KR101593855B1 - Blocked polyisocyanate water dispersion, fiber processing agent composition, and fabric - Google Patents

Abstract

An object of the present invention is to provide an aqueous dispersion of block polyisocyanate which is capable of obtaining a fabric having good water dispersion stability, high film strength, excellent mechanical stability as a fluorine fiber treating agent and having high wash durability, And a fiber treatment agent composition containing the same. In order to solve this problem, a block polyisocyanate aqueous dispersion comprising a block polyisocyanate having at least the following constitutional units 1) to 3) and water and having an average dispersed particle diameter of the block polyisocyanate: to provide. 1) a polyisocyanate unit having at least one diisocyanate monomer unit selected from the group consisting of an aliphatic diisocyanate monomer and an alicyclic diisocyanate monomer, 2) a polyethylene oxide unit which is a terminal hydroxyl group at one end, 3)

Description

BLOCKED POLYISOCYANATE WATER DISPERSION, FIBER PROCESSING AGENT COMPOSITION, AND FABRIC}

An aqueous dispersion of block polyisocyanate, a fiber treatment composition comprising it, and a fabric treated by the fiber treatment composition.

Fiber treatment agents are used to impart various functions to fibers. Examples of its functions include water-repellent oiling preventing water and oil from adhering, feeling of comfort to comfort, prevention of frame collapse of a sewn product, and the like.

Among them, a composition having a fluororesin having a perfluoroalkyl group having 8 or more carbon atoms has been used as a fiber treatment agent for imparting water repellency. However, it has been pointed out that a fluororesin having a perfluoroalkyl group having 8 or more carbon atoms is decomposed when discharged into the environment, and there is a possibility that perfluorooctanoic acid, which is concerned with accumulation and harmfulness, may be generated. Therefore, studies have been made actively to replace the perfluoroalkyl group with a fluorine resin which does not generate perfluorooctanoic acid with the carbon number of the perfluoroalkyl group being 8 to 6 or less.

However, the fluororesin having a perfluoroalkyl group having 6 or less carbon atoms has a deteriorated performance such as water repellency after repetition of washing, compared with a fluororesin having 8 or more carbon atoms. As a method, it has been studied to add a block polyisocyanate to a fiber treatment agent to maintain the performance (Patent Documents 1 to 7).

Japanese Patent Publication No. 2002-511507 Japanese Patent Publication No. 2006-506226 Japanese Patent Publication No. 11-512772 International Publication No. 00/58416 brochure International Publication No. 2012/014850 pamphlet WO 97/037076 Pamphlet U.S. Patent Application Publication No. 2012/0238697

However, the block polyisocyanates described in Patent Documents 1 to 7 are unstable in water dispersibility, and the film strength is insufficient. Further, these fiber treatment composition compositions mixed with a fluororesin have a problem that aggregates are generated when they are exposed to a high shear pressure. Furthermore, it is difficult for the fabric treated with the fiber treating composition of Patent Documents 1 to 7 to maintain high washing durability.

Disclosure of the Invention An object of the present invention is to provide a water repellent agent of a block polyisocyanate having a good water dispersion stability and a high film strength, a fiber treatment composition excellent in mechanical stability as a fluorine fiber treatment agent, and a fabric having high wash durability .

As a result of intensive studies, the inventors of the present invention have found that an aqueous dispersion of a block polyisocyanate having a polyisocyanate and a specific compound component unit achieves the above-mentioned object, and completed the present invention. That is, the present invention is as follows.

〔One〕

A block polyisocyanate having at least the following 1) to 3) component units and water,

Wherein the block polyisocyanate has an average dispersed particle diameter of 1 to 250 nm.

1) a polyisocyanate unit having at least one diisocyanate monomer unit selected from the group consisting of an aliphatic diisocyanate monomer and an alicyclic diisocyanate monomer

2) Polyethylene oxide unit which is a terminal hydroxyl group

3) block unit

〔2〕

The aqueous dispersion of a block polyisocyanate according to the above [1], wherein the average dispersed particle diameter of the block polyisocyanate:? Satisfies the following formula 1:

[Formula 1]

(A is the mass% of polyethylene oxide units which are one-end hydroxyl groups in the block polyisocyanate)

[3]

The aqueous dispersion of a block polyisocyanate according to [1] or [2], wherein the block polyisocyanate has the following composition.

1) 45 to 65% by mass of a polyisocyanate unit

2) 15 to 30% by mass of a polyethylene oxide unit

3) 15 to 30% by mass of block units

〔4〕

The aqueous dispersion of a block polyisocyanate according to any one of [1] to [3], wherein the average number of isocyanate functional groups of the polyisocyanate unit is 4 to 20.

[5]

The aqueous dispersion of a block polyisocyanate according to any one of [1] to [4], wherein the block agent is a pyrazole compound.

[6]

The aqueous dispersion of a block polyisocyanate according to any one of [1] to [5], wherein at least one of the diisocyanate monomers is hexamethylene diisocyanate.

[7]

The aqueous dispersion of a block polyisocyanate according to any one of the above items [1] to [6], wherein the block polyisocyanate has an average dispersed particle diameter:? Of 1 to 80 nm.

〔8〕

A fiber treatment agent composition comprising a fluororesin having substantially no perfluoroalkyl group having 8 or more carbon atoms and an aqueous dispersion of a block polyisocyanate according to any one of [1] to [7].

[9]

A fabric treated by the fiber treatment composition according to the preceding paragraph [8].

[10]

The contact angle of water / isopropyl alcohol (1/1 by mass ratio) after washing 10 times was 90 degrees or more,

A fabric coated with a fluororesin having substantially no perfluoroalkyl groups of 8 or more carbon atoms.

[11]

(10) above, wherein the retention ratio of the contact angle of water / isopropyl alcohol (1/1 by mass ratio) after washing 10 times to the contact angle of water / isopropyl alcohol (1/1 by mass ratio) fabric.

The water dispersion of the block polyisocyanate of the present invention can obtain a coating film having good water dispersion stability of the block polyisocyanate and high film strength. Further, the fiber treatment composition comprising the water dispersion is excellent in mechanical stability, and the fabric treated with the fiber treatment composition has high wash durability.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto, and various modifications are possible without departing from the gist of the present invention.

[Water dispersion of block polyisocyanate]

The water dispersion of the block polyisocyanate of the present invention may contain,

At least the following block polyisocyanates having the constituent units 1) to 3) and water, wherein the block polyisocyanate has an average dispersed particle diameter:? Of 1 to 250 nm. The average dispersed particle diameter is preferably 1 to 180 nm, more preferably 1 to 80 nm. By the above range, water dispersion stability and mechanical stability tend to be more excellent. The mean dispersed particle diameter as used herein means a volume average dispersed particle diameter and can be measured in detail by the method described in the Examples.

1) a polyisocyanate unit having at least one diisocyanate monomer unit selected from the group consisting of an aliphatic diisocyanate monomer and an alicyclic diisocyanate monomer

2) Polyethylene oxide unit which is a terminal hydroxyl group

3) block unit

The block polyisocyanate of the present invention contains polyethylene oxide as a unit having a terminal hydroxyl group as a hydrophilic group as a unit and can reduce the average dispersed particle diameter at a smaller amount of a hydrophilic group than in the prior art. Specifically, the average dispersed particle diameter of the block polyisocyanate preferably satisfies the following formula (1). With the above range, there is a tendency that a higher water dispersion stability and a higher film strength can be compatible with each other.

[Formula 1]

(A is the mass% of polyethylene oxide units which are one-end hydroxyl groups in the block polyisocyanate)

[Polyisocyanate Unit]

The block polyisocyanates of the present invention have polyisocyanate units. The aliphatic diisocyanate monomer and the alicyclic diisocyanate monomer which can be used as a raw material of the polyisocyanate do not contain a benzene ring in the structure thereof. The aliphatic diisocyanate monomer is not particularly limited, but preferably has 4 to 30 carbon atoms, and examples thereof include tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate (HDI) , 2,2,4-trimethyl-hexamethylene-1,6-diisocyanate, lysine diisocyanate, and the like. The alicyclic diisocyanate is not particularly limited, but preferably has 8 to 30 carbon atoms, and examples thereof include isophorone diisocyanate (IPDI), 1,3-bis (isocyanatomethyl) -cyclohexane, '-Dicyclohexylmethane diisocyanate, and the like. Among them, HDI is preferable because of weatherability and industrial availability. These may be used in combination of two or more.

As the raw material of the polyisocyanate used in the present invention, a 1 to 6-valent alcohol other than the diisocyanate monomer may be used.

Examples of the univalent to hexavalent alcohols (polyols) that can be used as raw materials for the polyisocyanate of the present invention include non-condensed polyols and polymerized polyols. The non-polymerized polyol is a polyol that does not undergo polymerization, and the polymerized polyol is a polyol obtained by polymerizing a monomer.

Examples of the non-polymerized polyol include monohydric alcohols, diols, triols, and tetraols. The monohydric alcohols are not particularly limited and include, for example, alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, N-nonanol, 2-ethylbutanol, 2,2-dimethylhexanol, 2-ethylhexanol, cyclohexanol, methylcyclohexanol, ethylcyclohexanol and the like. Examples of the diols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, Butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, Hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethylhexanediol 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2- -Propanediol, and the like. The triol is not particularly limited, and examples thereof include glycerin, trimethylolpropane, and the like. The tetraol is not particularly limited, and examples thereof include pentaerythritol and the like.

The polymerization polyol is not particularly limited, and examples thereof include a polyester polyol, a polyether polyol, an acrylic polyol, and a polyolefin polyol.

The polyester polyol is not particularly limited, and examples thereof include dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, dimeric acid, maleic anhydride, phthalic anhydride, isophthalic acid and terephthalic acid, , A polyester polyol obtained by condensation reaction with a polyhydric alcohol such as propylene glycol, diethylene glycol, neopentyl glycol, trimethylol propane or glycerin, or a mixture thereof, or a polyhydric alcohol is subjected to ring-opening polymerization And polycaprolactones to be obtained.

Examples of the polyether polyol include, but are not particularly limited to, strong bases such as hydroxides of lithium, sodium, and potassium, strong bases such as alcoholates and alkyl amines, complex metal cyanide complexes such as metal porphyrin and hexacyanocobaltate complex Alone or a mixture of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide and styrene oxide may be used alone or in a mixture of a polyhydric hydroxy compound and a random or block additive And polyether polyols obtained by reacting an alkylene oxide with a polyamine compound such as ethylenediamine. Called polymer polyols obtained by polymerizing acrylamide or the like using these polyethers as a medium.

The polyisocyanate used in the present invention preferably contains an isocyanurate group. A coating film cured by using a polyisocyanate having an isocyanurate group has good weather resistance.

The polyisocyanate used in the present invention may simultaneously contain functional groups other than isocyanurate groups such as a biuret group, urea group, uretdione group, urethane group, allophanate group and oxadiazine trione group .

The polyisocyanate having an isocyanurate group is obtained by, for example, carrying out an isocyanurization reaction with a catalyst or the like, stopping the reaction at a predetermined conversion rate, and removing the diisocyanate monomer. As the isocyanuration reaction catalyst to be used at this time, it is generally preferable to have a basicity. Specifically, it is preferable to use (a) an organic solvent such as hydroxides of tetraalkylammonium such as tetramethylammonium and tetraethylammonium, (B) an organic acid such as a hydroxy group or acetic acid of a hydroxyalkyl ammonium such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium or triethylhydroxyethylammonium, (c) Zinc, lead and the like, (d) metal alcoholates such as sodium and potassium, (e) hexamethyldisilazane, (e) hexamethyldisilazane, and (e) alkali metal salts of alkylcarboxylic acids such as acetic acid, octylic acid, (F) Mannich bases, (g) a combination of tertiary amines and an epoxy compound, and (h) phosphorus compounds such as tributylphosphine. The amount of these catalysts to be used is selected from the range of 10 ppm to 1% with respect to the total mass of the raw material diisocyanate and polyol. In order to terminate the reaction, these isocyanuration reaction catalysts are inactivated by addition of an acidic substance such as phosphoric acid or acidic phosphate ester which neutralizes the catalyst, pyrolysis and chemical decomposition.

The yield of the polyisocyanate is 10 to 70 mass%. The polyisocyanate obtained at a high yield tends to have an increased viscosity.

The reaction temperature of the isocyanuration reaction is preferably 20 占 폚 or higher from the viewpoint of enhancing the reactivity and is preferably 200 占 폚 or lower from the viewpoint of inhibiting the coloration of the product and the occurrence of side reactions. More preferably, it is 50 to 150 ° C.

After completion of the reaction, the diisocyanate monomer is removed by a thin-film evaporator, extraction, or the like, so that the polyisocyanate does not substantially contain a diisocyanate monomer. The residual unreacted diisocyanate concentration in the obtained polyisocyanate is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less from the viewpoint of enhancing curability.

The viscosity of the polyisocyanate usable in the present invention is 100 to 30000 mPa · s, preferably 500 to 10000 mPa · s, more preferably 550 to 4000 mPa · s at 25 ° C.

The number average molecular weight of the polyisocyanate used in the present invention is preferably 500 to 2000, more preferably 550 to 1000.

The statistical average isocyanate group number (average number of isocyanate functional groups) of one molecule of the polyisocyanate is preferably 4 or more from the viewpoint of enhancing the crosslinking property, and from the viewpoint of improving solubility in solvents and dispersion stability in water, Or less. More preferably 4 to 15, still more preferably 4 to 9.

The isocyanate group concentration in the polyisocyanate is preferably from 5 to 25 mass%, more preferably from 10 to 24 mass%, and still more preferably from 15 to 24 mass%.

[Polyethylene oxide unit which is a terminal hydroxyl group]

The block polyisocyanate of the present invention has a polyethylene oxide unit which is an end-capped hydroxyl group. A polyethyleneoxide residue which is an end-capped hydroxyl group, a compound having a hydroxyl group at one end of polyethylene oxide, and a compound obtained by adding ethylene oxide to the starting monohydric alcohol. The number of carbon atoms of the starting monoalcohol is preferably 1 to 10. The starting monoalcohol is not particularly limited, and examples thereof include methanol, ethanol, 2-propanol, n-butanol, sec-butanol and 2-ethyl-1-hexanol. Among others, the preferred starting monoalcohol is methanol.

The molecular weight of the polyethylene oxide as the one-terminal hydroxyl group is preferably 300 to 2000, more preferably 300 to 1500, still more preferably 500 to 1000.

[Block unit]

The block polyisocyanate of the present invention has a block unit (a block-derived unit). Examples of the blocking agent include compounds having one active hydrogen in the molecule, such as alcohol compounds, alkylphenol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, An imidazole compound, an oxime compound, an amine compound, an imide compound, a pyrazole compound, and the like. An example of a more specific blocking agent is shown below.

(1) an alcohol compound; Butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol and the like,

(2) alkylphenol compounds; Mono- and dialkylphenols having an alkyl group of 4 or more carbon atoms as a substituent, for example, n-propylphenol, i-propylphenol, n-butylphenol, sec-butylphenol, t- - monoalkylphenols such as ethylhexylphenol, n-octylphenol and n-nonylphenol, and monoalkylphenols such as di-n-propylphenol, diisopropylphenol, isopropylcresol, di- , Di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol and di-

(3) phenolic compounds; Phenol, cresol, ethyl phenol, styrenated phenol, hydroxybenzoic acid ester,

(4) active methylene-based compounds; Dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and the like,

(5) mercaptan-based compounds; Butyl mercaptan, dodecyl mercaptan, etc.,

(6) acid amide compounds; Acetanilide, acetic acid amide,? -Caprolactam,? -Valerolactam,? -Butyrolactam, and the like,

(7) acid imide compounds; Succinic acid imide, maleic acid imide,

(8) imidazole-based compounds; Imidazole, 2-methylimidazole, etc.,

(9) urea-based compounds; Element, thio element, ethylene element, etc.,

(10) oxime compounds; Phosgene toxicity, acetaldehyde, acetoxime, methylethylketoxime, cyclohexanone oxime, and the like,

(11) an amine compound; Diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, isopropylethylamine,

(12) an imine compound; Ethyleneimine, polyethyleneimine, and the like

(13) a pyrazole-based compound; Pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.

These may be used in combination of two or more. A preferred block agent is an amine compound (preferably an aliphatic amine compound) or a pyrazole compound, more preferably a block agent is a pyrazole compound, and 3,5-dimethylpyrazole is particularly preferable. The use of a pyrazole-based compound, especially 3,5-dimethylpyrazole, tends to further improve the curability at low temperatures or in short-term drying.

When the block polyisocyanate is obtained, a monool obtained by polymerizing an alkylene oxide having 3 or more carbon atoms can be used.

A monool polymerized with an alkylene oxide having 3 or more carbon atoms is derived from an initiating monoalcohol and an alkylene oxide having 3 or more carbon atoms. The number of carbon atoms of the starting monoalcohol is 1 to 10, preferably 2 to 8, and more preferably 4 to 8. Specific examples of these monoalcohols include, but are not limited to, alcohols such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol and 2-ethyl-1-hexanol.

Examples of the alkylene oxide having 3 or more carbon atoms include, but not limited to, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide. Propylene oxide is preferred. Examples of the alkylene oxide having 3 or more carbon atoms include, but are not limited to, hydroxides such as lithium, sodium and potassium, strong basic catalysts such as alcoholate and alkylamine, metal complexes such as metal porphyrin and zinc hexacyanocobaltate complex Cyan compound complexes or the like, alone or in admixture of these alkylene oxides to the above-mentioned starting monoalcohol.

The number-average molecular weight of the monools obtained by polymerizing alkylene oxides having 3 or more carbon atoms is preferably 300 or more from the viewpoint of improving the compatibility of the block polyisocyanate with the polyol. From the viewpoint of increasing the hardness of the obtained coating film, it is preferably 2000 or less. More preferably from 300 to 1,500, and still more preferably from 350 to 1,000.

The mass concentrations of the components in the block polyisocyanates of the present invention are described. When the block polyisocyanate of the present invention is 100 mass%, the component concentration of the polyethylene oxide unit as one terminal hydroxyl group is preferably 15 mass% or more from the viewpoint of improving the solubility in water and the dispersibility. Further, from the viewpoint of enhancing the strength of the obtained coating film, 30 mass% or less is preferable. And more preferably 15 to 25 mass%.

From the viewpoint of increasing the isocyanate group concentration, the component concentration of the polyisocyanate unit when the block polyisocyanate of the present invention is 100 mass% is preferably 45 mass% or more and preferably 65 mass% or less Do. And more preferably 50 to 60 mass%.

When the block polyisocyanate of the present invention is used in an amount of 100 mass%, the component concentration in the block unit is preferably 15 mass% or more from the viewpoint of enhancing the curability. As the component concentration of the block agent increases, the component concentration of the polyethylene oxide which is one terminal hydroxyl group is decreased. Therefore, from the viewpoint of increasing the proportion of the constituent unit derived from polyethylene oxide which is one terminal hydroxyl group, 30 mass% or less is preferable in order to obtain good water dispersion stability. More preferably from 20 to 30% by mass.

The concentration of the component in the block polyisocyanate of the present invention in the unit of a polyethylene oxide unit, a polyisocyanate unit, and a block unit, which is an end-capped hydroxyl group, can be specified, for example, by ¹ H-NMR or ¹³ C- Can also be specified.

The block polyisocyanate of the present invention includes a polyisocyanate unit and a polyethylene oxide unit which is an end-capped hydroxyl group, and a polyisocyanate unit and a block unit.

The component concentration of the diisocyanate trimer in the block polyisocyanate of the present invention is preferably 5% by mass or more from the viewpoints of the hardness and the high weather resistance of the obtained coating film. Further, from the viewpoint of enhancing the elongation of the obtained coating film, it is preferably 40 mass% or less. , More preferably 10 to 40 mass%, and further preferably 10 to 30 mass%. The diisocyanate trimer component is a polyisocyanate having an isocyanate group number of 3 per molecule and a block polyisocyanate derived from a block third molecule, which are obtained from three diisocyanate monomers.

The number average molecular weight of the block polyisocyanate of the present invention is preferably 1,000 or more from the viewpoint of increasing the isocyanate group concentration in order to increase the curability. Further, from the viewpoint of good compatibility with the polyol, it is preferably 3,000 or less. And more preferably from 1000 to 2500.

The isocyanate group concentration blocked with the blocking agent of the block polyisocyanate of the present invention is preferably 5% by mass or more from the viewpoint of enhancing the curability. Further, from the viewpoint of strengthening the obtained coating film, 15 mass% or less is preferable.

An aqueous dispersion of the block polyisocyanate of the present invention can be obtained by using the raw materials described in detail above. An example of the production method thereof will be described in detail.

First, polyisocyanate is reacted with polyethylene oxide which is a hydroxyl group at one end. In the reaction, organic metal salts such as tin, zinc and lead, and tertiary amine compounds, alcoholates of alkali metals such as sodium, and the like may be used as catalysts.

The reaction temperature at this time is preferably -20 占 폚 or higher from the viewpoint of enhancing the reactivity. From the standpoint of suppressing the side reaction, the temperature is preferably 150 占 폚 or lower. More preferably 30 to 100 ° C.

It is preferable to completely react with the polyisocyanate so that the polyethyleneoxide which is the terminal hydroxyl at one end does not remain in the unreacted state. In a state remaining in an unreacted state, the water dispersion stability and curability of the block polyisocyanate may be lowered.

The residual isocyanate group of the polyisocyanate reacted with polyethylene oxide as the one-end hydroxyl group thus obtained is allowed to react with the blocking agent. The reaction conditions such as the reaction temperature and the catalyst can be performed in the same manner as the above reaction. When an isocyanate group is present after the reaction, it is preferable to add a block agent or the like to completely eliminate the isocyanate group. These reactions can be carried out in the presence of a solvent. The solvent in this case preferably contains no active hydrogen.

Thereafter, water is added. Water is preferably added by dividing or dropping a predetermined amount. In the case of dividing, it is preferable to divide a predetermined amount into 4 to 8 parts. If the block polyisocyanate concentration is 50% by mass or more, it is preferable to maintain the temperature at 50 to 80 ° C, and at 10% by mass or more and less than 50% by mass, the temperature is maintained at 20 to 50 ° C or less.

When the water is added all at once or when the liquid temperature is outside the above range, the average dispersed particle diameter of the block polyisocyanate becomes large, and precipitation or separation may occur.

The inventors of the present invention have found that the water addition method and the liquid temperature at the time of addition greatly affect the average dispersed particle diameter of the block polyisocyanate, and the influence varies depending on the block polyisocyanate concentration. Conventionally, when it is desired to reduce the average dispersed particle diameter of the block polyisocyanate, the addition amount of the hydrophilic group is increased. However, it is surprising that the average dispersed particle diameter can be made small by a small amount of hydrophilic group, that is, polyethylene oxide having less terminal hydroxyl group than the conventional one. As described above, the average dispersed particle diameter of the block polyisocyanate of the aqueous dispersion of the present invention can be controlled to 1 to 250 nm, preferably 1 to 180 nm, more preferably 1 to 80 Nm.

Also, by doing the above, the average dispersed particle diameter of the block polyisocyanate: [phi] can satisfy the following expression (1).

[Formula 1]

(A is the mass% of polyethylene oxide units which are one-end hydroxyl groups in the block polyisocyanate)

The water dispersion of the block polyisocyanate of the present invention may contain up to 20% by mass of a solvent other than water. Examples of the solvent in this case include, but are not limited to, 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene Propanol, iso-butanol, 1-butanol, 2-ethyl-1-butanol, isobutanol, isobutanol, propanol, isobutanol, Hexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol , Isobutanol, isobutanol, 1,4-butanediol, 1,3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso- pentane, hexane, isohexane, cyclohexane, . These solvents may be used alone or in combination of two or more. From the viewpoint of dispersibility in water, the solvent preferably has a solubility in water of 5% by mass or more, and specifically, dipropylene glycol dimethyl ether and dipropylene glycol monomethyl ether are preferable.

The block polyisocyanate concentration of the water dispersion thus obtained is preferably 10 to 40%.

[Textile treating composition]

The fiber treatment composition of the present invention includes a fluororesin having substantially no perfluoroalkyl group of 8 or more carbon atoms and an aqueous dispersion of the block polyisocyanate.

The fluororesin used in the present invention is a fluororesin which does not substantially contain a perfluoroalkyl group having 8 or more carbon atoms and may contain a perfluorohexyl group having 6 carbon atoms. The fluororesin may be a polymer obtained by polymerizing an acrylate or methacrylate containing fluorine as a monomer. The fluorine-containing acrylate or methacrylate is not particularly limited, but specifically includes a perfluoroalkyl group having 3 to 6 carbon atoms. A perfluorooctyl group having 8 carbon atoms is pointed out to generate perfluorooctanoic acid which is likely to accumulate in the environment or human body. Thus, by using a fluorine resin containing a perfluoroalkyl group having a low carbon number and substantially not containing a perfluoroalkyl group having 8 or more carbon atoms, a fiber treatment composition in which perfluorooctanoic acid is not substantially generated can be obtained .

When the number of carbon atoms of the perfluoroalkyl group is 6 or less, the performance may be lowered as compared with the case where the number of carbon atoms thereof is 8 or more. The block polyisocyanate of the present invention improves the mechanical stability of a fluororesin containing substantially no perfluoroalkyl group having at least 8 carbon atoms.

In addition to the fluorine monomer, other monomers may be used in combination. Monomers that can be used in combination include the following. Examples of other monomers copolymerizable with acrylate and / or methacrylate having a perfluoroalkyl group include the followings.

Examples of acrylic acid or methacrylic acid esters include, but are not particularly limited to, acrylic acid, methacrylic acid, Diallyl acrylate, glycidyl methacrylate, aziridyl acrylate, aziridyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, Alkylene diol acrylate, and the like.

Examples of the acrylamide or methacrylamide include, but are not limited to, acrylamide such as alkylene diol dimethacrylate, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, diacetone Acrylamide, diacetone methacrylamide, methylol diacetone acrylamide, and the like.

Examples of the maleic acid alkyl esters include, but are not limited to, dibutyl maleate and the like.

Examples of the olefins include, but are not limited to, ethylene, propylene, butadiene, isoprene, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride and chloroprene.

The vinyl carboxylate is not particularly limited, and examples thereof include vinyl acetate and the like.

Examples of the styrenes include, but are not limited to, styrene,? -Methylstyrene,? -Methylstyrene, and the like.

Examples of the vinyl ethers include, but are not limited to, ethyl vinyl ether, cyclohexyl vinyl ether, halogenated alkyl vinyl ether, and the like.

The proportion of the acrylate and / or methacrylate having a perfluoroalkyl group and the other monomer copolymerizable therewith is preferably such that the total amount of the acrylate and / or methacrylate having a perfluoroalkyl group Is preferably 40 mass% or more, more preferably 50 to 80 mass%.

These copolymers can be produced by solution polymerization, emulsion polymerization, suspension polymerization, or the like, which is a known polymerization method, but they are preferably produced by emulsion polymerization.

The fluororesin thus obtained and the aqueous dispersion of the block polyisocyanate are suitably used as a fiber treatment composition in the treatment of a fabric.

The resin mass ratio of the fluororesin and the block polyisocyanate aqueous dispersion is 50:50 to 95: 5, preferably 70:30 to 95: 5, and more preferably 80:20 to 90:10. When the content is in the above range, water repellency tends to be more excellent.

The fiber treatment composition of the present invention may further contain other additives such as flame retardants, dye stabilizers, antiblocking agents, antibacterial agents, antifungal agents, insect repellents, antifouling agents, antistatic agents, aminoplast resins, acrylic polymers, glyoxal resins, A melamine resin, a natural wax, a silicone resin, a thickener, a polymer compound and the like.

The fiber treatment composition of the present invention thus formulated is diluted with water if necessary. The resin concentration after dilution is usually 0.5 to 5 mass%, preferably 0.5 to 3 mass%.

〔fabric〕

The fabric of the present invention is treated with the above fiber treatment composition. The fluororesin is used as a fiber treatment agent for imparting water repellency to the fabric. As a method for evaluating the water repellency, a spray test of JIS-L-1092 and a contact angle measurement of water / isopropyl alcohol (1/1 by mass ratio) can be mentioned.

Also, the water repellency (washing durability) of the fabric after washing is also a very important performance. One of the washing methods is JIS-L-0217-103. The decrease in water repellency can be evaluated, for example, by comparing before washing and after 10 times of washing.

As described above, a fluororesin containing substantially no perfluoroalkyl group having 8 or more carbon atoms is generally inferior in durability to washing as compared with a fluororesin containing a perfluoroalkyl group having 8 or more carbon atoms. Surprisingly, however, the fabric treated with the fiber treating composition of the present invention can exhibit very good washing durability.

It is preferable that the fabric of the present invention is coated with a fluororesin having a contact angle of water / isopropyl alcohol (1/1 by mass ratio) 10 times or more after washing to 90 degrees or more and having substantially no perfluoroalkyl group having 8 or more carbon atoms Do. The contact angle after 10 times of washing is more preferably 90 degrees or more, and more preferably 92 degrees or more. With the above range, washing durability tends to be more excellent.

Further, the maintenance ratio of the contact angle of water / isopropyl alcohol (ratio by mass: 1/1) after washing 10 times to the contact angle of water / isopropyl alcohol (1/1 by mass ratio) Contact angle:%) is preferably 94% or more, more preferably 96% or more, and further preferably 98% or more. The above range tends to further improve the durability of washing.

The fluororesin coated on the fabric and substantially not containing a perfluoroalkyl group having 8 or more carbon atoms can be specified by a combustion ion chromatography method and TOF-SIMS. Also, the polyisocyanate coated on the fabric can be specified by TOF-SIMS. Here, "substantially free of perfluoroalkyl groups having 8 or more carbon atoms" means that m / z 377, m / z 427 and m / z 461 are not detected by measurement by TOF-SIMS using the following apparatus .

Device: TRIFT III (made by Physical Electronics)

Primary ion: Ga +

Acceleration voltage: 15kV

Current: 600pA

Analysis area: 200 탆 x 200 탆

Detection ion: cation

Electron gun: Yes

The treatment of the fiber using the fiber treatment composition of the present invention can be carried out by attaching a resin to the fiber and then heating it. The resin can be adhered by, for example, a pad method, a dipping method, a spray method, a coating method, a printing method, or the like.

Thereafter, it is adjusted to a predetermined pickup amount (resin adhesion amount) by using a mangle or the like, and then heated at a temperature of 100 캜 or higher. Preferably at a temperature of about 140 to 180 DEG C for 10 seconds to 10 minutes, preferably 30 seconds to 3 minutes.

Examples of the type of fabric to which the treatment liquid of the present invention can be applied include cotton, kapok, flax, horse, jute, manila hemp, sisal, wool, cashmere, mohair, alpaca, camel, Natural fibers, regenerated fibers such as rayon, polynosic, cupra and tencel, semisynthetic fibers such as cellulose acetate fiber and pro mix, polyamide fiber, polyester fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride Synthetic fibers such as fibers, polyurethane fibers, polyoxymethylene fibers, polytetrafluoroethylene fibers, benzoide fibers, polyparaphenylene benzbisthiazole fibers, polyparaphenylenebenzbisoxazole fibers and polyimide fibers, asbestos fibers , Glass fibers, carbon fibers, alumina fibers, silicon carbide fibers, boron fibers, tirano fibers, inorganic whiskers, lock fibers, slag fibers and the like Fibers, composite fibers thereof, and blend fibers. Examples of the form include a woven fabric, a knitted fabric, and a nonwoven fabric.

Example

The present invention will be described concretely with reference to the following examples and the like, but the present invention is not limited thereto.

(1) Viscosity measurement:

The viscosity was measured using the following apparatus.

Device: RE-80R (Ax soldering)

Rotor: Cone plate 1 ° 34 '× R24

Measuring temperature: 25 ° C

(2) Measurement of number average molecular weight:

The number average molecular weight was determined to be the number average molecular weight based on polystyrene by gel permeation chromatography using the following apparatus.

Apparatus: HLC-802A (a plasticizer)

Column: G1000HXL x 1 (made by Tosoh Corporation)

G2000HXL × 1 (made by Tosoh)

G3000HXL × 1 (made by Tosoh Corporation)

Carrier: tetrahydrofuran

Flow rate: 0.6 mL / min

Sample concentration: 1.0 mass%

Injection volume: 20 μL

Temperature: 40 ° C

Detection method: Differential refractometer

(3) Content of isocyanate group of polyisocyanate:

1 to 3 g of polyisocyanate is precisely weighed (Wg) into an Erlenmeyer flask and then 20 ml of toluene is added to dissolve the polyisocyanate. Thereafter, 10 ml of a toluene solution of 2-di-n-butylamine of the formula 2 was added, mixed, and allowed to stand at room temperature for 15 minutes. 70 ml of isopropyl alcohol is added and mixed. Titrate this solution with 1 N hydrochloric acid solution (Factor F) and indicator. The same operation as in Example 1 was carried out without polyisocyanate, and the appropriate value was taken as V1 ml. The isocyanate group content of the polyisocyanate was calculated from the following equation.

[Formula 2]

Isocyanate group content (mass%) = (V1 - V2) x F 42 / (W x 1000) x 100

(4) Method of measuring the average number of isocyanate functional groups:

And the average number of isocyanate functional groups was determined by the following formula 3.

[Formula 3]

Average number of isocyanate functional groups = polyisocyanate number average molecular weight (Mn) x isocyanate group content (mass%) x 0.01) / 42

(5) Average dispersed particle diameter (volume average dispersed particle diameter):

The volume average particle diameter was measured using the following apparatus.

Apparatus: Nanotrac UPA-EX150 (manufactured by Nikkiso)

Solvent: water

Temperature: 23 ° C

(6) Water dispersion stability:

The presence or absence of a precipitate was visually observed for a water-dispersed composition having a block polyisocyanate content of 30% by mass, and it was shown that when no precipitate was observed, it was indicated by o, when a small amount of precipitate was present, and when there was separation or a large amount of precipitate, .

(7) Coating strength:

Using the TENSILON RTE-1210 (manufactured by A & D), the film strength was measured under the following conditions. Curing of the coating film was carried out at 150 ° C for 30 minutes. The breaking strength of the coating film at this time was recorded. The higher the value, the higher the strength.

Tensile speed: 20 mm / min

Sample size: 20 mm length x 10 mm width x thickness 20 to 40 m

Temperature: 23 ° C

Humidity: 50%

(8) Mechanical stability:

The mixture of block polyisocyanate and fiber treatment composition was diluted to 20% with water. The mixture was heated to 50 DEG C and stirred at a rate of 5,000 rpm for 10 minutes using a homomixer. Then, the resulting aggregates were filtered with a cotton cloth and dried to measure the weight of the aggregates. The numerical value calculated by the following formula 4 was taken as an aggregation occurrence rate and used as an index of mechanical stability. The lower the incidence of aggregates, the better the mechanical stability.

[Formula 4] Rate of occurrence of aggregates (mass%) = 100 占 (weight of aggregate / weight of mixed liquid)

(9) Contact angle:

Using a contact angle meter (manufactured by FIBRO system ab), the contact angle of the fabric (contact angle to water / isopropyl alcohol (mass ratio 1/1)) was measured by a droplet method.

Retention ratio (%) = contact angle after washing 10 times / contact angle before washing

(10) Water repellency test:

A spray test of JIS-L-1092 was carried out to observe and evaluate the wet state of the surface. The evaluation was done in this way. The higher the value, the better the water repellency.

5: No wetting or adhesion of water droplets on the surface.

4: No wetting on the surface, but showing adhesion of small droplets.

3: Wetting of small individual water phase on the surface.

2: exhibited wetting in half of the surface, and small individual wetting penetrated the fabric.

1: Wetted throughout the surface.

(11) Specification of a fluororesin substantially free of a perfluoroalkyl group of at least 8 carbon atoms coated on a fabric:

The fluororesin substantially free from perfluoroalkyl groups of 8 or more carbon atoms coated on the fabric was specified by the following two analytical methods.

Analysis 1: Combustion ion chromatography

The presence or absence of fluorine was confirmed by a combustion ion chromatography method using the following apparatus.

Apparatus: AQF-100 (manufactured by Mitsubishi Chemical Industries, Ltd.)

Combustion tube: quartz

Burning temperature: 1000 ℃

Column: SurperIC-AZ (Toso Co.)

Temperature: 40 ° C

Flow rate: 0.8 mL / min

Detection method: Electrical conductivity

Analysis 2: TOF-SIMS

Whether m / z 377, m / z 427, and m / z 461 were not detected or not was determined by measurement by TOF-SIMS using the following apparatus to determine whether or not a fluororesin containing substantially no perfluoroalkyl group having 8 or more carbon atoms And whether or not it will be.

Device: TRIFT III (made by Physical Electronics)

Primary ion: Ga +

Acceleration voltage: 15kV

Current: 600pA

Analysis area: 200 탆 x 200 탆

Detection ion: cation

Electron gun: Yes

(Preparation Example 1: Production of polyisocyanate)

1000 parts by mass of HDI and 22 parts by mass of trimethylol propane (molecular weight 134), which is a trivalent alcohol, were put into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen suction tube, Was maintained at 90 占 폚 for 1 hour to carry out urethanization. Thereafter, the temperature of the reaction solution was maintained at 60 占 폚, and tetracyanoammonium capribenzoate as an isocyanurating catalyst was added. Phosphoric acid was added at a point of time when the conversion rate reached 48%, and the reaction was terminated. Thereafter, the reaction solution was filtered, and unreacted HDI was removed by a thin-film distillation apparatus.

The obtained polyisocyanate had a viscosity of 25,000 mPa 25 at 25 캜, an isocyanate group content of 19.9% by mass, a number average molecular weight of 1080 and an average number of isocyanate functional groups of 5.1.

(Production Example 2: Production of polyisocyanate)

A nitrogen atmosphere was set in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube and a dropping funnel, and 1000 parts by mass of HDI was introduced. The temperature in the reactor under stirring was maintained at 70 占 폚. The isocyanuration catalyst, tetramethylammonium capribenzoate, was added and, when the yield reached 40%, phosphoric acid was added and the reaction was terminated. The reaction solution was filtered, and unreacted HDI was removed using a thin-film evaporator.

The obtained polyisocyanate had a viscosity of 2700 mPa 25 at 25 캜, an isocyanate content of 21.7%, a number average molecular weight of 660 and an average number of isocyanate functional groups of 3.4.

(Example 1)

100 parts by mass of the polyisocyanate obtained in Preparation Example 1, 1.5 parts by mass of monool (trade name "EXCENOL 908" available from Asahi Glass Co., Ltd.), 1.5 parts by mass of polyethylene oxide (Nippon Kogyo Co., 42.5 parts by mass of a product of Nippon Kayaku Co., Ltd., trade name " MPG-081 ") and 0.01 part by mass of an urethane formation catalyst (trade name: Neostan U-810, manufactured by Nitto Kasei Kogyo K.K.) Lt; 0 > C for 2 hours. Thereafter, 39.4 parts by mass of 3,5-dimethylpyrazole was added, and it was confirmed that the characteristic absorption of the isocyanate group was eliminated by an infrared spectrum (Nippon Bunko Co., Ltd .: product name: FT / IR-4000).

Thereafter, 185 parts by mass of water was added at a rate of 25 parts by mass per minute while maintaining the liquid temperature at 80 to 50 占 폚, and the mixture was maintained for 10 minutes after the addition. Thereafter, 242.9 parts by mass of water were added at a rate of 25 parts by mass per minute while maintaining the liquid temperature at 50 to 40 占 폚, and the mixture was stirred for 30 minutes to obtain an aqueous block polyisocyanate aqueous dispersion.

The obtained block polyisocyanate aqueous dispersion had a block polyisocyanate concentration of 30.0% by mass, a water concentration of 70.0% by mass, an average dispersed particle diameter of 25 nm, and good water dispersion stability.

(Examples 2 to 5, 7 to 9)

Except for those described in Table 1, the same procedures as in Example 1 were carried out. The results are shown in Table 1.

(Example 6)

100 parts by mass of the polyisocyanate obtained in Preparation Example 1, 1.5 parts by mass of monool (trade name "EXCENOL 908" available from Asahi Glass Co., Ltd.), 1.5 parts by mass of polyethylene oxide (Nippon Kogyo Co., 42.5 parts by mass of a product of Nippon Kayaku Co., Ltd., trade name " MPG-081 ") and 0.01 part by mass of an urethane formation catalyst (trade name: Neostan U-810, manufactured by Nitto Kasei Kogyo K.K.) Lt; 0 > C for 2 hours. Thereafter, 39.4 parts by mass of 3,5-dimethylpyrazole was added, and it was confirmed that the characteristic absorption of the isocyanate group was eliminated by an infrared spectrum (Nippon Bunko Co., Ltd .: product name: FT / IR-4000).

Thereafter, 427.9 parts by mass of water was added at a rate of 25 parts by mass per minute while maintaining the liquid temperature at 80 ° C, and the mixture was stirred for 30 minutes to obtain an aqueous block polyisocyanate aqueous dispersion.

The obtained block polyisocyanate aqueous dispersion had a block polyisocyanate concentration of 30.0% by mass, a water concentration of 70.0% by mass, an average dispersed particle diameter of 100 nm, and good water dispersion stability.

(Comparative Example 1)

In a reactor similar to that of Production Example 1, 109.7 parts by mass of the polyisocyanate obtained in Preparation Example 1, 0.2 parts by mass of monool (trade name "EXCENOL 908" available from Asahi Glass Co., Ltd.), and polyethylene oxide 27.5 parts by mass, trade name " MPG-081 ", manufactured by Nippon Kayaku Co., Ltd.) and 0.01 part by mass of urethanation catalyst (trade name: Neostan U-810, manufactured by Nitto Kasei Kogyo K.K.) Lt; 0 > C for 2 hours. Thereafter, 46.0 parts by mass of 3,5-dimethylpyrazole was added, and it was confirmed that the characteristic absorption of the isocyanate group was eliminated by an infrared spectrum (Nippon Bunko Co., Ltd .: product name: FT / IR-4000).

Thereafter, 427.9 parts by mass of water at 15 캜 was added and mixed by stirring for 30 minutes to obtain an aqueous block polyisocyanate aqueous dispersion.

The concentration of the block polyisocyanate in the obtained block polyisocyanate aqueous dispersion was 30.0 mass%, the concentration of water was 70.0 mass%, the average dispersed particle diameter was 262 nm, and the water dispersion stability was poor.

(Comparative Examples 2 and 3)

Except for those described in Table 1, the same procedures as in Example 1 were carried out. The results are shown in Table 1.

(Comparative Example 4)

100 parts by mass of the polyisocyanate obtained in Production Example 2 and 150 parts by mass of methyl isobutyl ketone were charged in the same reactor as in Production Example 1, and the mixture was heated to 80 占 폚 in a nitrogen atmosphere. Then, 50 parts by mass of 3,5-dimethylpyrazole , And it was confirmed that the characteristic absorption of the isocyanate group was eliminated by an infrared spectrum (product name: FT / IR-4000, manufactured by Nippon Bunko Co., Ltd.).

Thereafter, 3 parts of dialkyl (cured Uji) dimethyl ammonium chloride and 30 parts of polyoxyethylene polyoxypropylene block polymer are added, and stirring is started. Then, 221 parts by mass of water was slowly added thereto. After completion of the addition, the mixture was added to a homomixer and further dispersed. Thereafter, methyl isobutyl ketone was distilled off under reduced pressure to obtain an emulsion having a solid content of 45% and an average dispersed particle diameter of 170 nm.

A-1: Polyisocyanate of Preparation Example 1

A-2: Polyisocyanate of Preparation Example 2

A-3: Isocyanurate type polyisocyanate of IPDI monomer (trade name "VESTANAT T1890 / 100" manufactured by Evonik Degussa)

B: Monool (Trade name of Exenol 908, product of Asahi Glass Co., Ltd.)

C: Polyethylene oxide (trade name of MPG-081, manufactured by Nippon Nyuga Co., Ltd.)

D-1: 3,5-Dimethylpyrazole

D-2: Methyl ethyl ketoxime

E: Urethanization catalyst (trade name of Neostan U-810)

F: dipropylene glycol dimethyl ether

(Example 10)

A solution of dimethylaminoethanol neutralized product 100 (product name) of an aqueous polyester polyol "SETAL6306 SS-60 (trade name)" (product of NUPLEX, a hydroxyl group concentration of 2.7 mass% (based on resin), an acid value of 43 mg KOH / g , 133 parts by mass of the block polyisocyanate aqueous dispersion obtained in Example 1 and 52 parts by mass of dipropylene glycol monomethyl ether were mixed to prepare a coating material having a solid content of 35% by mass. This paint was applied to a polypropylene plate so as to have a dry film thickness of 30 占 퐉. After setting at room temperature for 15 minutes, the coating film was cured at 150 ° C for 30 minutes. The film strength was 22 MPa.

(Examples 11 to 18 and Comparative Examples 5 to 8)

The procedure of Example 10 was repeated except that the aqueous dispersion of block polyisocyanate shown in Table 2 was used. The results of the film strength are shown in Table 2.

(Example 19)

90 parts by mass of a fluorine-based fiber treatment agent "Asahi Guard AG-E061 (trade name)" (manufactured by Asahi Glass Co., Ltd., solid content 20%), 6.7 parts by mass of the block polyisocyanate obtained in Example 1 and 3.3 parts by mass To prepare a mixed solution having a solid content of 20 mass%. As a result of measuring the mechanical stability of this mixed solution, the aggregation occurrence rate was 0.03 mass%.

Further, water was added to the mixed solution, and the solution was diluted to 1.0% by mass of the resin component concentration to obtain a treatment solution. A nylon cloth (Japan Standard Society Code No. 670108) was immersed in this treatment liquid and then squeezed with a roller so as to have a wet pickup of 50%. This was dried at 120 DEG C for 60 seconds and further dried at 170 DEG C for 60 seconds to obtain a test fabric. The contact angle was 95 degrees, and the water repellency test was 5.

The test fabric was also washed in accordance with JIS-L-0217-103. The detergent used was the product name of Attack of Kao Corporation. The number of times of washing was evaluated 10 times. The contact angle after washing was 93 degrees, and the water repellency test was 5.

In the combustion ion chromatography method, fluorine was detected, but the measurement result of the fluororesin containing substantially no perfluoroalkyl group of 8 or more carbon atoms coated on the fabric by TOF-SIMS was not detected.

(Examples 20 to 27 and Comparative Examples 9 to 12)

The procedure of Example 19 was repeated except that the aqueous dispersion of block polyisocyanate shown in Table 2 was used. The results of the flocculation rate, contact angle and water repellency test are shown in Table 3.

In Comparative Examples 9, 10 and 11, the stability of the water dispersion of the block polyisocyanate was poor, and the aggregate adhered to the surface of the test fabric, so that the contact angle and water repellency were not evaluated.

This application is based on Japanese Patent Application (Japanese Patent Application No. 2011-233472) filed with the Japanese Patent Office on October 25, 2011, the contents of which are incorporated herein by reference.

≪ Industrial applicability >

INDUSTRIAL APPLICABILITY The water dispersion of the block polyisocyanate of the present invention and the fiber treatment composition containing it can be suitably used in the fields of water repellent for fibers and the like.

Claims (12)

A block polyisocyanate having at least the following 1) to 3) component units and water,
Wherein the block polyisocyanate has an average dispersed particle diameter of 1 to 250 nm.
1) a polyisocyanate unit having at least one diisocyanate monomer unit selected from the group consisting of an aliphatic diisocyanate monomer and an alicyclic diisocyanate monomer
2) Polyethylene oxide unit which is a terminal hydroxyl group
3) block unit The aqueous dispersion of a block polyisocyanate according to claim 1, wherein the average dispersed particle diameter of the block polyisocyanate:? Satisfies the following formula (1).
[Formula 1]

(A is the mass% of polyethylene oxide units which are one-end hydroxyl groups in the block polyisocyanate) The aqueous dispersion of a block polyisocyanate according to claim 1, wherein the block polyisocyanate has the following composition.
1) 45 to 65% by mass of a polyisocyanate unit
2) 15 to 30% by mass of a polyethylene oxide unit
3) 15 to 30% by mass of block units The aqueous dispersion of a block polyisocyanate according to any one of claims 1 to 3, wherein the average number of isocyanate functional groups of the polyisocyanate unit is 4 to 20. 4. The water dispersion of block polyisocyanate according to any one of claims 1 to 3, wherein the block agent is a pyrazole compound. 4. The water dispersion of block polyisocyanate according to any one of claims 1 to 3, wherein at least one of said diisocyanate monomers is hexamethylene diisocyanate. The aqueous dispersion of a block polyisocyanate according to any one of claims 1 to 3, wherein the block polyisocyanate has an average dispersed particle diameter:? Of 1 to 80 nm. The block polyisocyanate according to any one of claims 1 to 3, wherein the average number of functional groups of isocyanate groups in the polyisocyanate unit is 4 to 20 and the average dispersed particle diameter of the block polyisocyanate is 1 to 80 nm. / RTI > A fluororesin containing a perfluoroalkyl group having 3 to 6 carbon atoms and having a perfluoroalkyl group with no more than 8 carbon atoms detected by measurement with TOF-SIMS, and a block poly A fiber treatment agent composition comprising an isocyanate water dispersion. A fabric treated by the textile treatment composition of claim 9. delete delete