JP2011178846A - Aqueous dispersion of polyester resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion that contains a polyester resin particle having a small particle size and is excellent in preservation (storage) stability. <P>SOLUTION: An aqueous dispersion of polyester resin (X) is an aqueous dispersion prepared by dispersing a resin particle (A) including a polyester resin (a) produced by polycondensation of an alcohol component (x) and a carboxylic acid component (y) in an aqueous medium (W), if necessary, containing an organic solvent (S). In the aqueous dispersion, the content of a free carboxylic acid in the polyester resin (a) is not more than 2,000 ppm and the SP value of the polyester resin (a) is 10.5 to 12.5 (cal/cm<SP>3</SP>)<SP>1/2</SP>. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aqueous dispersion containing polyester resin particles and polyester resin particles.

In recent years, research and development in consideration of the environment has been actively performed in various industrial fields. Among these, aqueous dispersions of resin fine particles have attracted attention in the field of paints and electrophotography, and there is a potential need for reducing the size of polymer fine particles.
Conventional techniques such as a solvent method, a phase inversion emulsification method, and a high temperature emulsification method are known as methods for obtaining an aqueous dispersion of polymer fine particles, but the storage (storage) stability of the aqueous dispersion may be insufficient. there were.
In addition, as a method for obtaining an aqueous dispersion of polymer particles having a small particle size, in the presence of a nonionic surfactant, in the aqueous medium within a temperature range of 10 ° C. above and below the cloud point of the nonionic surfactant. A method for making the polymer fine particles has been proposed (see Patent Document 1). However, in this method, it cannot be said that the grain size of the polymer fine particles is sufficient, and further grain size reduction is desired.

JP 2006-106679 A

  An object of the present invention is to provide an aqueous dispersion containing small-sized polyester resin particles and excellent in storage (storage) stability.

As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention. That is, the present invention is a polyester resin (polyester resin obtained by polycondensation of an alcohol component (x) and a carboxylic acid component (y)). An aqueous dispersion in which the resin particles (A) containing a) are dispersed in an aqueous medium (W) containing an organic solvent (S) if necessary, comprising free carboxylic acid in (a) A polyester resin aqueous dispersion (X) having an amount of 2000 ppm or less and an SP value of (a) of 10.5 to 12.5 (cal / cm ³ ) ^1/2 ; and the above polyester resin aqueous dispersion Polyester resin particles (A) obtained by removing the aqueous medium (W) from (X).

  The aqueous polyester resin dispersion of the present invention contains polyester resin particles having a small particle diameter, has very good emulsifying properties, and is excellent in storage (storage) stability.

The present invention is described in detail below.
The polyester resin (a) in the present invention is obtained by polycondensation of an alcohol component (x) and a carboxylic acid component (y).
Examples of the alcohol component (x) include monool (X1), diol (X2), and trivalent to octavalent or higher polyol (X3). Examples of the carboxylic acid component (y) include monocarboxylic acid ( and y1), dicarboxylic acid (y2), and trivalent to octavalent or higher polycarboxylic acid (y3).

As monool (x1), C1-C30 alkanol (methanol, ethanol, isopropanol, dodecyl alcohol, stearyl alcohol, etc.), C3-C24 alkenol (allyl alcohol, propenyl alcohol, oleyl alcohol, etc.), and A C7-36 aromatic alcohol (benzyl alcohol etc.) etc. are mentioned.
Among these, from the viewpoint of blocking resistance, preferred are aromatic alcohols having 7 to 36 carbon atoms (such as benzyl alcohol).

Examples of the diol (X2) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol. , 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol) , And polytetramethylene ether glycol); alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.); (poly) oxyalkylenes of the above alicyclic diols The same applies to polyoxyalkylene groups having 2 to 4 carbon atoms (oxyethylene, oxypropylene, and the like) of the alkylene group) ether [numbers 1 to 30 of oxyalkylene units (hereinafter abbreviated as AO units)]; And polyoxyalkylene ethers (number of AO units 2-30) of bisphenols (for example, hydroquinone) and bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.);
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, polyoxyalkylene ethers of bisphenols (2 to 30 AO units), and particularly preferred are alkylene glycols having 2 to 10 carbon atoms, It is a polyoxyalkylene ether of bisphenols (number of AO units 2 to 5).

Examples of the trivalent to octavalent or higher polyol (X3) include trihydric to octavalent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof, such as Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; sugars and derivatives thereof such as sucrose and methylglucoside); (poly) oxyalkylenes of the above aliphatic polyhydric alcohols Ether (number of AO units 1-30); polyoxyalkylene ether of trisphenols (trisphenol PA, etc.) (number of AO units 2-30); novolak resin (phenol novolak, cresol novolac, etc.) average degree of polymerization 3 60) Etc. (the number 2 to 30 of AO units) polyoxyalkylene ether.
Of these, preferred are aliphatic polyhydric alcohols having 3 to 8 valences or higher, and polyoxyalkylene ethers of novolac resins (number of AO units: 2 to 30), and particularly preferred are polyoxyalkylenes of novolac resins. An alkylene ether (number of AO units 2 to 30).

  The alcohol component (x) preferably contains 80 mol% or more of one or more diols (X2), more preferably 85 mol% or more, and particularly preferably 90 mol%. When it is 80 mol or more, the glass transition temperature (Tg) of the polyester resin (a) is increased, and the heat resistant storage stability of the polyester resin (a) is improved.

As monocarboxylic acid (y1), C1-C30 alkane monocarboxylic acid (formic acid, acetic acid, propionic acid, butanoic acid, isobutanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid , Behenic acid, serotic acid, monitoring acid, melissic acid, etc.), C3-C24 alkene monocarboxylic acid (acrylic acid, methacrylic acid, oleic acid, linoleic acid, etc.), C7-C36 aromatic monocarboxylic acid Examples include acids (benzoic acid, methylbenzoic acid, Pt-butylbenzoic acid, phenylpropionic acid, naphthoic acid, and the like).
Among these, preferred are aromatic monocarboxylic acids having 7 to 36 carbon atoms, and more preferred are benzoic acid, methylbenzoic acid, and Pt-butylbenzoic acid.

Examples of the dicarboxylic acid (y2) include alkane dicarboxylic acids having 4 to 36 carbon atoms (for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedioic acid, and 1,18-octadecanedicarboxylic acid); alicyclic dicarboxylic acid having 6 to 40 carbon atoms [for example, dimer acid (dimerized linoleic acid)]; alkenedicarboxylic acid having 4 to 36 carbon atoms (for example, alkenyl succinic acid such as dodecenyl succinic acid) , Maleic acid, fumaric acid, citraconic acid, and mesaconic acid); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthal, isophthal, terephthal, and naphthalenedicarboxylic acid, etc.); and ester-forming derivatives thereof; It is done.
Examples of the ester-forming derivatives include acid anhydrides, alkyl (C1-C24: methyl, ethyl, butyl, stearyl, etc.) esters, and partial alkyl (same as above) esters. The same applies to the following ester-forming derivatives. These can be used alone or in combination of two or more.

Examples of the tri- to hexavalent or higher polycarboxylic acid (y3) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and ester-forming derivatives thereof.
Of these, preferred are trimellitic acid and pyromellitic acid and their ester-forming derivatives.

  The carboxylic acid component (y) preferably contains 80 mol% or more of one or more dicarboxylic acids (y2), more preferably 85 mol% or more, and particularly preferably 90 mol%. When it is 80 mol or more, the glass transition temperature (Tg) of the polyester resin (a) is increased, and the heat resistant storage stability of the polyester resin (a) is improved.

The polyester resin (a) in the present invention can be produced in the same manner as in an ordinary polyester production method. For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280 ° C, more preferably 170 to 260 ° C, particularly preferably 190 to 240 ° C. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
At this time, an esterification catalyst can be used as needed. Examples of esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide), antimony trioxide, titanium-containing catalysts, zirconium-containing catalysts (eg, zirconyl acetate), zinc acetate, and the like. Among these, a titanium-containing catalyst is preferable from the viewpoint of response to environmental problems and catalytic activity.

The titanium-containing catalyst is not particularly limited, and examples thereof include titanium alkoxide (tetrabutoxy titanate, etc.), carboxylate titanate (potassium oxalate titanate, etc.), titanium carboxylate (titanium terephthalate, etc.), and JP, Catalysts described in Japanese Patent Application Publication No. 2007-11307 (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.) and the like can be used, but in the following general formulas (I) and (II) More preferably, at least one titanium-containing catalyst (e) selected from the group consisting of the titanium-containing compounds represented is used.
_{Ti (-X) m (-OR 1} ) n (I)
O = Ti (-X) p (-OR < ₁ >) q (II)
[In the formulas (I) and (II), R ₁ is H, an alkyl group having 1 to 18 carbon atoms which may contain 1 to 5 ether bonds, or an acyl group having 1 to 18 carbon atoms. X is a residue obtained by removing one OH group H from a mono- or polyalkanolamine having 2 to 12 carbon atoms. In the case of polyalkanolamine, an OH group in which other OH groups are directly bonded to the same Ti atom. (When R _{1 of} OR ₁ group is H) and may be polycondensed in the molecule to form a ring structure, and OH group directly bonded to other Ti atoms (when R _{1 of} OR ₁ group is H) ) And molecules may be polycondensed between molecules to form a repeating structure. The degree of polymerization in the case of forming a repeating structure is 2-5. m is an integer of 1 to 4, n is an integer of 0 to 3, and the sum of m and n is 4. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. When n is 2 or more, each R ₁ may be the same or different. ]

In the catalyst (a1) represented by the general formula (I) or (II), R ₁ is H (becomes an OH group) and has 1 to 18 carbon atoms which may contain 1 to 5 ether bonds. Or an acyl group having 1 to 18 carbon atoms.
Specific examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n- Examples include lauryl group, n-stearyl group, β-methoxyethyl group, β-ethoxyethyl group and the like.
Specific examples of the acyl group having 1 to 18 carbon atoms include one COOH group from an aliphatic monocarboxylic acid, aliphatic polycarboxylic acid, aromatic monocarboxylic acid or aromatic polycarboxylic acid having 1 to 18 carbon atoms. It is a residue excluding OH in the middle. Specific examples of the aliphatic monocarboxylic acid include acetic acid, propionic acid, lauric acid, stearic acid, acrylic acid, methacrylic acid and the like. Specific examples of the aliphatic polycarboxylic acid include oxalic acid, adipic acid, succinic acid, maleic acid, fumaric acid and the like. Specific examples of the aromatic monocarboxylic acid include benzoic acid, salicylic acid, naphthylic acid and the like. Specific examples of the aromatic polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and the like.
Of these R ₁ , H and preferably an acyl group having 1 to 18 carbon atoms, and more preferably, OH in one COOH group is removed from H and an aliphatic monocarboxylic acid and aromatic polycarboxylic acid. A residue, particularly preferably H and an acetyl group, most preferably H.

X is a residue obtained by removing the H atom of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms, and the number of nitrogen atoms, that is, the total of primary, secondary, and tertiary amino groups The number is usually 1 to 2, preferably 1.
Examples of the monoalkanolamine include ethanolamine and propanolamine. Polyalkanolamines include dialkanolamines (such as diethanolamine, N-methyldiethanolamine, and N-butyldiethanolamine), trialkanolamines (such as triethanolamine, and tripropanolamine), and tetraalkanolamines (N, N, N). ', N'-tetrahydroxyethylethylenediamine and the like).
In the case of polyalkanolamine, at least one OH group is present in addition to the OH group that is a residue other than H used to form a Ti—O—C bond with a Ti atom, and this is the same Ti atom. The OH group directly bonded (when R _{1 of the} OR ₁ group is H) may be polycondensed in the molecule to form a ring structure, and the OH group directly bonded to another Ti atom (R _{1 of the} OR ₁ group) ₁ may be H) and may be polycondensed between molecules to form a repeating structure. The degree of polymerization in the case of forming a repeating structure is 2-5. When the degree of polymerization is 6 or more, the catalyst activity decreases, so the oligomer component increases, which causes deterioration in storage stability.
Preferred as X are residues of monoalkanolamines (especially ethanolamine), residues of dialkanolamines (especially diethanolamine), and residues of trialkanolamines (especially triethanolamine). Particularly preferred are trialkanolamines (especially triethanolamine). It is a residue of ethanolamine.

In Formula (I), m is an integer of 1-4, Preferably it is an integer of 1-3. n is an integer of 0 to 3, preferably an integer of 1 to 3. The sum of m and n is 4.
In formula (II), p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, a plurality of Xs may be the same or different, but are preferably the same.
When n is 2 or more, a plurality of R ₁ may be the same or different but are preferably all the same.

Specific examples of the titanium-containing catalyst (e) will be given below. In the following examples, in the illustration of the substituent X, it means a residue obtained by removing the H atom of one OH group from the exemplified compound, and in the illustration of the substituent OR ₁ , _{one from} the exemplified compound. It means a residue obtained by removing an H atom from an OH group or one COOH group.
Specific examples of the compound represented by the general formula (I) include titanium / triethanolamine (4) [meaning a compound in which four triethanolamines are coordinated to titanium. Hereinafter, the same notation is used. ], Titanium / diethanolamine (4), titanium / monoethanolamine (4), titanium / triethanolamine (3) / diethanolamine (1), titanium / triethanolamine (2) / diethanolamine (2), titanium / triethanolamine Amine (1) · Diethanolamine (3), Titanium · Triethanolamine (3) · OH (1), Titanium · Diethanolamine (3) · OH (1), Titanium · Triethanolamine (2) · Diethanolamine (1) · OH (1), Titanium / Triethanolamine (1) / Diethanolamine (2) / OH (1), Titanium / Triethanolamine (2) / OH (2), Titanium / Diethanolamine (2) / OH (2), Titanium / monoethanolamine (2) / OH (2), titanium / monopropano Amine (2) · OH (2), Titanium · N-methyldiethanolamine (2) · OH (2), Titanium · N-butyldiethanolamine (2) · OH (2), Titanium · Triethanolamine (2) · OH (1) · Acetic acid (1), Titanium · Triethanolamine (2) · OH (1) · Fumaric acid (1), Titanium · Triethanolamine (2) · OH (1) · Terephthalic acid (1), Titanium · Triethanolamine (2) · OH (1) · Isophthalic acid (1), Titanium · Diethanolamine (2) · OH (1) · Acetic acid (1), Titanium · Diethanolamine (2) · OH (1) · Propionic acid (1), titanium / diethanolamine (2) / OH (1) / fumaric acid (1), titanium / diethanolamine (2) / OH (1) / terephthalic acid (1), titanium / dieta Uramine (2), OH (1), isophthalic acid (1), titanium, monoethanolamine (2), OH (1), fumaric acid (1), titanium, N-methyldiethanolamine (2), OH (1)・ Isophthalic acid (1), titanium, triethanolamine (1), diethanolamine (1), OH (2), titanium, triethanolamine (1), diethanolamine (1), OH (1), acetic acid (1), Titanium, triethanolamine (1), diethanolamine (1), OH (1), fumaric acid (1), titanium, triethanolamine (1), diethanolamine (1), OH (1), terephthalic acid (1), Titanium, triethanolamine (1), diethanolamine (1), OH (1), isophthalic acid (1), titanium, monopropanolamine (1), Triethanolamine (1), OH (1), fumaric acid (1), titanium, triethanolamine (1), OH (3), titanium, triethanolamine (1), OH (1), acetic acid (2) , Titanium, Triethanolamine (1), OH (2), Acetic acid (1), Titanium, Triethanolamine (1), OH (1), Fumaric acid (2), Titanium, Triethanolamine (1), OH (1) phthalic acid (2), titanium, triethanolamine (1), OH (1), terephthalic acid (2), titanium, triethanolamine (1), OH (1), isophthalic acid (2), Titanium, triethanolamine (1), OH (1), acetic acid (1), fumaric acid (1), titanium, triethanolamine (1), OH (1), acetic acid (1), terephthalic acid (1), Titanium / Triethanol Min (1) · OH (1) · Acetic acid (1) · Isophthalic acid (1), Titanium · Diethanolamine (1) · OH (1) · Acetic acid (2), Titanium · Diethanolamine (1) · OH (1) · Fumaric acid (2), Titanium, diethanolamine (1), OH (1), Terephthalic acid (2), Titanium, diethanolamine (1), OH (1), Isophthalic acid (2), Titanium, diethanolamine (1), OH (1) Acetic acid (1) Fumaric acid (1) Titanium diethanolamine (1) OH (1) Acetic acid (1) Terephthalic acid (1) Titanium diethanolamine (1) OH (1) Acetic acid (1), isophthalic acid (1), titanium, monopropanolamine (1), OH (1), acetic acid (2), titanium, N-butyldiethanolamine (1), OH (1), malein (1) adipic acid (1), titanium N, N, N ′, N′-tetrahydroxyethylethylenediamine (1) OH (1) trimellitic acid (2), tetrahydroxy titanium and N, N, Reaction products with N ′, N′-tetrahydroxyethylethylenediamine, and intramolecular or intermolecular polycondensates thereof may be mentioned.
Specific examples of the intramolecular or intermolecular polycondensate include at least one compound represented by the following general formula (I-1), (I-2), or (I-3).

[Wherein, Q ₁ and Q ₆ are H, or an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. Q _{2 to} Q ₅ and Q _{7 to} Q ₉ are alkylene groups having 1 to 6 carbon atoms. X is a residue obtained by removing one OH group H from a mono- or polyalkanolamine having 2 to 12 carbon atoms. ]

Specific examples of the compound represented by the general formula (II) include titanyl triethanolamine (2) [means a compound in which two triethanolamines are coordinated to a titanyl group. Hereinafter, the same notation is used. ], Titanyl / diethanolamine (2), titanyl / monoethanolamine (2), titanyl / ethanol (1) / triethanolamine (1), titanyl / triethanolamine (1) / OH (1), titanyl / triethanol Amine (1), isopropanol (1), titanyl, triethanolamine (1), acetic acid (1), titanyl, triethanolamine (1), stearic acid (1), titanyl, triethanolamine (1), maleic acid (1), titanyl / triethanolamine (1) / fumaric acid (1), titanyl / triethanolamine (1) / methacrylic acid (1), titanyl / triethanolamine (1) / terephthalic acid (1), titanyl・ Triethanolamine (1) ・ Isophthalic acid (1), titanyl ・ Triethanolamine (1) Naphthylic acid (1), titanyl diethanolamine (1) OH (1), titanyl diethanolamine (1) acetic acid (1), titanyl diethanolamine (1) propionic acid (1), titanyl diethanolamine (1) fumaric acid (1), titanyl diethanolamine (1) terephthalic acid (1), titanyl diethanolamine (1) isophthalic acid (1), titanyl monoethanolamine (1) OH (1), Examples thereof include titanyl, monoethanolamine (1), acetic acid (1), and intramolecular or intermolecular polycondensates thereof.
Specific examples of the intramolecular or intermolecular polycondensate include at least one compound represented by the following general formula (II-1) or (II-2).

[Wherein, Q ₁ and Q ₆ are H, or an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. Q < ₂ > -Q < ₅ > is a C1-C6 alkylene group. ]

  Of these, preferred are compounds represented by the general formula (I), more preferably titanium / triethanolamine (2) / OH (2), titanium / diethanolamine (2) / OH (2). , Titanium, Triethanolamine (1), Diethanolamine (1), OH (2), Titanium, Triethanolamine (2), OH (1), Acetic acid (1), Titanium, Diethanolamine (2), OH (1) Acetic acid (1), titanium, triethanolamine (1), diethanolamine (1), OH (1), acetic acid (1), titanium, triethanolamine (1), OH (1), acetic acid (2), titanium Diethanolamine (1) OH (1) Acetic acid (2) Titanium Triethanolamine (2) OH (1) Fumaric acid (1) Titanium diethanolamine (2・ OH (1) ・ Fumaric acid (1), Titanium ・ Triethanolamine (1) ・ Diethanolamine (1) ・ OH (1) ・ Fumaric acid (1), Titanium ・ Triethanolamine (2) ・ OH (1)・ Terephthalic acid (1), Titanium ・ Diethanolamine (2) ・ OH (1) ・ Terephthalic acid (1), Titanium ・ Triethanolamine (1) ・ Diethanolamine (1) ・ OH (1) ・ Terephthalic acid (1), Titanium, triethanolamine (2), OH (1), isophthalic acid (1), Titanium, diethanolamine (2), OH (1), isophthalic acid (1), Titanium, triethanolamine (3), OH (1 ), Titanium / diethanolamine (3) / OH (1), titanium / triethanolamine (2) / diethanolamine (1) / OH (1), titanium / trie Noruamin (1) Diethanolamine (2) OH (1), and is within the molecules or intermolecular condensates.

  Particularly preferably, titanium / triethanolamine (2) / OH (2), titanium / diethanolamine (2) / OH (2), titanium / triethanolamine (1) / diethanolamine (1) / OH (2), titanium · Triethanolamine (2) · OH (1) · Acetic acid (1), Titanium · Diethanolamine (2) · OH (1) · Acetic acid (1), Titanium · Triethanolamine (1) · Diethanolamine (1) · OH (1) · Acetic acid (1), Titanium · Triethanolamine (1) · OH (1) · Acetic acid (2), Titanium · Diethanolamine (1) · OH (1) · Acetic acid (2), and their molecules Or an intermolecular condensate, most preferably titanium / triethanolamine (2) / OH (2), titanium / diethanolamine (2) / OH (2), Down Triethanolamine (1) Diethanolamine (1) OH (2), and is within the molecules or intermolecular condensates.

  These titanium-containing catalysts (e) can be obtained stably by reacting, for example, commercially available titanium dialkoxybis (alcohol aminates) (manufactured by Dupont, etc.) at 70 to 90 ° C. in the presence of water. Can do. The polycondensate can be obtained by further distilling off the condensed water at 100 ° C. under reduced pressure.

  The free carboxylic acid in the polyester resin (a) in the present invention is an unreacted product of the carboxylic acid component (y) used as a raw material when the polyester resin (a) is polycondensed.

In the present invention, the content of free carboxylic acid in the polyester resin (a) is 2000 ppm or less, preferably 1800 ppm or less, more preferably 1500 ppm or less, and particularly preferably 100 to 1300 ppm.
When the amount of the free carboxylic acid is higher than 2000 ppm, the emulsifiability deteriorates, the volume average particle size of the resin particles (A) is coarsened, and the particle size distribution is widened.
As means for reducing the content of free carboxylic acid in the polyester resin (a), esterification such as increasing the reaction temperature, extending the reaction time, using a highly active catalyst such as a titanium-containing catalyst, and increasing the amount of catalyst. Means for promoting the reaction can be mentioned.

In the present invention, the free carboxylic acid content in the polyester resin (a) is measured under the following conditions using high performance liquid chromatography (HPLC).
Device (example): SIL20AHT / 20ACHT
Prominence UFLC [manufactured by Shimadzu Corporation]
Column (example): Capcellpack C18 [manufactured by Shiseido Co., Ltd.]
Mobile phase: 0.05% phosphoric acid aqueous solution / acetonitrile = 1/4 (volume ratio)
Flow rate: 0.6 ml / min
Column temperature: 40 ° C
Solution injection amount: 10 μm
Detection apparatus: UV detector In addition, in the above and the following,% means weight% unless there is particular notice.

<Preparation method of standard sample solution>
1. 0.02 g of the carboxylic acid component (y) used as a raw material when the polyester resin (a) is polycondensed is put into a 100 ml volumetric flask and mixed with a 0.05% phosphoric acid aqueous solution / acetonitrile mixed solution having a volume ratio of 1/4. Prepare exactly 100 ml.
This is filtered with a 0.5 μm filter to obtain [standard sample solution 1].
2. [Standard sample solution 1] is accurately weighed in 50 ml with a pipette or the like and transferred to a 100 ml volumetric flask. This is exactly 100 ml with a 0.05% aqueous solution of phosphoric acid / acetonitrile mixed at a volume ratio of 1/4, and [Standard sample solution 1] is diluted 2 times.
This is filtered with a 0.5 μm filter to obtain [standard sample solution 2].
3. [Standard sample solution 2] is accurately weighed in 20 ml with a pipette or the like and transferred to a 100 ml volumetric flask. This is exactly 100 ml with a 0.05% aqueous solution of phosphoric acid / acetonitrile mixed at a volume ratio of 1/4, and [standard sample solution 2] is diluted 4 times.
This is filtered with a 0.5 μm filter to obtain [standard sample solution 3].
The above [standard sample solutions 1 to 3] are measured by high performance liquid chromatography (HPLC), and a calibration curve of each carboxylic acid component (y) is created from the relationship between the concentration and the peak area.

<Method for preparing sample solution>
1. 2 g of the polyester resin is completely dissolved in 20 g of chloroform.
2. A 0.05% phosphoric acid aqueous solution / acetonitrile mixed solution having a volume ratio of 1/4 was added thereto, and the mixture was shaken well for 1 minute, and then allowed to stand for 12 hours.
3. Thereafter, the upper phase (aqueous phase) was extracted and filtered through a 0.5 μm filter to prepare a sample solution for high performance liquid chromatography.
The sample solution is measured by high performance liquid chromatography (HPLC), and the free carboxylic acid content in the resin is determined using the calibration curve of each carboxylic acid component (y).

The SP value (solubility parameter) of the polyester resin (a) is 10.5 to 12.5 [(cal / cm ³ ) ^1/2 , the same shall apply hereinafter], preferably 10.6 to 12.4. More preferably, it is 10.8-12.0.
If the SP value is less than 10.5, the dispersibility in the aqueous medium (W) is insufficient, and if it exceeds 12.5, the dispersion tends to be affected by environmental conditions, Tg decreases, and the polyester resin aqueous dispersion (X ) Preservation (storage) stability deteriorates.
The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147-154)"

The acid value of the polyester resin (a) is preferably 5 to 50 (mg KOH / g, the same shall apply hereinafter), more preferably 5 to 45, and particularly preferably 9 to 40. When the acid value is in the range of 5 to 50, the dispersion stability is good when (a) is dispersed in the aqueous medium (W).
The hydroxyl value of (a) is preferably 0 to 100 (mg KOH / g, the same shall apply hereinafter), more preferably 0 to 70, particularly preferably 0 to 50. When the hydroxyl value is 100 or less, the heat resistant storage stability of the polyester resin particles (A) becomes better.

In the present invention, the acid value and hydroxyl value of the polyester resin are measured by the method defined in JIS K0070 (1992 version).
When the sample has a solvent-insoluble component accompanying crosslinking, the sample after melt-kneading is used as a sample by the following method.
Kneading device: Labo plast mill MODEL4M150 manufactured by Toyo Seiki Co., Ltd.
Kneading conditions: 130 ° C., 70 rpm, 30 minutes

  The peak top molecular weight of the polyester resin (a) soluble in tetrahydrofuran (THF) (hereinafter referred to as Mp) is preferably 2,000 to 15,000, more preferably 2,500 to 13,000, particularly preferably 3. , 1,000 to 11,000. When the Mp is in the range of 2,000 to 15,000, the flowability of the polyester resin (a) is improved, and the emulsifying property is further improved.

In the present invention, the Mp of the polyester resin is measured under the following conditions using gel permeation chromatography (GPC).
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25% THF (tetrahydrofuran) solution Injection amount: 100 μl
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)
The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight (Mp). The molecular weight is measured by dissolving a polyester resin in THF and filtering out the insoluble matter with a glass filter.

The glass transition temperature (Tg) of the polyester resin (a) used for this invention becomes like this. Preferably it is 45 degreeC or more, More preferably, it is 48-80 degreeC, Most preferably, it is 50-70 degreeC.
When Tg of (a) is 45 ° C. or higher, reaggregation of the resin particles (A) in the aqueous polyester resin dispersion (X) can be prevented, and storage (storage) stability is improved.
In addition, in the above and below, Tg is measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Denshi Kogyo Co., Ltd. DSC20, SSC / 580.

The flow softening point [Tm] of (a) is preferably 90 to 150 ° C, more preferably 95 to 145 ° C, and particularly preferably 100 to 140 ° C. Within this range, both the dispersibility of (a) in the aqueous medium (W) and the storage (storage) stability of the aqueous polyester resin dispersion (X) after dispersion are good. In the present invention, Tm is measured by the following method.
<Flow softening point [Tm]>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and graph the temperature corresponding to 1/2 of the maximum plunger descent amount The value (temperature when half of the measurement sample flows out) is taken as the flow softening point [Tm].

As a method of dispersing the resin particles (A) containing the polyester resin (a) in the aqueous medium (W) to obtain an aqueous polyester resin dispersion (X),
(I) The resin particles (A) are precipitated by adding a poor solvent to the resin solution in which the polyester resin (a) is dissolved in the solvent, or by cooling the resin solution previously heated and dissolved in the solvent. Removing the resin particles (A) and then dispersing them in water in the presence of a suitable dispersant;
(Ii) A method in which a resin solution in which a polyester resin (a) is dissolved in a solvent is dispersed in an aqueous medium (W) in the presence of a suitable dispersant, and the solvent is removed by heating or decompression,
(Iii) A method in which a suitable dispersant is dissolved in a resin solution obtained by dissolving the polyester resin (a) in a solvent, and then water is added to perform phase inversion emulsification.
Etc.
In the methods (ii) and (iii), a neutralizing agent is added to a resin solution obtained by dissolving the polyester resin (a) in a solvent, and the carboxyl group of (a) is ionized to form an aqueous medium (W). It may be dispersed. As the neutralizing agent, an aqueous amine solution such as aqueous ammonia and sodium hydroxide, and amines such as amines having 2 to 18 carbon atoms such as allylamine, isopropylamine, ethylamine and triethylamine can be used.

When the polyester resin (a) or an organic solvent solution thereof is dispersed in the aqueous medium (W), a dispersing device can be used.
The dispersion apparatus used for producing the polyester resin aqueous dispersion (X) of the present invention is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a homogenizer (manufactured by IKA), Batch emulsifiers such as Polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Special Machine Industries), Ebara Milder (manufactured by Ebara Seisakusho), TK Fillmix, TK Pipeline Homo Mixer (special machine industry) ), Colloid mill (made by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (Mitsui Miike Chemical Co., Ltd.), Captron (Eurotech Co., Ltd.), fine flow mill (made by Taiheiyo Kiko Co., Ltd.), etc. Emulsifier, microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), nanomizer (manufactured by Nanomizer), APV Gaurin (Gaurin) High-pressure emulsifiers such as membrane emulsifiers (made by Chilling Industries Co., Ltd.), vibratory emulsifiers such as Vibro mixers (made by Chilling Industries Co., Ltd.), ultrasonic homogenizers (made by Branson), etc. Examples include an ultrasonic emulsifier. Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size.

  Examples of the dispersant used for the production of the aqueous polyester resin dispersion (X) of the present invention include a polymeric dispersant (F1), an anionic surfactant (F2), a cationic surfactant (F3), and an amphoteric surfactant. Agents (F4), nonionic surfactants, and mixtures thereof. Specific examples include the following.

  Examples of the polymeric dispersant (F1) include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic , Chitin, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, sodium hydroxide of polyacrylic acid) Partially neutralized product, sodium acrylate-acrylic acid ester copolymer), sodium hydroxide of styrene-maleic anhydride copolymer Um (partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

  Examples of the anionic surfactant (F2) include carboxylic acids or salts thereof, sulfate esters, carboxymethylated salts, sulfonates, and phosphate esters.

  Examples of carboxylic acids or salts thereof include saturated or unsaturated fatty acids having 8 to 22 carbon atoms or salts thereof. Specifically, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. , Oleic acid, linoleic acid, ricinoleic acid and a mixture of higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, beef tallow and the like. Examples of the salt include salts of sodium, potassium, ammonium, alkanolamine and the like.

  Examples of sulfate salts include higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms) and higher alkyl ether sulfate esters salts (1 to 10 moles of ethylene oxide of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated oils or unsaturated waxes that have been neutralized by sulfation), sulfated fatty acid esters (sulfurized lower alcohol esters of unsaturated fatty acids) And sulphated olefins (sulphated and neutralized olefins having 12 to 18 carbon atoms). Examples of the salt include sodium salt, potassium salt, ammonium salt, and alkanolamine salt. Specific examples of higher alcohol sulfates include octyl alcohol sulfate, decyl alcohol sulfate, lauryl alcohol sulfate, stearyl alcohol sulfate, alcohols synthesized using Ziegler catalysts (for example, ALFOL 1214: CONDEA's sulfate ester salt, alcohols synthesized by the oxo method (for example, Dovanol 23, 25, 45: Mitsubishi Yuka, Tridecanol: Kyowa Hakko, Oxocol 1213, 1215, 1415: Nissan Chemical, Diadol 115 -L, 115H, 135: manufactured by Mitsubishi Chemical); specific examples of higher alkyl ether sulfates include lauryl alcohol ethylene oxide 2-mol adduct sulfate, octyl alcohol ethylene Oxide 3-mole adduct sulfate ester; Specific examples of sulfated oils include sodium, potassium, ammonium, alkanolamine salts sulfated fatty acids of castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, sheep fat, etc. Specific examples of the ester include sodium, potassium, ammonium, and alkanolamine salts of sulfates such as butyl oleate and butyl ricinoleate; specific examples of the sulfated olefin include Typol (manufactured by Shell).

  Examples of the carboxymethylated salt include a carboxymethylated salt of an aliphatic alcohol having 8 to 16 carbon atoms and a carboxymethylated salt of an ethylene oxide 1 to 10 mol adduct of an aliphatic alcohol having 8 to 16 carbon atoms. It is done. Specific examples of salts of carboxymethylated products of aliphatic alcohols include octyl alcohol carboxymethylated sodium salt, decyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, dovanol 23 carboxymethylated sodium salt, tridecanol Specific examples of salts of carboxymethylated sodium salt of carboxymethylated product of aliphatic alcohol ethylene oxide 1-10 mol adduct include octyl alcohol ethylene oxide 3 mol adduct carboxymethylated sodium salt, lauryl alcohol ethylene oxide 4 Mole adduct carboxymethylated sodium salt, dovanol 23 ethylene oxide 3 mol adduct carboxymethylated sodium salt, tridecanol ethylene oxide Such as 5 mole adduct carboxymethylated sodium salt.

  Examples of the sulfonate include alkylbenzene sulfonate, alkyl naphthalene sulfonate, sulfosuccinic acid diester type, α-olefin sulfonate, Igepon T type, and sulfonates of other aromatic ring-containing compounds. Specific examples of alkylbenzene sulfonate include sodium dodecylbenzene sulfonate; specific examples of alkyl naphthalene sulfonate; sodium dodecyl naphthalene sulfonate; specific examples of sulfosuccinic acid diester type include di-2 sulfosuccinic acid di-2 -Ethylhexyl ester sodium salt and the like. Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether, styrenated phenol sulfonate, and the like.

  Examples of phosphoric acid ester salts include higher alcohol phosphoric acid ester salts and higher alcohol ethylene oxide adduct phosphoric acid ester salts.

  Specific examples of higher alcohol phosphoric acid ester salts include lauryl alcohol phosphoric acid monoester disodium salt, lauryl alcohol phosphoric acid diester sodium salt; specific examples of higher alcohol ethylene oxide adduct phosphoric acid ester salts include oleyl alcohol ethylene oxide 5 mol adduct phosphate monoester disodium salt.

  Examples of the cationic surfactant (F3) include a quaternary ammonium salt type and an amine salt type.

  The quaternary ammonium salt type is obtained by a reaction between a tertiary amine and a quaternizing agent (an alkylating agent such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, dimethyl sulfate; ethylene oxide, etc.) For example, lauryl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, stearyl trimethyl ammonium bromide, lauryl dimethyl benzyl ammonium chloride (benzalkonium chloride), cetyl pyridinium chloride, polyoxyethylene trimethyl ammonium chloride, stearamide ethyl diethyl Examples include methylammonium methosulfate.

  As amine salt type, primary to tertiary amines are inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid, alkylphosphoric acid, etc.) It is obtained by neutralizing with For example, the primary amine salt type includes inorganic or organic acid salts of higher aliphatic amines (higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine); Examples include fatty acid (stearic acid, oleic acid, etc.) salts and the like. Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as ethylene oxide adducts of aliphatic amines. Examples of the tertiary amine salt type include aliphatic amines (triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), ethylene oxides of aliphatic amines (2 moles). Above) Adducts, alicyclic amines (N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine, 1,8-diazabicyclo (5,4,0) -7-undecene, etc.) , Inorganic acid salts or organic acid salts of nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole, 4,4′-dipyridyl, etc.); triethanolamine monostearate, stearamide ethyl diethyl methyl ethanol Examples include inorganic acid salts or organic acid salts of tertiary amines such as amines.

  Examples of the amphoteric surfactant (F4) include a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, and a phosphate ester type amphoteric surfactant. The carboxylate-type amphoteric surfactants further include amino acid-type amphoteric surfactants and betaine-type amphoteric surfactants.

Examples of the carboxylate-type amphoteric surfactants include amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants. Examples of amphoteric surfactants having an amino group and a carboxyl group include compounds represented by the following general formula.
_{[R-NH- (CH 2)} n-COO] mM
[Wherein R is a monovalent hydrocarbon group; n is usually 1 or 2; m is 1 or 2; M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium cation, an amine cation, an alkanolamine cation. Etc. ]
Specifically, for example, an alkylaminopropionic acid type amphoteric surfactant (sodium stearylaminopropionate, sodium laurylaminopropionate, etc.); an alkylaminoacetic acid type amphoteric surfactant (such as sodium laurylaminoacetate), etc. .

  Betaine-type amphoteric surfactants are amphoteric surfactants having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule. For example, alkyldimethylbetaine (stearyl) represented by the following general formula: Dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, etc.), amide betaine (coconut oil fatty acid amide propyl betaine etc.), alkyl dihydroxyalkyl betaine (lauryl dihydroxyethyl betaine etc.) etc. are mentioned.

  Furthermore, examples of the imidazoline type amphoteric surfactant include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

  Examples of other amphoteric surfactants include glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; pentadecylsulfotaurine, etc. Examples include sulfobetaine-type amphoteric surfactants.

  Examples of the nonionic surfactant (F5) include alkylene oxide addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants.

  Alkylene oxide addition type nonionic surfactants include polyalkylene glycols obtained by adding alkylene oxide directly to higher alcohols, higher fatty acids or alkylamines, or by adding alkylene oxides to glycols. It is obtained by reacting a higher fatty acid with a higher fatty acid, adding an alkylene oxide to an esterified product obtained by reacting a higher fatty acid with a polyhydric alcohol, or adding an alkylene oxide to a higher fatty acid amide.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Of these, preferred are ethylene oxide and random or block adducts of ethylene oxide and propylene oxide. The number of moles of alkylene oxide added is preferably 10 to 50 moles, and 50 to 100% of the alkylene oxide is preferably ethylene oxide.

  Specific examples of the alkylene oxide addition type nonionic surfactant include oxyalkylene alkyl ethers (for example, octyl alcohol ethylene oxide addition product, lauryl alcohol ethylene oxide addition product, stearyl alcohol ethylene oxide addition product, oleyl alcohol ethylene oxide addition product). , Lauryl alcohol ethylene oxide propylene oxide block adduct, etc.); polyoxyalkylene higher fatty acid ester (eg, stearyl acid ethylene oxide adduct, lauric acid ethylene oxide adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid ester (For example, polyethylene glycol lauric acid diester, polyethylene glycol oleic acid diester, polyethylene glycol Polyoxyalkylene alkyl phenyl ether (eg, nonylphenol ethylene oxide adduct, nonylphenol ethylene oxide propylene oxide block adduct, octylphenol ethylene oxide adduct, bisphenol A ethylene oxide adduct, dinonylphenol ethylene oxide addition) Polyoxyalkylene alkylamino ether and (for example, laurylamine ethylene oxide adduct, stearylamine ethylene oxide adduct, etc.); polyoxyalkylene alkyl alkanolamide (for example, Hydroxyethyl lauric acid amide ethylene oxide adduct, hydroxypropyl oleic acid Ethylene oxide adducts of bromide, ethylene oxide adducts of dihydroxy ethyl lauric acid amide, etc.) and the like.

  Examples of the polyhydric alcohol type nonionic surfactant include polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid ester alkylene oxide adducts, polyhydric alcohol alkyl ethers, and polyhydric alcohol alkyl ether alkylene oxide adducts.

  Specific examples of polyhydric alcohol fatty acid esters include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dioleate, sucrose monostearate, etc. Is mentioned. Specific examples of the polyhydric alcohol fatty acid ester alkylene oxide adduct include ethylene glycol monooleate ethylene oxide adduct, ethylene glycol monostearate ethylene oxide adduct, trimethylolpropane monostearate ethylene oxide propylene oxide random adduct, sorbitan mono Examples include laurate ethylene oxide adduct, sorbitan monostearate ethylene oxide adduct, sorbitan distearate ethylene oxide adduct, sorbitan dilaurate ethylene oxide propylene oxide random adduct, and the like. Specific examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside, lauryl glycoside and the like. Specific examples of the polyhydric alcohol alkyl ether alkylene oxide adduct include sorbitan monostearyl ether ethylene oxide adduct, methylglycoside ethylene oxide propylene oxide random adduct, lauryl glycoside ethylene oxide adduct, stearyl glycoside ethylene oxide propylene oxide random adduct Etc.

The organic solvent (S) that is optionally contained in the aqueous medium (W) is used as necessary during emulsification dispersion. Specific examples of the organic solvent (S) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane. Solvents: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Ester solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, Ketone solvents such as ruisobutyl 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 An amide solvent such as dimethylformamide and dimethylacetamide; a sulfoxide solvent such as dimethyl sulfoxide; a heterocyclic compound solvent such as N-methylpyrrolidone; and a mixed solvent of two or more of these.
From the viewpoint of affinity with the polyester resin (a), tetrahydrofuran, toluene, acetone, methyl ethyl ketone, and ethyl acetate are preferably used.

When the organic solvent (S) is used when the polyester resin (a) is dispersed, the resin particles (A) are formed by further removing (S).
The method for removing the organic solvent (S) in the above method is not particularly limited, and a known method can be applied. For example, the following [1] to [2] and a combination of these can be applied.
[1] A method of removing a solvent by heating and / or reducing pressure in a general stirring / desolving tank or a film evaporator.
[2] A method of removing the solvent by air blowing on the liquid surface or in the liquid.
The temperature at the time of heating by the method [1] is preferably not higher than the glass transition temperature (Tg) of the resin (a), usually preferably not higher than 5 ° C of Tg, more preferably not higher than 10 ° C, particularly preferably Preferably it is 20 degrees C or less. The degree of decompression (gauge pressure) during decompression is preferably −0.03 MPa or less, more preferably −0.05 MPa or less.

The content of the organic solvent (S) in the aqueous polyester resin dispersion (X) of the present invention is measured using gas chromatography. For preventing reaggregation of (X) and improving storage (storage) stability, it is preferably 0.02 to 2%, more preferably 0.03 to 1%.
The content of the resin particles (A) in the aqueous polyester resin dispersion (X) is preferably 50% or less in order to prevent reaggregation of (A) in (X). More preferably, it is 45% or less, and particularly preferably 5 to 40%.

The volume average particle diameter of the resin particles (A) is 0.01 to 0.2 μm, more preferably 0.01 to 0.15 μm, from the viewpoint of storage (storage) stability of the polyester resin aqueous dispersion (X). Especially preferably, it is 0.01-0.1 micrometer.
In the present invention, the resin particles have a volume average particle size of LAS-920 (manufactured by Horiba) or Multisizer III (manufactured by Coulter), ELS-800 using the laser Doppler method as an optical system. (Otsuka Electronics Co., Ltd.) can be measured. If there is a difference in the measured value of the particle diameter between the measuring devices, the measured value by ELS-800 is adopted.

  The polyester resin particles (A) of the present invention can be obtained by removing the aqueous medium (W) from the aqueous polyester resin dispersion (X).

As a method of removing the aqueous medium,
[1] A method of drying the polyester resin particles (A) under reduced pressure or normal pressure [2] A method of solid-liquid separation with a centrifuge, a spatula filter, a filter press, etc., and drying the resulting powder [3] Polyester Examples thereof include a method of freezing the resin particles (A) and drying them (so-called freeze drying).
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
Moreover, it can classify | classify using a wind classifier etc. as needed, and can also be set as predetermined particle size distribution.

The resin particles (A) containing the polyester resin (a) may contain other resins as long as the properties are not impaired. Other resins include, for example, polyester resins other than (a) having a number average molecular weight of 1,000 to 1,000,000, styrene-based polymers, styrene-acrylic copolymers, styrene-butadiene copolymers, polyolefin resins, and vinyl resins. Resin having a grafted structure, epoxy resin, polyurethane resin.
It may be blended with (a) or partially reacted. The content of other resins is preferably 10% or less, more preferably 5% or less.

In the resin particles (A) containing the polyester resin (a) of the present invention, additives (pigments, fillers, antistatic agents, colorants, mold release agents, charge control agents, ultraviolet absorbers, antioxidants, An anti-blocking agent, a heat-resistant stabilizer, a flame retardant, etc.) may be contained. The total content of additives in (A) is preferably 5% or less, more preferably 3% or less. As a method of adding an additive in (A),
(1) A method in which a polyester resin (a) and an additive are mixed in advance and then dispersed. (2) A polyester resin aqueous dispersion (X) that does not contain an additive is formed, and then a known dyeing method. A method of adding an additive or impregnating with an organic solvent (S).
Is mentioned.

  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The following parts mean parts by weight unless otherwise specified.

Production Example 1
[Synthesis of Polyester Resin (a-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, propylene oxide of bisphenol A (hereinafter referred to as PO) adduct: New Paul BP-2P (manufactured by Sanyo Chemical Industries: PO2 mol adduct 98%, 3 Mole adduct 2%) 512 parts (0.90 mol part), PO adduct of bisphenol A: Newpol BP-3P (manufactured by Sanyo Chemical Industries: PO2 mol adduct 30%, 3 mol adduct 41%, 4 mol) 23% of adduct, 5% or more adduct 6%) 238 parts (0.36 mol part), 271 parts of terephthalic acid (1.00 mol part), 5 parts of titanium diisopropoxybistriethanolamate as a polymerization catalyst The temperature was raised to 230 ° C. After stirring at 230 ° C. for 1 hour, the reaction was conducted at the same temperature while distilling off water under reduced pressure of 5 to 20 mmHg. When the acid value became 2 or less, the mixture was cooled to 180 ° C. and trimellitic anhydride 17 Part (0.05 mol part) was added, and after reacting under normal pressure for 1 hour, the reaction was carried out at the same temperature for 1 hour while distilling off water under reduced pressure of 5 to 20 mmHg, and then taken out. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (a-1).
Tg of (a-1) was 55 ° C., Tm was 105 ° C., Mp was 6000, acid value was 9, SP value was 10.8, and free carboxylic acid content was 800 ppm.
In addition, the molar part in () means a relative molar ratio (the same applies hereinafter).

Production Example 2
[Synthesis of Polyester Resin (a-2)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 714 parts of 1,2-propylene glycol (2.00 mole parts), 679 parts of terephthalic acid (0.87 mole parts), 89 parts of adipic acid ( 0.13 mol part), 5 parts of titanium diisopropoxybistriethanolamate as a polymerization catalyst were added, and the reaction was carried out for 12 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while removing generated water under a nitrogen stream, and further reacted under reduced pressure of 5 to 20 mmHg, and cooled when the softening point reaches 99 ° C. did. The recovered 1,2-propylene glycol was 338 parts (0.95 mole part). Next, the mixture was cooled to 180 ° C., 29 parts (0.03 mol) of trimellitic anhydride was added, reacted for 1 hour under normal pressure, and then at the same temperature for 1 hour while distilling off water under reduced pressure of 5 to 20 mmHg. After the reaction, it was taken out. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (a-2).
Tg of (a-2) was 64 ° C., Tm was 115 ° C., Mp was 9500, acid value was 14, SP value was 11.7, and free carboxylic acid content was 900 ppm.

Production Example 3
[Synthesis of Polyester Resin (a-3)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 419 parts (0.50 mole part) of terephthalic acid, 419 parts (0.50 mole part) of isophthalic acid, 626 parts of ethylene glycol (2.00 moles) Part), 0.5 part of tetrabutoxy titanate was added as a polymerization catalyst, and the reaction was allowed to proceed for 5 hours while distilling off the water produced in a nitrogen stream at 210 ° C., and then for 1 hour under reduced pressure of 5-20 mmHg. . Next, 25 parts of trimellitic anhydride was added, and the mixture was reacted for 3 hours under normal pressure. Then, the reaction was carried out at the same temperature for 10 hours while distilling off water under reduced pressure of 5 to 20 mmHg, and then taken out. The recovered monoethylene glycol was 303 parts (0.97 mol part). The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (a-3).
Tg of (a-3) was 62 ° C., Tm was 125 ° C., Mp was 11000, acid value was 10, SP value was 12.4, and free carboxylic acid content was 1200 ppm.

Production Example 4
[Synthesis of Polyester Resin (a-4)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 155 parts (0.53 mol part) of 1,2-propylene glycol, 339 parts (0.85 mol part) of neopentyl glycol, 643 parts of terephthalic acid (0.95 mole part), 30 parts (0.05 mole part) adipic acid, 0.5 part of tetrabutoxy titanate as a polymerization catalyst, and 12 hours while distilling off the water produced in a nitrogen stream at 180 ° C Reacted. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while removing generated water under a nitrogen stream, and further reacted under reduced pressure of 5 to 20 mmHg, and cooled when the softening point reaches 99 ° C. did. The recovered 1,2-propylene glycol was 74 parts (0.25 mol part). Next, the mixture was cooled to 180 ° C., 22 parts (0.03 mole part) of trimellitic anhydride was added, reacted for 3 hours under normal pressure, and then at the same temperature while distilling off water under reduced pressure of 5 to 20 mmHg. After reacting for 10 hours, it was taken out. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (a-4).
Tg of (a-4) was 56 ° C., Tm was 107 ° C., Mp was 10500, acid value was 15, SP value was 11.5, and free carboxylic acid content was 1100 ppm.

Production Example 5
[Synthesis of Polyester Resin (a-5)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 413 parts (1.50 mole part) of ethylene glycol, 231 parts (0.50 mole part) of neopentyl glycol, 442 parts of terephthalic acid (0.60 part) Mol part), 295 parts (0.40 mole part) of isophthalic acid, and 0.5 part of tetrabutoxytitanate as a polymerization catalyst were allowed to react at 180 ° C. for 12 hours while distilling off the water generated in a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while removing generated water under a nitrogen stream, and further reacted under reduced pressure of 5 to 20 mmHg, and cooled when the softening point reaches 99 ° C. did. The recovered monoethylene glycol was 260 parts (0.94 mole part). Next, after cooling to 180 ° C. and adding 34 parts (0.04 mole part) of trimellitic anhydride and reacting under normal pressure for 3 hours, water was distilled off under reduced pressure of 5 to 20 mmHg at the same temperature. After reacting for 10 hours, it was taken out. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (a-5).
Tg of (a-5) was 56 ° C., Tm was 107 ° C., Mp was 10500, acid value was 20, SP value was 11.8, and free carboxylic acid content was 1500 ppm.

Production Example 6
[Synthesis of Polyester Resin (a-6)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 340 parts of 1,2-propylene glycol (1.00 mol part), 232 parts of neopentyl glycol (0.50 mol part), 708 parts of terephthalic acid (0.96 mol part), 29 parts (0.05 mol part) of adipic acid, 5 parts of titanium diisopropoxybistriethanolamate as a polymerization catalyst, and water generated under a nitrogen stream at 180 ° C. was distilled off. The reaction was continued for 12 hours. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while removing the generated water under a nitrogen stream, and further reacted under reduced pressure of 5 to 20 mmHg, and taken out when the softening point becomes 110 ° C. It was. The recovered 1,2-propylene glycol was 150 parts (0.44 mole part). The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (a-6).
Tg of (a-6) was 50 ° C., Tm was 110 ° C., Mp was 9100, acid value was 1, SP value was 11.3, and free carboxylic acid content was 800 ppm.

Production Example 7
[Synthesis of Polyester Resin (a-7)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 309 parts (1,0 mol part) of 1,2-propylene glycol, 212 parts (0.50 mol part) of neopentyl glycol, 645 parts of terephthalic acid (0.96 mole part), 27 parts (0.05 mole part) adipic acid, 5 parts titanium diisopropoxybistriethanolamate as a polymerization catalyst, and distilled off the water produced at 180 ° C under a nitrogen stream. The reaction was continued for 12 hours. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while removing generated water under a nitrogen stream, and cooling was performed when the softening point reached 100 ° C. Next, the mixture was cooled to 180 ° C., added with 89 parts (0.11 mol part) of trimellitic anhydride, reacted for 1 hour under normal pressure, and then at the same temperature for 1 hour while distilling off water under reduced pressure of 5 to 20 mmHg. After the reaction, it was taken out. The recovered 1,2-propylene glycol was 136 parts (0.44 mole part). The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (a-7).
Tg of (a-7) was 59 ° C., Tm was 120 ° C., Mp was 9400, acid value was 52, SP value was 11.7, and free carboxylic acid content was 950 ppm.

Comparative production example 1
[Synthesis of Polyester Resin (Ra-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1,2-propylene glycol 330 parts (1.00 mol part), neopentyl glycol 226 parts (0.50 mol part), terephthalic acid 688 parts (0.96 mole part), 29 parts (0.05 mole part) of adipic acid, 0.5 part of tetrabutoxy titanate as a polymerization catalyst, and 12 hours while distilling off the water produced at 180 ° C. under a nitrogen stream Reacted. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while removing generated water under a nitrogen stream, and further reacted under reduced pressure of 5 to 20 mmHg, and cooled when the softening point reaches 99 ° C. did. The recovered 1,2-propylene glycol was 145 parts (0.44 mole part). Subsequently, it cooled to 180 degreeC, 26 parts (0.03 mol part) trimellitic anhydride was added, and it took out after reacting under a normal pressure for 1 hour. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (Ra-1).
(Ra-1) had a Tg of 64 ° C., a Tm of 112 ° C., an Mp of 9800, an acid value of 14, an SP value of 11.5, and a free carboxylic acid content of 3000 ppm.

Comparative production example 2
[Synthesis of polyester resin (Ra-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 674 parts of hydrogenated bisphenol A (1.05 mol part), 39 parts of terephthalic acid (0.10 mol part), 351 parts of adipic acid (0.90) Mol part) and 0.5 part of tetrabutoxy titanate as a polymerization catalyst were added and reacted at 180 ° C. for 12 hours while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while removing generated water under a nitrogen stream, and further reacted under reduced pressure of 5 to 20 mmHg, and cooled when the softening point reaches 99 ° C. did. Subsequently, it cooled to 180 degreeC, 26 parts (0.05 mol part) trimellitic anhydride was added, and it took out after reacting under a normal pressure for 1 hour. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (Ra-2).
(Ra-2) had a Tg of 62 ° C., a Tm of 111 ° C., an Mp of 9900, an acid value of 17, an SP value of 10.3, and a free carboxylic acid content of 1000 ppm.

  Table 1 below shows polyester resins (a-1) to (a-7) obtained in Production Examples 1 to 7, and polyester resins (Ra-1) and (Ra) obtained in Comparative Production Examples 1 and 2. The analysis values of -2) were summarized.

Example 1
[Preparation of aqueous polyester resin dispersion (X-1)]
10 parts of the polyester resin (a-1) obtained in Production Example 1 was dissolved in 30 parts of tetrahydrofuran (THF), and 2 parts of triethylamine was added. After gradually adding 23 parts of water to this well-stirred solution, the solvent was removed until the THF content measured by gas chromatography at 40 ° C. and −0.03 MPa was 0.1% by weight. An aqueous dispersion (X-1) of resin particles containing the resin (a-1) was obtained. (X-1) was desolvated with an evaporator at 40 ° C. and 0.01 MPa, then filtered and dried to obtain polyester resin particles (A-1).
The volume average particle diameter of the resin particles measured with ELS-800 was 0.03 μm.

Example 2
[Preparation of aqueous polyester resin dispersion (X-2)]
An aqueous dispersion (X-2) of resin particles containing the polyester resin (a-2), in the same manner as in Example 1, except that the polyester resin (a-1) is changed to the polyester resin (a-2). And polyester resin particles (A-2) were obtained.
The volume average particle diameter of the resin particles measured with ELS-800 was 0.03 μm.

Example 3
[Preparation of aqueous polyester resin dispersion (X-3)]
10 parts of the polyester resin (a-3) obtained in Production Example 3 was dissolved in 30 parts of tetrahydrofuran (THF), and 2 parts of triethylamine and a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “Eleminol”). MON-7 ") 1 part was added. After gradually adding 23 parts of water to this well-stirred solution, the solvent was removed until the THF content measured by gas chromatography at 40 ° C. and −0.03 MPa was 0.1% by weight. An aqueous dispersion (X-3) of resin particles containing the resin (a-3) was obtained. (X-3) was desolvated with an evaporator at 40 ° C. and 0.01 MPa, then filtered and dried to obtain polyester resin particles (A-3).
The volume average particle size of the resin particles measured with ELS-800 was 0.05 μm.

Example 4
[Preparation of aqueous polyester resin dispersion (X-4)]
Except changing the polyester resin (a-1) to the polyester resin (a-4), in the same manner as in Example 1, an aqueous dispersion (X-4) of resin particles containing the polyester resin (a-4), And polyester resin particles (A-4) were obtained.
The volume average particle diameter of the resin particles measured with ELS-800 was 0.04 μm.

Example 5
[Preparation of aqueous polyester resin dispersion (X-5)]
An aqueous dispersion (X-5) of resin particles containing the polyester resin (a-5), in the same manner as in Example 1, except that the polyester resin (a-1) is changed to the polyester resin (a-5), And polyester resin particles (A-5) were obtained.
The volume average particle diameter of the resin particles measured with ELS-800 was 0.06 μm.

Example 6
[Preparation of aqueous polyester resin dispersion (X-6)]
An aqueous dispersion (X-6) of resin particles containing the polyester resin (a-6), in the same manner as in Example 1, except that the polyester resin (a-1) is changed to the polyester resin (a-6), And polyester resin particles (A-6) were obtained.
The volume average particle diameter of the resin particles measured with ELS-800 was 0.15 μm.

Example 7
[Preparation of aqueous polyester resin dispersion (X-7)]
An aqueous dispersion (X-7) of resin particles containing the polyester resin (a-7), in the same manner as in Example 1, except that the polyester resin (a-1) is changed to the polyester resin (a-7), And polyester resin particles (A-7) were obtained.
The volume average particle size of the resin particles measured with ELS-800 was 0.20 μm.

Comparative Example 1
[Preparation of aqueous polyester resin dispersion (RX-1)]
An aqueous dispersion (RX-1) of resin particles containing the polyester resin (Ra-1), in the same manner as in Example 1, except that the polyester resin (a-1) is changed to the polyester resin (Ra-1), And polyester resin particles (RA-1) were obtained.
The volume average particle diameter of the resin particles measured with ELS-800 was 0.50 μm.

Comparative Example 2
[Preparation of aqueous polyester resin dispersion (RX-2)]
An aqueous dispersion (RX-2) of resin particles containing the polyester resin (Ra-2), in the same manner as in Example 1, except that the polyester resin (a-1) is changed to the polyester resin (Ra-2), And polyester resin particles (RA-2).
The volume average particle diameter of the resin particles measured with ELS-800 was 0.40 μm.

[Test example]
Table 2 shows the evaluation results of storage (storage) stability in which the aqueous polyester resin dispersions (X-1) to (X-7) and (RX-1) and (RX-2) were evaluated by the following method. .
[Preservation (storage) stability]
The aqueous polyester resin dispersion was allowed to stand for 24 hours in a dryer controlled to 50 ° C., and evaluated according to the following criteria depending on the state of the precipitate.
○: No precipitate.
Δ: Precipitate is generated, but disperses easily when lightly shaken.
×: Precipitate is generated and does not disperse even if lightly shaken.

  As described above, the aqueous polyester resin dispersions (X-1) to (X-7) of the present invention exhibit high storage (storage) stability and can obtain resin particles having a small particle size. On the other hand, in the comparative polyester resin aqueous dispersions (RX-1) and (RX-2), sufficient storage (storage) stability cannot be obtained, and the particle size tends to be coarse.

  The aqueous polyester resin dispersion and the polyester resin particles of the present invention are aqueous polyester resin dispersions having a small particle size and high storage (storage) stability, and are used for coating additives, cosmetic additives, and paper coating. Additives, resin for slush molding, powder paint, base particles for electrophotographic toner, spacers for manufacturing electronic parts, standard particles for electronic measuring instruments, particles for electronic paper, carriers for medical diagnosis, particles for electroviscous, and other moldings Useful as resin particles.

Claims (7)

Resin particles (A) containing a polyester resin (a) obtained by polycondensation of an alcohol component (x) and a carboxylic acid component (y) are contained in an aqueous medium (W) containing an organic solvent (S) if necessary. In which the free carboxylic acid content in (a) is 2000 ppm or less, and the SP value in (a) is 10.5 to 12.5 (cal / cm ³ ). Polyester resin aqueous dispersion (X) which is ^1/2 .   The aqueous polyester resin dispersion (X) according to claim 1, wherein the acid value of the polyester resin (a) is 5 to 50 (mg KOH / g).   The polyester resin aqueous dispersion (X) according to claim 1 or 2, wherein the polyester resin (a) has a peak top molecular weight of 2000 to 15000 and a softening point of 90 to 150 ° C.   The polyester resin aqueous dispersion (X) according to any one of claims 1 to 3, wherein the polyester resin (a) is obtained by polycondensation of the alcohol component (x) and the carboxylic acid component (y) in the presence of a titanium-containing catalyst. .   The polyester resin aqueous dispersion (X) according to any one of claims 1 to 4, wherein the content of the organic solvent (S) in the aqueous polyester resin dispersion (X) is 0.02 to 2% by weight.   The polyester resin aqueous dispersion (X) according to any one of claims 1 to 5, wherein the resin particles (A) have a volume average particle size of 0.01 to 0.2 µm.   Polyester resin particles (A) obtained by removing the aqueous medium (W) from the aqueous polyester resin dispersion (X) according to any one of claims 1 to 6.