Aqueous dispersions of resins

Abstract

To provide a polyester resin aqueous dispersion that is excellent in abrasion resistance, water resistance and storage stability.SOLUTION: Provided is a resin aqueous dispersion, which contains a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component, characterized in which the alcohol component contains ethylene glycol, the carboxylic acid component contains terephthalic acid, and the polyester resin (A) contains calcium in a range of 10 to 4000 ppm as measured by fluorescent X-ray analysis.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an aqueous resin dispersion.

Background Art

[0002] Since polyester resins are excellent in processability, chemical resistance, weather resistance, and adhesion to various substrates, they are widely used as binder components and film-forming materials in various fields such as paints, inks, adhesives, and coating agents. In recent years, from the viewpoints of environmental protection and resource conservation, the use of organic solvents has tended to be restricted, and in the above fields, there is a desire for water-based conversion from solvent-based types using organic solvents as solvents to water-based media that do not require organic solvents. Furthermore, from the viewpoint of effective utilization of resources, the need for polyester resins obtained by recovering and recycling polyethylene terephthalate (PET) products discarded and recovered from fibers, films, and other molded products is increasing, and their use as binder components in the above fields is being considered. In the water-based conversion of the above applications, proposals have been made to form an aqueous polyester resin dispersion in which a polyester resin is finely dispersed in an aqueous medium (see Patent Document 1). In addition, Patent Document 2 proposes a recycling method for reusing recovered polyester to obtain a modified polyester resin applicable as a polyester resin for solvent-based paints. However, the polyester resins obtained in Patent Documents 1 and 2 had problems with the abrasion resistance of the coating film.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] The object of the present invention is to provide an aqueous dispersion of polyester resin that has excellent abrasion resistance, water resistance, and storage stability. [Means for solving the problem]

[0005] The present inventors have arrived at the present invention as a result of diligent research. Specifically, the present invention is an aqueous resin dispersion comprising a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component, wherein the alcohol component comprises ethylene glycol, the carboxylic acid component comprises terephthalic acid, and the polyester resin (A) contains calcium in the range of 10 to 4000 ppm as measured by X-ray fluorescence analysis. [Effects of the Invention]

[0006] The present invention makes it possible to provide an aqueous dispersion of polyester resin with excellent abrasion resistance, water resistance, and storage stability. [Modes for carrying out the invention]

[0007] The present invention relates to an aqueous resin dispersion comprising a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component, wherein the alcohol component comprises ethylene glycol, the carboxylic acid component comprises terephthalic acid, and the polyester resin (A) contains calcium in the range of 10 to 4000 ppm as measured by X-ray fluorescence analysis. The aqueous resin dispersions of the present invention will be described sequentially below.

[0008] The aqueous resin dispersion of the present invention comprises a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component.

[0009] First, let's explain polyester resin (A). Polyester resin (A) is a polyester resin obtained by polycondensation of an alcohol component and a carboxylic acid component, wherein the alcohol component contains ethylene glycol and the carboxylic acid component contains terephthalic acid. Polyester resin (A) may also be a modified polyester resin containing urethane groups and urea groups.

[0010] The alcohol component may also contain a polyol component (x) in addition to ethylene glycol. Examples of polyol components (x) include diols other than ethylene glycol (x1) and polyols with a valentity of 3 or higher (x2). These may be used individually or in combination of two or more types.

[0011] Examples of diols (x1) include alkylene glycols with 3 to 36 carbon atoms (propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol, etc.), and alkylene ether glycols with 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropyl glycol, etc.). Examples include pyrene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol, etc.; alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.); (poly)alkylene oxide adducts of the above alicyclic diols (preferably with an average number of added moles of 1 to 30); aromatic diols [monocyclic divalent phenols (e.g., hydroquinone, etc.) and bisphenols, etc.]; and alkylene oxide adducts of the above aromatic diols (preferably with an average number of added moles of 2 to 30).

[0012] The alkylene oxide adducts of the above-mentioned bisphenols are obtained by adding alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to bisphenols.

[0013] Examples of bisphenols include those represented by the following general formula (1). HO-Ar-P-Ar-OH (1) [In the formula, P represents an alkylene group having 1 to 3 carbon atoms, -SO2-, -O-, -S-, or a direct bond, and Ar represents a phenylene group in which a hydrogen atom may be substituted with a halogen atom or an alkyl group having 1 to 30 carbon atoms.]

[0014] Specific examples of bisphenols include, for example, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A, and 2,2'-diethylbisphenol F, and two or more of these can be used in combination.

[0015] Examples of alkylene oxides to be added to bisphenols include alkylene oxides having 2 to 30 carbon atoms, such as ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO), propylene oxide ("propylene oxide" may be abbreviated as PO), butylene oxide, tetrahydrofuran, and combinations of two or more of these.

[0016] Of these diols (x1), from the viewpoint of the solvent solubility of the resulting polyester resin, alkylene oxide adducts of alkylene glycols having 3 to 36 carbon atoms and aromatic diols are preferred, alkylene oxide adducts of alkylene glycols having 3 to 10 carbon atoms and bisphenols (average number of added moles is preferably 2 to 5) are more preferred, alkylene oxide adducts of alkylene glycols having 3 to 10 carbon atoms and bisphenol A (average number of added moles is preferably 2 to 5) are even more preferred, and branched alkylene glycols having 3 to 10 carbon atoms and EO and / or PO adducts of bisphenol A (average number of added moles is preferably 2 to 3) are particularly preferred.

[0017] In addition, from the viewpoint of storage stability (solvent solubility), it is preferable that the alcohol component of the polyester resin (A) contains an alkylene glycol having a branch with 3 to 10 carbon atoms or an alkylene oxide adduct of bisphenol A. More preferably, the alcohol component of the polyester resin (A) contains neopentyl glycol or an EO2 molar adduct of bisphenol A.

[0018] Examples of the polyol (x2) having a valence of 3 or more include aliphatic polyhydric alcohols having a valence of 3 or more and 3 to 36 carbon atoms, saccharides and their derivatives, alkylene oxide adducts of aliphatic polyhydric alcohols (the average number of added moles is preferably 1 to 30), alkylene oxide adducts of trisphenols (such as trisphenol PA, etc.) (the average number of added moles is preferably 2 to 30), alkylene oxide adducts of novolak resins (including phenol novolak and cresol novolak, etc., and the average degree of polymerization is preferably 3 to 60) (the average number of added moles is preferably 2 to 30), and the like.

[0019] Examples of the aliphatic polyhydric alcohol having a valence of 3 or more and 3 to 36 carbon atoms include alkane polyols and their intramolecular or intermolecular dehydrates, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol. Examples of the saccharides and their derivatives include sucrose and methyl glucoside.

[0020] Among these polyols (x2) having a valence of 3 or more, from the viewpoint of achieving both scratch resistance and water resistance, aliphatic polyhydric alcohols having a valence of 3 or more and 3 to 36 carbon atoms, and alkylene oxide adducts of novolak resins (including phenol novolak and cresol novolak, etc., and the average degree of polymerization is preferably 3 to 60) (the average number of added moles is preferably 2 to 30) are preferable. Aliphatic polyhydric alcohols having a valence of 3 and 3 to 8 carbon atoms are more preferable, and trimethylolpropane is particularly preferable.

[0021] The diol (x1) in the polyol component (x) of the polyester resin (A) is preferably 80 to 100 mol% from the viewpoint of abrasion resistance.

[0022] In one embodiment, the alcohol component can be derived from biomass-based raw materials. Biomass-based raw materials refer to raw materials derived from plants and microorganisms.

[0023] Examples of alcohol components derived from biomass include propylene glycol, 1,3-propanediol, 1,4-butanediol, and neopentyl glycol.

[0024] Furthermore, the polyester resin (A) may contain a monool component in addition to the polyol component (x) as needed. Examples of monools include linear or branched alkyl alcohols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol, etc.).

[0025] Of these monools, linear or branched alkyl alcohols having 8 to 24 carbon atoms are preferred from the viewpoint of abrasion resistance, linear alkyl alcohols having 8 to 24 carbon atoms are more preferred, and dodecyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol are even more preferred.

[0026] The polyester resin (A) may also contain a polycarboxylic acid component (y) in addition to terephthalic acid. Examples of polycarboxylic acid components (y) include dicarboxylic acids other than terephthalic acid (y1) and polycarboxylic acids with a valency of three or higher (y2). These may be used individually or in combination of two or more types.

[0027] Examples of dicarboxylic acids (y1) include aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, etc.), aliphatic dicarboxylic acids having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, reparginic acid, and sebacic acid, etc.), alicyclic dicarboxylic acids having 6 to 40 carbon atoms (dimeric acid (dimerized linoleic acid), etc.), alkenedicarboxylic acids having 4 to 36 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid, etc.), and ester-forming derivatives thereof. Here, ester-forming derivatives refer to carboxylic acid anhydrides, alkyl (methyl, ethyl, butyl, stearyl, etc., having 1 to 24 carbon atoms, preferably having 1 to 4 carbon atoms) esters, and partially alkyl esters.

[0028] Of these dicarboxylic acids (y1), aromatic dicarboxylic acids having 8 to 36 carbon atoms, aliphatic dicarboxylic acids having 2 to 50 carbon atoms, and alkene dicarboxylic acids having 4 to 36 carbon atoms are preferred from the viewpoint of achieving both abrasion resistance, water resistance, and storage stability. Phthalic acid, isophthalic acid, adipic acid, succinic acid, maleic acid, and fumaric acid are more preferred, and phthalic acid, isophthalic acid, and adipic acid are even more preferred. Anhydrides or lower alkyl esters of these acids may also be used. In particular, the carboxylic acid component of the polyester resin (A) is preferably isophthalic acid, from the viewpoint of abrasion resistance and water resistance.

[0029] Examples of polycarboxylic acids with a valency of 3 or higher (y2) include aromatic polycarboxylic acids with 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), aliphatic (including alicyclic) tricarboxylic acids with 6 to 36 carbon atoms (such as hexanetricarboxylic acid and decanetricarboxylic acid), and ester-forming derivatives thereof.

[0030] Of these trivalent or higher polycarboxylic acids (y2), aromatic polycarboxylic acids having 9 to 20 carbon atoms are preferred from the viewpoint of achieving both abrasion resistance and water resistance, with trimellitic acid and pyromellitic acid being more preferred. Furthermore, anhydrides or lower alkyl esters of these acids may also be used.

[0031] In the polycarboxylic acid component (y) of the polyester resin (A), the dicarboxylic acid (y1) is preferably 80 to 100 mol%, and more preferably 100 mol%, from the viewpoint of abrasion resistance.

[0032] In one embodiment, dicarboxylic acid (y1) can be derived from biomass-based raw materials. Biomass-based raw materials refer to raw materials derived from plants and microorganisms.

[0033] Examples of biomass-derived dicarboxylic acids include malonic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, and dimer acid.

[0034] Furthermore, the polyester resin (A) may contain monocarboxylic acid components as needed. Examples of monocarboxylic acids include aromatic monocarboxylic acids with 7 to 37 carbon atoms (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.) and aliphatic (including alicyclic) monocarboxylic acids with 2 to 50 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, and behenic acid, etc.).

[0035] Of these monocarboxylic acids, aromatic monocarboxylic acids having 7 to 37 carbon atoms are preferred from the viewpoint of abrasion resistance and storage stability, and benzoic acid is more preferred.

[0036] In the case where the polyester resin (A) is a modified polyester resin containing urethane groups and urea groups, the constituent components of the modified polyester resin containing urethane groups and urea groups include, in addition to the alcohol component and carboxylic acid component mentioned above, polyisocyanate, active hydrogen group-containing compounds, chain extenders, and the like.

[0037] Examples of active hydrogen group-containing compounds include diols having a carboxyl group and 2 to 10 carbon atoms [dialkylol alkanes (e.g., 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, and 2,2-dimethyloloctanoic acid), tartaric acid, etc.], compounds having a sulfo group and 2 to 16 carbon atoms [e.g., 3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid], compounds having a sulfamic acid group and 2 to 10 carbon atoms [e.g., N,N-bis(2-hydroxyethyl)sulfamic acid], etc., and salts obtained by neutralizing these compounds with the neutralizing agents described later. Of these, preferred are diols having a carboxyl group and 2 to 10 carbon atoms, and salts obtained by neutralizing these compounds with a neutralizing agent; more preferred are 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and salts obtained by neutralizing these compounds with a neutralizing agent; and even more preferred are 2,2-dimethylolpropionic acid and salts obtained by neutralizing this compound with a neutralizing agent. The active hydrogen group-containing compound may be used alone or in combination of two or more. When a modified polyester resin contains an active hydrogen group-containing compound as a constituent monomer, it is preferable because it results in an aqueous resin dispersion with small particle size and a sharp particle size distribution.

[0038] Examples of neutralizing agents used to neutralize the above-mentioned active hydrogen group-containing compounds include ammonia, amine compounds having 1 to 20 carbon atoms, and hydroxides of alkali metals (such as sodium, potassium, and lithium). Examples of amine compounds having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine, monoethanolamine, and 2-amino-2-methyl-1-propanol; secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine, and N-methyldiethanolamine; and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, N,N-diethylethanolamine (diethylaminoethanol), and triethanolamine. Of these, ammonia and amine compounds having 1 to 20 carbon atoms are preferred from the viewpoint of the drying properties of the resulting aqueous resin dispersion and the water resistance of the resulting film, and more preferred are ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, dimethylethylamine, and N,N-diethylethanolamine (diethylaminoethanol).

[0039] The weight percentage of the active hydrogen group-containing compound is preferably 2.5 to 7.5% by weight, and more preferably 4.0 to 6.0% by weight, relative to the total weight of the alcohol component, carboxylic acid component, and polyisocyanate, from the viewpoint of the volume-average particle size of the aqueous resin dispersion and storage stability.

[0040] Examples of polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon atoms in the isocyanate groups, the same applies hereinafter) and having two or more isocyanate groups, aliphatic polyisocyanates having 2 to 18 carbon atoms, alicyclic polyisocyanates having 4 to 15 carbon atoms, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms, and derivatives of these polyisocyanates (e.g., isocyanurates). The polyisocyanate component may be used alone, or two or more may be used in combination.

[0041] Examples of aromatic polyisocyanates having 6 to 20 carbon atoms include 1,3- or 1,4-phenylenediisocyanate, 2,4- or 2,6-tolylenediisocyanate (TDI), 4,4'- or 2,4'-diphenylmethanediisocyanate (MDI), 1,5-naphthylenediisocyanate, 4,4',4''-triphenylmethanetriisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, crude MDI, and the like.

[0042] Examples of aliphatic polyisocyanates having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

[0043] Examples of alicyclic polyisocyanates having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate.

[0044] Examples of aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms include m- or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI).

[0045] From the viewpoint of volume-average particle size and mechanical strength of the polyester resin, aromatic polyisocyanates having 6 to 20 carbon atoms and alicyclic polyisocyanates having 4 to 15 carbon atoms are preferred as the polyisocyanate component, and 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, and dicyclohexylmethane-4,4-diisocyanate are more preferred.

[0046] Examples of chain extenders include water, C2-C10 diamines (e.g., ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine, and piperazine), C2-C10 polyalkylene polyamines (e.g., diethylenetriamine, triethylenetetramine, and tetraethylenepentamine), hydrazine or its derivatives (dibasic acid dihydrazides, e.g., adipic acid dihydrazide), C2-C30 polyepoxy compounds (e.g., 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, etc.), and C2-C10 amino alcohols (e.g., ethanolamine, diethanolamine, 2-amino-2-methylpropanol, and triethanolamine). C2-C10 diamines are preferred as chain extenders, secondary diamines are more preferred, and isophoronediamine is even more preferred. When a modified polyester resin contains the above compound as a constituent monomer, the cohesive force of the urethane group portion is improved, and the degree of swelling in water is reduced, resulting in excellent wet friction fastness. Furthermore, the use of diamines is preferable because the generation of carbon dioxide is suppressed by the extension reaction caused by the amine, and the amount of amine carbonate salt produced is reduced, thereby improving storage stability.

[0047] Polyester resin (A) can be obtained by mixing an alcohol component containing ethylene glycol and a carboxylic acid component containing terephthalic acid, and carrying out a polycondensation reaction in the presence of a polymerization catalyst. Furthermore, the ethylene glycol and terephthalic acid components contained in the polyester resin (A) may be derived from PET (polyethylene terephthalate). In this case, the polyester resin (A) can be obtained by mixing PET with other alcohol and carboxylic acid components and carrying out a polycondensation reaction in the presence of a polymerization catalyst.

[0048] Specifically, polyester resin (A) can be produced, for example, as follows: For example, ethylene glycol and terephthalic acid are subjected to a polycondensation reaction in an inert gas (such as nitrogen gas) atmosphere at a reaction temperature preferably 150 to 280°C, more preferably 160 to 250°C, and even more preferably 170 to 235°C. By adding a calcium-containing compound during this reaction, a calcium-containing polyester resin (A) can be obtained. Examples of calcium-containing compounds include calcium carbonate, calcium bicarbonate, calcium chloride, calcium sulfate, calcium oxide, calcium phosphate, calcium hydroxide, calcium hydride, calcium acetate, aliphatic carboxylates of calcium, and aromatic carboxylates of calcium. Furthermore, the reaction time is preferably 30 minutes or more, and more preferably 2 to 40 hours, from the viewpoint of ensuring that the polycondensation reaction is carried out reliably. Reducing the pressure is also effective in improving the reaction rate at the end of the reaction. By using polyester resin synthesized with calcium present, the amount of cyclic compounds in the aqueous resin dispersion is reduced. Reducing the amount of cyclic compounds in the aqueous resin dispersion improves the storage stability of the aqueous resin dispersion and the abrasion resistance of coatings and other materials.

[0049] Furthermore, polyol components other than ethylene glycol and (poly)carboxylic acid components other than terephthalic acid may be added during this reaction. Furthermore, as mentioned above, PET may be mixed in place of ethylene glycol and terephthalic acid, or together with ethylene glycol and terephthalic acid.

[0050] An esterification catalyst can be used as needed at this time. Examples of esterification catalysts include tin-containing catalysts (e.g., dibutyltin oxide), antimony trioxide, titanium-containing catalysts [e.g., titanium alkoxides (e.g., tetrabutoxytitanate), potassium titanate oxalate, titanium terephthalate, titanium terephthalate alkoxide, catalysts described in Japanese Patent Publication No. 2006-243715 {titanium diisopropoxybis(triethanolamine), titanium dihydroxybis(triethanolamine), titanium monohydroxytris(triethanolamine), titanylbis(triethanolamine) and their intramolecular polycondensates, etc.} and catalysts described in Japanese Patent Publication No. 2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate and titanium diisopropoxyditeterephthalate, etc.)], zirconium-containing catalysts (e.g., zirconyl acetate), and zinc acetate. Among these, titanium-containing catalysts are preferred.

[0051] Furthermore, stabilizers may be added to ensure stable polymerization of polyester. Examples of stabilizers include hydroquinone, methylhydroquinone, and hindered phenol compounds.

[0052] If the polyester resin (A) is a modified polyester resin containing urethane groups and urea groups, the polyester resin (A) can be obtained simultaneously with the aqueous resin dispersion by the method shown below.

[0053] Polyester resin (A) contains calcium in the range of 10 to 4000 ppm as measured by X-ray fluorescence analysis. Preferably, it contains calcium in the range of 100 to 4000 ppm. The calcium content of polyester resin (A) can be determined by adjusting the amount of calcium-containing compound added during the manufacturing of polyester resin (A). In this specification, the determination of calcium content by X-ray fluorescence analysis is described below.

[0054] <Sample adjustment> A pressure molding method can be used to compress polyester resin powder into pellets. For example, a 5mm thick ring made of polyvinyl chloride resin can be filled with enough powder to form a slight mound in the center, and then pressed with a press machine under a load of 10t to form pellets. Care must be taken to avoid contamination by other components, especially calcium, during this process. In the case of an aqueous resin dispersion, the film obtained by drying the aqueous resin dispersion at 105°C for 3 hours can be pelletized using the same method as described above. <Measurement Method> A calibration curve can be prepared using standard samples with known calcium concentrations, and the analytical value can be determined from the X-ray intensity of the analytical sample. Alternatively, if the majority of the resin composition is known, the approximate content can be determined using the fundamental parameter method (FP method). However, since the FP method is relatively inaccurate, it is preferable to use a calibration curve method that can measure calcium concentration more accurately. <Measuring device> For example, it can be measured using an X-ray fluorescence analyzer (Axios, manufactured by Malvern Panalytical).

[0055] From the viewpoint of storage stability, the acid value of polyester resin (A) is preferably 0 to 40 mg KOH / g, and more preferably 0.1 to 30 mg KOH / g. The acid value can be measured using the method specified in JIS K0070.

[0056] The glass transition temperature of the polyester resin (A) is preferably -50 to 100°C, and more preferably -30 to 80°C, from the viewpoint of abrasion resistance. The glass transition temperature (Tg) of polyester resin (A) can be determined by the method specified in ASTM D3418-82 (DSC method). For measuring the glass transition temperature (Tg), for example, a DSC Q20 manufactured by TA Instruments Co., Ltd. can be used. The glass transition temperature (Tg) can be measured under the following conditions. <Measurement conditions> (1) Increase the temperature from 30°C to 150°C at a rate of 20°C / min. (2) Hold at 150°C for 10 minutes (3) Cool to -35°C at 20°C / min (4) Hold at -35°C for 10 minutes. (5) Heat up to 150°C at a rate of 20°C / min (6) The differential scanning calorimetry curve measured in process (5) is analyzed, and the position of the inflection point is defined as the glass transition temperature.

[0057] Furthermore, the peak-top average molecular weight of the polyester resin (A) is preferably 3,000 to 20,000, and more preferably 4,000 to 18,000, from the viewpoint of abrasion resistance, water resistance, and storage stability.

[0058] In the present invention, the peak-top average molecular weight can be measured using gel permeation chromatography (GPC) under the following conditions. Equipment (example): HLC-8120 manufactured by Tosoh Corporation Column (example): TSK GEL GMH6 (2 pieces) [Manufactured by Tosoh Corporation] Measurement temperature: 40℃ Sample solution: 0.25% by weight THF solution Solution injection volume: 100μL Detection device: Refractive index detector Reference material: 12 samples of standard polystyrene (TSKstandard POLYSTYRENE) manufactured by Tosoh Corporation (molecular weights: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) To measure the molecular weight, the sample is dissolved in tetrahydrofuran (THF) to a concentration of 0.25% by weight, and the undissolved portion is filtered out using a PTFE filter with a 220 nm aperture to obtain the sample solution.

[0059] In one embodiment, the biomass concentration in the polyester resin (A) is preferably 1% by weight or more, more preferably 10% by weight or more, and even more preferably 20% by weight or more, from the viewpoint of resolving the depletion of petroleum resources and considering the environment. The above biomass concentration refers to the weight ratio (percentage) of constituent monomers derived from biomass to the total amount of alcohol components and carboxylic acid components, excluding PET flakes from the polyester resin (A).

[0060] The method for producing the aqueous resin dispersion of the present invention is not particularly limited, as long as it includes a step of mixing the organic solvent solution of the polyester resin obtained by the production method of the present invention with an aqueous medium.

[0061] Examples of methods for producing an aqueous resin dispersion containing polyester resin (A) include the following methods [1] to [3].

[0062] [1] A method for producing a polyester resin solution by dissolving polyester resin (A) in an organic solvent, then, if necessary, dispersing the carboxyl groups of the polyester resin as salts with a neutralizing agent such as triethylamine in an aqueous medium, and then, if necessary, distilling off the organic solvent.

[0063] [2] A method for producing polyester resin (A) by polycondensing an alcohol component and a carboxylic acid component in the presence of a catalyst and additives, reacting a polyisocyanate and, if necessary, a chain extender in one or multiple steps in the presence or absence of an organic solvent, and if necessary, dispersing the carboxyl group as a salt with a neutralizing agent such as triethylamine in an aqueous medium, and then distilling off the organic solvent if necessary.

[0064] [3] A method comprising: polycondensing an alcohol component and a carboxylic acid component in the presence of a catalyst and additives to obtain a polyester resin; reacting the polyisocyanate with the polyisocyanate in one or more steps in the presence or absence of an organic solvent to produce a polyester resin having isocyanate groups; then, if necessary, dispersing the carboxyl groups in the polyester resin as a salt in an aqueous medium with a neutralizing agent such as triethylamine; reacting the chain extender with the isocyanate groups; and, if necessary, distilling off the organic solvent.

[0065] Of the methods [1] to [3], method [3] is preferred from the viewpoint of storage stability of the modified polyester resin and mechanical strength of the dried film.

[0066] In the case of [1], in the step of dispersing the polyester resin (A) in an aqueous medium, it is preferable to use a rotary dispersion and mixing apparatus as described later, and the temperature is preferably 60°C or lower, and more preferably 40°C or lower. The dispersion time can be appropriately selected depending on the apparatus used, but is generally preferably 1 minute to 2 hours, and more preferably 3 minutes to 1 hour. In the case of [2] or [3], the formation of the modified polyester resin is preferably carried out by a reaction at 20°C to 150°C, more preferably 60°C to 110°C, and the reaction time is preferably 2 to 20 hours. The formation of the modified polyester resin can be carried out in or without the presence of an organic solvent, as described later, but it is preferable to carry it out in or without the presence of an organic solvent that is substantially inactive with isocyanate groups, and tetrahydrofuran is even more preferable.

[0067] Examples of organic solvents that are substantially nonreactive with isocyanate groups include ketone solvents, ester solvents, ether solvents, amide solvents, and aromatic hydrocarbon solvents.

[0068] In the production of aqueous resin dispersions, catalysts commonly used in urethane reactions may be used, if necessary, to accelerate the reaction of the modified polyester resin. Examples of catalysts include amine catalysts, such as triethylamine, N-ethylmorpholine, triethylenediamine, and cycloamidines described in U.S. Patent No. 4,524,104 [e.g., 1,8-diaza-bicyclo(5,4,0)undecene-7 (manufactured by Sunapro, DBU)]; tin-based catalysts, such as dibutyltin dilaurylate, dioctyltin dilaurylate, and tin octoate; and titanium-based catalysts, such as tetrabutoxytitanate.

[0069] In the method for producing an aqueous resin dispersion of the present invention, examples of organic solvents for the organic solvent solution of polyester resin (A) include aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halogen solvents, esters, ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixed solvents of two or more of these. Specific examples of organic solvents include aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene, and tetralin, etc.); aliphatic or alicyclic hydrocarbon solvents (n-hexane, n-heptane, mineral spirits, and cyclohexane, etc.); halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylenedichloride, carbon tetrachloride, trichloroethylene, and perchloroethylene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl acetate Examples of organic solvents include ether solvents such as Rosolve and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, and benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; and mixed solvents of two or more of these. Among the above organic solvents, volatile ones with a boiling point of less than 100°C are preferred. Preferred organic solvents include ethyl acetate, acetone, tetrahydrofuran, and methyl ethyl ketone.

[0070] The amount of organic solvent used per 100 parts by weight of polyester resin is preferably 25 to 300 parts by weight, more preferably 25 to 150 parts by weight, and even more preferably 25 to 100 parts by weight.

[0071] In the method for producing the aqueous resin dispersion of the present invention, the aqueous solvent used in the step of mixing the organic solvent solution of polyester resin (A) with an aqueous solvent can be any liquid in which water is an essential component, and can be water, an aqueous solution of an organic solvent, an aqueous solution of a surfactant (s) as described later, an aqueous solution of a water-soluble polymer (t), or a mixture of two or more of these.

[0072] To improve the dispersibility of polyester resin (A) in aqueous solvents, a neutralizing agent may be used to neutralize the carboxyl groups of polyester resin (A). Examples of neutralizing agents include organic compounds such as ammonia and triethylamine, and inorganic compounds such as sodium hydroxide.

[0073] The amount of neutralizing agent used is preferably 1 to 150 mol%, more preferably 5 to 100 mol%, relative to the carboxyl groups of the polyester resin (A), from the viewpoint of dispersibility.

[0074] When dispersing the polyester resin (A) in an aqueous solvent, known surfactants (s) and inorganic dispersants can be used as emulsifiers or dispersants as needed.

[0075] The surfactant (s) is not particularly limited and includes anionic surfactants (s-1), cationic surfactants (s-2), amphoteric surfactants (s-3), and nonionic surfactants (s-4). The surfactant (s) may also be a combination of two or more surfactants.

[0076] Examples of anionic surfactants (s-1) include carboxylic acids or their salts, sulfate esters, carboxymethylated salts, sulfonates, and phosphate esters. Examples of cationic surfactants (S-2) include quaternary ammonium salt type surfactants and amine salt type surfactants. Examples of amphoteric surfactants (S-3) include carboxylate-type amphoteric surfactants, sulfate-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate-type amphoteric surfactants. Examples of nonionic surfactants (s-4) include AO-added nonionic surfactants and polyhydric alcohol-type nonionic surfactants. Specific examples of these surfactants (s) include those described in Japanese Patent Publication No. 2002-284881.

[0077] Examples of inorganic dispersants include polyvalent metal phosphate salts such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; inorganic salts such as calcium metasilicate, calcium sulfate, and barium sulfate; and inorganic compounds such as magnesium hydroxide and aluminum hydroxide.

[0078] When dispersing polyester resin (A) in an aqueous solvent, a known water-soluble polymer (t) can be used as an emulsifier or dispersant.

[0079] Examples of water-soluble polymers (t) include cellulose compounds (e.g., methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose and their saponified products), gelatin, starch, dextrin, acacia gum, chitin, chitosan, polyethylene glycol, and the like.

[0080] The method of dispersion when mixing the organic solvent solution of the polyester resin (A) of the present invention with an aqueous medium is not particularly limited, but it is preferable to use a rotary dispersion mixer, an ultrasonic disperser, or a kneader, and among these, a rotary dispersion mixer, which has particularly excellent dispersion capabilities, is even more preferable.

[0081] Examples of rotary dispersion mixing devices include mixing devices with common agitators such as MaxBlend and helical blades, TK Homomixer [Primix Co., Ltd.], Creamix [M-Technique Co., Ltd.], Philmix [Primix Co., Ltd.], UltraTarlux [IKA Co., Ltd.], Ebara Milder [Ebara Corporation], Cavitron (Eurotech Co., Ltd.), and Biomixer [Nippon Seiki Co., Ltd.].

[0082] The amount of aqueous medium used per 100 parts by weight of the organic solvent solution of polyester resin (A) is preferably 100 to 500 parts by weight, more preferably 150 to 400 parts by weight, and even more preferably 150 to 300 parts by weight.

[0083] From the viewpoint of storage stability, the particle size of the particles in the aqueous resin dispersion is preferably 20 to 300 nm, more preferably 35 to 200 nm. In this invention, particle size refers to the volume-average particle size. The particle size can be measured and determined by light scattering measurement.

[0084] The aqueous resin dispersion of the present invention is preferably used as an aqueous resin dispersion for inkjet inks from the viewpoint of the abrasion resistance and water resistance of the coating film obtained by drying the aqueous resin dispersion. The aqueous resin dispersion of the present invention can be used in the manufacture of inkjet inks. Inkjet inks preferably contain pigments in addition to the aqueous resin dispersion of the present invention. Inkjet inks may contain humectants, penetrating agents, etc.

[0085] The solid content of the aqueous resin dispersion of the present invention in the inkjet ink is preferably 0.1 to 60% by weight, more preferably 1 to 20% by weight, based on the weight of the inkjet ink. The content of the aqueous resin dispersion is preferably 1 to 90% by weight, more preferably 5 to 50% by weight, based on the weight of the inkjet ink.

[0086] The pigment content is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the weight of the inkjet ink. The humectant content is preferably 0.1 to 90% by weight, more preferably 1 to 50% by weight, based on the weight of the inkjet ink.

[0087] Examples of pigments include conventionally known organic and inorganic pigments (for example, white pigments, black pigments, gray pigments, red pigments, brown pigments, yellow pigments, green pigments, blue pigments, purple pigments and metallic pigments, naturally occurring organic pigments, synthetic organic pigments, nitroso pigments, nitro pigments, pigment-type azo pigments, azo lakes made from water-soluble dyes, azo lakes made from poorly soluble dyes, lakes made from basic dyes, lakes made from acid dyes, xanthan lakes, anthraquinone lakes, pigments and phthalocyanine pigments from vat dyes, and organic pigments such as daylight fluorescent pigments).

[0088] Examples of specific organic and inorganic pigments are given below. Examples of white pigments include inorganic pigments such as titanium dioxide, zinc oxide, zinc sulfide, antimony oxide, and zirconium oxide. In addition to inorganic pigments, hollow resin microparticles and polymer microparticles can also be used. The average particle size of the pigment is preferably 200-300 nm. If the average particle size is less than 200 nm, the opacity tends to be insufficient, and if it exceeds 300 nm, the discharge stability tends to be insufficient.

[0089] In particular, titanium dioxide is preferred from the viewpoint of opacity. Similarly, the average particle size of the titanium dioxide is preferably 200 to 300 nm.

[0090] Examples of pigments for magenta include CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 48:1, CI Pigment Red 53:1, CI Pigment Red 57:1, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 139, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 178, and CI Pigment Red 222.

[0091] Pigments for yellow are not particularly limited, but examples include CI Pigment Orange 31, CI Pigment Orange 43, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 17, CI Pigment Yellow 74, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 128, CI Pigment Yellow 138, and Pigment Yellow 180.

[0092] Pigments for cyan are not particularly limited, but examples include CI Pigment Blue 15, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 16, CI Pigment Blue 60, and CI Pigment Green 7.

[0093] Moisturizers are used as moisturizing ingredients in water-based inks. Examples of humectants, though not particularly limited, include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol, polyethylene glycol with Mn of 2,000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, glycerin, mesoerythritol, pentaerythritol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. A single humectant may be used, or two or more may be used in combination.

[0094] Penetrants play a role in promoting the penetration of inkjet ink into permeable media. Penetrants are not particularly limited, but examples include glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monobutyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether Organic solvents such as nonpropyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether (e.g., nonpropyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether) and aliphatic diols having 4 to 8 carbon atoms (1,2-alkyl diols such as 1,2-pentanediol and 1,2-hexanediol, and linear alcohols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol); acetylene glycol-based surfactants; acetylene alcohol-based surfactants; ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and polyoxyalkylene alkyl ether;Examples of surfactants include ester-based surfactants such as polyoxyethylene oleic acid, polyoxyethylene oleic acid esters, polyoxyethylene distearate esters, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, and polyoxyethylene stearate; silicone-based surfactants such as dimethylpolysiloxane; and fluorine-based surfactants such as fluorinated alkyl esters and perfluoroalkyl carboxylates. Penetrating agents may be used individually or in combination of two or more.

[0095] In addition to the polyester resin (A) in the aqueous resin dispersion of the present invention, other aqueous media dispersible resins or water-soluble resins may be used in combination with the inkjet ink as needed, for purposes such as assisting in film formation or improving binder function.

[0096] Other aqueous media dispersible resins or water-soluble resins used in combination with inkjet inks include, for example, aqueous media dispersible or water-soluble polyester resins other than polyester resin (A) in the present invention, polyacrylic resins, and polyurethane resins.

[0097] Inkjet ink may further contain one or more of the following: pH adjusters, viscosity adjusters, defoamers, preservatives, degradation inhibitors, stabilizers, antifreeze agents, and water.

[0098] The inkjet ink containing the resin aqueous dispersion of the present invention can be suitably used, for example, as an inkjet ink for coated paper for printing, corrugated cardboard, and cotton fabrics. While not particularly limited, the printing method using the inkjet ink can include home printing, business printing, sign graphics printing, and pigment printing.

[0099] The aqueous resin dispersion of the present invention is preferably used as an aqueous resin dispersion for surface modifiers for recording media, from the viewpoint of the abrasion resistance of the coating film obtained by drying the aqueous resin dispersion. A surface modifier for recording media is a material that imparts abrasion resistance, hydrophilicity, antifouling properties, etc., to the surface of a recording media, and a recording media is a material on which characters, figures, images, etc., are recorded by various printing methods. By using the aqueous resin dispersion of the present invention as a surface modifier for recording media, the abrasion resistance of the recording media can be improved. The aqueous resin dispersion of the present invention can be used in the manufacture of surface modifiers for recording media. The surface modifier for recording media may, if necessary, partially use organic solvents other than water, for example, water-soluble organic solvents. A water-soluble organic solvent refers to an organic solvent that can be mixed with water in any proportion.

[0100] The water-soluble organic solvent used is not particularly limited, and specific examples include methanol, ethanol, isopropyl alcohol, acetone, dioxane, dimethylformamide, dimethylacetamide, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexa Examples include polyhydric alcohols such as hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, and 2,2,4-trimethyl-1,3-pentanediol; polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; and polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

[0101] The solid content of the aqueous resin dispersion of the present invention in the surface modifier for recording media is preferably 0.1 to 60% by weight, more preferably 1 to 20% by weight, based on the weight of the surface modifier for recording media.

[0102] The surface modifier for recording media may contain the above-mentioned nonionic surfactant (s-4) as needed. These may be used individually or in combination of two or more.

[0103] The surface modifier for recording media may optionally contain a water-soluble nonionic polymer. Examples of water-soluble nonionic polymers include polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylamide. These may be used individually or in combination of two or more.

[0104] The surface modifier for recording media may further contain one or more viscosity modifiers, defoaming agents, preservatives, degradation inhibitors, and stabilizers.

[0105] The surface modifier for recording media containing the resin aqueous dispersion of the present invention can be suitably used, for example, for surface modification of permeable and impermeable recording media. Permeable recording media are not particularly limited, but examples include paper media such as fine paper, art paper, coated paper, and cast coated paper. Non-permeable recording media are not particularly limited, but examples include resin media such as polycarbonate, rigid PVC, flexible PVC, polystyrene, expanded polystyrene, polymethyl methacrylate, polypropylene, polyethylene, and polyethylene terephthalate, as well as metal media such as glass and stainless steel.

[0106] The aqueous resin dispersion of the present invention is preferably used as an aqueous resin dispersion for textile treatment agents from the viewpoint of the abrasion resistance of the coating film obtained by drying the aqueous resin dispersion. A textile treatment agent is a material that imparts abrasion resistance, permeability, and bleeding properties to the surface of a fiber. By using the aqueous resin dispersion of the present invention as a textile treatment agent, the abrasion resistance of the fiber can be improved. The aqueous resin dispersion of the present invention can be used in the manufacture of textile treatment agents. In addition to the aqueous resin dispersion of the present invention, the textile treatment agent may contain dispersants, pH adjusters, preservatives and antifungal agents, chelating reagents, rust inhibitors, ultraviolet absorbers, viscosity modifiers, colorfastness inhibitors, surface tension modifiers, defoamers, and water.

[0107] The solid content of the aqueous resin dispersion of the present invention in the textile treatment agent is preferably 0.1 to 60% by weight, more preferably 1 to 20% by weight, based on the weight of the textile treatment agent.

[0108] The fibers to which the fiber treatment agent containing the resin aqueous dispersion of the present invention is used are not particularly limited, but examples include natural fibers such as cotton and wool, and synthetic fibers such as polyester, nylon, and polypropylene.

[0109] The aqueous resin dispersion of the present invention is preferably used as an aqueous resin dispersion for water-based paints from the viewpoint of the abrasion resistance of the coating film obtained by drying the aqueous resin dispersion. The aqueous resin dispersion of the present invention can be used in the manufacture of water-based paints. Water-based paints preferably contain pigments in addition to the aqueous resin dispersion of the present invention. Furthermore, they may contain a coating film-forming auxiliary resin, a crosslinking agent, a pigment dispersant, a viscosity modifier, an antifoaming agent, a preservative, a degradation inhibitor, a stabilizer, and an antifreeze agent.

[0110] The solid content of the aqueous resin dispersion of the present invention in an aqueous paint is preferably 20 to 60% by weight, and more preferably 30 to 50% by weight, based on the weight of the aqueous paint.

[0111] Examples of resins used to aid in film formation include polyacrylic resins and polyurethane resins. The content of the film-forming auxiliary resin is usually 40% by weight or less, preferably 30% by weight or less, based on the weight of the water-based paint.

[0112] Examples of crosslinking agents include water-soluble or water-dispersible amino resins, water-soluble or water-dispersible polyepoxides, water-soluble or water-dispersible polyisocyanate compounds, and polyethylene urea. The amount of crosslinking agent added is usually 0 to 30% by weight, preferably 0.1 to 20% by weight, based on the solid content weight of the aqueous dispersion.

[0113] Examples of pigments include inorganic pigments with a water solubility of 1 or less, such as white pigments, black pigments, gray pigments, red pigments, brown pigments, yellow pigments, green pigments, blue pigments, purple pigments, and metallic pigments; and organic pigments, such as natural organic pigments, synthetic organic pigments, nitroso pigments, nitro pigments, pigment-type azo pigments, azo lakes made from water-soluble dyes, azo lakes made from poorly soluble dyes, lakes made from basic dyes, lakes made from acid dyes, xanthan lakes, anthraquinone lakes, pigments from vat dyes, and phthalocyanine pigments. The pigment content is usually 50% by weight or less, preferably 30% by weight or less, based on the weight of the water-based paint.

[0114] Examples of pigment dispersants include various surfactants [anionic, cationic, nonionic, amphoteric] and high molecular weight emulsifying dispersants (Mn 1,000 to 20,000), with high molecular weight emulsifying dispersants being preferred. The content of the pigment dispersant is usually 20% by weight or less, preferably 15% by weight or less, based on the weight of the pigment.

[0115] Examples of viscosity modifiers include thickeners such as inorganic viscosity modifiers (e.g., sodium silicate and bentonite), cellulose viscosity modifiers (e.g., methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, etc., with Mn usually 20,000 or more), protein-based (e.g., casein, sodium caseinate, ammonium caseinate), acrylic-based (e.g., sodium polyacrylate, ammonium polyacrylate, etc., with Mn usually 20,000 or more), and vinyl-based (e.g., polyvinyl alcohol, with Mn usually 20,000 or more). The content of the viscosity modifier is usually 5% by weight or less, preferably 3% by weight or less, based on the weight of the water-based paint.

[0116] Examples of defoaming agents include long-chain alcohols (such as octyl alcohol), sorbitan derivatives (such as sorbitan monooleate), and silicone oils (such as polymethylsiloxane and polyether-modified silicone). The content of the defoaming agent is usually 5% by weight or less, preferably 3% by weight or less, based on the weight of the water-based paint.

[0117] Examples of preservatives include organic nitrogen sulfur compound-based preservatives and organic sulfur halide-based preservatives. The preservative content is usually 5% by weight or less, preferably 3% by weight or less, based on the weight of the water-based paint.

[0118] Examples of degradation inhibitors and stabilizers (UV absorbers, antioxidants, etc.) include hindered phenols, hindered amines, hydrazines, phosphorus, benzophenones, and benzotriazoles. The content of degradation inhibitors and stabilizers (UV absorbers, antioxidants, etc.) is usually 5% by weight or less, preferably 3% by weight or less, based on the weight of the water-based paint.

[0119] Examples of antifreeze agents include ethylene glycol and propylene glycol. The content of the antifreeze agent is usually 5% by weight or less, preferably 3% by weight or less, based on the weight of the water-based paint.

[0120] A solvent may be added to the water-based paint. Examples of solvents that can be added include monohydric alcohols (methanol, ethanol, propanol, etc.), glycols (ethylene glycol, propylene glycol, diethylene glycol, etc.), trihydric or higher alcohols (GL, etc.), and cellosolves (methyl and ethyl cellosolve, etc.). The content of the added solvent is preferably 20% by weight or less, and more preferably 15% by weight or less, of the weight of the water-based paint.

[0121] The solid content concentration of the water-based paint is preferably 20-70% by weight, and more preferably 30-60% by weight.

[0122] This specification discloses the following:

[0123] This disclosure (1) is an aqueous resin dispersion comprising a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component, The alcohol component comprises ethylene glycol, and the carboxylic acid component comprises terephthalic acid. The aforementioned polyester resin (A) is an aqueous resin dispersion characterized by containing calcium in the range of 10 to 4000 ppm as measured by X-ray fluorescence analysis.

[0124] Disclosure (2) is an aqueous resin dispersion according to Disclosure (1) wherein the alcohol component of the polyester resin (A) comprises a branched alkylene glycol or an alkylene oxide adduct of bisphenol A having 3 to 10 carbon atoms.

[0125] Disclosure (3) is an aqueous resin dispersion according to Disclosure (1) or (2) wherein the carboxylic acid component of the polyester resin (A) contains isophthalic acid.

[0126] Disclosure (4) is an aqueous resin dispersion according to any one of Disclosures (1) to (3), wherein the aqueous resin dispersion is for use as an inkjet ink.

[0127] Disclosure (5) is an aqueous resin dispersion according to any one of Disclosures (1) to (3), wherein the aqueous resin dispersion is for use as a surface modifier for recording media.

[0128] Disclosure (6) is an aqueous resin dispersion according to any one of Disclosures (1) to (3), wherein the aqueous resin dispersion is for use as a treatment agent for fibers.

[0129] Disclosure (7) is an aqueous resin dispersion according to any one of the disclosures (1) to (3), wherein the aqueous resin dispersion is for use in aqueous coatings. [Examples]

[0130] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0131] <Manufacturing Example 1> [Manufacturing of Polyester Resin (A-1)] In a reaction vessel equipped with a condenser, thermometer, stirrer, and nitrogen inlet tube, 148 parts neopentyl glycol, 34 parts trimethylolpropane, 692 parts PET flakes (commercial PET bottles cut into 1 cm cubes), 207 parts isophthalic acid, 2 parts calcium carbonate, and 1 part tetrabutoxytitanate as a condensation catalyst were added. The reaction was carried out at 200°C under a nitrogen stream for 6 hours, while distilling off the water produced. The reaction was further carried out under reduced pressure of 0.5 to 2.5 kPa, and the reactants were removed from the reaction vessel to obtain polyester resin (A-1). The physical properties of polyester resin (A-1) are shown in Table 1.

[0132] <Manufacturing Examples 2-7, Comparative Manufacturing Example 2> In a reaction vessel equipped with a condenser, a stirrer, and nitrogen inlet tube, the alcohol and carboxylic acid components listed in Table 1 were charged, and the reaction was carried out in the same manner as in Production Example 1, yielding polyester resins (A-2) to (A-7) and (A'-2). The physical properties of each polyester resin are shown in Table 1.

[0133] <Comparative Manufacturing Example 1> [Manufacturing of Polyester Resin (A'-1)] In a reaction vessel equipped with a condenser, thermometer, stirrer, and nitrogen inlet, 106 parts ethylene glycol, 504 parts bisphenol A·PO2 molar adduct, 283 parts terephthalic acid, 210 parts isophthalic acid, 14 parts trimellitic anhydride, and 1 part tetrabutoxytitanate as a condensation catalyst were added. The reaction was carried out at 200°C under a nitrogen stream for 6 hours, while distilling off the water produced. The reaction was further carried out under reduced pressure of 0.5 to 2.5 kPa to obtain polyester resin (A'-1). The physical properties of polyester resin (A'-1) are shown in Table 1.

[0134] The details of the biomass-derived raw materials in Table 1 are as follows: • RADIANOL 4713: Biomass-derived propylene glycol [Manufactured by OLEON] • Biomass-derived 1,4-butanediol: 100% plant-derived 1,4-butanediol made from sugarcane and corn [Genomatica 1,4-butanediol] • Biomass-derived sebacic acid: Sebacic acid made from castor oil [Sebacic acid manufactured by Toyokuni Seiyu Co., Ltd.] Furthermore, the biomass concentration (weight %) shown in Table 1 represents the proportion (weight %) of biomass-derived raw materials to the total of alcohol and carboxylic acid components, and does not take into account the weights of PET flakes, other components, catalysts, and additives shown in Table 1.

[0135] <Example 1> A tetrahydrofuran solution of polyester resin (A-1) was prepared by charging 100 parts of polyester resin (A-1) and 100 parts of tetrahydrofuran into a simple pressurized reaction apparatus equipped with a stirrer and a heating device, and heating and stirring to 70°C. Next, 3.6 parts of triethylamine as a neutralizing agent were added to the tetrahydrofuran solution of the obtained polyester resin (A-1) and homogenized. Then, 250 parts of deionized water as an aqueous medium were added while stirring at 200 rpm to disperse the polyester resin (A-1) in water. The resulting dispersion was heated to 60°C under reduced pressure to remove the tetrahydrofuran by distillation. After that, water was added to adjust the solid content concentration to 30% by weight to obtain the aqueous resin dispersion (X-1).

[0136] <Examples 2-7, Comparative Examples 1-2> Resin aqueous dispersions (X-2) to (X-7) and (X'-1) were obtained in the same manner as in Example 1, except that the amount of raw materials used was changed to those listed in Table 2. In Comparative Example 2, which used polyester resin (A'-2), the resin aggregated during the distillation of tetrahydrofuran by heating the dispersion under reduced pressure to 60°C, and an aqueous resin dispersion could not be obtained.

[0137] <Manufacturing Example 8, Example 8> In a reaction vessel equipped with a condenser, thermometer, stirrer, and nitrogen inlet tube, 16.7 parts neopentyl glycol, 36.6 parts PET flakes (commercial PET bottles cut into 1 cm cubes), 6.7 parts isophthalic acid, 11.3 parts adipic acid, 0.13 parts calcium carbonate, and 0.07 parts tetrabutoxytitanate as a condensation catalyst were added. The mixture was reacted at 200°C under a nitrogen stream for 6 hours while distilling off the water produced, and then further reacted under reduced pressure of 0.5 to 2.5 kPa. Next, 0.48 parts of 1,4-butanediol, 5.0 parts of 2,2-dimethylolpropionic acid as an active hydrogen group-containing compound, 26.6 parts of 4,4'-diphenylmethanediisocyanate as a polyisocyanate, and 100 parts of tetrahydrofuran as an organic solvent for the reaction were charged, and the reaction was carried out by stirring at 70°C for 12 hours to produce a tetrahydrofuran solution of polyester resin (A-8). Next, 3.8 parts of triethylamine, used as a neutralizing agent, were added to the obtained tetrahydrofuran solution of polyester resin to homogenize it. Then, 250 parts of deionized water, used as an aqueous medium, were added while stirring at 200 rpm to disperse the polyester resin in water. To the obtained dispersion, 10.6 parts of a 10% by weight aqueous solution of isophorone diamine, used as an extension agent, were added under stirring to carry out the extension reaction for 30 minutes. The mixture was then heated under reduced pressure to 60°C to remove the tetrahydrofuran by distillation. After that, water was added to adjust the solid content concentration to 30% by weight to obtain an aqueous resin dispersion (X-8).

[0138] <Manufacturing Examples 9-10, Examples 9-10> Resin aqueous dispersions (X-9) to (X-10) were obtained in the same manner as in Production Example 8 and Example 8, except that the amount of raw materials used was changed to those listed in Tables 1 and 2.

[0139] [Evaluation Method] <Method for evaluating particle size of aqueous resin dispersions> The volume-average particle size (Dv) was measured using a light scattering particle size distribution analyzer [Horiba, Ltd. "LA950 V2"]. The measurement results are shown in Table 2.

[0140] <Method for evaluating the storage stability of aqueous resin dispersions> A polyester resin aqueous dispersion was left to stand for one week at 70°C in a circulating air dryer [SPH-201 manufactured by ESPEC Corporation], and the particle size after removal was measured using the method described above. The rate of change was calculated from the particle size measurements before and after the test, and the rate of change in particle size was classified as follows to evaluate long-term stability. ◎: Less than 20% ○: 20% or more, less than 40% ×: 40% or more

[0141] <Manufacturing of inkjet inks (L-1) to (L-10) and (L'-1)> Inkjet inks (L-1) to (L-10) and (L'-1) were prepared by placing 2.7 parts of the resin aqueous dispersion (X-1) to (X-10) or (X'-1) obtained in Examples 1 to 10 or Comparative Example 1, 25 parts of pigment [carbon black aqueous dispersion {Aqua-Black 162 manufactured by Tokai Carbon Co., Ltd., solid content concentration 20% by weight}], 10 parts of propylene glycol as a humectant, 1.0 part of 1,2-hexanediol as a penetrating agent, 1.0 part of 2-pyrrolidone, and 63 parts of water into a container and mixing for 10 minutes.

[0142] <Method for evaluating the abrasion resistance of inkjet ink> Test specimens were prepared by coating polyester film (PET) [Toyobo Co., Ltd.'s "Espet E-5102" (thickness 12 μm)] with inkjet inks (L-1) to (L-10) and a comparative inkjet ink (L'-1) using a bar coater so that the thickness after drying was 1 μm, and drying at 90°C for 10 minutes, thereby coating each resin film with polyester resin. Abrasion resistance tests were conducted on the inkjet ink-coated surface of the fabricated test specimens using a Japan Society for the Promotion of Science (JSPS) type friction fastness tester. A friction element fitted with a 60mm x 60mm cotton cloth (Kanakin No. 3) was rubbed back and forth 100 times with a load of 200g. The images after the test were analyzed using image processing software [product name "WinROOF", version 5.5, manufactured by Mitani Corporation], and the area of ​​the remaining image (S) was determined. A ) and the area rubbed with the JSPS-type friction fastness tester (S BThe image retention rate was determined using the following formula, and the scratch resistance of the inkjet ink was evaluated according to the following criteria. Survival rate (%)=100×S A / S B ◎: Image retention rate is 70-100% ○: Image retention rate is 50-69% ×: Image retention rate is less than 50%

[0143] <Method for evaluating the water resistance of inkjet ink> Test specimens were prepared by coating polyester film (PET) [Toyobo Co., Ltd.'s "Espet E-5102" (thickness 12 μm)] with inkjet inks (L-1) to (L-10) and a comparative inkjet ink (L'-1) using a bar coater so that the thickness after drying was 1 μm, and drying at 90°C for 10 minutes, thereby coating each resin film with polyester resin. A water resistance test was conducted on the inkjet ink-coated surface of the prepared test specimens using a Japan Society for the Promotion of Science (JSPS) type friction fastness tester. A 60mm x 60mm cotton cloth (Kanakin No. 3) was moistened with 0.3g of water, and then rubbed 100 times back and forth with a friction element attached, under a load of 200g. The image retention rate after the test was determined in the same manner as described above, and the water resistance of the inkjet ink was evaluated according to the following criteria. ◎: Image retention rate is 70-100% ○: Image retention rate is 50-69% ×: Image retention rate is less than 50%

[0144] <Manufacturing of surface modifier (M-1) for recording media> A surface modifier for recording media (M-1) was prepared by mixing 60 parts of deionized water and 10 parts of an aqueous resin dispersion (X-1).

[0145] <Manufacturing of surface modifiers (M-2) to (M-10) and (M'-1) for recording media> Using the same method as described above, surface modifiers for recording media (M-2) to (M-10) and (M'-1) were manufactured using aqueous resin dispersions (X-2) to (X-10) and (X'-1) instead of aqueous resin dispersion (X-1).

[0146] <Method for evaluating the abrasion resistance of surface modifiers for recording media> Surface modifiers for recording media (M-1) to (M-10) and a comparative surface modifier for recording media (M'-1) were applied to coated printing paper [high-grade art paper manufactured by Mitsubishi Paper Mills Ltd.] using a bar coater so that the thickness after drying was 1 μm. The paper was dried at 70°C for 2 minutes to prepare test pieces (4 cm x 12 cm) on which polyester resin was coated onto the coated printing paper. The prepared test specimens were attached to the measurement area of ​​a speed-variable friction measuring machine [(Trinity Lab Co., Ltd. Tribomaster μv1000)], and a 1cm x 1cm cotton cloth (Kanakin No. 3) was attached to the indenter with double-sided tape. A load of 200g was then applied, and 100 reciprocations were performed with a friction stroke of 2cm and a friction speed of 2400mm / min. The fuzziness of the surface of the test specimens after the test was visually judged, and the abrasion resistance of the surface modifier for recording media was evaluated according to the following criteria. ◎: No pilling ○: Some pilling is visible. ×: Fraying is visible throughout.

[0147] <Manufacturing of textile treatment agent (N-1)> Sixty parts of deionized water and ten parts of a resin aqueous dispersion (X-1) were mixed to produce a textile treatment agent (N-1).

[0148] <Manufacturing of textile treatment agents (N-2) to (N-10) and (N'-1)> Using the same method as described above, fiber treatment agents (N-2) to (N-10) and (N'-1) were prepared using aqueous resin dispersions (X-2) to (X-10) and (X'-1) instead of aqueous resin dispersion (X-1).

[0149] <Method for evaluating the abrasion resistance of textile treatment agents> Plain cotton broadcloth was coated with textile treatment agents (N-1) to (N-10) and a comparative textile treatment agent (N'-1) using a bar coater to a dry thickness of 1 μm, and dried at 160°C for 10 minutes to prepare test pieces (4 cm x 12 cm) coated with polyester resin on the plain cotton broadcloth. Abrasion resistance tests were conducted on the dried film surface of the fabricated test specimens coated with the textile treatment agent using a Japan Society for the Promotion of Science (JSPS) type friction fastness tester. A friction element fitted with a 60mm x 60mm cotton cloth (Kanakin No. 3) was rubbed back and forth 100 times under a load of 200g. The fuzziness of the test specimen surface after the test was visually assessed, and the abrasion resistance of the textile treatment agent was evaluated according to the following criteria. ◎: No pilling ○: Some pilling is visible. ×: Fraying is visible throughout.

[0150] <Manufacturing of water-based paint (O-1)> 90 parts of deionized water, 70 parts of thickener ("BisLizer AP-2", manufactured by Sanyo Chemical Industries, Ltd.), 10 parts of pigment dispersant ("Caribon L-400", manufactured by Sanyo Chemical Industries, Ltd.), 140 parts of titanium dioxide ("CR-93", manufactured by Ishihara Sangyo Co., Ltd.), carbon black ("FW200P", manufactured by Degussa Co., Ltd.), and 160 parts of calcium carbonate were mixed and dispersed in paint conditioner for 30 minutes. To this, 20 parts of 1-octanol, 200 parts of acrylic emulsion ("Polytron Z330", manufactured by Asahi Kasei Corporation), and 200 parts of the resin aqueous dispersion (X-1) obtained above were mixed under stirring. Further, the mixture was adjusted using deionized water to a viscosity of 150 mPa·s (25℃, TOKIMEC Corporation rotary viscometer (60 rpm)) to obtain aqueous paint (O-1).

[0151] <Manufacturing of water-based paints (O-2) to (O-10) and (O'-1)> Using the same method as described above, aqueous paints (O-2) to (O-10) and (O'-1) were manufactured using aqueous resin dispersions (X-2) to (X-10) and (X'-1) instead of aqueous resin dispersion (X-1).

[0152] <Method for evaluating the abrasion resistance of water-based paints> Water-based paints (O-1) to (O-10) and a comparative water-based paint (O'-1) were applied to polyester film (PET) [Toyobo Co., Ltd. "Espet E-5102" (thickness 12 μm)] using a bar coater so that the thickness after drying was 1 μm. Test specimens were prepared in which polyester resin was coated onto each resin film. Abrasion resistance tests were conducted on the dried film surface of the water-based paint on the prepared test specimens using a Japan Society for the Promotion of Science (JSPS) type friction fastness tester. A friction element fitted with a 60mm x 60mm cotton cloth (Kanakin No. 3) was rubbed back and forth 100 times under a load of 200g. The remaining coating film after the test was determined in the same manner as the remaining coating film shown in the image above, and the abrasion resistance of the printing ink was evaluated according to the following criteria. ◎: Coating film retention rate is 70-100% ○: Coating film retention rate is 50-69% ×: Coating film retention rate is less than 50%

[0153] [Table 1]

[0154] [Table 2]

[0155] Examples 1 to 10, in which the polyester resin (A) contains calcium in the range of 10 to 4000 ppm, exhibit excellent abrasion resistance and water resistance when used as an inkjet ink. Furthermore, it also exhibits excellent abrasion resistance when used as a surface modifier for recording media, a treatment agent for textiles, and a water-based paint. In Comparative Example 1, where polyester resin (A) did not contain calcium, the abrasion resistance was poor in all applications, and the water resistance when used as an inkjet ink was also poor. Furthermore, in Comparative Example 2, where polyester resin (A) contained more than 4000 ppm of calcium, a dispersion could not be obtained. [Industrial applicability]

[0156] The aqueous resin dispersion of the present invention contains a polyester resin with excellent abrasion resistance, water resistance, and storage stability, and is therefore suitable for use in applications such as inkjet inks, surface modifiers for recording media, treatment agents for textiles, and aqueous paints.

Claims

1. A resin aqueous dispersion containing a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component, The alcohol component comprises ethylene glycol and a branched alkylene glycol having 3 to 10 carbon atoms or an alkylene oxide adduct of bisphenol A, and the carboxylic acid component comprises terephthalic acid. The acid value of the polyester resin (A) is 15 mg KOH / g or more. An aqueous resin dispersion characterized in that the polyester resin (A) contains calcium in the range of 10 to 4000 ppm as measured by X-ray fluorescence analysis.

2. The aqueous resin dispersion according to claim 1, wherein the carboxylic acid component of the polyester resin (A) is isophthalic acid.

3. The aqueous resin dispersion according to claim 1 or 2, wherein the aqueous resin dispersion is for use with inkjet ink.

4. The aqueous resin dispersion according to claim 1 or 2, wherein the aqueous resin dispersion is for use as a surface modifier for recording media.

5. The aqueous resin dispersion according to claim 1 or 2, wherein the aqueous resin dispersion is for use as a treatment agent for fibers.

6. The aqueous resin dispersion according to claim 1 or 2, wherein the aqueous resin dispersion is for use in aqueous paints.

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