JPH05247451A - Water and oil repellent - Google Patents

Abstract

(57) [Summary] [Purpose] To obtain water and oil repellency that is excellent in flame retardancy of treated textiles and can exhibit higher water repellency than before. A water and oil repellent agent comprising a reaction product of a fluorine-containing active hydrogen compound having a perfluoroalkyl group having 10 or more carbon atoms and a polyisocyanate compound as an active ingredient.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water / oil repellent which can impart high water / oil repellency without impairing the flame retardancy of textiles and the like.

[0002]

2. Description of the Related Art As water and oil repellents for imparting water and oil repellency to textiles and the like, fluorine compounds having polyfluoroalkyl groups, especially perfluoroalkyl groups, are widely used as water and oil repellents. There is. Of these fluorine-based compounds, polyfluoroalkyl group-containing acrylate-based or methacrylate-based fluorine-containing polymers are apt to impair the flame retardancy of objects to be treated such as textiles, and are not suitable for applications requiring high flame retardancy. It is said to be absent. For example,
In fields such as car seats, carpets, curtains, and shower curtains that require flame retardancy, it has been pointed out that the water-repellent and oil-repellent treatment impairs the flame retardancy of the fabric and facilitates combustion.

On the other hand, as a water / oil repellent agent which is hard to impair flame retardancy, a polyfluoroalkyl group-containing carboxylic acid ester (Japanese Patent Laid-Open No. 54-5039) which volatilizes at 200 to 300 ° C. or a flow starting temperature depending on the melting point of the material is used. Polyfluoroalkyl group-containing urethane oligomer having a low viscosity (JP-A-60-1
7170) has been proposed. Although these compounds do not easily impair flame retardancy, they have a drawback that they have insufficient water and oil repellency as compared with polyfluoroalkyl group-containing acrylate-based or methacrylate-based fluoropolymers.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a water and oil repellent agent which does not impair the flame retardancy of an object to be treated and which can exhibit high water and oil repellency. ..

[0005]

Means for Solving the Problems The present inventor has studied improvement of water and oil repellency of a water and oil repellent agent which hardly impairs the flame retardancy of an object to be treated such as urethane oligomer having a polyfluoroalkyl group. As a result, in such a type of water and oil repellent, the carbon number of the polyfluoroalkyl group has a great influence on the water and oil repellency, and the polyfluoroalkyl group having particularly good water and oil repellency has 10 carbon atoms. It was found that they are the above perfluoroalkyl groups. The present invention is the following water and oil repellent having this specific perfluoroalkyl group.

A fluorine-containing active hydrogen compound having an active hydrogen-containing functional group capable of reacting with an isocyanate group and a perfluoroalkyl group, and 50% by weight or more of which has a perfluoroalkyl group having 10 or more carbon atoms. Reaction product of a fluorine-containing active hydrogen compound (a) which is a fluorine-containing active hydrogen compound and a polyisocyanate compound (b) having two or more isocyanate groups, or (a), (b) and a perfluoroalkyl group A water- and oil-repellent agent containing a reaction product of an active hydrogen compound (C) which does not have an active ingredient.

The reason why the water / oil repellent of the present invention is superior in water / oil repellency to the conventional one is not clear, but it is presumed as follows. That is, in the conventional polyfluoroalkyl group-containing urethane oligomer type water and oil repellent agent, the orientation of the polyfluoroalkyl group is not sufficient as compared with the acrylate-based polymer, so that high water and oil repellency is not exhibited. However, when the chain length of the polyfluoroalkyl group reaches a constant chain length (C10F21), the crystallinity based on the polyfluoroalkyl group increases, and as a result, the surface orientation of the polyfluoroalkyl group increases and high water and oil repellency is exhibited. Presumed to be done.

The fluorine-containing active hydrogen compound having a perfluoroalkyl group and an active hydrogen-containing functional group capable of reacting with an isocyanate group is usually a mixture of compounds having different carbon numbers in the perfluoroalkyl group. That is, when the perfluoroalkyl group is represented by Cn F2n + 1-, it means a mixture of compounds having different n (all are mixtures of the same compound except for Cn F2n + 1-). For example, the conventional one is a mixture of a compound having 8 carbon atoms as a main component and having less carbon atoms and a compound having more carbon atoms than that, and the average n is 9.

In the present invention, a compound having a perfluoroalkyl group having 10 or more carbon atoms is the main component, and substantially only or a compound having less carbon atoms and / or having more carbon atoms than that. It must be a mixture of compounds. Particularly, when the fluorine-containing active hydrogen compound (a) in the present invention is 50% by weight or more of the fluorine-containing active hydrogen compound having a perfluoroalkyl group having 10 carbon atoms, and contains another fluorine-containing active hydrogen compound. The fluorine-containing active hydrogen compound is preferably a compound having a perfluoroalkyl group having 9 or less and / or 11 or more carbon atoms. In addition, it is particularly preferable that the compound having a perfluoroalkyl group having 6 to 14 carbon atoms is 80% by weight.

The perfluoroalkyl group is preferably a linear perfluoroalkyl group. However, a small number of branches may be present, in which case it is preferable that the number of branches is 1 to 2 and the number of carbon atoms in the side chain is shorter than that of the main chain.

The fluorine-containing active hydrogen compound (a) in the present invention, which has a perfluoroalkyl group having 10 or more carbon atoms, has one active hydrogen-containing functional group capable of reacting with an isocyanate group. When it has two or more, it is preferable that the second and subsequent active hydrogen-containing functional groups have lower activity than the first active hydrogen-containing functional group. That is, it is preferable that the fluorine-containing active hydrogen compound is substantially monofunctional with respect to the isocyanate group. Other fluorine-containing active hydrogen compounds are preferably monofunctional as well, but in some cases a small amount of polyfunctional compound may be present.

Examples of the active hydrogen-containing functional group capable of reacting with the isocyanate group include a hydroxyl group, a mercapto group, a primary amino group, a secondary amino group, a carboxy group, and other functional groups having an active hydrogen atom. The secondary amino group is preferably a secondary amino group having a lower alkyl group having 4 or less carbon atoms. The most preferred active hydrogen-containing functional group is a hydroxyl group.

Various linking groups are known as a linking group for linking a perfluoroalkyl group and an active hydrogen-containing group. For example, a single bond (a specific compound is, for example, perfluorocarboxylic acid), -R-, -CON (R1) -Q.
-, -SO2-Q-, etc. However, R is an alkylene group, R1 is an alkyl group, and Q is a divalent organic group. Preferably, R is an alkylene group having 2 to 6 carbon atoms, R1 is a lower alkyl group, and Q is an alkylene group having 2 to 8 carbon atoms.

Except for the number of carbon atoms in the perfluoroalkyl group, the fluorine-containing active hydrogen compound itself having a perfluoroalkyl group in the present invention is a known type of compound. The fluorine-containing active hydrogen compound in the present invention,
Compounds of this known type can be used. Specific preferred compounds include, but are not limited to, the following. R in the following chemical formula
f represents a perfluoroalkyl group.

Rf-CH2CH2-OH Rf-CON (CH3) CH2CH2-OH Rf-SO2N (CH3) CH2CH2-OH Rf-CH2CH2-SH Rf-SO2N (CH3) CH2CH2-SH Rf-CH2CH2-NH2 Rf-SO2N (CH3 ) CH2CH2-NH2

As the polyisocyanate compound (b) having two or more isocyanate groups, various polyisocyanate compounds of aliphatic type, alicyclic type, aromatic type and the like, modified products thereof, or a mixture thereof are used. Can be used. In particular, a polyisocyanate compound having 3 or more isocyanate groups and a mixture thereof with a diisocyanate compound are preferable.

As the polyisocyanate compound having three or more isocyanate groups, a triisocyanate compound is particularly preferable. As the triisocyanate compound, a modified product of the diisocyanate compound is preferable. As the triisocyanate compound that is a modified product of the diisocyanate compound, a tris-burette modified product, an isocyanurate modified product, and a triol modified product (such as a trimethylolpropane modified product) are preferable. The triisocyanate compound, which is a modified product of this diisocyanate compound, usually contains a polyisocyanate compound having 4 or more isocyanate groups and an unmodified diisocyanate compound. In the present invention, a triisocyanate compound containing these impurities is contained. Nate compounds can be used.

Examples of the polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene triisocyanate, lysine ester triisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate. , Toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate and the like. Particularly, a triisocyanate compound which is a modified product of hexamethylene diisocyanate, such as a modified product of tris-burette of hexamethylene diisocyanate, is preferable.

The water- and oil-repellent agent of the present invention is a water- and oil-repellent agent containing the reaction products of (a) and (b) as active ingredients. However, it may also be a water / oil repellent agent containing as an active ingredient a reaction product of (a) and (b) with an active hydrogen compound (c) having no perfluoroalkyl group. The active hydrogen compound (c) having no perfluoroalkyl group is
It is a compound having one or more active hydrogen-containing functional groups capable of reacting with the above isocyanate group. Two or more kinds of this active hydrogen compound (c) can be used in combination.

This active hydrogen compound (c) has an active hydrogen-containing functional group capable of reacting with the isocyanate group as described above.
A compound having one or more groups and having a functional group other than the above is preferable. Examples of the functional group include a long-chain hydrocarbon group, an epoxy group, a cyano group, a nitro group, a halogen atom, and a hydrogen-containing functional group having a relatively low reactivity with the first hydrogen-containing functional group. is there.

Specific active hydrogen compounds (C) are:
For example, there are the following compounds, but the compounds are not limited to these.

Monool: A monool having 1 to 23 carbon atoms is suitable, and a monool having 6 to 20 carbon atoms such as stearyl alcohol and 2-ethylhexyl alcohol is particularly preferable. Mercaptan: Monomercaptan having 1 to 23 carbon atoms is suitable, and monomercaptan having 6 to 20 carbon atoms such as stearyl mercaptan and octyl mercaptan is particularly preferable. Monocarboxylic acid: A monocarboxylic acid having 1 to 23 carbon atoms is suitable, and particularly 6 to 6 carbon atoms such as stearic acid and octanoic acid.
20 monocarboxylic acids are preferred.

Mono (or di) alkylamine: Monoalkylamine or dialkylamine having alkyl having 1 to 23 carbon atoms is suitable, and particularly amine having alkyl having 6 to 20 carbon atoms such as 2-ethylhexylamine and dioctylamine. Is preferred. Epoxy group-containing compound: Glycidol (that is, 2,3-
Epoxy-1-propanol), glycerin diglycidyl ether. Polyol: polyethylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol,
Glycerin, trimethylolpropane.

Polyamine: ethylenediamine, triethylenediamine, toluenediamine, isophoronediamine, hexamethylenediamine. Alkanolamines: monoethanolamine, diethanolamine, triethanolamine, dipropanolamine. Others: 2-cyanoethanol, 2-nitroethanol, ethyleneimine, dialkylketoxime.

In the production of a reaction product of the fluorine-containing active hydrogen compound (a) and the polyisocyanate compound (b), or further the active hydrogen compound (c), the fluorine-containing active compound is added to 1 mol of the polyisocyanate compound (b). The active hydrogen compound (a) needs to be 1 mol or more. That is, the reaction product must have at least one residue of the fluorine-containing active hydrogen compound (a) on average per molecule. When reacting less than an equivalent amount of the fluorine-containing active hydrogen compound (a) with the polyisocyanate compound (b), the active hydrogen compound (c) is used and the total amount of the fluorine-containing active hydrogen compound (a) is It is preferable to use the compound in an amount equivalent to that of the isocyanate compound (II).

When the active hydrogen compound (c) is used, the equivalent ratio of the fluorine-containing active hydrogen compound (a) to the total equivalent of the active hydrogen compound (c) and the fluorine-containing active hydrogen compound (a) is 50% or more. Preferably. However, when the active hydrogen compound (C) is a polyfunctional compound that reacts with an isocyanate group, the ratio of (A) to the total of (C) and (A) is 50% by weight or more, and particularly 75% by weight. The above is preferable.

The water and oil repellent of the present invention can be used, if necessary, as a solution dissolved in a solvent or as an emulsified emulsion or dispersion.

Examples of the solvent include fluorine-based solvents such as trichlorotrifluoroethane (R-113) and metaxylenehexafluoride, chlorine-based solvents such as 1,1,1-trichloroethane, perchloroethylene and methylene chloride, tetrahydrofuran and methylisobutyl. It is possible to widely use other organic solvents such as ketones. Further, when dispersing in water, various surfactants such as nonionic, cationic and anionic surfactants can be used as the emulsifier, and these may be appropriately used in combination.

As the organic solvent used in combination in water, tetrahydrofuran, dioxane, water-soluble ethers such as ethylpropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, Water-soluble glycol ethers such as dipropylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ether, alcohols such as methanol, ethanol and propanol, esters such as ethyl acetate, butyl acetate and ethyl succinate. Can be mentioned. If desired, these organic solvents may be removed by distillation after dispersion. An appropriate amount of such organic solvent added is 10 to 300 parts by weight per 100 parts by weight of the water and oil repellent.

[0030]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the text, parts and% are based on weight unless otherwise specified. The water repellency and oil repellency shown in the following Examples and Comparative Examples were evaluated by the following evaluation tests.

Water repellency: Water repellency No. by the spray method of JIS L-1092. (See Table 1). The water repellency No. In the evaluation results represented by adding a + mark to each evaluation, each evaluation is No. It is slightly better than that represented by. Oil repellency: A few drops (diameter about 4 mm) of the test solution shown in Table 2 were placed at two places on the test cloth, and the state of permeation after 30 seconds was used to judge (AATCC-TM118-1966).

[0032]

[Table 1]

[0033]

[Table 2]

[Example 1] Dimroth cooling pipe, thermometer,
HBU 100 parts, C10A 203 parts, S in a 500 ml four-necked flask equipped with a nitrogen gas introduction tube and a stirrer.
tO 24.35 parts, GD 6.66 parts, and MBK
A raw material consisting of 83.5 parts (see below for abbreviations) was charged and the temperature was raised to 80 ° C. with stirring. Nitrogen was bubbled through for 2 minutes, and then 0.1 g of catalyst dibutyltin dilaurate was added and stirring was continued for 2 hours. Furthermore, the temperature is 100 ° C.
The stirring was continued for 1 hour. After that, IR (infrared absorption spectrum) was measured, and it was confirmed that no isocyanate group remained, and the reaction was terminated. M in a vacuum dryer
BK was removed to give a white solid with a melting point of 96-97 ° C.

Conceptually, the main component of the reaction product is one molecule of HBU, which is a triisocyanate compound, reacted with three molecules of C10A, two molecules of C10A and one molecule of St.
It is considered to be a mixture of O reacted, 2 molecules of C10A reacted with 1 molecule of GD, and 1 molecule of C10A reacted with 1 molecule of StO with 1 molecule of GD.

The compounds represented by the above abbreviations are as follows. In addition, the abbreviations of the compounds used in Examples 2 and after and Comparative Examples are also shown in the same manner.

HBU: modified tris-buret of hexamethylene diisocyanate (NCO value 22.7 wt%)
[Sumitomo Bayer "Sumijour N-3200"] NHP: hexamethylene diisocyanate modified trimethylolpropane IPN: isophorone diisocyanate modified isocyanurate

C10A; C10F21CH2CH2OH C11A; C11F23CH2CH2OH C8A; C8F17CH2CH2OH C10SA; C10F21SO2N (CH3) CH2CH2OH C10S; C10F21CH2CH2SH StO; C18H37OH StN; C18H37NH2

StS; C18H37SH StA; C17H35COOH GD; glycidol MBK; methyl isobutyl ketone MEK; methyl ethyl ketone DGM; diglyme

[Example 2] Dimroth condenser, thermometer,
In a 500 ml four-necked flask equipped with a nitrogen gas introduction tube and a stirrer, 100 parts of HBU, C10A 166.2
Part, C8 A 110.8 part, StO 24.35 part, G
A raw material consisting of D 6.66 parts and MBK 102 parts was charged and reacted in the same manner as in Example 1 to obtain a white solid.

[Example 3] Dimroth cooling pipe, thermometer,
Into a 500 ml four-necked flask equipped with a nitrogen gas introduction tube and a stirrer, 100 parts of HBU and 100 parts of MBK were put and heated to 80 ° C. with stirring, and then the inside of the flask was replaced with nitrogen, and then dibutyltin dilaurate 0 .1 part was added. Next, 110.8 parts of C8A was added dropwise over 1 hour, and then 166.2 parts of C10A and StO 48.7 were added.
A portion was dropped in the same manner. After the dropping, raise the temperature to 90 ° C 3
Stirring was continued for 0 minutes. Then, IR was measured to confirm that no isocyanate group remained, and the reaction was terminated.

Table 3 shows the types and ratios of the raw materials, the synthesis temperature, and the melting points of the products in Examples 1 to 3 above.

[0043]

[Table 3]

[Examples 4 to 10] Reaction products were produced in the same manner as in Example 3 except that the raw materials shown in Table 4 were used. Table 4 shows the types and ratios of raw materials, synthesis temperatures, and melting points of products.
Shown in.

[0045]

[Table 4]

[Comparative Example 1] A reaction product was produced under the same conditions and conditions except that all C10A in Example 1 was replaced by an equivalent amount of C8A.

Comparative Example 2 C10A and C in Example 2
Instead of the combination of 8 A, Cn F2n + 1CH2 CH2 O
Compounds represented by H having different n (n is 8, 1
A mixture of compounds which are 0, 12, and 14 (n = 8)
A reaction product was produced under the same conditions and the same conditions except that the weight ratio of / 10/12/14 was 60/25/10/5 and the average n was about 9). The mixture of this compound is called C9A.

Table 5 shows the types and ratios of the raw materials, the synthesis temperature, and the melting points of the products in Comparative Examples 1 and 2 above.

[0049]

[Table 5]

[Example 11] The reaction product obtained in Example 1 was emulsified in water according to the following method to obtain an aqueous dispersion system.
That is, 100 parts of the reaction product obtained in Example 1, MBK 2
0 parts, nonionic emulsifier [Emulgen manufactured by Kao Corporation]
A mixture of 4 parts of E-950 "] and 1 part of a cationic emulsifier [" Farmin DMC.AcOH "manufactured by Kao Corporation] was heated to 85 ° C and emulsified by a high pressure homogenizer. MBK was distilled off under reduced pressure to obtain a dispersion having a particle size of about 0.1 μm. The reaction products of Examples 2 to 10 and the reaction products of Comparative Examples 1 and 2 were similarly emulsified to obtain dispersions.

These samples were diluted with water to 0.2 wt.
% Aqueous solution was prepared. Dip a polyester doskin cloth and nylon stunner cloth, and pick up each 60
It was adjusted with mangle so that it would be 40% by weight.
This was heat-dried at 110 ° C. for 90 seconds and then at 170 ° C. for 60 seconds to obtain a test cloth. The results of oil repellency and water repellency tests conducted using this test cloth are shown in Table 6.

Example 12 The dispersion samples prepared in Example 11 were each diluted with water to give 1.5 w.
A t% aqueous solution was prepared, and a polyester car sheet was dipped in the aqueous solution to adjust the pickup to 60 wt%. This was heat-dried at 120 ° C. for 3 minutes and then at 160 ° C. for 2 minutes to obtain a test cloth.

Table 6 shows the results of oil repellency and water repellency tests conducted using this test cloth. In Table 6, the reaction products are indicated by the numbers of the Examples and Comparative Examples in which they were produced.

[0054]

[Table 6]

[0055]

EFFECTS OF THE INVENTION Conventional water- and oil-repellent agents containing an Rf group-containing urethane compound as an active ingredient are excellent in flame retardancy of treated textiles, but have high water repellency, particularly water repellency by spray method evaluation. No water- and oil-repellent agent comparable to the water- and oil-repellent agent such as Rf group-containing acrylate polymer could not be obtained. According to the present invention, it is possible to easily obtain an Rf group-containing urethane compound-type water and oil repellent which can exhibit high water repellency even when evaluated by a spray method.

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[Procedure amendment]

[Submission date] September 9, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water / oil repellent which can impart high water / oil repellency without impairing the flame retardancy of textiles and the like.

[0002]

2. Description of the Related Art As water and oil repellents for imparting water and oil repellency to textiles and the like, fluorine compounds having polyfluoroalkyl groups, especially perfluoroalkyl groups, are widely used as water and oil repellents. There is. Of these fluorine-based compounds, polyfluoroalkyl group-containing acrylate-based or methacrylate-based fluorine-containing polymers are apt to impair the flame retardancy of objects to be treated such as textiles, and are not suitable for applications requiring high flame retardancy. It is said to be absent. For example,
In fields such as car seats, carpets, curtains, and shower curtains that require flame retardancy, it has been pointed out that the water-repellent and oil-repellent treatment impairs the flame retardancy of the fabric and facilitates combustion.

On the other hand, as a water / oil repellent agent which is hard to impair flame retardancy, a polyfluoroalkyl group-containing carboxylic acid ester (Japanese Patent Laid-Open No. 54-5039) which volatilizes at 200 to 300 ° C. or a flow starting temperature depending on the melting point of the material is used. Polyfluoroalkyl group-containing urethane oligomer having a low viscosity (JP-A-60-1
7170) has been proposed. Although these compounds do not easily impair flame retardancy, they have a drawback that they have insufficient water and oil repellency as compared with polyfluoroalkyl group-containing acrylate-based or methacrylate-based fluoropolymers.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a water and oil repellent agent which does not impair the flame retardancy of an object to be treated and which can exhibit high water and oil repellency. ..

[0005]

Means for Solving the Problems The present inventor has studied improvement of water and oil repellency of a water and oil repellent agent which hardly impairs the flame retardancy of an object to be treated such as urethane oligomer having a polyfluoroalkyl group. As a result, in such a type of water and oil repellent, the carbon number of the polyfluoroalkyl group has a great influence on the water and oil repellency, and the polyfluoroalkyl group having particularly good water and oil repellency has 10 carbon atoms. It was found that they are the above perfluoroalkyl groups. The present invention is the following water and oil repellent having this specific perfluoroalkyl group.

A fluorine-containing active hydrogen compound having an active hydrogen-containing functional group capable of reacting with an isocyanate group and a perfluoroalkyl group, and 50% by weight or more of which has a perfluoroalkyl group having 10 or more carbon atoms. Reaction product of a fluorine-containing active hydrogen compound (a) which is a fluorine-containing active hydrogen compound and a polyisocyanate compound (b) having two or more isocyanate groups, or (a), (b) and a perfluoroalkyl group A water- and oil-repellent agent containing a reaction product of an active hydrogen compound (C) which does not have an active ingredient.

The reason why the water / oil repellent of the present invention is superior in water / oil repellency to the conventional one is not clear, but it is presumed as follows. That is, in the conventional polyfluoroalkyl group-containing urethane oligomer type water and oil repellent agent, the orientation of the polyfluoroalkyl group is not sufficient as compared with the acrylate-based polymer, so that high water and oil repellency is not exhibited. However, when the chain length of the polyfluoroalkyl group reaches a constant chain length (C ₁₀ F ₂₁ ), the crystallinity based on the polyfluoroalkyl group increases, and as a result, the surface orientation of the polyfluoroalkyl group increases and the high water repellency It is presumed that oiliness is exhibited.

The fluorine-containing active hydrogen compound having a perfluoroalkyl group and an active hydrogen-containing functional group capable of reacting with an isocyanate group is usually a mixture of compounds having different carbon numbers in the perfluoroalkyl group. That is, when the perfluoroalkyl group is represented by C _n F _{2n + 1-} , it is a mixture of compounds having different n (all are mixtures of the same compound except for C _n F _{2n + 1-} ). For example, the conventional one is a mixture of a compound having 8 carbon atoms as a main component and having less carbon atoms and a compound having more carbon atoms than that, and the average n is 9.

In the present invention, a compound having a perfluoroalkyl group having 10 or more carbon atoms is the main component, and substantially only or a compound having less carbon atoms and / or having more carbon atoms than that. It must be a mixture of compounds. Particularly, when the fluorine-containing active hydrogen compound (a) in the present invention is 50% by weight or more of the fluorine-containing active hydrogen compound having a perfluoroalkyl group having 10 carbon atoms, and contains another fluorine-containing active hydrogen compound. The fluorine-containing active hydrogen compound is preferably a compound having a perfluoroalkyl group having 9 or less and / or 11 or more carbon atoms. In addition, it is particularly preferable that the compound having a perfluoroalkyl group having 6 to 14 carbon atoms is 80% by weight.

The perfluoroalkyl group is preferably a linear perfluoroalkyl group. However, a small number of branches may be present, in which case it is preferable that the number of branches is 1 to 2 and the number of carbon atoms in the side chain is shorter than that of the main chain.

The fluorine-containing active hydrogen compound (a) in the present invention, which has a perfluoroalkyl group having 10 or more carbon atoms, has one active hydrogen-containing functional group capable of reacting with an isocyanate group. When it has two or more, it is preferable that the second and subsequent active hydrogen-containing functional groups have lower activity than the first active hydrogen-containing functional group. That is, it is preferable that the fluorine-containing active hydrogen compound is substantially monofunctional with respect to the isocyanate group. Other fluorine-containing active hydrogen compounds are preferably monofunctional as well, but in some cases a small amount of polyfunctional compound may be present.

Examples of the active hydrogen-containing functional group capable of reacting with the isocyanate group include a hydroxyl group, a mercapto group, a primary amino group, a secondary amino group, a carboxy group, and other functional groups having an active hydrogen atom. The secondary amino group is preferably a secondary amino group having a lower alkyl group having 4 or less carbon atoms. The most preferred active hydrogen-containing functional group is a hydroxyl group.

Various linking groups are known as a linking group for linking a perfluoroalkyl group and an active hydrogen-containing group. For example, a single bond (Specific compound example perfluorocarboxylic acid), - R -, - CON (R 1) -Q
-, - SO ₂ -Q-, and the like. However, R is an alkylene group, R ¹ is an alkyl group, and Q is a divalent organic group. Preferably, R is an alkylene group having 2 to 6 carbon atoms, R ¹ is a lower alkyl group, and Q is an alkylene group having 2 to 8 carbon atoms.

Except for the number of carbon atoms in the perfluoroalkyl group, the fluorine-containing active hydrogen compound itself having a perfluoroalkyl group in the present invention is a known type of compound. The fluorine-containing active hydrogen compound in the present invention,
Compounds of this known type can be used. Specific preferred compounds include, but are not limited to, the following. R in the following chemical formula
_f represents a perfluoroalkyl group.

R _f -CH ₂ CH ₂ -OH R _f -CON (CH ₃ ) CH ₂ CH ₂ -OH R _f -SO ₂ N (CH ₃ ) CH ₂ CH ₂ -OH R _f -CH ₂ CH _2- SH R _f -SO ₂ N (CH ₃ ) CH ₂ CH ₂ -SH R _f -CH ₂ CH ₂ -NH ₂ R _f -SO ₂ N (CH ₃ ) CH ₂ CH ₂ -NH ₂

As the polyisocyanate compound (b) having two or more isocyanate groups, various polyisocyanate compounds of aliphatic type, alicyclic type, aromatic type and the like, modified products thereof, or a mixture thereof are used. Can be used. In particular, a polyisocyanate compound having 3 or more isocyanate groups and a mixture thereof with a diisocyanate compound are preferable.

As the polyisocyanate compound having three or more isocyanate groups, a triisocyanate compound is particularly preferable. As the triisocyanate compound, a modified product of the diisocyanate compound is preferable. As the triisocyanate compound that is a modified product of the diisocyanate compound, a tris-burette modified product, an isocyanurate modified product, and a triol modified product (such as a trimethylolpropane modified product) are preferable. The triisocyanate compound, which is a modified product of this diisocyanate compound, usually contains a polyisocyanate compound having 4 or more isocyanate groups and an unmodified diisocyanate compound. In the present invention, a triisocyanate compound containing these impurities is contained. Nate compounds can be used.

Examples of the polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene triisocyanate, lysine ester triisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate. , Toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate and the like. Particularly, a triisocyanate compound which is a modified product of hexamethylene diisocyanate, such as a modified product of tris-burette of hexamethylene diisocyanate, is preferable.

The water- and oil-repellent agent of the present invention is a water- and oil-repellent agent containing the reaction products of (a) and (b) as active ingredients. However, it may also be a water / oil repellent agent containing as an active ingredient a reaction product of (a) and (b) with an active hydrogen compound (c) having no perfluoroalkyl group. The active hydrogen compound (c) having no perfluoroalkyl group is
It is a compound having one or more active hydrogen-containing functional groups capable of reacting with the above isocyanate group. Two or more kinds of this active hydrogen compound (c) can be used in combination.

This active hydrogen compound (c) has an active hydrogen-containing functional group capable of reacting with the isocyanate group as described above.
A compound having one or more groups and having a functional group other than the above is preferable. Examples of the functional group include a long-chain hydrocarbon group, an epoxy group, a cyano group, a nitro group, a halogen atom, and a hydrogen-containing functional group having a relatively low reactivity with the first hydrogen-containing functional group. is there.

Specific active hydrogen compounds (C) are:
For example, there are the following compounds, but the compounds are not limited to these.

Monool: A monool having 1 to 23 carbon atoms is suitable, and a monool having 6 to 20 carbon atoms such as stearyl alcohol and 2-ethylhexyl alcohol is particularly preferable. Mercaptan: Monomercaptan having 1 to 23 carbon atoms is suitable, and monomercaptan having 6 to 20 carbon atoms such as stearyl mercaptan and octyl mercaptan is particularly preferable. Monocarboxylic acid: A monocarboxylic acid having 1 to 23 carbon atoms is suitable, and particularly 6 to 6 carbon atoms such as stearic acid and octanoic acid.
20 monocarboxylic acids are preferred.

Mono (or di) alkylamine: Monoalkylamine or dialkylamine having alkyl having 1 to 23 carbon atoms is suitable, and particularly amine having alkyl having 6 to 20 carbon atoms such as 2-ethylhexylamine and dioctylamine. Is preferred. Epoxy group-containing compound: Glycidol (that is, 2,3-
Epoxy-1-propanol), glycerin diglycidyl ether. Polyol: polyethylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol,
Glycerin, trimethylolpropane.

Polyamine: ethylenediamine, triethylenediamine, toluenediamine, isophoronediamine, hexamethylenediamine. Alkanolamines: monoethanolamine, diethanolamine, triethanolamine, dipropanolamine. Others: 2-cyanoethanol, 2-nitroethanol, ethyleneimine, dialkylketoxime.

In the production of a reaction product of the fluorine-containing active hydrogen compound (a) and the polyisocyanate compound (b), or further the active hydrogen compound (c), the fluorine-containing active compound is added to 1 mol of the polyisocyanate compound (b). The active hydrogen compound (a) needs to be 1 mol or more. That is, the reaction product must have at least one residue of the fluorine-containing active hydrogen compound (a) on average per molecule. When reacting less than an equivalent amount of the fluorine-containing active hydrogen compound (a) with the polyisocyanate compound (b), the active hydrogen compound (c) is used and the total amount of the fluorine-containing active hydrogen compound (a) is It is preferable to use the compound in an amount equivalent to that of the isocyanate compound (II).

When the active hydrogen compound (c) is used, the equivalent ratio of the fluorine-containing active hydrogen compound (a) to the total equivalent of the active hydrogen compound (c) and the fluorine-containing active hydrogen compound (a) is 50% or more. Preferably. However, when the active hydrogen compound (C) is a polyfunctional compound that reacts with an isocyanate group, the ratio of (A) to the total of (C) and (A) is 50% by weight or more, and particularly 75% by weight. The above is preferable.

The water and oil repellent of the present invention can be used, if necessary, as a solution dissolved in a solvent or as an emulsified emulsion or dispersion.

Examples of the solvent include fluorine-based solvents such as trichlorotrifluoroethane (R-113) and metaxylenehexafluoride, chlorine-based solvents such as 1,1,1-trichloroethane, perchloroethylene and methylene chloride, tetrahydrofuran and methylisobutyl. It is possible to widely use other organic solvents such as ketones. Further, when dispersing in water, various surfactants such as nonionic, cationic and anionic surfactants can be used as the emulsifier, and these may be appropriately used in combination.

As the organic solvent used in combination in water, tetrahydrofuran, dioxane, water-soluble ethers such as ethylpropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, Water-soluble glycol ethers such as dipropylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ether, alcohols such as methanol, ethanol and propanol, esters such as ethyl acetate, butyl acetate and ethyl succinate. Can be mentioned. If desired, these organic solvents may be removed by distillation after dispersion. An appropriate amount of such organic solvent added is 10 to 300 parts by weight per 100 parts by weight of the water and oil repellent.

[0030]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the text, parts and% are based on weight unless otherwise specified. The water repellency and oil repellency shown in the following Examples and Comparative Examples were evaluated by the following evaluation tests.

Water repellency: Water repellency No. by the spray method of JIS L-1092. (See Table 1). The water repellency No. In the evaluation results represented by adding a + mark to each evaluation, each evaluation is No. It is slightly better than that represented by. Oil repellency: A few drops (diameter about 4 mm) of the test solution shown in Table 2 were placed at two places on the test cloth, and the state of permeation after 30 seconds was used to judge (AATCC-TM118-1966).

[0032]

[Table 1]

[0033]

[Table 2]

[Example 1] Dimroth cooling pipe, thermometer,
In a 500 ml four-necked flask equipped with a nitrogen gas introduction tube and a stirrer, HBU 100 parts, C ₁₀ A 203 parts, S
tO 24.35 parts, GD 6.66 parts, and MBK
A raw material consisting of 83.5 parts (see below for abbreviations) was charged and the temperature was raised to 80 ° C. with stirring. Nitrogen was bubbled through for 2 minutes, and then 0.1 g of catalyst dibutyltin dilaurate was added and stirring was continued for 2 hours. Furthermore, the temperature is 100 ° C.
The stirring was continued for 1 hour. After that, IR (infrared absorption spectrum) was measured, and it was confirmed that no isocyanate group remained, and the reaction was terminated. M in a vacuum dryer
BK was removed to give a white solid with a melting point of 96-97 ° C.

Conceptually, the main component of the reaction product is one molecule of HBU, which is a triisocyanate compound, reacted with 3 molecules of C ₁₀ A, 2 molecules of C ₁₀ A and 1 molecule of St.
It is considered to be a mixture of O reacted, 2 molecules of C ₁₀ A reacted with 1 molecule of GD, and 1 molecule of C ₁₀ A reacted with 1 molecule of StO and 1 molecule of GD. Be done.

The compounds represented by the above abbreviations are as follows. In addition, the abbreviations of the compounds used in Examples 2 and after and Comparative Examples are also shown in the same manner.

HBU: modified tris-buret of hexamethylene diisocyanate (NCO value 22.7 wt%)
[Sumitomo Bayer "Sumijour N-3200"] NHP: hexamethylene diisocyanate modified trimethylolpropane IPN: isophorone diisocyanate modified isocyanurate

C ₁₀ A; C ₁₀ F ₂₁ CH ₂ CH ₂ OH C ₁₁ A; C ₁₁ F ₂₃ CH ₂ CH ₂ OH C ₈ A; C ₈ F ₁₇ CH ₂ CH ₂ OH C ₁₀ SA; C ₁₀ F ₂₁ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OH C ₁₀ S; C ₁₀ F ₂₁ CH ₂ CH ₂ SH StO; C ₁₈ H ₃₇ OH StN; C ₁₈ H ₃₇ NH ₂

StS; C ₁₈ H ₃₇ SH StA; C ₁₇ H ₃₅ COOH GD; glycidol MBK; methyl isobutyl ketone MEK; methyl ethyl ketone DGM; diglyme

[Example 2] Dimroth condenser, thermometer,
In a 500 ml four-necked flask equipped with a nitrogen gas introducing tube and a stirrer, 100 parts of HBU, C ₁₀ A 166.2
Part, C ₈ A 110.8 part, StO 24.35 part, G
A raw material consisting of D 6.66 parts and MBK 102 parts was charged and reacted in the same manner as in Example 1 to obtain a white solid.

[Example 3] Dimroth cooling pipe, thermometer,
Into a 500 ml four-necked flask equipped with a nitrogen gas introduction tube and a stirrer, 100 parts of HBU and 100 parts of MBK were put and heated to 80 ° C. with stirring, and then the inside of the flask was replaced with nitrogen, and then dibutyltin dilaurate 0 .1 part was added. Next, 110.8 parts of C ₈ A was added dropwise over 1 hour, and then 166.2 parts of C ₁₀ A and StO 48.7 were added.
A portion was dropped in the same manner. After the dropping, raise the temperature to 90 ° C 3
Stirring was continued for 0 minutes. Then, IR was measured to confirm that no isocyanate group remained, and the reaction was terminated.

Table 3 shows the types and ratios of the raw materials, the synthesis temperature, and the melting points of the products in Examples 1 to 3 above.

[0043]

[Table 3]

[Examples 4 to 10] Reaction products were produced in the same manner as in Example 3 except that the raw materials shown in Table 4 were used. Table 4 shows the types and ratios of raw materials, synthesis temperatures, and melting points of products.
Shown in.

[0045]

[Table 4]

[Comparative Example 1] A reaction product was produced under the same conditions and conditions except that all C ₁₀ A were replaced by equivalent amounts of C ₈ A in Example 1.

Comparative Example 2 C ₁₀ A and C in Example 2
Instead of the combination of ₈ A, C _n F _{2n + 1} CH ₂ CH ₂ O
Compounds represented by H having different n (n is 8, 1
A mixture of compounds which are 0, 12, and 14 (n = 8)
A reaction product was produced under the same conditions and the same conditions except that the weight ratio of / 10/12/14 was 60/25/10/5 and the average n was about 9). The mixture of this compound is called C ₉ A.

Table 5 shows the types and ratios of the raw materials, the synthesis temperature, and the melting points of the products in Comparative Examples 1 and 2 above.

[0049]

[Table 5]

[Example 11] The reaction product obtained in Example 1 was emulsified in water according to the following method to obtain an aqueous dispersion system.
That is, 100 parts of the reaction product obtained in Example 1, MBK 2
0 parts, nonionic emulsifier [Emulgen manufactured by Kao Corporation]
A mixture of 4 parts of E-950 "] and 1 part of a cationic emulsifier [" Farmin DMC.AcOH "manufactured by Kao Corporation] was heated to 85 ° C and emulsified by a high pressure homogenizer. MBK was distilled off under reduced pressure to obtain a dispersion having a particle size of about 0.1 μm. The reaction products of Examples 2 to 10 and the reaction products of Comparative Examples 1 and 2 were similarly emulsified to obtain dispersions.

These samples were diluted with water to 0.2 wt.
% Aqueous solution was prepared. Dipping polyester doskin cloth and nylon stunner cloth and picking up each 60
It was adjusted with mangle so that it would be 40% by weight.
This was dried at 110 ° C. for 90 seconds and then at 170 ° C. for 60 seconds to obtain a test cloth. The results of oil repellency and water repellency tests conducted using this test cloth are shown in Table 6.

Example 12 The dispersion samples prepared in Example 11 were each diluted with water to give 1.5 w.
A t% aqueous solution was prepared, and a polyester car sheet was dipped in the aqueous solution to adjust the pickup to 60 wt%. This was heat-dried at 120 ° C. for 3 minutes and then at 160 ° C. for 2 minutes to obtain a test cloth.

Table 6 shows the results of oil repellency and water repellency tests conducted using this test cloth. In Table 6, the reaction products are indicated by the numbers of the Examples and Comparative Examples in which they were produced.

[0054]

[Table 6]

[0055]

EFFECTS OF THE INVENTION Water-repellent and oil-repellent agents containing conventional R _f -group-containing urethane compounds as active ingredients are excellent in flame retardancy of treated textiles and the like, but have high water repellency, especially repellency by spray method evaluation. It was not possible to obtain a water / oil repellent comparable to a water / oil repellent such as an R _f group-containing acrylate polymer in water. According to the present invention, a water repellent agent of the R _f group-containing urethane compound type that can exhibit high water repellency even when evaluated by a spray method can be easily obtained.

Claims (7)

[Claims] 1. A fluorine-containing active hydrogen compound having an active hydrogen-containing functional group capable of reacting with an isocyanate group and a perfluoroalkyl group, 50% by weight or more of which is a perfluoroalkyl group having 10 or more carbon atoms. Reaction product of a fluorine-containing active hydrogen compound (a), which is a fluorine-containing active hydrogen compound having, and a polyisocyanate compound (b) having two or more isocyanate groups, or (a), (b), and perfluoro A water- and oil-repellent agent which comprises a reaction product of an active hydrogen compound (c) having no alkyl group as an active ingredient. 2. A fluorine-containing active hydrogen compound (a) is C10F.
21- 50 to 100% by weight of a fluorine-containing active hydrogen compound having a perfluoroalkyl group and 0 to 50% by weight of a fluorine-containing active hydrogen compound having a C9 or less and / or a C11 or more perfluoroalkyl group % Of the water and oil repellent of claim 1. 3. The fluorine-containing active hydrogen compound is a fluorine-containing active hydrogen compound having one active hydrogen-containing functional group selected from a hydroxyl group, a mercapto group, and a primary amino group.
The water and oil repellent according to claim 1 or 2. 4. The water and oil repellent according to claim 1, wherein the polyisocyanate compound (b) is a triisocyanate compound. 5. The water- and oil-repellent agent according to claim 4, wherein the triisocyanate compound is a compound selected from tris-burette modified products, isocyanurate modified products, and triol modified products of diisocyanate compounds. 6. The active hydrogen compound (C) is a compound having no fluorine atom and having at least one active hydrogen-containing functional group selected from a hydroxyl group, a mercapto group, a carboxy group, and a primary amino group. The water and oil repellent according to claim 1. 7. The water and oil repellent according to claim 6, wherein the active hydrogen compound (c) is a compound further having an epoxy group or a long chain hydrocarbon group.