JP2003183563A - Aqueous flame-retardant coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous coating material comprises an aqueous dispersion of a polymer which generate no harmful substance when combustion and has no environmental hormone problem, to provide the coating material forming a film and a laminate which are excellent in flame retardance, scratch resistance, flexibility, non-tacking properties, water resistance, cold resistance, odorless properties or coating properties. <P>SOLUTION: The aqueous coating material is used, which comprises an ethylene-polar monomer copolymer, or an olefin resin of an olefin elastomer, and a polyester containing phosphorus in a polymer chain. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant water-based coating material containing an olefin resin (A) and a polyester (B) containing phosphorus in a resin skeleton as main components. More specifically, it is possible to provide a film having excellent properties such as flame retardancy, scratch resistance, flexibility, non-tackiness, water resistance, cold resistance, odorlessness, and light weight, and good coatability. Flame-retardant water-based coating materials, laminates having the film, and nets, meshes, sheets used at construction sites, outdoor tents such as tent warehouses and pipe tents, and flammability. The present invention relates to a textile product that requires.

Further, the present invention is an aqueous dispersion which uses the resin and the compound which do not generate harmful halogen compounds upon incineration while satisfying the above-mentioned performance, and which does not use a solvent which causes environmental pollution such as air pollution. A flame-retardant water-based coating material comprising

[0003]

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

Textile products (in a broad sense) polyester or nylon fibers have been used for curing nets, meshes, sheets, etc. used in construction sites, but they have flame retardancy, waterproofness, weather resistance, durability, etc. These fibers were usually coated with a polyvinyl chloride sol for application.

However, due to the recent increase in environmental problems, there is a problem that toxic gases such as dioxins are generated when these curing nets are incinerated, and there is a problem of environmental hormones of plasticizers such as DOP. , The demand for substitution with other products of polyvinyl chloride sol is increasing.

[0006] Further, a fiber product having a high specific gravity and treated with a polyvinyl chloride sol has a problem that it is difficult to handle since it is heavy, and from this point also, there is an increasing demand for substitution.

Although polyvinyl chloride itself has a certain degree of flame retardancy, it is often used with a flame retardant added. Conventionally, this flame retardant is also often a compound containing halogen such as bromine or chlorine, and has a problem of generating toxic gas such as dioxin. In order to solve such problems, phosphorus compounds such as polyphosphates and phosphoric acid esters, and inorganic compounds such as magnesium hydroxide are used. However, if they are added in large amounts, the scratch resistance of the coating film However, there is a problem that the performance such as flexibility is deteriorated, and the flame retardancy is insufficient when added in a small amount, and a satisfactory product has not been obtained.

On the other hand, as a medium of the coating agent, there is a strong demand that an aqueous medium should be adopted in order to prevent waste solvent, prevent air pollution, and maintain a good working environment.

Under the circumstances as described above, as an aqueous coating material, an aqueous dispersion of polyolefin is desired, which does not produce harmful substances when burning textiles, has no problem of environmental hormones, and has a low specific gravity. Was there. However, the film formed from conventional vinyl chloride sol coating has flame retardancy, scratch resistance, flexibility, non-tackiness, water resistance, cold resistance,
A water-based coating material that simultaneously satisfies odorlessness and coatability has not been obtained.

Therefore, it is possible to form a film excellent in flame retardance, abrasion resistance, flexibility, non-tackiness, water resistance, cold resistance, odorlessness, light weight, etc., and produce a harmful substance when incinerated. There is a demand for the appearance of an aqueous coating material that does not contain an environmental hormone and is composed of an aqueous dispersion of a resin or a compound, and has good coatability.

[0011]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and includes flame retardancy, scratch resistance, flexibility, non-tackiness, water resistance,
A coating that is capable of forming a film with excellent cold resistance, odorlessness, lightness, etc., does not produce harmful substances when incinerated, and is an aqueous dispersion of a resin or compound that does not cause environmental hormone problems. The purpose is to provide a water-based coating material having good properties.

[0012]

Means for Solving the Problems That is, the present invention is specified by the following items [1] to [12]. [1] A flame-retardant water-based coating material comprising an olefin resin (A) and a polyester (B) containing phosphorus in the resin skeleton (hereinafter referred to as “phosphorus-containing polyester”) . [2] The flame-retardant water-based coating material according to [1], which contains 1 to 200 parts by weight of the phosphorus-containing polyester (B) with respect to 100 parts by weight of the olefin resin (A). [3] The olefin resin (A) is an ethylene-polar monomer copolymer (A-1) and / or an olefin elastomer (A-2), [1] or [2] Flame-retardant water-based coating material described in. [4] The olefin resin (A) is an ethylene-vinyl acetate copolymer, [1] to [3]
The flame-retardant water-based coating material according to any one of 1. [5] The main monomer constituting the phosphorus-containing polyester (B) is a phosphorus compound (C) having an aromatic dicarboxylic acid component, a diol component, and an acid component and / or an alcohol component. , [1] to [4]
The flame-retardant water-based coating material according to any one of 1. [6] The phosphorus compound (C) having the acid component and / or the alcohol component is dihydro-3-[(6-oxide-6H-dibenz [c, e] [1,2] oxaphosphorin-6- Il) methyl] -2,5-furandion (C-
1) or a divalent carboxylic acid in which a carboxylic acid anhydride thereof is opened, or an alkyl ester thereof, and / or 6- (2,
5-dihydroxyphenyl) -6H-dibenz [c, e]
[1,2] oxaphosphorin-6-oxide (C-
2) The flame-retardant water-based coating material according to any one of [1] to [5]. [7] An acid-modified polyolefin compound (D) and / or a fatty acid compound (E) is contained in an amount of 0.5 to 30 parts by weight with respect to 100 parts by weight of the olefin resin (A), [1 ] The flame-retardant water-based coating material according to any of [6]. [8] The urethane resin (F) is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the olefin resin (A), according to any one of [1] to [7]. Flame-retardant water-based coating material. [9] 1 to 100 parts by weight of a polyphosphate-based flame retardant (G) and / or a phosphate ester-based flame retardant (H) is contained with respect to 100 parts by weight of the phosphorus-containing polyester (B). The flame-retardant water-based coating material according to any one of [1] to [8]. [10] A film formed from the flame-retardant water-based coating material according to any one of [1] to [9] has an elongation at break: 200 to 1500%, a breaking strength: 3 to 50 MPa, a 100% modulus: 0. [1] to [9] characterized by having a tensile physical property of 8 to 10 MPa.
The flame-retardant water-based coating material according to any one of 1. [11] At least the flame-retardant water-based coating material according to any one of [1] to [10] is selected from the group consisting of plastic, metal, paper, wood, fiber, glass, rubber, ceramic, and concrete. A laminate obtained by applying a coating on one type of substrate, drying, and forming a flame-retardant film. [12] A fiber product having a flame-retardant coating formed from the flame-retardant water-based coating material according to any one of [1] to [10].

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant water-based coating material according to the present invention will be specifically described below.

[Word "water-based"] In the present invention, the "water-based" means a state in which a resin is dispersed in water and / or a part thereof is dissolved, and includes "water-based dispersion". .

The form of the olefin resin, phosphorus-containing polyester and urethane resin contained in the water-based coating material of the present invention is not particularly limited as long as it is dissolved or dispersed in the water-based medium. However, the dispersed state is preferable in that a high solid content concentration is possible.

The olefin resin (A) used in the present invention is not particularly limited, but ethylene-
It is preferably any resin selected from the polar monomer copolymer (A-1) and / or the olefin elastomer (A-2).

Ethylene-polar monomer copolymer (A-
As a preferable embodiment of 1), ethylene- (meth) acrylic acid acrylate copolymer, ethylene- (meth) acrylic acid methyl copolymer, ethylene- (meth) acrylic acid propyl copolymer, ethylene- (meth) acrylic Butyl acid acid copolymer, ethylene- (meth) acrylic acid hexyl copolymer, ethylene- (meth) acrylic acid-2-hydroxyethyl copolymer, ethylene- (meth) acrylic acid-2-hydroxypropyl copolymer, Ethylene- (meth) acrylic acid ester copolymers such as ethylene- (meth) glycidyl acrylate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene-maleic acid copolymers, ethylene-
Fumaric acid copolymer, ethylene-itaconic acid copolymer, ethylene- (iso) crotonic acid copolymer and other ethylene-unsaturated acid copolymers, and the side chains of these ethylene-unsaturated acid copolymers At least a part of the carboxyl group,
Ethylenic ionomer neutralized with a monovalent metal cation, organic amine, ammonia, etc., and further ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl butyrate copolymer, ethylene -Ethylene-vinyl ester copolymers such as vinyl stearate can be mentioned, but ethylene-vinyl acetate copolymers are particularly preferable.

The ethylene-vinyl acetate copolymer has a vinyl acetate content of 10 to 50% by weight, particularly 15% from the viewpoint of film flexibility, water resistance, cold resistance, non-tackiness, odorlessness and the like.
~ 45% by weight is preferred, and the scratch resistance of the film,
MFR according to ASTM D 1238 from the aspect of film formation
(190 ° C.) is preferably 0.05 to 1000 g / 10 min, particularly 0.1 to 500 g / 10 mi.
Those with n are preferred.

As the olefinic elastomer (A-2) used in the present invention, a low crystalline or amorphous olefinic copolymer can be used, and if desired, it may contain a diene. The crystallinity measured by X-ray diffractometry is preferably 50% or less, particularly 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 is an α-olefin having 2 to 20 carbon atoms, preferably an α-olefin having 2 to 10 carbon atoms, and more preferably an α-olefin having 2 to 8 carbon atoms. Specific examples include 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.

As the above-mentioned diene, specifically,
Isoprene, butadiene, dicyclopentadiene, 1,4-
Pentadiene, 2-methyl-1,4-pentadiene, 1,4-hexadiene, divinylbenzene, methylidene norbornene, ethylidene norbornene and the like can be mentioned. These dienes can be used alone or in combination of two or more.

The preferred olefin elastomer (A-2) in the present invention is a rubbery copolymer of ethylene and α-olefin and / or 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 an α-olefin other than ethylene is contained. The amount is usually 5 to 75 mol%, 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
It is preferably mol%, in which case the constitutional unit content derived from α-olefins other than ethylene is 4.5
It is preferably ˜74.5 mol%.

The composition of this rubbery copolymer is ¹³ C.
-Measured by NMR method.

Specific examples of the olefin copolymer include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, Propylene-ethylene copolymer, propylene / 1-butene copolymer, propylene / 1-butene / ethylene 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 Examples thereof include copolymers, 1-butene / propylene copolymers, 1-butene / ethylene copolymers and the like.

The intrinsic viscosity [η] measured in a 135 ° C. decalin solution of an olefin copolymer 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.

As the block constitution of the styrene-conjugated diene block copolymer, a styrene-conjugated diene diblock copolymer, a styrene-conjugated diene-styrene triblock copolymer, or a block number of more than that is used. The block copolymer which has is mentioned.

Examples of such styrene-conjugated diene block copolymers include, for example, US Patent 3,265,265.
Examples thereof include block copolymers produced by the method described in Japanese Patent No. 765, JP-A-61-292743, and the like.

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

The hydrogenated product of the styrene-conjugated diene block copolymer is, for example, Japanese Patent Publication No.
Examples include hydrogenated products produced by the methods described in JP-A-20504, JP-B-48-3555 and the like.

A hydrogenated product of a styrene-conjugated diene block copolymer, for example, a hydrogenated product of a styrene-butadiene block copolymer is specifically described by Kraton G-1.
652 and 1657 (both manufactured by Shell Chemical Co., Ltd.) are commercially available. Hydrogenated products of styrene-isoprene block copolymers are specifically Septon 2
002 and 2007 (both manufactured by Kuraray Co., Ltd.) are commercially available.

The content of the structural unit derived from styrene in the above-mentioned styrene-conjugated diene block copolymer or its water additive is in terms of scratch resistance, flexibility and the like of the film obtained from the water-based coating material. To 10 to 70% by weight, more preferably 20 to 50% by weight
Is.

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

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

The acid-modified polyolefin compound (D) used in the present invention is an olefin resin and is a group of a salt of a carboxylic acid bonded to a polymer chain of a polyolefin (partially neutralized product or partially saponified product). Is a carboxylic acid group),
As an OO-group, 0.05 to 5 mmol, preferably 0.1.
It is an olefin resin that is contained at a concentration of 1 to 4 mmol.

The acid-modified polyolefin compound (D)
Is a monomer having a carboxylic acid group which is neutralized or not neutralized, and / or a saponified or non-saponified carboxylic acid, for example, to a polyolefin such as α-olefin. It can be obtained by graft-copolymerizing a monomer having an ester.

As the polyolefin before acid modification used in the preparation of the acid-modified polyolefin compound (D),
The number average molecular weight (Mn) measured by GPC is 500.
To 10,000, preferably 700 to 5,000, more preferably 1,000 to 3,000, α
-Olefin homopolymers or copolymers of two or more α-olefins are preferred.

The α-olefin constituting the above-mentioned homocopolymer or 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 etc. can be mentioned.

Among these homopolymers and copolymers of α-olefin, ethylene homopolymer and propylene homopolymer are particularly preferable.

The above-mentioned graft monomers for grafting to the polyolefin include the above-mentioned monomer having a neutralized or non-neutralized carboxylic acid group and a saponified or non-saponified carboxylic acid group. It is a monomer having an acid ester group, and examples thereof include an ethylenically unsaturated carboxylic acid, an anhydride thereof or an ester thereof. Specific examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid and isocrotonic acid.

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

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

As a method of grafting the above-mentioned polyolefin with a graft monomer, a conventionally known graft copolymerization method can be adopted. The acid-modified polyolefin compound is 0.5 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the olefin resin.
More preferably, it is used in a proportion of 5 to 15 parts by weight.
When the fatty acid compound described below 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 proportion.

The fatty acid compound (E) 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, and The water-based coating material may contain a fatty acid and / or a fatty acid ester in addition to the fatty acid salt.

In the present invention, the fatty acid compound (E) has usually 25 to 60 carbon atoms, preferably 25 to 40 carbon atoms. In the present invention, the fatty acid is preferably montanic acid. The fatty acid salts 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 salts, iron salts, amine salts and the like can be mentioned, and more preferable is an alkali metal salt of montanic acid.

The alcohol residue constituting the ester preferably has 2 to 30 carbon atoms, and particularly preferably 6 to 20 carbon atoms. The residue may be linear or branched. It may be a mixture having different carbon numbers. Specific examples of the alcohol residue include residues of higher alcohols such as cetyl alcohol, stearyl alcohol and oleyl alcohol. The ester wax of montanic acid and montan wax are particularly preferable. 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 (E) is used, 0.5 to 30 parts by weight, preferably 2 to 30 parts by weight of the fatty acid compound is used with respect to 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 (D) and the fatty acid compound (E) can be used alone or in combination. When used in combination, the weight ratio is preferably (A) / [(D) + (E)] = 100 / 0.5 to 30.

The method for preparing the olefin resin (A) in the 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 (D) and / or a fatty acid compound (E) are melt-kneaded, and then the resulting kneaded product is mixed with a base. Neutralizing and / or saponifying and dispersing the olefinic polymer in the aqueous phase (phase inversion) by adding a reactive substance and water and further melt-kneading
And a basic substance and water are 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 it. Is melted and kneaded with the olefin polymer, and then water is further added and melt-kneaded to perform phase inversion (dispersion) of the olefin polymer into an aqueous phase to obtain an aqueous dispersion. preferable.

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

The preferred ratio of neutralization or saponification in the above 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 inversion of the olefin resin into the aqueous phase may be any known means, but melt-kneading means using a melt-kneading device such as a kneader, a Banbury mixer or a multi-screw extruder. Is preferred.

Specific examples of the basic substance used for the above neutralization and saponification include metals such as lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminum, zinc and iron, hydroxylamine and hydroxide. Inorganic amines such as ammonium and hydrazine, ammonia, N, N-dimethylethanolamine,
Organic amines such as triethylamine, methylamine, ethylamine, triethanolamine, ethanolamine, cyclohexylamine, tetramethylammonium hydroxide, sodium oxide, sodium peroxide, potassium oxide, potassium peroxide, calcium oxide, strontium oxide, barium oxide, Lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydride, barium hydroxide, magnesium hydroxide,
Metal oxides, hydroxides, hydrides such as aluminum hydroxide, zinc hydroxide, iron hydroxide, sodium hydride, potassium hydride, calcium hydride; sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate Examples thereof include weak acid salts of metals such as calcium hydrogen carbonate, sodium acetate, potassium acetate and calcium acetate.

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

The phosphorus-containing polyester (B) used in the present invention is not particularly limited, but is mainly a polycondensation product of an acid component monomer and an alcohol component monomer, and the acid component and / or Alternatively, it can be obtained by using a phosphorus compound (C) containing an alcohol component as a monomer. As the phosphorus-free acid component, for example, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, trimellitic acid, trimesic acid, pyromellitic acid, benzoic acid,
p-oxybenzoic acid, p- (hydroxyethoxy) benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, suberic acid, brassic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, hexahydroorthophthalic acid, tricyclodecanedicarboxylic acid, tetrahydroterephthalic acid, tetrahydroorthophthalic acid, etc., or methyl ester of these acids, or anhydrides Etc. can also be used. Among these, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid naphthalene dicarboxylic acid are preferably used, and terephthalic acid and dimethyl terephthalate are particularly preferable. These acid components can be used alone or in combination. Examples of alcohol components containing no phosphorus include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1 , 4
-Butanediol, 1,2-butanediol, 1,5-
Pentanediol, 2-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 1,8-octanediol, 1,9 -Nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, Bisphenol-ethylene oxide adduct, bisphenol propylene oxide adduct, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol,
1,3-cyclohexanedimethanol, 1,3-cyclohexanediol, hydrogenated bisphenol A, spiroglycol, tricyclodecanediol, tricyclodecanedimethanol, resorcinol and 1,3-bis (2-
(Hydroxyethoxy) benzene and the like are used, and among them, ethylene glycol and diethylene glycol are preferably used, and these alcohol components can be used alone or in combination of two or more.

Further, the phosphorus compound (C) containing an acid and / or alcohol component is not particularly limited, but the following general formulas (1) to (5) ([Chemical formula 1] to
Examples thereof include phosphorus compounds represented by [Chemical formula 5].

[0056]

[Chemical 1]

[0057]

[Chemical 2]

[0058]

[Chemical 3]

[0059]

[Chemical 4]

[0060]

[Chemical 5] [In the general formulas (1) to (5), R ¹ and R ⁶ are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, and a carbon atom. Number 6 to 1
4 aryl group, or an arylalkyl group having 1 to 4 carbon atoms and substituted with an alkylene group, which may be the same or different, and R ¹ and R ⁶ together form a ring with the bonding phosphorus atom P. May be. R ² is an aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms or an aryl group having 6 to 14 carbon atoms, an alkylene group-substituted arylalkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom or carbon number The alkyl group having 1 to 12 and R ⁴ and R ⁵ each represent an aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms. m represents an integer of 0 to 4. ] In particular, dihydro-3-[(6-oxide-6H-dibenz [c, e] [1,2] oxaphosphorin-6-yl)
Methyl] -2,5-furandion (C-1) [Chemical formula 6]
And 6- (2,5-dihydroxyphenyl) -6H-dibenz [c, e] [1,2] oxaphosphorin-6-oxide (C-2) [Chemical formula 7] are preferred.

[0061]

[Chemical 6] [(C-1), all or part of the carboxylic acid anhydride may be ring-opened to form a divalent carboxylic acid or an alkyl ester having 1 to 6 carbon atoms. ]

[0062]

[Chemical 7] Furthermore, the ratio of the olefin resin (A) and the phosphorus-containing polyester (B) is not particularly limited, but in terms of flame retardancy, flexibility, and scratch resistance of the film, a value converted into resin solid weight, The range of 100/1 to 200 is preferable, and 100
The range of / 10 to 100 is more preferable.

Urethane resin (F) used in the present invention
The component constituting the polyfunctional isocyanate compound, 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,
Aliphatic polyisocyanates such as 2,6-di (isocyanatomethyl) furan,

Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, 4,4'-dicyclohexylmethane-diisocyanate, cyclohexanediisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethanediisocyanate, 2,2-dimethyldicyclohexylmethanediisocyanate, bis (4-isocyanato) -N-butylidene)
Pentaerythritol, diisocyanate 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, tetrahydronaphthylenediisocyanate, hexahydrobenzenediisocyanate, 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, dibenzofurandiocyanate, carbazole diisocyanate, ethylcarbazole 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'-diisocyanate, 3,3'4,4'-diisocyanatodibenzyl thioether, bis (4-isocyanatomethylbenzene) sulfide, Aromatic sulfide-based isocyanate such as 4,4′-methoxybenzenethioethylene glycol-3,3′-diisocyanate,

Diphenyldisulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'- Dimethyldiphenyl disulfide-6
6'-diisocyanate, 4,4'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,
3'-dimethoxydiphenyldisulfide-4,4'-
Aliphatic disulfide 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'-diisocyanate dibenzyl sulfone, 4,4'-dimethyldiphenyl sulfone-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 Type isocyanate,

4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester, 4
-Methoxy-3-isocyanatobenzenesulfonyl-
Sulfonic acid ester-based isocyanate such as 4'-isocyanatophenol ester,

4,4'-Dimethylbenzenesulfonyl-
Ethylenediamine-4,4'-diisocyanate, 4,
4'-dimethoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonylanilide-4-methyl-
Aromatic sulfonic acid amide type isocyanate such as 3′-isocyanate,

Thiophene-2,5-diisocyanate,
Thiophene-2,5-diisocyanatomethyl, 1,4-
Examples thereof include sulfur-containing heterocyclic compounds such as dithian-2,5-diisocyanate and 1,4-dithian-2,5-diisocyanatomethyl.

Further, these alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer modified products with polyhydric alcohols, carbodiimide modified products, urea modified products,
A modified burette, a dimerized or trimerized reaction product and the like can be used, but a polyfunctional isocyanate compound other than the above compounds may be used. Further, these polyfunctional isocyanate compounds can be used alone or in a mixture of two or more kinds.

Among the above compounds, the obtained resin, and the yellowing resistance, heat stability, and light stability of the film formed by coating the resin, or obtaining a polyfunctional isocyanate compound are available. From the standpoint of easiness, aliphatic polyisocyanates and alicyclic polyisocyanate compounds are preferable, and among them, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,5-bisisocyanatomethylnorbornane, 2 Particularly preferred is 6,6-bisisocyanatomethylnorbornane and derivatives thereof, and hexamethylene diisocyanate is 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, tri Glycerose, diglycerol, polyethylene glycol, polypropylene glycol, Litetramethylene ether glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, 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] nonanedi 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, and 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-
Aromatic polyols such as bis- (2-hydroxyethyl ether) and bisphenol S,

A halogenated polyol such as dibromoneopentyl glycol,

Polyester polyol, polyethylene glycol, polyether polyol, polythioether polyol, polyacetal polyol, polycarbonate polyol, polycaprolactone polyol, silicone polyol, flange methanol,

Furthermore, a condensation reaction product of an organic acid such as oxalic acid, glutamic acid, adipic acid, acetic acid, phthalic acid, isophthalic acid, salicylic acid, and pyromellitic acid with the above polyol,

Addition reaction products of the above-mentioned polyol and ethylene oxide or alkylene oxide such as propylene oxide,

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, 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-hydroxyethyl Thio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenyl sulfone, 2-
(2-mercaptoethylthio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulfylate), hydroxyethylthiomethyl-tris (mercaptoethylthio) methane and the like can be mentioned.

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 straight chain structure having no branched skeleton, and further, a polyester polyol, a polyether polyol having a melting point (Tm) of 40 ° C. or lower, Polycarbonate polyols, polycaprolactone polyols, polyolefin polyols and their copolymers and mixtures are preferably used, and polyether polyols are particularly preferably used. From the viewpoint of flexibility and scratch resistance of the film, it is preferable to use 50 parts by weight or more and 98 parts by weight or less of the above-mentioned active hydrogen compounds in 100 parts by weight of all active hydrogen compounds. These compounds may be used alone or as a mixture of two or more kinds.

Further, in order to stabilize the urethane resin (F) used in the present invention as an aqueous resin, known materials and stabilization techniques can be used. In the molecule, a carboxyl group, a sulfonyl group and an ethylene oxide are used. It is preferable to have one or more groups, and a carboxyl group and / or
Alternatively, it is more preferable to have one or more sulfonyl groups.

As the constituents for introducing these atomic groups, 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, polyaddition product of ethylene oxide and propylene oxide, ethylene glycol and the active hydrogen compound However, the present invention is not limited to these. The introduction of these atomic groups into the molecule tends to improve the mechanical stability of the water-based resin and the mixing stability with other components.

The preferable amount of the above-mentioned carboxyl group- and / or sulfonyl group-containing compound is the mechanical stability of the water-based urethane resin (F), the mixing stability with other components, the flexibility of the film, etc. From the viewpoint, the urethane resin (F) has an acid value of 3 to 30 KOHmg in terms of solid content.
/ G, more preferably 3 to 25 KOHmg / g, and further preferably 5 to 20 KOHmg / g. Here, the measuring method of the acid value is, for example, Japanese Industrial Standard JIS K.
5400 and the like.

The method for producing the water-based urethane resin is not particularly limited, but the following method may be mentioned as an example. Polyfunctional isocyanate compound, in the active hydrogen compound, a compound having an active hydrogen group capable of reacting with an isocyanate group, 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 the presence or absence of a suitable organic solvent at an equivalent ratio such that the isocyanate group is in excess, and a urethane having an isocyanate group at the molecular end. A prepolymer is produced. Then, the prepolymer having a carboxyl group and / or a sulfonyl group is neutralized with a neutralizing agent such as a tertiary amine. Then, the neutralized prepolymer is added to an aqueous solution containing a chain extender to react, and if an organic solvent is contained in the system, it is removed to obtain a method. The unneutralized urethane prepolymer obtained by the above method,
A method in which a neutralizing agent is added and a chain extender is added to an aqueous solution and reacted. A method in which an aqueous solution having a chain extender is added to and reacted with the neutralized urethane prepolymer obtained by the above method. A method of obtaining an aqueous dispersion by adding an aqueous solution containing a neutralizing agent and having a chain extender to the unneutralized urethane prepolymer obtained by the above method and reacting.

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, aluminum hydroxide and zinc hydroxide, and quaternary ammonium compounds such as tetramethylammonium hydroxide. These compounds are one kind, or It can be used as a mixture of two or more kinds.

From the viewpoint of the stability of the urethane resin (F) in water, the amount of the neutralizing agent used is 0. 1 with respect to 1 equivalent of the carboxyl group and / or the sulfonyl group in the urethane resin (F). 5 to 3 equivalents, more preferably 0.7 to
It is 1.5 equivalents.

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
-Xylenediamine, isophoronediamine, NBDA
(Trade name, manufactured by Mitsui Chemicals, Inc.), N-methyl-3,
Polyamines such as 3'-diaminopropylamine and adducts of diethylenetriamine and acrylates or their hydrolysis products are suitable.

Examples of the solvent used for obtaining the water-based urethane resin (F) include ketones such as methyl ethyl ketone and acetone, esters such as methyl acetate and ethyl acetate, tetrahydrofuran and the like. Is not particularly limited as long as it is 100 ° C. or lower, and these solvents can be used alone or in a mixed state of two or more kinds. The use of a solvent having a boiling point of more than 100 ° C, that is, a boiling point of water or more, makes it difficult to completely distill only the solvent from the solution after formation of the water dispersion, and the high-boiling solvent remains in the film. Since it affects the physical properties of the resin, it is preferably used in an amount of 10 parts by weight or less based on 100 parts by weight of the water-based urethane resin (F) when it is unavoidably used due to performance development.

The urethane resin (F) used in the present invention can also be used as a modified product by reacting it with other components such as other monomers and resin components. Further, the urethane resin (F) used in the present invention is acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, methacrylamide, styrene, acrylonitrile, butadiene, vinyl acetate, ethylene, propylene, itaconic acid, It can also be used as a complex obtained by polymerizing at least one monomer such as maleic acid.

The water-based coating material of the present invention is mainly composed of an olefin resin (A), a phosphorus-containing polyester (B) and, in some cases, a water-based urethane resin (F). As a method of coexisting with each other, an aqueous olefin resin (A) obtained by the above production method, an aqueous phosphorus-containing polyester (B), and in some cases, a urethane resin (F) and the like are separately produced, and then a suitable A method of mixing using an agitator, or addition of an olefin resin (A) and a phosphorus-containing polyester (B) and, in some cases, a urethane resin (F) when melt-kneading the olefin resin, phase inversion, and aqueous dispersion. Examples of the method for obtaining the product as a body include, but are not particularly limited to.

The ratio of the olefin resin (A) to the urethane resin (F) is not particularly limited, but is 100 in terms of resin solid weight in terms of film flexibility, scratch resistance and cost. / 1 to 100 range is preferable, 100
The range of / 5 to 50 is more preferable.

The flame-retardant water-based coating material of the present invention may contain a flame retardant in order to impart a stronger 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, or the like that produces a harmful substance during incineration is not preferable. Therefore, a phosphorus-based or inorganic flame-retardant that does not generate harmful substances and has a relatively high flame-retardant effect is preferable.

The phosphorus-based flame retardant used in the present invention is not particularly limited, but examples thereof include polyphosphate-based flame retardants (G) such as ammonium polyphosphate, triphenyl phosphate, tricresyl phosphate, Trixylenyl phosphate, cresyl diphenyl phosphate,
Trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, di- (polyoxyethylene) -hydroxymethyl phosphate, diethyl phenyl phosphate, dimethyl phenyl phosphate, diethoxy- Phosphate ester flame retardants (H) such as bis- (2-hydroxyethyl) -aminomethylphosphonate, resorcinol diphenylphosphate, bisphenol A diphenylphosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl Reactive phosphorous flame retardants such as phosphonates, inorganic phosphoric acid flame retardants such as titanium phosphate, red phosphorus flame retardants such as red phosphorus, phenylphosphonic acid, etc. Such as those flame retardants and water of the like.

Further, the inorganic flame retardant used in the present invention is not particularly limited, but for example, antimony compounds such as antimony trioxide, antimony pentoxide, antimony silicon oxide, magnesium hydroxide, aluminum hydroxide. Such as metal hydroxides, hydrated metal compounds, tin compounds such as tin oxide, tin hydroxide and zinc stannate, zirconium compounds such as zirconium oxide and zirconium hydroxide, borate compounds such as zinc borate and barium metaborate. , Guanidine compounds such as guanidine phosphate and nitrogenated guanidine, molybdenum compounds such as molybdenum trioxide, silicone resins, silicone compounds such as silicone oil, triazine compounds such as organic triazine, etc., and water-based inorganic flame retardants Etc.

These flame retardants can be used either individually or in combination of two or more. In particular, from the aspects of flame retardancy, scratch resistance, and flexibility, polyphosphate flame retardant (G),
And a phosphate ester flame retardant (H) are preferable, and 1 to 100 parts by weight of the phosphorus-containing polyester (B) is a polyphosphate flame retardant (G) and / or a phosphate ester flame retardant (H). It is preferable to contain 100 parts by weight.

The method of incorporating the flame retardant into the flame-retardant water-based coating material according to the present invention is not particularly limited, but the olefin resin (A) and the phosphorus-containing polyester (B) may be preliminarily used. Method of mixing and then water system,
Alternatively, there may be mentioned a method of mixing in the step of water-based conversion, or a method of mixing the water-based flame retardant separately with a water-based coating material.

The tensile properties of the film formed by coating the flame-retardant water-based coating material of the present invention are as follows: load 5 kg, chuck distance 20 mm, test piece size 40 mm × 10 mm, marked line distance 10
mm, pulling speed 50 mm / min, temperature 23 ° C, humidity 5
When measured under the condition of 0%, the elongation at break: 200 to 1500%, the breaking strength: 3 to 50 MPa, the 100% modulus: 0.8 to 10 MPa, and the flexibility and scratch resistance are satisfied. Achieve both. Generally, a value of 100% modulus corresponds to the flexibility of the coating.

The substrate to which the flame-retardant water-based coating material of the present invention is applied is not particularly limited, and examples thereof include plastic, metal, paper, wood, fiber, glass, rubber, ceramics, concrete and the like. The shape is a film,
Sheets, plates, fibers, various molded bodies, etc. can be mentioned,
It is not particularly limited. The laminate obtained by applying the flame-retardant water-based coating material of the present invention to these substrates has properties such as flame retardancy, scratch resistance, flexibility, water resistance and durability.

The above-mentioned substrates will be described in detail below.

Examples of the plastic include acetal, acryl, methyl methacrylate, acetyl cellulose, nitrocellulose, ethylene / acryl, fluororesin, polyacrylonitrile, polyamide such as nylon, polybutadiene / acrylonitrile, polybutadiene / styrene, polycarbonate, polyethylene, polyethylene. Saturated polyester such as terephthalate, polyhydroxy ether, polyimide, polyphenylene oxide, polypropylene, polystyrene and copolymers thereof, polysulfone, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyvinyl alcohol, polyvinyl alkyl ether, polyvinyl butyral, polychlorinated Thermoplastic resin such as vinyl, polyvinyl methyl ether, polyurethane, alkyd, In, cyanoacrylate, diallyl phthalate, epoxy and its modified products, furan, melamine formaldehyde, phenol formaldehyde, phenol furfural, unsaturated polyester, polysulfide, resorcinol / phenol formaldehyde, silicone, thermosetting resin such as urea formaldehyde, epoxy- Novolac, epoxy-phenolic, epoxy-polysulfide, epoxy-silicone, phenolic-butyral, phenolic-nitrile, phenolic-polyamide, polyamide-epoxy, polyimide-epoxy, silicone-vinylphenolic, silicone-phenolic, vinylformal-phenolic, vinylbutyral. -Alloys such as phenolic.

Examples of the metal include iron, carbon steel, cast iron,
Examples thereof include galvanized steel sheet, Zn-Fe-based and Zn-Ni-based alloy-plated steel sheets, organic composite-plated steel sheets, stainless steel, aluminum and its alloys, copper and its alloys, titanium and its alloys, and the like.

Examples of the paper include glassine paper, high-quality paper,
Examples include kraft paper, newsprint, impregnated base paper, thin paper, imitation paper, paperboard and tissue paper.

The wood species include, for example, fir, Todomatsu, syrabe, taiwan cypress, cypress, sawara, cedar,
Larch, spruce, spruce, red pine, himematsu,
Coniferous wood such as black pine, hiba, hemlock, Itaya maple, horse chestnut, oak, citrus birch, vine, camphor tree, camphor tree, beech, nigrum, tab, honoki, doronoki, linden, yachidamo, hagiri, etc. Hardwood, Akarawan, Sirolawan and other Philippine wood.

Examples of the fibers include regenerated fibers of cellulose such as rayon and cupra, cellulose of acetate, semi-synthetic fibers of protein such as Promix, polyamide such as nylon, polyvinyl alcohol, polyvinylidene chloride and poly. Synthetic fibers such as vinyl chloride type, polyester type, polyacrylonitrile type, polyethylene type, polypropylene type, polyurethane type, polyalkylene paraoxybenzoate type, phenol type, glass fiber,
Examples thereof include inorganic fibers such as carbon fibers, vegetable fibers such as cotton, flax, potato, jute, animal fibers such as wool and silk, and mineral fibers such as asbestos.

Examples of the glass include borosilicate glass, lead glass, soda lime glass, zinc glass and quartz glass.

Examples of the rubber include silicone rubber, butyl rubber, ethylene-propylene-terpolymer, natural rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, polysulfide rubber, epichlorohydrin rubber, acrylic rubber, urethane rubber and the like. Can be mentioned.

Examples of ceramics include alumina, steatite, forsterite, zircon, beryllia,
Examples thereof include zirconia, silicon nitride, aluminum nitride and silicon carbide.

Examples of concrete include ordinary concrete, lightweight concrete, heavy concrete, crushed stone concrete, AE concrete, watertight concrete, cement mortar, lightweight cellular concrete, carbon fiber reinforced concrete, glass fiber reinforced concrete and the like.

The application to which the laminate of the present invention can be applied is not particularly limited, but examples thereof include wood materials such as plywood, laminated wood, and single-layer laminate materials, floors, walls, ceilings, interior tiles, Building materials such as bricks, road pavement, waterproofing of bridges,
Civil materials such as repair, reinforcement and foundations, joints, corrosion protection of steel structures, automobile interior parts, exterior parts, automobile materials such as engine parts and brake parts, and vehicle roofs, wind ducts, decorative boards, Rail vehicle materials such as insulation, windows, floors, doors, etc.
And structural materials such as aluminum alloys, titanium alloys, FRP, and other aerospace materials, and semiconductors, batteries, cable materials, magnetic disks and tapes, small motors, piezoelectric elements, conductive materials, sensors, photosensitive materials, terminals Precision for use in materials such as telephones and facsimiles, electrical and electronic materials such as copper flash laminated board materials, and communication equipment materials mainly composed of optical components such as optical fibers, and cameras, watches, measuring instruments, copiers, etc. , Materials for office automation equipment, materials for sports equipment such as skis, archery, golf and tennis, nets for construction curing, meshes, sheets and tents, curtains, table cloths, textile materials such as gloves, shoe uppers,
Footwear materials such as bottoms, shins, heels, toplifts, insoles, and fiber flocking materials such as binders for flocking, and packaging materials that use paper, plastic, aluminum foil, etc. as a base film, and cover sheets, Bookbinding materials such as upholstery and spines, musical instrument materials such as pianos, electric tones, electronic musical instruments, furniture materials such as chests, shelves, desks, chairs, sofas, artificial joints, artificial bones and blood vessels, skin adhesion, stitching, dentistry Examples include medical materials used in the areas of orthodontics, prosthesis, preservation, and the like.

Of the above-mentioned substrates, the substrate suitable for applying the flame-retardant water-based coating material of the present invention is fiber, and particularly polyester-based fiber, nylon-based fiber, cotton and the like are preferable.
By coating these fibers with the flame-retardant water-based coating material of the present invention, it is possible to impart properties such as flame retardancy, scratch resistance, flexibility, water resistance, and durability. In particular, it is suitable for application to textile products such as nets for construction curing, meshes, sheets, tents, curtains and curtains that require flame retardancy.

The solid content concentration in the water-based coating material of the present invention is not particularly limited, but it is easy to maintain the viscosity range described later, the drying time is shortened, and the difference in the ease of thick film coating is large. From the viewpoint of workability, it is preferably 30 to 70% by weight, more preferably 35 to 60% by weight.

In the present invention, a viscoelasticity adjusting agent can be used in order to adjust the solution viscosity of the water-based coating material to a viscoelasticity suitable for coating. The viscoelasticity adjusting agent is not particularly limited, but an acrylic resin type viscoelasticity adjusting agent such as polyacrylic acid or polyacrylamide, a polyether type viscoelasticity adjusting agent such as polyvinyl methyl ether or polyethylene oxide, a polyester type viscoelasticity adjusting agent. Elasticity modifiers, polyurethane-based viscoelasticity modifiers, cellulose-based viscoelasticity modifiers such as carboxymethylcellulose, carboxyethylcellulose, methylcellulose, hydroxyethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, poly (N-
It is possible to use organic viscoelasticity adjusting agents such as vinylacetamide) and inorganic viscoelasticity adjusting agents such as silicon dioxide, activated clay, bentonite and calcium carbonate. Particularly, in terms of scratch resistance and flexibility retention of the coating film. Therefore, an acrylic resin-based viscoelasticity modifier having a carboxylic acid or a carboxylic acid salt is preferable.

The flame-retardant water-based coating material used in the present invention is
Amino resin, if necessary to improve coating performance
Reactive resins and compounds such as epoxy resins, carbodiimide-based resins, hydrazide-based compounds, isocyanate-based compounds and oxazoline-based compounds can be contained.

The water-based coating material used in the present invention may contain a surfactant in order 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, sodium melanin resin sulfonate, special polyacrylic Acid salt, gluconate, potassium oleate,
Olefin-maleic acid copolymer, sodium carboxymethyl cellulose, sodium oleate, potassium stearate, sodium stearate, ammonium stearate, triethanolamine stearate, potassium tallow, sodium tallow, and metallic soaps (Zn, Al, Na) , K salt) and the like; 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 Nonionic surfactants such as 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 amphoteric surfactants such as casein; water-soluble polyvalent metal salts and the like. These surfactants can be used alone or in combination of two or more.

In addition to the above compounds, if necessary, a slipperiness-imparting agent (synthetic wax, natural wax, etc.), tackiness-imparting agent, adhesion-imparting agent, rust preventive, antifungal agent, ultraviolet absorber,
Heat resistance stabilizer, weather resistance stabilizer, light resistance stabilizer, foaming agent, defoaming agent, dye, cross-linking agent, plasticizer, auxiliary binder, leveling agent, thixotropy imparting agent, film forming aid, defoaming agent, anti-settling agent, Antioxidants, antistatic agents, thickeners, thickeners, pigments (eg titanium white, red iron oxide, phthalocyanine, carbon black, permanent yellow etc.), fillers (eg calcium carbonate, magnesium carbonate, barium carbonate, talc, water) Additives such as aluminum oxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, etc.) can be added within the range not impairing the object of the present invention.

All of the above additives were added in the raw material resin or raw material compound production step, added in the raw material resin or raw material compound water-based step, and the water-based additives were also water-based (A), ( B), (F), etc., addition in the mixing step, addition after mixing, etc. can be added, and the additive may be dispersed in the resin or dissolved in water. Alternatively, it may be dispersed.

The method of applying the water-based coating material of the present invention is not particularly limited, but for example, dip coating, blade coater, air knife coater, rod coater, hydrobar coater, transfer roll coater, reverse Coaters, gravure coaters, die coaters, curtain coaters, spray coaters, flow coaters, roll coaters, brush coating, etc.
It can be applied to a part or the whole surface of the substrate. Although the drying temperature of the film formed from the water-based coating material according to the present invention may be room temperature, it may be 5 to 60 at 50 to 200 ° C.
It is also possible to heat for 0 seconds.

Further, a method of laminating a film formed from the flame-retardant water-based coating material of the present invention with another film, a method of bonding the films with each other by heat or high frequency, and with another material and a multilayer coating It can also be formed.
Furthermore, it is also possible to apply the main coating material to the substrate and use it as a texture and a non-slip effect imparting material.

The film obtained from the flame-retardant water-based coating material of the present invention is characterized in that it has excellent flame retardancy. The micro burner method, the Meckel burner method, and the coil method with a support angle of 45 ° specified by the Ordinance of the Ministry of Home Affairs No. 3) are mentioned.
A laminated body in which the flame-retardant water-based coating material of the present invention is applied to fibers,
It is desirable to pass the above test.

Further, the film obtained from the water-based coating material of the present invention is characterized by being excellent in scratch resistance (scratch resistance), and JIS K720 is one of the methods for evaluating scratch resistance.
4 includes the Taber abrasion test, and the abrasion reduction amount after measuring the abrasion wheel at 3000 revolutions is 0 to 50 mg.
Is desirable.

[0126]

The present invention will be described below with reference to examples.
The present invention is not limited to the examples. (Production Example) Production Example of Olefin Resin (A) Aqueous Dispersion

1. Ethylene-polar monomer copolymer (A
-1), and an aqueous dispersion comprising a fatty acid compound (E)
Production of (a-1) 100 parts by weight of ethylene-vinyl acetate copolymer (Evaflex 270 manufactured by Mitsui DuPont Chemical: vinyl acetate content 28% by weight, MFR = 1), montanic acid (Hoechst S manufactured by Clariant Co .: carbon number 28) ~ 32, acid value 150
mgKOH / g) 5 parts by weight and mixed at a rate of 3000 g / hour from the hopper of a twin-screw extruder (Ikegai Tekko PCM-30; L / D = 40) to the vent section of the extruder. From the supply port provided, 1 of potassium hydroxide
300 g / hour of 3% aqueous solution (10
%) And continuously extruded at a heating temperature of 160 ° C. The extruded resin mixture was cooled to 90 ° C. by a static mixer with a jacket installed in the same extruder port, and further put into warm water at 80 ° C., and the yield was 99.
An aqueous dispersion (a-1) having a pH of 12 and 3% was obtained. The average particle size of the obtained aqueous dispersion (a-1) was 0.6 μm as measured by Microtrac.

2. Olefin-based elastomer (A-2)
And an aqueous component comprising the acid-modified polyolefin compound (D)
Production of powder (a-2) As an olefin elastomer, a propylene / 1-butene copolymer (manufactured by Grand Polymer; Tufmer XR110
T) 100 parts by weight and maleic anhydride-modified polyethylene wax (Mitsui Chemicals; Hiwax 2203A) 10
1 part by weight and 3 parts by weight of potassium oleate are mixed and supplied to the extruder at a rate of 3000 g / hour from a hopper of a twin-screw extruder, and water is supplied from a supply port provided in a vent part of the extruder. 90 g of a 15% aqueous solution of potassium oxide /
It was continuously fed at a rate of 3 hours (3% in total) and continuously extruded at a heating temperature of 230 ° C. Next, the extruded mixture was cooled to 90 ° C. with a jacketed static mixer installed in the extruder port, and further poured into warm water of 80 ° C. to prepare an aqueous dispersion (a-2) having a pH of 9 at 9 ° C.
Obtained in a yield of 8.0%. Obtained aqueous dispersion (a-2)
The average particle diameter of the dispersed particles of No. 2 was 0.8 μm as measured by Microtrac.

Aqueous Dispersion of Polyester (B) Containing Phosphorus
Production Example of (b) 56 parts of terephthalic acid, 496 parts of diethylene glycol and dihydro-3-[(6-oxide-6H-dibenz
[c, e] [1,2] oxaphosphorin-6-yl) methyl] -2,5-furandion (C-1) 110 parts, manganese acetate 0.2 part as catalyst, lithium acetate 0.8
Parts, antimony trioxide (0.05 parts) are mixed, and atmospheric pressure is adjusted to 16
The transesterification reaction is carried out by heating at 0 to 220 ° C. for 3 hours, the theoretical amount of water is distilled off, and then the system temperature is set to 250.
C., the pressure was gradually reduced to 1 Torr or less, and the reaction was carried out for 6 hours to obtain a polyester having a weight average molecular weight of 8000 and a phosphorus content of 5%. 150 parts of the polyester, 100 parts of dimethylformamide, 30 parts of nonylphenol ethylene oxide 15 mol adduct, 20 parts of lauryl alcohol ethylene oxide 18 mol adduct are uniformly dissolved at 80 ° C, and 700 parts of warm water at 80 ° C is gradually added to the particles. After liquefying and cooling to room temperature, it was continuously pulverized for 30 minutes with a horizontal wet fine powder disperser (IMEX; Viscomill) to obtain an aqueous dispersion (b) of the phosphorus-containing polyester (B). The resulting aqueous dispersion (b) had a pH of 6.5 and an average particle size of 0.
It was 3 μm.

Of the urethane resin (F) aqueous dispersion (f)
Production Example Polytetramethylene ether glycol (Hodogaya Chemical Co., Ltd .; PTG 2000SN, molecular weight 2000) 3
99.5 parts, 2,2-dimethylolbutanoic acid 21.0
Parts, 12.4 parts of 1,4-butanediol, 96.3 parts of hexamethylene diisocyanate, and 374.0 parts of methyl ethyl ketone were charged in a reaction vessel and reacted at 90 ° C. for 6 hours in a nitrogen gas atmosphere. Then, it cooled to 60 degreeC, 13.3 parts of triethylamines were added, and it was made to mix at this temperature for 30 minutes. 0.86 of the obtained prepolymer
% Hexamethylenediamine aqueous solution 1275.7 g, and stirred, and then the solvent of methyl ethyl ketone is removed under reduced pressure at 60 ° C. to obtain a solid content acid value of 15 KOH mg / g,
An aqueous dispersion (f) of urethane resin (F) having a pH of 7.8 and an average particle diameter of 0.2 μm was obtained.

Production of flame-retardant water-based coating material Each water-based dispersion (a- of the above-mentioned olefin resins (A-1), (A-2), phosphorus-containing polyester (B) and urethane resin (F). 1), (a-2), (b), (f), and an aqueous dispersion (g) of ammonium polyphosphate (G).
(Fan GP-7 manufactured by Daiwa Chemical Co., Ltd.), an aqueous dispersion (h) of a phosphoric acid ester (H) (manufactured by Marubishi Yuka; Nonnen 98)
After mixing and stirring each aqueous dispersion of 4) at the compounding ratio (solid content ratio) shown in Table 1 [Table 1], an acrylic viscoelasticity adjusting agent (manufactured by San Nopco; Thickener 636) was added as a viscoelasticity adjusting agent. The water-based coating material was manufactured by adjusting the viscosity of the solution to be 10,000 mPa · s.

Manufacture of Textile Product Each of the water-based coating materials manufactured by the above method was applied to a base cloth composed of polyester fibers with an applicator so that the film thickness after drying would be 120 μm on average, and at 120 ° C. The step of drying for 3 minutes was performed on both sides to produce a film-formed product.
The evaluation contents, test conditions and results of the above flame retardant water-based coating material are shown below.

Flame Retardancy Evaluation Method With respect to the above-mentioned base cloth coating sample, a supporting angle of 45 ° defined by the Ministry of Internal Affairs and Communications Fire Department Fire Prevention Test Regulations (Ministry of Internal Affairs Ordinance No. 3).
The evaluation was performed by the micro burner method and the coil method. Afterflame time in micro burner method is 3 seconds or less, carbonization area is 30 cm ² or less, and number of flame contact is 3 in coil method
Passed more than once.

Abrasion resistance evaluation method The sample was abraded using a Taber abrasion tester (manufactured by Toyo Seiki Seisakusho Ltd.) and an abrasion wheel CS-17 under a load of 500 g and a rotation speed of 3000, and the weight of the base fabric before and after the test Was measured, and the weight of the film scraped off was calculated. The less the wear loss is, the better the wear resistance is.
The following were accepted.

Flexibility Evaluation Method The base cloth coated sample was cut into a circle with a diameter of 11 cm,
One end thereof was supported horizontally, and the angle at which the base fabric sample drooped was measured with reference to the horizontal plane of the fulcrum, and 30 ° or more was regarded as a pass.

Non-tackiness evaluation method The texture of the base fabric coated sample was judged by touch, and ◯ and Δ were passed. ○: No stickiness △: Slight stickiness ×: Stickiness

[0137]

[Table 1]

[0138]

The water-based coating material according to the present invention comprises a water-based dispersion of a polymer that does not produce harmful substances when incinerated and has no problem of environmental hormones. It has become possible to form films and laminates with excellent performance such as flame retardancy, scratch resistance, flexibility, non-tackiness, water resistance, cold resistance, odorlessness, coatability, and lightness. .

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 131/04 C09D 131/04 167/00 167/00 175/04 175/04 D06M 13/188 D06M 13 / 188 13/292 13/292 15/333 15/333 15/507 15/507 ZF term (reference) 4J038 CB051 CB052 CB061 CB062 CB101 CB102 CB142 CF031 CF032 CP032 CQ011 CQ012 DD101 DD102 DG062 DG062 DG082 DG082 DG092 DG082 DG092 DG082 DG092 JA44 JA56 JC24 KA12 MA08 MA10 NA04 NA10 NA11 NA12 NA13 NA15 NA27 PA18 PB02 PC02 PC03 PC04 PC06 PC08 PC10 4L033 AA07 AB04 AC05 BA17 BA39 CA12 CA28

Claims (12)

[Claims] 1. A flame-retardant water-based coating material comprising an olefin resin (A) and a polyester (B) containing phosphorus in a resin skeleton. 2. The phosphorus-containing polyester (B) is contained in an amount of 1 to 2 with respect to 100 parts by weight of the olefin resin (A).
The flame-retardant water-based coating material according to claim 1, which contains 100 parts by weight. 3. The olefin resin (A) is an ethylene-polar monomer copolymer (A-1) and / or an olefin elastomer (A-2), characterized in that Flame-retardant water-based coating material described in. 4. The flame-retardant water-based coating material according to any one of claims 1 to 3, wherein the olefin resin (A) is an ethylene-vinyl acetate copolymer. 5. The main monomer constituting the phosphorus-containing polyester (B) is a phosphorus compound (C) having an aromatic dicarboxylic acid component, a diol component, and an acid component and / or an alcohol component. The flame-retardant water-based coating material according to any one of claims 1 to 4. 6. The phosphorus compound (C) having the acid component and / or alcohol component is dihydro-3-[(6-
Oxide-6H-dibenz [c, e] [1,2] oxaphosphorin-6-yl) methyl] -2,5-furandione (C-1) or its divalent ring-opened carboxylic acid anhydride Carboxylic acid or its alkyl ester, and / or 6
-(2,5-Dihydroxyphenyl) -6H-dibenz
A flame-retardant water-based coating material according to any one of claims 1 to 5, which is [c, e] [1,2] oxaphosphorin-6-oxide (C-2). . 7. The acid-modified polyolefin compound (D) and / or 100 parts by weight of the olefin resin (A).
Alternatively, the flame-retardant water-based coating material according to any one of claims 1 to 6, which contains 0.5 to 30 parts by weight of the fatty acid compound (E). 8. The urethane resin (F) is contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the olefin resin (A), according to any one of claims 1 to 7. The flame-retardant water-based coating material described. 9. The phosphorus-containing polyester (B) 100
1 to 100 parts by weight of a polyphosphate-based flame retardant (G) and / or a phosphate ester-based flame retardant (H) are contained with respect to parts by weight. The flame-retardant water-based coating material according to the item. 10. A film formed from the flame-retardant water-based coating material according to any one of claims 1 to 9 has a breaking elongation: 200 to 1500%, a breaking strength: 3 to 50 MPa, 100% modulus: It has a tensile physical property of 0.8-10 MPa, It is characterized by the above-mentioned.
The flame-retardant water-based coating material according to any one of 1. 11. The flame-retardant water-based coating material according to any one of claims 1 to 10 is selected from the group consisting of plastic, metal, paper, wood, fiber, glass, rubber, ceramic and concrete. Coated on at least one substrate,
A laminate obtained by drying and forming a flame-retardant film. 12. A fiber product having a flame-retardant film formed from the flame-retardant water-based coating material according to claim 1.