JP2002235027A - Aqueous coating material, coating film formed from the coating material, method for coating film formation and coated material having the coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous coating material comprising an aqueous dispersion of a polymer which does not form a harmful substance in incineration and has no problem of endocrine disrupter, forming a coating film having excellent scratch resistance, flexibility, non-tackiness, water resistance, cold resistance, odorless properties, flame retardance, coating properties, lightweight properties, and the like, and a coating film obtained from the coating material, to provide a method for coating film formation and to obtain a coated material having the coating film. SOLUTION: The aqueous coating material comprises an olefin-based resin and/or a urethane-based resin, an amino resin and at least one kind of a modifier selected from a urea-based compound and a carbodiimide-based resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin resin and / or a urethane resin and at least one resin selected from an amino resin, a urea compound and a carbodiimide resin.
The present invention relates to an aqueous coating material containing a kind of modifier. More specifically,
The present invention relates to an aqueous coating material capable of providing a film having excellent performance such as abrasion resistance, flexibility, non-tackiness, water resistance, cold resistance, odorlessness, flame retardancy, coating properties, and lightness. In addition, the present invention provides a net, mesh, sheet,
Ground reinforcement nets, outdoor tents such as tent warehouses and pipe tents, hoods such as trucks and bellows, canvas, gloves, flags,
Film-forming products for the purpose of improving the texture and surface protection of base materials such as textiles, leather, paper, and synthetic resins, such as banners, clothes, footwear, furniture, bags, sanitary products, and pressure-removable sheets. The present invention relates to an aqueous coating material comprising an aqueous dispersion of a resin, which does not generate harmful halogen compounds when incinerated. The present invention also relates to a coated article having a film formed from the above-mentioned aqueous coating material of the present invention. More specifically, the present invention relates to a coated article such as a net, a mesh, a sheet, a canvas, a hood, a glove, a flag, a banner, a garment, etc., having a film formed from the aqueous coating material of the present invention.

[0002]

2. Description of the Related Art In recent years, an aqueous coating material using an aqueous dispersion resin has been actively studied. It is no exception in the field of processing fibers, leather materials, etc., in addition to the conventional required performance of coating materials, protection of base material, addition of texture, flammability in the work of base material processing, Improvements such as improvement of environment such as odor, improvement of workability, and reduction of industrial waste such as waste solvent are required. It can be said that the use of a water-based coating material is promising as a means for solving the above problems.

Polyester or nylon fibers have been used in textile products (broadly defined), such as industrial curing nets, canvas used in construction sites, and the like. These fibers were usually coated with polyvinyl chloride sol.

[0004] However, with the recent increase in environmental problems, there is a problem that chlorine-based gas is generated when these nets and canvases are incinerated, and furthermore, a plasticizer such as DOP is a problem of environmental hormones. There is a growing demand for replacement of polyvinyl chloride sol with other products. Furthermore, a fiber product coated with a polyvinyl chloride sol having a high specific gravity has a problem that it is difficult to handle due to its heavy weight. From this point of view, there is an increasing demand for an alternative.

On the other hand, there is a strong demand that a water-based medium should be employed as a medium for the coating agent in order not to generate waste solvent, prevent air pollution and maintain a good working environment.

[0006] Under the circumstances described above, an aqueous dispersion of a polyolefin having a low specific gravity, which does not generate harmful substances during incineration of textiles, does not cause environmental hormones, and is desired as an aqueous coating material. Had a coating formed from conventional vinyl chloride sol coating,
A water-based coating material that simultaneously satisfies such properties as flexibility, non-tackiness, water resistance, cold resistance, odorlessness, flame retardancy, and coatability has not been obtained.

Therefore, it is possible to form a film having excellent scratch resistance, flexibility, non-tackiness, water resistance, cold resistance, odorlessness, flame retardancy, coating properties, light weight, etc. There is a need for an aqueous coating that comprises an aqueous dispersion of a polymer that does not produce harmful substances and is free from environmental hormone problems.

[0008]

SUMMARY OF THE INVENTION The present invention aims to solve the problems associated with the prior art as described above.
It can form a film excellent in odorlessness, flame retardancy, coating properties, light weight, etc., and does not generate harmful substances when incinerated,
Another object of the present invention is to provide an aqueous coating material comprising an aqueous dispersion of a polymer having no problem with environmental hormones.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have completed the following invention. [1] Olefin resin (A) and / or urethane resin (B), amino resin (C), urea compound (D)
And an at least one modifier selected from carbodiimide-based resins (E). [2] The aqueous coating according to [1], wherein the amino resin (C) is at least one amino resin selected from methyl etherified melamine, methyl etherified benzoguanamine, methyl etherified urea, and methyl etherified glycoluril. Construction materials. [3] The aqueous coating material according to [1] or [2], wherein the amino resin (C) is an amino resin containing an imino group and a methylol group. [4] The weight ratio of the olefin resin (A) and / or urethane resin (B) to the amino resin (C) ((A) +
The aqueous coating material according to any one of [1] to [3], wherein (B)) / (C) is 100 / 0.1 to 100/10. [5] The urea compound (D) is urea [1] to
The aqueous coating material according to any one of [4]. [6] The weight ratio of the olefin resin (A) and / or urethane resin (B) to the urea compound (D) ((A)
+ (B)) / (D) is 100/1 to 100/100, the aqueous coating material according to any one of [1] to [5]. [7] The weight ratio ((A) + (B)) / (E) of the olefin resin (A) and / or the urethane resin (B) to the carbodiimide resin (E) is 100 / 0.1 to 100.
The aqueous coating material according to any one of [1] to [6], which is / 10. [8] The aqueous coating material according to any one of [1] to [7], wherein the olefin resin (A) is an ethylene-vinyl acetate copolymer containing 10 to 50% by weight of a vinyl acetate unit. [9] An acid-modified polyolefin compound (F) and / or a fatty acid compound (G) is contained in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the olefin resin (A).
The water-based coating material according to any one of [1] to [8]. [10] The physical properties of a film formed by using the olefin resin (A) alone with the olefin resin (A) are as follows: elongation at break, 300 to 1300%; strength at break, 3 to 30 MPa;
The aqueous coating material according to any one of [1] to [9], which has a 100% modulus and a value of 0.5 to 6.5 MPa. [11] The water-based coating material according to any one of [1] to [10], wherein the urethane-based resin (B) comprises a component containing a polyether polyol and hexamethylene diisocyanate. [12] The physical properties of the film formed by the urethane-based resin (B) alone using the urethane-based resin (B) are determined by the elongation at break
00 to 1500%; breaking strength, 10 to 50 MPa;
The aqueous coating material according to any one of [1] to [11], which has a 0% modulus and a value of 0.5 to 3.5 MPa. [13] The solid weight ratio of the olefin resin (A) to the urethane resin (B) is (A) / (B) = 99/1 to 50.
Water-based coating material according to any one of [1] to [12], wherein the aqueous coating material is / 50. [14] The water-based coating material according to any one of [1] to [13], wherein the coating formed from the water-based coating material has an elongation at break of 400 to 2000%; 80 MPa;
An aqueous coating material having a 100% modulus and a value of 0.3 to 5 MPa. [15] The aqueous coating material according to any one of [1] to [14], wherein the aqueous coating material contains a phosphorus-based flame retardant (H) and / or an inorganic flame retardant (I). , The solid content weight ratio ((A) + (B)) of the olefin resin (A) and / or urethane resin (B) and the phosphorus flame retardant (H) and / or the inorganic flame retardant (I) ) / ((H) + (I)) is 1
An aqueous coating material having a ratio of 00/1 to 100/100. [16] The aqueous coating material according to any one of [1] to [15], which contains an acrylic resin-based viscoelasticity modifier having a carboxylic acid group or a carboxylate group, and has a solution viscosity of 10
A water-based coating material having a thickness of from 00 to 50,000 mPa · s. [17] A film formed from the aqueous coating material according to any one of [1] to [16]. [18] A method for forming a film, comprising applying the aqueous coating material according to any one of [1] to [17] to a substrate and drying. [19] The method for forming a film according to [18], wherein the substrate is at least one selected from the group consisting of fibers, synthetic fibers, leather, synthetic leather, synthetic resin, and paper. [20] A coated article having a film formed from the aqueous coating material according to any one of [1] to [16].

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The fiber treating agent according to the present invention will be specifically described below.

[Word "Aqueous"] In the present invention, "aqueous" means a state in which a resin is dispersed in water and / or a state in which a resin is partially dissolved, and includes "aqueous dispersion". .

The olefin-based resin, urethane-based resin, amino resin, urea-based compound and carbodiimide-based resin contained in the aqueous coating material of the present invention may be in a state of being dissolved and dispersed in an aqueous medium. Although not particularly limited, a dispersed state is preferable in that a high solid content concentration is possible.

The amino resin (C) used as a modifier in the present invention is not particularly limited.
Examples thereof include an alkyl etherified glycouril resin, and a diguanamine alkyl etherified resin in which two triazine rings are bonded to a phenylene nucleus or a dicyclopentane nucleus. These amino resins (C) can be used alone or in combination of two or more. As the alkyl group, a methyl group is preferable from the viewpoint of aqueous conversion.

The reactive group may be completely alkylated or partially alkylated, and an imino group and / or a methylol group may remain. From the viewpoint of reducing the amount of free formalin in the amino resin and improving the scratch resistance of the coating by self-condensation of the amino resin, a partially alkylated amino resin containing an imino group and a methylol group is preferred.

[0015] From the viewpoints of making water-soluble, reducing the amount of free formalin, and improving the abrasion resistance of the coating film, methyletherified melamine resins, methyletherified urea resins and methyletherified glycouril resins containing imino groups and methylol groups are particularly preferred. preferable.

The amino resin (C) used in the present invention has a solid weight ratio of ((A) + (B)) / olefin resin (A) and / or urethane resin (B).
(C) = preferably used in the range of 100 / 0.1 to 100/10, more preferably used in the range of 100 / 0.3 to 100/5, and 100 / 0.6 to 100 / 0.6.
More preferably, it is used in the range of 100/3.

When the amount of the amino resin (C) used is less than the above range, a sufficient effect of improving the scratch resistance of the coating cannot be obtained. The problem may arise.

The urea compound (D) used as a modifier in the present invention is not particularly limited.
Thiourea, N, N'-diacetylurea, N, N'-dibenzoylurea, N, N-dibenzoylurea, benzenesulfonylurea, p-toluenesulfonylurea, trimethylurea, tetramethylurea, triethylurea, tetraethylurea, triethylurea Phenylurea, tetraphenylurea, N-
Benzoyl urea, o-methyl urea, o-ethyl urea, φ urea, cyanuric acid, biuret, cyanuric triureide, urea nitrate, urea phosphate, urea oxalate, urea acetate,
Examples thereof include urea derivatives such as tartaric acid-urea, malonic acid-urea, lime urea nitrate, urea gypsum, malonyl urea, methoxalyl urea, monomethylol urea, dimethylol urea, urea double salts, urea adducts, and urea decomposition products. These urea compounds (D) can be used alone,
Also, two or more kinds can be used in combination. Urea is particularly preferred in that the flexibility of the coating is improved, and it is inexpensive and easy to handle.

The urea compound (D) used in the present invention has a solid weight ratio to the olefin resin (A) and / or urethane resin (B) of ((A) + (B)) /
(D) = preferably used in the range of 100/1 to 100/100, more preferably used in the range of 100/2 to 100/50, and 100/4 to 100 /
More preferably, it is used in the range of 30.

If the amount of the urea-based compound (D) is less than the above range, the effect of imparting sufficient flexibility and flame retardancy of the film is not exhibited. The problem may occur.

Carbodi used as a modifier in the present invention
The imide resin (E) is not particularly limited.
Is synthesized by the carbonic acid condensation reaction of diisocyanate.
It is preferably a linear polycarbodiimide. material
As the diisocyanate, for example, ethylene diisocyanate
Nate, trimethylene diisocyanate, tetramethyl
Diisocyanate, hexamethylene diisocyanate
G, octamethylene diisocyanate, nonamethylene diisocyanate
Isocyanate, 2,2-dimethylpentane diisocyan
Nate, 2,2,4-trimethylhexamethylenediiso
Cyanate, decamethylene diisocyanate, butene
Isocyanate, 1,3-butadiene-1,4-diiso
Cyanate, 2,4,4-trimethylhexamethylenedi
Isocyanate, bis (isocyanatoethyl) carbonate
, Bis (isocyanatoethyl) ether, 1,4-
Butylene glycol dipropyl ether-ω, ω'-di
Isocyanate, lysine diisocyanatomethyl ester
, Xylylene diisocyanate, bis (isocyanato
Ethyl) benzene, bis (isocyanatopropyl) ben
Zen, α, α, α ', α'-tetramethylxylylenediene
Isocyanate, bis (isocyanatobutyl) benzene
Bis (isocyanatomethyl) naphthalene, bis (a
Socyanatomethyl) diphenyl ether, bis (isocyanate)
Anatoethyl) phthalate, mesitylene triisocyanate
Fats such as 2,6-di (isocyanatomethyl) furan
Aliphatic diisocyanate, isophorone diisocyanate,
Bis (isocyanatomethyl) cyclohexane, 4,4 '
-Dicyclohexylmethane-diisocyanate, cyclo
Hexane diisocyanate, methyl cyclohexane dii
Socyanate, dicyclohexyl dimethyl methane diiso
Cyanate, 2,2-dimethyldicyclohexylmethane
Diisocyanate, bis (4-isocyanato-n-butyl)
Riden) pentaerythritol, diisocyane dimerate
2,6-bisisocyanatomethylnorbornane
Alicyclic diisocyanate, phenylene diisocyanate, etc.
Sheet, tolylene diisocyanate, ethyl phenylene diene
Isocyanate, isopropylene phenylene diisocyanate
Nitrate, dimethylphenylene diisocyanate, diethyl
Ruphenylene diisocyanate, diisopropyl phenyl
Range isocyanate, trimethylbenzene triisocy
Anate, benzene triisocyanate, naphthalenedi
Isocyanate, methyl naphthalene diisocyanate,
Biphenyl diisocyanate, tolidine diisocyanate
G, 4,4′-diphenylmethane diisocyanate,
3,3'-dimethyldiphenylmethane-4,4'-dii
Socyanate, bibenzyl-4,4'-diisocyanate
G, bis (isocyanatophenyl) ethylene, 3,3 '
-Dimethoxybiphenyl-4,4'-diisocyanate
G, phenyl isocyanatoethyl ethyl isocyanate
G, tetrahydronaphthylene diisocyanate, hexa
Hydrobenzene diisocyanate, hexahydrodife
Nylmethane-4,4'-diisocyanate, diphenyl
Ether diisocyanate, ethylene glycol dife
Nyl ether diisocyanate, 1,3-propylene glycol
Recohol diphenyl ether diisocyanate, benzo
Phenone diisocyanate, diethylene glycol diph
Phenyl ether diisocyanate, dibenzofurandai
Socyanate, carbazole diisocyanate, ethyl
Carbazole diisocyanate, dichlorocarbazole
Aromatic diisocyanate such as diisocyanate, thiodi
Ethyl diisocyanate, thiopropyl diisocyanate
G, thiodihexyl diisocyanate, dimethyl sulf
Diisocyanate, dithiodimethyldiisocyanate
G, dithiodiethyl diisocyanate, dithiopropyl
Diisocyanate, dicyclohexyl sulfide-4,
Sulfur-containing aliphatic diisocyanate such as 4'-diisocyanate
G, diphenyl sulfide-2,4'-diisocyanate
G, diphenyl sulfide-4,4'-diisocyanate
G, 3,3'4,4'-diisocyanatodibenzylthio
Ether, bis (4-isocyanatomethylbenzene) s
Sulfide, 4,4'-methoxybenzenethioethylene
Aromatic sulfol such as recol-3,3'-diisocyanate
Fide-based isocyanate, diphenyl disulfide-
4,4'-diisocyanate, 2,2'-dimethyldiph
Enyl disulfide-5,5′-diisocyanate,
3,3'-dimethyldiphenyl disulfide-5,5 '
-Diisocyanate, 3,3'-dimethyldiphenyldi
Sulfide-6,6'-diisocyanate, 4,4'-
Dimethyldiphenyl disulfide-5,5'-diisos
Anate, 3,3'-dimethoxydiphenyl disulfy
Do-4,4'-diisocyanate, 4,4'-dimethoxy
Sidiphenyl disulfide-3,3'-diisocyanate
Aliphatic disulfide-based isocyanates such as
Rusulfone-4,4'-diisocyanate, diphenyl
Sulfone-3,3'-diisocyanate, benzidine
Sulfone-4,4'-diisocyanate, diphenylmeth
Tansulfone-4,4'-diisocyanate, 4-methyl
Rudiphenylmethanesulfone-2,4'-diisocyane
4,4'-dimethoxydiphenylsulfone-3,
3'-diisocyanate, 3,3'-dimethoxy-4,
4'-diisocyanate dibenzyl sulfone, 4,4 '
-Dimethyldiphenylsulfone-3,3'-diisocyanate
Nate, 4,4'-di-tert-butyldiphenyls
Rufone-3,3'-diisocyanate, 4,4'-dimension
Toxibenzene ethylene disulfone-3,3'-diiso
Cyanate, 4,4'-dichlorodiphenyl sulfone-
Aromatic sulfone diisocyanates such as 3,3'-diisocyanate
Socyanate, 4-methyl-3-isocyanatobenzene
Sulfonyl-4′-isocyanatophenol ester,
4-methoxy-3-isocyanatobenzenesulfonyl-
Sulfonic acid such as 4'-isocyanatophenol ester
Ester diisocyanate, 4,4'-dimethylben
Zensulfonyl-ethylenediamine-4,4'-diiso
Cyanate, 4,4'-dimethoxybenzenesulfonyl
-Ethylenediamine-3,3'-diisocyanate, 4
-Methyl-3-isocyanatobenzenesulfonylanily
Aromatic sulfo such as do-4-methyl-3'-isocyanate
Honamide diisocyanate, thiophene-2,5
-Diisocyanate, thiophene-2,5-diisocyanate
Natomethyl, 1,4-dithiane-2,5-diisocyane
, 1,4-dithiane-2,5-diisocyanatomethy
And sulfur-containing heterocyclic compounds such as

These diisocyanates can be used alone or in combination of two or more.

The carbodiimide-based resin (E) used in the present invention has a solid weight ratio of ((A) +
(B)) / (E) = 100 / 0.1 to 100/10, preferably 100 / 0.3 to 10/100
It is more preferably used in the range of 0/5, and 100
More preferably, it is used in the range of /0.6 to 100/3.

If the amount of the carbodiimide-based resin (E) is less than the above range, a sufficient effect of improving the scratch resistance of the coating cannot be obtained. , The problem may arise.

The amino resin (C) and / or urea compound (D) and / or carbodiimide resin (E)
If a hardener, a plasticizer, or the like other than the above is added, there is a possibility that problems such as abrasion resistance, flexibility, non-tackiness, and water resistance are reduced.

The method for incorporating the amino resin (C) and / or urea compound (D) and / or carbodiimide resin (E) into the aqueous coating material of the present invention is not particularly limited. Is preliminarily mixed with the olefin-based resin (A) and / or urethane-based resin (B) and then made aqueous, or (A) and / or (B) is mixed during the step of making water-soluble, or Separately hydrated (A) and / or (B), also hydrated (C) and / or (D) and / or (E)
And a method of mixing with a water-based coating material. As long as the final aqueous state is maintained, a chemical reaction or chemical interaction due to mixing may be involved.

The olefin resin (A) used in the present invention is not particularly limited, but ethylene-
It is preferably any resin selected from a polar monomer copolymer and / or an olefin-based elastomer.

Preferred embodiments of the ethylene-polar monomer copolymer include ethylene-ethyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene-propyl (meth) acrylate copolymer,
Ethylene- (meth) butyl acrylate copolymer, ethylene- (meth) acrylic acid hexyl copolymer, ethylene- (meth) acrylic acid-2-hydroxyethyl copolymer,
Ethylene- (meth) acrylate copolymer such as ethylene- (meth) acrylic acid-2-hydroxypropyl copolymer, ethylene- (meth) glycidyl acrylate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- Ethylene-ethylenically unsaturated acid copolymers such as maleic acid copolymer, ethylene fumaric acid copolymer, ethylene-crotonic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene Examples thereof include vinyl butyrate copolymers and ethylene-vinyl ester copolymers such as ethylene-vinyl stearate. Ethylene-vinyl ester copolymers and ethylene- (meth) acrylate copolymers are preferred. Is preferably an ethylene-vinyl acetate copolymer.

The ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 10 to 50% by weight, particularly 15 to 40% by weight.
FR (190 ° C.) is 0.05 to 1000 g / 10 mi
n is preferable, especially 0.1 to 500 g / 10
min is preferred.

When the vinyl acetate content of the ethylene-vinyl acetate copolymer is less than the above range, the flexibility of the coating is insufficient, and when the content is more than the above range, water resistance, cold resistance and non-tackiness of the coating are obtained. However, there is a possibility that a problem that odorlessness is reduced may occur.

As the olefin elastomer used in the present invention, a low-crystalline or amorphous olefin copolymer can be used, and may contain a diene if desired. The crystallinity measured by the X-ray diffraction method is
It is preferably at most 50%, particularly preferably at most 30%. In the present invention, a styrene-conjugated diene block copolymer or a hydrogenated product thereof can also be used. The olefin constituting the olefin copolymer is an α-olefin having 2 to 20 carbon atoms, preferably 2 to 20 carbon atoms.
Α-olefins having 10 to 10 carbon atoms, more preferably α-olefins having 2 to 8 carbon atoms, specifically, α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene Can be mentioned. These α-olefins can be used alone or in combination of two or more.

Further, as the diene, specifically,
Isoprene, butadiene, dicyclopentadiene, 1,4-
Examples include pentadiene, 2-methyl-1,4-pentadiene, 1,4-hexadiene, divinylbenzene, methylidene norbornene, and ethylidene norbornene. These dienes can be used alone or in combination of two or more.

In the present invention, the preferred olefin copolymer is a rubbery copolymer of ethylene and an α-olefin and / or a diene. The content of the structural unit derived from ethylene in the rubbery copolymer is usually 25 to 95 mol%, particularly preferably 50 to 95 mol%, and the content of the structural unit derived from α-olefin other than ethylene is included. The amount is usually 5 to 75 mol%
And particularly preferably 5 to 50 mol%. When the rubbery copolymer contains a diene, the content of the structural unit derived from the diene is preferably 0.5 to 10 mol%, and in this case, the content of the structural unit derived from an α-olefin other than ethylene is included. Preferably the amount is between 4.5 and 74.5 mol%.

The rubbery copolymer has a composition of 13C
-Measured by NMR method.

Examples of the olefin copolymer include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, Propylene / 1-butene copolymer, propylene / 1-hexene copolymer, propylene / 1-
Octene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene /
5-vinyl-2-norbornene copolymer, ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-butene / dicyclopentadiene copolymer, ethylene / butadiene copolymer and the like. Can be

The intrinsic viscosity [η] of the olefin copolymer measured at 135 ° C. in decalin solution is 0.5 to 2.0.
dl / g is preferable, and more preferably 0.7 to 1.5.
dl / g. Examples of the conjugated diene constituting the styrene-conjugated diene block copolymer include isoprene and butadiene. These conjugated dienes can be used alone or in combination of two or more.

The block structure of the styrene-conjugated diene block copolymer may be a diblock copolymer of styrene-conjugated diene, a triblock copolymer of styrene-conjugated diene-styrene, or more blocks. And a block copolymer having the same.

As such a styrene-conjugated diene block copolymer, for example, US Pat.
And block copolymers produced by the methods described in JP-A No. 765 and JP-A-61-192743.

Styrene-conjugated diene block copolymer,
For example, styrene-isoprene block copolymers are specifically exemplified by Kraton TR-1107, 1111, 11
12 (both manufactured by Shell Chemical Co., Ltd.).

Examples of the hydrogenated product of the styrene-conjugated diene block copolymer include, for example,
And hydrogenated products produced by the methods described in JP-B-20504 and JP-B-48-3555.

The hydrogenated product of the styrene-conjugated diene block copolymer, for example, the hydrogenated product of the styrene-butadiene block copolymer is specifically exemplified by Kraton G-1.
652, 1657 (both manufactured by Shell Chemical Co., Ltd.), and the hydrogenated product of the styrene-isoprene block copolymer is, specifically, Septon 2
002 and 2007 (both manufactured by Kuraray Co., Ltd.).

The content of the structural unit derived from styrene in the styrene-conjugated diene block copolymer or its water additive as described above is determined in consideration of the abrasion resistance, flexibility and the like of the film obtained from the aqueous coating material. To 10 to 70% by weight, more preferably 20 to 50% by weight.
It is.

The styrene-conjugated diene block copolymer or its water additive has a melt flow rate (M
FR; ASTM D 1238, 230 ° C, 2.16 kg
The load is preferably 0.1 to 1000 g / 10 min, more preferably 1 to 500 g / 10 min, and particularly preferably 10 to 200 g / 10 min.

In order to stabilize the olefin resin (A) as an aqueous dispersion, a specific acid-modified polyolefin compound (F) and / or fatty acid compound (G) can be used, if necessary.

The acid-modified polyolefin compound (F) used in the present invention is a polyolefin-based resin and is a carboxylic acid salt group (partially neutralized or partially saponified) bonded to a polyolefin polymer chain. Is a polyolefin-based resin containing as a -COO- group a concentration of 0.05 to 5 mmol, preferably 0.1 to 4 mmol per gram of the polyolefin-based resin.

Further, the acid-modified polyolefin compound (F)
Is a monomer having a neutralized or non-neutralized carboxylic acid group and / or a saponified or unsaponified carboxylic acid It can be obtained by graft copolymerizing a monomer having an ester.

The polyolefin before acid modification used in the preparation of the acid-modified polyolefin compound (F) includes:
Number average molecular weight (Mn) measured by GPC is 500
Α in the range of from 10,000 to 3,000, preferably from 700 to 5,000, more preferably from 1,000 to 3,000
-Homopolymers of olefins or copolymers of two or more α-olefins are preferred. As the α-olefin constituting the homopolymer or the copolymer, an α-olefin having 2 to 20 carbon atoms, preferably an α-olefin having 2 to 10 carbon atoms, more preferably 2 carbon atoms Α-8 olefins, specifically ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
1-octene and the like can be mentioned.

Among homopolymers and copolymers composed of these α-olefins, ethylene homopolymer and propylene homopolymer are particularly preferred.

The graft monomers grafted onto the polyolefin include the above-described monomers having a neutralized or non-neutralized carboxylic acid group, and the above-mentioned monomers having a saponified or non-saponified carboxylic acid group. A monomer having an acid ester group, for example, an ethylenically unsaturated carboxylic acid, an anhydride thereof, or an ester thereof.

Here, as the ethylenically unsaturated carboxylic acid, specifically, (meth) acrylic acid, maleic acid,
Fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and the like.

Specific examples of the anhydride of the ethylenically unsaturated carboxylic acid include nadic acid TM (endosis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, And citraconic anhydride.

Specific examples of the ethylenically unsaturated carboxylic acid ester include mono- or diesters of the above-mentioned ethylenically unsaturated carboxylic acid such as methyl, ethyl and propyl. These monomers are
They can be used alone or in combination of two or more.

As a method for grafting a graft monomer to the above-mentioned polyolefin, a conventionally known graft copolymerization method can be employed. The acid-modified polyolefin compound is used in an amount of 0.5 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the olefin polymer.
More preferably, it is used in a proportion of 5 to 15 parts by weight.
When a fatty acid compound described later is used in combination, the above ratio is the total amount of the acid-modified polyolefin compound and the fatty acid compound. It is more preferable to contain the acid-modified polyolefin compound at the above ratio.

The fatty acid compound (G) used in the present invention means a fatty acid, a salt of the fatty acid, and an ester of the fatty acid. In the present invention, these compounds can be used alone or in combination. The aqueous coating material may contain a fatty acid and / or a fatty acid ester in addition to the salt of the fatty acid.

In the present invention, the fatty acid compound (G) usually has 25 to 60 carbon atoms, preferably 25 to 40 carbon atoms. The fatty acid is preferably montanic acid in the present invention. The salts of the fatty acid include sodium salts, potassium salts, alkali metal salts such as lithium salts, magnesium salts, alkaline earth metal salts such as calcium salts, zinc salts,
Examples thereof include an aluminum salt, an iron salt, an amine salt and the like, and more preferred are alkali metal salts of montanic acid.

The alcohol residue constituting the ester preferably has 2 to 30 carbon atoms, particularly preferably 6 to 20 carbon atoms. The residue may be linear or branched. A mixture of different carbon numbers may be used. Specific examples of the alcohol residue include higher alcohol residues such as cetyl alcohol, stearyl alcohol, and oleyl alcohol. Particularly preferred are montanic acid ester waxes and montan wax. The fatty acid salt can be obtained by neutralizing a fatty acid having 25 to 60 carbon atoms and / or saponifying a fatty acid ester having 25 to 60 carbon atoms.

When the fatty acid compound (G) is used, the fatty acid compound is used in an amount of 0.5 to 30 parts by weight, preferably 2 to 30 parts by weight, based on 100 parts by weight of the olefin resin (A).
15 parts by weight, more preferably 3 to 10 parts by weight.

The acid-modified polyolefin compound (F) and the fatty acid compound (G) can be used alone or in combination. When used together, (A) / ((F) + (G)) = 100 / 0.5 to 100 as a weight ratio.
/ 30 is preferred.

Acid-modified polyolefin compound (F) and / or
Alternatively, if the fatty acid compound (G) is less than the above range, a stable aqueous dispersion cannot be obtained.

The method of preparing the olefin resin (A) into an aqueous dispersion is not particularly limited,
For example, an olefin resin (A) and at least one component selected from the group consisting of an acid-modified polyolefin compound (F) and / or a fatty acid compound (G) are melt-kneaded, and then a base is added to the obtained kneaded product. A method of obtaining an aqueous dispersion by neutralizing and / or saponifying and dispersing (phase inverting) the olefin-based polymer into an aqueous phase by further adding and melting and kneading a water-soluble substance and an aqueous dispersion. , A basic substance and water were added to at least one component selected from the group consisting of an acid-modified polyolefin compound, a fatty acid and a fatty acid ester to neutralize and / or saponify and melt-kneaded with the olefin polymer. Thereafter, a method of obtaining an aqueous dispersion by inverting (dispersing) the olefin polymer into an aqueous phase by further adding water and melt-kneading the mixture is preferred.

In the present invention, the former method is simple,
In addition, a uniform aqueous dispersion having a small diameter of dispersed particles can be obtained, which is particularly preferable.

The preferred ratio of neutralization or saponification in the above-mentioned acid-modified polyolefin compound, fatty acid or fatty acid ester is 60 to 200% of the total carboxylic acid or carboxylic acid ester.

The melt-kneading means used for inverting the olefin-based resin to an aqueous phase may be any known means. Is preferred.

Specific examples of the basic substance used for the neutralization and saponification include: alkali metals such as sodium and potassium; alkaline earth metals such as calcium, strontium and barium; hydroxylamine, ammonium hydroxide and hydrazine Inorganic amines such as ammonia; organic amines such as ammonia, N, N-dimethylethanolamine, triethylamine, methylamine, ethylamine, ethanolamine, cyclohexylamine, and tetramethylammonium hydroxide; sodium oxide, sodium peroxide, potassium oxide, and peroxide Potassium, calcium oxide, strontium oxide, barium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydride, barium hydroxide, sodium hydride,
Oxides, hydroxides and hydrides of alkali metals and alkaline earth metals such as potassium hydride and calcium hydride; sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, sodium acetate, acetic acid Examples include weak acid salts of alkali metals and alkaline earth metals such as potassium and calcium acetate.

As the carboxylic acid group or carboxylic ester group neutralized or saponified by a basic substance,
Alkali metal carboxylate such as sodium carboxylate and potassium carboxylate are preferred.

The urethane resin (B) used in the present invention
As a polyfunctional isocyanate compound which is a component constituting, for example, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate,
2,2-dimethylpentane diisocyanate, 2,2
4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate,
1,3-butadiene-1,4-diisocyanate, 2,
4,4-trimethylhexamethylene diisocyanate,
1,6,11-undecatriisocyanate, 1,3
6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2,
5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butyleneglycoldipropylether-
ω, ω'-diisocyanate, lysine diisocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatoethyl-2,6
-Diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, xylylene diisocyanate, bis (isocyanatoethyl)
Benzene, bis (isocyanatopropyl) benzene,
α, α, α ′, α′-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesitylene Triisocyanate,
Aliphatic polyisocyanate such as 2,6-di (isocyanatomethyl) furan; isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, 4,4′-dicyclohexylmethane-diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate , 2,2-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.
2.1] -Heptane, 2-isocyanatomethyl-3-
(3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5
Isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2.
2.1] -Heptane, 2-isocyanatomethyl-3-
(3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane, 2-
Isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.1.1] -heptane, 2-isocyanatomethyl-
2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2.1.1] -heptane,
2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane, 2,5-bisisocyanatomethylnorbornane, 2,6 Alicyclic polyisocyanates such as bisisocyanatomethylnorbornane; phenylene diisocyanate, tolylene diisocyanate,
Ethyl phenylene diisocyanate, isopropylene phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate , 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4 '
-Diisocyanate, bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-
Diisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-
Triisocyanate, 4-methyl-diphenylmethane-
3,5,2 ′, 4 ′, 6′-pentaisocyanate, phenylisocyanatomethylisocyanate, phenylisocyanatoethylethylisocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,
Aromatic polyisocyanates such as 4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofuran isocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, dichlorocarbazole diisocyanate; Diethyl diisocyanate, thiopropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiopropyl diisocyanate, dicyclohexyl Sulfur-containing aliphatic isocyanates such as sulfide-4,4'-diisocyanate;diphenylsulfide-2,4'-diisocyanate,diphenylsulfide-4,4'-diisocyanate,3,3'4
4′-diisocyanatodibenzylthioether, bis (4-isocyanatomethylbenzene) sulfide, 4,
4'-methoxybenzenethioethylene glycol-3,
Aromatic sulfide-based isocyanates such as 3'-diisocyanate;diphenyldisulfide-4,4'-diisocyanate,2,2'-dimethyldiphenyldisulfide-5,5'-diisocyanate,3,3'-dimethyldiphenyldisulfide-5,5'-Diisocyanate,3,3'-dimethyldiphenyldisulfide-6
6′-diisocyanate, 4,4′-dimethyldiphenyldisulfide-5,5′-diisocyanate, 3,
3'-dimethoxydiphenyl disulfide-4,4'-
Aliphatic disulfide-based isocyanates such as diisocyanate and 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate; diphenylsulfone-
4,4'-diisocyanate, diphenylsulfone-
3,3'-diisocyanate, benzidine sulfone-
4,4′-diisocyanate, diphenylmethanesulfone-4,4′-diisocyanate, 4-methyldiphenylmethanesulfone-2,4′-diisocyanate, 4,
4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatedibenzylsulfone, 4,4'-dimethyldiphenylsulfone-3,3'-diisocyanate,
4,4'-di-tert-butyldiphenylsulfone-
3,3′-diisocyanate, 4,4′-dimethoxybenzeneethylenedisulfone-3,3′-diisocyanate, 4,4′-dichlorodiphenylsulfone-3,3 ′
Aromatic sulfone isocyanates such as diisocyanate; sulfones such as 4-methyl-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester and 4-methoxy-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester Acid ester-based isocyanate; 4,4′-dimethylbenzenesulfonyl-ethylenediamine-4,4′-diisocyanate;
4,4'-dimethoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3
Aromatic sulfonic acid amide-based isocyanates such as -isocyanatobenzenesulfonylanilide-4-methyl-3'-isocyanate; thiophen-2,5-diisocyanate, thiophen-2,5-diisocyanatomethyl;
1,4-dithiane-2,5-diisocyanate, 1,4
And sulfur-containing heterocyclic compounds such as -dithiane-2,5-diisocyanatomethyl.

These alkyl-substituted, alkoxy-substituted and nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products,
A modified burette, a dimerization or trimerization reaction product, and the like can be used, but a polyfunctional isocyanate compound other than the above compounds may be used. In addition, these polyfunctional isocyanate compounds can be used alone or as a mixture of two or more.

Among the above compounds, the obtained resin and the coating obtained by coating and forming a film are obtained from the viewpoints of yellowing resistance, heat stability, light stability, and polyfunctional isocyanate compounds. From the viewpoint of easiness, aliphatic polyisocyanates and alicyclic polyisocyanate compounds are preferred. Among them, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,5-bisisocyanatomethylnorbornane, Particularly preferred are 2,6-bisisocyanatomethylnorbornane and derivatives thereof, with hexamethylene diisocyanate being most preferred.

Examples of the active hydrogen compound having at least two active hydrogen groups capable of reacting with the polyfunctional isocyanate compound in one molecule include the following.

Polyol compound: ethylene glycol,
Diethylene glycol, triethylene glycol, 1,
4-butanediol, 1,3-butanediol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglycoside, pentaerythritol, Dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dorsitol, iditol, glycol, inositol, hexanetriol, triglycerose, digiperol, polyethylene glycol, polypropylene glycol, polytetramethylene Ether glycol, tris (2-hydroxyethyl) isocyanurate, Rob Tan diol, cyclopentane diol, cyclohexane diol, cycloheptane diol, cyclooctane diol, cyclohexane dimethanol, hydroxypropyl cyclohexanol,
Tricyclo [5.2.1.0 ^2,6 ] decane-dimethanol, bicyclo [4.3.0] -nonanediol, dicyclohexanediol, tricyclo [5.3.1.1] dodecanediol, bicyclo [4 .3.0] nonanedimethanol, tricyclo [5.3.1.1] dodecanediethanol, hydroxypropyltricyclo [5.3.1.
1] Dodecanol, spiro [3,4] octanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol, aliphatic polyols such as maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene Benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol,
Aromatic polyols such as di (2-hydroxyethoxy) benzene, bisphenol A-bis- (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-bis- (2-hydroxyethyl ether), bisphenol S, Halogenated polyols such as dibromoneopentyl glycol, polyester polyols, polyethylene glycol, polyether polyols, polythioether polyols, polyacetal polyols, polycarbonate polyols, polycaprolactone polyols, silicone polyols, furandmethanol, furthermore, oxalic acid, glutamic acid, adipic acid, Acetic acid, phthalic acid, isophthalic acid, salicylic acid, condensation reaction product of an organic acid such as pyromellitic acid and the polyol, Reaction product of an alkylene polyamine with an alkylene oxide, 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2- Dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, and caprolactone modified products thereof, 2-mercaptoethanol, 3-mercapto- 1,2-propanediol, glycerin di (mercaptoacetate), 1
-Hydroxy-4-mercaptocyclohexane, 2,4
-Dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1,3
-Butanediol, pentaerythritol tris (3-
Mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol tris (thioglycolate), pentaerythritol pentakis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) Methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4′-mercaptodiphenylsulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethylsulfide mono (3-mercaptopropionate), Dimercaptoethane mono (sulcylate), hydroxyethylthiomethyl-tris (mercaptoethylthio) methane and the like.

In addition, ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, butylenediamine, hexamethylenediamine, cyclohexylenediamine, piperazine, 2-methylpiperazine, phenylenediamine, tolylenediamine, xylenediamine, α, α′- Methylenebis (2-chloroaniline) 3,3′-dichloro-α, α′-biphenylamine, m-xylenediamine, isophoronediamine, N
Polyamino compounds such as -methyl-3,3'-diaminopropylamine and norbornenediamine, and α-amino acids such as serine, lysine and histidine can also be used.

In the present invention, as the active hydrogen compound, it is preferable to use a compound having a linear structure without a branched skeleton. It is preferable to use polycarbonate polyols, polycaprolactone polyols, polyolefin polyols, copolymers and mixtures thereof, and it is particularly preferable to use polyether polyols. In addition, the active hydrogen compound 5 described above was used in 100 parts by weight of the total active hydrogen compound.
It is preferable to use 0 to 98 parts by weight.
When the amount is less than 50 parts by weight, the flexibility of the film obtained from the aqueous coating material tends to deteriorate, and when it exceeds 98 parts by weight, the abrasion resistance of the film tends to decrease. These compounds may be used alone or in combination of two or more.

In order to stabilize the aqueous dispersion of the urethane resin (B) used in the present invention, known materials and stabilization techniques can be used. It preferably has one or more groups, more preferably one or more carboxyl groups and / or sulfonyl groups.

The constituents for introducing these atomic groups include, for example, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid,
2,2-dimethylolvaleric acid, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, polyethylene glycol, a polyadduct of ethylene oxide and propylene oxide, ethylene glycol and the active hydrogen compound But are not limited thereto. By introducing these atomic groups into the molecule, the mechanical stability of the resin and the mixing stability with other components tend to be improved.

The preferred amount of the above-mentioned compound containing a carboxyl group and / or a sulfonyl group is such that the acid value of the aqueous polyurethane resin in terms of solid content is 3 to 30 KO.
Hmg / g, more preferably in the range of 3 to 25 KOHmg / g, and still more preferably in the range of 5 to 20 KOHmg / g. When the acid value is less than the above range, the mechanical stability of the resin and the mixing stability with the aqueous olefin resin component tend to be poor. When the acid value exceeds 30 KOHmg / g, the texture of the obtained film tends to decrease. Here, the method for measuring the acid value is disclosed in, for example, Japanese Industrial Standard JIS K5400.

The method for producing the aqueous urethane-based resin is not particularly limited, but examples thereof include the following method. A polyfunctional isocyanate compound, a compound having an active hydrogen group capable of reacting with an isocyanate group in the active hydrogen compound, and an active hydrogen group capable of reacting with an isocyanate group in the compound, and a carboxyl group in the molecule; At least one compound having a sulfonyl group or an ethylene oxide group is reacted in an equivalent ratio such that the isocyanate group becomes excessive in the presence or absence of a suitable organic solvent, and a urethane having an isocyanate group at a molecular terminal is obtained. Produce a prepolymer. Thereafter, those having a carboxyl group and / or a sulfonyl group in the prepolymer are neutralized with a neutralizing agent such as a tertiary amine. Then, the neutralized prepolymer is charged into an aqueous solution containing a chain extender and reacted, and if an organic solvent is contained in the system, it is removed to obtain the neutralized prepolymer. Unneutralized urethane prepolymer obtained by the above method,
A method comprising adding a neutralizing agent and introducing it into an aqueous solution containing a chain extender to cause a reaction. A method in which an aqueous solution having a chain extender is added to the neutralized urethane prepolymer obtained by the above method, followed by reaction. A method in which an aqueous solution containing a neutralizing agent and having a chain extender is added to the unneutralized urethane prepolymer obtained by the above method and reacted to obtain an aqueous dispersion.

The neutralizing agent used in the present invention is not particularly limited, but alkanolamines such as N, N-dimethylethanolamine and N, N-diethylethanolamine, N-methylmorpholine, N-ethylmorpholine, pyridine, N-methylimidazole,
Ammonia, tertiary amines such as trimethylamine, triethylamine, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, alkali metal compounds such as aluminum hydroxide, tetramethylammonium hydroxide Such quaternary ammonium compounds can be mentioned, and these compounds can be used alone or as a mixture of two or more.

The amount of the neutralizing agent used is preferably 0.5 to 3 equivalents, more preferably 0 to 3 equivalents to 1 equivalent of the carboxyl group and / or sulfonyl group in the urethane resin having the carboxyl group and / or sulfonyl group. .7
１．５1.5 equivalents. If it is less than the above range, the stability of the aqueous urethane resin in water tends to decrease.

Examples of the chain extender used in the present invention include water, ethylenediamine, diethylenetriamine,
Triethylenetetramine, propylenediamine, butylenediamine, hexamethylenediamine, cyclohexylenediamine, piperazine, 2-methylpiperazine, phenylenediamine, tolylenediamine, xylenediamine, α, α′-methylenebis (2-chloroaniline),
3,3′-dichloro-α, α′-biphenylamine, m
-Xylene diamine, isophorone diamine, NBDA
(Trade name, manufactured by Mitsui Chemicals, Inc.), N-methyl-3,
Polyamines such as 3'-diaminopropylamine and adducts of diethylenetriamine and acrylate or hydrolysis products thereof are suitable.

Examples of the solvent used for obtaining the aqueous urethane-based resin include ketones such as methyl ethyl ketone and acetone, esters such as methyl acetate and ethyl acetate, and tetrahydrofuran.
The solvent is not particularly limited as long as it is lower than or equal to ° C., and these solvents can be used alone or in a mixed state of two or more kinds. The use of a solvent whose boiling point exceeds 100 ° C., that is, the boiling point of water, makes it difficult to completely remove only the solvent from the solution after the formation of the aqueous dispersion,
Since the high boiling point solvent remains in the film and affects the physical properties, when it is unavoidable to use it for the purpose of developing performance, it is preferable to use 10 parts by weight or less based on 100 parts by weight of the aqueous urethane resin.

The urethane resin (B) used in the present invention can be used as a modified product by reacting with another component such as another monomer or resin component. Further, the urethane resin (B) used in the present invention includes acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylamide, methacrylamide, styrene, acrylonitrile, butadiene, vinyl acetate, ethylene, propylene, itaconic acid, It can also be used as a composite in which at least one or more monomers such as maleic acid are polymerized.

The aqueous coating material of the present invention is an olefin resin
(A) and / or a urethane-based resin (B) is constituted as a main component, and as a method for coexisting these components, an aqueous olefin-based resin and an aqueous urethane-based resin obtained by the production method are used. A method of mixing using an appropriate stirrer after each production, and a method of melt-kneading an aqueous urethane-based resin and / or an isocyanate terminal group-containing or non-isocyanate-containing urethane prepolymer as a precursor thereof with an olefin-based resin. Examples of the method include addition and phase inversion to obtain a water dispersion, but the method is not particularly limited.

The ratio of the olefin resin (A) to the urethane resin (B) is not particularly limited, but is preferably in the range of 99/1 to 50/50 in terms of resin solid weight, The range of ６０60/40 is more preferred.
Within the above range, it is possible to achieve both flexibility and abrasion resistance of the film, and it is possible to supply a coating material at low cost. As the olefin-based resin (A) ratio increases, the flexibility and non-tackiness of the obtained film tend to be improved, and the cost tends to be reduced. On the other hand, as the urethane-based resin (B) ratio increases, the resulting coating tends to have improved scratch resistance.

The olefin-based resin (A) and the urethane-based resin (B) of the present invention, when formed into a film by themselves, have film properties of a load of 5 kg and a distance between chucks of 20 kg.
mm, specimen size 40 mm x 10 mm, distance between marked lines 10 m
m, pulling speed 50 mm / min, temperature 23 ° C, humidity 50
% When measured under the following conditions: Olefin resin (A) Elongation at break: 300-1300% Elongation at break: 3-30 MPa 100% Modulus: 0.5-6.5 MPa Urethane resin (B) Elongation at break: 500 to 1500% Breaking strength: 10 to 50 MPa 100% modulus: 0.5 to 5 MPa Further, the film properties of the film formed from the aqueous coating material of the present invention under the same conditions as described above are as follows: Elongation at break: 400 to 2000 % Breaking strength: 8 to 80 MPa 100% modulus: 0.3 to 5 MPa By satisfying any of the performances, both flexibility and scratch resistance are achieved. Generally, a value of 100% modulus corresponds to the flexibility of the coating.

Further, a flame retardant can be added to the aqueous coating material of the present invention in order to impart flame retardancy. The flame retardant that can be used is not particularly limited, but from the viewpoint of environmental protection, a halogen-based flame retardant containing chlorine, bromine, and the like, which generates harmful substances when incinerated, is not preferred. Therefore, a phosphorus-based or inorganic flame-retardant that does not generate harmful substances and has a relatively high flame-retardant effect is preferred.

The phosphorus flame retardant (H) used in the present invention
Is not particularly limited, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, Phosphoric acid such as octyl diphenyl phosphate, di- (polyoxyethylene) -hydroxymethylphosphonate, diethylphenylphosphonate, dimethylphenylphosphonate, diethoxy-bis- (2-hydroxyethyl) -aminomethylphosphonate Ester-based flame retardants, condensed phosphate ester-based flame retardants such as resorcinol diphenyl phosphate, bisphenol A diphenyl phosphate,
Examples include inorganic phosphoric acid-based flame retardants such as ammonium polyphosphate and titanium phosphate, red phosphorus-based flame retardants such as red phosphorus, phenylphosphonic acid, and the like, and those obtained by making these phosphorus-based flame retardants aqueous.

The inorganic flame retardant (I) used in the present invention is not particularly limited. Examples thereof include antimony compounds such as antimony trioxide, antimony pentoxide and antimony silicoxide, magnesium hydroxide, Metal hydroxides such as aluminum hydroxide, hydrated metal compounds, tin oxide, tin hydroxide, tin compounds such as zinc stannate, zirconium compounds such as zirconium oxide and zirconium hydroxide, zinc borate, barium metaborate and the like Boric acid compounds, guanidine phosphate, guanidine compounds such as nitrogenated guanidine, molybdenum compounds such as molybdenum trioxide, silicone resins, silicone compounds such as silicone oils, triazine compounds such as organic triazines, etc. And the like.

These flame retardants can be used alone or in combination of two or more. In particular, the inorganic flame retardant (I) tends to act as a flame retardant aid, and a more excellent flame retardant effect can be expected when used in combination with the phosphorus flame retardant (H).

The method for incorporating the above flame retardant into the aqueous coating material of the present invention is not particularly limited, but the olefin resin (A) and / or urethane resin (B), or amino resin may be used. (C) and / or a urea-based compound (D) and / or a carbodiimide-based resin (E) or the like, and then a method of making the mixture aqueous, or a method of mixing during the step of making the mixture aqueous, A method of mixing a flame retardant with an aqueous coating material and the like can be mentioned.

The solution viscosity of the aqueous coating material in the present invention is:
The value measured at 25 ° C. with a BM viscometer is 1000 to
It is preferably in the range of 50,000 mPa · s, more preferably 5,000 to 30,000 mPa · s. When the solution viscosity is lower than the above range, an appropriate coating film thickness cannot be obtained, a plurality of coating operations are required, and the workability is reduced, and further, the storage stability of the emulsion is insufficient. Can occur. When the solution viscosity is higher than the above range, the workability at the time of applying the substrate tends to decrease.

Further, in the present invention, a viscoelasticity modifier can be used to adjust the solution viscosity of the aqueous coating material to the above range. The viscoelasticity adjuster is not particularly limited, but an acrylic resin type viscoelasticity adjuster such as polyacrylic acid and polyacrylamide, a polyether type viscoelasticity adjuster such as polyvinyl methyl ether and polyethylene oxide, a polyester type Viscoelasticity modifier, polyurethane-based viscoelasticity modifier, cellulose-based viscoelasticity modifier such as carboxymethylcellulose, carboxyethylcellulose, methylcellulose, hydroxyethylcellulose, etc., organic viscoelasticity adjustment such as polyvinyl alcohol, polyvinylpyrrolidone, poly (N-vinylacetamide) Agents, silicon dioxide, activated clay, bentonite, calcium carbonate and other inorganic viscoelasticity modifiers can be used.

Particularly, an acrylic resin-based viscoelasticity modifier having a carboxylic acid or a carboxylate is preferable. When other viscoelasticity modifiers are used, there is a possibility that agglomerates will be formed at the time of addition, and problems such as a decrease in abrasion resistance and flexibility of the coating film will occur.

The solid content concentration in the water-based coating material of the present invention is not particularly limited. However, it is difficult to maintain the viscosity range described later, to shorten the drying time, and to make it easier to apply a thick film. From the viewpoint of workability, the content is 35 to 70% by weight, and more preferably 40 to 65% by weight. If it is less than the above range, a sufficient film thickness cannot be obtained by one application, and the coating liquid tends to be impregnated depending on the application substrate, and the workability tends to decrease, such as an increase in the amount of application and the number of applications. is there. In addition, when the amount is more than the above range, the solution tends to gel or solidify, and the workability during coating tends to decrease.

The substrate on which the aqueous coating material of the present invention is applied is not particularly limited. For example, natural fibers typified by cotton and the like, synthetic fibers typified by polyester and nylon, leather, synthetic fibers Leather, synthetic resin, paper, film and the like can be mentioned.In addition, for example, a coating material can be applied to a specific mold, and the film obtained after drying can also be used for applications in which the film can be detached from the mold again. is there.

The water-based coating material used in the present invention may further contain, if necessary, a reactive resin and a compound such as an epoxy resin and a hydrazide compound in order to improve the film performance.

In the aqueous coating material used in the present invention, a surfactant can be used to improve the dispersion stability in water. For example, alkyl naphthalene sulfonate, naphthalene sulfonate, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium salt of formaldehyde condensate, sodium alkyl diphenyl ether disulfonate, calcium lignin sulfonate, melanin resin sodium sulfonate, special polyacryl Acid salt, gluconate, potassium oleate,
Olefin / maleic acid copolymer, sodium carboxymethylcellulose, sodium oleate, potassium stearate, sodium stearate, ammonium stearate, triethanolamine stearate, potassium tallowate, sodium tallowate, and metal soaps (Zn, Al, Na , K salt), etc .; fatty acid monoglyceride, sorbitan fatty acid ester, sugar fatty acid partial ester, polyglycerin fatty acid partial ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid partial ester , Polyoxyethylene sorbitol fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester, polyoxyethylene fatty acid fatty acid Nonionic surfactants such as min, polyoxyethylene (hardened) castor oil, polyoxyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block copolymer, hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, and methyl cellulose; alkyl ammonium chloride , Trimethylalkylammonium bromide, alkylpyridinium chloride, and casein; and water-soluble polyvalent metal salts. These surfactants can be used alone or in combination of two or more.

In addition to the above compounds, if necessary, lubricating agents (synthetic waxes, natural waxes, etc.), rust inhibitors, fungicides, ultraviolet absorbers, heat stabilizers, weather stabilizers, foaming agents, Defoaming agents, dyes, auxiliary binders, leveling agents, thixotropy-imparting agents, defoaming agents, anti-settling agents, ultraviolet absorbers, antioxidants, antistatic agents, thickeners, pigments (e.g., titanium white, red iron, phthalocyanine, Carbon black, permanent yellow, etc.), fillers (for example, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin,
Additives such as mica, asbestos, mica, calcium silicate and the like can be added within a range not to impair the object of the present invention.

All of the above-mentioned additives were added in the raw resin or raw material compound production process, added in the raw resin or raw material compound aqueous conversion process, and the aqueous additives were similarly made aqueous (A) and / or Or (B) and / or (C) and / or (D) and / or (E), an addition in these mixing steps, an addition after mixing, and the like. It may be dispersed in a resin, or may be dissolved or dispersed in water.

The method of applying the water-based coating material of the present invention is not particularly limited. For example, dip coating, blade coater, air knife coater, rod coater, hydro bar coater, transfer roll coater, reverse coater Coater, gravure coater, die coater, curtain coater, spray coater, flow coater, roll coater, brush coating, etc.,
The coating can be applied to a part or the entire surface of the substrate. The drying temperature of the film formed from the aqueous coating material according to the present invention may be room temperature,
It can be heated for 0 seconds.

A method of laminating a film formed from the aqueous coating material of the present invention with another film, a method of bonding the films to each other by heat or high frequency, and a method of forming a multilayer film with another material Is also possible. Furthermore, it is also possible to apply the present coating material to a base material and use it as a texture and anti-slip effect imparting material.

The film obtained from the water-based coating material of the present invention is characterized by having excellent abrasion resistance (scratch resistance) while maintaining flexibility. One of the methods for evaluating the abrasion resistance is as follows. A Taber abrasion test defined by JIS K7204 is mentioned, and it is preferable that the amount of reduction in abrasion after measuring the abrasion wheel 3000 times is 0 to 50 mg. When the abrasion reduction exceeds the above range, it can be determined that the abrasion resistance is insufficient.

[0102]

The present invention will be described below with reference to examples.
The present invention is not limited at all by the examples.

[0103] (Production Example) (A) an aqueous olefin resin production example 1. Ethylene-polar monomer copolymer and fatty acid compound
Of an aqueous dispersion composed of a product : 100 parts by weight of an ethylene-vinyl acetate copolymer (manufactured by MDP, Evaflex 270), montanic acid (Hoechst S: 28 to 32 carbon atoms, acid value 150 mg KO)
H / g) of 5 parts by weight, and supplied from a hopper of a twin screw extruder (PCM-30, L / D = 40, manufactured by Ikegai Tekko Co., Ltd.) at a speed of 3000 g / hour. A 13% aqueous solution of potassium hydroxide was continuously supplied from the provided supply port at a rate of 300 g / hour (10% based on the whole), and was continuously extruded at a heating temperature of 160 ° C.
The extruded resin mixture was cooled to 90 ° C. by a jacketed static mixer installed at the extruder port,
The mixture was further poured into warm water at 80 ° C. to obtain an aqueous dispersion (A-1) having a yield of 99.3%, a solid content of 44%, and a pH of 12. The average particle size of the obtained aqueous dispersion was 0.6 μm as measured by Microtrac.

[0104] 2. Olefin elastomer resin and fat
Production of Aqueous Dispersion Consisting of Fatty Acid Compound As an olefin elastomer, an ethylene / 1-butene copolymer (trade name: Tuffmer A40, manufactured by Mitsui Chemicals, Inc.)
90) 100 parts by weight, 10 parts by weight of montanic acid, and 3 parts by weight of potassium oleate are mixed, and 3,000 g from a hopper of a twin-screw extruder (PCM-30, L / D = 40, manufactured by Ikegai Iron Works, Ltd.) / Extruder at a rate of 150 g / h (ethylene / 1-) from a supply port provided at the vent of the extruder.
5% based on the total amount of butene copolymer, maleic anhydride-modified polyethylene wax and potassium oleate)
And extruded continuously at a heating temperature of 180 ° C.

Next, the extruded mixture was mixed with a jacketed static mixer installed at the extruder opening at 90 ° C.
C., and further poured into warm water at 80.degree. C. to obtain an aqueous dispersion (A-2) having a solid content concentration of 40% and pH 11 of 99.
% Yield. The average particle size of the dispersed particles of the obtained aqueous dispersion was 0.6 μ
m.

(B) Production Example of Aqueous Urethane Resin 3000 equipped with thermometer, stirrer, nitrogen inlet tube, and cooling tube
399.5 g of PTG 2000SN (manufactured by Hodogaya Chemical Industry Co., Ltd., polytetramethylene ether glycol, molecular weight: 2,000) in a four-necked four-neck flask was
-Dimethylolbutanoic acid 21.0 g, 1,4-butanediol 12.4 g, hexamethylene diisocyanate 9
6.3 g and 374.0 g of methyl ethyl ketone were charged and reacted at 90 ° C. for 6 hours in a nitrogen gas atmosphere. Thereafter, the mixture was cooled to 60 ° C., 13.3 g of triethylamine was added, and mixed at this temperature for 30 minutes. The obtained prepolymer was treated with a 0.86% aqueous solution of hexamethylenediamine 1
The mixture was mixed and stirred with 275.7 g, and then methyl ethyl ketone was removed under reduced pressure at 60 ° C. to give a solid content of 30%.
%, A solid content acid value of 15 KOH mg / g, pH 7.8 and an average particle size of 0.2 μm were obtained as an aqueous urethane resin (B-1).

(C) Aqueous amino resin Cymel 38 as aqueous amino resin (C-1)
5 (manufactured by Mitsui Cytec, solid content concentration 80%, partially methyl etherified melamine containing a methylol group and an imino group) was used.

(D) Urea-Based Compound As the urea-based compound (D-1), urea (manufactured by Wako Pure Chemical Industries, special grade of reagent) was used.

(E) Aqueous carbodiimide-based resin As the aqueous carbodiimide-based resin (E-1), carbodilite E-01 (manufactured by Nisshinbo, solid content concentration 40%, carbodiimide equivalent 425) was used.

Production of Water- based Coating Material The above-mentioned water-based olefin resin, water-based urethane resin, water-based amino resin, urea, water-based carbodiimide-based resin and other components were mixed and stirred at a mixing ratio (solid content ratio) shown in Table 1. Thereafter, Thickener 636 (manufactured by San Nopco, acrylic viscoelasticity adjuster) was added as a viscoelasticity adjuster, and the viscosity of the solution was adjusted to 10,000 mPa · s to produce an aqueous coating material.

Production of Textile Products Each of the aqueous coating materials produced by the above method was applied to a base fabric composed of polyester fibers with an applicator so that the average film thickness after drying was 120 μm. For 3 minutes to produce a film-formed product.

The evaluation contents, test conditions and results of the above water-based coating materials are shown below.

Abrasion resistance evaluation method The sample was worn using a Taber abrasion tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) and a wear wheel CS-17 under the conditions of a load of 500 g and a rotation speed of 3000, and the weight of the base cloth before and after the test. Was measured, and the weight of the shaved film was calculated. The less wear loss, the better the wear resistance, 50 mg
The following were accepted.

[0114] Cut the flexibility evaluation method the base cloth coating sample in a circle with a diameter of 11cm,
One end was supported horizontally, and the angle at which the base fabric sample hangs was measured with reference to the horizontal plane of the fulcrum.

Non-tackiness evaluation method The base cloth-coated sample was judged by the touch, and ○ was judged as acceptable.

：: no stickiness Δ: slightly sticky X: sticky

[0117]

[Table 1]

[0118]

The water-based coating material according to the present invention comprises an aqueous dispersion of a polymer which does not generate harmful substances when incinerated and has no problem with environmental hormones, and is difficult with conventional water-based coating materials. It has become possible to form a film having excellent properties such as scratch resistance, flexibility, non-tackiness, water resistance, cold resistance, odorlessness, flame retardancy, coating properties, and light weight.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 131/04 C09D 131/04 133/02 133/02 161/20 161/20 175/04 175/04 175 / 08 175/08 179/00 179/00 D21H 19/10 D21H 19/10 F term (reference) 4J038 CA031 CA032 CB001 CB002 CB041 CB042 CB051 CB052 CB101 CB102 CB142 CG002 CQ011 CQ012 DA132 DA142 DA172 DG001 DG002 DG131 MA10 NA04 NA11 NA15 PC09 PC10 4L055 AG35 AG58 AG62 AG64 AG75 AG80 AG85 AG93 BE08 EA19 EA32 FA16 FA19 FA30 GA50

Claims (20)

[Claims] 1. An olefin resin (A) and / or a urethane resin (B) and at least one kind of modification selected from an amino resin (C), a urea compound (D) and a carbodiimide resin (E). Aqueous coating material containing an agent. 2. The amino resin according to claim 1, wherein the amino resin (C) is at least one amino resin selected from methyl etherified melamine, methyl etherified benzoguanamine, methyl etherified urea, and methyl etherified glycoluril. Aqueous coating material. 3. The water-based coating material according to claim 1, wherein the amino resin (C) is an amino resin containing an imino group and a methylol group. 4. The weight ratio ((A) + (B)) / (C) of the olefin resin (A) and / or the urethane resin (B) to the amino resin (C) is 100 / 0.1 to 4. 100
The aqueous coating material according to any one of claims 1 to 3, wherein the ratio is / 10. 5. The aqueous coating material according to claim 1, wherein the urea compound (D) is urea. 6. The weight ratio ((A) + (B)) / (D) of the olefin resin (A) and / or urethane resin (B) to the urea compound (D) is from 100/1 to 100. / 1
The aqueous coating material according to any one of claims 1 to 5, which is 00. 7. The weight ratio ((A) + (B)) / (E) of the olefin resin (A) and / or urethane resin (B) to the carbodiimide resin (E) is 100 / 0.1. ~
The aqueous coating material according to any one of claims 1 to 6, which is 100/10. 8. The aqueous coating material according to claim 1, wherein the olefin resin (A) is an ethylene-vinyl acetate copolymer containing 10 to 50% by weight of a vinyl acetate unit. 9. An acid-modified polyolefin compound (F) and / or a fatty acid compound (G) in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the olefin resin (A). An aqueous coating material according to any one of the above. 10. The physical properties of a film formed by using the olefin resin (A) alone with the olefin resin (A) are as follows: elongation at break: 300-1300%; strength at break: 3-30 MP
a: The aqueous coating material according to any one of claims 1 to 9, which has a 100% modulus and a value of 0.5 to 6.5 MPa. 11. The aqueous coating material according to claim 1, wherein said urethane resin (B) comprises a component containing a polyether polyol and hexamethylene diisocyanate. 12. The physical properties of a film formed by using the urethane resin (B) alone with the urethane resin (B) are as follows: elongation at break: 500 to 1500%; strength at break: 10 to 50 MPa.
a: The aqueous coating material according to any one of claims 1 to 11, which has a 100% modulus and a value of 0.5 to 3.5 MPa. 13. The solid weight ratio of the olefin resin (A) to the urethane resin (B) is (A) / (B) = 99/1.
2 to 50/50.
3. The aqueous coating material according to any one of 2. 14. The aqueous coating material according to claim 1, wherein a film formed from the aqueous coating material is:
Elongation at break, 400-2000%; breaking strength, 8-80
MPa: an aqueous coating material having a 100% modulus and a value of 0.3 to 5 MPa. 15. The water-based coating material according to claim 1, wherein said water-based coating material contains a phosphorus-based flame retardant (H) and / or an inorganic-based flame retardant (I). The olefin-based resin (A) and / or the urethane-based resin (B) and the phosphorus-based flame retardant (H) and / or the inorganic-based flame retardant (I)
((A) + (B)) / ((H) +
An aqueous coating material wherein (I)) is 100/1 to 100/100. 16. The aqueous coating material according to claim 1, which contains an acrylic resin-based viscoelasticity modifier having a carboxylic acid group or a carboxylate group, and has a solution viscosity of 1000. An aqueous coating material having a viscosity of up to 50,000 mPa · s. 17. A film formed from the water-based coating material according to claim 1. 18. A method for forming a film, comprising applying the aqueous coating material according to claim 1 to a substrate and drying. 19. The method according to claim 18, wherein the substrate is at least one selected from the group consisting of fiber, synthetic fiber, leather, synthetic leather, synthetic resin, and paper. 20. A coated article having a film formed from the aqueous coating material according to claim 1.