WO2013061954A1

WO2013061954A1 - Blocked polyisocyanate water dispersion, fiber processing agent composition, and fabric

Info

Publication number: WO2013061954A1
Application number: PCT/JP2012/077333
Authority: WO
Inventors: 祐一三輪; 朝比奈　芳幸
Original assignee: 旭化成ケミカルズ株式会社
Priority date: 2011-10-25
Filing date: 2012-10-23
Publication date: 2013-05-02
Also published as: JP5809705B2; CN103890034B; TW201326243A; JPWO2013061954A1; TWI592434B; KR101593855B1; CN106008904A; KR20140040276A; CN103890034A

Abstract

The purpose of the present invention is to provide: a blocked polyisocyanate water dispersion having favorable water dispersion stability, capable of achieving high coating strength, exhibiting excellent mechanical stability as a fluorine-doped fiber processing agent, and capable of producing a fabric having high washability; and a fiber processing agent composition containing the same. The blocked polyisocyanate water dispersion contains water and a blocked polyisocyanate at least having component units (1-3), and has an average dispersed particle diameter of the blocked polyisocyanate of φ=1-250nm. 1) A polyisocyanate unit having at least one type of diisocyanate monomer unit selected from a group consisting of aliphatic diisocyanate monomers and alicyclic diisocyanate monomers. 2) A polyethylene oxide unit having a hydroxyl group on one end. 3) A blocking agent unit.

Description

Aqueous dispersion of block polyisocyanate, fiber treatment agent composition, and fabric

TECHNICAL FIELD The present invention relates to an aqueous dispersion of block polyisocyanate, a fiber treatment agent composition containing the same, and a fabric treated with the fiber treatment agent composition.

Fiber treatment agents are used to impart various functions to the fibers. Its functions include water and oil repellency to prevent the adhesion of water and oil, texture to make the comfort comfortable, and prevention of deformation of the sewn product.

Among these, as a fiber treatment agent imparting water repellency, a composition having a fluororesin having a perfluoroalkyl group having 8 or more carbon atoms has been used. However, a fluororesin having a perfluoroalkyl group having 8 or more carbon atoms may be decomposed to generate perfluorooctanoic acid, which is of concern for accumulation and toxicity when discharged into the environment. It has been pointed out that there is. For this reason, studies are being actively conducted to replace the fluorocarbon resin with a perfluoroalkyl group having 8 to 6 carbon atoms and generating no perfluorooctanoic acid.

However, a fluororesin having a perfluoroalkyl group having 6 or less carbon atoms may have lower performance such as water repellency after repeated washing than a resin having 8 or more carbon atoms. ing. As one method, in order to maintain performance, it has been studied to add a block polyisocyanate to a fiber treatment agent (Patent Documents 1 to 7).

Japanese translation of PCT publication No. 2002-511507 JP 2006-506226 A Special table 11-512772 gazette International Publication No. 00/58416 Pamphlet International Publication No. 2012/014850 Pamphlet International Publication No. 97/037076 Pamphlet US Patent Application Publication No. 2012/0238697

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

An object of the present invention is to provide an aqueous dispersion of a block polyisocyanate having good water dispersion stability and high coating strength, and a fiber treatment agent having excellent mechanical stability as a fluorine fiber treatment agent. It is to provide a composition and a fabric having high washing durability.

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

[1]
A block polyisocyanate having at least the following 1) to 3) component units and water,
The average dispersed particle size of the block polyisocyanate: φ is 1 to 250 nm.
Water dispersion of block polyisocyanate.
1) Polyisocyanate unit having at least one diisocyanate monomer unit selected from the group consisting of aliphatic diisocyanate monomer and alicyclic diisocyanate monomer 2) Polyethylene oxide unit which is a hydroxyl group at one end 3) Block agent unit [2]
The average dispersion particle diameter of the block polyisocyanate: The aqueous dispersion of the block polyisocyanate according to [1], wherein φ satisfies the following formula 1.
[Formula 1] 1 ≦ φ ≦ 310-8 × A
(A is the mass% of the polyethylene oxide unit which is a one-terminal hydroxyl group in the block polyisocyanate)
[3]
The aqueous dispersion of block polyisocyanate according to [1] or [2] above, 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 which is a hydroxyl group at one end 3) 15 to 30% by mass of a blocking agent unit [4]
The aqueous dispersion of blocked polyisocyanate according to any one of [1] to [3] above, wherein the polyisocyanate unit has an isocyanate average functional group number of 4 to 20.
[5]
The aqueous dispersion of blocked polyisocyanate according to any one of [1] to [4], wherein the blocking agent is a pyrazole compound.
[6]
The aqueous dispersion of blocked polyisocyanate according to any one of [1] to [5] above, wherein at least one of the diisocyanate monomers is hexamethylene diisocyanate.
[7]
The aqueous dispersion of blocked polyisocyanate according to any one of [1] to [6] above, wherein the average dispersed particle diameter of the blocked polyisocyanate: φ is 1 to 80 nm.
[8]
A fiber treating agent composition comprising a fluororesin having substantially no perfluoroalkyl group having 8 or more carbon atoms and an aqueous dispersion of the block polyisocyanate according to any one of [1] to [7] above. .
[9]
A fabric treated with the fiber treatment composition according to item [8].
[10]
The contact angle of water / isopropyl alcohol (mass ratio 1/1) after washing 10 times is 90 degrees or more,
A fabric coated with a fluororesin having substantially no perfluoroalkyl group having 8 or more carbon atoms.
[11]
The retention rate of the contact angle of water / isopropyl alcohol (mass ratio 1/1) after 10 washings with respect to the contact angle of water / isopropyl alcohol (mass ratio 1/1) when washing is not performed is 94% or more. The fabric according to [10] above.

The aqueous dispersion of the block polyisocyanate of the present invention has good water dispersion stability of the block polyisocyanate and can provide a coating film having high coating strength. Furthermore, the fiber treatment composition containing the water dispersion is excellent in mechanical stability, and the fabric treated with the fiber treatment composition has high washing durability.

Hereinafter, although the form for implementing this invention is described in detail, this invention is not limited to this, A various deformation | transformation is possible in the range which does not deviate from the summary.

[Aqueous dispersion of block polyisocyanate]
The aqueous dispersion of the block polyisocyanate of the present invention is
The block polyisocyanate having at least the following 1) to 3) component units and water are included, and the average dispersed particle diameter φ of the block polyisocyanate is 1 to 250 nm. The average dispersed particle size is preferably 1 to 180 nm, more preferably 1 to 80 nm. By being in the above-mentioned range, it tends to be more excellent in water dispersion stability and mechanical stability. The average dispersed particle diameter referred to here is a volume average dispersed particle diameter, and can be measured in detail by the method described in Examples.
1) Polyisocyanate unit having one or more diisocyanate monomer units selected from the group consisting of aliphatic diisocyanate monomers and alicyclic diisocyanate monomers 2) Polyethylene oxide units which are hydroxyl groups at one end 3) Block agent units

The block polyisocyanate of the present invention contains polyethylene oxide, which is a hydroxyl group at one end, which is a hydrophilic group, as a unit, and can reduce the average dispersed particle size with a smaller amount of hydrophilic groups than conventionally. Specifically, the average dispersed particle size of the blocked polyisocyanate preferably satisfies the following formula 1. By being in the above range, higher water dispersion stability and higher coating strength tend to be compatible.
[Formula 1] 1 ≦ φ ≦ 310-8 × A
(A is the mass% of the polyethylene oxide unit which is a one-terminal hydroxyl group in the block polyisocyanate)

[Polyisocyanate unit]
The block polyisocyanate of the present invention has a polyisocyanate unit. The aliphatic diisocyanate monomer and the alicyclic diisocyanate monomer that can be used as a raw material for polyisocyanate do not contain a benzene ring in the structure. The aliphatic diisocyanate monomer is not particularly limited, but is preferably one having 4 to 30 carbon atoms, such as 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 those having 8 to 30 carbon atoms are preferable. For example, isophorone diisocyanate (IPDI), 1,3-bis (isocyanatemethyl) -cyclohexane, 4,4′-dicyclohexylmethane diisocyanate. Etc. Of these, HDI is preferred because of weather resistance and industrial availability. Two or more of these can be used in combination.

In addition to the diisocyanate monomer, a monovalent to hexavalent alcohol can be used as a raw material for the polyisocyanate used in the present invention.

Examples of 1 to 6-valent alcohols (polyols) that can be used as a raw material for the polyisocyanate of the present invention include non-polymerized polyols and polymerized polyols. The non-polymerized polyol is a polyol that does not undergo polymerization history, and the polymerized polyol is a polyol obtained by polymerizing monomers.

Non-polymerized polyols include monoalcohols, diols, triols, tetraols and the like. Examples of monoalcohols include, but are not limited to, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, s-butanol, n-pentanol, n-hexanol, n-octanol, Examples thereof include n-nonanol, 2-ethylbutanol, 2,2-dimethylhexanol, 2-ethylhexanol, cyclohexanol, methylcyclohexanol, ethylcyclohexanol and the like. The diol is not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2- Butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3- Butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2- Ethyl-hexanediol, 1,2-octanediol, 1,2-decanedio Le, 2,2,4-trimethylpentane diol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol. Although it does not specifically limit as triol, For example, glycerol, a trimethylol propane, etc. are mentioned. Tetraols are not particularly limited, and examples thereof include pentaerythritol.

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

Polyester polyol is not particularly limited, for example, succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid or the like, or ethylene glycol, Obtained by ring-opening polymerization of ε-caprolactone using a polyester polyol obtained by a condensation reaction with a single or mixture of polyhydric alcohols such as propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane and glycerin, or a mixture thereof. Such as polycaprolactones.

The polyether polyol is not particularly limited. For example, hydroxides such as lithium, sodium and potassium, strong basic catalysts such as alcoholates and alkylamines, complex metal cyanide complexes such as metal porphyrins and hexacyanocobaltate zinc complexes Polyether obtained by random or block addition of a single or mixture of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide to a single or mixture of polyvalent hydroxy compounds Examples include polyether polyols obtained by reacting an alkylene oxide with a polyol or a polyamine compound such as ethylenediamine. Examples include so-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 using a polyisocyanate having an isocyanurate group has good weather resistance.

The polyisocyanate used in the present invention can also contain functional groups other than isocyanurate groups, for example, biuret groups, urea groups, uretdione groups, urethane groups, allophanate groups, oxadiazine trione groups and the like.

The polyisocyanate having an isocyanurate group can be obtained by, for example, carrying out an isocyanuration reaction with a catalyst or the like, stopping the reaction when a predetermined conversion rate is reached, and removing the diisocyanate monomer. As the isocyanuration reaction catalyst used in this case, those having basicity are generally preferred. Specifically, (a) tetraalkylammonium hydroxides such as tetramethylammonium and tetraethylammonium, and weak organic acids such as acetic acid. Salt, (b) hydroxy weak ammonium salt such as hydroxyalkylammonium hydroxide and acetic acid such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium and triethylhydroxyethylammonium, (c) acetic acid, octylic acid, capric acid Alkali metal salts of alkyl carboxylic acids such as myristic acid such as tin, zinc and lead, metal alcoholates such as (d) sodium and potassium, and (e) amino acids such as hexamethyldisilazane Le group-containing compound, (f) a Mannich bases, (g) in combination with tertiary amines and epoxy compounds include phosphorus compounds such as (h) tributylphosphine. The amount of these catalysts used is selected from the range of 10 ppm to 1% with respect to the total mass of the diisocyanate and polyol as raw materials. In order to complete the reaction, these isocyanuration reaction catalysts are inactivated by addition of acidic substances such as phosphoric acid and acidic phosphoric acid esters that neutralize the catalyst, thermal decomposition, and chemical decomposition.

The yield of polyisocyanate is 10 to 70% by mass. Polyisocyanates obtained in high yields tend to have high viscosities.

The reaction temperature of the isocyanurate reaction is preferably 20 ° C. or higher from the viewpoint of increasing the reactivity, and preferably 200 ° C. or lower from the viewpoint of suppressing product coloring and side reaction generation. 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, and the polyisocyanate is substantially free of the 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 increasing curability.

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

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 number of isocyanate groups (number of isocyanate average functional groups) possessed by one molecule of the polyisocyanate is preferably 4 or more from the viewpoint of enhancing the crosslinkability, and the viewpoint of improving the solubility in a solvent and the dispersion stability in water. To 20 or less. More preferably, it is 4-15, and still more preferably 4-9.

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

[Polyethylene oxide unit which is a hydroxyl group at one end]
The block polyisocyanate of the present invention has a polyethylene oxide unit that is a hydroxyl group at one end. Polyethylene oxide which is a hydroxyl group at one end is a compound having a hydroxyl group at one end of polyethylene oxide, and is a compound obtained by adding ethylene oxide to a starting monoalcohol. The starting monoalcohol preferably has 1 to 10 carbon atoms. The starting monoalcohol is not particularly limited, and examples thereof include methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol and the like. Of these, the preferred starting monoalcohol is methanol.

The molecular weight of polyethylene oxide, which is a hydroxyl group at one end, is preferably 300 to 2000, more preferably 300 to 1500, and still more preferably 500 to 1000.

(Block agent unit)
The block polyisocyanate of this invention has a block agent unit (unit derived from a block agent). The blocking agent is a compound having one active hydrogen in the molecule, for example, alcohol compounds, alkylphenol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds. Imidazole compounds, urea compounds, oxime compounds, amine compounds, imide compounds, pyrazole compounds, and the like. Examples of more specific blocking agents are shown below.

(1) Alcohol compounds: methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.
(2) Alkylphenol compounds: mono- and dialkylphenols having an alkyl group having 4 or more carbon atoms as a substituent, such as n-propylphenol, i-propylphenol, n-butylphenol, sec-butylphenol, t-butylphenol, n Monoalkylphenols such as hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-t-butylphenol, di- dialkylphenols such as sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, and di-n-nonylphenol;
(3) phenolic compounds; phenol, cresol, ethylphenol, styrenated phenol, hydroxybenzoic acid ester, etc.
(4) Active methylene compounds; dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc.
(5) Mercaptan compounds; butyl mercaptan, dodecyl mercaptan, etc.
(6) Acid amide compounds; acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, etc.
(7) Acid imide compounds; succinimide, maleic imide, etc.
(8) Imidazole compounds; imidazole, 2-methylimidazole, etc.
(9) Urea compounds; urea, thiourea, ethylene urea, etc.
(10) Oxime compounds; formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, cyclohexanone oxime, etc.
(11) Amine compounds; diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, isopropylethylamine, etc.
(12) imine compounds; ethyleneimine, polyethyleneimine, and the like; and (13) pyrazole compounds; pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, and the like.

These can be used in combination of two or more. Preferred blocking agents are amine compounds (preferably aliphatic amine compounds) or pyrazole compounds, and more preferred blocking agents are pyrazole compounds, with 3,5-dimethylpyrazole being particularly preferred. By using a pyrazole compound, particularly 3,5-dimethylpyrazole, the curability tends to be more excellent at low temperature or short time drying.

When obtaining block polyisocyanate, monools in which alkylene oxides having 3 or more carbon atoms are polymerized can be used.

A monool obtained by polymerizing an alkylene oxide having 3 or more carbon atoms is derived from a starting monoalcohol and an alkylene oxide having 3 or more carbon atoms. The starting monoalcohol has 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 4 to 8 carbon atoms. 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.

The alkylene oxide having 3 or more carbon atoms is not particularly limited, and examples thereof include propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, and the like, and propylene oxide is preferable. The alkylene oxide having 3 or more carbon atoms is not particularly limited. For example, hydroxides such as lithium, sodium and potassium, strong basic catalysts such as alcoholates and alkylamines, metalloporphyrins, complex metal cyanides such as hexacyanocobaltate zinc complexes, etc. In the presence of a compound complex or the like, these alkylene oxides can be obtained by adding one or a mixture of these alkylene oxides to the above starting monoalcohol.

The monool number average molecular weight obtained by polymerizing an alkylene oxide having 3 or more carbon atoms is preferably 300 or more from the viewpoint of improving the compatibility between the block polyisocyanate and the polyol. Moreover, 2000 or less is preferable from a viewpoint of making the hardness of the coating film obtained high. More preferably, it is 300-1500, and more preferably 350-1000.

The mass concentration of the components in the block polyisocyanate of the present invention will be described. When the block polyisocyanate of the present invention is 100% by mass, the component concentration of the polyethylene oxide unit which is a hydroxyl group at one end is preferably 15% by mass or more from the viewpoint of improving solubility in water and dispersibility. Moreover, 30 mass% or less is preferable from a viewpoint of making the intensity | strength of the coating film obtained high. More preferably, it is 15 to 25% by mass.

The component concentration of the polyisocyanate unit when the block polyisocyanate of the present invention is 100% by mass is preferably 45% by mass or more from the viewpoint of increasing the isocyanate group concentration in order to increase curability, and 65% by mass. The following is preferred. More preferably, it is 50 to 60% by mass.

The component concentration of the blocking agent unit when the block polyisocyanate of the present invention is 100% by mass is preferably 15% by mass or more from the viewpoint of increasing curability. Increasing the component concentration of the blocking agent results in a decrease in the component concentration of polyethylene oxide, which is a hydroxyl group at one end. Therefore, in order to obtain good water dispersion stability, 30% by mass or less is preferable from the viewpoint of increasing the proportion of structural units derived from polyethylene oxide which is a hydroxyl group at one end. More preferably, it is 20 to 30% by mass.

The component concentrations of the polyethylene oxide unit, polyisocyanate unit, and blocking agent unit which are one-end hydroxyl groups in the block polyisocyanate of the present invention can be specified by, for example, ¹ H-NMR, ¹³ C-NMR, etc. It is also possible to specify from the quantity.

The block polyisocyanate of the present invention includes those comprising a polyisocyanate unit and a polyethylene oxide unit which is a hydroxyl group at one terminal, and those comprising a polyisocyanate unit and a blocking agent 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 viewpoint of high hardness and high weather resistance of the resulting coating film. Moreover, 40 mass% or less is preferable from a viewpoint of making the elongation of the coating film obtained high. More preferably, it is 10 to 40% by mass, and still more preferably 10 to 30% by mass. The diisocyanate trimer component is a block polyisocyanate derived from three diisocyanate monomer molecules and a polyisocyanate having three isocyanate groups per molecule and three blocking agent molecules.

The number average molecular weight of the block polyisocyanate of the present invention is preferably 1000 or more from the viewpoint of increasing the isocyanate group concentration in order to increase curability. Moreover, 3000 or less is preferable from a viewpoint of favorable compatibility with a polyol. More preferably, it is 1000-2500.

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

Using the raw materials detailed above, an aqueous dispersion of the block polyisocyanate of the present invention can be obtained. An example of the manufacturing method will be described in detail.

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

In this case, the reaction temperature is preferably −20 ° C. or higher from the viewpoint of increasing the reactivity. Moreover, 150 degrees C or less is preferable from a viewpoint of suppressing a side reaction. More preferably, it is 30 to 100 ° C.

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

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

Then add water. It is preferable to add water by dividing or dropping a predetermined amount. When dividing, a predetermined amount of 4 to 8 is preferable. When the block polyisocyanate concentration is 50% by mass or more, it is preferably maintained at a liquid temperature of 50 to 80 ° C. or 10% by mass or less and less than 50% by mass at a temperature of 20 to less than 50 ° C.

When water is added all at once or when the liquid temperature is out of the above range, the average dispersed particle size of the block polyisocyanate may increase and precipitate or separate.

The present inventors have found that the method of adding water and the liquid temperature at the time of addition have a great influence on the average dispersed particle size of the blocked polyisocyanate, and that this influence varies depending on the concentration of the blocked polyisocyanate. Conventionally, when it is desired to reduce the average dispersed particle size of the block polyisocyanate, the amount of hydrophilic groups added has been increased. However, it is surprising that it is possible to reduce the average dispersed particle size with a small amount of hydrophilic groups, that is, with polyethylene oxide which is a hydroxyl group at one end less than before. As described above, the average dispersed particle size of the blocked polyisocyanate in the aqueous dispersion of the present invention can be controlled to 1 to 250 nm, preferably 1 to 180 nm, more preferably 1 to It can be controlled to 80 nm.

Moreover, the average dispersion particle diameter: (phi) of block polyisocyanate can satisfy | fill following formula 1 by doing as mentioned above.
[Formula 1] 1 ≦ φ ≦ 310-8 × A
(A is the mass% of the polyethylene oxide unit which is a one-terminal hydroxyl group in the block polyisocyanate)

The water dispersion of the block polyisocyanate of the present invention can contain up to 20% by mass of a solvent other than water. Examples of the solvent in this case are not particularly limited. For example, 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene 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 glycol dimethyl ether, propylene glycol dimethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, propylene glycol mono Mechi Ether acetate, ethanol, methanol, iso-propanol, 1-propanol, iso-butanol, 1-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4 -Butanediol, 1,3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, mineral spirit and the like. 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 aqueous dispersion thus obtained is preferably 10 to 40%.

[Fiber treatment agent composition]
The fiber treatment agent composition of this invention contains the fluororesin which does not have a C8 or more perfluoroalkyl group substantially, and the aqueous dispersion of the said block polyisocyanate.

The fluororesin used in the present invention is a fluororesin substantially not containing a perfluoroalkyl group having 8 or more carbon atoms, and may contain a perfluorohexyl group having 6 carbon atoms. Examples of the fluororesin include those polymerized using a fluorine-containing acrylate or methacrylate as a monomer. The acrylate and methacrylate containing fluorine are not particularly limited, and specific examples include those containing a perfluoroalkyl group and having 3 to 6 carbon atoms. It has been pointed out that the perfluorooctyl group having 8 carbon atoms produces perfluorooctanoic acid, which is likely to accumulate in the environment and the human body. Therefore, it is possible to obtain a fiber treatment agent composition that does not substantially generate perfluorooctanoic acid by using a fluororesin that does not substantially contain a perfluoroalkyl group having 8 or more carbon atoms and contains a perfluoroalkyl group having a low carbon number. it can.

When the carbon number of the perfluoroalkyl group is 6 or less, the performance may be lower than that of 8 or more. The block polyisocyanate of the present invention improves the mechanical stability of the fluororesin substantially free of perfluoroalkyl groups having 8 or more carbon atoms.

In addition to the fluorine monomer, other monomers can be used in combination. The following monomers can be used in combination. The following are mentioned as another monomer copolymerizable with the acrylate and / or methacrylate which have a perfluoroalkyl group.

The acrylic acid or methacrylic acid ester is not particularly limited. Hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, alkylene diol acrylate, and the like.

Acrylamide or methacrylamides are not particularly limited. For example, acrylamide such as alkylene diol dimethacrylate, methacrylamide, N- methylol acrylamide, N- methylol methacrylamide, diacetone acrylamide, diacetone methacrylamide, methylolated di- Acetone acrylamide etc. are mentioned.

The maleic acid alkyl esters are not particularly limited, and examples thereof include dibutyl maleate.

The olefin is not particularly limited, and examples thereof include ethylene, propylene, butadiene, isoprene, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and chloroprene.

The vinyl carboxylates are not particularly limited, and examples thereof include vinyl acetate.

Examples of styrenes include, but are not limited to, styrene, α-methyl styrene, β-methyl styrene, and the like.

Vinyl ethers are not particularly limited, and examples thereof include ethyl vinyl ether, cyclohexyl vinyl ether, and halogenated alkyl vinyl ether.

The amount ratio between the acrylate and / or methacrylate having a perfluoroalkyl group and the other monomer copolymerizable with these is the ratio of the acrylate having a perfluoroalkyl group and the acrylate having a perfluoroalkyl group among all monomers used for copolymerization. The total of methacrylates is preferably 40% by mass or more, and more preferably 50 to 80% by mass.

These copolymers can be produced by known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, etc., but are preferably produced by emulsion polymerization.

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

The resin mass ratio of the aqueous dispersion of the fluororesin and the blocked polyisocyanate is 50:50 to 95: 5, preferably 70:30 to 95: 5, and more preferably 80:20 to 90:10. is there. By setting it as the above range, the water repellency tends to be more excellent.

In addition, the fiber treatment composition of the present invention includes flame retardants, dye stabilizers, antibacterial agents, antibacterial agents, antifungal agents, insect repellents, antifouling agents, antistatic agents, aminoplast resins, acrylic polymers, and glyoxal. Resins, melamine resins, natural waxes, silicone resins, thickeners, polymer compounds, and the like can be blended.

The fiber treatment agent composition of the present invention blended in this way is diluted with water as necessary and used. The resin concentration after dilution is usually 0.5 to 5% by mass, preferably 0.5 to 3% by mass.

[Fabric]
The fabric of the present invention is treated with the fiber treatment composition. The fluororesin is used as a fiber treatment agent that imparts water repellency to the fabric. Examples of the water repellency evaluation method include a spray test of JIS-L-1092 and a contact angle measurement of water / isopropyl alcohol (mass ratio 1/1).

Furthermore, water repellency (washing durability) after washing the fabric 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 washings.

As described above, a fluororesin substantially not containing a perfluoroalkyl group having 8 or more carbon atoms is generally inferior in washing durability as compared with a fluororesin containing a perfluoroalkyl group having 8 or more carbon atoms. Surprisingly, however, the fabric treated with the fiber treating agent composition of the present invention can exhibit very excellent washing durability.

The fabric of the present invention is coated with a fluororesin having a contact angle of water / isopropyl alcohol (mass ratio 1/1) of 90 degrees or more after 10 washings and having substantially no perfluoroalkyl group having 8 or more carbon atoms. It is preferred that The contact angle after 10 washings is more preferably 90 degrees or more, and further preferably 92 degrees or more. By being the said range, it exists in the tendency which is excellent in washing durability.

Further, the retention rate of the contact angle of water / isopropyl alcohol (mass ratio 1/1) after 10 washings with respect to the contact angle of water / isopropyl alcohol (mass ratio 1/1) when washing is not performed (after 10 washings). The contact angle / contact angle before washing:%) is preferably 94% or more, more preferably 96% or more, and further preferably 98% or more. It exists in the tendency which is excellent by washing durability by being the said range.

The fluororesin substantially not containing a perfluoroalkyl group having 8 or more carbon atoms, which is coated on the fabric, can be identified by combustion ion chromatography and TOF-SIMS. Further, the polyisocyanate coated on the fabric can be specified by TOF-SIMS. Here, “substantially free” of a perfluoroalkyl group having 8 or more carbon atoms means that m / z 377, m / z 427, and m / z 461 are not measured by TOF-SIMS using the following apparatus. This is the case of detection.
Apparatus: TRIFT III (manufactured by Physical Electronics)
Primary ion: Ga +
Acceleration voltage: 15 kV
Current: 600 pA
Analysis area: 200 μm × 200 μm
Detected ion: Positive ion Electron gun: Available

The treatment of the fiber using the fiber treatment agent composition of the present invention can be performed by attaching a resin to the fiber and then heating it. Examples of the resin adhesion method include a pad method, a dipping method, a spray method, a coating method, and a printing method.

After that, after adjusting to a predetermined pickup amount (resin adhesion amount) using a mangle or the like, heating is performed at a temperature of 100 ° C. or higher. Preferably, heating is performed at a temperature of about 140 to 180 ° C. for 10 seconds to 10 minutes, preferably about 30 seconds to 3 minutes.

Examples of the types of fabrics to which the treatment liquid of the present invention can be applied include natural fibers such as cotton, kapok, flax, hemp, burlap, manila hemp, sisal hemp, wool, cashmere, mohair, alpaca, camel hair, silk, and feathers, Recycled fibers such as rayon, polynosic, cupra and tencel, cellulose acetate fibers, semi-synthetic fibers such as promix, polyamide fibers, polyester fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyurethane fibers, polyoxy Synthetic fibers such as methylene fiber, polytetrafluoroethylene fiber, benzoate fiber, polyparaphenylene bisbisthiazole fiber, polyparaphenylenebenzbisoxazole fiber, polyimide fiber, asbestos, glass fiber, carbon fiber, alumina fiber, silicon carbide fiber , Boron fiber, Tyranno fiber, inorganic whisker,-lock fiber, inorganic fibers such as slag off Ivor, these composite fibers, blended fibers, and the like. Examples of this form include woven fabric, knitted fabric, and non-woven fabric.

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

(1) Viscosity measurement:
The viscosity was measured using the following apparatus.
Equipment: RE-80R (manufactured by Toki Sangyo)
Rotor: Cone plate 1 ° 34 '× R24
Measurement temperature: 25 ° C

(2) Measurement of number average molecular weight:
The number average molecular weight was a polystyrene-based number average molecular weight determined by gel permeation chromatography using the following apparatus.
Apparatus: HLC-802A (manufactured by Tosoh)
Column: G1000HXL x 1 (Tosoh product)
G2000HXL x 1 (Tosoh product)
G3000HXL x 1 (Tosoh)
Carrier: Tetrahydrofuran Flow rate: 0.6 mL / min Sample concentration: 1.0% by mass
Injection volume: 20 μL
Temperature: 40 ° C
Detection method: Differential refractometer

(3) Isocyanate group content of polyisocyanate:
Weigh accurately 1-3 g of polyisocyanate in an Erlenmeyer flask (Wg), and then add 20 ml of toluene to dissolve the polyisocyanate. Thereafter, 10 ml of a 2N di-n-butylamine toluene solution is added, and after mixing, left at room temperature for 15 minutes. Add 70 ml of isopropyl alcohol and mix. This solution is titrated with 1N hydrochloric acid solution (factor F) to an indicator. The titration value was set to 2 ml, the same operation was performed without polyisocyanate, the titration value was set to V1 ml, and the isocyanate group content of the polyisocyanate was calculated from the following formula.
[Formula 2]
Isocyanate group content (mass%) = (V1-V2) × F × 42 / (W × 1000) × 100

(4) Measuring method of isocyanate average functional group number:
The number of isocyanate average functional groups was determined by the following formula 3.
[Formula 3]
Isocyanate average functional group number = polyisocyanate number average molecular weight (Mn) × isocyanate group content (mass%) × 0.01) / 42

(5) Average dispersed particle size (volume average dispersed particle size):
The volume average particle diameter was measured using the following apparatus.
Equipment: Nanotrac UPA-EX150 (manufactured by Nikkiso)
Solvent: Water Temperature: 23 ° C

(6) Water dispersion stability:
Observe the presence or absence of precipitates by visually observing an aqueous dispersion composition containing 30% by weight of block polyisocyanate. If there is no precipitate, ○, if there is a small amount of precipitate, if there is separation or a large amount of precipitate. Was represented as x.

(7) Coating strength:
Using TENSILON RTE-1210 (manufactured by A & D), the coating strength was measured under the following conditions. The coating film was cured at 150 ° C. for 30 minutes. The breaking strength of the coating film at this time was recorded. The larger the value, the higher the strength.
Tensile speed: 20mm / min
Sample size: 20 mm long x 10 mm wide x 20-40 μm thick
Temperature: 23 ° C
Humidity: 50%

(8) Mechanical stability:
A mixed solution of the block polyisocyanate and the fiber treating agent composition was diluted to 20% with water. The mixture was heated to 50 ° C., stirred at 5000 rpm for 10 minutes with a homomixer, and then the generated aggregate was filtered with a cotton cloth and dried, and the weight of the aggregate was measured. The numerical value calculated by the following formula 4 was used as an aggregate generation rate and used as an index of mechanical stability. The lower the aggregate generation rate, the better the mechanical stability.
[Formula 4] Aggregate generation rate (% by mass) = 100 × (aggregate weight / mixture weight)

(9) Contact angle:
Using a contact angle meter (manufactured by FIBRO system ab), the contact angle of the fabric (contact angle with respect to water / isopropyl alcohol (mass ratio 1/1)) was measured by a droplet method.
Retention rate (%) = contact angle after 10 washings / contact angle before washing

(10) Water repellency test:
A spray test of JIS-L-1092 was conducted, and the wet state of the surface was observed and evaluated. The evaluation was as follows. The higher the value, the better the water repellency.
5: There was no wetness or adhesion of water droplets on the surface.
4: Although it did not get wet on the surface, it showed adhesion of small water droplets.
3: Shows small individual water droplets on the surface.
2: Shows wetness on half of the surface, with small individual wetness penetrating the fabric.
1: The entire surface showed wetness.

(11) Specification of fluororesin substantially not containing a perfluoroalkyl group having 8 or more carbon atoms coated on the fabric:
The fluororesin substantially not containing a perfluoroalkyl group having 8 or more carbon atoms coated on the fabric was identified by the following two analytical methods.
Analysis 1: Combustion ion chromatography The presence or absence of fluorine was confirmed by a combustion ion chromatography using the following apparatus.
Equipment: AQF-100 (Mitsubishi Chemical Analytech)
Combustion tube: Quartz Combustion temperature: 1000 ° C
Column: SuperIC-AZ (manufactured by Tosoh)
Temperature: 40 ° C
Flow rate: 0.8 mL / min Detection method: Electrical conductivity Analysis 2: TOF-SIMS
Whether or not the fluororesin does not substantially contain a perfluoroalkyl group having 8 or more carbon atoms is determined according to TOF-SIMS using the following apparatus: m / z 377, m / z 427, m / z 461 It was confirmed whether it was not detected.
Apparatus: TRIFT III (manufactured by Physical Electronics)
Primary ion: Ga +
Acceleration voltage: 15 kV
Current: 600 pA
Analysis area: 200 μm × 200 μm
Detected ion: Positive ion Electron gun: Available

(Production Example 1: Production of polyisocyanate)
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube is placed in a nitrogen atmosphere, charged with HDI: 1000 parts by mass, trimethylolpropane (molecular weight 134) 22 parts by mass as a trihydric alcohol, While stirring, the temperature in the reactor was maintained at 90 ° C. for 1 hour for urethanization. Thereafter, the temperature of the reaction solution was kept at 60 ° C., an isocyanurate-forming catalyst tetramethylammonium capriate was added, and phosphoric acid was added when the conversion rate reached 48% to stop the reaction. Then, after filtering a reaction liquid, unreacted HDI was removed with the thin film distillation apparatus.

The viscosity of the obtained polyisocyanate at 25 ° C. was 25,000 mPa · s, the isocyanate group content was 19.9% by mass, the number average molecular weight was 1080, and the isocyanate average functional group number was 5.1.

(Production Example 2: Production of polyisocyanate)
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel was placed in a nitrogen atmosphere, 1000 parts by mass of HDI was charged, and the temperature in the reactor was kept at 70 ° C. with stirring. Isocyanuration catalyst tetramethylammonium capriate was added, and when the yield reached 40%, phosphoric acid was added to stop the reaction. After the reaction solution was filtered, unreacted HDI was removed using a thin film evaporator.

The viscosity of the obtained polyisocyanate at 25 ° C. was 2700 mPa · s, the isocyanate content was 21.7%, the number average molecular weight was 660, and the number of isocyanate average functional groups was 3.4.

Example 1
100 parts by mass of the polyisocyanate obtained in Production Example 1 in the same reactor as in Production Example 1, 1.5 parts by mass of monool (trade name “Exenol 908” manufactured by Asahi Glass Co., Ltd.), polyethylene oxide which is a hydroxyl group at one end (Nippon Emulsifier Co., Ltd., trade name “MPG-081”) 42.5 parts by mass, Urethane catalyst (Nitto Kasei Kogyo Co., Ltd., trade name “Neostan U-810”) 0.01 parts by mass was charged with nitrogen. The atmosphere was maintained at 80 ° C. for 2 hours. Thereafter, 39.4 parts by mass of 3,5-dimethylpyrazole was added, and it was confirmed by infrared spectrum (manufactured by JASCO Corporation: product name FT / IR-4000) that there was no characteristic absorption of isocyanate groups.

Thereafter, 185 parts by mass of water was added at a rate of 25 parts by mass per minute while keeping the liquid temperature from 80 ° C. to 50 ° C., and held for 10 minutes after the addition. Thereafter, 242.9 parts by mass of water was added at a rate of 25 parts by mass per minute while keeping the liquid temperature from 50 ° C. to 40 ° C., and stirred for 30 minutes to obtain an aqueous dispersion of an aqueous block polyisocyanate. .

The concentration of the block polyisocyanate in the aqueous dispersion of the obtained block polyisocyanate was 30.0% by mass, the concentration of water was 70.0% by mass, the average dispersed particle size was 25 nm, and the water dispersion stability was good. there were.

(Examples 2 to 5, 7 to 9)
Except as described in Table 1, the same procedure as in Example 1 was performed. The results are shown in Table 1.

(Example 6)
100 parts by mass of the polyisocyanate obtained in Production Example 1 in the same reactor as in Production Example 1, 1.5 parts by mass of monool (trade name “Exenol 908” manufactured by Asahi Glass Co., Ltd.), polyethylene oxide which is a hydroxyl group at one end (Nippon Emulsifier Co., Ltd., trade name “MPG-081”) 42.5 parts by mass, Urethane catalyst (Nitto Kasei Kogyo Co., Ltd., trade name “Neostan U-810”) 0.01 parts by mass was charged with nitrogen. The atmosphere was maintained at 80 ° C. for 2 hours. Thereafter, 39.4 parts by mass of 3,5-dimethylpyrazole was added, and it was confirmed by infrared spectrum (manufactured by JASCO Corporation: product name FT / IR-4000) that there was no characteristic absorption of isocyanate groups.

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

The concentration of the block polyisocyanate in the aqueous dispersion of the obtained block polyisocyanate was 30.0% by mass, the concentration of water was 70.0% by mass, the average dispersed particle size was 100 nm, and the water dispersion stability was good. there were.

(Comparative Example 1)
In the same reactor as in Production Example 1, 109.7 parts by mass of the polyisocyanate obtained in Production Example 1, 0.2 parts by mass of monool (trade name “Exenol 908”, manufactured by Asahi Glass Co., Ltd.), and hydroxyl group at one end 27.5 parts by mass of polyethylene oxide (made by Nippon Emulsifier Co., Ltd., trade name “MPG-081”) and 0.01 parts by mass of urethanization catalyst (made by Nitto Kasei Kogyo Co., Ltd., trade name “Neostan U-810”) are charged. And kept at 80 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, 46.0 parts by mass of 3,5-dimethylpyrazole was added, and it was confirmed by infrared spectrum (manufactured by JASCO Corporation: product name FT / IR-4000) that there was no characteristic absorption of isocyanate groups.

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

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

(Comparative Examples 2 and 3)
Except as described in Table 1, the same procedure as in Example 1 was performed. The results are shown in Table 1.

(Comparative Example 4)
In a reactor similar to Production Example 1, 100 parts by mass of the polyisocyanate obtained in Production Example 2 and 150 parts by mass of methyl isobutyl ketone were charged, heated to 80 ° C. in a nitrogen atmosphere, and then 50 parts by mass of 3,5-dimethylpyrazole. Part was added, and it was confirmed by infrared spectrum (manufactured by JASCO Corporation: product name FT / IR-4000) that the characteristic absorption of the isocyanate group disappeared.

Then, 3 parts of dialkyl (cured beef tallow) dimethylammonium chloride and 30 parts of polyoxyethylene polyoxypropylene block polymer are added and stirring is started. Thereto, 221 parts by mass of water are gradually added, and after the addition is completed, the mixture is further dispersed by a homomixer. 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 size of 170 nm.

A-1: Polyisocyanate of Production Example 1 A-2: Polyisocyanate of Production Example 2 A-3: Isocyanurate type polyisocyanate of IPDI monomer (trade name “VESTANAT T1890 / 100” of Evonik Degussa)
B: Monool (Asahi Glass Co., Ltd., “Exenol 908”)
C: Polyethylene oxide (trade name of Nippon Emulsifier Co., Ltd., “MPG-081”)
D-1: 3,5-dimethylpyrazole D-2: Methyl ethyl ketoxime E: Urethane catalyst (trade name of Nitto Kasei Co., Ltd., “Neostan U-810”)
F: Dipropylene glycol dimethyl ether

(Example 10)
Dimethylaminoethanol of aqueous polyester polyol “SETAL6306 SS-60 (trade name)” (manufactured by NUPLEX, hydroxyl group concentration 2.7% by mass (resin standard), acid value 43 mgKOH / g (resin standard), resin solid content 60%) 100 parts by mass of the neutralized product, 133 parts by mass of the aqueous dispersion of the block polyisocyanate 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 an applicator on a polypropylene plate to a dry film thickness of 30 μm. After setting at room temperature for 15 minutes, the coating film was cured at 150 ° C. for 30 minutes. The coating film strength was 22 MPa.

(Examples 11 to 18, Comparative Examples 5 to 8)
The same procedure as in Example 10 was carried out except that the aqueous dispersion of blocked polyisocyanate described in Table 2 was used. Table 2 shows the results of coating strength.

(Example 19)
Fluorine fiber treating agent “Asahi Guard AG-E061 (trade name)” (manufactured by Asahi Glass Co., Ltd., 20% solid content) 90 parts by mass and 6.7 parts by mass of an aqueous dispersion of the block polyisocyanate obtained in Example 1 Then, 3.3 parts by mass of water was mixed to prepare a mixed solution having a solid content of 20% by mass. As a result of measuring the mechanical stability of this mixed solution, the aggregate generation rate was 0.03% by mass.

Further, water was added to the mixed solution and diluted to a resin concentration of 1.0% by mass to obtain a treatment solution. A nylon cloth (Japanese Standards Association code number 670108) was immersed in this treatment solution, and then squeezed with a roller so that the wet pick-up was 50%. This was dried at 120 ° C. for 60 seconds and further dried at 170 ° C. for 60 seconds to obtain a test fabric. The contact angle was 95 degrees and the water repellency test was 5.

Further, this test fabric was washed according to JIS-L-0217-103. The detergent used was the product name Attack of Kao Corporation. Evaluation was performed at 10 washings. The contact angle after washing was 93 degrees, and the water repellency test was 5.

In the combustion ion chromatographic method, fluorine was detected, but the measurement result of the fluororesin substantially not containing a perfluoroalkyl group having 8 or more carbon atoms coated on the fabric by TOF-SIMS was not detected. .

(Examples 20 to 27, Comparative Examples 9 to 12)
The same operation as in Example 19 was carried out except that the aqueous dispersion of blocked polyisocyanate described in Table 2 was used. Table 3 shows the results of the aggregate generation rate, contact angle, and water repellency test.

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

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

The aqueous dispersion of the block polyisocyanate of the present invention and the fiber treatment composition containing the same can be suitably used in the field of water repellents for fibers and the like.

Claims

A block polyisocyanate having at least the following 1) to 3) component units and water,
The average dispersed particle size of the block polyisocyanate: φ is 1 to 250 nm.
Water dispersion of block polyisocyanate.
1) Polyisocyanate unit having one or more diisocyanate monomer units selected from the group consisting of aliphatic diisocyanate monomers and alicyclic diisocyanate monomers 2) Polyethylene oxide units which are hydroxyl groups at one end 3) Block agent units
The block polyisocyanate aqueous dispersion according to claim 1, wherein the average dispersed particle diameter of the block polyisocyanate: φ satisfies the following formula 1.
[Formula 1] 1 ≦ φ ≦ 310-8 × A
(A is the mass% of the polyethylene oxide unit which is a one-terminal hydroxyl group in the block polyisocyanate)
The aqueous dispersion of block polyisocyanate according to claim 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 which is a hydroxyl group at one end 3) 15 to 30% by mass of a blocking agent unit
The aqueous dispersion of blocked polyisocyanate according to any one of claims 1 to 3, wherein the polyisocyanate unit has an average number of isocyanate functional groups of 4 to 20.
The block polyisocyanate aqueous dispersion according to any one of claims 1 to 4, wherein the blocking agent is a pyrazole compound.
The block polyisocyanate aqueous dispersion according to any one of claims 1 to 5, wherein at least one of the diisocyanate monomers is hexamethylene diisocyanate.
The block polyisocyanate aqueous dispersion according to any one of claims 1 to 6, wherein the block polyisocyanate has an average dispersed particle size: φ of 1 to 80 nm.
A fiber treating agent composition comprising a fluororesin having substantially no perfluoroalkyl group having 8 or more carbon atoms and an aqueous dispersion of the block polyisocyanate according to any one of claims 1 to 7.
A fabric treated with the fiber treatment composition according to claim 8.
The contact angle of water / isopropyl alcohol (mass ratio 1/1) after washing 10 times is 90 degrees or more,
A fabric coated with a fluororesin having substantially no perfluoroalkyl group having 8 or more carbon atoms.
The retention rate of the contact angle of water / isopropyl alcohol (mass ratio 1/1) after 10 washings with respect to the contact angle of water / isopropyl alcohol (mass ratio 1/1) when washing is not performed is 94% or more. The fabric according to claim 10.