JP2002012812A - Water-based coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based coating material capable of forming such a coating film excellent in any physical properties including scratch resistance, abrasion resistance and touch feeling as to have been hard to afford in the case of conventional water-based coating materials. SOLUTION: This water-based coating material is such as to form a coating film by coating a substrate therewith, a being characterized by comprising an olefin-based resin aqueous dispersion and a water-based polyurethane resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous coating material using an aqueous olefin dispersion and an aqueous polyurethane resin. More specifically, an aqueous coating water comprising an aqueous dispersion of a polymer capable of providing a film having excellent physical properties of both scratch resistance, abrasion resistance and texture, and which does not generate harmful halogen compounds when incinerated. It is about materials.

[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 and 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 for textile products (in a broad sense) such as industrial curing nets and canvas used at construction sites. However, these fibers are used to impart weather resistance and durability. Was usually coated with a vinyl chloride sol. However, due to the recent increase in environmental problems, there is a strong demand for alternatives of vinyl chloride sol with other products because of the generation of chlorine-based gas when incinerating these nets and canvases. On the other hand, there is a strong demand that an aqueous medium should be used as a medium for the coating material in order to maintain a favorable working environment.

[0004] Under the circumstances described above, an aqueous dispersion resin which does not generate a harmful halogen compound when the coated substrate is incinerated is desired as a coating material. A coating material that simultaneously satisfies the performances such as scratch resistance (durability) and texture has not been obtained. Therefore, the emergence of an aqueous coating material comprising an aqueous dispersion of a polymer that can provide a fiber product excellent in scratch resistance (durability) and texture and that does not generate a harmful halogen compound when incinerated is desired. ing.

[0005]

SUMMARY OF THE INVENTION The present invention aims to solve the problems associated with the prior art as described above, and provides a textile product (broadly defined) having excellent scratch resistance (durability) and texture. It is an object of the present invention to provide an aqueous coating material comprising an aqueous dispersion of a polymer which can be produced and which does not generate a harmful halogen compound upon incineration.

[0006] In particular, the present invention relates to industrial nets, canvases used in construction sites, ground reinforcing nets, outdoor tents such as tent warehouses and bi-tents, hoods such as trucks and shears, gloves, flags, clothing,
Typified by footwear, furniture, bags, crimp-removable sheets, etc.
Consists of an aqueous dispersion of a polymer that can provide a film-forming product for the purpose of improving the texture and surface protection of substrates such as fibers, leather, paper, and synthetic resins, and that does not generate harmful halogen compounds during incineration. It is intended to provide an aqueous coating material.

[0007]

That is, the present invention is specified by the following items [1] to [19]. [1] An aqueous coating material which can be applied on a substrate to form a film, comprising an aqueous dispersion of an olefin resin (component A) and an aqueous polyurethane resin.
A water-based coating material comprising (Component B). [2] The ratio of component (A) / component (B) in terms of resin solid weight is 99/1
The water-based coating material according to [1], which is 50 to 50/50. [3] Resin solid content concentration of 35 to 70% by weight, solution viscosity of 5
The aqueous coating material according to [1] or [2], which has a molecular weight of 000 to 50,000 mPa · s. [4] The component (A) in the aqueous coating material is selected from an ethylene-polar monomer copolymer and / or an olefin-based elastomer.
The aqueous coating material according to any one of [1] to [3], which is any resin. [5] The aqueous coating material according to [4], wherein the ethylene-polar monomer copolymer in the component (A) in the aqueous coating material is an ethylene-vinyl acetate copolymer. [6] The water-based coating material according to [5], wherein the ratio of the benzyl acetate component in the ethylene-vinyl acetate copolymer in [5] is 10 to 50% by weight. [7] The aqueous coating according to [4], wherein the olefin-based elastomer in the component (A) in the aqueous coating material is a styrene-conjugated diene block copolymer or a hydrogenated product thereof. Wood. [8] The component (A) in the water-based coating material, when formed into a film by itself, has a film property of: elongation at break: 300 to 1300%, breaking strength: 3 to 30 MPa, 100% modulus: 0.5 to The water-based coating material according to any one of [1] to [7], which has any physical properties of 6.5 MPa. [9] The component (B) in the water-based coating material has the following film properties when formed into a film by itself: elongation at break: 500-1500% breaking strength: 10-50 MPa 100% modulus: 0.5-3.5 MPa The water-based coating material according to any one of [1] to [8], which has any of the following physical properties. [10] The coating formed from the component (A) and the component (B) in the aqueous coating material has an elongation at break of 400 to 1000%, a breaking strength of 5 to 30 MPa, and a physical property of 100% modulus: 0.5 to 5 MPa. The aqueous coating material according to any one of [1] to [9], further comprising: [11] The base is made of natural fiber, synthetic fiber, leather, synthetic leather,
The aqueous coating material according to any one of [1] to [10], which is at least one selected from the group consisting of a synthetic resin and paper. [12] A film formed from the aqueous coating material according to any one of [1] to [11]. [13] A method of applying the aqueous coating material according to any one of [1] to [11] to a substrate and drying to form a film. [14] An industrial net having a coating formed from the aqueous coating material according to any one of [1] to [11]. [15] A canvas having a film formed from the aqueous coating material according to any one of [1] to [11]. [16] A hood having a film formed from the aqueous coating material according to any one of [1] to [11]. [17] A glove having a film formed from the aqueous coating material according to any one of [1] to [11]. [18] A tent having a film formed from the aqueous coating material according to any one of [1] to [11]. [19] A flag having a film formed from the aqueous coating material according to any one of [1] to [11].

[0008]

DETAILED DESCRIPTION OF THE INVENTION [Term "Aqueous"] In the present invention,
"Aqueous" means a state in which the resin is dispersed in water and / or
Or, it means a state in which a part is dissolved, and includes “water dispersion”.

The form of the olefin-based aqueous dispersion and the aqueous polyurethane resin contained in the aqueous coating material of the present invention is not particularly limited as long as it is dissolved and dispersed in an aqueous medium. The dispersed state is preferable in that a high solid content concentration is possible.

The component (A) constituting the olefin-based aqueous dispersion used in the present invention is not particularly limited, but any component selected from an ethylene-polar monomer copolymer and / or an olefin-based elastomer can be used. It is preferable that such a resin is used.

Preferred examples of the ethylene-polar monomer copolymer include ethylene-ethyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, and ethylene-propyl (meth) acrylate copolymer. Coalescence, ethylene-butyl (meth) acrylate copolymer, ethylene-
Hexyl (meth) acrylate copolymer, ethylene- (meth) acrylate-2-hydroxyethyl copolymer, ethylene- (meth) acrylate-2-hydroxypropyl copolymer, ethylene-glycidyl (meth) acrylate Ethylene- (meth) acrylate copolymer such as copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-maleic acid copolymer, ethylene-fumaric acid copolymer, ethylene-crotonic acid copolymer Ethylene-ethylenically unsaturated acid copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl propionate copolymers, ethylene-vinyl butyrate copolymers, ethylene-vinyl ester copolymers such as ethylene-vinyl stearate, etc. Examples of the polymer include ethylene-vinyl ester copolymer and ethylene-vinyl ester.
(Meth) acrylic acid ester copolymers are preferred, and ethylene-vinyl acetate copolymers are particularly preferred.

The ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 10 to 50% by weight, particularly preferably 15 to 40% by weight, and has a melt flow rate (MFR; J
ISK6760) is 0.05 to 1000 g / 10 mi.
n is preferable, especially 0.1 to 500 g / 10
min is preferred.

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 preferably 50% or less, particularly preferably 30% or less. 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 has 2 to 2 carbon atoms.
20 α-olefins, preferably 2 to 10 carbon atoms
Α-olefins, more preferably 2 to 8 carbon atoms
Α-olefins, specifically, α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene. 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 thereof 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, a preferable 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 this 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 0.5 to 10%.
Mol%, and in this case, the content of the structural unit derived from α-olefin other than ethylene is 4.5.
It is preferably about 74.5 mol%. The composition of the rubbery copolymer was measured by 13C-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 in a 135 ° C. decalin solution is 0.5 to 2.0.
dl / g is preferred, and more preferably 0.7 to 1.5.
dl / g.

The conjugated diene constituting the styrene-conjugated diene block copolymer includes, for example, isoprene,
Butadiene and the like. These conjugated dienes are
One type may be used alone, or two or more types may be used in combination. The block configuration of the styrene-conjugated diene block copolymer may be a styrene-conjugated diene diblock copolymer, a styrene-conjugated diene-styrene triblock copolymer, or a block copolymer having a larger number of blocks. Polymers.

As such a styrene-conjugated diene block copolymer, for example, US Pat. No. 3,265,265
And block copolymers produced by the methods described in JP-A No. 765 and JP-A-61-192743. Styrene-conjugated diene block copolymers, such as styrene-isoprene block copolymers, are specifically exemplified by Kraton TR-1107, 111
1, 1112 (all manufactured by Shell Chemical Co., Ltd.).

Examples of the hydrogenated 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. A hydrogenated product of a styrene-conjugated diene block copolymer, for example, a hydrogenated product of a styrene-butadiene block copolymer, is specifically exemplified by Kraton G-
1652 and 1657 (both manufactured by Shell Chemical Co., Ltd.), and hydrogenated styrene-isoprene block copolymers are specifically exemplified by Septon 2002 and 2007 (both are available from ) Made by Kuraray).

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

The styrene-conjugated diene block copolymer or its water additive has a melt flow rate (M
FR; ASTM D 1238, 230 ° C, 2.16kg load) is 0.1 ~
It is preferably 1000 g / 10 min, more preferably 1 to 500 g / 10 min, particularly preferably 10 to 2 g.
00 g / 10 minutes.

In order to stabilize the olefin polymer as an aqueous dispersion, a specific acid-modified polyolefin compound and / or fatty acid compound can be used, if necessary.
The acid-modified polyolefin compound used in the present invention is a polyolefin-based resin and includes a carboxylic acid salt group bonded to a polyolefin polymer chain (including a carboxylic acid group when it is a partially neutralized product or a partially saponified product). ) As a -COO- group in a concentration of 0.05 to 5 mmol, preferably 0.1 to 4 mmol per gram of the polyolefin resin.

The acid-modified polyolefin compound is, for example, a polyolefin comprising α-olefin or the like,
Graft copolymerizing a monomer having a neutralized or non-neutralized carboxylic acid group and / or a monomer having a saponified or unsaponified carboxylic acid ester Can be obtained.

The polyolefin before acid modification used in the preparation of the acid-modified polyolefin compound is GPC
Number average molecular weight (Mn) of 500 to 1
Preferred are α-olefin homopolymers or copolymers of two or more α-olefins in the range of 000, preferably 700 to 5,000, more preferably 1,000 to 3,000.

The above-mentioned homo-copolymer or α-olefin constituting the copolymer includes α-olefins having 2 to 20 carbon atoms.
Olefins, preferably α-olefins having 2 to 10 carbon atoms, more preferably α-olefins having 2 to 8 carbon atoms, specifically ethylene, propylene, 1-butene, 1-pentene, 1-hexene , 1-octene and the like. Among homopolymers and copolymers composed of these α-olefins, ethylene homopolymer and propylene homopolymer are particularly preferred.

The graft monomers grafted to the polyolefin include the above-mentioned monomers having a neutralized or non-neutralized carboxylic acid group and the above-mentioned monomers having a saponified or unsaponified carboxylic acid group. It is a monomer having an acid ester group, and examples thereof include an ethylenically unsaturated carboxylic acid, an anhydride thereof, and 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 a monoester or diester of the above-mentioned ethylenically unsaturated carboxylic acid such as methyl, ethyl or propyl. These monomers 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 adopted. The acid-modified polyolefin compound is based on 100 parts by weight of the olefin polymer.
It is used in a proportion of 0.5 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 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 in the above ratio.

The fatty acid compound used in the present invention means a fatty acid, a salt of the fatty acid, or an ester of the fatty acid. In the present invention, these compounds can be used alone or in combination. The ingredients are fatty acid salts,
Fatty acids and / or fatty acid esters may be included.

In the present invention, the fatty acid compound has usually 25 to 60 carbon atoms, preferably 25 to 40 carbon atoms. As the fatty acid, montanic acid is preferred in the present invention. Examples of the salt of the fatty acid include alkali metal salts such as sodium salt, potassium salt and lithium salt, alkaline earth metal salts such as magnesium salt and calcium salt, zinc salt, aluminum salt, iron salt, 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 is used, the fatty acid compound is used in an amount of 0.5 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the olefin polymer. It is.

Further, in order to impart anti-blocking properties of the film, a specific ionomer resin and / or a specific low-molecular-weight olefin polymer can be used in the aqueous coating material. It is a polymer composed of a polymer main chain mainly composed of hydrocarbon, having a carboxyl group in a side chain, and at least a part of the carboxyl group is neutralized with a metal ion, an organic amine, ammonia or the like. Specific examples of the ionomer resin include an ionomer resin which is an ethylene-unsaturated carboxylic acid copolymer and is a partially neutralized product in which at least a part of the carboxyl group contained is neutralized with a metal cation. Can be.

The ethylene-unsaturated carboxylic acid copolymer constituting the main skeleton of the ionomer resin may be a random copolymer or a graft copolymer of unsaturated carboxylic acid onto polyethylene. -The unsaturated carboxylic acid copolymer may contain only one kind of unsaturated carboxylic acid, or may contain two or more kinds of unsaturated carboxylic acids.

The unsaturated carboxylic acid which is a component of the ethylene-unsaturated carboxylic acid copolymer includes an unsaturated carboxylic acid having 3 to 8 carbon atoms. 3-8 carbon atoms
Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, isocrotonic acid, citraconic acid, allyl succinic acid, mesaconic acid, glutaconic acid, nadic acid, methylnadic acid , Tetrahydrophthalic acid, methylhexahydrophthalic acid, and the like. Among these, acrylic acid and methacrylic acid are particularly preferred.

The ethylene-unsaturated carboxylic acid copolymer constituting the main skeleton of the ionomer resin may contain a third component in addition to ethylene and the unsaturated carboxylic acid. Examples of the third component include unsaturated carboxylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate and isobutyl (meth) acrylate, and vinyl esters such as vinyl acetate.

The content of ethylene and unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid copolymer is usually a ratio of 5 to 40 parts by weight of unsaturated carboxylic acid to 95 to 60 parts by weight of ethylene. Preferably, 8 to 2 unsaturated carboxylic acids are added to 92 to 75 parts by weight of ethylene.
5 parts by weight. When the ethylene-unsaturated carboxylic acid copolymer contains a third component, the third component is 40%.
Preferably, it is present in an amount of less than or equal to weight percent.

In this ionomer resin, at least a part of the carboxyl group in the side chain of the ethylene-unsaturated carboxylic acid copolymer is neutralized with a trivalent metal cation, an organic amine, ammonia or the like. . Specifically, examples of the monovalent metal ion include Na, K, and Li.
As divalent metal ions, Mg, Zn, Ca, Cu,
Fe, Ba, etc., and trivalent metal ions include Al and the like.

In the ionomer resin, the ratio of the carboxyl group neutralized with the metal cation to the carboxyl group in the side chain of the ethylene-unsaturated carboxylic acid copolymer, that is, the degree of neutralization is usually 20 to 100. %, Preferably 30 to 80%. Also, this ionomer resin has an M value according to ASTM D1238.
FR (190 ° C) is 0.05-100g / 10min
Is preferable, and especially 0.1 to 50 g / 10 mi
n is preferred.

As the low molecular weight polyolefin polymer,
An α-olefin homopolymer or a copolymer of two or more α-olefins having a number average molecular weight (Mn) in the range of 500 to 10,000 is preferred. Specific examples of the α-olefin include ethylene, propylene, butene, pentene, hexene, octene and the like. Among these, ethylene homopolymer and ethylene-propylene copolymer are particularly preferred.

When the above compound is used, 1 to 60 parts by weight of the ionomer resin and / or 0.5 to 20 parts by weight of the low molecular weight polyolefin per 100 parts by weight of the olefin polymer,
Further, when the fatty acid compound is contained, the content is 5 to 30 parts by weight. Particularly preferred embodiments are 5 to 30 parts by weight of the ionomer resin and / or 0.5 to 15 parts by weight of the low molecular weight polyolefin and 1 to 15 parts by weight of the fatty acid compound, based on 100 parts by weight of the olefin polymer. .

The method for preparing the aqueous dispersion of the olefin polymer is not particularly limited. For example, an olefin polymer, an acid-modified polyolefin compound,
At least one component selected from the group consisting of a fatty acid and a fatty acid ester is melt-kneaded, and then a basic substance and water are added to the obtained kneaded product and further melt-kneaded to neutralize and / or neutralize and / or A method of obtaining an aqueous dispersion by performing saponification and dispersing (phase inversion) an olefin polymer in an aqueous phase, and at least one kind selected from the group consisting of an acid-modified polyolefin compound, a fatty acid, and a fatty acid ester in advance. A basic substance and water are added to the components to neutralize and / or saponify, and this is melt-kneaded with the olefin polymer, and then water is further added and melt-kneaded to obtain water of the olefin polymer. A method of performing phase inversion (dispersion) into a phase to obtain an aqueous dispersion is preferred.
In the present invention, the former method is particularly preferred because it is simple and a uniform aqueous dispersion having a small diameter of dispersed particles can be obtained.

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 polymer to the aqueous phase may be any known means.
A melt kneading means using a melt kneading device such as a kneader, a Banbury mixer, a multi-screw extruder or the like is preferable.

Specific examples of the basic substance used for the above 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;
N, N-dimethylethanolamine, triethylamine, methylamine, ethylamine, ethanolamine,
Organic amines such as cyclohexylamine and tetramethylammonium hydroxide; sodium oxide, sodium peroxide, potassium oxide, potassium peroxide, calcium oxide, strontium oxide, barium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrogenation Oxides, hydroxides and hydrides of alkali metals and alkaline earth metals such as strontium, barium hydroxide, sodium hydride, potassium hydride and calcium hydride; sodium carbonate, potassium carbonate, sodium hydrogencarbonate, hydrogencarbonate Examples thereof include weak acid salts of alkali metals and alkaline earth metals, such as potassium, calcium hydrogen carbonate, sodium acetate, potassium acetate, and calcium acetate.

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

It is preferable to add the ionomer resin and the low-molecular-weight polyolefin in the form of an aqueous dispersion to the above-mentioned aqueous dispersion from the viewpoint of simplifying the operation. The ionomer resin is known to have self-emulsifying properties, and a commercially available aqueous dispersion product can be used. On the other hand, the aqueous dispersion of the low-molecular-weight polyolefin preferably does not use a low-molecular-weight surfactant in the emulsification.

The polyfunctional isocyanate compound which is a component constituting the aqueous polyurethane resin (B) used in the present invention includes, 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-butylene glycol dipropyl ether-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, 2,6-
Aliphatic polyisocyanates such as 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, dimer 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, alicyclic polyisocyanate such as 2,6-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-4,4'- Diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofurandisocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, dichlorocarbazole diisocyanate, etc. Aromatic polyisocyanate,

Sulfur-containing aliphatic isocyanates such as thiodiethyl diisocyanate, thiopropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiopropyl diisocyanate, dicyclohexyl sulfide-4,4'-diisocyanate, diphenyl sulfide -2,4 '
-Diisocyanate, diphenyl sulfide-4,4 '
Fragrances such as diisocyanate, 3,3'4,4'-diisocyanatodibenzylthioether, bis (4-isocyanatomethylbenzene) sulfide, 4,4'-methoxybenzenethioethylene glycol-3,3'-diisocyanate Group sulfide isocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2 '
-Dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate, 4,4'-dimethyl Diphenyl disulfide-5
5′-diisocyanate, 3,3′-dimethoxydiphenyl disulfide-4,4′-diisocyanate, 4,
4'-dimethoxydiphenyldisulfide-3,3'-
Aliphatic disulfide-based isocyanates such as diisocyanate,

Diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidinesulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylmethanesulfone
2,4′-diisocyanate, 4,4′-dimethoxydiphenylsulfone-3,3′-diisocyanate, 3,
3'-dimethoxy-4,4'-diisocyanate dibenzylsulfone, 4,4'-dimethyldiphenylsulfone-3,3'-diisocyanate, 4,4'-di-ter
Aromatic sulfones such as t-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-dimethoxybenzeneethylenedisulfone-3,3'-diisocyanate, 4,4'-dichlorodiphenylsulfone-3,3'-diisocyanate System isocyanate, 4-methyl-3-
Sulfonic ester isocyanates such as isocyanatobenzenesulfonyl-4′-isocyanatophenol ester and 4-methoxy-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester;
4'-dimethylbenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-dimethoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonylanilide-4-methyl- Aromatic sulfonic amide based isocyanates such as 3'-isocyanate, thiophen-2,5-diisocyanate, thiophen-
2,5-diisocyanatomethyl, 1,4-dithiane-
2,5-diisocyanate, 1,4-dithiane-2,5
And sulfur-containing heterocyclic compounds such as diisocyanatomethyl.

Further, these alkyl-substituted, alkoxy-substituted, nitro-substituted, prepolymer-modified with polyhydric alcohol, carbodiimide-modified, urea-modified,
A modified buret, 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 in a mixture of two or more.

Among the above-mentioned compounds, the obtained resin, and the coating obtained after coating and forming the coating, yellowing resistance, heat stability, light stability, or obtaining polyfunctional isocyanate compounds. From the viewpoint of easiness, an aliphatic polyisocyanate and an alicyclic polyisocyanate compound are preferable, and among them, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,5-bisisocyanatomethylnorbornane, 2 , 6-Bisisocyanatomethylnorbornane and derivatives thereof are particularly 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 compounds: 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, tri Glycerose, diglyperol, polyethylene glycol, polypropylene glycol, Litetramethylene ether glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5.2.1 0.0 ^2,6 ] decane-dimethanol, bicyclo [4.3.0] -nonanediol, dicyclohexanediol, tricyclo [5.3.1.1] dodecanediol, bicyclo [4.3.0] nonane Methanol, tricyclo [5.3.1.1] dodecanediethanol, hydroxypropyltricyclo [5.3.1.1]
Dodecanol, spiro [3,4] octanediol,
Aliphatic polyols such as 1,1'-bicyclohexylidenediol, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl ) Pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2-hydroxyethoxy) benzene, bisphenol A-bis- (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-bis -(2-hydroxyethyl ether), aromatic polyols such as bisphenol S,

Halogenated polyols such as dibromoneopentyl glycol, polyester polyols, polyethylene glycols, polyether polyols, polythioether polyols, polyacetal polyols, polycarbonate polyols, polycaprolactone polyols, silicone polyols, furandimethanol,
Condensation reaction products of organic acids such as oxalic acid, glutamic acid, adipic acid, acetic acid, phthalic acid, isophthalic acid, salicylic acid, and pyromellitic acid with the polyol, and addition reactions of the polyol with ethylene oxide and alkylene oxides such as propylene oxide Product, addition reaction product of alkylene polyamine and alkylene oxide, 2,2
-Dimethylol lactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, 3,4-diaminobutanesulfonic acid, 3,
6-diamino-2-toluenesulfonic acid and their caprolactone modified products, 2-mercaptoethanol,
-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-mercaptoethyl Thio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (saltylate), 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 having no branched skeleton, and further, a polyester polyol, polyether polyol having a melting point (Tm) of 40 ° C. or less, It is preferable to use the polycarbonate polyol, polycaprolactone polyol, polyolefin polyol and their copolymers and mixtures in an amount of 50 to 98 parts by weight based on 100 parts by weight of the total active hydrogen compound. 50
If the amount is less than part by weight, the texture of the film obtained from the aqueous coating material tends to deteriorate, and if it exceeds 98 parts by weight, the film strength, hardness and scratch resistance tend to decrease.
These compounds may be used alone or in combination of two or more.

In order to stabilize the aqueous polyurethane resin used in the present invention as an aqueous dispersion, known materials and stabilization techniques can be used, but a carboxyl group, a sulfonyl group and an ethylene oxide group are contained in the molecule. It preferably has one or more, more preferably one or more carboxyl groups and / or sulfonyl groups.

The components 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. The introduction of these atomic groups into the molecule tends to improve the mechanical stability of the resin and the mixing stability with other components.

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 olefin-based aqueous dispersion component tend to be poor. If the acid value exceeds 30 KOHmg / g, the texture of the obtained film tends to decrease. Here, the method of measuring the acid value is disclosed in, for example, Japanese Industrial Standard JIS K5400.

The method for producing the aqueous polyurethane resin is not particularly limited, but for example, the following method may be mentioned. 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 an 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. Next, after the neutralized prepolymer is charged into an aqueous solution containing a chain extender and reacted, if the system contains an organic solvent, it is removed,
How to get. Unneutralized urethane prepolymer obtained by the above method,
A method comprising adding a neutralizing agent and pouring 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, and the mixture is reacted. 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,
Tertiary amines such as ammonia, trimethylamine, triethylamine, lithium hydroxide, potassium hydroxide,
Examples thereof include alkali metal compounds such as sodium hydroxide, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide, and quaternary ammonium compounds such as tetramethylammonium human {roxide). These compounds may be used alone or in combination of two or more. It can be used as a mixture.

The amount of the neutralizing agent used is preferably 0.5 to 0.5 equivalent to 1 equivalent of the carboxyl group and / or the sulfonyl group in the polyurethane resin having the carboxyl group and / or the sulfonyl group.
It is 3 equivalents, more preferably 0.7 to 1.5 equivalents. If it is less than the above range, the stability of the aqueous polyurethane 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 polyurethane resin include ketones such as methyl ethyl ketone and acetone, esters such as methyl acetate and ethyl acetate, and tetrahydrofuran.
It is not particularly limited as long as it is 0 ° C. or less,
These solvents can be used alone or in a mixture of two or more. The boiling point of the solvent exceeds 100 ° C.,
That is, the use of a solvent exceeding the boiling point of water makes it difficult to completely remove only the solvent from the solution after the formation of the aqueous dispersion, and the high-boiling solvent remains in the film and affects the physical properties.
When it is unavoidable to use it for the purpose of exhibiting the performance, it is preferable to use 10 parts by weight or less with respect to 100 parts by weight of the aqueous polyurethane resin.

The aqueous polyurethane resin used in the present invention can be used as a modified product by reacting with other components such as other monomers and resin components. Further, in the aqueous polyurethane resin obtained in the present invention, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, methacrylamide, styrene, acrylonitrile, butadiene, vinyl acetate,
It can also be used as a composite obtained by polymerizing at least one or more monomers such as ethylene, propylene, itaconic acid and maleic acid.

The water-based coating material of the present invention comprises, as main components, an olefin-based aqueous dispersion (component A) and an aqueous urethane resin (component B). A method in which the component (A) and the component (B) are separately produced by a production method, and then mixed using a suitable stirrer, and the aqueous urethane resin (B) and / or a precursor thereof containing or not containing an isocyanate terminal group. Examples of the method include adding the urethane resin as a melt dispersion and kneading the olefin resin, inverting the phase, and obtaining an aqueous dispersion, but the method is not particularly limited.

The ratio of the above components (A) and (B) is not particularly limited as long as both resins are mixed, but the ratio in terms of the resin solid weight is 99/1 to 50/50. This is more preferable because it can achieve both the texture, hardness, and scratch resistance, and can supply a coating material at low cost. component
(A) As the ratio increases, the texture of the obtained film tends to improve. On the other hand, as the component (B) ratio increases, the hardness and abrasion resistance of the obtained film tend to improve.

The olefin-based aqueous dispersion (component A) and the aqueous urethane resin (component B) of the present invention, when formed into a film by themselves, have a film property of a load of 5 kg, a distance between chucks of 20 mm, and a test piece. Size ゛ 40mm × 10mm, 10 between marked lines
mm, pulling speed 50 mm / min, temperature 23 ° C, humidity 5
When measured under the condition of 0%, the olefin-based aqueous dispersion (component A) elongation at break: 300 to 1300% Breaking strength: 3 to 30 MPa 100% modulus: 0.5 to 6.5 MPa

Aqueous urethane resin (component B) elongation at break: 500 to 1500%, preferably 500 to 1500%
1000%, breaking strength: 10 to 50 MPa, preferably 15 to 40 M
Pa, 100% modulus: 0.5 to 3.5 MPa, preferably 0.5 to 3.0 MPa

The film properties of the film formed from the components (A) and (B) under the same conditions as described above were as follows: elongation at break: 400 to 1000%, breaking strength: 5 to 30 MPa, 100% modulus: 0.5. By satisfying any of the performances of 5 MPa to 5 MPa, both texture and scratch resistance are achieved. Generally, a value of 100% modulus affects the texture of the coating.

The film obtained from the water-based coating material of the present invention is characterized by being excellent in scratch resistance (scratch resistance) while maintaining a feeling.
A coin scratch test in which the side surface of a 100-yen coin is rubbed 10 times against the film surface is mentioned. When the film surface state after the test is visually observed, it is preferable that the surface is not damaged at all. When the surface of the film is damaged, it can be determined that the scratch resistance is insufficient.

Further, the film obtained from the water-based coating material of the present invention is characterized by having excellent abrasion resistance (durability) while maintaining the texture.
The Taber abrasion test stipulated in K7204 is mentioned, and the abrasion loss after measuring the abrasion wheel 3000 times is 0 to 50 m.
g is preferable. If the wear reduction exceeds the above range, it can be determined that the wear resistance is insufficient.

The solid content concentration in the water-based coating material of the present invention is not particularly limited. However, the solid content concentration may be easily maintained in the range of viscosity described below, the drying time may be shortened, and the difference in easy application of thick film may be reduced. From the viewpoint of workability, the content is 35 to 70% by weight, and more preferably 40 to 55% 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.

Further, the solution viscosity of the coating material is 5,000 to 50,000 when measured at 25 ° C. with a BM viscometer.
It is preferably in the range of mPa · s, more preferably 60
It is 00 to 30000 mPa · s. As described above, as the distance from the above range increases, the workability at the time of applying the substrate 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 nylon and polypropylene nonwoven fabric, leather, Synthetic leather, synthetic resin,
Paper, film and the like can be mentioned, but in addition to this, for example, a coating material can be applied to a specific mold, and after drying, the obtained film can be used again for applications in which the film can be detached from the mold.

In particular, in the present invention, industrial nets, canvases used at construction sites, tents such as tent warehouses and bi-tents, hoods such as trucks and jars, gloves, flags, clothing, footwear, furniture, bags,
It is suitably used for a material such as a press-removable sheet,
The above-mentioned product having the film formed from the aqueous coating material of the present invention is excellent in its texture and surface protection.

The water-based coating material used in the present invention may be, if necessary, other than the above, for example, a water-soluble amino resin such as a water-soluble melamine resin or a water-soluble benzoguanamine resin, or a water-soluble epoxy resin in order to improve the film performance. And reactive resins and compounds such as water-soluble hydrazide compounds and water-soluble carbodiimides. For the purpose of improving the stability of the aqueous dispersion and adjusting the viscosity, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyethylene oxide, polyacrylamide, polyacrylic acid, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, poly (N-vinylacetamide) Organic thickeners such as polyurethane-based thickeners, and inorganic thickeners such as silicon dioxide, activated clay, and bentonite can be used.

Further, in order to improve the stability of the aqueous dispersion, a surfactant can be used. 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 polyacrylic Acid salt, gluconate, potassium oleate, olefin / maleic acid copolymer, sodium carboxymethylcellulose, sodium oleate, potassium stearate, sodium stearate, ammonium stearate, triethanolamine stearate, potassium tallowate, tallow acid Sodium and metal soaps (Zn, Al, Na,
Anionic surfactants such as K salt); 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 amine, polyoxyethylene (hardened) castor oil, polyoxyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block copolymer, hydroxyethyl cellulose Nonionic surfactants such as, polyvinyl alcohol, polyvinylpyrrolidone, and methylcellulose; Le ammonium chloride, trimethyl alkyl ammonium bromide, alkylpyridinium chlorides, and amphoteric surfactants such as casein; water-soluble polyvalent metal salts. These surfactants can be used alone or in combination of two or more.

Further, the water-based coating material used in the present invention may use a non-halogen flame retardant for imparting flame retardancy. For example, antimony-based flame retardants such as antimony oxide and inorganic compound flame retardants such as magnesium hydroxide, aluminum hydroxide and zinc borate, and tricresyl phosphate, diphenylcresyl phosphate, trioctyl phosphate, tributyl phosphate, triphenyl phosphate , Di- (polyoxyethylene)
-Hydroxymethylphosphonate, diethylphenylphosphonate, dimethylphenylphosphonate, phenylphosphonic acid, ammonium polyphosphate, guanidine phosphate, phosphoric acid esters such as red phosphorus, and phosphorus compounds. These flame retardants can be used alone or in combination of two or more.

In addition to the above compounds, if necessary, rust inhibitors, fungicides, ultraviolet absorbers, heat stabilizers, weather stabilizers, foaming agents, defoamers, dyes, auxiliary binders, leveling agents, thixotropes Imparting agent, defoaming agent, anti-settling agent, ultraviolet absorber, antioxidant, antistatic agent, thickener, pigment (for example, titanium white, red phthalocyanine, phthalocyanine, carbon black, permanent yellow, etc.), filler (for example, carbonic acid) Additives such as calcium, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, etc.) can be added as long as the object of the present invention is not impaired. .

All of the above-mentioned additives are added in the raw resin production process, in the resin aqueous process, and further in the aqueous solution, irrespective of the aqueous olefin resin dispersion (A) or the aqueous polyurethane resin (B). The agents and the additives which have been previously made water-soluble can be added by a method such as addition after the production of the aqueous resin, addition in the parent process of (A) and (B), and the additives are dispersed in the 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, but includes, for example, dip coating, blade coater, air knife coater, rod coater, hydro bar coater, transfer roll coater, reverse coater, and the like. Coater, gravure coater, die coater, curtain coater, spray coater, flow coater, roll coater, brush coating, etc.,
It can be applied to a part or the entire surface of the substrate.

The drying temperature of the film formed from the water-based coating material according to the present invention may be room temperature.
It can also be heated at 0 ° C. for 5 to 600 seconds.

A method of laminating a film formed from the water-based 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 multi-layer coating with another material. Is also possible. Furthermore, it is also possible to apply the present coating material to the substrate and use it as a texture and anti-slip effect imparting material.

[0092]

The present invention will be described below with reference to examples.
The present invention is not limited at all by the examples. (Production Example) Ethylene-Polar Monomer Copolymer and Fatty Acid Compound
Producing ethylene Ranaru aqueous dispersion - vinyl acetate copolymer (MDP manufactured Evaflex 270) 100 parts by weight, product of Hoechst montanic acid (Hoechst S: carbon atoms 28-32, acid value 150mgKO
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 Iron Works) at a speed of 3000 g / hour. A 13% aqueous solution of potassium hydroxide was continuously supplied at a rate of 300 g / hour (10% of the whole) from the supply port provided, and was continuously extruded at a heating temperature of 160 ° C.
The extruded resin mixture was cooled to 90 ° C. with a jacketed static mixer installed at the extruder port,
It 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 Microtrack.

From olefin elastomer resin and fatty acid compound
Production of Water Dispersion As an olefin elastomer, an ethylene / 1-butene copolymer (trade name: Tuffmer A20, manufactured by Mitsui Chemicals, Inc.)
085) 100 parts by weight, 10 parts by weight of montanic acid, and 3 parts by weight of potassium oleate are mixed, and a twin screw extruder (PCM-30, manufactured by Ikegai Iron Works, L / D = 40)
And supplied to the extruder at a speed of 3000 g / hour from a hopper of 150 g / hour (ethylene ·
5 to the total amount of 1-butene copolymer, maleic anhydride-modified polyethylene wax and potassium oleate
%) And continuously extruded at a heating temperature of 180 ° C.

Next, the extruded mixture was mixed with a static mixer with a jacket installed at the mouth of the extruder for 90 minutes.
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.

Production of aqueous polyurethane resin 3000 equipped with thermometer, stirrer, nitrogen inlet tube, cooling tube
399.5 g of PTG 2000SN (manufactured by Hodogaya Chemical Industry Co., Ltd., polytetramethylene ether glycol, molecular weight 2000) 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
Then, the mixture was stirred with 275.7 g, and 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 polyurethane resin (B-1).

Production of Water-based Coating Material After mixing and stirring the above-mentioned water-dispersed polyolefin, aqueous urethane resin and other components in the mixing ratio shown in Table 1, ADECANOL UH462 (manufactured by Asahi Denka, polyurethane-based And a 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 is applied to a base fabric composed of polyester fibers by an applicator so that the film thickness after drying becomes 120 μm, and then at 120 ° C. After drying for 3 minutes, a film-formed product was produced. The evaluation contents, test conditions and results of the above water-based coating materials are shown below.

Abrasion resistance (durability) evaluation method: The sample was subjected to a Taber abrasion tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.)
Using S-17, abrasion was performed under the conditions of a load of 500 g and a rotation number of 3000, the weight of the base fabric before and after the test was measured, and the weight of the shaved film was calculated. It was determined that the smaller the weight, the better the scratch resistance.

Evaluation method for scratch resistance (scratch resistance):
The sample was rubbed 10 times with the side of a 100 yen coin, and the degree of damage was visually determined. ：: No damage is observed. Δ: Although slightly damaged, it did not reach the base cloth. X: The damage reaches the base cloth.

Texture Evaluation Method The base fabric coated sample was cut into a circle having a diameter of 11 cm,
One end was supported horizontally, and the angle at which the base fabric sample was dropped was measured with reference to the horizontal plane of the fulcrum.

[0101]

[Table 1]

[0102]

The water-based coating material of the present invention is an aqueous water-based coating material comprising an aqueous dispersion of a polymer which does not generate a harmful halogen compound when incinerated, and has both physical properties such as scratch resistance, abrasion resistance and texture. It is possible to provide an excellent film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09D 153/02 C09D 153/02 175/04 175/04 D06M 15/227 D06M 15/227 15/564 15 / 564 F-term (reference) 4F100 AJ01B AK01B AK03A AK04A AK04J AK12A AK28A AK41 AK51A AK65 AK68A AL01A AL02A AL05A AL06A AL09A AS00B BA02 DG10B DG12B GB32 GB72 GB87 JA06A JB05A JK02A JK07A JK08A JK09 JK16 JL00 JM01A YY00A 4J038 CA041 CA042 CB051 CB052 CB061 CB062 CB101 CB102 CC041 CC042 CF031 CF032 CG141 CG142 CJ011 CJ012 DG051 DG052 DG081 DG082 DG091 DG092 DG111 DG112 DG121 DG122 DG131 DG132 GA06 GA13 HA176 JA20 JA21 JA63 JB01 JB03 JB04 JB05 JB07 PCB JA07 PCB CA50

Claims (19)

[Claims] A water-based coating material which can be coated on a substrate to form a film, comprising an aqueous olefin resin dispersion (component A) and an aqueous polyurethane resin (component B). Construction materials. 2. Component (A) / component converted to resin solid weight
The aqueous coating material according to claim 1, wherein (B) the ratio is 99/1 to 50/50. 3. The resin solid content concentration is 35 to 70% by weight, and the solution viscosity is 5000 to 50,000 mPa · s.
Or the aqueous coating material according to 2. 4. Component (A) in the aqueous coating material is ethylene-
The aqueous coating material according to any one of claims 1 to 3, wherein the coating material is any resin selected from a polar monomer copolymer and / or an olefin-based elastomer. 5. The aqueous coating according to claim 4, wherein the ethylene-polar monomer copolymer in the component (A) in the aqueous coating material is an ethylene-vinyl acetate copolymer. Wood. 6. The water-based coating material according to claim 5, wherein the ratio of the phenyl acetate component in the ethylene-vinyl acetate copolymer according to claim 5 is 10 to 50% by weight. 7. The aqueous solution according to claim 4, wherein the olefin-based elastomer in the component (A) in the aqueous coating material is a styrene-conjugated diene block copolymer or a hydrogenated product thereof. Coating materials. 8. The component (A) in the aqueous coating material, when formed into a film by itself, has a film property of: elongation at break: 300 to 1300%, breaking strength: 3 to 30 MPa, 100% modulus: 0.1%. The aqueous coating material according to any one of claims 1 to 7, wherein the coating material has any physical properties of 5 to 6.5 MPa. 9. The component (B) in the water-based coating material, when formed into a film by itself, has the following film properties: elongation at break: 500-1500%, breaking strength: 10-50 MPa, 100% modulus: 0.5- The aqueous coating material according to any one of claims 1 to 8, wherein the coating material has any physical properties of 3.5 MPa. 10. The component (A) and the component (B) in the aqueous coating material.
The film formed from the above has an elongation at break: 400 to 1000%, a breaking strength: 5 to 30 MPa, a modulus of 100%, and a physical property of 0.5 to 5 MPa. An aqueous coating material as described in Crab. 11. The method according to claim 11, wherein the substrate is made of natural fiber, synthetic fiber, leather,
The aqueous coating material according to any one of claims 1 to 10, wherein the coating material is at least one selected from the group consisting of synthetic leather, synthetic resin, and paper. 12. A coating formed from the aqueous coating material according to claim 1. 13. A method for applying a water-based coating material according to any one of claims 1 to 11 to a substrate, followed by drying to form a film. 14. An industrial net having a coating formed from the aqueous coating material according to claim 1. Description: 15. A canvas having a film formed from the aqueous coating material according to any one of claims 1 to 11. 16. A hood having a film formed from the aqueous coating material according to claim 1. Description: A glove having a film formed from the aqueous coating material according to any one of claims 1 to 11. 18. A tent having a coating formed from the aqueous coating material according to claim 1. Description: 19. A flag having a coating formed from the aqueous coating material according to claim 1. Description: