JP2006161018A - Aqueous dispersion of resin particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion of resin particles having excellent preservation stability and adhesivity, in particular, an adhesive agent comprising the aqueous dispersion of resin particles, and a treating agent for fiber processing. <P>SOLUTION: The aqueous dispersion of resin particles are provided by consisting of resin particles (C) as a main component in which a surface of resin particles (A) are coated with resin particles (B), wherein a volume average particle diameter DA of the resin particles (A) and a volume average particle diameter DB of the resin particles (B) is different, a glass transition temperature of resin particles (A) is ≥-50°C to ≤50°C, a glass transition temperature of resin particles (B) is ≥30°C to ≤100°C, DA is ≥1 μm to ≤30 μm, DB is ≥0.01 μm to ≤0.95 μm, the ratio of the average particle diameter (DA/DB) is ≥1.05 to ≤3,000. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aqueous dispersion of resin particles. More specifically, the present invention relates to an aqueous dispersion of resin particles excellent in storage stability and adhesiveness to a base material after heat curing.

While environmental issues are attracting attention, various aqueous dispersions are used in a wide range of fields from the viewpoints of VOC reduction and skin irritation. For example, there are aqueous dispersion type cosmetics, aqueous cutting oils, and aqueous dispersions of edible oils. Among them, a high-concentration and low-viscosity aqueous dispersion is desired for an aqueous dispersion of an adhesive composition in the adhesive field and an aqueous dispersion of a fiber processing resin in the fiber processing field.
As an aqueous dispersion corresponding to this, a high-concentration and low-viscosity aqueous dispersion obtained by setting the median particle size distribution of the aqueous dispersion to 1 to 10 μm and making the particles relatively larger than before (for example, patent documents) 1) has been proposed.
Japanese Patent Laid-Open No. 8-120042

However, the high-concentration aqueous dispersion obtained by the above method has problems such as poor long-term storage stability and insufficient adhesion.
That is, an object of the present invention is to provide an aqueous resin particle dispersion excellent in storage stability and adhesiveness, in particular, an adhesive and a fiber processing agent made of the aqueous resin particle dispersion.

  As a result of investigations to obtain an aqueous dispersion capable of solving the above problems, the present inventors have reached the present invention. That is, the present invention comprises resin particles (C) whose surfaces are coated with resin particles (B) and water as essential components, and the volume average particle diameter DA of the resin particles (A) and the resin The volume average particle diameter DB of the particles (B) is different, the glass transition temperature of the resin particles (A) is −50 ° C. or more and 50 ° C. or less, and the glass transition temperature of the resin particles (B) is 30 ° C. or more and 100 ° C. A resin particle aqueous dispersion, a method for producing the aqueous dispersion, an adhesive comprising the aqueous dispersion, and a fiber processing agent, characterized by the following:

Since the resin particle aqueous dispersion of the present invention has the following effects, it is extremely useful as an adhesive and a fiber processing agent.
(1) The particles do not coalesce and have excellent storage stability.
(2) When water is removed, the particles easily coalesce and have excellent adhesion after treatment.

The resin particle aqueous dispersion of the present invention comprises, as an essential component, resin particles (C) in which the surfaces of the resin particles (A) are coated with the resin particles (B). Preferably, the resin particles (A) and / Or consisting of resin particles (B). More preferably, it further comprises a curing agent (D).
In the case of the adhesive and the fiber processing agent that are embodiments of the resin particle aqueous dispersion of the present invention, as the main component, for example, (1) (C) only, or (2) (B), It may consist of (C) or (3) (B), (C), (D).

The volume average particle diameter DA of the resin particles (A) and the volume average particle diameter DB of the resin particles (B) are different, and preferably DA is larger than DB.
The average particle diameter DA in the present invention is preferably 1 μm or more from the viewpoint of storage stability, preferably 30 μm or less, more preferably 25 μm or less, and further preferably 20 μm or less from the viewpoint of adhesiveness.
The average particle diameter DB in the present invention is preferably 0.01 μm or more, more preferably 0.02 μm or more from the viewpoint of storage stability, and the resin particles (A) can be coated with the resin particles (B) with improved efficiency. From the viewpoint, it is preferably 0.95 μm or less, more preferably 0.7 μm or less, and still more preferably 0.5 μm or less.

  The volume average particle diameter ratio (DA / DB) between the resin particles (A) and the resin particles (B) in the present invention is preferably 1 from the viewpoint of improving the coating efficiency of the resin particles (B) onto the resin particles (A). .05 or more, more preferably 10 or more, more preferably 20 or more, preferably 3000 or less, more preferably 1000 or less.

The glass transition temperature (hereinafter abbreviated as Tg) of the resin particles (A) is −50 ° C. or higher, preferably −20 ° C. or higher, more preferably 0 ° C. or higher, 50 ° C. or lower, preferably 45 ° C. or lower, More preferably, it is 40 degrees C or less. When the Tg of (A) is less than −50 ° C., it is difficult to maintain the particle shape of the resin particles (C) at room temperature, and when it exceeds 50 ° C., the adhesiveness during construction deteriorates.
The Tg of the resin particles (B) is 30 ° C. or higher, preferably 35 ° C. or higher, 100 ° C. or lower, preferably 90 ° C. or lower, more preferably 85 ° C. or lower. When the Tg of (B) is less than 30 ° C., the storage stability of the resin particles (C) deteriorates, and when it exceeds 100 ° C., the adhesiveness and transparency after construction deteriorate.
Here, Tg was measured using a differential scanning calorimeter [eg, Seiko Co., Ltd .: UV-SSC220C].

  As a method for measuring the Tg of the resin particles (A) and the resin particles (B), for example, an aqueous dispersion of resin particles is settled by centrifugation, the resin particles (A) and the resin particles (B) are separated, and the sediment is obtained. The Tg of the resin particles (A) can be measured by the dried residue, and the Tg of the resin particles (B) can be measured by the residue obtained by drying the supernatant.

  As the resin particles constituting the resin particle aqueous dispersion in the present invention, (C) is an essential component. More preferably, (A) and / or (B) may be used in addition to (C). In either case, two or more aggregates of the same type or different types may be used.

In the present invention, based on the total amount of all the particles constituting the proportion of the particles having a volume average particle size of 2 times or more of the volume average particle size DA, preferably 20% by volume or less from the viewpoint of the adhesiveness of the coating film. More preferably 18% by volume or less, and based on the total amount of all the particles constituting the proportion of particles having a volume average particle size of 1/2 or less of the volume average particle size DA, the storage stability From the viewpoint, it is preferably 50% by number or less, and more preferably 45% by number or less.
Here, the particles having a volume average particle diameter of 2 times or more of DA include (C), (A), (B), and two or more aggregates of the same or different types. The same applies to particles having a volume average particle size of 1/2 or less of DA.
The volume average particle diameter and number average particle diameter of the resin particles (C) are 50% volume average particle diameter and 50% number measured by a flow type particle image analyzer [for example, FPIA-2100 manufactured by Sysmex Corporation]. This represents the average particle diameter, and the same applies hereinafter.

In the following description, the resin particles (A) and the resin particles (B) are combined to form the resin particles (C) by coating the surfaces of the resin particles (A) with the resin particles (B). To do.
That the surface of (A) is covered with (B) means that (B) is buried or attached to the surface of (A). Moreover, that the surface of (A) is covered with (B) means that (B) is attached to at least a part of the surface of (A), and all the surfaces of (A) are (B ) Is particularly preferred.

  As a method for confirming that the resin particle (C) is a particle formed by coating the surface of (A) with (B), for example, a particle is taken out from a resin particle aqueous dispersion by freeze-drying, and scanning type This can be confirmed by observing with an electron microscope [SEM]. As a measuring method of the volume average particle diameter DA of the resin particles (A) and the volume average particle diameter DB of the resin particles (B), for example, it is measured by sampling about 100 from the image of the scanning electron microscope. Is possible.

  The resin particles (C) contained in the resin particle aqueous dispersion preferably have a content of 50 to 100% based on the total amount of all particles constituting the resin from the viewpoint of the adhesiveness of the resin after construction. Preferably it is 55 to 100%, particularly preferably 60 to 100%.

  The volume average particle diameter DC of the resin particles (C) is preferably 1 μm or more, more preferably 1.1 μm or more, more preferably 1.15 μm or more from the viewpoint of storage stability, and from the viewpoint of adhesiveness. To preferably 40 μm or less, more preferably 30 μm or less, and even more preferably 25 μm or less.

The ratio of the specific surface area / volume average particle diameter of the resin particles (C) is preferably 25/1 or more, more preferably 30/1 or more, from the viewpoint of the coverage of (B) with respect to (A), more preferably Preferably, it is 35/1 or more, preferably 900/1 or less from the viewpoint of storage stability, more preferably 850/1 or less, more preferably 800/1 or less.
The specific surface area of (C) here was measured according to JIS R 1626 (Method for measuring specific surface area of fine ceramic powder by gas adsorption BET method). For example, the measuring instrument is a measuring device (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen) using a specific surface area meter [manufactured by Yuasa Ionics: QUANTASORB].

The method for forming the resin particles (C) is not particularly limited, and examples thereof include a dry compounding method and a wet compounding method.
As the dry compounding method, a machine having a compounding function (for example, mechano mill, mechano fusion, CF mill, sample mill and super mixer) for pulverization, mixing and / or sizing is used, and (1) (A ) Or (B) at a temperature at which at least one surface melts, (A) and (B) are mixed, combined and cooled, (2) The binder component is combined with (A) and (B) Method of mixing and compounding, (3) Method of compounding by ionic attraction of the charge charged on the surface of (A) and the charge charged on the surface of (B) when mixing (A) and (B) [In this case, a machine having the above-mentioned composite function is used]. Here, the ionic attractive force is, for example, an attractive force between the particles when (A) is anionic or cationic and (B) is opposite to (A).

  As the wet compounding, in (A) and (B) in an organic solvent [for example, a solvent that does not dissolve (A) and (B) such as methanol] or in water, while stirring in a batch reactor or homomixer. A method of compounding during solvent removal or using the ionic attractive force of each particle may be mentioned.

As a method for forming the resin particles (C) to obtain the resin particle aqueous dispersion of the present invention, the following methods are preferred.
A solution in which the resin (a) is dissolved in the resin (a) or the solvent (g) in an aqueous dispersion obtained by dispersing the resin particles (B) made of the resin (b) containing the dispersant (E). When the resin (a) is dissolved in the solvent (g), the resin particle (C) is formed by further removing the solvent (g), thereby obtaining the resin particle aqueous dispersion of the present invention. A method is mentioned.

As a method for dispersing the resin (a) in the aqueous dispersion, (1) a method in which the resin particles (A) made of the resin (a) are dispersed in the aqueous dispersion, and (2) the molten resin (a) in the aqueous dispersion. There is a way to distribute. Among these, (2) is preferable from the viewpoint of storage stability. The molten resin (a) may be either a molten resin at room temperature or a molten resin heated.
It is preferable to add a curing agent (D) described later in any step of the production method, and it is more preferable to add it in the resin (a).

  Specific examples of the solvent (g) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit and cyclohexane. Solvents: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Ester or ester ether solvents; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl Ketone solvents such as sobutyl ketone, di-n-butyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; dimethyl Examples include amide solvents such as formamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, heterocyclic compound solvents such as N-methylpyrrolidone, and mixed solvents of two or more of these.

  The aqueous dispersion contains a dispersant (E) in an aqueous medium and the resin particles (B) are dispersed. The aqueous medium refers to water or a mixed solvent of water-miscible solvent and water. Examples of the water-miscible solvent include alcohol solvents and ketone solvents. Specifically, alcohol solvents: methanol, isopropanol, ethanol, n-propanol, etc., ketone solvents: acetone, methyl ethyl ketone, etc. are mentioned. The mixing ratio of the water and the water-miscible solvent is preferably 100/0 to 100/20, more preferably 100/0 to 100/5.

  The resin constituting the resin particles (A) and the resin particles (B) in the present invention is preferably a resin that melts by heating and has a film-forming property. For example, a resin that is usually used as an adhesive is used. Can be mentioned. Preferably, the thermosetting resin (I) and / or the thermoplastic resin containing one or more reactive functional groups that react with each other or react with the curing agent (D) at the side chain and / or terminal in the molecule. (II) is mentioned. Among these, preferred from the viewpoint of coating strength is that when one of (A) and (B) consists of (I) and the other consists of (I) or (II), more preferred are (A) and This is a case where (B) consists of (I).

  As said thermosetting resin (I), 1 or more types of resin chosen from the group which consists of a vinyl resin, a polyester resin, an epoxy resin, a polyurethane resin, and a fluororesin is mentioned. Of these, vinyl resins, polyester resins, epoxy resins and fluororesins are preferred from the viewpoint of weather resistance, vinyl resins, polyester resins and fluororesins are more preferred, and vinyl resins and polyester resins are particularly preferred.

  Examples of the reactive functional group in the thermosetting resin (I) include a carboxyl group, an epoxy group, a hydroxyl group, a hydrolyzable silyl group, a blocked carboxyl group, a blocked amino group, and a blocked isocyanate group. From the viewpoint of storage stability during storage, a carboxyl group, an epoxy group, a hydroxyl group, a blocked carboxyl group, a blocked amino group and a blocked isocyanate group are preferred, and an epoxy group, a hydroxyl group and a blocked isocyanate are more preferred. It is a group.

Examples of the blocking agent in the blocked carboxyl group include ammonia, tertiary alcohols (having 4 to 19 carbon atoms, for example, t-butanol, triethyl carbinol, tributyl carbinol, triphenyl carbinol) and vinyl compounds (having 4 to 4 carbon atoms). 18, for example, 2-methylpropene, 2-methylhexene) and the like. Of these, tertiary alcohols are preferable from the viewpoint of storage stability and ease of desorption during heat treatment, and t-butanol and triethylcarbinol are more preferable.
Examples of the blocking agent in the blocked amino group include ketones [having 3 to 15 carbon atoms, such as aliphatic ketones (acetone, methyl isobutyl ketone, etc.), aromatic ketones (benzophenone, etc.), alicyclic ketones (dicyclohexyl ketone), etc. Is mentioned. Of these, aliphatic ketones are preferred from the viewpoint of storage stability and ease of desorption during heat treatment, and methyl isobutyl ketone is more preferred.

  Examples of the blocking agent in the blocked isocyanate group include oxime (3 to 10 carbon atoms such as acetoxime and methylethyl ethoxyme), alcohol (monohydric alcohol having 1 to 18 carbon atoms such as methyl alcohol, isopropyl alcohol, t- Butyl alcohol), phenol compounds [monohydric phenols having 6 to 20 carbon atoms, such as monocyclic phenols (phenol, nitrophenol, etc.), polycyclic phenols (1-naphthol, etc.)], lactams (4-15 carbon atoms, for example, γ-butyrolactam, ε-caprolactam, γ-valerolactam) and the like. Of these, oxime and lactam are preferable from the viewpoint of storage stability and ease of elimination during heat treatment, and acetoxime and ε-caprolactam are more preferable.

  The number of reactive functional groups in the thermosetting resin (I) is preferably 1 or more, more preferably 2 or more, particularly preferably 2 to 20, most preferably 2 to 15 from the viewpoint of resin strength. It is.

The method for forming the thermosetting resin (I) by introducing the reactive functional group includes (co) polymerizing a monomer having the reactive functional group, and a polymerization initiator having the reactive functional group. And a method of performing (co) polymerization and a method of introducing a reactive functional group by modifying a resin after performing (co) polymerization.
Among these, from the viewpoint of ease of introduction of the reactive functional group, a method of (co) polymerizing the monomer having the reactive functional group is preferable.

  Among the (I) in the present invention, the vinyl resin includes those obtained by homopolymerizing the vinyl monomer having the reactive functional group, and other various vinyl monomers having the vinyl monomer as an essential component and not having the reactive functional group. And those copolymerized therewith. In addition, you may use 2 or more types together for the vinyl monomer which has this reactive functional group. Examples of the vinyl monomer having a reactive functional group include the following (a) to (f).

(A) Carboxyl group-containing vinyl monomer / monocarboxylic acid [3 to 15 carbon atoms, for example, (meth) acrylic acid, crotonic acid, cinnamic acid]
Dicarboxylic acid [C4-15, such as (anhydrous) maleic acid, fumaric acid, itaconic acid, citraconic acid]
Dicarboxylic acid monoester [monoalkyl (1 to 8 or more carbon atoms) ester of the above dicarboxylic acid, such as maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, citraconic acid monoalkyl ester, etc.]
A product obtained by blocking the carboxyl group of the monomer with a blocking agent (described above).

(B) Epoxy group-containing vinyl monomer. Epoxy group-containing (meth) acrylate having 6 to 15 carbon atoms such as glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. Glycidyl ether having 5 to 15 carbon atoms such as Glycidyl vinyl ether, glycidyl allyl ether, glycidyl propenyl ether and glycidyl vinyl phenyl ether (glycidyloxystyrene)

(C) amino group-containing vinyl monomer / primary or secondary amino group-containing (meth) acrylate having 5 to 15 carbon atoms [aminoalkyl (1 to 6 carbon atoms) (meth) acrylate such as aminoethyl (meth) acrylate , Alkyl (C1-6) aminoalkyl (C1-6) (meth) acrylate, such as t-butylaminoethyl (meth) acrylate, etc.]
-C3-C10 amino group-containing allyl compounds [(meth) allylamine, diallylamine, etc.]
-C5-C10 amino group-containing acrylamide [N-aminoalkyl (C1-6) (meth) acrylamide, N-aminoethyl (meth) acrylamide, etc.]
-The amino group of the above monomer is blocked with a blocking agent (as described above).

(D) Isocyanate group-containing vinyl monomer / C5-C15 aliphatic vinyl monomer [isocyanate alkyl (C1-6) (meth) acrylate such as isocyanate ethyl (meth) acrylate]
・ Aromatic aliphatic vinyl monomers having 9 to 20 carbon atoms (m-isopropenyl-α, α-dimethylmethylbenzyl isocyanate, etc.)
-The isocyanate group of the above monomer is blocked with a blocking agent (as described above).

(E) Hydroxyl group-containing vinyl monomer / hydroxyl group-containing styrene compound having 8 to 15 carbon atoms (hydroxystyrene, dihydroxystyrene, etc.)
-C4-C10 hydroxyl group-containing (meth) acrylamide [N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide, N, N-bishydroxyethyl (meth) acrylamide, N, N-bishydroxy Propyl (meth) acrylate, etc.]
・ Unsaturated carboxylic acid ester having 5 to 12 carbon atoms (1) Hydroxyalkyl (1 to 6 carbon atoms) (meth) acrylate [hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, etc. ]
(2) Hydroxyl group-containing monomer having a poly (n = 2 to 30, preferably 5 to 15, more preferably 8 to 12) oxyalkylene (alkylene group having 2 to 4 carbon atoms) chain [polyoxyalkylene unsaturated monocarboxylic acid Acid ester [poly (n = 10) oxyethylene mono (meth) acrylate and the like] and poly (n = 2-30) oxyalkylene (alkylene having 2 to 4 carbon atoms) unsaturated dicarboxylic acid diester [poly (n = 10 ) Oxyethylene maleic acid diester, etc.]]
(3) Poly (n = 2 to 30) oxyalkylene (carbon number 2 to 4) unsaturated carboxylic acid (di) ester [poly (n = 10) oxyethylenemaleic acid (di) ester, etc.], poly (n = 2-30) Oxyalkylene (2-4 carbon atoms) (meth) allyl ether [poly (n = 10) oxyethylene (meth) allyl ether, etc.]
・ C3-C8 alcohol [(meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-butene-3-ol, 2-butene-1,4-diol, etc.]
A hydroxyl group-containing ether having 5 to 20 carbon atoms [hydroxyalkyl (1 to 6 carbon atoms) alkenyl (3 to 6 carbon atoms) ether such as 2-hydroxyethylpropenyl ether, an allyl ether of a polyhydric alcohol (described later), For example, sucrose allyl ether]

(F) Hydrolyzable silyl group-containing vinyl monomer / vinyl having 5 to 40 carbons [alkyl (1 to 6 carbon atoms)] alkoxy (1 to 12 carbon atoms) silane [vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, etc.]
C6-C40 (meth) acryloxyalkoxy (C1-C12) silane [γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ -Methacryloxypropylmethyldiethoxysilane, etc.]

  Among these vinyl monomers having a reactive functional group, a blocked isocyanate group-containing vinyl monomer is preferable from the viewpoint of resin strength, and an epoxy group-containing vinyl monomer and a hydroxyl group-containing vinyl monomer are particularly preferable. Glycidyl (meth) acrylate and hydroxyethyl (meth) acrylate.

  Examples of other vinyl monomers that do not have the reactive functional group and are used for copolymerization with the vinyl monomers (a) to (f) include the following (g) to (m).

(G) Vinyl hydrocarbon-Aliphatic vinyl hydrocarbon (alkene) having 2 to 18 or more carbon atoms, such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene and octadecene; 4-10 or more dienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene and 1,7-octadiene. C 4-18 or more alicyclic vinyl hydrocarbons such as Cyclohexene, (di) cyclopentadiene, pinene, limonene, indene, vinylcyclohexene and ethylidenebicycloheptene. Aromatic vinyl hydrocarbons having 8 to 20 or more carbon atoms, such as styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene Ethylstyrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, vinyl naphthalene, divinyl benzene, divinyl toluene, divinyl xylene and trivinylbenzene

(H) Alkyl (meth) acrylate Alkyl (meth) acrylate having an alkyl group (1 to 50 carbon atoms), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and eicosyl (meth) acrylate

(I) (Poly) (n = 1 to 30) Vinyl monomer having an oxyalkylene (2 to 4 carbon atoms) chain Polyoxyalkylene glycol [number average molecular weight (hereinafter abbreviated as Mn; measurement method is based on GPC) 100 1,000] di (meth) acrylate, such as polyethylene glycol (Mn300) di (meth) acrylate and polypropylene glycol (Mn500) di (meth) acrylate, polyoxyalkylene monool, such as polyoxyalkylene alkyl (1 to 18) Ether (meth) acrylate [Methyl alcohol ethylene oxide (ethylene oxide is hereinafter abbreviated as EO) 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.]

(J) Phosphoric acid group-containing vinyl monomer / hydroxyalkyl (meth) acrylate (2 to 4 carbon atoms of alkyl group) phosphoric acid triester, for example, phosphoric acid diester and glycidyl (meth) acrylate described in Japanese Patent No. 3052072 Phosphoric acid ester having a structure formed from the reaction of: (meth) acrylic acid alkyl (carbon group having 2 to 4 carbon atoms) phosphonic acid diester, for example, 2-acryloyloxyethyl stearylphosphonic acid diester, 2-acryloyloxyethylbutyl Phosphonic acid diester and 2-acryloyloxyethylmethylphosphonic acid

(K) nitrogen-containing vinyl monomer (k1) amide group-containing vinyl monomer-(meth) acrylamide compound having 3 to 30 carbon atoms (meth) acrylamide; N-alkyl (1 to 6 carbon atoms) (meth) acrylamide, for example, N -Methyl (meth) acrylamide, N-butyl (meth) acrylamide, diacetone acrylamide, N, N'-methylene-bis (meth) acrylamide; and N, N-dialkyl (1-6 carbon atoms) or diaralkyl (carbon number) 7-15) (Meth) acrylamide, for example, N, N-dimethylacrylamide and N, N-dibenzylacrylamide, etc.Amide group-containing vinyl compound having 4 to 20 carbon atoms excluding the (meth) acrylamide compound, for example, Methacrylformamide, N-methyl-N-vinylacetamide, Katsura Cinamic acid amide, cyclic amide (N-vinylpyrrolidone, N-allylpyrrolidone, etc.), quaternary ammonium group-containing vinyl compound [tertiary amino group-containing vinyl compound such as dimethylaminoethyl (meth) acrylamide and diethylaminoethyl (meth) acrylamide) Quaternized product (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride and dimethyl carbonate)]

(K2) (meth) acrylate compound-C6-C20 dialkyl (C1-C4) aminoalkyl (C1-C4) (meth) acrylate, for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylates and t-butylaminoethyl (meth) acrylates ・ Heterocycle-containing (meth) acrylates such as morpholinoethyl (meth) acrylate ・ Quaternary ammonium group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate And quaternized products of tertiary amino group-containing (meth) acrylates such as diethylaminoethyl (meth) acrylate (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride and dimethyl carbonate), Methyl - Acetaminophen acrylate

(K3) Heterocycle-containing vinyl compound Vinyl group-containing pyridine compound having 7 to 14 carbon atoms (such as 4-vinylpyridine and 2-vinylpyridine), and vinyl group-containing imidazole compound having 5 to 12 carbon atoms (such as N-vinylimidazole) , C6-C13 vinyl group-containing pyrrole compounds (N-vinyl pyrrole and N-methyl-β-vinyl pyrrole, etc.)

(K4) Nitrile group-containing vinyl compound C3-C15 nitrile group-containing vinyl compound, for example, (meth) acrylonitrile, cyanostyrene, cyanoalkyl (carbon number 1-4) acrylate, etc. (k5) Other vinyl compounds, carbon number 8 ~ 16 nitro group-containing vinyl compounds such as nitrostyrene

(M) Vinyl ester, propenyl ester, vinyl ether, vinyl ketone, sulfide group-containing monomer, unsaturated dicarboxylic acid diester (m1) Vinyl ester, propenyl ester-C4-15 aliphatic vinyl ester such as vinyl acetate, vinyl butyrate Rate, vinyl propionate, vinyl butyrate, diallyl adipate, vinyl methoxyacetate, vinyl benzoate and isopropenyl acetate. Aromatic vinyl esters having 9 to 20 carbon atoms such as diallyl phthalate, methyl-4-vinylbenzoate and acetoxystyrene

(M2) Vinyl ether-Aliphatic vinyl ether having 3 to 15 carbon atoms, for example, vinyl alkyl (alkyl group having 1 to 10 carbon atoms) ether [vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2- Ethyl hexyl ether, etc.], vinyl alkoxy (alkoxy group having 1 to 6 carbon atoms) alkyl (1 to 4 carbon atoms) ether [vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4- Dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, etc.] and poly (2-4) (meth) allyloxyalkanes (carbon number of alkane group 2 -6) [diallyloxyethane, triaryloxy Ethane, tetraallyloxyethane, tetra allyloxy propane, tetra Ali Loki Shiv Tan, tetra meth allyloxy ethane]
Aromatic vinyl ethers having 8 to 20 carbon atoms, such as vinyl phenyl ether and phenoxystyrene

(M3) Vinyl ketone-Aliphatic vinyl ketone having 4 to 25 carbon atoms such as vinyl methyl ketone and vinyl ethyl ketone-Aromatic vinyl ketone having 9 to 21 carbon atoms such as vinyl phenyl ketone

(M4) Sulfide group-containing monomer Sulfide group-containing monomer having 4 to 20 carbon atoms, for example, divinyl sulfide, p-vinyldiphenyl sulfide, and vinyl ethyl sulfide

(M5) Unsaturated dicarboxylic acid diester An unsaturated dicarboxylic acid diester having 4 to 34 carbon atoms, for example, dialkyl (C1 to C22 of alkyl group) or dicycloalkyl (C2 to C22 of cycloalkyl group) fumarate, Dialkyl (alkyl group having 1 to 22 carbon atoms) or dicycloalkyl (cycloalkyl group having 4 to 22 carbon atoms) maleate

(N) Halogen-containing vinyl monomer Halogen-containing vinyl monomer having 2 to 18 carbon atoms such as vinyl chloride, allyl chloride, vinylidene chloride, chloroprene, 8-bromo-1-octene and 8-bromo-2,6-dimethyl-2 -Octene

  Of the other vinyl monomers used for the copolymerization with the vinyl monomer having a reactive functional group, (g), (h), (j) and (n) are preferable from the viewpoint of coating strength. Further preferred are aromatic vinyl hydrocarbons, alkyl (C1-4) (meth) acrylates and (n), and particularly preferred are styrene, methyl (meth) acrylate and butyl (meth) acrylate.

  Examples of the polymerization method of the vinyl monomer include ordinary polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. Among these, solution polymerization and suspension polymerization are preferable from the viewpoint of adjusting the molecular weight. Further preferred is solution polymerization, and particularly preferred is solution polymerization in which the solvent is removed after solution polymerization in an organic solvent.

Among the thermosetting resins (I) in the present invention, as the polyester resin, poly (divalent to tetravalent or higher) carboxylic acid and / or ester-forming derivative thereof and polyol (divalent to tetravalent or higher). ) And a polymerized ester of a lactone.
Examples of the polycarboxylic acid include aromatic polycarboxylic acids [C8-35, such as ortho-, iso- and terephthalic acid, trimellitic acid, pyromellitic acid]; aliphatic polycarboxylic acids [C3-24, For example, malonic acid, succinic acid, glutaric acid, adipic acid, dodecenyl succinic acid, n-octyl succinic acid, dodecanedioic acid]; alicyclic polycarboxylic acid [having 9 to 50 carbon atoms such as 1,2,4-cyclohexanetricarboxylic acid] , 1,4-cyclohexanedicarboxylic acid, etc.], and mixtures thereof.

Examples of the ester-forming derivative include acid anhydrides, acid halides, and lower alcohol (carbon number 1 to 4) esterified products of the above polycarboxylic acids.
Examples of the polyol include alkylene (carbon number 2 to 4) oxide (2 to 40 mol) adducts of polyhydric phenols (having 6 to 70 carbon atoms, such as bisphenol A, catechol, and phenol novolac), and aliphatic polyols (2 to Hexavalent or higher) [C4-12, such as ethylene glycol, propylene glycol, 1,4-, 1,3- and 2,3-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolpropane, pentaerythritol, sorbitol and their alkylene (2 to 4 carbon) oxide (2 to 40 mol) adduct], alicyclic polyol (2 to 4 or more) [carbon number 8 to 20 For example, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and these Alkylene (1-4 carbon atoms) oxide (2-40 moles) adduct, and the like and mixtures thereof.
Examples of the lactone include γ-lactone having 4 to 18 carbon atoms such as γ-butyrolactone and γ-caprolactone; δ-lactone having 5 to 6 carbon atoms such as δ-valerolactone and δ-caprolactone; 9 to 17 carbon atoms. And macrocyclic lactones.

  Of the above polyester resins, aromatic polycarboxylic acids and / or ester-forming derivatives thereof, alkylene oxide adducts of polyhydric phenols, aliphatic polyols and / or alicyclic polyols are preferable from the viewpoint of resin strength. And more preferably, isophthalic acid, terephthalic acid and / or an ester-forming derivative thereof and an alkylene (1 to 4 carbon) oxide (2 to 40 mol) adduct of bisphenol A, 1,6- It is a polyester formed from hexanediol, neopentyl glycol, hydrogenated bisphenol A and / or an alkylene (2 to 4 carbon) oxide (2 to 40 mol) adduct of these polyols.

Examples of the method for introducing a reactive functional group (carboxyl group, hydroxyl group, etc.) into the polyester resin include a method for adjusting the equivalent ratio (COOH / OH) in the reaction between the carboxyl group-containing component and the hydroxyl group-containing component.
The appropriate amount ratio in the case of introducing a carboxyl group is preferably 1 to 10, more preferably 1.1 to 3, more preferably in the case of introducing a hydroxyl group from the viewpoint of resin adhesiveness and resin pigment dispersibility. The amount ratio is preferably 0.2 to 1, and more preferably 0.7 to 0.9, from the viewpoint of the weather resistance of the resin composed of the resin particle aqueous dispersion after curing and the pigment dispersibility of the resin.
Examples of the method for producing the polyester resin include ordinary polyester polymerization methods such as a dehydration polycondensation reaction between a polycarboxylic acid and a polyol, and an ester exchange reaction between an ester-forming derivative of a polycarboxylic acid and a polyol.

Among the thermosetting resins (I) in the present invention, examples of the epoxy resin include those formed from aromatic, heterocyclic, alicyclic and aliphatic epoxides.
Aromatic epoxides include glycidyl esters of aromatic poly (divalent to tetravalent or higher) carboxylic acids, polyvalent (divalent to tetravalent or higher) phenols or alkylene (2 to 4 carbon atoms) oxides thereof. (2 to 40 mol) Adduct glycidyl ether, glycidyl aromatic amine and the like.
Examples of the glycidyl ester of the aromatic polycarboxylic acid include 14 to 20 carbon atoms, such as diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, and diglycidyl trimellitic acid.

The glycidyl ether of a polyhydric phenol or an alkylene (2 to 4 carbon) oxide (2 to 40 mol) adduct thereof has 12 to 80 carbon atoms, for example, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B di Glycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octa Loro-4,4′-dihydroxybiphenyl diglycidyl ether, glycidyl ether of phenol or cresol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or Polyglycidyl ether (epoxy equivalent 200 to 1,000) of polyphenol [weight average molecular weight (hereinafter abbreviated as Mw) 500 to 10,000] obtained by condensation reaction of formaldehyde, and polyphenol (polyphenol obtained by condensation reaction of resorcin and acetone ( Mw 500-10,000) polyglycidyl ether (epoxy equivalent 200-1,000) and bisphenol A alkylene oxide [EO or propylene oxide (hereinafter Include diglycidyl ethers of PO hereinafter)] adducts.
Examples of the glycidyl aromatic amine include 12-30 carbon atoms such as N, N-diglycidylaniline and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine. Furthermore, in the present invention, the aromatic system includes a diglycidyl urethane compound obtained by an addition reaction of an aromatic diisocyanate having 9 to 15 carbon atoms (such as tolylene diisocyanate or diphenylmethane diisocyanate) and glycidol, and the two reactants include a polyol. Also included are glycidyl group-containing urethane (pre) polymers obtained by reaction.

Examples of the heterocyclic epoxide include 12 to 30 carbon atoms such as trisglycidyl melamine.
Examples of the alicyclic epoxide include 8 to 20 carbon atoms, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3 , 4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4- And epoxy-6-methylcyclohexylmethyl) butylamine. The alicyclic system also includes a nuclear hydrogenated product of the aromatic polyglycidyl ether compound.

Aliphatic epoxides include poly (2-20) glycidyl ethers of aliphatic polyols (2 to 4 or more), poly (2 to 20 or more) of fatty acid polycarboxylic acids (2 to 4 or more). ) Glycidyl esters, and glycidyl aliphatic amines.
Poly (2-20) glycidyl ethers of aliphatic polyols are alkylene (2-4 carbon) glycol polyglycidyl ethers such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether; polyalkylene (C2-C4) glycol polyglycidyl ether, such as polyethylene glycol (Mw 500-2000) diglycidyl ether, polypropylene glycol (Mw 500-2000) diglycidyl ether; polyglycidyl of trihydric to tetrahydric or higher polyhydric alcohol Ethers such as trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol poly (2-20) glycol Such as Jill ether, and the like.
Examples of the poly (2-20) glycidyl ester of the aliphatic polycarboxylic acid include diglycidyl adipate. In the present invention, the aliphatic epoxy resin also includes a (co) polymer (Mw 5,000 to 20,000) of glycidyl (meth) acrylate.
Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine.

  Of the above epoxides, aromatic and aliphatic epoxides are preferable from the viewpoint of resin strength, and more preferable are glycidyl ethers of polyhydric phenols or alkylene oxide adducts thereof and polyglycidyls of aliphatic polycarboxylic acids. Esters, particularly preferred are bisphenol A diglycidyl ether and diglycidyl adipate.

  As a method for producing an epoxy resin in the present invention, the above epoxide is used as a catalyst [an alkaline inorganic compound such as alkali hydroxide (such as sodium hydroxide or potassium hydroxide), quaternary ammonium salt (such as tetramethylammonium bromide), or tertiary. And ring-opening polymerization using an amine (such as triethylamine or benzyldiethylamine).

  Among the thermosetting resins (I) in the present invention, examples of the polyurethane resin include resins having urethane or urethane and urea bonds in the molecule, but preferred are resins having urethane or urethane and urea bonds in the main chain. It is. The resin comprises an active hydrogen-containing polyfunctional polymer compound (a) having functional groups (hydroxyl groups, primary amino groups, secondary amino groups, etc.) having reactivity with isocyanate groups at the molecular terminals and / or side chains. Although it is a thing obtained by making an isocyanate compound (b) react, you may make it react using the low molecular compound (c) which has reactivity with an isocyanate group if necessary.

Examples of (a) include polymer polyols (acrylic polyol, polybutadiene polyol, polyester polyol, polyether polyol, etc.).
Among the polymer polyols, the acrylic polyol includes a vinyl monomer having a hydroxyl group [(e), eg, hydroxyethyl methacrylate] and another vinyl monomer [eg, methyl (meth) acrylate, styrene, butyl (meth) acrylate]. Can be mentioned.
Examples of the method for producing the acrylic polyol include a method of performing radical polymerization in the presence of an azo radical polymerization initiator having a hydroxyl group and a chain transfer agent having a hydroxyl group, and a method of (co) polymerizing a hydroxyl group-containing monomer.
Examples of the polybutadiene polyol (including hydrogenated product) include a copolymer of butadiene containing a hydroxyl group at a terminal and other vinyl monomers (for example, styrene and acrylonitrile).
Examples of the polyester polyol include condensed polyester polyol, lactone polyester polyol, and polycarbonate diol. Examples of the condensed polyester polyol include those obtained by a dehydration condensation reaction between a dicarboxylic acid (for example, adipic acid) and a diol (for example, ethylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol).
Examples of the lactone polyester polyol include polyesters obtained by ring-opening polymerization of ε-caprolactone.
Examples of the polycarbonate diol include polyesters obtained by addition polymerization of diol (for example, 1,6-hexanediol) and ethylene carbonate.
Examples of the polyether polyol include those obtained by addition polymerization of an alkylene oxide (for example, EO, PO, THF) to an initiator [for example, water, low molecular weight polyol (diol, triol, etc.)].

  The number of functional groups of the active hydrogen-containing polyfunctional polymer compound (a) is usually 2 to 4 or more, preferably 2 to 3, and the equivalent (molecular weight per functional group) is usually at least 250, preferably 250 to 4, 000, more preferably 350 to 2,500, and particularly preferably 400 to 2,000.

  As the isocyanate compound (b), (1) a monofunctional such as an aliphatic isocyanate having 2 to 12 carbon atoms (excluding carbon in the NCO group) [propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, etc. Isocyanate; bifunctional isocyanate such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, etc.] (2) alicyclic isocyanate having 4 to 15 carbon atoms (excluding carbon in the NCO group) [monofunctional isocyanate such as cyclohexyl isocyanate; isophorone di Bisocyanate such as socyanate (IPDI), dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, etc.]; (3) Aromatic aliphatic isocyanate having 7 to 12 carbon atoms (excluding carbon in NCO group) [benzyl isocyanate Monofunctional isocyanates such as xylylene diisocyanate, etc.]; (4) aromatic isocyanates [monofunctional isocyanates such as phenyl isocyanate; 1,3- and / or 1,4-phenylene diisocyanate, 2,4- And / or bifunctional isoforms such as 2,6-tolylene diisocyanate (TDI), 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, etc. Bifunctional or higher isocyanates such as anate, crude TDI, and crude MDI]; (5) Modified products of the above isocyanates (modified MDI (urethane modified MDI, carbodiimide modified MDI), trihydrocarbyl phosphate modified MDI), urethane modified TDI, view Let-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI, etc.] and a mixture of two or more of (1) to (5). Among these, preferred are bifunctional or higher isocyanates capable of introducing urethane and / or urea bonds into the resin main chain, and more preferred are aliphatic and aliphatic from the viewpoint of resin flexibility. Cycloaliphatic isocyanates, particularly preferred are isophorone diisocyanate.

Examples of the low molecular weight compound (c) used as necessary include alcohols and amines having a hydroxyl group equivalent of less than 250.
Examples of the alcohol include monohydric alcohol (1 to 30 carbon atoms), 2 to 8 polyhydric alcohol (2 to 30 carbon atoms), alkylene oxide of the polyhydric alcohol (2 to 20 carbon atoms such as EO, PO, 1,2-, 1,3-, 2,3- or 1,4-butylene oxide, styrene oxide, epichlorohydrin) adduct, monohydric phenol compound and alkylene oxide adduct of 2-6 polyhydric phenol compound, Examples thereof include phosphorus-based polyols and mixtures thereof.

  Examples of the monohydric alcohol include aliphatic alcohols (saturated or unsaturated alcohols having 1 to 30 carbon atoms such as methanol, ethanol, n- and i-propanol, n-, i-, sec- and t-butanol, 2- Ethyl hexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether), alicyclic alcohol (saturated or unsaturated alcohol having 1 to 30 carbon atoms such as cyclohexyl alcohol), araliphatic alcohol (7 carbon atoms) To 30 alcohols such as benzyl alcohol).

  Among the polyhydric alcohols, dihydric alcohols are aliphatic, alicyclic or araliphatic saturated or unsaturated alcohols having 2 to 30 carbon atoms [ethylene glycol, propylene glycol, 1,4-, 1,3- and 2 , 3-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4,4 ' -Hydroxycyclohexyl) propane, 1,4-bis (hydroxyethyl) benzene, phthalyl alcohol, etc.], 3 to 8 valent polyhydric alcohols are aliphatic or aromatic saturated or unsaturated alcohols having 3 to 30 carbon atoms [Glycerin, trimethylolpropane, pentaerythritol, jig Serine, alpha-methyl glucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose, sucrose, etc.] and the like.

Examples of the monohydric phenol compound include 6 to 12 carbon atoms, such as phenol, o-, m- and p-cresol, 3,5-xylenol, carvacrol, thymol, α-naphthol and β-naphthol.
The polyhydric phenol has 6 to 15 carbon atoms, for example, monocyclic polyhydric phenols such as pyrogallol, catechol, and hydroquinone; bisphenol compounds (bisphenol A, bisphenol F, bisphenol S, etc.); The above-mentioned alkylene oxide adducts such as phosphoric acid, phosphonic acid and dibutyl pyrophosphoric acid can be mentioned.

  Among the above alcohols, preferred are polyhydric alcohols capable of introducing a urethane bond into the resin main chain, more preferred are aliphatic and / or alicyclic polyhydric alcohols, and particularly preferred is 1,6- Hexanediol and / or neopentyl glycol.

Examples of the amine include aliphatic amine (saturated or unsaturated primary or secondary amine having 1 to 22 carbon atoms), alicyclic amine (saturated or unsaturated primary or secondary amine having 5 to 22 carbon atoms), aromatic ( Aliphatic) amines (primary or secondary amines having 6 to 30 carbon atoms), and mixtures thereof.
Aliphatic amines include monoamines [methylamine, ethylamine, n- and i-propylamine, n-, i-, sec- and t-butylamine, hexylamine, octylamine, 2-ethylhexylamine, dodecylamine, alkanolamine. (Monoethanolamine, diethanolamine, etc.)], diamine (ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,6-hexamethylenediamine, etc.), trivalent to pentavalent or higher polyamines (diethylenetriamine, triethylenetetramine, etc.) Is mentioned.
Examples of alicyclic amines include monoamines (cyclobutylamine, cyclopentylamine, cyclohexylamine, etc.), diamines, and trivalent to pentavalent or higher polyamines.
Aromatic (aliphatic) amines include monoamines (aniline, o-, m- and p-toluidine, diphenylamine, α-naphthylamine, benzylamine, etc.), diamines (1,3- and / or 1,4-phenylenediamine, 2,4- and / or 2,6-tolylenediamine, 2,4′- and / or 4,4′-diphenylmethanediamine, etc.), trivalent to pentavalent or higher polyamines.

  Among the above amines, a divalent or higher polyamine capable of introducing a urea bond into the resin main chain is preferred, an aliphatic diamine is more preferred, ethylenediamine and 1,6- Hexamethylenediamine.

The proportion of the active hydrogen-containing polyfunctional polymer compound (a) in the polyurethane resin is preferably 60 to 95% by weight, more preferably 70 to 90% by weight.
The equivalent ratio of the isocyanate group to the active hydrogen-containing functional group such as a hydroxyl group and amino group that reacts with the isocyanate group is preferably 1: 0. From the viewpoint of the water resistance of the resin comprising the resin particle aqueous dispersion after curing. It is 8 to 1: 2, more preferably 1: 0.9 to 1: 1.8.
The ratio of functional groups (hydroxyl group / amino group) is an equivalent ratio, preferably 0.2 to 10, more preferably from the viewpoint of the weather resistance of the resin comprising the resin particle aqueous dispersion after curing and the pigment dispersibility of the resin. 0.7-3. The terminal of the polyurethane resin may be either a hydroxyl group or an isocyanate group, but is preferably a hydroxyl group.

The method for producing the polyurethane resin is not particularly limited as long as it is a method for producing a general polyurethane resin. As a general method for producing a polyurethane resin, a prepolymer method or a semiprepolymer method via a prepolymer or a semiprepolymer (a mixture of a free polyisocyanate and a prepolymer) and a one-shot (one-stage) method can be mentioned. .
In order to introduce urethane and urea bonds, an NCO-terminated prepolymer solution is obtained by reacting a hydroxyl group-containing polymer polyol with a polyfunctional isocyanate exceeding the equivalent of the hydroxyl group in a non-reactive solvent. A method in which a hydroxyl group-terminated urethane urea resin is obtained by reacting a hydroxyl group-containing amine in a solvent, and then the solvent is distilled off under reduced pressure. The difunctional amine and dimerized in the resin solution having the urethane bond and the isocyanate group are dimerized. A method in which monoamine having a hydroxyl group such as alkanolamine is mixed, heated and reacted while dispersed in water to obtain a urethane having a hydroxyl group at the end and a resin having a urea bond, and then dehydrated and desolventized under heating and reduced pressure Etc.
Of the above production methods, the preferred is that the resin solution having an isocyanate group is mixed with a monofunctional amine having a hydroxyl group such as dialkanolamine and a bifunctional amine having a spherical particle shape and excellent adhesion. This is a method in which the mixture is heated and reacted while being dispersed, and then dehydrated and desolvated under reduced pressure by heating. The reaction temperature of (a) and (b) and (c) added as necessary varies depending on the type of functional group and isocyanate, but is usually 10 to 160 ° C., preferably 20 to 130 ° C., particularly preferably 50 to 120 ° C. It is. The reaction time is usually 1 to 20 hours, preferably 3 to 10 hours.

  Among the thermosetting resins (I) in the present invention, fluorine resins include fluorine-containing monomers [fluorinated olefins having 1 to 20 fluorine atoms and 2 to 10 carbon atoms [tetrafluoroethylene, hexafluoropropylene, One or more monomers selected from fluorinated alkyl (C1-10) (meth) acrylate [perfluorohexylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, etc.], etc.] And a (co) polymer of the vinyl monomer having the reactive functional group.

  In the present invention, Mn of the thermosetting resin (I) is preferably 1,000 to 20,000, more preferably 1,500 in the case of vinyl resin, polyester resin and fluororesin from the viewpoint of storage stability and adhesiveness. To 15,000, particularly preferably 2,500 to 8,500. In the case of epoxy resins and polyurethane resins, preferably 1,000 to 10,000, more preferably 1,500 to 8,500, particularly preferably 2. , 5,000 to 5,000.

Examples of the thermoplastic resin (II) in the present invention include vinyl resins [polyolefin resins, styrene resins, acrylic resins, diene (co) polymers, etc.], polyamide resins, polyester resins, fluorine resins, polyurethane resins, and the like.
Of these, from the viewpoint of weather resistance, one or more resins selected from the group consisting of vinyl resins, polyamide resins, polyester resins, fluororesins and polyurethane resins are preferable, and vinyl resins, polyamide resins and fluorine are more preferable. Resins, particularly preferred are vinyl resins and polyamide resins.

  Examples of the vinyl resin include those of the type described in (I) above, and those having a melt flow rate (hereinafter abbreviated as MFR, measurement is based on JIS K7210: 1999 B method) of 0.5 to 150. The MFR is preferably 1 to 100, more preferably 2 to 80, from the viewpoint of adhesiveness of the cured coating film.

As the polyamide resin, a polyamide formed from a polyamide-forming component having 6 to 12 or more carbon atoms (a combination of diamine and dicarboxylic acid having 6 to 12 carbon atoms, aminocarboxylic acid, lactam, etc.), for example, nylon 66, nylon 69, nylon 610, nylon 612, nylon 6, nylon 11, nylon 12 and nylon 46.
The MFR of the polyamide resin is preferably 0.5 to 150, more preferably 1 to 100, and particularly preferably 2 to 80 from the viewpoint of adhesiveness.

Examples of the polyester resin include those of the type described in (I) above and having an intrinsic viscosity of 0.1 to 4. The intrinsic viscosity is preferably 0.2 to 3.5, more preferably 0.3 to 3.0, from the viewpoint of adhesiveness of the cured coating film.
Above and below, the intrinsic viscosity is measured with an Ubbelohde 1A viscometer at 25 ° C. using a 0.5% solution of the sample orthochlorophenol.

  Examples of the fluororesin include those of the type described in (I) above and those having an MFR of 0.5 to 150. MFR is preferably 1 to 100, more preferably 2 to 80, from the viewpoint of adhesiveness.

Examples of the polyurethane resin include those of the type described in (I) above and having a melting point of 120 to 270 ° C. The melting point is preferably 130 to 260 ° C., more preferably 140 to 250 ° C. from the viewpoint of curability.
Here, the melting point is a value measured by DSC (Differential Scanning Calorimetry), and is a peak top temperature under a temperature rising rate condition of 10 ° C./min.

The curing agent (D) in the present invention preferably has a functional group that reacts with the reactive functional group in the thermosetting resin (I).
Curing agents (D) include those having two or more carboxyl groups in one molecule (D1), those having two or more epoxy groups in one molecule (D2), and two or more amino groups in one molecule. Having one or more hydroxyl groups in one molecule (D4), one having two or more isocyanate groups in one molecule (D5), two or more hydrolyzable silyl groups in one molecule (D6), those having two or more blocked amino groups in one molecule (D7), those having two or more blocked isocyanate groups in one molecule (D8), and mixtures thereof. Specific examples include the following.

(D1): Polycarboxylic acid described in the polyester resin, etc. (D2): Epoxy resin, etc. (D3): Divalent amine and polyvalent amine exceeding divalent described in the polyurethane resin (D7): (D3 ) Blocked products [Examples of the blocking agent include ketones (having 3 to 8 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone), acid anhydrides (having 4 to 10 carbon atoms, such as phthalic anhydride), and the like. ]
(D4): Polyhydric alcohol [as described in (C) above], polyester polyol having hydroxyl groups at both ends, acrylic polyol, polyether polyol [as described in (A) above], etc. (D5): Bifunctional Reaction product of the above polyisocyanate [described in the above (b)] and the above (C3) and / or (C4) and an excess equivalent of a bifunctional or higher polyisocyanate [described in the above (b)] (D8): Blocked product of (D5) [as the blocking agent, those mentioned above and secondary amines (4 to 20 carbon atoms such as diethylamine, di-n-butylamine), basic nitrogen-containing compounds (carbon number) 4-20, for example, N, N-diethylhydroxyamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine), active methyle Group-containing compound (5 to 15 carbon atoms, such as diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone) and the like can be mentioned.
In addition to the blocked isocyanates in which the isocyanate groups are blocked by the blocking agent, oligomers (uretodione type blocked isocyanate group-containing compounds) such as HDI or TDI (polymerization degree: 2 to 15) And compounds having a structure obtained by reacting the terminal isocyanate group of these oligomers with the blocking agent described above. ]
(D6): Di-, tri-, and tetraalkoxysilanes having a C 1-8 alkoxy group and condensates thereof.

  Of the curing agents (D), (D1), (D5), (D6) and (D8) are preferable from the viewpoint of reactivity, and dodecanedioic acid, trimethoxysilane and ε-caprolactam blocked isophorone are more preferable. Diisocyanate.

  Of the combinations of the reactive functional group of the thermosetting resin (I) / the reactive functional group of the curing agent (D), epoxy group / carboxyl group, hydroxyl group / blocked isocyanate are preferable from the viewpoint of the obtained resin strength. Groups, and their reverse combinations, more preferred are glycidyl / carboxyl groups, hydroxyl / uretdione-type blocked isocyanate groups, and their reverse combinations.

The equivalent ratio of the reactive functional group of the thermosetting resin (I) to the reactive functional group of the curing agent (D) is preferably (1 / 0.7) to (1/1) from the viewpoint of the temporal stability of the resin. .4), more preferably (1 / 0.8) to (1 / 1.2), and particularly preferably (1 / 0.9) to (1 / 1.1).
The curing agent (D) may be mixed with the resin particles (A) and the resin particles (B) to form the resin particle aqueous dispersion of the present invention. From the viewpoint of the obtained resin strength, the resin is preferable. When contained in at least one of the particles (A) and the resin particles (B), it is more preferred that they are contained in both particles.

In the reaction of the thermosetting resin (I) and the curing agent (D), a curing catalyst may be used. As the curing catalyst, a combination of reactive functional groups (I) and (D) is, for example, In the case of hydroxyl group / (blocked) isocyanate group and vice versa, catalysts usually used in urethanization reactions [metal catalysts [tin-based (dibutyltin dilaurate, stannous octoate, etc.), lead-based (lead oleate, naphthenic acid] Lead, lead octenoate, etc.)], amine-based catalysts [triethylenediamine, dimethylethanolamine, etc.]], carboxyl groups / epoxy groups and vice versa, acids (such as boron trifluoride), bases (amines, Alkali earth metal hydroxides), salts (quaternary onium salts, etc.), organometallic catalysts (stannous chloride, tetrabutyl zirconate, etc.), hydroxyl groups, etc. For amino groups and vice versa, organic acids (p-toluenesulfonic acid, and dodecyl benzene sulfonic acid), inorganic acids (such as phosphoric acid), and the like.
When using a curing catalyst, the amount used is preferably 1% by weight or less based on the total weight of the resin particle aqueous dispersion, more preferably 0.005 to 0.8% by weight, particularly from the viewpoint of adhesiveness. Preferably it is 0.01 to 0.5 weight%.
When a curing catalyst is used, the curing catalyst may be contained in either of the resin particles (A) and (B), but is preferably contained in both (A) and (B).

  In the present invention, the dispersant (E) includes a polymeric dispersant (E1), an anionic surfactant (E2), a cationic surfactant (E3), an amphoteric surfactant (E4), and a nonionic interface. Activators and mixtures thereof. Specific examples include the following.

  Examples of the polymeric dispersant (E1) include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic , Chitin, chitosan, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, sodium hydroxide of polyacrylic acid Partially neutralized product, sodium acrylate-acrylic acid ester copolymer), sodium hydroxide of styrene-maleic anhydride copolymer Um (partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

  Examples of the anionic surfactant (E2) include carboxylic acids or salts thereof, sulfate esters, carboxymethylated salts, sulfonates, and phosphate esters.

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

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

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

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

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

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

  Examples of the cationic surfactant (E3) include a quaternary ammonium salt type and an amine salt type.

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

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

  The amphoteric surfactant (E4) used in the present invention includes a carboxylate amphoteric surfactant, a sulfate ester amphoteric surfactant, a sulfonate amphoteric surfactant, and a phosphate ester amphoteric surfactant. Examples of the carboxylate-type amphoteric surfactant include amino acid-type amphoteric surfactants and betaine-type amphoteric surfactants.

Examples of the carboxylate-type amphoteric surfactants include amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants. Examples of amphoteric surfactants having an amino group and a carboxyl group include compounds represented by the following general formula.
[R—NH— (CH ₂ ) n —COO] mM [wherein R is a monovalent hydrocarbon group; n is usually 1 or 2; m is 1 or 2; M is a hydrogen atom, an alkali metal atom, an alkali An earth metal atom, an ammonium cation, an amine cation, an alkanolamine cation and the like. Specific examples include, for example, alkylaminopropionic acid type amphoteric surfactants (such as sodium stearylaminopropionate and sodium laurylaminopropionate); alkylaminoacetic acid type amphoteric surfactants (such as sodium laurylaminoacetate), and the like. It is done.

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

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

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

  Examples of the nonionic surfactant (E5) include alkylene oxide addition type nonionic surfactants and polyvalent alcohol type nonionic surfactants.

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

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

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

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

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

In the resin particle aqueous dispersion of the present invention, other components usually used in the field of adhesives, such as a leveling agent, a colorant, an antioxidant and / or a plasticizer, if necessary, as long as the effects of the present invention are not impaired. Additives can be added. The other additive may be contained in either one of the resin particles (A) or (B), or may be contained in both, or separately from (A) and (B). The dispersion may be added and mixed.
Further, the resin particle aqueous dispersion of the present invention contains other additives usually used in the field of fiber processing such as stabilizers (ultraviolet absorbers, antioxidants, etc.), thickeners, film-forming aids and the like. Can be added. The other additive may be contained in either one of the resin particles (A) or (B), or may be contained in both, or separately from (A) and (B). The dispersion may be added and mixed.

Examples of the leveling agent include olefin polymers (Mw 500 to 5,000, for example, low molecular weight polyethylene, low molecular weight polypropylene), olefin copolymers [Mw 500 to 20,000, for example, ethylene-acrylic (acrylonitrile, etc.) copolymers, Ethylene-methacrylic copolymer], (meth) acrylic copolymer [Mw 1,000 to 20,000, for example, trade name: Modaflow [manufactured by Solusia Co., Ltd.]], polyvinylpyrrolidone (Mw 1,000 to 20,000), Silicone leveling agents [Mw 1,000 to 20,000, such as polydimethylsiloxane, polyphenylsiloxane, organic (carboxyl, ether, epoxy, etc.) modified polydimethylsiloxane, fluorinated silicone], low molecular weight compounds (benzoin, etc.) and these Such compounds, and the like.
The amount of the leveling agent used is usually 5% or less, preferably 0.3 to 3%, based on the total weight of the resin particle aqueous dispersion.

Examples of the colorant include inorganic pigments, organic pigments, and dyes.
Examples of inorganic pigments include white pigments (titanium oxide, lithopone, lead white, zinc white, etc.); cobalt compounds (aureolin, cobalt green, cerulean blue, cobalt blue, cobalt violet, etc.); iron compounds (iron oxide, bitumen, etc.); Examples thereof include chromium compounds (chromium oxide, lead chromate, barium chromate, etc.); sulfides (cadmium sulfide, cadmium yellow, ultramarine, etc.) and mixtures thereof.
Organic pigments include azo lakes such as azo lake, monoazo, disazo, and chelate azo; benzimidazolone, phthalocyanine, quinacridone, dioxazine, isoindolinone, thioindigo, perylene, quinophthalone, anthraquinone Polycyclic pigments such as systems; and mixtures thereof.
As dyes, azo, anthraquinone, indigoid, sulfide, triphenylmethane, pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, nitro, Examples thereof include nitroso, aniline, and mixtures thereof.
Although the usage-amount of a coloring agent changes with kinds, it is 30% or less normally based on the total weight of the resin particle aqueous dispersion, Preferably it is 5-25%.

Antioxidants include phenolic [2,6-di-t-butyl-p-cresol (BHT), 2,2′-methylenebis (4-methyl-6-t-butylphenol), tetrakis [methylene- (3 , 5-di-t-butyl-4-hydroxyhydrocinnamate)] methane [trade name: Irganox 1010, manufactured by Ciba Geigy Co., Ltd.], sulfur-based [dilauryl 3,3′-thiodipropionate (DLTDP) ), Distearyl 3,3'-thiodipropionate (DSTDP), etc.], phosphorus [triphenyl phosphite (TPP), triisodecyl phosphite (TDP), etc.], amine [octylated diphenylamine, N- n-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine, etc.] and mixtures thereof. And the like.
The amount of the antioxidant used is usually 5% or less, preferably 0.1 to 2%, based on the total weight of the resin particle aqueous dispersion.

Aromatic carboxylic acid ester type [phthalic acid ester (dioctyl phthalate, dibutyl phthalate, etc.)], aliphatic monocarboxylic acid ester type [methyl acetyl ricinolate, triethylene glycol dibenzoate, etc.], aliphatic dicarboxylic acid ester type [di (2-ethylhexyl) adipate, adipic acid-propylene glycol-based polyester, etc.], aliphatic tricarboxylic acid ester-based [citrate esters (such as triethyl citrate), etc.], phosphate triester-based [triphenyl phosphate, etc.], and Examples thereof include a mixture thereof.
The amount of the plasticizer used is usually 20% or less, preferably 5 to 15%, based on the total weight of the resin particle aqueous dispersion.

The method for mixing the components constituting the resin particles (A) and (B) in the present invention is not particularly limited. For example, the thermosetting resin (I) and / or the thermoplastic resin (II) in the present invention If necessary, the above-mentioned other additives are added to the powder, and when the thermosetting resin (I) is used, a curing agent (D), a curing catalyst, etc. are added as necessary to obtain a mixture, and the mixture is used as a Henschel mixer or the like. And a method of kneading in a heated and melted state, a method of dehydrating or removing a solvent after mixing the above components in the presence of water or a solvent (such as toluene or xylene).
The method for dry blending is not particularly limited, and examples include a container rotating type and a container fixing type [mechanical stirring type (Henschel mixer etc.), airflow stirring type, gravity type, etc.]. Among these, the mechanical stirring type is preferable from the viewpoint of being able to cope with a small volume to a large volume and having good mixing efficiency.

  In addition, the above-mentioned other additives may be added as a method of mixing when synthesizing the resin, a melt kneading method in which the resin is synthesized and then added under melting, or the resin is once dissolved in a solvent and added for homogenization. Examples thereof include a method of distilling off the solvent after mixing the agent, a method of adding and impregnating after the powder resin is prepared. Among these methods, the method of adding and impregnating a powder resin is preferable from the viewpoint that it can be easily added without adversely affecting the resin composition.

  In the melt-kneading method, the curing agent (D) and the curing catalyst are added at a temperature equal to or higher than the softening temperature of the resin [(I) and / or (II)] using a melt-kneader such as a heating roll, an extruder, or a twin-screw extruder. When it does, it is carried out in a temperature range (usually 60 to 160 ° C., preferably 70 to 130 ° C., more preferably 90 to 120 ° C.) that is at least 10 ° C. lower than the catalyst action temperature.

The shape of the resin particles (A) and the resin particles (B) may be indefinite or spherical, but from the viewpoint of curability, at least one of (A) and (B) is preferred. It is spherical and the other is spherical or irregular, more preferably (B) is spherical and the other is spherical or irregular, and particularly preferred is the case where both (A) and (B) are spherical. Here, the term “spherical” means that the ratio of the shortest diameter / longest diameter of the particles (hereinafter abbreviated as sphericity) is in the range of 0.7 to 1.0.
The spherical particles in the total particles of the resin particles (A) and the resin particles (B) preferably have a volume average content of 70 to 100%, more preferably 80 to 100%, from the viewpoint of adhesiveness.

  The method for making the resin particles (A) and the resin particles (B) spherical is not particularly limited, and a known method can be used. For example, (1) a solid obtained by cooling a molten mixture of resin and other components is once pulverized (particle size 20 to 100 μm), and the temperature is adjusted so that individual pulverized particles do not coalesce, For example, a method of making particles spheroidized by flowing temperature-controlled particles in a pipe or the like. (2) Shibata Scientific Instruments Industry (10-20 ° C. or less from the softening point of the resin) in a molten state in a molten state. (3) Resin organic solvent (xylene, toluene, ethyl acetate, etc.) solution using a spraying device such as a mini spray dryer B-191 manufactured by Co., Ltd. Of 0.1 to 30% by weight of water using a stirring device such as a homomixer or a planetary mixer, and then the solvent is distilled off under reduced pressure, and (4) a spherical resin is obtained by suspension polymerization. Etc. It is. Among these, the methods (2) and (3) are preferable from the viewpoint of the sharp particle size distribution of the particles.

  When spherical particles are produced by the above method, the spherical particles (primary particles) once obtained may be bonded together to form amorphous aggregates (secondary particles). The volume average content of the secondary particles in all the particles is preferably 20% or less, more preferably 0.1% or more and 15% or less from the viewpoint of adhesiveness.

The resin particle aqueous dispersion of the present invention comprises the resin particles (A), the resin particles (B), and, if necessary, the curing agent (D) and the other additives as described above in the dry compounding method or wet compounding. According to the method, it can be produced by mixing and compounding. The mixing ratio of the resin particles (A) and the resin particles (B) is preferably 1: 3000 to 1: 1 by weight, and more preferably 1: 1000 to 1: 2.
When the resin particle aqueous dispersion of the present invention is used as an adhesive or a fiber processing agent, the resin particle aqueous dispersion can be used as it is.

   Means for applying the resin particle aqueous dispersion of the present invention to an adherend as an adhesive includes brush coating, roll coating, spray coating, flow coating, immersion, and the like. Adhesion is performed by applying an adhesive to one adherend and adhering it directly to the other adherend (without drying) (wet adhesion) or after adhering to the other adherend. (Dry bonding) and curing the adhesive layer can be performed. Moreover, it can also be made to adhere | attach by interposing between the to-be-adhered bodies the adhesive dry film, and making it harden | cure. Curing can be performed by curing at normal temperature or under heating (for example, about 60 to 80 ° C.), or curing at normal temperature and then heating to about 60 to 80 ° C. to promote 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 comprising the aqueous dispersion of the present invention is useful, for example, as an adhesive for woodwork, an adhesive for metal parts, an adhesive for plastics, an adhesive for electronic boards, and an adhesive for cloth.

The coating amount of the resin particle aqueous dispersion in the present invention is not particularly limited, but is 0.05 to 0.5 kg / m ² , preferably 0.08 to 0.3 kg / m ² from the viewpoint of adhesiveness. It is desirable.

  The aqueous dispersion of the present invention has a fiber processing binder (pigment printing binder, nonwoven fabric binder, reinforcing fiber bundling agent, antibacterial agent binder, etc.) and coating (waterproof coating, water repellent coating, antifouling coating, etc.) It can be used widely for raw materials for artificial leather and synthetic leather.

  Pigment printing can be performed by printing on a fabric in the same manner as ordinary pigment printing. Specifically, for example, a color paste (a pigment dispersed finely and uniformly in water), the aqueous dispersion of the present invention, a thickener, and other auxiliaries are blended to prepare a printing paste, and then Is printed on fabrics. A vertical mixing tank is used for blending. For printing, an auto screen printing machine, a rotary screen printing machine, a roller printing machine, or the like can be used. For the fabric, 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 fibers applied when used as a sizing agent for reinforcing fibers include inorganic fibers (glass fibers, carbon fibers, etc.) and high-strength organic fibers (polyamide fibers, polyester fibers, etc.) of British Patent No. 1543099. included. When used as a sizing agent for glass fibers, the aqueous dispersion of the present invention contains a silane coupling agent (γ-aminopropylethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyl, if necessary. Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc.), lubricant (fatty acid amide, soap, etc.), antistatic agent (such as surfactant), plasticizer (phthalate ester, adipate ester, etc.), One or more additives such as an antifoaming agent (as described above) can be added. The sizing agent may be used in combination with other sizing agents, such as starch, modified starch, dextrin, amylose, gelatin, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, aqueous polyester resin, aqueous epoxy resin, Aqueous acrylic resins and the like are included. A treatment liquid is prepared by blending an aqueous dispersion and optional additives, applied to fibers, and heated and dried as necessary to fix. A mixing tank (such as a bowl) is used for blending. The concentration of the treatment liquid is usually 1 to 10%. Application to the fiber is done by roller coating, spray coating, impregnation coating and the like. The adhesion amount to the fiber is usually 0.1 to 10%. Drying and fixing can be performed with hot air of 50 to 100 ° C., for example.

When used as a raw material for antibacterial agent binders, coatings, artificial leather / synthetic leather, additives, concentration of treatment liquid, means for application to fibers, amount attached to fibers, treatment conditions, etc. may be the same as above, It can be appropriately selected depending on the application.
Examples of the heat source used in the melting and curing step of the coating film obtained by applying the resin particle aqueous dispersion in the present invention include infrared rays, far infrared rays, electromagnetic waves (including microwaves) and hot air. From the viewpoint of adhesiveness, infrared rays, far infrared rays and hot air are preferable.

  The resin particle aqueous dispersion of the present invention is an adhesive formed by applying it to the surface of the adherend, and the fiber processing agent can be a resin having a low glass transition temperature. For example, when used as an adhesive for preventing loosening of screws, the adhesive film on the screw surface of a bolt or nut does not peel off when tightened, and thus high adhesive strength can be obtained. Moreover, when using as a binder for nonwoven fabrics, since the space | gap between fibers is filled, high intensity | strength is obtained.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Hereinafter, a part shows a weight part.

<Production Example 1>
795 parts of ion exchange water, 5 parts of sodium dodecyl sulfate, and 80 parts of ethyl acetate were added and stirred well. Desmophen A575X (hydroxyl group-containing acrylic polymer) [manufactured by Sumitomo Bayer Urethane Co., Ltd.] / Duranate TPA-B-80E (HDI isocyanurate type blocked product) [manufactured by Asahi Kasei Kogyo Co., Ltd.] / Dibutyltin laurate (weight) 286 parts of a mixed solution with a ratio of 67/32/1) were added. The obtained mixed solution is stirred at 12000 rpm for 2 minutes using a TK homomixer [manufactured by Tokushu Kika Kogyo Co., Ltd.], then transferred to a pressure resistant reactor and desolvated at normal pressure while raising the temperature to 40 ° C. Thus, a resin particle dispersion was obtained. The resin particle dispersion was taken out as a powder by freeze-drying to obtain resin particles (A-1). The volume average particle diameter DA was 19 μm, and Tg was 28 ° C.

<Production Example 2>
In Production Example 1, desmophen A575X (hydroxyl group-containing acrylic polymer) [manufactured by Sumitomo Bayer Urethane Co., Ltd.] / Duranate TPA-B80E (blocked product of HDI isocyanurate type) [manufactured by Asahi Kasei Kogyo Co., Ltd.] / Dibutyltin laurate (weight ratio 67) / 32/1), desmophen A565X (hydroxyl group-containing acrylic polymer) [manufactured by Sumitomo Bayer Urethane Co., Ltd.] / Duranate TPA-B80E (HDI isocyanurate type blocked product) [manufactured by Asahi Kasei Kogyo Co., Ltd.] / Dibutyltin A resin particle dispersion was obtained in the same manner as in Production Example 1 except that the mixed solution was laurate (weight ratio 64/35/1). The resin particle dispersion was taken out as a powder by freeze drying to obtain resin particles (A-2). The volume average particle diameter DA was 18 μm, and Tg was −8 ° C.

<Production Example 3>
In Production Example 1, desmophen A575X (hydroxyl group-containing acrylic polymer) [manufactured by Sumitomo Bayer Urethane Co., Ltd.] / Duranate TPA-B80E (curing agent: HDI isocyanurate type blocked product) [manufactured by Asahi Kasei Kogyo Co., Ltd.] / Dibutyltin laurate ( A mixed solution having a weight ratio of 67/32/1) was mixed with Alfon UC-3920 (carboxylic acid-containing acrylic polymer) [manufactured by Toagosei Co., Ltd.] / Alfon UG-4010 (epoxy group-containing acrylic polymer) [Toagosei Co., Ltd. The resin particle dispersion was obtained in the same manner as in Production Example 1 except that the mixture was changed to a mixed solution of ethyl acetate (weight ratio 20/60/20). The resin particle dispersion was taken out as a powder by freeze-drying to obtain resin particles (A-3). The volume average particle diameter DA was 18 μm, and Tg was 48 ° C.

<Production Example 4>
In Production Example 1, desmophen A575X (hydroxyl group-containing acrylic polymer) [manufactured by Sumitomo Bayer Urethane Co., Ltd.] / Duranate TPA-B80E (curing agent: HDI isocyanurate type blocked product) [manufactured by Asahi Kasei Kogyo Co., Ltd.] / Dibutyltin laurate ( A mixed solution having a weight ratio of 67/32/1) is mixed with Alfon UH-2900 (hydroxyl group-containing acrylic polymer) [manufactured by Toagosei Co., Ltd.] / VESTANAT B1358 / 100 (curing agent: IPDI isocyanurate type blocked product) [Degussa Japan Manufactured in the same manner as in Production Example 1 except that a mixed solution of ethyl acetate / dibutyltin laurate (weight ratio 50/29/20/1) was used to obtain a resin particle dispersion. The resin particle dispersion was taken out as a powder by freeze drying to obtain resin particles (A-4). The volume average particle diameter DA was 18 μm, and Tg was 65 ° C.
<Production Example 5>
A pressure-resistant reaction vessel was charged with 735 parts of ion-exchanged water, 50 parts of sodium dodecyl sulfate, 5 parts of ammonium persulfate, and 10 parts of sodium hydrogen carbonate. After the air in the reaction vessel was replaced with nitrogen, the reaction vessel was sealed up to 80 ° C. The temperature rose. Then, 200 parts of a mixed monomer of styrene / methacrylic acid / butyl acrylate (weight ratio 30/30/40) was added dropwise over 2 hours. Further, the mixture was aged at the same temperature for 2 hours to obtain a resin particle dispersion (BL-5). The volume average particle diameter DB of the resin particles in the resin particle dispersion (BL-5) was 0.05 μm, and Tg was 75 ° C.

<Production Example 6>
The resin particle dispersion (BL-5) was taken out as a powder by freeze-drying to obtain resin particles (B-6). The volume average particle diameter DB of the resin particles was 0.05 μm, and Tg was 75 ° C.

<Production Example 7>
In Production Example 5, the same procedure as in Production Example 5 except that the mixed monomer of styrene / methacrylic acid / butyl acrylate (weight ratio 30/30/40) was replaced with the mixed monomer of styrene / methacrylic acid (weight ratio 90/10). To obtain a resin particle dispersion (BL-7). The volume average particle diameter DB of the resin particles in the resin particle dispersion (BL-7) was 0.08 μm, and Tg was 98 ° C.

<Production Example 8>
The resin particle dispersion (BL-7) was taken out as a powder by freeze-drying to obtain resin particles (B-8). The volume average particle diameter DB of the resin particles was 0.08 μm, and Tg was 98 ° C.

<Production Example 9>
In Production Example 5, the mixed monomer of styrene / methacrylic acid / butyl acrylate (weight ratio 30/30/40) was replaced with the mixed monomer of styrene / methacrylic acid / butyl acrylate (weight ratio 20/20/60). In the same manner as in Production Example 5, a resin particle dispersion (BL-9) was obtained. The volume average particle diameter DB of the resin particles in the resin particle dispersion (BL-9) was 0.06 μm, and Tg was 37 ° C.

<Production Example 10>
The resin particle dispersion (BL-9) was taken out as a powder by freeze-drying to obtain resin particles (B-10). The volume average particle diameter DB of the resin particles was 0.06 μm, and Tg was 37 ° C.

<Production Example 11>
In Production Example 5, the mixed monomer of styrene / methacrylic acid / butyl acrylate (weight ratio 30/30/40) was replaced with the mixed monomer of styrene / methacrylic acid / butyl acrylate (weight ratio 10/20/70). In the same manner as in Production Example 5, a resin particle dispersion (BL-11) was obtained. The volume average particle diameter DB of the resin particles in the resin particle dispersion (BL-11) was 0.07 μm, and Tg was 10 ° C.

<Production Example 12>
The resin particle dispersion (BL-11) was taken out as a powder by freeze drying to obtain resin particles (B-12). The volume average particle diameter DB of the resin particles was 0.07 μm, and Tg was 10 ° C.

<Example 1>
695 parts of ion exchange water, 100 parts of resin particle dispersion (BL-5), 5 parts of sodium dodecyl sulfate, and 80 parts of ethyl acetate were added and stirred well. There, desmophen A575X (hydroxyl group-containing acrylic polymer) [manufactured by Sumitomo Bayer Urethane Co., Ltd.] / Duranate TPA-B80E (curing agent: HDI isocyanurate type blocked product) [manufactured by Asahi Kasei Kogyo Co., Ltd.] / Dibutyltin laurate (weight ratio) After adding 286 parts of a mixed solution of 67/32/1), the obtained mixed solution was stirred at 12000 rpm for 2 minutes using a TK homomixer [manufactured by Tokushu Kika Kogyo Co., Ltd.]. Then, it moved to the pressure | voltage resistant reaction container, the resin particle water dispersion (CL-1) was obtained by removing at normal pressure, heating up to 40 degreeC. The volume average particle diameter (DC) of the resin particles (C-1) in the resin particle aqueous dispersion (CL-1) is 20 μm, the volume average particle diameter DA of the resin particles (A-1) is 19 μm, and Tg is 28 ° C. there were. The ratio of particles having a volume average particle diameter of 2 times or more of the volume average particle diameter DA is 11% by volume, the ratio of particles having a volume average particle diameter of 1/2 or less of the volume average particle diameter DA is 38% by number, The ratio of the surface area / volume average particle diameter was 180/1. The volume average particle diameter DA here is the particle diameter of the resin particles (A-1) obtained by removing the resin particles on the surface layer of the resin particles (C-1) by image processing, and the Tg of the resin particles (A-1). Was obtained by measuring the resin particles (A-1) obtained in Production Example 1.

<Example 2>
In Example 1, desmophen A575X (hydroxyl group-containing acrylic polymer) [manufactured by Sumitomo Bayer Urethane Co., Ltd.] / Duranate TPA-B80E (curing agent: HDI isocyanurate type blocked product) [manufactured by Asahi Kasei Kogyo Co., Ltd.] / Dibutyltin laurate ( A mixed solution having a weight ratio of 67/32/1) was added to desmophen A565X (hydroxyl group-containing acrylic polymer) [manufactured by Sumitomo Bayer Urethane Co., Ltd.] / Duranate TPA-B80E (curing agent: HDI isocyanurate type blocked product) [Asahi Kasei Corporation The same as in Example 1 except that the resin particle dispersion (BL-5) was replaced with (BL-7) in a mixed solution of [made by company] / dibutyltin laurate (weight ratio 64/35/1), and resin A particle water dispersion was obtained. (C-2) was obtained. The volume average particle diameter DC of the resin particles in the resin particle aqueous dispersion (C-2) was 19 μm, the volume average particle diameter DA was 18 μm, and Tg was −8 ° C. The ratio of particles having a volume average particle diameter that is twice or more of the volume average particle diameter DA is 13% by volume, and the ratio of particles having a volume average particle diameter of 1/2 or less of the volume average particle diameter DA is 40% by number. The ratio of surface area / volume average particle diameter was 185/1. The volume average particle diameter DA here is the particle diameter of the resin particles obtained by removing the resin particles in the surface layer portion by image processing, and the Tg of the resin particles (A-2) is the resin composition of the resin particles (A-2). Obtained by measuring.

<Example 3>
A resin particle composite is obtained by filling 900 parts of resin particles (A-1) with 100 parts of resin particles (B-6) in a hybridization system [manufactured by Nara Machinery Co., Ltd.] and treating at 12000 rpm for 50 seconds. It was. By adding 595 parts of ion-exchanged water and 5 parts of sodium dodecyl sulfate to 400 parts of the obtained resin particle composite, the resin was stirred at 12000 rpm for 2 minutes using a TK homomixer [manufactured by Tokushu Kika Kogyo Co., Ltd.] A particle water dispersion (C-3) was obtained. The volume average particle diameter DC of the resin particles in the resin particle aqueous dispersion (C-3) was 20 μm. The ratio of particles having a volume average particle diameter that is twice or more of the volume average particle diameter DA is 18% by volume, and the ratio of particles having a volume average particle diameter of 1/2 or less of the volume average particle diameter DA is 30% by number. The ratio of surface area / volume average particle diameter was 110/1.

<Example 4>
In Example 3, except having replaced the resin particle (B-6) with (B-10), it carried out similarly to Example 3 and obtained the resin particle water dispersion (C-4). The volume average particle diameter DC of the resin particles in the resin particle aqueous dispersion (C-4) was 18 μm. The ratio of particles having a volume average particle diameter that is at least twice the volume average particle diameter DA is 17% by volume, and the ratio of particles having a volume average particle diameter of 1/2 or less of the volume average particle diameter DA is 39% by number. The ratio of surface area / volume average particle diameter was 115/1.

<Example 5>
In Example 3, resin particles (A-1) were replaced with (A-3), and resin particles (B-6) were replaced with (B-8). A body (C-5) was obtained. The volume average particle diameter DC of the resin particles in the resin particle aqueous dispersion (C-5) was 19 μm. The ratio of particles having a volume average particle diameter that is twice or more of the volume average particle diameter DA is 14% by volume, and the ratio of particles having a volume average particle diameter of 1/2 or less of the volume average particle diameter DA is 29% by number. The ratio of the surface area / volume average particle diameter was 105/1.

<Comparative Example 1>
In Example 1, desmophen A575X (hydroxyl group-containing acrylic polymer) [manufactured by Sumitomo Bayer Urethane Co., Ltd.] / Duranate TPA-B80E (curing agent: HDI isocyanurate type blocked product) [manufactured by Asahi Kasei Kogyo Co., Ltd.] / Dibutyltin laurate ( A mixed solution having a weight ratio of 67/32/1) is mixed with Alfon UH-2900 (hydroxyl group-containing acrylic polymer) [manufactured by Toagosei Co., Ltd.] / VESTANAT B1358 / 100 (curing agent: IPDI isocyanurate type blocked product) [Degussa Japan Co., Ltd.] / Ethyl acetate / dibutyltin laurate (weight ratio 50/29/20/1) and Example 1 except that the resin particle dispersion (BL-5) was replaced with (BL-11). It carried out similarly and obtained resin particle water dispersion (H-1). The volume average particle diameter DH of the resin particles in the resin particle aqueous dispersion (H-1) was 18 μm, the volume average particle diameter DA was 18 μm, and Tg was 65 ° C. The ratio of particles having a volume average particle diameter that is twice or more of the volume average particle diameter DA is 29% by volume, and the ratio of particles having a volume average particle diameter of 1/2 or less of the volume average particle diameter DA is 45% by number. The ratio of surface area / volume average particle diameter was 190/1. The volume average particle diameter DA here is the particle diameter of the resin part from which the resin particles in the surface layer part have been removed by image processing, and the Tg of the resin particle (A-4) is the resin particle of the resin particle (A-4). Was obtained.

<Comparative example 2>
In Example 3, except having replaced the resin particle (B-6) with (B-12), it carried out similarly to Example 3 and obtained the resin particle water dispersion (H-2). The volume average particle diameter DH of the resin particles in the resin particle aqueous dispersion (H-2) was 17 μm. The ratio of the particles having a volume average particle diameter more than twice the volume average particle diameter DA is 38% by volume, and the ratio of the particles having a volume average particle diameter of 1/2 or less of the volume average particle diameter DA is 49% by number. The ratio of surface area / volume average particle diameter was 110/1.

<Comparative Example 3>
In Example 3, resin particles (A-1) were replaced with (A-3), and resin particles (B-6) were replaced with (B-12). The body (H-3) was obtained. The volume average particle diameter DH of the resin particles in the resin particle aqueous dispersion (H-3) was 18 μm. The ratio of particles having a volume average particle diameter of 2 times or more of the volume average particle diameter DA is 28% by volume, and the ratio of particles having a volume average particle diameter of 1/2 or less of the volume average particle diameter DA is 31% by number. The ratio of surface area / volume average particle diameter was 125/1.

<Comparative example 4>
In Example 3, except having replaced the resin particle (A-1) with (A-4), it carried out similarly to Example 3 and obtained the resin particle water dispersion (H-4). The volume average particle diameter DC of the resin particles in the resin particle aqueous dispersion (H-4) was 18 μm. The ratio of particles having a volume average particle diameter of 2 or more times the volume average particle diameter DA is 19% by volume, and the ratio of particles having a volume average particle diameter of 1/2 or less of the volume average particle diameter DA is 42% by number. The ratio of surface area / volume average particle size was 120/1.

<Creation of adhesion test piece using resin particle aqueous dispersion>
The resin particle aqueous dispersion was applied on the release substrate to a thickness of about 150 μm by spraying, and then dried at 80 ° C. for 20 minutes to form an adhesive layer having a thickness of 100 μm, thereby preparing an adhesive sheet. A laminator (temperature: 100 ° C., pressure: 5 kg / cm, speed: 2 m) is formed on a polyimide film (Ube Industries, Ltd .: trade name: Upirex 75S) having a thickness of 75 μm, and the adhesive sheet cut to a width of 10 mm and a length of 50 mm. / Min), and after removing the release substrate, the polyimide film having a thickness of 75 μm (manufactured by Ube Industries, Ltd .: trade name Iupirex 75S) is pressed again (temperature: 200 ° C., time) : 1 second, pressure: 5 kg / cm). Furthermore, it was cured in a hot air oven at 150 ° C. for 2 hours to obtain a test piece.

  The resin particle aqueous dispersion and the adhesion test piece were evaluated for performance according to the evaluation methods (1) and (2) described later. The results are shown in Table 1.

[Evaluation methods]
(1) Storage stability (Evaluation of aqueous dispersion of resin particles)
20 g of the resin particle aqueous dispersion was placed in a cylindrical glass container having a height of 20 cm and a diameter of 3 cm, and left in a constant temperature bath at 40 ° C. for 1 week. Evaluation was based on criteria.
○ No blocking at all.
Δ: There is a blocking mass, but it can be easily disintegrated by shaking the container.
X There is a blocking mass and it does not collapse even if the container is shaken.

(2) Peel adhesion strength (Evaluation of adhesion test piece)
After leaving for 30 minutes under an atmospheric condition of a temperature of 23 ° C. and a humidity of 65% RH, the film was pulled in the 90 ° direction at a pulling speed of 50 mm / min, and the center value was defined as the peel adhesive strength (N / 10 mm).

The adhesive comprising the aqueous dispersion of the present invention can be widely used for substrates such as wood, resin, resin film, rubber, leather, cloth, paper and metal. It is particularly useful for adhesives for woodwork, adhesives for metal parts, adhesives for plastics, adhesives for electronic boards, and adhesives for fabrics.
In addition, the aqueous dispersion of the present invention comprises a fiber processing binder (a pigment printing binder, a nonwoven fabric binder, a reinforcing fiber sizing agent, an antibacterial agent binder, etc.) and a coating (waterproof coating, water repellent coating, antifouling coating). Etc.) and can be used widely for raw materials for artificial leather and synthetic leather.

Claims (9)

Resin particles (C) whose surfaces are coated with resin particles (B) and water as essential components, the volume average particle diameter DA of the resin particles (A) and the resin particles (B) The volume average particle diameter DB is different, the glass transition temperature of the resin particles (A) is −50 ° C. or more and 50 ° C. or less, and the glass transition temperature of the resin particles (B) is 30 ° C. or more and 100 ° C. or less. A resin particle aqueous dispersion characterized. The resin particle aqueous dispersion according to claim 1, further comprising the resin particles (A) and / or the resin particles (B). The volume average particle diameter DA of the resin particles (A) is 1 μm or more and 30 μm or less, the volume average particle diameter DB of the resin particles (B) is 0.01 μm or more and 0.95 μm or less, and the average particle diameter ratio DA / DB is 1. The resin particle aqueous dispersion according to claim 1 or 2, which is from 05 to 3,000. The ratio of the particles having a volume average particle diameter that is twice or more the volume average particle diameter DA is 20% by volume or less based on the total amount of all the particles constituting the volume average particle diameter DA and 1/2 of the volume average particle diameter DA. The resin particle aqueous dispersion according to any one of claims 1 to 3, wherein the proportion of particles having the following volume average particle diameter is 50% by number or less based on the total amount of all particles constituting the particles. The resin particle aqueous dispersion according to any one of claims 1 to 4, wherein the resin particles (C) have a volume average particle diameter DC of 1 µm or more and 40 µm or less. The resin particle aqueous dispersion according to any one of claims 1 to 5, wherein the resin particle (C) has a specific surface area / volume average particle diameter ratio of from 25/1 to 900/1. An adhesive comprising the resin particle aqueous dispersion according to claim 1. A fiber processing agent comprising the resin particle aqueous dispersion according to claim 1. A solution in which the resin (a) is dissolved in the resin (a) or the solvent (g) in an aqueous dispersion obtained by dispersing the resin particles (B) made of the resin (b) containing the dispersant (E). When the resin (a) is dispersed and dissolved in the solvent (g), the resin particles (A) comprising the resin (a) are formed by further forming the resin particles (C) by removing the solvent (g). The volume average particle diameter DA of the resin particles and the volume average particle diameter DB of the resin particles (B) are different, the glass transition temperature of the resin particles (A) is −50 ° C. or more and 50 ° C. or less, and the glass transition temperature of the resin particles (B). A method for producing an aqueous dispersion of resin particles, wherein the resin particles (C) are obtained by coating the surface of the resin particles (A) with the resin particles (B).