylene glycolone, and 1614 g of neopentyl glycol was heated in an autoclave at 260 ° C. for 4 hours to carry out an esterification reaction.
- 1.8 g of antimony triacid was added as a catalyst, the temperature of the system was raised to 280 ° C, and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours.
- a mixture consisting of 2907 g of terephthalic acid, 1246 g of isophthalic acid, 1133 g of ethylene glycolone, and 1614 g of neopentyl glycol was heated in an autoclave at 260 ° C. for 4 hours to perform an esterification reaction.
- 1.8 g of antimony trioxide was added as a catalyst, the temperature of the system was increased to 280 ° C, and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under this condition, the polycondensation reaction was continued.After 6 hours, the system was brought to normal pressure with nitrogen gas, the temperature of the system was lowered, and when the temperature reached 250 ° C, 79 g of trimellitic acid was added.
- a mixture consisting of 2907 g of terephthalic acid, 1246 g of isophthalic acid, 1133 g of ethylene glycol and 1614 g of neopentyl glycol was heated in an autoclave at 260 ° C. for 4 hours to carry out an Esterich reaction.
- 1.8 g of antimony trioxide was added as a catalyst, the temperature of the system was increased to 280 ° C, and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under this condition, the polycondensation reaction was continued.After 6 hours, the system was brought to normal pressure with nitrogen gas, the temperature of the system was lowered, and when the temperature reached 250 ° C, 289 g of trimellitic acid was added.
- the mixture was stirred to perform a depolymerization reaction. Thereafter, the resin was discharged in a sheet shape while being pressurized with nitrogen gas. Then, this was cooled sufficiently to room temperature, then powdered with a crusher, and a fraction having an opening of 1 to 6 mm was collected using a sieve to obtain a granular polyester resin P-10.
- Table 1 shows the results of analyzing or evaluating the properties of the polyester resin obtained as described above.
- Example 3 [Dissolution process] 400 g of polyester resin P_1 and 480 g of MEK are charged into a 3 L polyethylene container, and the container is heated with warm water of about 60 ° C, and a stirrer (MAZELA1000, manufactured by Tokyo Rika Co., Ltd.) is used. The polyester resin was completely dissolved in MEK by stirring, and then 120 g of ethylene glycol monobutyl ether was added. After stirring for about 10 minutes, the solid content concentration of the polyester resin was 40% by mass. A solution of 48% by mass ⁇ 1 £ 1: 12% by mass ethylene glycol monobutyl ether was obtained.
- MAZELA1000 manufactured by Tokyo Rika Co., Ltd.
- Example 5 Same as Example 5 except that the polyester resin was changed to P-2, 22.2 g of triethylamine was added, and the distilled water added in the phase inversion emulsification step was changed to 477.8 g. To obtain an aqueous dispersion.
- Example 5 Same as Example 5 except that the polyester resin was changed to P-3, 22.9 g of triethylamine was added, and the distilled water added in the phase inversion emulsification step was changed to 477.1 g. To obtain an aqueous dispersion.
- Example 1 2 Same as Example 5 except that the polyester resin was changed to P-4, 22.5 g of triethylamine was added, and the distilled water added in the phase inversion emulsification step was changed to 477.5 g. To obtain an aqueous dispersion. (Example 1 2)
- Example 5 was repeated except that the polyester resin was changed to p-5, 22.7 g of triethylamine was added, and the distilled water added in the phase inversion emulsification step was changed to 477.3 g. An aqueous dispersion was obtained in the same manner.
- Example 5 Same as Example 5 except that the polyester resin was changed to p-6, 8.5 g of triethylamine was added, and the distilled water added in the phase inversion emulsification step was changed to 491.5 g. To obtain an aqueous dispersion.
- Example 6 except that the polyester resin was changed to p-7, 22.7 g of triethylamine was added, and the distilled water added in the phase inversion emulsification step was changed to 477.3 g. An aqueous dispersion was obtained in the same manner as in 5.
- An aqueous dispersion was prepared in the same manner as in Example 5, except that the amount of triethylamine was changed to 1.9 g, and the amount of distilled water added in the phase inversion emulsification step was changed to 498.1 g. Obtained.
- Example 5 The procedure was the same as in Example 5, except that the amount of triethylamine was changed to 62.0 g, and the amount of distilled water added in the phase inversion emulsification step was changed to 438.0 g. When the solvent was used, the polyester resin was aggregated, and an aqueous dispersion was not obtained.
- Example 5 Performed except changing the polyester resin to P-9, adding 8.7 g of triethylamine, and changing the amount of distilled water added in the phase inversion process to 491.3 g. The same operation as in Example 5 was performed to obtain an aqueous dispersion.
- Example 8 The same as Example 5 except that the polyester resin was changed to P_10, 14.6 g of triethylamine was added, and the distilled water added in the phase inversion emulsification step was changed to 485.4 g. The operation was performed to obtain an aqueous dispersion. (Comparative Example 8)
- Desolvation step Next, 800 g of the above aqueous dispersion and 52.3 g of distilled water were placed in a 2 L flask, and the solvent was removed under reduced pressure while adjusting the internal temperature to 50 ° C or lower. However, the polyester resin aggregated during the solvent removal step, and an aqueous dispersion was not obtained. For this reason, in evaluation, the thing before solvent removal was used.
- Table 2 shows the equivalence ratio of the basic compound used in Examples and Comparative Examples to the total molar amount of lipoxyl groups of the polyester resin, the values on the left and right sides of Formula (1), and the acid value of the used polyester resin. , And the results obtained by examining the organic solvent content, the volume average particle diameter, and the storage stability of the obtained aqueous dispersion. Regarding the organic solvent content, for those without desolvation, the content was calculated from the charged amount during phase inversion, and for those with desolvation, the results measured by gas chromatography were used.
- Table 3 shows the results of examining the adhesion, water resistance, and solvent resistance of the resin film formed from the aqueous dispersion, and the values of the molecular weight retention and the viscosity at 10 ° C and 40 ° C of the aqueous dispersion. Shows additive properties. Tables 2 and 3 do not show Comparative Examples 1, 3 and 5 for which no aqueous dispersion was obtained. Table 2
- the aqueous polyester resin dispersion of the present invention has excellent storage stability, and the resin film formed therefrom has excellent adhesion to the substrate, water resistance, solvent resistance, It turns out that it is excellent in workability. Furthermore, the polyester resin aqueous dispersion of the present invention has a high molecular weight retention and a small difference in viscosity between 10 ° C. and 40 ° C. when the organic solvent content is small. Understand. In addition, when the phase inversion emulsification step is performed at a temperature exceeding 40 ° C., an aqueous dispersion having excellent storage stability may not be obtained. When a basic compound is contained outside the range of the formula (1) in the phase inversion emulsification step, an aqueous dispersion cannot be obtained, or if obtained, storage stability is poor. It turns out that there is.
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Abstract
Description
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US10/531,308 US20060069231A1 (en) | 2002-10-22 | 2003-10-21 | Aqueous polyester resin dispersion and method for production thereof |
JP2004546429A JP4748987B2 (ja) | 2002-10-22 | 2003-10-21 | ポリエステル樹脂水性分散体の製造方法 |
AU2003301544A AU2003301544A1 (en) | 2002-10-22 | 2003-10-21 | Aqueous polyester resin dispersion and method for production thereof |
EP03756721A EP1555295B1 (en) | 2002-10-22 | 2003-10-21 | Aqueous polyester resin dispersion and method for production thereof |
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JP2006036920A (ja) * | 2004-07-27 | 2006-02-09 | Toyo Kasei Kogyo Co Ltd | 水性樹脂組成物およびその製造方法 |
JP2006182983A (ja) * | 2004-12-28 | 2006-07-13 | Nippon Ester Co Ltd | 塗料用ポリエステル樹脂の製造方法、および塗料用ポリエステル樹脂 |
JP4652046B2 (ja) * | 2004-12-28 | 2011-03-16 | 日本エステル株式会社 | 塗料用ポリエステル樹脂およびそれを用いた塗料用樹脂組成物 |
JP2007039535A (ja) * | 2005-08-02 | 2007-02-15 | Unitika Ltd | 樹脂被覆金属用水性接着剤およびこれを用いてなる樹脂被覆金属 |
JP2007044879A (ja) * | 2005-08-05 | 2007-02-22 | Unitika Ltd | 感熱孔版印刷原紙用水性接着剤および感熱孔版印刷原紙 |
KR100963711B1 (ko) | 2005-09-06 | 2010-06-14 | 유니띠까 가부시키가이샤 | 폴리에스터 수지 수성 분산체, 그로부터 얻어지는 피막 및이 피막을 이용한 포장 백 |
WO2007029728A1 (ja) * | 2005-09-06 | 2007-03-15 | Unitika Ltd. | ポリエステル樹脂水性分散体、それから得られる被膜、および該被膜を利用した包装袋 |
JP5241232B2 (ja) * | 2005-09-06 | 2013-07-17 | ユニチカ株式会社 | ポリエステル樹脂水性分散体、それから得られる被膜、および該被膜を利用した包装袋 |
WO2007086266A1 (ja) * | 2006-01-24 | 2007-08-02 | Unitika Ltd. | ポリエステル樹脂水性分散体およびその製造方法 |
KR101004241B1 (ko) | 2006-01-24 | 2010-12-24 | 유니띠까 가부시키가이샤 | 폴리에스터 수지 수성 분산체 및 그 제조 방법 |
JP5241240B2 (ja) * | 2006-01-24 | 2013-07-17 | ユニチカ株式会社 | ポリエステル樹脂水性分散体およびその製造方法 |
JP2007321038A (ja) * | 2006-05-31 | 2007-12-13 | Unitika Ltd | ポリエステル樹脂水分散体 |
WO2008001795A1 (fr) * | 2006-06-30 | 2008-01-03 | Toyo Boseki Kabushiki Kaisha | Dispersion aqueuse de résine polyester, dispersion aqueuse de résine hybride, et adhésif, matière de revêtement et matière de peinture les utilisant |
JP2008056764A (ja) * | 2006-08-30 | 2008-03-13 | Unitika Ltd | ポリエステル樹脂水分散体、およびその製造方法、ならびにそれから得られる皮膜形成物 |
JP4708290B2 (ja) * | 2006-08-30 | 2011-06-22 | ユニチカ株式会社 | ポリエステル樹脂水分散体、およびその製造方法、ならびにそれから得られる皮膜形成物 |
JP2008239691A (ja) * | 2007-03-26 | 2008-10-09 | Unitika Ltd | ポリエステル樹脂水分散体混合物、およびその製造方法、それから得られる皮膜形成物ならびに該皮膜を利用した包装袋 |
JP2009084380A (ja) * | 2007-09-28 | 2009-04-23 | Unitika Ltd | ポリエステル樹脂水性分散体およびその製造方法 |
JP2009221316A (ja) * | 2008-03-14 | 2009-10-01 | Unitika Ltd | ポリエステル樹脂水性分散体、それから得られる被膜、および該被膜を利用した包装袋 |
WO2010092889A1 (ja) | 2009-02-10 | 2010-08-19 | ユニチカ株式会社 | ポリエステル樹脂水性分散体およびその製造方法 |
JP5666919B2 (ja) * | 2009-02-10 | 2015-02-12 | ユニチカ株式会社 | ポリエステル樹脂水性分散体およびその製造方法 |
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Also Published As
Publication number | Publication date |
---|---|
US20060069231A1 (en) | 2006-03-30 |
EP1555295A4 (en) | 2006-02-01 |
JP4748987B2 (ja) | 2011-08-17 |
CN1726257A (zh) | 2006-01-25 |
KR20050075757A (ko) | 2005-07-21 |
KR101043152B1 (ko) | 2011-06-20 |
JPWO2004037924A1 (ja) | 2006-02-23 |
AU2003301544A1 (en) | 2004-05-13 |
EP1555295A1 (en) | 2005-07-20 |
EP1555295B1 (en) | 2011-05-11 |
JP2011099125A (ja) | 2011-05-19 |
CN1329447C (zh) | 2007-08-01 |
JP4852665B2 (ja) | 2012-01-11 |
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