JP2502061B2 - Highly flexible water and oil repellent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water and oil repellent agent which is composed of a specific compound having a polyfluoroalkyl group and which is particularly excellent in flexibility and can impart high water repellency.

[Prior Art] Conventionally, in order to make a textile fabric less likely to be soiled, processing utilizing the water / oil repellency of a polyfluoroalkyl group has been widely performed. Thus, various water- and oil-repellent finishing agents made of polyfluoroalkyl group-containing compounds or polymers have been proposed. For example, a high molecular polymer type water and oil repellent represented by a copolymer containing a perfluoroalkyl group-containing acrylate or methacrylate as a main component is known.

However, a fiber product processed with a conventional water- and oil-repellent agent containing a perfluoroalkyl group generally has a hard feel, and there is a problem that the original texture of the fiber product is impaired. In addition, processing with conventional polymer-type water and oil repellents containing perfluoroalkyl groups is
High performance under curing conditions above ℃, 100 ℃
It is also recognized that the desired performance is difficult to be exhibited at a low curing temperature below.

On the other hand, in order to impart water repellency to textiles, processing with organic silicone compounds such as organopolysiloxanes has been proposed, and it is possible to give textiles a unique and soft texture, but the processing takes a long time. Alternatively, high temperature heating is required, and the processed textile product has an essential drawback that it is easily stained with oil.

An attempt was made to solve the combination difficulty of the perfluoroalkyl group-containing polymer and the organopolysiloxane due to poor compatibility, and to satisfy both the oil repellency of the former and the water repellency and flexibility of the latter. It is proposed by Japanese Patent No. 3331813, West German Patent No. 2062816, and US Patent No. 3903123. In these attempts, optimization of both performances has not been achieved because the perfluoroalkyl group is directly attached to the polysiloxane backbone.

Thus, it is manufactured using a perfluoroalkyl group-containing diol, a diisocyanate, and a reactive group-containing organopolysiloxane. A urethane polymer in which a perfluoroalkyl group-containing unit and a polysiloxane unit are bonded as separate segments by a diisocyanate is proposed in US Pat. No. 4098742 and the like. According to the water and oil repellent agent comprising such a segmented urethane polymer,
It is said that optimization of both performances of oil repellency and water repellency / flexibility is achieved. However, since the perfluoroalkyl group-containing diol is adopted, the perfluoroalkyl group is incorporated in the polymer main chain. It is linked as a side chain, and it is recognized that the advantage of segmentation cannot be fully utilized. Further, since it is a polymer type, there remains a drawback that high temperature curing conditions are required for performance expression. In particular, it is difficult to obtain a satisfactory result for the purpose of maintaining high water repellency and imparting oil repellency and flexibility.

[Problems to be Solved by the Invention] The present invention solves the above-mentioned problems and not only imparts high water / oil repellency to a textile product even under low curing conditions, but also a processed textile product. Has a soft texture. It is an object of the present invention to provide a novel water and oil repellent agent which is sufficiently satisfactory for practical use.

[Means for Solving Problems] The present inventor has conducted various researches and studies on conventionally known fluorine-containing urethane type water and oil repellents, and as a result, obtained the following interesting findings. . That is, a compound having a specific molecular weight range in which at least two molecules of a polyfluoroalkyl group-containing terminal structure are linked through a specific organosiloxane molecular chain in the middle, impairs other properties such as oil repellency and antifouling property. In addition, the present inventors have found a new fact that a high degree of water repellency can be exhibited and a soft texture can be achieved. For example, a polyfunctional alkyl compound-containing alcohol is reacted with a polyfunctional isocyanate compound to obtain a urethane compound having a polyfluoroalkyl group and an isocyanate group, and an organo group having an isocyanate group of the urethane compound and active hydrogen at both ends. By reacting with the siloxane molecular chain-containing compound, the end groups of the polyfluoroalkyl group-containing urethane compound are attached to both ends of the organosiloxane molecular chain-containing compound with -NHCO.
-A compound is obtained which is linked via a linking group. The compound having a specific intermediate linking molecular chain thus obtained can exhibit higher water repellency than the conventional fluorine-containing urethane compound without the intermediate linking molecular chain and is also excellent in flexibility. Is.

Thus, the present invention has been completed based on the above findings and has a molecular weight of 800 to 20,000 composed of at least two polyfluoroalkyl group-containing terminal structures and an intermediate structure connecting the terminal structures. A compound, wherein the terminal constituent is a reaction product formed when an active hydrogen compound containing a polyfluoroalkyl group-containing active hydrogen compound and a polyfunctional isocyanate compound react with each other at a ratio in which one isocyanate group remains. Is a monovalent residue obtained by removing one isocyanate group from the above, and the intermediate structure is at least a divalent organosiloxane obtained by removing active hydrogen from an organosiloxane oligomer having two or more active hydrogen groups. It is a residue containing a molecular chain and is characterized by comprising a compound having a structure in which the above-mentioned terminal constituent and intermediate constituent are bound by a -CONH- linking group. The present invention newly provides a water and oil repellent having high flexibility.

In the present invention, it is important that the compound is composed of a specific terminal structure and a specific intermediate structure.
The terminal structure can be derived by the reaction of a compound containing a polyfunctional isocyanate group and a compound containing an active hydrogen group. The intermediate construct may be derived from a difunctional reactive group-containing organopolysiloxane, such as a polyorganosiloxane having two active hydrogen groups, and an isocyanate group-containing compound and an organosiloxane molecular chain containing an active hydrogen group. It can also be derived by reaction with contained oligomers. Further, the specific terminal construct and the specific intermediate construct are -CONH-
It is important that they are bound by a linking group, which also can be formed by the reaction of an isocyanate group with an active hydrogen group. Thus, certain terminal constructs contain a polyfluoroalkyl group attached via a -CONH- linking group,
A particular intermediate construct comprises an oligomer containing organosiloxane molecular chains, which may optionally have a -CONH- linking group, wherein at least two of the particular terminal constructs are bound by a -CONH- linking group. It is important that it is connected to the intermediate structure.

The compound having a molecular weight of 800 to 20,000 having the above constitution of the present invention can be synthesized by various synthetic routes. Normally,
A specific terminal constituent compound and a specific intermediate constituent compound, leaving an isocyanate group in one constituent and leaving an active hydrogen group in the other constituent, respectively synthesized,
The specific compound of the present invention can be obtained by reacting these both constituent compounds. Preferably, a polyfunctional isocyanate compound is reacted with a polyfluoroalkyl group-containing active hydrogen compound and, if necessary, another active hydrogen compound to give at least one —NCO group-containing polyfluoroalkyl group-containing isocyanate. A nato (terminal constituent) is obtained, and an organosiloxane molecular chain-containing oligomer (intermediate constituent) having at least two active hydrogen groups is reacted therewith, and both constituents are reacted with an isocyanate group and an active hydrogen group. The method of connecting by is adopted. Alternatively, as described above, an end structure having at least one —NCO group remaining therein is prepared, and then at least two active hydrogen groups are prepared by reacting a polyvalent active hydrogen compound containing an organosiloxane molecular chain with a polyfunctional isocyanate compound. Is used to prepare an organosiloxane molecular chain-containing oligomer (intermediate constituent), and the two constituents are linked by a reaction between an isocyanate group and an active hydrogen group.

Further, the above-mentioned polyfluoroalkyl group-containing isocyanate (terminal constituent) is reacted with a polyvalent active hydrogen compound containing an organosiloxane molecular chain and a polyfunctional isocyanate compound to form the above intermediate constituent and both constituents. Is also employed in a single reaction system, further by reacting the intermediate constituent with a polyfluoroalkyl group-containing active hydrogen compound and a polyfunctional isocyanate compound, to form the terminal constituent. It is also possible to employ a method in which the two constituents are linked in one reaction system. Of course, as long as a compound having the specific constitution and molecular weight of the present invention is provided, the raw material compounds used in the synthesis of both the above-mentioned constituents are reacted together, and the formation of each constituent and the connection of both constituents are carried out in one reaction system. You can also do it.

In addition, in the present invention, contrary to the preferred embodiment of the synthesis, at least one active hydrogen group is left in the terminal structure and at least two -NCO groups are left in the intermediate structure. It is also possible to adopt a method such as reacting the constituents, or to leave active hydrogen groups in both constituents and connect both constituents using a polyfunctional isocyanate compound, or both constituents are isocyanate-containing. It is also possible to employ a method of leaving the nato group and connecting both constituents using a polyvalent active hydrogen compound.

Furthermore, in the present invention, a monovalent active hydrogen compound containing an organosiloxane molecular chain, a polyvalent active hydrogen compound such as 1,6-hexamethylene glycol, and a polyfunctional isocyanate compound are reacted during the formation of the intermediate constituent. Then, a method of forming an oligomer-type intermediate structure containing a -CONH-bonding group and an organosiloxane molecular chain can also be employed.

The compound having the specific constitution and molecular weight of the present invention can be synthesized by various synthetic routes as described above, and the embodiment will be described below by taking the above-mentioned preferred synthetic mode as a typical example.

The polyfunctional isocyanate compound used for forming the specific terminal structure and the oligomer-type intermediate structure in the present invention is not particularly limited as long as it is bifunctional or more, and various compounds can be exemplified. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, and dianisidine diisocyanate, 2-
Methyl-cyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated MDI And bifunctional isocyanate compounds such as alicyclic diisocyanates, hexamethylene diisocyanate, decamethylene diisocyanate, and other aliphatic isocyanates. If these are represented by the general formula OCN-Y-NCO, if OCN-Y-NCOs are reacted in the presence of water, OCN-Y-NCO
Although a dimer such as -Y-NHCONH-Y-NCO is produced, the difunctional isocyanate compound also means such a dimer. In addition to bifunctional, trifunctional, tetrafunctional, pentafunctional, and other polyfunctional isocyanate compounds may also be mentioned. Specific examples of the trifunctional isocyanato compound may include the following compounds, but as described above, the dimeric OCN-Y-NH 2
Trimer obtained by reacting CONH-Y-NCO with monomer OCN-Y-NCO Furthermore, the tetramer that the dimer comrades reacted And a compound having three —NCO groups such as

Examples of other trifunctional isocyanate compounds are: Etc.

Thus, in the present invention, in the formation of the specific terminal constitution, among the polyfunctional isocyanate compounds as described above,
A trifunctional compound is preferably used, and an aliphatic trifunctional isocyanate compound is particularly preferably used. Further, as the polyfunctional isocyanate compound used for forming the specific oligomer-type intermediate constituent, a bifunctional isocyanate compound is preferable since a trifunctional or higher functional compound may gel during the reaction. For higher water repellency,
Usually, aromatic polyfunctional isocyanate compounds are preferable, and bifunctional aromatic isocyanates are particularly preferable. Of course, in the formation of both constituents, two or more kinds of polyfunctional isocyanate compounds having different kinds or functionalities or functional numbers may be used in combination, and the above-mentioned suitable polyfunctional isocyanate compound and an isocyanate having a larger number of functional groups may be used. A mixture with a nato compound may be adopted.

As the polyhydroalkyl group-containing active hydrogen compound used for the reaction with the polyfunctional isocyanate compound as described above in the formation of the specific terminal structure, compounds represented by the general formula R _f -XAH are typically exemplified. obtain. As such R _f -XAH, an R _f -R-OH type fluorinated alcohol is usually preferably used. Also, R _f in which A is -S-
-R-SH type fluorine-containing thioalcohol is also adopted,
Is a fluorine-containing amine or A in which is -N (R ² )- Fluorine-containing carboxylic acids and the like may also be used. It is of course possible to use, as a raw material, a mixture of fluorine-containing alcohols having different carbon numbers in R _f or R.

In the above general formula, R _f is a linear or branched polyfluoroalkyl group having 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, and usually a terminal one having a perfluoroalkyl group is selected. However, those containing a hydrogen atom or a chlorine atom at the terminal portion, or an oxyperfluoroalkylene-containing group can also be used. A preferred embodiment of R _f is a perfluoroalkyl group represented by C _n F _{2n + 1} (where n is an integer of 4 to 16), and n is preferably 6 to 12. X is -R-,-CON (R ¹ ) -Q- or -SO ₂ N (R
¹ ) -Q- (wherein R represents a divalent alkylene group, R ¹ represents a hydrogen atom or a lower alkyl group, and Q represents a divalent organic group), and preferably has 1 to 10 carbon atoms. A divalent alkylene group, especially a divalent alkylene group having 2 to 4 carbon atoms is selected. Q is a divalent organic group, but is usually -R
The divalent alkylene group represented by-is exemplified as a suitable one.

In the present invention, the R _f group-containing active hydrogen compound such as R _f -XAH may be used in combination with another active hydrogen compound represented by the general formula ZA ¹ -H, if necessary. As ZA ¹ -H, similar to the case of R _f -XAH, alcohols in which A ¹ is -O-, thioalcohols in which A ¹ is -S-, A ¹
But And the amines in which A ¹ is —N (R ² ) — and the like. For example, as ZA ¹ -H, nC
By adopting a linear stearyl group-containing active hydrogen compound such as ₁₈ H ₃₇ OH, nC ₁₈ H ₃₇ SH, nC ₁₈ H ₃₇ NH ₂ , the water repellent performance of the water and oil repellent agent of the present invention can be further enhanced, Or as ZA ¹ -H, in order to increase the affinity with the surface of the synthetic fiber etc. which is the object to be treated and further improve the durability, Alcohols such as those mentioned above can be adopted, and further, alkanolamines, diamines, or a combination of ammonia and a methylolating agent may be used.

 The above general formula R_f-X-A-H and Z-A¹-H, A and A¹
Are respectively -O-, -S-,Or -N (R²)-(However, R²Is a hydrogen atom or a monovalent organic group
A) is -O from the viewpoint of easy availability.
− And A¹Is -O- or -N (R²)-Is selected
Be done. Z is a monovalent organic group, and R is²same as
May also be R²Form a ring with
May be. For example, -A¹-Z is -OR '(R' is
Rukyi group), -NHCH₂OH, -NHCH₂CH₂OH, -OCH₂CH₂CN, -OCH₂CH₂NO₂, -OCH₂CH₂OH, -N (CH₂CH₂OH)₂,-N (R ′)₂, -NH (R '),- NN (CH₃)₂CH₂CH₂OH,Can be illustrated.

In the general formula ZA ¹ -H, Z is a monovalent organic group, but specific examples in which Z is an alkyl group, an aralkyl group, or an alicyclic group include the following alcohols, thioalcohols, Amine etc. can also be illustrated.

CH ₃ (CH ₂ ) _q OH, [CH ₃ (CH ₂ ) _q ] ₂ CHOH, (CH ₃ ) ₃ COH, [CH ₃ (CH ₂ ) _q ] ₂ CHSH, CH ₃ (CH ₂ ) _q NH ₂ ,, [CH ₃ (CH ₂ ) _q ] ₂ NH, (However, q is 0 or an integer of 1 to 30) Next, in the formation of a specific intermediate constitutional body, an organosiloxane molecule which may be optionally used for the reaction with the polyfunctional isocyanate compound as described above. Examples of the chain-containing polyvalent active hydrogen compound include compounds containing two or more active hydrogen groups such as polyhydric alcohols, polyvalent thioalcohols, polyvalent amines and polyvalent carboxylic acids. Usually, a dimethylsiloxane oligomer can be preferably used as the organosiloxane molecular chain. Further, the Si side chain group includes not only a methyl group but also a hydrogen atom, an ethyl group, an octyl group, a stearyl group, a trifluoropropyl group, a chloropropyl group, a phenyl group, a glycidoxypropyl group, Of course it is possible. For example, as a polyvalent active hydrogen compound containing a dimethylsiloxane molecular chain, Or a bifunctional one, or It is possible to exemplify trifunctional or higher functional compounds such as. Of course,
It is also possible to use two or more of these in combination. In the above, Me is a methyl group, s is 0 or an integer of 1 to 100,
u is an integer of 1 to 100, r is an integer of 3 to 20, and x, y and z are 0.
Or the integer of 1-50, t and p show the integer of 0 or 1-100.

In the present invention, the dimethylsiloxane molecular chain-containing polyvalent active hydrogen compound as described above is preferably used for the formation of the specific intermediate constitutional body, and particularly, those having 3 to 50 dimethylsiloxane units are excellent in flexibility. It is suitable because it can impart high water and oil repellency as well as imparting properties. If the number of dimethylsiloxane units in the specific intermediate structure is too large, the oil repellency is deteriorated, the oil is likely to be contaminated, and the durability is also disadvantageous. Further, when the number of dimethylsiloxane units is too small, the effect of imparting flexibility becomes small. Normally,
A bifunctional polyvalent active hydrogen compound is suitable, and when a trifunctional or higher functional polyvalent active hydrogen compound is used, a gel may be formed during the reaction, and thus it is generally not preferable.

In the present invention, the following monofunctional active hydrogen compounds can be used to introduce the organosiloxane molecular chain when forming the specific intermediate structural body.
For example, Monofunctional active hydrogen compounds such as Note that Me, x, y and z in the above are as described above. An oligomer type intermediate constituent containing an organosiloxane molecular chain is prepared by a method of reacting a monofunctional or more active hydrogen compound with a trifunctional or more polyfunctional isocyanate compound and a difunctional or more polyvalent active hydrogen compound. Can be formed. Examples of the polyvalent active hydrogen compound in this case include compounds having two or more active hydrogen groups such as polyhydric alcohols, polyvalent thioalcohols and polyvalent amines. For example, HO (CH ₂ ) _e OH, CH ₃ (CH ₂ ) _i NH (CH ₂ ) ₂ NH (CH ₂ ) _i CH ₃ , HS (CH ₂ ) _e SH, A bifunctional polyvalent active hydrogen compound such as N (CH ₂ CH ₂ OH) ₃ , C ₂ H ₅ C (CH ₂ OH) ₃ , CH ₃ (CH ₂ ) _i NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) _i CH ₃ and other trifunctional polyvalent active hydrogen compounds, Examples include tetrafunctional polyvalent active hydrogen compounds such as CH ₃ (CH ₂ ) _i NH (CH ₂ ) ₂ NH (CH ₂ ) -NH (CH ₂ ) _i CH _3, and the like. Examples thereof include those having 5 or more functional groups, such as partial alkyl, aryl esters, ethers, and amides. Of course, it is also possible to use two or more of these in combination. In the above, e is 1 to 20, f, g, and h are 1
-50, i is 0 or an integer of 1-20. As is clear from the above examples, the polyvalent active hydrogen compound used in combination with the organosiloxane molecular chain-containing monovalent active hydrogen compound does not necessarily have to contain the organosiloxane molecular chain, and may contain it in reverse. good.

In the present invention, the polyvalent active hydrogen compound used for the formation of the specific oligomer type intermediate constituent as described above is preferably trifunctional or less, and a bifunctional polyvalent active hydrogen compound is particularly preferable. Is. Further, as such a polyvalent active hydrogen compound, 2 or more methylene chains, especially 2
Those containing ~ 12 methylene chains are the most preferable because of high water repellency and the like. It is not preferable to use a tetrafunctional or higher polyvalent active hydrogen compound because a gel may be formed during the reaction.

In the present invention, a compound represented by the general formula HA ² —BA ² —H can be exemplified as a preferred embodiment of the organosiloxane molecular chain-containing polyvalent active hydrogen compound used for forming the specific intermediate structure. In this general formula, A ² is -O-, -S-, like A or A ¹ above. Or --N (R ² )-(wherein R ² represents a hydrogen atom or a monovalent organic group), preferably A ² is --O-- or --N (R
² ) -is selected. B is a divalent organic residue containing an organosiloxane molecular chain obtained by removing ^two -A ² -H groups from a polyfunctional active hydrogen compound containing a bifunctional organosiloxane molecule as described above. Thus, B may have other organic groups attached through A ² . Preferably, B is a divalent organic residue containing a dimethylsiloxane molecular chain, particularly 3 to 50 dimethylsiloxane units.
It is a divalent organic residue contained individually.

The formation reaction of the terminal constituents and the intermediate constituents or the ligation reaction of both constituents using the above-mentioned raw materials can be carried out by employing various reaction conditions, reaction devices and the like. As a typical example, the reaction between a fluorine-containing alcohol R _f -XAH and a polyfunctional isocyanate compound will be described. The reaction temperature is usually 0 to 200 ° C, preferably 40 to 100 ° C.
The degree is adopted. Further, the reaction is preferably carried out in an inert organic solvent, but in some cases, it can be carried out without using an inert organic solvent. Here, as the inert organic solvent preferably used, those capable of dissolving the raw material polyfunctional isocyanate compound are desirable, for example, 1,1,1
-Halogenated hydrocarbons such as trichloroethane, trichloroethylene, trichloromethane, trichlorotrifluoroethane, hydrocarbons such as benzene, toluene, hexane, ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, acetone, Ketones such as methyl ethyl ketone and methyl isobutyl ketone,
Examples thereof include esters such as ethyl acetate and butyl acetate, dimethylformamide, dimethylsulfoxide, and acetonitrile. By adopting an inert organic solvent, a homogeneous reaction can be smoothly and advantageously carried out. Thus, the inert organic solvent is usually 1 to 1 mol per mol of the starting isocyanate compound.
It can be employed in a ratio of about 50 mol, preferably about 5 to 20 mol.

It is advantageous to suppress the side reaction that the above reaction is carried out under substantially anhydrous conditions. That is, the presence of water is detrimental to the -NCO group. For example, the water content of the raw materials and the reaction device is sufficiently controlled, and the reaction is carried out in a stream of an inert gas such as dry nitrogen. In addition, such a reaction is carried out by a salt of alkyltin such as dibutyltin dilaurate, or
It smoothly and advantageously proceeds in the presence of a catalyst composed of a compound having a pKa of 5.0 or more, preferably 7 to 10. As such a catalyst,
Although various examples can be given, trimethylamine, triethylamine, tripropylamine, tributylamine, triallylamine, N-methylpiperidine, N-methylpyrrolidine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylbenzylamine, pyridine , 4-methylpyridine,
Dimethyllaurylamine, dimethylmyristylamine,
Tertiary amines such as dimethylstearylamine, tricaprylamine, methyldistearylamine, methyldilaurylamine, dimethylcaprylamine, dimethylpalmitylamine, tetramethylpropylenediamine, pentamethyldiethylenetriamine can be preferably used.
In addition, alkali alcoholates, inorganic alkali salts with pKa of 5.0 or more, inorganic alkaline earth salts, ammonium salts, and metal inorganic salts such as tin, cobalt, iron, titanium, zinc, antimony and lead, organic salts, etc. as catalysts Can be adopted. The amount of the catalyst used may be selected from the range of about 0.001 to 10 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the starting isocyanate compound.

Terminal constructs synthesized by various synthetic routes as described above,
Preferred embodiments of the intermediate constituent and the compound having a specific structure and having a molecular weight of 800 to 20,000 (hereinafter abbreviated as a specific R _f urethane compound) are shown by the general formulas as follows. That is,
Suitable specific examples of the specific end structure of the present invention have the general formula Is represented by Further, the intermediate structure has the general formula A ² -BA ^2-
CONH-Y-NHCO _m A ² -BA ^2- , and the specific R _f urethane compound has the general formula Is represented by

In these general formulas, R _f , X, Z, A, A ¹ , A ² , and B
Is as described above. W is t-NCO from a t-functional isocyanate compound having t-NCO groups.
It is a t-valent residue with the group removed, and t is 3 as described above.
Is preferably a trivalent organic residue, and W is preferably a residue from an aliphatic polyfunctional isocyanate compound. And a is an integer of 1 to 5, b is 0 or 1
An integer of 4 and a + b is an integer of 1 to 5, preferably a
Is 1 or 2, b is 0 or 1, a + b is 2. Y is
As described above, a divalent organic residue obtained by removing two -NCO groups from a bifunctional isocyanate compound having two -NCO groups is preferable, and an aromatic polyfunctional isocyanate compound is preferably used. Is preferred. Therefore,
A trifunctional polyvalent active hydrogen compound or a trifunctional isocyanate compound can be used in the formation of the intermediate structure. In such a case, another organic group in which B is bonded via A ² is used. May have, or Y is -CO
It may have another organic group bonded via an NH-group, such as an R _f -XA-group or a ZA ¹ -group. m is 0 or 1 to 50
And is preferably selected from 0 or an integer of 1-10.

In the present invention, as the specific R _f urethane compound, a compound having an organic group containing an organosiloxane molecule chain bonded via a —CONH— group as Y in the above-mentioned general formula may be adopted, In this case, B may not contain the organosiloxane molecular chain as described above. For example, an organic residue from a trifunctional isocyanate compound is adopted as Y, and one -NCO group is reacted with a monofunctional active hydrogen compound containing an organosiloxane molecular chain, and the remaining two -NCO groups are reacted. Group and bifunctional HA ² -B-
It is possible to form an oligomer-type intermediate component by reaction with a polyvalent active hydrogen compound such as A ² -H (in this case, B may not contain an organosiloxane molecular chain).

The molecular weight of the specific R _f urethane compound of the present invention having the above structure is usually 800 to 20,000, preferably 1,000 to 1
It is 0,000, and if the molecular weight is too small, the water and oil repellency will be significantly reduced by washing and dry cleaning.If it is too high, the performance will be exhibited under low temperature curing conditions. Difficult to do and disadvantageous in imparting a soft texture are recognized.

In the present invention, the specific R _f urethane compound can be used in the form of an organic solution or an organic dispersion, and in consideration of application to a dyeing process or the like, or the influence on the working environment, use in an aqueous dispersion. It is particularly suitable. in this case,
As the surfactant as the dispersant, various types such as nonionic, anionic, cationic and amphoteric surfactants can be adopted, and these may be appropriately used in combination. An organic solvent may be used in combination for the purpose of promoting the dispersion of the specific R _f urethane compound.
Examples of the organic solvent used in combination in water include dioxane, tetrahydrofuran, water-soluble ethers such as ethylpropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene. Glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol Monop Water-soluble glycol ethers such as pill ether, triethylene glycol monobutyl ether, amides such as formamide, dimethylformamide, acetamide, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diacetone alcohol, methanol, ethanol , Alcohols such as propanol and butanol, and esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate. The amount of the organic solvent added is 100 parts by weight of the specific R _f urethane compound,
It is usually selected from the range of 10 to 300 parts by weight, preferably 50 to 200 parts by weight.

Specification when the water- and oil-repellent agent of the present invention is an aqueous dispersion type
R _f urethane compound solid content concentration is not particularly limited,
It is usually adjusted to 5 to 60% by weight, preferably 10 to 50% by weight, and for processing, this is 0.4 to 4% by weight with water.
Used in a diluted state. And, such an aqueous dispersion type processing agent has advantages such as a high flash point of the undiluted solution and a high solid content concentration as compared with those of an organic solvent type, and further work during processing. It has various advantages such as minimizing environmental pollution.

The article that can be treated with the water and oil repellent of the present invention is not particularly limited and various examples can be given. Examples include textile fabrics, glass, paper, wood, leather, fur, asbestos, bricks, cements, metals and oxides, ceramic products, plastics, painted surfaces and plasters. As the textile fabric, cotton,
Natural animal and vegetable fibers such as hemp, wool and silk, various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers and asbestos fibers. Examples include woven fabrics of inorganic fibers or mixed fibers thereof. In particular, it is useful as a processing agent for fibers such as wool and silk where the texture is important and can be applied before the dyeing step or during the spinning of the raw yarn.

The method for applying the water and oil repellent of the present invention is not particularly limited, and various known or known methods can be adopted.For example, by known methods of coating such as dipping, spraying and coating, It can be applied by a method of adhering to the surface of the object to be treated, or absorbing and drying it.
Further, at the time of construction, an antistatic agent, an insect repellent, a flame retardant, a dye stabilizer, an anti-wrinkle agent, and various other treatment agents and additives may be used in combination.

EXAMPLES Next, examples of the present invention will be described more specifically, but it goes without saying that the present invention is not limited to these examples. Percentages are% by weight or parts by weight, unless stated otherwise.

In addition, in the following Examples and Comparative Examples, water repellency and oil repellency were measured as follows. In other words, the water repellency was determined by the JIS L-1005 spray method to be no.
(See the table), and the oil repellency is shown in Table 2 below.
m) for 30 seconds and then determine the permeation state (AATCC-TM
118-1966).

Synthesis Example 1 Of 23.9 g (0.05 _{mol), (C 4 H 9)} 2 Sn (OCOC 11 H 23) 2 ( Catalyst:
0.03 g of dibutyltin dilaurate) and 7 of dioxane
6.3 g was placed in a four-necked flask having an inner volume of 300 ml equipped with a stirrer, a dropping funnel, a thermometer and a cooling tube.
Maintaining the temperature at 70 ° C, the formula C _n F _{2n + 1} C ₂ H ₄ OH (where n is 6,
A mixture of 8,10,12 has an average of 9.0) 51.4g of alcohol
(0.1 mol) was added over 2 hours using a dropping funnel. After continuing stirring for 1 hour, 21 g (0.025 mol) of was added as a 50% dioxane solution. The reaction was carried out for 1 hour with stirring to obtain a product having a structure shown in Table 3 below. A gel permeation chronograph and infrared absorption spectrum show a reaction rate of 10
It was 0%, and it was confirmed that no unreacted component remained in the product.

Synthesis example 2 Of 23.9 g (0.05 _{mol), (C 4 H 9)} 2 Sn (OCOC 11 H 23) 2 ( Catalyst:
0.03 g of dibutyltin dilaurate) and 8 of dioxane
4 g was placed in a four-necked flask with an internal volume of 500 ml equipped with a stirrer, a dropping funnel, a thermometer and a cooling tube. Maintaining the temperature at 70 ° C, the formula C _n F _{2n + 1} C ₂ H ₄ OH (where n is 6,8,1
An average of 9.0 in a mixture of 0,12 and 51.4 g (0.1
Mol) was added in 2 hours using a dropping funnel. After continuing stirring for 1 hour as it is, 8.71 g (0.05 mol) of tolylene-2,4-diisocyanate, and then 42 g (0.05 mol) of was added as a 50% dioxane solution. The reaction was carried out for 1 hour with stirring to obtain a product having a structure shown in Table 3 below. A gel permeation chronograph and infrared absorption spectrum show a reaction rate of 10
It was 0%, and it was confirmed that no unreacted component remained in the product.

Synthesis Examples 3 to 5 In the same manner as in Synthesis Example 1 or 2, various reaction products having the structures shown in Table 3 below were obtained.

In Table 3 below, Me represents a methyl group, and Σ
_f is [C _n F _{2n + 1} C ₂ H ₄ OCONH (CH ₂ ) ₆ NHCO] ₂ NCH _{2 6} .

Examples 1 to 4 Each _Rf urethane compound shown in Table 4 below was diluted with a mixed solution of tetrahydrofuran / trichlorotrifluoroethane (50/50 weight ratio) to prepare a treatment bath having a solid content of 0.3%. Wool (tropical, 195 g / m ² ) was dipped in the treatment bath with a pickup of 120%, air-dried, and then dried (curing) at a drying temperature shown in Table 4 below for 3 minutes to measure water repellency and oil repellency. . The results are shown in Table 4. The treated wool is
All had a soft texture.

Comparative Examples 1 to 2 C ₈ F ₁₇ C ₂ H ₄ OCOCH = 10 g of CH ₂ , C ₁₈ H ₃₇ OCOCH = 10 of CH ₂
g, 0.01 g of C ₈ H ₁₇ SH, 47 g of acetone, and 0.1 g of azobisisobutyronitrile were charged into a glass ampoule having an internal volume of 100 ml. The mixture was shaken at 70 ° C for 16 hours to obtain a fluoroacrylate copolymer. Wool was treated in the same manner as in Examples 1 to 4 using this copolymer. The results of measurement of water repellency and oil repellency are shown in Table 4 below. The treated wool had a soft feel, which was peculiar to wool, and had a stiff feel.

Examples 5 to 11 In the same manner as in Examples 1 to 4, using each R _f urethane compound shown in Table 5 below, nylon taffeta (65 g / m ² ) was treated at various treatment bath concentrations, and at 100 ° C. It was dried for 3 minutes. The amount of the R _f urethane compound attached to the cloth is as shown in Table 5 below, and the measurement results of water repellency and oil repellency are summarized in Table 5. The texture of the treated fabric retained its flexibility.

[Effects of the Invention] The water and oil repellent of the present invention can exert an excellent effect that it can impart high water and oil repellency to a textile product even under low curing conditions. In addition, the textile product processed with the water and oil repellent of the present invention retains a soft texture.
That is, the present invention has an excellent effect that a soft texture can be maintained and a high water / oil repellency can be imparted to a textile product.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D06M 15/59 D06M 15/59

Claims (14)

(57) [Claims] 1. A compound having a molecular weight of 800 to 20,000, which is composed of at least two polyfluoroalkyl group-containing terminal structures and an intermediate structure connecting the terminal structures, wherein the terminal structure is A reaction product produced by reacting an active hydrogen compound containing a fluoroalkyl group-containing active hydrogen compound with a polyfunctional isocyanate compound in a proportion in which one isocyanate group remains is obtained by removing one isocyanate group from the reaction product. A valent residue, wherein the intermediate construct is at least a divalent organosiloxane molecular chain-containing residue obtained by removing active hydrogen from an organosiloxane molecular chain-containing oligomer having two or more active hydrogen groups, A highly flexible water- and oil-repellent agent comprising a compound having a structure in which the terminal constituent and the intermediate constituent are bonded by a -CONH-bonding group. 2. The water and oil repellent according to claim 1, wherein the polyfluoroalkyl group contained in the terminal constitutional body is a perfluoroalkyl group having 4 to 16 carbon atoms. 3. When the end constituent reacts with a polyfluoroalkyl group-containing active hydrogen compound, an active hydrogen compound containing another active hydrogen compound, and a polyfunctional isocyanate compound at a rate of leaving one isocyanate group. The water and oil repellent according to claim 1 or 2, which is a monovalent residue in which one isocyanate group is removed from the reaction product formed. 4. The water and oil repellent according to any one of claims 1 to 3, wherein the polyfunctional isocyanate compound constituting the terminal constitution body is a trifunctional isocyanate compound. 5. The water and oil repellent according to claim 4, wherein the polyfunctional isocyanate compound constituting the terminal constitution body is an aliphatic trifunctional isocyanate compound. 6. A polyfluoroalkyl group-containing active hydrogen compound which constitutes the terminal structure is a compound represented by the general formula R _f -XAH. Water and oil repellent. However, in the above general formula, R _f is C _n F _{2n + 1} (where n is
Is an integer of 4 to 16), X is -R-, -CON (R ¹ ) -Q- or -SO ₂ N (R ¹ ) -Q- (where R is 2 A valent alkylene group, R ¹ is a hydrogen atom or a lower alkyl group, Q is a divalent alkylene group), and A is —O—, —S—, Or -N (R ² )-(wherein R ² represents a hydrogen atom or a monovalent organic group). 7. The water and oil repellent according to claim 3, wherein the other active hydrogen compound constituting the terminal structure is a compound represented by the general formula ZA ¹ -H. However, in the above general formula, Z is a monovalent organic group, A ¹ is —O—, —S—, Or —N (R ² ) — (wherein R ² represents a hydrogen atom or a monovalent organic group, and Z and R ² may form a ring in some cases). 8. The terminal structure has the general formula (However, R _f is a perfluoroalkyl group represented by C _n F _{2n + 1} , X is ^{one of} -R-, -CON (R ¹ ) -Q- or -SO ₂ N (R ¹ ) -Q- And A and A ¹ are —O—, —S—, Or -N (R ² )-, Z is a monovalent organic group, and a is 1
To an integer of 5, b is 0 or an integer of 1 to 4, a + b is 1 to 5
, W is a t-valent organic residue obtained by removing t -NCO groups from a t-functional isocyanate compound having t -NCO groups, n is an integer of 4 to 16, and R is a divalent Is an alkylene group, R ¹ is a hydrogen atom or a lower alkyl group, Q is a divalent alkylene group, R ² is a hydrogen atom or a monovalent organic group, and in some cases, Z and R ² form a ring. May be t is a
The water- and oil-repellent agent according to any one of claims 1 to 7, which is a group represented by an integer of + b + 1). 9. An intermediate structure is formed when an organosiloxane molecule chain-containing oligomer having two or more active hydrogen groups and a polyfunctional isocyanate compound react with each other in such a ratio that at least two active hydrogen groups remain. The water and oil repellent according to any one of claims 1 to 8, which is at least a divalent organosiloxane molecular chain-containing residue obtained by removing active hydrogen from a reaction product. 10. The water and oil repellent according to claim 9, wherein the polyfunctional isocyanate compound constituting the intermediate constitutional body is a bifunctional isocyanate compound. 11. The water and oil repellent according to claim 10, wherein the polyfunctional isocyanate compound constituting the intermediate constitutional body is an aromatic bifunctional isocyanate compound. 12. The water and oil repellent according to any one of claims 9 to 10, wherein the organosiloxane molecular chain-containing oligomer constituting the intermediate structural body is a compound having two active hydrogen groups. 13. The intermediate construct has the general formula A ² -BA ² -CONH-YN.
HCO _m A ² -BA ^2- (where A ² is -O-, -S-, Or -N (R ² )-, and B is a divalent organic residue obtained by removing ^two -A ² -H groups from a divalent active hydrogen compound containing an organosiloxane molecular chain, According to the above, B may have another organic group bonded via A ² , Y is a divalent organic residue obtained by removing two -NCO groups from a bifunctional isocyanate compound, and optionally Y Is a divalent group represented by the formula (m may be 0 or an integer of 1 to 50), which may have another organic group bonded through an -NHCO- group. 13. The water and oil repellent according to any one of item 12. 14. A compound having a molecular weight of 800 to 20,000 is represented by the general formula Claims 1 to 13 which are compounds represented by
The water and oil repellent according to any one of items. However, R _f is a perfluoroalkyl group represented by C _n F _{2n + 1} , X is ^{one of} -R-, -CON (R ¹ ) -Q- or -SO ₂ N (R ¹ ) -Q- A, A ¹ and A ² are each —O—, —S—, Or -N (R ² )-, Z is a monovalent organic group, and a is 1
To an integer of 5, b is 0 or an integer of 1 to 4, a + b is 1 to 5
, W is a t-valent organic residue obtained by removing t -NCO groups from a t-functional isocyanate compound having t -NCO groups, t is an integer of a + b + 1, and B is an organosiloxane molecular chain. From difunctional polyfunctional active hydrogen compounds containing 2
Is a divalent organic residue obtained by removing -A ² -H, and optionally B may have another organic group bonded through A ² , Y is a bifunctional isocyanate compound. -NCO
A divalent organic residue having a group removed, and Y is-
It may have another organic group bonded through an NHCO- group, m is 0 or an integer of 1 to 50, R is a divalent alkylene group, R ¹ is a hydrogen atom or a lower alkyl group, Q Is a divalent alkylene group, R ² is a hydrogen atom or a monovalent organic group,
In some cases, Z and R ² may form a ring.