JP2003321648A - Coating material, adhesive and composition for textile processing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a paint, an adhesive and a composition for textile processing that has high concentration, low viscosity, excellent workability, high stability with time and film-forming properties, when being dried. <P>SOLUTION: The composition is composed of an aqueous dispersion of synthetic resin particles and the particles have a particle size distribution curve that has 2 or more peaks. The aqueous dispersion satisfies either (i) or (ii) or both of them: (i) the larger particle size (P1) and the smaller particle size (P2) of the highest peak and the second peak have the peak height ratio of the large peak (P1)/the small peak (P2) of 2/1-100/1 and 1/1-10/1 and (P1) and (P2) have a peak variation index of 0.1-150%, distortion of -10-10 and convexity of 0-10; (ii) the aqueous dispersion has a concentration of 20-70 wt.% and satisfies relation (1): 1/log (η/η<SB>0</SB>)=Aϕ+B where A=-2 to 0 and B=1 to 5, η<SB>0</SB>and η are viscosities of water and the aqueous solution having a resin concentration of ϕ wt.% in mPas at 25°C, respectively. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

The present invention relates to a paint, an adhesive, a pressure-sensitive adhesive and a fiber processing agent composition comprising an aqueous dispersion of a synthetic resin, and more particularly to a high-concentration paint, an adhesive, a pressure-sensitive adhesive and a fiber processing agent composition. .

[0002]

2. Description of the Related Art Conventionally, coating compositions, adhesive compositions, pressure-sensitive adhesive compositions and fiber processing agent compositions (hereinafter referred to as "coating compositions, etc.") composed of synthetic resin water dispersions have a wide range of fields. It has been desired to provide coating compositions and the like which have a high concentration and a low viscosity. As a method for producing these, JP-A-8-120042 proposes a method in which the median value of the particle size distribution in an aqueous dispersion is set to 1 to 10 μm, and the particles are made larger and have a lower viscosity than ever before. .

[0003]

However, the above method has problems such as poor storage stability of the obtained coating composition and poor film-forming property and drying speed during drying.

[0004]

Means for Solving the Problems As a result of investigations by the present inventors to obtain a coating composition or the like which can solve the above problems,
The present invention has been reached. That is, the present invention is a polyaddition resin,
A coating composition comprising an aqueous dispersion containing particles of at least one resin selected from the group consisting of polycondensation resins, addition condensation resins, ring-opening polymerization resins and addition polymerization resins; Has at least two peaks in the particle size distribution curve; at least one of the peaks is selected from the group consisting of polyaddition resins, polycondensation resins, addition condensation resins and ring-opening polymerization resins. The coating composition comprises at least one resin selected from the following:
A coating composition comprising a dispersion satisfying one or both of (i) and (ii): (i) In a particle size distribution curve, the peak having the highest peak height and the second peak Peak with larger particle size
(P1) and the smaller particle size peak (P2) are 2/1 to 10
The ratio of (P1) peak top particle size / (P2) peak top particle size in the range of 0/1, and (P1) height / (P2) in the range of 1/1 to 10/1 Given the height ratio, both (P1) and (P2) have a coefficient of variation of the peak of 0.1 to 150%, -10 to
Having a skewness of 10 and a saliency of 0-10, and (i
i) The aqueous dispersion satisfies the following relational expression (1) having a coefficient A of −2 to 0 and a constant term B of 1 to 5 within a concentration range of 20 to 70% by weight of an aqueous dispersion. : 1 / log (η / η ₀ ) = Aφ + B (1) In the formula, η ₀ and η are water and Brookfield viscosity (mPa · s, 25 ° C.) of an aqueous dispersion having a resin concentration of φ% by weight, respectively. ) Is represented. And an adhesive composition, a pressure-sensitive adhesive composition or a fiber processing agent composition comprising the dispersion.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In one embodiment of the present invention, a resin aqueous dispersion satisfying the above requirement (i) [hereinafter referred to as an aqueous dispersion (I)] has a specific particle size distribution curve described below. . The particle size distribution curve is created by measuring the weight distribution of the particle size at room temperature by the photon correlation method or the ultrasonic measurement method, and the particle size distribution in the histogram format with the particle size as the horizontal axis and the scattering intensity as the vertical axis. It is a curve. As an apparatus used for the measurement, the photon correlation method is "EL manufactured by Otsuka Electronics Co., Ltd.
S-2000 ", ultrasonic measurement method" D
T-1200 "can be used. The photon correlation method is a preferable measurement method in terms of good resolution in the submicron region.

The resin aqueous dispersion (I) is preferably 2 to 8, more preferably 2 to 4, especially 2 in terms of giving an aqueous dispersion of higher concentration and low viscosity in the particle size distribution curve. Has a peak of. In the particle size distribution curve, of the peak with the highest peak height and the second peak, the peak with the larger particle diameter (P1) and the peak with the smaller particle diameter (P2), the peak top of (P1) Particle size of
The particle size ratio of the peak top of (P2) is preferably 2/1 to 10 both in the photon correlation method and in the ultrasonic measurement method.
It is 0/1, more preferably 2.2 / 1 to 20/1, and particularly preferably 2.5 / 1 to 15/1. If the ratio is at least 2/1, the viscosity tends to be kept low even at a high concentration, and if the ratio does not exceed 100/1, the storage stability tends to be improved. Also, (P1) and (P2) have a ratio of (P1) height / (P2) height of at least 1/1 (preferably at least 1.5 / 1, especially at least 1.8 / 1). Which gives good storage stability; a height of (P1) of at most 10/1 (especially at most 5/1) / P
It has a height ratio of 2), which makes it possible to maintain low viscosity even at high concentrations.

(P1) and (P2) are usually 0.1 to 150%
(Preferably 1 to 100%, especially 15 to 70%) Coefficient of variation, -10 to 10 (preferably -5 to 5 and especially 0)
It has a skewness of 2) and a protrusion of 0-10 (preferably 0.5-10, especially 1-5), thereby giving an aqueous dispersion of low viscosity. The coefficient of variation of peak, saliency and skewness are
It is calculated by the following equations (2), (3) and (4), respectively.

[0008]

[Chemical 1]

Where X is the scattering intensity at each particle size, X
_i is the average value of the scattering intensity at each particle size, n is the degree of freedom,
s represents the standard deviation of the peak that can be calculated from the following formula (5).

[0010]

[Chemical 2]

In another embodiment of the present invention, the above requirement (ii)
A resin aqueous dispersion satisfying the above [hereinafter referred to as an aqueous dispersion (II)] is within a concentration range of 20 to 70% (in the above and below,% represents% by weight unless otherwise specified) of the aqueous dispersion. , The concentration φ and the viscosity η have a relationship represented by the above equation (1). Formula (1) is derived from Malone's formula [“Chemistry of Polymer Latex” (Souichi Muroi, published in 1965), page 125] applied to a high-concentration dispersion system.

The coefficient A and the constant term B in the equation (1) are calculated by the following method. 1) Dilute or concentrate the aqueous dispersion to prepare an aqueous dispersion having a resin concentration φ adjusted to 35, 45, 55 and 65%. 2) Measure the Brookfield viscosity η of the aqueous dispersion of each concentration. 3) Measure the viscosity η ₀ of water. 4) A linear expression expressing the relationship between φ and 1 / log (η / η ₀ ) is obtained by the method of least squares, and the coefficient A and the constant term B are calculated. Equation (1) is usually regressed by a linear equation,
When the contribution rate of φ to 1 / log (η / η ₀ ) is less than 0.6, approximation by a polynomial of second order or higher, approximation by power, or the like can be performed. In that case, the rate of change of 1 / log (η / η ₀ ) with respect to φ is set as the coefficient A. For the concentration φ, 1 to 1.5 g of the sample was precisely weighed on a glass petri dish having a diameter of 9 cm, and the residual weight when it was heated to 130 ° C. for 45 minutes in an air-circulation dryer to evaporate to dryness was precisely weighed. It is expressed as a percentage of the residual weight with respect to the sample weight. The adjustment of each concentration is performed by diluting with water or distilling off water to concentrate. In the latter case (for example, when the concentration is 65% or less).
% Of the aqueous dispersion) can be carried out by heating the aqueous dispersion under reduced pressure (40 to 60 ° C.). The viscosity is
It can be measured using a rotary viscometer manufactured by TOKIMEC Corporation. Viscosity is 20 to 150 mPa · s, No. 1 rotor, 150 to 750 mP
No. 2 rotor for as or less, No. 3 rotor for 750 mPas or less, and No. 3 rotor for 3,000 mPas or less Rotor number 6 with 4 rotors
Measured at 0 rpm.

The aqueous dispersion (II) usually has a viscosity of at least -2 (preferably at least -1).
In particular, a coefficient A of at least -0.5 and at least 1 (preferably at least 1.1, especially at least 1.
15) B; in view of stability over time (no sedimentation), at most 0 (preferably at most -0.001)
A coefficient A of at most -0.015) and a B of at most 5 (preferably at most 4.5, especially at most 3).
Have.

Of the aqueous dispersions (I) and (II),
From the viewpoint that an aqueous dispersion having a lower viscosity can be easily obtained, an aqueous dispersion (I) satisfying the above requirement (i) is preferable, and particularly one satisfying the above requirements (i) and (ii) at the same time. The aqueous dispersion [(I) and (II)] in the present invention is usually 30-
80%, preferably 50-75%, more preferably 6
It has a concentration of 0-70%. The viscosity (25 ° C.) of the aqueous dispersion of the present invention varies depending on the concentration, but the concentration is 65%.
Is usually 10 to 20,000 mPa · s, preferably 20 to 10,000 mPa · s, especially 30 to 5,0.
It is 00 mPa · s.

The aqueous dispersion of the present invention comprises particles of at least one resin selected from the group consisting of polyaddition resins, polycondensation resins, addition condensation resins, ring-opening polymerization resins and addition polymerization resins. Become. In the aqueous dispersion of the present invention, at least one of the peaks in the particle size distribution curve is a polyaddition resin, a polycondensation resin,
The resin comprising at least one kind of resin selected from the group consisting of addition condensation-type resins and ring-opening polymerization-type resins and constituting the other peak may be addition-polymerization type resins.

Polyurethane resins for polyaddition resins; polyester resins, silicone resins, polyamide resins and polycarbonate resins for polycondensation resins; vinyl resins (eg acrylic resins, styrene / polystyrene resins) for addition polymerization resins.
Alkadiene resins and vinyl acetate resins); addition condensation resins include phenol resins and amino resins (for example, urea resins and melamine resins); ring-opening polymerization resins include epoxy resins. Of these resins, preferred is at least one resin selected from the group consisting of polyaddition resins, polycondensation resins and polyaddition resins and / or combined use of polycondensation resins and addition polymerization resins, In particular, one selected from the group consisting of a polyurethane resin (U), a polyester resin (E), (U) and / or (E) in combination with an acrylic resin (M) and / or a styrene / alkadiene resin (D). Alternatively, it is a combination of two or more kinds.

The aqueous dispersion according to the present invention has at least two peaks in the particle size distribution curve, but the kinds of resins constituting those peaks may be the same or different. When different, the preferred combination is
(U) / (E) and (U) / (M).

(U) is an organic polyisocyanate (a
1) and an active hydrogen atom-containing component composed of the polyol (a2) are reacted with each other.

As (a1), those conventionally used for producing polyurethane can be used. Such a polyisocyanate has 2 to 3 or more isocyanate groups and has a carbon number (hereinafter abbreviated as C) (N
The same shall apply hereinafter except carbon in CO group) 6-20 aromatic polyisocyanate, C2-18 aliphatic polyisocyanate, C4-15 alicyclic polyisocyanate, C
8 to 15 araliphatic polyisocyanates, modified products of these polyisocyanates, and combinations of two or more thereof.

As the aromatic polyisocyanate, 1,
3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 4,4′- and / or
Or 2,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane with a small amount (for example, 5 to 20% by weight)] Mixture with trifunctional or higher functional polyamine]: polyaryl polyisocyanate (PAPI)], 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,
4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5
-Naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m- and p-
Isocyanatophenylsulfonyl isocyanate, etc .;
As the aliphatic polyisocyanate, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2 , 6-Diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6
-Diisocyanato hexanoate, etc .; alicyclic polyisocyanates include isophorone diisocyanate (I
PDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl)-
4-cyclohexene-1,2-dicarboxylate,
2,5- and / or 2,6-norbornane diisocyanate and the like; araliphatic polyisocyanates include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene Diisocyanate (TMXDI) and the like; modified polyisocyanates include the above-mentioned modified polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, isocyanurate group and / or
Or a modified product containing an oxazolidone group; the free isocyanate group content is usually 8 to 33%, preferably 10 to 30
%, Especially 12-29%), eg modified MDI
(Urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI, and other polyisocyanate-modified products such as urethane-modified polyisocyanate [ Excess polyisocyanate (TD
I, MDI, etc.) and a free isocyanate-containing prepolymer obtained by reacting a polyol with a polyol] include a low-molecular polyol described later. Examples of the combination of two or more kinds include a combination of modified MDI and urethane modified TDI (isocyanate-containing prepolymer). Of these, those having 2-3 functional groups, particularly TDI, MDI, HDI and I are preferred.
PDI, hydrogenated MDI, XDI and TMXDI.

(A2) is a polymer polyol (a2) having a hydroxyl group equivalent (Mn per hydroxyl group) of 150 or more.
1), a low molecular weight polyol (a22) and a combination of two or more of these. [In the above and below, Mn
Is gel permeation chromatography (GPC)
Represents the number average molecular weight measured using. ]

(A21) includes polyester polyol (a211), polyether polyol (a212),
The polyolefin polyol (a213) and the polymer polyol (a214) are included. (A211) contains
Condensed polyester (a2111), polylactone polyol (a2112), polycarbonate polyol (a2113) and castor oil-based polyol (a211)
4) is included. (A212) includes an alkylene oxide (hereinafter abbreviated as AO) adduct (a2121) of a compound containing an active hydrogen atom, and a coupled body (a21) thereof.
22) are included.

(A22) is a divalent to octavalent or higher polyhydric alcohol (a221) having a hydroxyl equivalent of 30 or more and less than 150 and a low molar AO adduct of an active hydrogen atom-containing compound (a222). Is included. (A22
1) represents a dihydric alcohol, for example, a C2-12 or higher aliphatic, alicyclic and aromatic dihydric alcohol [(di) alkylene glycol (alkylene glycol and dialkylene glycol. Expression), for example (di) ethylene glycol,
(Di) propylene glycol, 1,2-, 1,3-,
2,3- and 1,4-butanediol, neopentyl glycol, 3-methyl-1,5 pentanediol,
1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol and 1,
12-dodecanediol; low-molecular diol having a cyclic group, such as those described in JP-B-45-1474: bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene, etc.]; trivalent to octavalent or higher Polyhydric alcohols such as alkane polyols (triols such as trimethylol propane,
Glycerin and hexanetriol; tetrafunctional or higher functional polyols such as pentaerythritol, sorbitol, xylitol and mannitol, their intermolecular or intramolecular dehydration products (diglycerin, dipentaerythritol, sorbitan, etc.), sugars (glucose, glucose, Fructose, sucrose, etc.) and derivatives thereof (glycosides such as α-methylglucoside); and hydrophilic group-containing polyols described later.

The AO used in the production of (a2121) and (a222) is C2-12 or higher A.
O, for example ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3- and 1,3-
Butylene oxide, tetrahydrofuran (TH
F), α-olefin oxide, styrene oxide, epihalohydrin (epichlorohydrin, etc.), and a combination of two or more thereof (random and / or block). (A212) and (a22)
The active hydrogen atom-containing compound used for the production of 2) includes 2 to
Includes compounds having 8 or more active hydrogen atoms (compounds having one or more kinds of hydroxyl group, amino group, mercapto group, carboxyl group, etc.); for example, polyhydric alcohols, polyhydric phenols, amines , Polycarboxylic acids, phosphoric acids, polythiols and these 2
Mixtures of more than one species are mentioned. Examples of the polyhydric alcohol include those mentioned above; examples of the polyhydric phenols include
Examples include monocyclic polyhydric phenols (pyrogallol, catechol, hydroquinone, etc.), and bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.). Amines include monoamines and polyamines. Monoamines include ammonia; primary monoamines such as C1-20 monohydrocarbyl (alkyl, cycloalkyl, aryl, aralkyl)
Amines (butylamine, cyclohexylamine, aniline, benzylamine, etc.); and alkanolamines (having a C2-4 hydroxyalkyl group: monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). Examples of the polyamine include C2-18 aliphatic polyamine [eg, alkylenediamine (ethylenediamine, trimethylenediamine, hexamethylenediamine, etc.) and polyalkylenepolyamine (diethylenetriamine, etc.)], C4-15 alicyclic polyamine (dicyclohexylmethanediamine). , Isophoronediamine, etc.), C8
˜15 araliphatic polyamines (xylylenediamine, etc.), C6-20 aromatic polyamines (phenylenediamine, tolylenediamine, diethyltolylenediamine,
Diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine and the like), and heterocyclic polyamines (piperazine, N-aminoethylpiperazine and others described in JP-B-55-21044). For polycarboxylic acid, divalent to
Octavalent or higher, C4-40 or higher,
Includes aliphatic, alicyclic and aromatic carboxylic acids; dicarboxylic acids such as aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc.), alicyclic dicarboxylic acids (dimer Acid, etc.)
And aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), and trivalent or higher polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.). Examples of phosphoric acids are phosphoric acid, phosphorous acid, phosphonic acid, etc .; As polythiols, polythiols corresponding to the above polyhydric alcohols (at least part of OH is replaced by SH), glycidyl group-containing compounds and hydrogen sulfide Examples thereof include polythiols obtained by the reaction.

The addition of AO to the active hydrogen atom-containing compound can be carried out by a conventional method, without catalyst or in the presence of a catalyst (for example, an alkali catalyst, an amine catalyst, an acidic catalyst) (particularly in the latter half of AO addition). Can be carried out in one step or in multiple steps under normal pressure or under pressure. For example, a method of charging an active hydrogen atom-containing compound and a catalyst into a pressure reactor and injecting AO under pressure can be mentioned. Examples of the catalyst include alkali catalysts such as alkali metal hydroxides (lithium, sodium, potassium, cesium, etc.); acids [perhalogen acids (perchloric acid, perbromic acid, periodic acid), sulfuric acid, phosphoric acid, nitric acid, etc. , Preferably perchloric acid] and salts thereof [preferably divalent or trivalent metals (Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu,
Al) salt]. Reaction temperature is usually 50 to 15
The reaction time is usually 0 to 20 hours at 0 ° C. When two or more types of AO are used together, either block addition (chip type, balanced type, active secondary type, etc.) or random addition, a mixed system of both [chips after random addition: ethylene oxide chains randomly distributed in the molecule 0 to 50
%, Preferably 0 to 40% by weight, and 0 to 30% by weight (preferably 5 to 25% by weight) EO chains are chipped at the molecular ends. Preferred among AOs are EO alone, PO alone, THF alone, PO and E.
Combined use of O, combined use of PO and / or EO and THF (in the case of combined use, random, block and mixed system of both)
Is. The number of moles of AO added is usually 1 to 140, preferably 1 to 110, and particularly preferably 1 to 90 per active hydrogen atom. When the number of added moles exceeds 140, the obtained polyurethane resin becomes soft and the strength is lowered. After completion of the AO addition reaction, the catalyst can be neutralized and treated with an adsorbent to remove and purify the catalyst, if necessary.

Examples of (a2121) include polyoxyethylene polyol [polyethylene glycol (hereinafter abbreviated as PEG)], polyoxypropylene polyol [polypropylene glycol (hereinafter abbreviated as PPG)], polyoxyethylene / propylene polyol, poly Examples include tetramethylene ether glycol, EO and / or PO adducts of bisphenols.
(A2122) includes a compound obtained by coupling two or more molecules of (a2121) with an alkylene halide (C1-6, for example, methylene dichloride). As (a212), the degree of unsaturation is small (0.1
Meq / g or less, preferably 0.05 meq / g or less, especially 0.02 meq / g or less) is desirable, and those having a primary hydroxyl group content of at least 30%, preferably at least 50%, especially at least 70%. desirable. (A2111) is a polycondensate of a polyol and a polycarboxylic acid (c1), (a2112) is a polyaddition product of a lactone (c2), and (a2113) is an alkylene carbonate (c3). The polyadduct, (a2114), includes castor oil and castor oil modified with a polyol or AO. As the polyol constituting these, (a22) and / or
Or (a212) [preferably having a hydroxyl equivalent of 500 or less], and (c1) includes the polycarboxylic acid mentioned above as the active hydrogen atom-containing compound [preferably dicarboxylic acid and a small proportion (20% or less) of trivalent). Combined use with the above polycarboxylic acid], and as (c2), C4
~ 12 lactones such as 4-butanolide, 5-pentanolide and 6-hexanolide, and (c3) includes C2-8 alkylene carbonates such as ethylene carbonate and propylene carbonate, which are used in combination of two or more kinds. May be.

(A211) can be produced by a usual method.
(A2111) is, for example, (c1) or an ester-forming derivative thereof [anhydride (maleic anhydride, phthalic anhydride, etc.), lower alkyl (C1-4) ester (dimethyl adipate, dimethyl terephthalate, etc.), acid Halide (acid chloride, etc.)] and an excess equivalent of polyol by dehydration polycondensation or transesterification reaction to give (c
1) or dehydration polycondensation or transesterification reaction of the ester-forming derivative with the polyol and then AO
Or by reacting a polyol with an acid anhydride and AO. (A
2112) and (a2113) can be produced by polyaddition of (c2) or (c3) using a polyol as an initiator. Modified castor oil can be produced by transesterification of castor oil and polyol and / or AO addition. Examples of (a2111) include polyethylene adipate diol, polybutylene adipate diol,
Polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3
-Methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, polyneopentyl terephthalate diol, etc .; (a2112) includes polycaprolactone diol, polyvalero Lactone diol, polycaprolactone triol, etc .; (a2113) as polyhexamethylene carbonate diol, etc .;
Examples of (a2112) include castor oil, trimethylolpropane-modified castor oil, pentaerythritol-modified castor oil, and EO (4 to 30 mol) adduct of castor oil.

Examples of (a213) include polyalkadiene-based polyols such as polybutadiene diol [polybutadiene having a 1,2-vinyl structure and / or a 1,4-trans structure (butadiene homopolymers and copolymers such as styrene butadiene copolymer, acrylonitrile butadiene). Copolymer) diol], and hydrogenated products thereof (hydrogenation ratio: for example, 20 to 10).
0%) and acrylic polyols such as hydroxyalkyl (C2-6) (meth) acrylate [ethyl hydroxyethyl (meth) acrylate and the like] and other monomers [styrene, alkyl (C1-8) (meth). ) Acrylate and the like]. Examples of polybutadiene diol include NISSO-PBG series (G-1000, G-2000, G-3000, etc.)
(Manufactured by Nippon Soda), Poly Bd (R-45M, R-
45HT, CS-15, CN-15, etc. (US ARC
O company).

In (a214), a radical-polymerizable monomer is a polyol [(a211) and / or (a) above].
212) and optionally a polymer-containing polyol obtained by in-situ polymerization in (a22)]. The monomers include styrene, (meth) acrylonitrile, (meth) acrylic acid ester, vinyl chloride and these 2 Mixtures of more than one species are included. Polymerization of the monomer is usually carried out in the presence of a polymerization initiator. The polymerization initiator is of a type that generates free radicals to initiate polymerization, such as 2,2′-azobisisobutyronitrile (AIBN),
Azo compounds such as 2,2′-azobis- (2,4-dimethylvaleronitrile) (AVN); dibenzoyl peroxide, dicumyl peroxide, and JP-A-61-7
Other peroxides or persulfates, perborates, persuccinic acids and the like described in Japanese Patent No. 6517 are included. Azo compounds, especially AIBN and AVN are preferred. The amount of the polymerization initiator used is usually 0.1 to 20 based on the total amount of the monomers.
%, Preferably 0.2 to 10%. The polymerization in the polyol can be carried out without a solvent, but when the polymer concentration is high, it is preferably carried out in the presence of an organic solvent. Examples of the organic solvent include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexane, heptane, dioxane, N, N-dimethylformamide, N,
N-dimethylacetamide, isopropyl alcohol,
Examples include n-butanol and the like. If necessary, the polymerization can be carried out in the presence of a chain transfer agent (alkyl mercaptans, carbon tetrachloride, carbon tetrabromide, chloroform, enol ethers described in JP-A-55-31880, etc.). The polymerization is carried out at a temperature not lower than the decomposition temperature of the polymerization initiator, usually 60 to 180 ° C, preferably 90 to 160 ° C.
It can be carried out under atmospheric pressure or under pressure, and further under reduced pressure. After the completion of the polymerization reaction, the obtained polymer polyol can be used as it is for the production of polyurethane, but it is desirable to remove impurities such as an organic solvent, a decomposition product of a polymerization initiator and unreacted monomers by a conventional means after the reaction. (A214) is usually 30 to 70%
(Preferably 40-60%, especially 50-55%) of the polymerized monomer or polymer dispersed in the polyol,
It is a translucent or opaque white or tan dispersion. The hydroxyl value of (a214) is usually 10 to 300, preferably 20 to 250, especially 30 to 200.

The hydroxyl equivalent of (a21) is usually from 150 to
5,000, preferably 250-3,000, especially 30
It is 0 to 2,500.

Among (a2), the combination of (a21) and (a21) with a small proportion (for example, 20% or less) of (a22) is preferable from the viewpoint of the physical properties of the polyurethane resin. Preferred among (a21) are (a212) and especially (a211).

As the active hydrogen atom-containing component used in the reaction with (a1), in addition to (a2), another active hydrogen atom-containing compound (a3) can be used if necessary.
(A3) includes a polyfunctional compound (a3 containing an active hydrogen atom).
1) and a monofunctional compound (a32) are included. (A
31) is the above polyamine, and polyether polyamine [(a212) and / or (a222) is a hydride of a cyanoalkyl (C2-4) compound (such as cyanated ethyl compound)]; Monoamines, secondary monoamines such as di-hydrocarbyl (C
1-20 alkyl, cycloalkyl, aryl and /
Or aralkyl) amine (such as dibutylamine) and its AO adduct, a monohydric alcohol (such as C1-20 alkanol, cyclohexanol, and benzyl alcohol) and its AO adduct.

By using the compound (d) containing a hydrophilic group and an active hydrogen atom-containing group in the molecule in at least a part of the active hydrogen atom-containing component consisting of the polyol (a2), a self-emulsifying polyurethane resin is obtained. It can be an aqueous dispersion.

The hydrophilic groups in (d) include anionic groups (sulfonic acid groups, sulfamic acid groups, phosphoric acid groups, carboxyl groups, etc., and salts thereof), cationic groups (quaternary ammonium bases, 1 to 4). Tertiary amine bases, and their salts) and nonionic groups (oxyethylene groups,
Hydroxyl groups, etc.) are included. Among the hydrophilic groups, preferred are a sulfamic acid group and a hydrophilic group (Q) having a number of groups peculiar to the atomic group by the Divis method of 0.3 or more. The number of radicals peculiar to the atomic group by the Divis method is described in “Introduction to New Surfactant Activators” (published by Sanyo Kasei Co., Ltd.), page 133. Q is sodium salt of carboxyl group (group number = 19.1), potassium salt of carboxyl group (group number = 19.1).
21.1), sodium salt of sulfonic acid group (group number = 3
8.7) and other anionic groups; quaternary ammonium bases,
Cationic groups such as tertiary amine acetate groups; and oxyethylene groups (group number = 0.33), hydroxyl groups (group number = 0.
5) such as non-ionic groups are included.

(D) includes those containing 1 or 2 to 8 or more (preferably 2) active hydrogen atom-containing groups, and the active hydrogen atom-containing groups include a hydroxyl group,
Carboxyl and amino groups are included. Preferred is one containing two or more (particularly two) active hydrogen atom-containing groups, and a combination thereof with one having one active hydrogen atom-containing group (the weight ratio of the combined use is 100/0 to 50). /
50).

Examples of (d) having an anionic group include diol sulfonate [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and the like], sulfopolycarboxylic acid [sulfoisophthalic acid, sulfosuccinic acid and the like].
And aminosulfonic acid [2-aminoethanesulfonic acid and 3-aminopropanesulfonic acid and the like]; sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or its AO addition Thing (AO is EO or PO, A
O addition mole number 1 to 6): for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 mole addition product]; bis (2-hydroxy Ethyl) phosphate, etc .; dialkylol alkanoic acid [C6-24, eg 2,2-dimethylolpropionic acid (DMP
A), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, etc.] and amino acids (2-aminoethanoic acid, etc.); and salts thereof such as amines ( Triethylamine,
Alkanolamines, morpholine, etc.) and / or alkali metal salts (sodium salts, etc.). The cationic group-containing (d) includes quaternary ammonium group-containing diols, tertiary amino group-containing diols and salts thereof (carboxylic acid salts and the like); alkyl (C
1-8) dialkanol (C2-4) amine (N-methyldiethanolamine etc.) and dialkyl (C1-C1)
6) Alkanol (C2-4) amines (N, N-dimethylethanolamine etc.), and these acids [organic acids such as C1-8 carboxylic acids (acetic acid etc.), sulfonic acids (toluenesulfonic acid etc.); inorganics Acid such as hydrochloric acid, sulfuric acid, phosphoric acid, etc.)] and a quaternizing agent [having a C1-8 alkyl group or a benzyl group,
Examples thereof include quaternary compounds of sulfuric acid ester, carbonic acid ester, halide and the like (dimethyl sulfate, dimethyl carbonate, methyl chloride, benzyl chloride, etc.)]. Specific examples of the ionic group (anionic group or cationic group) -containing polyurethane resin aqueous dispersion include Japanese Patent Publication No. 42-24.
192 and Japanese Patent Publication No. 43-9076.

PEG and polyethylene propylene glycol (Mn = 100) are included in (d) having a nonionic group.
~ 3,000) are included. You may use together nonionic (d) and anionic (d) or cationic (d).

The content of (d) in the self-emulsifying (U) aqueous dispersion is preferably 0.1% or more, more preferably 0.5 to 3 based on the weight of the polyurethane resin.
It is 0%. Particularly when (d) is a nonionic compound,
Preferably 3 to 30% [(a211) or (a21
When 2) is used and the polyoxyethylene chain (additional mole number of 2 or more) is contained therein, the weight thereof is also included], preferably 5 to 20%. When (d) is an ionic compound, the weight of (d) is preferably 0.1 to 10%, more preferably 0.5 to 5%, based on the weight of the polyurethane resin, and converted to equivalents. Then, it is preferably 0.01 to 2 meq / g, more preferably 0.05 to 1 meq / g.

The self-emulsifying aqueous dispersion of (U) includes, for example, an H component consisting of (a1), (a2) containing (d) and optionally a terminating agent (e1), and optionally an organic solvent. Is added to form a urethane prepolymer in a single stage or multiple stages, and then the prepolymer is hydrophilized (neutralized or quaternized), or while being hydrophilized, if necessary, a chain extender (f) and a crosslinking agent (x ) And / or a terminating agent (e2) and mixed with an aqueous medium to form an aqueous dispersion, which is reacted until the NCO groups are substantially eliminated [chain extension with water or (f), and optionally with (x) crosslinking. And / or stopping the reaction by (e2)]. Hydrophilization (neutralization or quaternization) may be performed after formation of the aqueous dispersion. Chain extension with (f) and optionally (x) and / or (e2)
When the reaction is stopped by (1), the prepolymer is dispersed in an aqueous medium, and then (f) and (x) if necessary.
It is preferred to add and / or (e2) to react with the prepolymer. In the presence of an organic solvent (a1)
And the above H component are reacted with each other to form a prepolymer solution, and the chain extender (f) and optionally the cross-linking agent (x) and / or the terminating agent (e2) are reacted with each other, or in the presence of an organic solvent (a1 ) And the above-mentioned H component and, if necessary, the crosslinking agent (x) and / or the terminating agent (e2) in a single step to form an organic solvent solution of (U) and disperse it in an aqueous medium. Thus, an aqueous dispersion of (U) can be formed. Also in this case, the hydrophilization (neutralization or quaternization) may be performed before the formation of the aqueous dispersion, at the stage of formation, or after the formation.

In the prepolymer, the equivalent ratio of isocyanate group / active hydrogen-containing group (excluding carboxyl group) of (a1) and H component is usually 1.01 to 2, preferably 1.1 to.
It is formed by reacting at a ratio of 1.6. The amount of (e1) optionally added to the H component is usually 5 equivalent% or less, preferably 3 equivalent% or less. The prepolymer is usually formed by a reaction at 20 ° C to 150 ° C, preferably 60 ° C to 110 ° C, and a reaction time is usually 2
~ 10 hours. The prepolymer can be formed in the presence or absence of an organic solvent that is substantially non-reactive with NCO groups. Prepolymer is usually 0.5-5%
It has a free NCO group content of. The hydrophilization of the prepolymer can be carried out by using a base [(d) is an anionic compound] or
It can be carried out using an acid or a quaternizing agent [when (d) is a cationic compound]. The aqueous dispersion contains the prepolymer, usually at 10 ° C to 60 ° C, preferably at 20 ° C.
At 40 ° C, mixed and dispersed with an aqueous medium [water or a mixture of water and a hydrophilic organic solvent optionally containing (f), (x) and / or (e)] to react, If necessary, it can be formed by distilling off the organic solvent.

The organic solvent used in the above reaction and the hydrophilic solvent contained in the aqueous medium are as described above (a2).
Of the organic solvents mentioned in 14), those which are substantially non-reactive with NCO groups and hydrophilic (water-miscible), respectively.
(Ketones, esters, ethers, amides, alcohols). The ratio of water to hydrophilic solvent is usually 100/0 to 50/50, preferably 100/0.
-80/20, especially 100/0.

As the chain extender (f) and the cross-linking agent (x), polyamine [(h32) above] can be used.
The amounts of (f) and (x) used are usually 0.5 to 2 equivalents of the primary and secondary amino groups of (f) and (x), preferably 1 to 2 equivalents of the isocyanate groups remaining in the prepolymer. Is 0.9 to 1.2 equivalents. The terminating agent (e1) includes a monofunctional compound [the above (a3
2): primary monoamine, secondary monoamine, monohydric alcohol, etc., and monofunctional ones of (d)]; for the terminating agent (e2), the above monofunctional compound, and [the above (h3
12): Mono- and di-alkanolamines and the like] are included. The amount of (e2) used is the free N of the prepolymer.
The amount is usually 0.5 equivalents or less, preferably 0.03 to 0.3 equivalents, relative to 1 equivalent of the CO group. (E
2) may be contained in an aqueous medium or may be added at the stage of chain extension of the prepolymer.

Instead of or in addition to using (d) as at least part of (a2), (e1) and / or
Alternatively, by using (d) as at least a part of (e2), it is possible to produce a self-emulsifying type (U) aqueous dispersion.

The aqueous dispersion of (U) can be made into an emulsifier-emulsified aqueous dispersion of (U) using an emulsifier.
The emulsifier emulsifying type aqueous dispersion of (U) is, for example, (a)
2) In the presence of an organic solvent in the same manner as described above except that an emulsifier is used instead of or together with (d) as at least a part of [or (e1) and / or (e2)]. Alternatively, it is produced by forming a prepolymer in the absence of the polymer, mixing it with an aqueous medium to obtain an aqueous dispersion, and carrying out a reaction [chain extension and, if necessary, crosslinking and / or reaction termination], and distilling off an organic solvent as necessary. be able to. The emulsifier may be added to either the prepolymer or the aqueous medium, or to both. If the emulsifier is reactive with the prepolymer, it is preferably added to the aqueous medium. The amount of the emulsifier added is usually 0.2 to 10%, preferably 0.3 to 6%, based on the weight of the urethane prepolymer.
However, when (d) is used, the amount may be smaller than the above range depending on the amount.

Emulsifiers include anionic, cationic, nonionic and amphoteric surfactants, polymeric emulsifying dispersants, and combinations of two or more thereof, eg US Pat. No. 3,929,678 and US Pat. No. 43314
No. 47 specification is mentioned.

Examples of the anionic surfactant include ether carboxylic acids having a C8-24 hydrocarbon group or salts thereof [sodium lauryl ether acetate, (poly) oxyethylene [degree of polymerization (hereinafter abbreviated as p) = 1 to 100]. ] Sodium lauryl ether acetate, etc.], sulfates or ether sulfates having a C8-24 hydrocarbon group and salts thereof [sodium lauryl sulfate, (poly)]
Oxyethylene (p = 1 to 100) sodium lauryl sulfate, (poly) oxyethylene (p = 1 to 100) lauryl sulfate triethanolamine, (poly) oxyethylene (p = 1 to 100) coconut oil fatty acid monoethanolamide sulfate Sodium, etc.], a sulfonate having a C8-24 hydrocarbon group [sodium dodecylbenzenesulfonate, etc.], and one or two C8-24 hydrocarbon groups.
Unique sulfosuccinates, phosphates or ether phosphates having C8-24 hydrocarbon groups and salts thereof [sodium lauryl phosphate,
(Poly) oxyethylene (p = 1 to 100) lauryl ether phosphate sodium, etc.], fatty acid salt having a C8-24 hydrocarbon group [sodium laurate, triethanolamine laurate etc.] and C8-24 carbonization Acylated amino acid salt having hydrogen group [sodium coconut oil fatty acid methyl taurine, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl -Sodium L-glutamate, sodium lauroylmethyl-β-alanine, etc.]; Nonionic surfactants include aliphatic alcohol (C8-24) AO (C2-8) adducts (p =
1 to 100), polyvalent (2 to 10 or more)
Alcohol fatty acid (C8-24) ester [GL monostearate, sorbitan monolaurate, etc.], fatty acid (C8-24) alkanolamide [1: 1 type coconut oil fatty acid diethanolamide, 1: 1 type lauric acid diethanolamide, etc.] , (Poly) oxyalkylene (C2-
8, p = 1 to 100) alkyl (C1 to 22) phenyl ether, (poly) oxyalkylene (C2 to 8, p)
= 1 to 100) alkyl (C8 to 24) amine and alkyl (C8 to 24) dialkyl (C1 to 6) amine oxide [lauryl dimethyl amine oxide and the like]; cationic surfactants include quaternary ammonium salt type [Stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate], amine salt type [stearic acid diethylaminoethylamide lactate, dilaurylamine hydrochloride, oleylamine Lactate and the like] etc .; amphoteric surfactants include betaine-type amphoteric surfactants [coconut oil fatty acid amide propyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N- Mud carboxymethyl betaine, lauryl hydroxy sulfobetaine, lauroyl amide ethyl hydroxyethyl carboxymethyl betaine hydroxypropyl sodium phosphate, etc.], amino acid type amphoteric surfactants [beta-lauryl amino sodium propionate, etc.] and the like.

Examples of the polymeric emulsifying dispersant include polyvinyl alcohol, starch and its derivatives, cellulose derivatives such as carboxymethylcellulose, methylcellulose and hydroxyethylcellulose, and carboxyl group-containing (co) polymers such as sodium polyacrylate in which Mn =
1,000 to 50,000 and US Patent No. 5
Polymer type dispersants having a urethane bond or an ester bond described in the specification of 906704 [for example, polycaprolactone polyol (a2112) and polyether diol (a2121) are mixed with polyisocyanate (a
Those linked in 1)] can be used.

Among these emulsifiers, preferred ones are
Nonionic surfactants and polymeric emulsion dispersants, especially the polymeric emulsion dispersants having a urethane bond or an ester bond described in the above publication.

The weight average particle diameter of the aqueous dispersion (U) in the present invention is usually 0.01 to 4 μm, preferably 0.
0 to 1 to 3 μm.

In the above urethanization reaction, in order to accelerate the reaction, a catalyst used in a usual urethane reaction may be used if necessary. The catalysts include amine catalysts such as triethylamine, N-ethylmorpholine, triethylenediamine and cycloamidines [1,8-diaza-bicyclo (5,4,0) undecene-7 described in US Pat. No. 4,524,104. (San Apro / Manufacturing, DBU), etc.]; tin-based catalysts such as dibutyltin dilaurylate, dioctyltin dilaurylate and tin octylate; titanium-based catalysts such as tetrabutyl titanate.

The apparatus for emulsifying and dispersing the prepolymer or (U) solution in an aqueous medium is not particularly limited, and examples thereof include the following emulsifiers: 1) anchor type stirring method, 2) rotor-stator. Formula method [eg "Ebara Milder" (manufactured by EBARA CORPORATION)], 3) Line mill method [eg line flow mixer], 4) Static tube mixing type [eg static mixer], 5) Vibration type [eg "VIBRO MIXER"
(Manufactured by Chilling Industry Co., Ltd.)], 6) ultrasonic impact type [eg ultrasonic homogenizer], 7) high pressure impact type [eg Gaulin homogenizer (Gaurin Co.)], 8) membrane emulsification type [eg membrane emulsification module], and 9) Centrifugal thin film contact type [for example, Filmix]. Of these, 5), 8) and 9) are preferable. When chain extension by (f) and optionally crosslinking by (x) and / or reaction termination by (e2) are carried out, a prepolymer is used by using a continuous emulsifier [preferably 2) above, eg, Ebara Milder]. Is dispersed in an aqueous medium, and then (f) and optionally (x) and / or (e2) are added and mixed by using a batch type emulsifying machine [preferably 1) anchor type stirring system], and mixed. It is preferable to react with.

The Mn of (U) is usually 2,000 to 2,000,000 in the case of the non-crosslinked (thermoplastic) (U).
Or more, preferably 10,000 to 1,50
It is especially 100,000-500,000. Crosslinking type (U) has Mn higher than the above range, G
A high Mn that cannot be measured by PC may be used.

The method for producing the aqueous dispersions (I) and (II) of the resin having at least two peaks in the particle size distribution curve according to the present invention includes, for example, I) having two or more different particle sizes. A method in which an aqueous dispersion of a resin (A1) and an aqueous dispersion of another resin (A2) are separately produced and then mixed; II) another resin (A2) is added to the aqueous dispersion of the resin (A1).
By dispersing the solution or melt of (A2p) or the precursor (A2p), and in the case of (A2p) further converting to (A2),
Method for producing a dispersion containing particles of (A2) having a particle size different from (A1); III) Method for simultaneously producing a dispersion having two or more different particle sizes; and IV) I) above. ~ II
A method combining two or more of I) is included. Preferred from the viewpoint of productivity are I), IV) and especially II).

In the method of II), as an example of the combination of (A1) and (A2) or its precursor, (A1) is (U),
(E), (M) or (D), wherein (A2p) is a urethane prepolymer, and (A1) is (U), (E), (M)
Alternatively, in (D), (A2) may be (E). Of these, (A1) is (U), (E) or (M), (A2p) is a urethane prepolymer (U2p), and particularly (A1) is (U) and (A2p) is ( U2p).

The method for producing the aqueous dispersions (I) and (II) may be batch type or continuous type. The continuous type is preferable from the viewpoint of productivity. The dispersion of resin (A1) and the method of the above II) can be carried out continuously, but resin (A1)
The precursor (A1p) was continuously dispersed in an aqueous medium (A1p)
A dispersion of (A1) is formed by continuously mixing and reacting (f) and (x) and / or (e2) with (b) in a batch manner and reacting them with each other. It is preferred to disperse the solution or melt of (A2) or (A2p) according to method II) above.

Aqueous dispersions (I) and (II) of (U)
Is a polyurethane resin (U
After the aqueous dispersion of 1) is produced by the above-mentioned method of self-emulsification type or emulsification type, while the aqueous dispersion is in a state of being fluidized or agitated, a liquid (melt or Solution type) urethane prepolymer (U2p)
Introduced into the aqueous dispersion of 1) and at the same time as or after dispersion, a chain extension reaction with water is carried out, or (f)
Can be produced by converting (U2p) into a polyurethane resin (U2) by adding and causing a chain extension reaction.

The aqueous dispersion of (U1) is preferably one obtained by adding (f) to the aqueous dispersion of the precursor (U1p) of (U1) and chain extending (U1p). If (U1p) is chain-extended, the standard deviation, skewness, and protrusion of the peaks of the above-mentioned particle size distribution curve tend to fall within the preferred ranges. in this case,
The chain extension reaction can be carried out in either a continuous reaction apparatus or a batch reaction apparatus, but it is preferable to carry out the chain reaction apparatus from the viewpoint of easily completing the reaction. Also, (U
(F) was previously added to the aqueous dispersion of 1) (U2p)
May be dispersed, and (U2p) may be dispersed, and at the same time, chain extension may be performed to form (U2). The emulsifying and dispersing device may be any of the above-mentioned vibration type, membrane emulsifying type, centrifugal thin film contact type and the like. When a resin or precursor solution is used, the organic solvent may be distilled off if necessary.

When the resin (A) is (U), the above (U2p)
However, 1) (U2p) can be used as a means to obtain a dispersion of (U2) having a particle size different from that of (U1) [for example, (U2) has a larger particle size]. In the case of emulsified urethane prepolymer, reduce the amount of hydrophilic group [(d) amount]; 2) If (U2p) is an emulsified urethane prepolymer, reduce the amount of added emulsifier; 3) When the dispersion of (U2) or (U2p) contains a hydrophilic organic solvent,
Reduce its content; 4) reduce the shear force of the urethane prepolymer during emulsification; include a combination of two or more of these.

In the case of 1), the amount of (d) in (U2p) is (U)
It is preferably 20% or less, more preferably 10% or less, especially 5% or less, based on the weight of 2p), and 70% or less, especially 50% or less of the content of (d) in (U1). In the case of 2), the added amount of emulsifier is preferably 6% or less, especially 0.2 to 5%, based on the weight of (U2p), and 70% or less of the added amount of emulsifier in the aqueous dispersion of (U1). It is particularly preferably 50% or less. In the case of 3),
The addition amount of the hydrophilic organic solvent is preferably 10% or less, particularly 0.3 to 8 based on the weight of (U2) or (U2p).
%, And preferably 70% or less, particularly 50% or less, of the amount of the hydrophilic organic solvent added to the aqueous dispersion of (U1).

In the aqueous dispersions (I) and (II) of (U), at least two of the particle sizes may be larger, but the particle size of the particles formed from the liquid urethane prepolymer is larger. It is preferable to do so from the viewpoint of ease of manufacturing.

In addition to (U), polyaddition resins include polythiourethane resins such as polyisothiocyanate (corresponding to (a1) above (NCO group replaced with NCS group)).
Compound] and a polyaddition product of H component consisting of polyol [(a2)]; poly (thio) urea resin such as polyamine [(h32) and / or (a312)] and polyiso (thio) cyanate [( a1) and / or a polyaddition product of the above polyisothiocyanate]; a polymethylenemalonamide, for example, a polyaddition product of diketene and polymethylenediamine; a dithiol [said (h6) eg hexamethylenedithiol] and a divinyl compound (described later Alkadienes, dicarboxylic acid divinyl esters and the like) are included. Method for producing aqueous dispersion of these polyaddition type resins, preferable content of (d) in self-emulsifying resin, emulsifier, amount of emulsifier used in aqueous dispersion of emulsifying resin, weight of aqueous dispersion of resin Average particle size, resin Mw, and aqueous dispersion (I)
The production methods of (II) and (II) are the same as in (U).

The resin (E) includes a polycondensate of polyols and polycarboxylic acid and a polycondensate of oxycarboxylic acid, and the latter includes polylactone.

The polyols include the above-mentioned (a22) and / or (a212). Aliphatic 2- to 4-hydric alcohols and combinations of two or more of these are preferred, and dihydric alcohols (particularly NPG and BE) are more preferred.
At least one selected from PD and HD and a trihydric alcohol and / or a tetrahydric alcohol (T
MP and / or PE). The ratio of the two, from the viewpoint of the hardness of the resulting coating film and the viscosity of the paint,
99.5 / 0.5 to 70/30, especially 98/2 to 80
/ 20 is preferable.

The polycarboxylic acid includes the above (h4). Preferred are C2-10 aliphatic dicarboxylic acids, C
8 to 18 aromatic dicarboxylic acids, C9 to 18 trivalent or higher valent aromatic polycarboxylic acids, and a combination of two or more thereof. More preferred are aliphatic dicarboxylic acids (particularly adipic acid and / or sebacic acid), aromatic divalent to tetravalent carboxylic acids (particularly at least one selected from isophthalic acid, terephthalic acid and trimellitic acid) and especially combinations thereof. (Ratio 20/8
0-50 / 50). For oxycarboxylic acid, C4
~ 12 hydroxyalkanoic acids, for example (c2) above.
Acid corresponding to.

(E) is an ordinary polyester forming method,
For example, esterification or transesterification of a polyol with a polycarboxylic acid or an ester-forming derivative thereof (for example, acid anhydride, lower alkyl (C1-4) ester, etc.), polycondensation of an oxycarboxylic acid, an initiator ( Oxycarboxylic acid, polyols and /
Or polycarboxylic acids, or their partial polycondensates)
Can be prepared by reacting (c2) (for example, ε-caprolactone) or an acid anhydride with AO. The esterification or transesterification can be performed usually at a reaction temperature of 100 to 250 ° C., if necessary using a catalyst and / or a solvent. As the catalyst and the solvent, those usually used in the polyesterification reaction can be used. Examples of the catalyst include dibutyltin dilaurate, tin octylate, p-toluenesulfonic acid, lithium naphthenate and the like; examples of the solvent include the aromatic hydrocarbons and ketones mentioned in the above (a214).

The method for producing the aqueous dispersion (E) is not particularly limited. The emulsifier-emulsion type aqueous dispersion (E) can be produced by using the same emulsifier as in the method for producing the emulsifier-emulsion type (U) aqueous dispersion. Further, the self-emulsifying type (E) aqueous dispersion has a hydroxyl group as an active hydrogen atom-containing group of (d) above as at least a part of the polyols (PEG, EO adduct of bisphenol A, Dialkylol alkanoic acid,
It can be produced by the combined use of sulfonic acid diol, etc.). Further, it can be produced by using a polycarboxylic acid (d1) having an anionic group other than a carboxyl group [for example, sulfoisophthalic acid (salt) and its ester-forming derivative] as a polycarboxylic acid.

The preferred content of (d) in the self-emulsifying type (E) and the amount of the emulsifier used in the emulsifying type aqueous dispersion (E) are the same as those in (U).

The weight average particle diameter of the aqueous dispersion (E) obtained by these methods is usually 0.01 to 4 μm, preferably 0.01 to 3 μm. The Mw of (E) is usually 2,000 to 2,000,000 or more, preferably 10,000 to 1,500,000.

Aqueous dispersions (I) and (II) of (E)
Is a polyester resin (E
After the aqueous dispersion of 1) is produced by the above-mentioned emulsifier emulsification type or self-emulsification type method, while the aqueous dispersion is being fluidized or stirred, using an emulsifier, a solution or melt The polyester resin (E2) can be produced by introducing it into the liquid of the aqueous dispersion of (E1) and dispersing it. In this case, to make (E2) a dispersion having an average particle diameter different from that of the aqueous dispersion of (E1) [for example, (E2) has a larger particle diameter], the aqueous dispersion of (U) As in the case of the dispersion, the method of reducing the amount of (d), the emulsifier and / or the hydrophilic solvent is used.

Polyamide resin is obtained by co-condensing a polycondensate of polyamine and polycarboxylic acid, a polycondensate of aminocarboxylic acid, and a polyamide-forming component (polyamine and polycarboxylic acid or aminocarboxylic acid) and polyols. The polyester polyamide is included. The polyamine includes the above (h32) and / or (a312).
Is included. Preferred are diamines, especially hexamethylenediamine. The polycarboxylic acid includes the above (h4). Preferred are C2-10 aliphatic dicarboxylic acids, C8-18 aromatic dicarboxylic acids, and C9-18 3
To tetravalent or higher aromatic polycarboxylic acid and a combination of two or more thereof, and more preferred are aliphatic dicarboxylic acid (especially adipic acid and / or sebacic acid) and aromatic dicarboxylic acid (especially isophthalic acid). And / or terephthalic acid). Aminocarboxylic acids include C4-12 aminoalkanoic acids such as ω-
Included are capron amino acids, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. Examples of the polyols used for forming the polyester polyamide are (a22) and / or
Alternatively, (a212) can be used. Polyamides can be prepared by a conventional polyamide forming method, for example, polycondensation of polyamine and polycarboxylic acid, polycondensation of aminocarboxylic acid, initiator (aminocarboxylic acid, polyamine and / or polycarboxylic acid, or partial polycondensation thereof). Lactam (eg caprolactam,
It can be produced by reacting at least one of enantolactam, capryllactam and laurolactam). The polyester polyamide is produced by, for example, a method of co-condensing polyols in addition to the above-mentioned polyamide-forming component to introduce an ester bond, or a method of reacting a polyamide containing a carboxyl group (or its ester-forming derivative group) and polyols. You can

The method for producing the aqueous dispersion of polyamide is not particularly limited. The emulsifier-emulsion type aqueous dispersion of polyamide can be produced by using the same emulsifier as in the method for producing the emulsifier-emulsion type (U) aqueous dispersion. The self-emulsifying polyamide aqueous dispersion has an amino group as an active hydrogen atom-containing group of (d) above as at least a part of polyamine and / or polycarboxylic acid [bis (3-aminopropyl ) Methylamine, 3,4-diaminobenzoic acid, diaminotoluenesulfonic acid, and their salts, polyoxyethylene chain-containing polyamines (PEG diaminoethyl ether, etc.)], and polycarboxylic acids having anionic groups other than carboxyl groups It can be produced by using the acid (d1) [for example, sulfoisophthalic acid (salt) and its ester-forming derivative]. In addition, those having a hydroxyl group as an active hydrogen atom-containing group in (d) (PEG,
By using an EO adduct of bisphenol A, dialkyrol alkanoic acid, sulfonic acid diol, etc.) and reacting this with a polyamide forming component or a carboxyl group (or ester forming derivative group) -containing polyamide, a self-emulsifying type Aqueous dispersions of polyester polyamide can be prepared. Preferred content of (d) in self-emulsifying polyamide, emulsifier, amount of emulsifier used in aqueous dispersion of emulsifying polyamide, weight average particle diameter of aqueous dispersion of polyamide, M of polyamide
w, and the production method of the aqueous dispersions (I) and (II) are the same as in (E).

In addition to the above, polycondensation resins include silicone resins; polycarbonate resins; polyimide resins such as pyromellitic dianhydride and diamine [above (h3
2): polycondensation product with hexamethylenediamine, nonamethylenediamine, etc .; polybenzimidazole resin such as tetraaminobiphenyl and dicarboxylic acid [above (h
4): polycondensate with sebacic acid, etc .; polyurea resin,
For example, polycondensate of urea and diamine [(h32)]; polysulfonamide resin, for example, polycondensate of benzyldisulfonyl chloride and diamine [(h32): hexamethylenediamine, etc.]; polysulfonate copolymer, For example, bisphenols (bisphenol A
Etc.) and two kinds of aromatic disulfonyl chlorides (one kind may be carboxylic acid chloride); polycondensates of polysulfone resins such as bisphenols (bisphenol A etc.) and dichlorodiphenyl sulfone;
Polysulfide resins, such as polycondensates of sodium polysulfide and dichloro compounds (ethylene dichloride, ethylene dichloride ether, etc.); poly-p-phenylene resins are included.

Examples of the silicone resin include organopolysiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, methylstyrene-modified silicone, olefin-modified silicone, fluorine-modified silicone, and hydrophilic group-modified silicone (polyether-modified silicone, alcohol-modified silicone, Amino-modified silicone, mercapto-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, etc.) are included.

The polycarbonate resin includes a dihydroxyl compound [for example, the dihydric alcohol of the above (a221), the dihydric phenol of the above (h2), and their AO.
[Alkylene carbonate (c
3) prepared by reaction (polyaddition and transesterification), transesterification with diphenyl carbonate, or phosgenation]. Specific examples include bisphenols such as 4,4′-dihydroxydiaryl (cyclo) alkane and halogen-substituted compounds thereof [bisphenol A, 4,4′-dihydroxydiphenyl-
2,2-butane, 4,4'-dihydroxydiphenyl-2,2- (4-methyl) pentane, 4,4'-dihydroxydiphenyl-1,1-cyclohexane, 4,4
'-Dihydroxy-3,3', 5,5'-tetrachlorodiphenyl-2,2-propane and the like] are included. Preferred is polycarbonate of bisphenol A. Method for producing aqueous dispersion of these polycondensation resins, preferable content of (d) in self-emulsifying resin, emulsifier, amount of emulsifier used in aqueous dispersion of emulsifying resin, weight of aqueous dispersion of resin Average particle size, resin Mw, and aqueous dispersion (I)
The production methods of (II) and (II) are the same as in (E).

The addition-condensation resins include phenolic resins such as phenols [phenol, cresol, xylenol, alkyl (C2-10) phenol, p-chlorophenol, etc.] and formaldehyde condensates (novolac and resole); and Amino resins such as amino group-containing compounds [(thio) urea, ethylene urea, melamine, dicyandiamide, benzoguanamine, aniline,
Toluenesulfonamide and the like] and a condensate of formaldehyde (urea resin, melamine resin, etc.) are included. These Mw are usually 2,000 to 2,000,000 or more, preferably at least 10,000.

Epoxy resins include, for example, British Patent No. 1
543099, U.S. Pat. Nos. 5,238,767 and 5,162,437, and "Epoxy Resins" (1957 issued by McGraw-Hill).
And glycidyl type epoxy resin (such as diglycidyl ether of bisphenol A) and non-glycidyl type epoxy resin (such as alicyclic epoxy resin). The Mw of the epoxy resin is usually 100 to 10,000 or more, preferably 200 to 5,000, and the epoxy equivalent is usually 50 to 5,000 or more, preferably 200 to 2,500. The epoxy resin is a commonly used curing agent such as polyamine [above (h
32)], polycarboxylic acid (anhydride) [(h4),
Or its anhydride] and the like. The Mw of the cured product is usually 2,000 to 2,000,000 or more, preferably at least 10,000.

Method for producing aqueous dispersion of these resins, preferred content of (d) in self-emulsifying resin, emulsifier, amount of emulsifier used in aqueous dispersion of emulsifying resin, weight of aqueous dispersion of resin The average particle diameter and the production method of the aqueous dispersions (I) and (II) are the same as those in (U). The epoxy resin may be cured during or after the formation of the aqueous dispersion, or may be pre-cured and dispersed in an aqueous medium, the precursor (A2 by the method II).
p) is dispersed using an epoxy resin and cured with a curing agent to obtain a cured epoxy resin (A1) having a particle diameter different from that of (A1).
Particles consisting of 2) can be produced.

In the aqueous dispersions [(I) and (II)] of the present invention, in addition to those having different particle diameters made of the same type of resin as described above, a polyaddition type resin and a heavy addition type resin can be used. Consists of at least two resins of different types selected from the group consisting of condensation resins, addition condensation resins and ring-opening polymerization resins [eg (U) and (E) and / or polyamide resins and / or phenols] And a combination of (E) with a polyamide resin and / or a phenol resin]. These aqueous dispersions can also be produced by any of the above methods I) to IV).

Further, the aqueous dispersion of the present invention [(I)
And (II)] are particles of at least one resin selected from the group consisting of polyaddition resins, polycondensation resins, addition condensation resins and ring-opening polymerization resins, and addition polymerization resins [vinyl resins] (V)], which includes particles of at least one resin selected from the group consisting of

The resin (V) contains 1 of the polymerizable unsaturated monomer.
Included are one or more (co) polymers. Polymerizable unsaturated monomers include:

(1) (Meth) acrylic acid ester: (1-1) Hydrocarbyl (C1-20) (meth) acrylate, for example, (cyclo) alkyl (meth) acrylate [methyl, ethyl, propyl, butyl, pentyl , Hexyl, cyclohexyl, 2-ethylhexyl and lauryl (meth) acrylate and the like], and aromatic ring-containing (meth) acrylate [benzyl (meth) acrylate and the like]; (1-2) hydroxyl group and / or ether bond-containing (meth)
Acrylate: (meth) acrylate of polyol [(a22) and / or (a212) above, preferably having a hydroxyl equivalent of 600 or less], for example, diol [C
2 to 12 aliphatic dihydric alcohols, their AO adducts (additional mol numbers 1 to 20) and dihydric phenol AO adducts (additional mol numbers 2 to 20) such as EG, PEG (p
= 2-20), PPG (p = 2-20) and EO adduct of bisphenol A] mono (meth) acrylate,
And trihydric to octahydric or higher polyols [aliphatic polyhydric alcohols (GL, TMP, PE, sorbitol, etc.), their AO adducts (additional mole numbers 1 to 20), etc.]
Mono (meth) acrylate of the above-mentioned polyol; (meth) acrylate of hydrocarbyl (C1-20) ether of the above-mentioned polyol, for example, methoxy PEG (meth) acrylate; mono- (meth) acrylate of the above-mentioned polyol [mono (meth) of dihydric alcohol]. Acrylate, etc.] [C1-30 monocarboxylic acid such as aliphatic monocarboxylic acid (formic acid, acetic acid, oleic acid, acetoacetic acid, etc.),
Alicyclic monocarboxylic acids (cyclohexanecarboxylic acid, abietic acid, etc.), alkyl groups (C1-10) and /
Or nuclear substitution with halogen (Cl, Br, etc.) (substitution degree 1 to 1
3) optionally aromatic monocarboxylic acid (benzoic acid, toluic acid, xylenecarboxylic acid, 4-butylbenzoic acid, 2-methyl-4-chlorobenzoic acid, nonylbenzoic acid, etc.)] ester, for example (meta ) Acryloyloxyethyl and (meth) acryloyloxypropyl acetyl acetate; and polyfunctional (meth) acrylates, such as poly (meth) acrylates of the above polyols [di (meth) acrylates of dihydric alcohols]; (1-3) Cationic group (amino group or quaternary ammonium salt group) -containing (meth) acrylate: primary to tertiary amino group-containing (meth) acrylate, for example, amino (hydroxy) alkyl (C2-4) (meth) acrylate [aminoethyl, amino Propyl and 3-amino-2-hydroxy-propyl (meth) a Relate, etc.],
(Di) alkyl (C1-4) aminoalkyl (C2-
4) (meth) acrylate [(di) methylaminoethyl, (di) ethylaminoethyl, (di) methylaminopropyl and 3- (di) methylamino-2-hydroxy-propyl (meth) acrylate], and complex Ring amino-containing (meth) acrylate [morpholinoalkyl (C2-4) (meth) acrylate such as morpholinoethyl (meth) acrylate, piperidinoalkyl (C
2-4) For example, piperidinoethyl (meth) acrylate and the like]; neutralized products and quaternized products thereof [neutralized products and quaternized products with the acids and quaternizing agents listed in (d) containing a cationic group] ], For example, (meth) acryloyloxyethyltrialkyl (C1-4) ammonium salt (chloride, methosulfate, acetate, etc.); and (1-4) anionic group (carboxyl group or sulfo group) -containing (meth) acrylate , For example, lactone (C3-12) adduct of (meth) acrylic acid (addition mole number 1 to
10) [ε-caprolactone of (meth) acrylic acid 1-
5 mol adduct, etc.] and sulfoalkyl (C2-
4) (meth) acrylate [sulfopropyl (meth) acrylate etc.]; salts thereof such as amines (triethylamine, alkanolamine, morpholine etc.)
Salt and / or alkali metal salt (such as sodium);

(2) Carboxyl group-containing monomers: unsaturated monocarboxylic acids such as (meth) acrylic acid, (iso) crotonic acid and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, Citraconic acid and mesaconic acid; monoalkyl (C1-20) esters of unsaturated dicarboxylic acids, such as maleic acid monomethyl ester, maleic acid monoethyl ester and itaconic acid monobutyl ester; unsaturated carboxylic acid anhydrides,
For example, maleic anhydride and itaconic anhydride; salts of these unsaturated carboxylic acids, for example, salts similar to the above (1-4);

(3) Amide group-containing monomer: (meth) acrylamide; N-hydroxyalkyl or hydrocarbyl (C1-20) -substituted (meth) acrylamide, such as N-methylol (meth) acrylamide, N-alkyl and N, N-dialkyl (meth) acrylamide [N-butyl (meth) acrylamide, etc.], (meth)
Acrylic formamide, N-methyl-N-vinyl acetamide, methyl α-acetamino acrylate, N-
Vinylpyrrolidone; cationic groups (amino groups or 4
(Meth) acrylamide containing a (quaternary ammonium salt group), for example, (meth) acrylamide [(meth) acrylamidoethyltrialkyl (C1-C1) corresponding to the above (1-3)]
4) Ammonium salt and the like]; (meth) acrylamide containing anionic group (carboxyl group or sulfo group), for example, (meth) acrylamidoalkyl (C2-4) sulfonic acid [(meth) acrylamidopropyl sulfonic acid, etc.], (meth) Lactam (C3-12) adduct of acrylic acid (addition mole number 1-10) [ε of (meth) acrylic acid
-Caprolactam 1 to 5 mol adduct, etc.], salts thereof, for example, salts similar to the above (1-4); polyfunctional (meth) acrylamides such as methylenebis (meth) acrylamide;

(4) Aromatic unsaturated hydrocarbons: styrenic monomers such as ST, hydrocarbyl-substituted ST (α- and o-methyl ST, vinyltoluene, ethyl ST, dimethyl ST, isopropyl ST, butyl ST) , Phenyl ST, cyclohexyl ST, benzyl ST, α-methyl ST dimer, etc.), crotylbenzene, vinylnaphthalene and indene, and polyfunctional aromatic unsaturated hydrocarbons such as divinylbenzene, divinyltoluene, divinylxylene and trivinylbenzene. ;

(5) Aliphatic or alicyclic unsaturated hydrocarbon: (5-1) olefinic monomer (monoene), for example, alkene [ethylene, propylene, butene-1, isobutylene, 3-methylbutene-1, Pentene-1, heptene-1, 4-methylpentene-1, diisobutylene, octene, dodecene, octadecene, 1-olefin (C2
0-36) etc.], and cycloalkene [cyclohexene etc.]; (5-2) Alkadienes, for example, C4-12 chain alkadienes (butadiene, isoprene, neoprene,
1,3- and 1,4-pentadiene, 1,6-hexadiene, 1,3- and 1,7-octadiene, 1,3
-Dodecadiene, etc.) and C5-12 cyclic alkadienes (cyclopentadiene, dicyclopentadiene,
Vinylcyclohexene, ethylidene bicycloheptene etc.); and (5-3) terpene [pinene, limonene etc.];

(6) Epoxy group (glycidyl group, etc.)-Containing monomer such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, 3,4-dihydro-1,
2-pyran and the like and (meth) allyl glycidyl ether;

(7) Nitrile group-containing monomer such as AN,
Methacrylonitrile, cyano ST and cyanoalkyl (C2-4) (meth) acrylate [cyanoethyl (meth) acrylate and the like];

(8) Hydroxyl group and / or ether bond-containing monomer other than (1-2) above: (8-1) Unsaturated mono- and polyol: C2-24 unsaturated monohydric alcohol, for example, alkenol [Vinyl alcohol, (meth) allyl alcohol, (iso) propenyl alcohol, crotonyl alcohol, etc.], aromatic unsaturated alcohol [cinnamyl alcohol, p-hydroxystyrene, etc.] and alkynol [propargyl alcohol, etc.]; and unsaturated ( Poly) ether mono- and polyols such as alkenyl or alkenyl aryl (C2-24) ethers of the low molecular weight polyols of (a22) above or their AO adducts [vinyl ether, (meth) allyl ether, (iso) propenyl ether, crotonyl. Ether, cinnamylete ,
Vinyl phenyl ether, etc.], AO (C2-4) adducts of the above unsaturated monohydric alcohols; and (8-2) unsaturated ethers such as unsaturated mono- and polyols [above (8-1)] Building (C1-2
0) ethers such as methoxy PEG (meth) allyl ether;

(9) Vinyl ester-based monomer: unsaturated monool [above (8)] and carboxylic acid [C above (1-2)]
1 to 30 monocarboxylic acid], for example, vinyl ester (vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl methoxyacetate, etc.), isopropenyl acetate, (meth) allyl acetate, benzoate Acid (meth) allyl, (meth) allyloxyethyl acetate and acetoxystyrene;
The unsaturated monool and polycarboxylic acid [(h
4)] with a polyfunctional vinyl ester such as the unsaturated monool and polycarboxylic acid [(h) above]
4)]; a polyfunctional vinyl ester, for example, a polyester (diester or the like) of the above unsaturated monool and the above polycarboxylic acid, and the above unsaturated monool and the above-mentioned unsaturated mono- or dicarboxylic acid (2). Esters with acid [(meth) acrylate, etc.]; (10) Halogen-containing vinyl monomers such as halogenated unsaturated hydrocarbons [vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, (meth) allyl chloride , Mono- and di-chloro ST, chloroprene, US Pat.
No. 238767, etc.], and halogen-substituted alkyl (meth) acrylates [such as fluorinated alkyl (meth) acrylates described in US Pat. No. 5,238,767]; (11) cations other than the above Unsaturated group-containing unsaturated monomer (amino group or quaternary ammonium salt group): amino group (1
, Secondary or tertiary) -containing unsaturated hydrocarbons such as alkenylamine [mono- and di- (meth) allylamine, crotylamine, etc.] and amino group-containing styrenic monomers [amino ST, N, N-dimethylamino] ST,
Vinylbenzylamine, etc.] and heterocyclic amino group-containing unsaturated monomers [4-vinylpyridine, 2-vinylpyridine, 2-methyl-5-vinylpyridine, vinylimidazole, N-vinylpyrrole, N-vinylcarbazole, etc. ]; Neutralized products and quaternized products thereof [neutralized products and quaternized products similar to 1-3) above, for example, vinylbenzyltrimethylammonium salt; (12) Unsaturated ketones, such as vinyl methyl ketone, vinyl ethyl Ketones, vinyl phenyl ketones, and polyfunctional unsaturated ketones (such as divinyl ketone); (13) Sulfur-containing unsaturated monomers such as p-vinyldiphenyl sulfide, vinylethyl sulfide, vinylethyl sulfone, and polyfunctional sulfur-containing unsaturated monomers. Saturated monomer (divinyl sulfone, divinyl sulfoxide,
Divinyl sulfide, etc.); and (14) isocyanate group unsaturated monomers such as isocyanatoethyl (meth) acrylate and m-isopropenyl-α, α-dimethylmethylbenzyl isocyanate.
Others, US Pat. Nos. 4,130,523 and 3,424
Monomers having at least one olefinically unsaturated group described in Japanese Patent No. 706 can also be used. The resin (V) includes acrylic resin (M), styrene resin,
Vinyl acetate resins, olefin resins, acrylonitrile resins, halogen-containing vinyl resins, and the like, and mixtures of two or more thereof are included.

The resin (M) contains at least one (meth) acrylic acid ester (1) (co) polymer and at least one (4) and at least one other monomer. A polymer is included. Preferred among (1) are (1-1), especially alkyl (meth) acrylates. More preferred are methyl methacrylate, 2-ethylhexyl methacrylate and butyl acrylate (hereinafter MM, respectively).
(Abbreviated as A, EHMA, and BA), especially in combination thereof. The other monomer is selected from the group consisting of (2) to (14),
Preferred among them are (4) (particularly ST), (6) (particularly AN) and combinations thereof. (1) in (M)
The content is usually 20 to 100%, preferably 50 to 99%, based on the weight of all monomers (the same applies hereinafter).

The styrene resin includes at least one (co) polymer of the styrene monomer (4) and at least 1
Included are copolymers of species (4) with at least one other monomer. Preferred among (4) is ST. The other monomer is selected from the group consisting of (1) to (3) and (5) to (14), and among them, preferred is (1) [more preferably
(1-1) especially alkyl (meth) acrylate], (5) [more preferably (5-2) especially butadiene and cyclopentadiene], (6) (especially AN) and combinations thereof. The content of (4) in the styrene resin is usually 20 to 1
It is 00%, preferably 50 to 99%. The content of (1) is usually less than 20%. Specific examples of the styrene-based resin include poly ST, ST / α-methyl ST copolymer, and ST / alkadiene-based resin (D). The resin (D) contains ST and at least one (5-2) (co) polymer, and ST, at least one (5-2) and at least one other monomer. Includes coalescence. The other monomer is selected from the group consisting of (1) to (3), (5-1), (5-3) and (6) to (14), among which preferred is (1) [More preferably (1-1) especially alkyl (meth) acrylate], and especially (6) (particularly AN). (D)
Specific examples include a butadiene / ST copolymer, an AN / butadiene / ST copolymer (ABS resin), and a cyclopentadiene / ST copolymer. ST / in ST / (D)
The ratio of (5-2) is usually 20/80 to 80/20, preferably 3
It is 0/70 to 70/30. The content of other monomers is usually 40% or less, preferably 30% or less, and the content of (1) is 2 or less.
It is less than 0%.

Vinyl acetate resins include vinyl acetate polymers and vinyl acetate (usually 20 to 100%, preferably 50%).
~ 99%) and at least one other monomer [preferably
Copolymers [(1) and (4) with (5) (especially ethylene), (8) (especially vinyl alcohol), other (9) (especially other vinyl ester) and a combination of two or more thereof] Content of less than 20%] is included. Specific examples are ethylene /
Included are vinyl acetate copolymers and partial hydrolysates thereof.

The olefin resin includes (co) polymers of at least one olefin monomer (5-1) (polyethylene, polypropylene, polybutene-1, polyisobutylene, poly-3-methylbutene-1, poly). -4-methylpentene-1, polyethylene / propylene copolymer, propylene / isobutylene copolymer, C8-18 olefin copolymer, etc.), and at least one (5-1) (usually 2)
0-100%, preferably 50-99%) and at least 1
Copolymers with other monomers of the species [content of (1), (4) and vinyl acetate less than 20%] are included. Acrylonitrile resins include poly AN and AN (usually 20 to 10).
0%, preferably 50-99%) and at least one other monomer (MMA, methyl acrylate, vinyl acetate, vinyl chloride, vinylidene chloride, N-methyl or ethyl acrylamide, 2-methyl-5-vinyl). (Pyridine, etc.)
A copolymer with [(1), (4), (5-1) and the content of vinyl acetate is less than 20%] is included. The halogen-containing vinyl-based resin includes at least one halogen-containing vinyl-based monomer.
(Co) polymer of (10) (polyvinyl chloride, polyvinylidene chloride, etc.), and at least one (10) (usually 20 to 1)
00%, preferably 50-99%) and at least one other monomer [(1), (4), (5-1), vinyl acetate and AN content is less than 20%]. (For example, vinylidene chloride copolymers described in US Pat. No. 3,424,706) are included.

Hydrophilic monomer in resin (V) [(1) to (1) above]
Hydrophilic group of (14) (anionic group, cationic group,
The ratio of a monomer having an oxyethylene group, a hydroxyl group, etc.) and / or a reactive emulsifier described later] is preferably 10% or less, more preferably 0.1 to 8%. 5% of polyfunctional monomer
It is particularly preferably 1% or less. (V) is usually 2,0
It has a Mn of 00 to 2,000,000 or higher, preferably 10,000 to 1,500,000.

The method for producing (V) and the aqueous dispersion thereof is not particularly limited, and it may be directly obtained by emulsion polymerization or suspension polymerization (V).
And a method of producing the molten or solution form (V) by bulk polymerization or solution polymerization. Emulsion polymerization and suspension polymerization are preferred. The aqueous dispersion of (V) obtained in a molten form or a solution form can be produced by emulsifying an emulsifier in the same manner as in the above (U). At the time of polymerization, known polymerization initiators, emulsifiers, chain transfer agents, organic solvents and the like may be used. Examples of the polymerization initiator include radical polymerization initiators such as azo compounds (AIBN, AVN, azobisisovaleric acid, etc.); peroxides such as organic peroxides (benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, and the like). Lauroyl peroxide, cumene hydroperoxide, etc.) and inorganic peroxides [persulfate (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), perborate, persuccinic acid], and two or more of these Can be used in combination. The amount of the polymerization initiator used is usually 0.1 to 5% with respect to the total amount of the monomers.
The emulsifiers used in the emulsion polymerization include the surfactants mentioned above as the emulsifiers, and the reactive emulsifiers which can be copolymerized in the emulsion polymerization step. Examples of the reactive emulsifier include anionic (meth) acrylic acid ester [bisphenol or its hydrocarbyl (C
1-24) Sulfates of mono (meth) acrylates of (poly) oxyalkylene (C2-4) ethers (such as EO1-8 mol adducts) of substituted compounds (bisphenol A, its styrenated and / or benzylated products, etc.) Ester salt, polyoxyalkylene (C2-4, p = 2-20
0) mono (meth) acrylate sulfate salt, etc.],
Anionic (meth) acrylamide [(meth) acrylamide alkane (C1-24) sulfonate, etc.], anionic (meth) allyl ester [alkyl (C8-2
4) (Meth) allylsulfosuccinate ester salt, etc.]
(These salts include alkali metal salts, ammonium salts, amine salts, quaternary ammonium salts, etc.), other European Patent EP0718379B1 specifications, international application PC
Those described in the T / JP01 / 09863 specification and the like are included. The amount of the emulsifier used is usually 0.1 to 8%, preferably 0.5 to 5%, based on the total amount of the monomers. Examples of chain transfer agents include mercaptans such as alkyl mercaptans (butyl mercaptan, dodecyl mercaptan, etc.); α
-Methylstyrene dimer; halogenated hydrocarbons such as chloroform, carbon tetrachloride and carbon tetrabromide; enol ethers such as those described in JP-A-55-31880; and mixtures of two or more thereof. Use of chain transfer agent is usually 5% based on the total amount of monomers
Below, it is preferably 0.1 to 3%. Organic solvents include
Those included in the above (a214) are included. Preferred are ketones (especially MIBK) and aromatic hydrocarbons. The organic solvent may be removed by a method such as distillation after the polymerization.

The weight average particle diameter of the aqueous dispersion (V) obtained by these methods is usually 0.005 to 4 μm, preferably 0.01 to 4 μm, and particularly 0.01 to 3 μm. In the case where a part of the resin (A) is (V), the dispersions (I) and (II) are prepared according to II) by adding II-1) an aqueous dispersion of the vinyl resin (V1) in advance as described above. After being produced in this manner, while the aqueous dispersion is being fluidized or stirred, another resin (A2) in a molten or solution state (a resin other than an addition polymerization type resin, using an emulsifying machine, For example, (U) and / or (E)] is introduced into an aqueous dispersion of (V1) to disperse it; or, conversely, II-2) an aqueous dispersion of another resin (A1) is previously added. After being produced as described above, the molten or solution vinyl resin (V2) is added to the aqueous dispersion of (A1) by using an emulsifier while the aqueous dispersion is in a state of being fluidized or stirred. It can be produced by a method of introducing and dispersing in. In this case, (V1) and (A2) or (V2)
Aqueous dispersions (I) and (II) having different particle sizes of (A2) can be formed. For example, in order to increase the particle size of (A2) by the method of II-1), 1) weaken the hydrophilicity of (A2), 2) decrease the amount of emulsifier added, and 3) of (A2) Methods such as reducing shear during emulsification, and combinations of two or more thereof are included. Preferred amount of emulsifier in case of 2)
Is similar to the case of (U) described above. In the above case, the dispersion of (V) constituting a part of (A) may be composed of one kind of (V) or two or more kinds of (V) having different particle diameters. The latter dispersion can be produced in the same manner as in the case (U).

Aqueous dispersions (I) and (I
(P1) and (P2) in the particle size distribution curve of I)
The difference in HLB between the resins constituting the above is 0.1 to 10, preferably 2 to 8, and more preferably 3 to 7. If the HLB difference is 0.1 or more, it can be dispersed by using a small amount of a surfactant during the production of the aqueous dispersion of the resin forming (P2), so that the water resistance of the coating film after drying can be improved. The tendency is to improve, and there is a tendency to improve the adhesion to the substrate. Also,
When the difference in HLB is 0.1 or more, it is possible to obtain the intended aqueous dispersion without requiring a large change in mechanical shearing force even when a surfactant is not used. on the other hand,
When the difference in HLB is 10 or less, the hydrophilicity of the resin having the larger HLB does not become too large and becomes almost water-soluble, so that a stable aqueous dispersion can be easily obtained. HLB here
Is the HLB of the Oda method, which is the value of the organic and inorganic properties of organic compounds [Ryohei Oda, Teijin Times, 22 ,. 9 (19
52)] is calculated by the following formula. HLB = 10 × inorganic / organic

In the present invention, the peak top particle size of (P1) in the particle size distribution curve measured by the photon correlation method is preferably 0.1 to 4 μm, more preferably 0.
It is 1 to 3.5 μm, particularly preferably 0.2 to 3 μm, and particularly preferably 0.3 to 2 μm. The peak top particle size of (P1) in the particle size distribution curve measured by an ultrasonic measurement method is preferably 0.1 to 4 μm, more preferably 0.3 to 3 μm, and particularly preferably 0.1.
It is 4-2 micrometers. When the particle size of the peak top of (P1) is 4 μm or less, the particles are less likely to settle over time, and the storage stability is improved.

The particle size of the peak top of (P1) and (P1
The ratio of the particle size at the peak top in 2) is preferably 2/1 to 10 both in the photon correlation method and in the ultrasonic measurement method.
It is 0/1, more preferably 2.2 / 1 to 20/1, and particularly preferably 2.5 / 1 to 15/1. If the ratio is at least 2/1, the viscosity tends to be kept low even at a high concentration, and if the ratio does not exceed 100/1, the storage stability tends to be improved. The particle size of the peak top of (P2) is preferably 0.01 to 1 μm, more preferably 0.01 to 0.3 μm, and particularly preferably 0.03 in both the photon correlation method and the ultrasonic measurement method.
To 0.2 μm, particularly preferably 0.05 to 0.2 μm
m. The particle size at the peak top of (P2) is 0.01
If it is at least μm, the viscosity tends to be low, and the fluidity is even better.

Also, in both the photon correlation method and the ultrasonic measurement method, at least one valley exists between (P1) and (P2) of the particle size distribution curve, and the lowest valley of them exists. Height (for example, valley 1 in FIG. 1, valley 2 in FIG. 2)
Height) is preferably 80% or less of the height of (P2),
It is more preferably 50% or less, and particularly preferably 30% or less. When the height of the valley is 80% or less of the height of (P2), an aqueous dispersion having a sufficiently low viscosity can be obtained.

Further, at least one of the resins forming (P1) and (P2) is a hydrophilic group having a number of groups peculiar to the atomic group by the Divis method of 0.3 or more (more preferably 1.5 or more, especially 2 or more). It is preferable to have (Q). The hydrophilic group Q includes the ionic group (anionic group, cationic group, etc.) and nonionic group exemplified in the above-mentioned self-emulsifying (U). Preferred are alkali metal salts of anionic groups, especially carboxyl groups (such as sodium salts) and alkali metal salts of sulfonic acid groups (such as sodium salts).

A resin having a Q of 0.3 or more can be dispersed by using a small amount of a surfactant, particularly when an aqueous dispersion of a resin forming (P2) is prepared. There is a tendency that the water resistance of the coating film is improved and the adhesion with the substrate is improved. Further, even when the surfactant is not used, it is not necessary to greatly change the mechanical shearing force, and the intended aqueous dispersion can be obtained. The content of Q in the resin forming (P1) and the resin forming (P2) is preferably 0.02 to 30%, particularly 0.05 to 15% based on the weight of the resin.
%, And the difference in Q content in the resins forming (P1) and (P2) is preferably 0.1% or more.
When Q is an ionic group, the difference in Q content is more preferably 0.3 to 10%, especially 0.5 to 3%. When Q is a nonionic group, the difference in Q content is more preferably 0.5 to 20%, especially 1 to 10%. The content of Q can be obtained by calculating the total of Q charged in the resin manufacturing process with respect to the finished resin.

The ratio of resins constituting (P1) and (P2) is usually 10/90 to 95/5, preferably 50/50 to 9
It is 0/10. The total of the resins constituting (P1) and (P2) is preferably 30 to 100%, especially 50 to 100%, based on the total weight of all the resins.

In the aqueous dispersion, those used as a dispersion medium are usually water and hydrophilic organic solvents. As the hydrophilic organic solvent, the solubility in water among the organic solvents mentioned in the above (a214) is used. Is over 30g / 100g
Water, such as monohydric alcohols (methanol, ethanol, i-propanol, etc.), glycols (E
G, PG, diethylene glycol and the like), trivalent or higher alcohols (GL and the like), cellosolves (methyl and ethyl cellosolve and the like) and the like. Among the dispersion media, the preferred one is an aqueous medium, especially water. When a hydrophilic organic solvent is used in combination, usually, the hydrophilic organic solvent is preferably 10% or less based on the total dispersion medium.

The coating composition, adhesive composition, pressure-sensitive adhesive composition and fiber processing composition of the present invention can be produced by using the above-mentioned aqueous dispersion.

In the coating composition (coating agent composition) of the present invention, the above aqueous dispersion can be used as a binder component and is usually applied to an aqueous coating composition. Preferred for this application are (U), (E), (M)
And (D).

The coating composition may contain a crosslinking agent for the purpose of improving the coating performance. The crosslinking agents include the following (x1) to (x4). (X1) Water-soluble or water-dispersible amino resins such as melamine resins and urea resins containing (alkoxy) methylol groups and / or imino groups [preferably methylol groups and / or
Or melamine resin containing imino group]; (x2) Water-soluble or water-dispersible polyepoxide, for example, bisphenol A type glycidyl ether, hydrogenated bisphenol A
Type glycidyl ether, polyol [above (a221)
(EG, GL, TMP, sorbitol, etc.), and their AO (C2-3) adduct (PEG, etc.)] glycidyl ether, and an emulsifier (such as the above-mentioned surfactant) are added to impart water dispersibility. Polyepoxide, etc. [preferably glycidyl ether of polyhydric alcohol,
In particular, sorbitol poly (di- to hexa) glycidyl ether and GL poly (di- and tri) glycidyl ether]; (x3) water-soluble or water-dispersible polyisocyanate compounds, for example, hydrophilic groups (such as polyoxyethylene chains) in the molecule. [, Such as "Coronate 3062" and "Coronate 3725" (manufactured by Nippon Polyurethane Industry Co., Ltd.)], and blocked polyisocyanate [said (a1) (isocyanurate modified I
PDI and the like blocking agent (US Pat. No. 4,524,410)
Phenols, active methylene compounds, lactams, oximes, bisulfites, tertiary alcohols, aromatic secondary amines, imides and mercaptans described in No. 4:
(Eg, phenol, MEK, ε-caprolactone, etc.)]; (x4) Others, polyethyleneurea (diphenylmethane-bis-4,4′-N,
N'-ethylene urea etc.).

The coating composition may contain one or more aqueous resins other than those of the present invention for the purpose of improving coating film performance. The water-based resin includes the following water-soluble resin (x5) and water-dispersible resin (x6). (X5) The water-soluble resin contains a hydroxyl group (a hydroxyl group-containing vinyl polymer such as polyvinyl alcohol, a natural polymer derivative such as carboxymethyl cellulose and methyl cellulose, a hydroxyl group-terminated polyester polycondensate) or a carboxyl group. Those containing carboxyl group-containing vinyl polymers such as polyacrylic acid and their neutralizing salts, carboxyl group-terminated polyester polycondensates and their neutralizing salts, etc., those containing sulfone groups (polystyrene sulfonic acid and its salts, etc.) And a polymer containing an alkylene oxide chain (polyethylene oxide, a copolymer of ethylene oxide and propylene oxide, etc.) and a polymer containing an ethyleneimine chain (polyethyleneimine, etc.).
Examples of the (x6) water-dispersible resin include polyaddition resins other than the present invention, polycondensation resins, addition condensation resins, ring-opening polymerization resins and aqueous dispersions of addition polymerization resins. Acrylic resins (methacrylic acid ester derivatives, copolymers of vinyl monomers such as styrene and butadiene), polyester resins (polyvalent carboxylic acids such as adipic acid, sebacic acid, isophthalic acid and ethylene glycol, trimethylolpropane, etc.) Polycondensates of polyhydric alcohols), alkyd resins (polyhydric carboxylic acids such as adipic acid, sebacic acid, isophthalic acid, and polyhydric alcohols such as ethylene glycol and trimethylolpropane, and oils and fats such as coconut oil and linseed oil) Polycondensation product), epoxy resin (bisphenol A diglycidyl ether and glycerin diglycidyl) Water-dispersible resins such as condensation products of polyhydric epoxy compounds such as ether and polyhydric amines, active hydrogen-containing compounds such as polycarboxylic acids, etc. The amount of the aqueous resin to be added is usually based on the weight of the pigment. 0 to
It is 3,000%, preferably 0 to 1,000%.
In the coating composition, if necessary, other additives such as a film-forming auxiliary resin, a pigment, a pigment dispersant, a viscosity modifier, a defoaming agent, a leveling agent, an antiseptic, a deterioration inhibitor, a stabilizer and an antifreeze agent. It is possible to add one kind or two kinds or more such as an agent.

Examples of the pigment include inorganic pigments such as white pigments (titanium white, zinc white, lithopone, lead white etc.), transparent white pigments (calcium carbonate, barium sulfate, calcium silicate etc.), black pigments (carbon black, Animal black, red lead, etc.), gray pigment (zinc dust, slate powder, etc.), red pigment (red iron oxide, red lead, etc.), brown pigment (amber, iron oxide powder, bandaiq tea, etc.), yellow pigment (yellow lead, etc.) Zinc chromate, yellow iron oxide, etc., green pigments (chrome green, chromium oxide, viridian, etc.), blue pigments (ultra-blue, navy blue, etc.), purple pigments (Mars purple, light-cobalt purple, etc.) and metallic pigments (aluminum flakes, copper) Bronze flakes, micaceous iron oxides, mica flakes, etc.) as well as organic pigments such as natural organic pigments (cochineal lake, mudder lake, etc.) ), And synthetic organic pigments such as nitroso pigments (Naphthol / Grin Y, Naphthol / Grin B, etc.), nitro pigments (Naphthol / Yellow S, Pigment / Chlorine, Litol / Fast / Yellow GG, etc.), pigment-type azo pigments ( Toluidine Red, Hansa Yellow, Naphthol AS-G, etc.),
Azo lakes made from water-soluble dyes (Persian orange, Ponceau 2R, Buildy B, etc.), Azo lakes made from sparingly soluble dyes (resole red, bone maroon, red lake, etc.), Lakes made from basic dyes (fanal color) Etc.), lakes made from acid dyes (acid green lakes, peacock blue lakes, etc.), xanthan lakes (Eosin, etc.), anthraquinone lakes (alizarin lake, purpurin lakes, etc.), pigments from vat dyes ( Indigo, argon, yellow, etc.) and phthalocyanine pigments (phthalocyanine blue, phthalocyanine green, etc.) are included.

Examples of the pigment dispersant include various surfactants listed as emulsifiers in the emulsifier-emulsion type resin aqueous dispersion described above [anionic, cationic, nonionic, amphoteric,
Polymer systems (Mn = 1,000 to 20,000)] are included. Examples of the viscosity modifier include thickeners such as inorganic viscosity modifiers (sodium silicate, bentonite, etc.), cellulose viscosity modifiers (methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, etc., Mw is usually 20,000 or more), proteins. System (casein, casein soda, casein ammonium, etc.), acrylic (sodium polyacrylate, ammonium polyacrylate, Mw is usually 20,000 or more), and vinyl (polyvinyl alcohol, Mw is usually 20,
000 or more) is included. Acrylic and vinyl are preferred. Antifoaming agents include long-chain alcohols (octyl alcohol, etc.), sorbitan derivatives (sorbitan monooleate, etc.), silicone oils (polymethylsiloxane, polyether-modified silicone, fluorine-modified silicone, etc.)
Preservatives include organic nitrogen-sulfur compound-based preservatives, organic sulfur-halogen compound-based preservatives, etc .; deterioration inhibitors and stabilizers (UV absorbers, antioxidants, etc.) include hindered phenol-based, hindered amine-based, Hydrazine-based, phosphorus-based, benzophenone-based, benzotriazole-based, etc .; Antifreezing agents include EG, PG and the like. The blending amount of these components varies depending on the use, but in general, in the case of a pigment-based coating composition, 10 to 300 parts (solid content) of the resin aqueous dispersion and 0 to 30% (crosslinking agent) per 100 parts of the pigment ( Solid content), aqueous resin 0-3,000 parts (solid content), viscosity modifier 0-5 parts, antifoaming agent 0-5 parts, preservative 0-5 parts, deterioration inhibitor or stabilizer 0-5. Parts, and 0 to 5 parts of antifreezing agent. In addition, in the clear coating composition, the defoaming agent is usually 0 to 100 parts (solid content) of the resin aqueous dispersion.
3 parts, 0 to 3 parts of antiseptic, 0 to 3 parts of UV inhibitor, and 0 to 8 parts of antifreezing agent.

The pigment-based aqueous coating composition is prepared by mixing the above-mentioned resin aqueous dispersion with a pigment dispersant, adding a pigment thereto to disperse the mixture, and optionally adding other additives, and filtering off an undispersed substance. It can be manufactured by a method or the like. For the above dispersion, a disperser (atomizer, bead mill, three rolls, ball mill, etc.) can be used.

The coating composition of the present invention is prepared by the usual coating means.
(Spray painting, brush painting, roll painting, etc.)
You can The viscosity of the coating composition depends on the coating method.
Therefore, it is appropriately selected. For example, in the case of spray painting,
Preferably shear rate 1000s ^-1Viscosity is 20 ~
50 mPa · s, shear rate 10 s^-1Viscosity is 180 ~
It is 280 mPa · s. Shearing speed 1000s^-1Stickiness in
If the degree is less than 50mPa ・ s, it will be sprayed.
Rake, shear rate 10s^-1Viscosity at 180 mPa · s or less
Sagging is unlikely to occur at the top. These viscosities are high
With a shear viscometer ("HSV-2" manufactured by Nippon Seiki Co., Ltd.)
To be measured. The coating composition of the present invention is directly applied to the object to be coated.
Can be painted through a primer or a single layer
Or it is possible to apply multiple layers (2-8 layers),
It can be used as a coating, a middle coating and a top coating. Cover
Painted materials include wood, paper, leather, metal (aluminum,
Iron, copper, various alloys, etc.), plastic (PVC resin,
Acrylic resin, styrene resin, etc.), inorganic materials
(Concrete, slate, calcium silicate board
Etc) are included. The form of the object to be coated may be film or fiber.
Fiber, non-woven fabric, sheet, board, rod, pipe, block,
Various molded bodies, constructs, etc. are included.

The coating composition of the present invention includes various coating compositions and coating compositions (top coatings, intermediate coatings and under coatings for automobiles, coatings for building materials, anticorrosion coatings for metals, and scratch protection for metals and resins). Coatings, water-resistant coatings for paper and leather, solvent-resistant coatings and moisture-proof coatings, and floor polish coatings), various binder compositions (binders for automobile paints, binders for external wall coatings, binders for coated papers, etc.) And a binder for ceramics). The coating amount of the coating composition varies depending on the use and purpose, but is usually 0.5 to 1,000 g / m ² , preferably 1 to 300 as the aqueous coating composition itself (wet form).
It is g / m ² . Drying conditions after painting are from room temperature to 200 ° C
It is a degree. The drying method is not particularly limited, for example, hot air,
Infrared rays, electric heaters, etc. are used.

In the adhesive composition of the present invention, the above aqueous dispersion can be used as a main agent. Preferred for this application are (U), (E), (M) and epoxy resins.

To the adhesive composition of the present invention, an aqueous resin and / or a cross-linking agent other than those of the present invention can be added in order to improve the adhesive function, and if necessary, an inorganic filler and a stabilizer. Additives such as surfactants, viscosity modifiers, preservatives and antifreezing agents can be added. Specific examples of these include the following. Aqueous resin: acrylic type, vinyl acetate type, vinyl chloride type other than the present invention,
Water-soluble resins and water-dispersed resins such as urethane-based, SBR-based, and NBR-based resins. Crosslinking agent: water-dispersible polyisocyanate compound, water-soluble or water-dispersible amino resin, water-soluble or water-dispersible polyepoxide, polyethylene urea, etc. Inorganic filler: calcium carbonate, silica, talc, etc. Stabilizer: hindered phenol Type, hydrazine type, phosphorus type, benzophenone type, benzotriazole type, oxalic acid anilide type, hindered amine type, etc. Dispersant: polyacrylic acid and its salts (Mw is usually 2
(Less than 10,000) etc. Surfactant: Nonionic surfactant such as alkylene oxide adduct of aliphatic alcohol. Thickeners: polyacrylic acid and its salts, cellulose derivatives, starch derivatives, polyvinyl alcohol and the like (these Mw are usually 20,000 or more). Preservative: Organic nitrogen-sulfur compound type, organic halogen compound type, etc. The blending amount of these components varies depending on the use, but generally 0 to 100 parts (solid content) of the aqueous resin other than the present invention and 0 to 100 parts (solid content) of the synthetic resin dispersion of the present invention. -30% (solid content), inorganic filler 0-30 parts, stabilizer 0-5 parts, dispersant 0-5 parts, surfactant 0-5.
Parts, thickener 0 to 5 parts, preservative 0 to 5 parts. The method for mixing the aqueous dispersion and the cross-linking agent is not particularly limited, and examples thereof include a method of mixing by a normal stirring and a mixing device (paint conditioner, ball mill, kneader, sand grinder, flatstone mill, etc.).

Means for applying the adhesive composition to an adherend include brush coating, roll coating, spray coating, flow coating,
Immersion etc. are included. Adhesion is performed by applying the adhesive composition to one adherend and bonding it to the other adherend as it is (without drying) (wet adhesion), or after drying it, the other adherend. It can be carried out by laminating with (dry adhesion) and curing the adhesive layer. In addition, a dry film of the adhesive composition may be interposed between the adherends and cured to bond the adherends. Curing is performed at room temperature or under heating (for example, 60 to 80 ° C).
Curing) or by curing at room temperature and then heating to about 60 to 80 ° C. to accelerate curing. The adherend is not particularly limited and can be widely used for substrates such as wood, resin film, rubber, leather, paper and metal. The adhesive composition of the present invention is, for example, an adhesive for woodworking, an adhesive for metal parts, an adhesive for plastics,
It is useful as an adhesive for electronic substrates and an adhesive for cloth.

The aqueous dispersion of the present invention comprises a binder composition for fiber processing (a binder composition for pigment printing, a binder composition for non-woven fabric, a sizing agent composition for reinforcing fibers, a binder composition for antibacterial agents, etc.) and a coating. Composition (waterproof coating composition, water repellent coating composition,
Antifouling coating composition), raw material composition for artificial leather / synthetic leather, etc.

Preferred binder compositions for pigment printing are (U), (E) and (M); Preferred binder compositions for non-woven fabric are (U), (E) and (M); Focusing for reinforcing fibers. Preferred for the agent composition are (U), (E),
(M) and epoxy resin; (U), (E) and (M) preferred for antibacterial binder composition; (U), (E) and (M) preferred for coating composition; artificial leather -(U) is preferable for the raw material composition for synthetic leather. When used as a binder composition for pigment printing, the aqueous dispersion may optionally contain an emulsifier, a stabilizer (such as an ultraviolet absorber and an antioxidant), a thickener, a film-forming aid, and other auxiliaries. One kind or two or more kinds thereof can be added. Emulsifiers include those similar to those mentioned above. Particularly, anionic surfactants and nonionic surfactants are preferable. Stabilizers and thickeners include those similar to those exemplified in the paints above. Film-forming aids include N-methyl-2-pyrrolidone and the like; other aids include printing suitability imparting agents and gum-up preventing agents. Pigment printing can be carried out by printing on a fabric in the same manner as ordinary pigment printing. Specifically, for example, a color paste (a pigment in which water is finely and uniformly dispersed), an aqueous dispersion of the present invention, a thickener, and other auxiliaries are mixed to prepare a printing paste. Is printed on fabrics. A paddle type mixing tank or the like is used for blending. For printing, an automatic screen printing machine, a rotary screen printing machine, a roller printing machine or the like can be used. For the cloth, natural fibers (cotton, hemp, wool, silk, etc.), semi-synthetic fibers (rayon, acetate, etc.), synthetic fibers (polyester, polyamide, polyAN, polyolefin, etc.) can be used.

The reinforcing fiber applied when used as the sizing composition for reinforcing fiber is described in British Patent No. 154309.
Inorganic fibers (glass fiber, carbon fiber, etc.) and high-strength organic fibers (polyamide fiber, polyester fiber, etc.) described in No. 9 are included. When used as a sizing agent composition for glass fibers, the aqueous dispersion of the present invention, if necessary,
Silane coupling agent (γ-aminopropylethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc.), lubricant (fatty acid amide, soap) Etc.), antistatic agents (such as the above-mentioned surfactants), plasticizers (such as phthalic acid esters and adipic acid esters), defoaming agents (as described above)
It is possible to add one kind or two or more kinds of additives such as. The sizing agent composition may be used in combination with other sizing agent composition, and examples thereof include starch, modified starch, dextrin, amylose, gelatin, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, aqueous polyester resin, A water-based epoxy resin and a water-based acrylic resin are included. A treatment liquid is prepared by mixing the aqueous dispersion and any additive, and the treatment liquid is applied to the fiber, and if necessary, heated and dried to be fixed. A mixing tank (such as a paddle type) is used for compounding. The concentration of the treatment liquid is usually 1 to 10%. The application to the fiber is performed by roller coating, spray coating, impregnation coating, or the like. The amount attached to the fiber is usually 0.1 to 10%. Drying and fixing can be performed with warm air of 50 to 100 ° C., for example.

When used as a binder composition for an antibacterial agent, a coating composition, a raw material composition for artificial leather / synthetic leather, an additive, a concentration of a treatment liquid, an application means to a fiber, an adhesion amount to a fiber, a treatment condition. The above may be the same as the above, and can be appropriately selected depending on the application.

[0121]

The present invention will be described in more detail with reference to Examples and Production Examples, but the present invention is not limited thereto. In the following, parts are based on weight unless otherwise specified. In addition, the viscosity was measured at 25 ° C. by a rotary viscometer (60 rpm) manufactured by TOKIMEC CORPORATION unless otherwise specified.

Production Example 1 [Urethane Prepolymer (u1)
Production]; PMPA (Mn = 2,000) in an autoclave equipped with a thermometer, a stirrer, and a gas blowing tube.
73 parts, BD 3 parts, dimethylolpropionic acid 5 parts, acetone 5 parts, IPDI 34 parts were charged, the gas phase part of the container was replaced with nitrogen and then sealed, and after urethanization at a temperature of 80 ° C. with stirring. , Cooled to 40 ℃, and acetone 3
6 parts of triethylamine and 4 parts of triethylamine were added, and the mixture was sealed and sufficiently homogenized to obtain a urethane prepolymer solution (u1).

Production Example 2 [Urethane prepolymer (u2)]
Production]; 2 parts of dimethylolpropionic acid charge,
A urethane prepolymer solution (u2) was obtained in the same manner as in Production Example 1 except that the amount of IPDI charged was 33 parts and the amount of triethylamine used was 2 parts.

Production Example 3 [Urethane prepolymer (u3)]
Production of;] Polytetramethylene glycol diol (Mn = 2,000) was used in place of PMPA, the amount of BD was 5 parts, and the amount of IPDI was 33 parts, in the same manner as in Production Example 1. , Urethane prepolymer solution (u
3) was obtained.

Production Example 4 [Urethane prepolymer (u4)]
Preparation of ;; urethane prepolymer solution (u4) in the same manner as in Production Example 3 except that the charged amount of dimethylolpropionic acid was 2 parts and the charged amount of triethylamine was 2 parts.
Got

Production Example 5 [Urethane Prepolymer (u5)
Production of]; PHCD (Mn = 2,0 instead of PMPA
00) is used, the amount of IPDI charged is 25 parts, and BD
A urethane prepolymer solution (u5) was obtained in the same manner as in Production Example 1 except that was not used.

Production Example 6 [Urethane prepolymer (u6)]
Production of]; A urethane prepolymer solution (u6) was obtained in the same manner as in Production Example 5 except that the charged amount of dimethylolpropionic acid was 2 parts and the charged amount of triethylamine was 2 parts.

Production Example 7 [Urethane Prepolymer (u7)]
Production of PCLD]; PCLD (manufactured by Daicel Chemical Industries, Ltd., trade name “PLACCEL L22” in place of 73 parts of PHCD
0AL ") 99 parts, dimethylolpropionic acid charge amount is 2.8 parts, acetone charge amount in the urethanization step is 54 parts, IPDI charge amount is 24 parts, acetone charge amount after cooling Was obtained, and a urethane prepolymer solution (u7) was obtained in the same manner as in Production Example 5, except that the charged amount of triethylamine was changed to 2 parts. (U1) to (u
Table 1 shows the NCO content per solid content of 7).

[0129]

[Table 1]

Production Examples 8 to 13 [Production of Polyurethane Resin Aqueous Dispersion (U1 to U6)]: Clearmix CLM-0.8S (manufactured by M Technique Co., Ltd.), which is a rotor-stator type mechanical emulsifier. Used, rotation speed 7,000-9,0
(U1) was continuously supplied at a rate of 45 parts / min and water at a rate of 45 parts / min into a rotor-stator rotating at 00 rpm, and dispersion was performed at room temperature. The residence time was 2 minutes. For the aqueous dispersion stored in the receiving tank with a stirrer,
Ethylenediamine in an amount equivalent to the isocyanate group of (u1) was added, the mixture was stirred at 30 ° C. for 30 minutes to cause a chain extension reaction until the isocyanate group was substantially eliminated, and then acetone was distilled off under reduced pressure. Then, the same amount of water as distilled off together with acetone and the same amount of triethylamine as distilled off together with acetone were respectively added to obtain 250 parts of the aqueous dispersion (U1) of the present invention. (U
Aqueous dispersions (U3) and (U5) were obtained in the same manner as in the production of (U1) except that (u3) or (u5) was used instead of 1). Further, in place of (u1), (u2), (u4) or (u6) was used, and the chain extension reaction after emulsification was carried out in water at 50 ° C. for 12 hours, except that (U1) was produced. Similarly, the aqueous dispersion (U
2), (U4) and (U6) were obtained respectively.

Production Example 14 [Production of Polyurethane Resin Aqueous Dispersion (U7)]: In a four-necked flask equipped with a thermometer, a stirrer and a cooling tube, which was previously charged with 125 parts of water,
230 parts of (u7) was added under high speed stirring to perform dispersion. Ethylenediamine 2 was added to the resulting aqueous dispersion.
4 parts of a solution prepared by dissolving 2 parts of water in 2 parts of water was added at 40 ° C.
After stirring for 2 hours, the isocyanate group at the molecular end is subjected to a chain extension reaction, acetone is distilled off under reduced pressure, and then water and triethylamine in the same amount as distilled water and triethylamine are added together with acetone to form an aqueous dispersion (U7 )
Got

Production Example 15 [Production of Polyester Resin Aqueous Dispersion (E1)]; To a four-necked flask equipped with a thermometer, a stirrer, a water separation tube and a gas blowing tube, toluene 4 was added.
Section, MIBK2 section, BEPD11 section, HD8 section, PE1
Part, 14 parts of sebacic acid, and 14 parts of isophthalic acid were charged, and the temperature was 180 ° C. with stirring while introducing nitrogen gas.
After dehydration esterification with, the solution was introduced into a four-necked flask containing 1 part of triethylamine, 1 part of polyoxyethylene lauryl ether (40 of oxyethylene) and 80 parts of water under high-speed stirring, and further, Toluene, MIB
K was distilled off under reduced pressure to obtain an aqueous dispersion (E1).

Production Example 16 [Acrylic resin aqueous dispersion (M
Production of 1)]: MMA 15 parts, EHMA 32 parts, BA3
0 parts, AN 5 parts, ST 10 parts, 8 parts of the polymerizable emulsifier Antox MS-60 (manufactured by Nippon Emulsifier Co., Ltd.) and 100 parts of water were mixed to obtain a monomer dispersion liquid. Next, a thermometer, a stirrer,
In an autoclave equipped with a pressure gauge, a monomer solution inlet, an initiator solution inlet and a nitrogen gas blowing tube, water 35
Section, Antox MS-60 (manufactured by Nippon Emulsifier Co., Ltd.) 8
Parts, 5 parts of ammonium persulfate, and 0.4 parts of diammonium hydrogen phosphate were charged, the inside of the container was replaced with nitrogen, and the above monomer dispersion was added dropwise at 75 to 85 ° C. over 6 hours while stirring. After that, stirring was continued at the same temperature for 3 hours, and then t-
1 part of butylperoxy-2-ethylhexanoate was added and stirring was continued for 2 hours at the same temperature to give an aqueous dispersion (M
1) was obtained. Table 2 shows the HLB and hydrophilic group contents of the synthetic resins constituting each aqueous dispersion obtained in Production Examples 8 to 16, and the concentration and viscosity of each aqueous dispersion.

[0134]

[Table 2]

Production Examples 17 to 21, Comparative Production Examples 1 to 3;
Two or one of (U1) to (U6), (E1) and (M1) was blended in solids at the blending parts shown in Table 3, and after stirring for 30 minutes, the temperature was adjusted to 60 ° C. by an evaporator.
The mixture was concentrated with to obtain an aqueous dispersion having a solid content concentration of 65% shown in Table 5. In addition, the particle size distribution of these aqueous dispersions was measured by the photon correlation method, and the average particle size, variation coefficient, skewness and salientity of (P1) and (P2) were calculated, and the results are shown in Table 4. Table 5 shows the particle diameter ratio of peak tops, the height ratio of peak tops, and the like.

[0136]

[Table 3]

[0137]

[Table 4]

[0138]

[Table 5]

Production Example 22 [Polyurethane resin aqueous dispersion (UU4)]: In a rotor-stator disperser [Ebara Milder (manufactured by EBARA CORPORATION)] rotated at a rotation speed of 9,000 rpm, ( U1) was supplied continuously at a rate of 380 parts / min and (u2) was continuously supplied for 2 minutes at a rate of 550 parts / min and dispersed at room temperature to obtain 1,860 parts of an aqueous dispersion. Was charged into a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, 100 parts of a 10% aqueous solution of ethylenediamine as a chain extender was added, and the mixture was stirred at 30 ° C. for 1 hour to extend the isocyanate group at the molecular end. After the reaction, acetone was distilled off under reduced pressure to obtain a solid content concentration of 65%.
An aqueous dispersion (UU4) of was obtained.

Production Example 23 [Polyester / Polyurethane Resin Aqueous Dispersion (EU2)]; (E1) in place of (U1) at 380 parts / min, and (u1) in place of (u1).
Was continuously fed at a rate of 80 parts / min for 2 minutes at the same time, and the amount of a 10% aqueous solution of ethylenediamine was set to 23 parts, in the same manner as in Production Example 6 and an aqueous dispersion having a solid content concentration of 65%. (EU2) was obtained.

Production Example 24 [Acrylic / Polyurethane Resin Aqueous Dispersion (MU2)]; Instead of (U1), (M
An aqueous dispersion (MU2) having a solid content of 65% was obtained in the same manner as in Production Example 6 except that 1) was supplied at 170 parts / min.

Production Example 25 [Aqueous Polyurethane Resin Dispersion (UU5)]; Membrane Dispersion Module (Ise Chemical Industry Co., Ltd.) Pore Diameter 0.05 μm, 10φ × 125 mm
The SPG film (Silas porous glass film: manufactured by SPG Techno Co., Ltd.) was attached, and the flow rate was adjusted so that (U2) passed through the inside of the SPG film at 20 parts / min. 40 parts of the back pressure (0.8MP
It was supplied at 4.6 parts / min using a), passed through the porous pores of the SPG membrane and contacted with (U2) inside to disperse (u1). Then, the mixture was further stirred at 50 ° C. for 12 hours in a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and the isocyanate at the molecular end was extended with water, and then acetone was distilled off under reduced pressure to give a solid. Aqueous dispersion with a concentration of 65% (U
U5) was obtained.

Production Example 26 [Polyurethane resin aqueous dispersion (UU6)]: The same dispersion machine "Ebara Milder" as in Production Example 6 was rotated at 12,000 rpm.
A production example in which 146 parts / min of water and (u1) were continuously supplied at a rate of 184 parts / min for 10 minutes to produce a dispersion, and the produced dispersion was subsequently rotated at a rotation speed of 9,000 rpm. A second disperser "Ebara Milder" similar to that of No. 6 was continuously supplied with 330 parts / min and (u2) at a rate of 550 parts / min for 10 minutes. The obtained aqueous dispersion (8,800 parts) was charged into a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and 1,000 parts of a 10% aqueous solution of ethylenediamine as a chain extender was added, After stirring at 30 ° C. for 1 hour to cause an isocyanate extension reaction of the molecular end, acetone was distilled off under reduced pressure to obtain an aqueous dispersion (UU6) having a solid content concentration of 65%.

Comparative Production Example 4 Using a disperser similar to that used in Production Example 6, (u1) was placed in a disperser rotating at a rotation speed of 9,000 rpm.
Of 550 parts / min and water at a rate of 500 parts / min for 2 minutes at the same time to disperse and disperse the aqueous dispersion (4
1,050 parts of a) were obtained. 525 parts of (4a) were further subjected to 500 with the same disperser at a rotation speed of 12,000 rpm.
The mixture was supplied at a rate of 1 part / min for 1 minute to disperse, and the aqueous dispersion (4
b) was obtained. In a four-necked flask equipped with a thermometer, a stirrer and a condenser, (4a) and (4b) were blended so that the solid content ratio was (4a) / (4b) = 75/25,
10% aqueous solution of ethylenediamine as a chain extender 100
Parts, and the mixture was stirred at 30 ° C. for 1 hour to cause elongation reaction of the isocyanate group at the molecular end, and then the acetone was distilled off under reduced pressure to give a solid content concentration of 65%, and the aqueous dispersion of Comparative Production Example 4 (H
U4) was obtained.

Comparative Production Example 5 Comparative Production Example 4 except that (u1) was replaced with (u2)
In the same manner as described above, an aqueous dispersion (HU5) of Comparative Production Example 5 having a solid content concentration of 65% was obtained. The particle size distributions of the aqueous dispersions obtained in the above Production Examples 6 to 10 and Comparative Production Examples 4 and 5 were measured by the photon correlation method, and the analyzed results are shown in Tables 6 and 7. In addition, the viscosities of these aqueous dispersions are shown in Table 7.
It was shown to.

[0146]

[Table 6]

[0147]

[Table 7]

Tables 8 and 9 show the results of analysis and measurement by the ultrasonic measurement method.

[0149]

[Table 8]

[0150]

[Table 9]

Table 10 shows the results of determining the coefficient A and the constant term B of the formula (1) of concentration and viscosity for the aqueous dispersions of Production Examples 1-10 and Comparative Production Examples 1-5.

[0152]

[Table 10]

Further, Table 11 shows the results of evaluating the daily stability of these aqueous dispersions by the following evaluation methods.

Evaluation method of stability over time: 80 m of aqueous dispersion
1 was placed in a glass settling tube having an inner diameter of 2.5 cm and a volume of 100 ml and stored at 25 ° C. The appearance was checked once a day and evaluated by the number of days until the separation interface appeared. Those that did not separate after 90 days were described as 90 days or longer.

[0155]

[Table 11]

The aqueous dispersion of the present invention has a high solid content concentration of more than 65%, yet exhibits a low viscosity, and has good stability over time.

Example 1 300 parts of (UU1) was placed in a beaker, 165 parts of ion-exchanged water was added, and Caribbon L-400 as a pigment dispersant was added.
0.1 part (manufactured by Sanyo Kasei Kogyo Co., Ltd.) is added, and the mixture is stirred and mixed for 15 minutes at a rotation speed of 300 rpm using a propeller type stirring blade. Then, this mixed solution was transferred to a bead mill container, 60 parts of Emmacor NS WHITE A426 (manufactured by Sanyo Dye Co.) as a pigment, 0.1 part of Nopco 8034L (manufactured by San Nopco) as an antifoaming agent, and Cymel 325 as a crosslinking agent.
(Mitsui Cyanamid Co., Ltd.) 75 parts added, diameter 1mm
250 parts of zirconium beads of No. 2 were added and shaken for 2 hours, and then the beads were removed to obtain an aqueous coating composition having a solid content concentration of 55%. High shear viscometer (“HSV-2” manufactured by Nippon Seiki Co., Ltd.) shear rate of 1000 s ⁻¹ and 10 s
The viscosity at ^-1 was measured. The water-based coating composition prepared above was applied to an aluminum plate of 8 cm × 15 cm with a thickness of 1.0 mm by using a spray gun and a back pressure of 2.0 kg / cm.
Spray-painted in ² . The coating was applied to a thickness of 200 μm (wet form) and dried at 80 ° C. using a normal air dryer.
The weight is measured every 1 minute after the start of drying, and the time when the rate of change of the coating film weight after drying is 0.1% or less (drying completion time), and then cooling to room temperature, contact-type digital The thickness of the coating film was measured with a film thickness meter (“GS-10” manufactured by OZAKI MGG.). In addition, the stability over time of these aqueous coating compositions was evaluated by the same evaluation method as for the above-mentioned aqueous dispersion. The results are shown in Table 12.

An aqueous coating composition having a solid content concentration of 55% was obtained in the same manner as in Example 1 except that the aqueous dispersions shown in Table 12 were used instead of Examples 2 to 10 (UU1). Table 12 shows the results of these evaluations.

Comparative Example 1 An aqueous coating composition having a solid content concentration of 55% was obtained in the same manner as in Example 1 except that (HU1) was used instead of (UU1). Shear speed of this coating composition 1000 s ^-1
The viscosity was 60 mPa · s and the viscosity was too high for spray coating. Therefore, ion-exchanged water was further added to obtain a water-based coating composition in which the solid content concentration was adjusted to 40%.
Table 12 shows the evaluation results.

Comparative Examples 2 to 5 (HU2) to (HU5) were used in place of (UU1) to obtain aqueous coating compositions having a solid content concentration of 55% in the same manner as in Example 1. Shear rate of these paint compositions 1
The viscosity at 000 s ⁻¹ was 45 to 58 mPa · s, and the viscosity was too high for spray coating, so ion-exchanged water was further added to adjust the solid content concentration to 40% to obtain an aqueous coating composition. Table 12 shows the results of these evaluations.

Comparative Example 6 An aqueous coating composition having a solid content concentration of 55% was obtained in the same manner as in Example 1 except that (HU4) was used instead of (UU1). In order to adjust the viscosity of this coating composition at a shear rate of 1000 s ^{−1 and} the viscosity at a shear rate of 10 s ⁻¹ , ion-exchanged water should be further added, and SN thickener A-as a viscosity modifier. 636
It was necessary to add 4.0 parts (manufactured by San Nopco Ltd.), and finally an aqueous coating composition having a solid content concentration of 20% was obtained. Table 12 shows the evaluation results of this aqueous coating composition.

Comparative Example 7 An aqueous coating composition having a solid content concentration of 20% was obtained in the same manner as in Comparative Example 1 except that (HU5) was used instead of (HU4). Table 12 shows the evaluation results of this aqueous coating composition.

[0163]

[Table 12]

From the results shown in Table 12, the aqueous coating composition obtained according to the present invention has a high solid content concentration of 55%, but has a viscosity at high shear and low shear of 2 or less.
It is equivalent to the addition of a viscosity modifier to a 0% aqueous coating composition. Therefore, while ensuring the same level of coating suitability as the conventional water-based coating composition, it is possible to greatly improve the drying speed and enable thick coating.

[0165]

EFFECT OF THE INVENTION The coating composition, adhesive composition, pressure-sensitive adhesive composition, fiber processing agent composition and the like of the present invention are excellent in storage stability even at high concentrations. In the case of a coating composition, the coating suitability is further excellent, and since the concentration is high, the drying speed can be greatly improved, and thick coating can be performed, which contributes to a large improvement in productivity. Further, in the case of the adhesive composition, since it has a low viscosity even at a high concentration, it quickly penetrates into the adhesive base material, and a quick-drying adhesive composition can be obtained. Further, in the case of the adhesive composition for dry laminating, the drying time is shortened, so that the productivity in the laminating step can be improved. Further, in the case of the binder composition for pigment printing among the fiber processing composition, the high concentration makes the meat less likely to become lean.

[Brief description of drawings]

FIG. 1 shows an example of a particle size distribution having two peaks.

[Explanation of symbols]

1 (P1) 2 valley 1 3 (P2)

FIG. 2 shows an example of a particle size distribution having three peaks.

[Explanation of symbols]

4 (P1) 5 valley 2 6 (P2)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 175/04 C09J 175/04 201/00 201/00 (72) Inventor Soichi Sotake Ichibashino, Higashiyama-ku, Kyoto 1 Honmachi No. 1 Sanyo Chemical Industry Co., Ltd. F-term (reference) 4J034 BA08 CA02 CA13 CA16 CA17 CB03 CB04 CB08 CC03 CC12 CC23 CC26 CC28 CC33 CC45 CC52 CC61 CC65 CC69 DA01 DC02 DC07 DC12 DC35 DC37 DC42 DC43 DF01 DF02 DF12 DG03 DG04 DG04 DG04 DG04 DG04 DG04 DG16 HA01 HA07 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC54 HC61 HC64 HC67 HC71 HC73 JA30 QC05 RA07 RA08 RA09 4J038 CC031 CC032 CG141 CG142 DA041 DA042 DA111 DA112 DB001 DB002 DD001 DD002 DE01 DE002 DE001 DE002 DG001 DG002 DG051 DG131 DG131 LA02 MA08 MA10 MA14 MA15 NA06 NA26 4J040 DB031 DB032 DF041 DF042 EB031 EB032 EB091 EB092 EC001 EC002 ED001 ED0 02 EF001 EF002 EF061 EF062 EG001 EG002 EK031 EK032 EL021 EL022 GA07 GA08 GA25 JA03 JB09 LA01 LA03 LA05 QA02

Claims (19)

[Claims] 1. From an aqueous dispersion containing particles of at least one resin selected from the group consisting of polyaddition resins, polycondensation resins, addition condensation resins, ring-opening polymerization resins and addition polymerization resins. Wherein the particles have at least two peaks in a particle size distribution curve; at least one of the peaks is a polyaddition resin, polycondensation resin, addition condensation resin And at least one resin selected from the group consisting of ring-opening polymerization resins; the coating composition comprising a dispersion satisfying one or both of the following (i) and (ii): Composition: (i) In the particle size distribution curve, the peak having the highest peak height or the second peak having the larger particle size
(P1) and the smaller particle size peak (P2) are 2/1 to 10
The ratio of (P1) peak top particle size / (P2) peak top particle size in the range of 0/1, and (P1) height / (P2) in the range of 1/1 to 10/1 Given the height ratio, both (P1) and (P2) have a coefficient of variation of the peak of 0.1 to 150%, -10 to
Having a skewness of 10 and a saliency of 0-10, and (i
i) The aqueous dispersion satisfies the following relational expression (1) having a coefficient A of −2 to 0 and a constant term B of 1 to 5 within a concentration range of 20 to 70% by weight of an aqueous dispersion. : 1 / log (η / η ₀ ) = Aφ + B (1) In the formula, η ₀ and η are water and Brookfield viscosity (mPa · s, 25 ° C.) of an aqueous dispersion having a resin concentration of φ% by weight, respectively. ) Is represented. 2. From an aqueous dispersion containing particles of at least one resin selected from the group consisting of polyaddition resin, polycondensation resin, addition condensation resin, ring-opening polymerization resin and addition polymerization resin. An adhesive composition comprising:
The particle size distribution curve has at least two peaks; at least one of the peaks is selected from the group consisting of polyaddition resins, polycondensation resins, addition condensation resins and ring-opening polymerization resins. An adhesive composition comprising at least one resin; the adhesive composition comprising a dispersion satisfying one or both of the following (i) and (ii): (i) Particle size distribution curve Of the highest peak and the second peak with the larger particle size
(P1) and the smaller particle size peak (P2) are 2/1 to 10
The ratio of (P1) peak top particle size / (P2) peak top particle size in the range of 0/1, and (P1) height / (P2) in the range of 1/1 to 10/1 Given the height ratio, both (P1) and (P2) have a coefficient of variation of the peak of 0.1 to 150%, -10 to
Having a skewness of 10 and a saliency of 0-10, and (i
i) The aqueous dispersion satisfies the following relational expression (1) having a coefficient A of −2 to 0 and a constant term B of 1 to 5 within a concentration range of 20 to 70% by weight of an aqueous dispersion. : 1 / log (η / η ₀ ) = Aφ + B (1) In the formula, η ₀ and η are water and Brookfield viscosity (mPa · s, 25 ° C.) of an aqueous dispersion having a resin concentration of φ% by weight, respectively. ) Is represented. 3. An aqueous dispersion containing particles of at least one resin selected from the group consisting of polyaddition resins, polycondensation resins, addition condensation resins, ring-opening polymerization resins and addition polymerization resins. A pressure-sensitive adhesive composition comprising:
The particle size distribution curve has at least two peaks; at least one of the peaks is selected from the group consisting of polyaddition resins, polycondensation resins, addition condensation resins and ring-opening polymerization resins. A pressure-sensitive adhesive composition comprising at least one resin; the pressure-sensitive adhesive composition comprising a dispersion satisfying one or both of the following (i) and (ii): (i) Particle size distribution curve Of the highest peak and the second peak with the larger particle size
(P1) and the smaller particle size peak (P2) are 2/1 to 10
The ratio of (P1) peak top particle size / (P2) peak top particle size in the range of 0/1, and (P1) height / (P2) in the range of 1/1 to 10/1 Given the height ratio, both (P1) and (P2) have a coefficient of variation of the peak of 0.1 to 150%, -10 to
Having a skewness of 10 and a saliency of 0-10, and (i
i) The aqueous dispersion satisfies the following relational expression (1) having a coefficient A of −2 to 0 and a constant term B of 1 to 5 within a concentration range of 20 to 70% by weight of an aqueous dispersion. : 1 / log (η / η ₀ ) = Aφ + B (1) In the formula, η ₀ and η are water and Brookfield viscosity (mPa · s, 25 ° C.) of an aqueous dispersion having a resin concentration of φ% by weight, respectively. ) Is represented. 4. From an aqueous dispersion containing particles of at least one resin selected from the group consisting of polyaddition resins, polycondensation resins, addition condensation resins, ring-opening polymerization resins and addition polymerization resins. A fiber processing agent composition comprising: the particles having at least two peaks in a particle size distribution curve; at least one of the peaks is a polyaddition resin, polycondensation resin, addition The treating agent composition comprises at least one resin selected from the group consisting of condensation type resins and ring-opening polymerization type resins;
i) A fiber processing agent composition characterized by comprising a dispersion satisfying one or both of the following: (i) In the particle size distribution curve, the particle size of the peak having the highest peak height and the second peak. The larger the peak
(P1) and the smaller particle size peak (P2) are 2/1 to 10
The ratio of (P1) peak top particle size / (P2) peak top particle size in the range of 0/1, and (P1) height / (P2) in the range of 1/1 to 10/1 Given the height ratio, both (P1) and (P2) have a coefficient of variation of the peak of 0.1 to 150%, -10 to
Having a skewness of 10 and a saliency of 0-10, and (i
i) The aqueous dispersion satisfies the following relational expression (1) having a coefficient A of −2 to 0 and a constant term B of 1 to 5 within a concentration range of 20 to 70% by weight of an aqueous dispersion. : 1 / log (η / η ₀ ) = Aφ + B (1) In the formula, η ₀ and η are water and Brookfield viscosity (mPa · s, 25 ° C.) of an aqueous dispersion having a resin concentration of φ% by weight, respectively. ) Is represented. 5. The resin forming (P1) and the resin forming (P2) have an HLB difference of 0.1 to 10.
A composition comprising the dispersion according to any one of 1 to 4. 6. A composition comprising the dispersion according to claim 1, wherein (P1) has a peak top particle size of 0.1 to 4 μm. 7. (P1) and (P2) are 2.2 / 1 to 20/1.
A composition comprising the dispersion according to any one of claims 1 to 6, having a ratio of (P1) peak top particle diameter / (P2) peak top particle diameter within the range of. 8. The particle size distribution curve is between (P1) and (P2),
A composition comprising the dispersion according to any one of claims 1 to 7 having a minimum valley whose height does not exceed 80% of the height of the peak top of (P2). 9. The resin is at least one resin selected from the group consisting of polyurethane resin, polyester resin, polyamide resin, silicone resin, polycarbonate resin, phenol resin, amino resin, epoxy resin, acrylic resin and styrene resin. A composition comprising the dispersion according to any one of claims 1 to 8. 10. At least one of (P1) and (P2) is
A composition comprising the dispersion according to any one of claims 1 to 9, which contains a hydrophilic group (Q) having a group number unique to the atomic group according to the Divis method of 0.3 or more. 11. The dispersion according to claim 10, wherein the group (Q) is at least one selected from the group consisting of a carboxyl group, a carboxylate group, a sulfonate group, a sulfonate group and an oxyethylene group. Composition. 12. The dispersion according to claim 10, wherein the resin forming (P1) and the resin forming (P2) have a difference in content of the group (Q) of 0.1% by weight or more. A composition consisting of the body. 13. A composition comprising the dispersion according to claim 1, which contains resin particles in an amount of 50 to 75% by weight. 14. An aqueous dispersion of a resin comprising a resin (A1) and another resin (A2), wherein the solution or melt of (A2) or the precursor of (A2) is used in the aqueous dispersion of (A1). Dispersed in
In the case of a precursor, a composition comprising the dispersion according to any one of claims 1 to 13, which is obtained by converting the precursor into (A2). 15. A rotor-stator emulsifier, a line mill emulsifier, a stationary tube mixing emulsifier, a vibration emulsifier, an ultrasonic impact emulsifier, a high-pressure impact emulsifier, a membrane emulsifier, Using at least one emulsifier selected from a centrifugal thin-film contact emulsifier and an anchor-type stirring emulsifier, the precursor (A
A composition comprising the dispersion according to claim 14 dispersed in the aqueous dispersion of 1). 16. The resin according to claim 14, wherein the resin comprises 10 to 50% by weight of (A1) and 50 to 90% by weight of (A2).
A composition comprising the dispersion according to any one of 5 above. 17. The aqueous dispersion of (A1) comprises a polyamine containing N
17. An aqueous dispersion of a polyurethane resin obtained by chain elongation of the CO-terminated urethane prepolymer in addition to the aqueous dispersion of the CO-terminated urethane prepolymer.
A composition comprising the described dispersion. 18. An aqueous dispersion of the prepolymer comprises a rotor-stator emulsifier, line mill emulsifier, stationary tube mixing emulsifier, vibration emulsifier, ultrasonic impact emulsifier, high pressure impact emulsifier. The composition comprising the dispersion according to claim 17, which is formed by using an emulsifying machine selected from an emulsifying machine, a membrane emulsifying type emulsifying machine, a centrifugal thin film contact type emulsifying machine and an anchor type stirring type emulsifying machine. 19. A composition comprising the dispersion according to claim 17 or 18, wherein the chain extension reaction of the polyamine and the prepolymer is carried out in a batch reactor.