JP2001098257A - Water- and oil-repellent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water- and oil-repellent composition which is excellent in initial water- and oil-repellent properties, gives a treating liquid having high capability for penetrating into fibers, and persistently retains excellent properties even when repeatedly used for treating objects. SOLUTION: This composition contains, as essential ingredients, (A) a polymer having polymerization units derived from a polymerizable monomer having a polyfluoroalkyl group, (B) a surfactant of which the Draves wetting time (at a concentration of 0.3 wt.% in water under specified conditions) is longer than 0 sec but not longer than 1.5 sec, and (C) an aqueous medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a water / oil repellent composition. INDUSTRIAL APPLICABILITY The present invention is excellent in initial water and oil repellency, has high permeability of a processing solution to fibers, and continues to provide excellent performance even when treating many sheets with the same processing solution. A water and oil repellent composition is provided.

[0002]

2. Description of the Related Art Conventionally, a polymer containing a polymerizable unit of a polymerizable monomer having a polyfluoroalkyl group (hereinafter referred to as an ^Rf group) or a compound having an ^Rf group is dispersed in an aqueous medium. For imparting water and oil repellency to the surface of fibers or the like by applying water to the surface (Japanese Patent Publication No. 47-404)
67). The water- and oil-repellent composition comprising the aqueous dispersion is generally prepared by adjusting the concentration to an appropriate concentration to form a processing bath, and immersing fibers or the like in the processing bath.

[0003]

However, when the conventional composition is treated, there is a problem that a long immersion time is required, the treatment speed is reduced, and the working efficiency is reduced. Further, if the treatment is continued with the same treating agent, there is a problem that the concentration of only the specific component is reduced or the water / oil repellency is deteriorated, and the state of the composition is frequently managed, and it is necessary to add a necessary component. was there.

On the other hand, in order to prevent a decrease in water and oil repellency, attempts have been made to improve the permeability of the composition by adding a low-boiling alcohol solvent or a penetrant to the composition. I have. However, the use of a low-boiling alcoholic solvent has problems such as flammability, work environment, natural environment, and the effect is not sustained.

In some cases, a nonionic surfactant having a hydrophilic / lipophilic balance value (HLB value) of about 7 to 15 is added as a penetrating agent. However, the addition of the surfactant causes foaming of the composition. However, there is a problem that this foam causes a reduction in the processing speed. There is also a problem that the effect of the penetrant decreases as the number of treatments increases. In some cases, an antifoaming agent is added to suppress foaming. However, there are problems that the effect of the antifoaming agent is not maintained and that the mechanical stability of the treatment liquid is reduced.

Further, since the effects of the penetrant, the antifoaming agent, and the alcoholic solvent having a low boiling point are not maintained, it is necessary to replenish them regularly. In addition, when a processing agent to which a penetrant or an antifoaming agent is added is used, there is a problem that processing unevenness occurs or the water / oil repellency of the processed product is reduced.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has a penetrating agent, an antifoaming agent,
Alternatively, even if the treatment is carried out without adding a low boiling point alcohol-based solvent or the like, the purpose is to provide a water / oil repellent composition which can be treated without lowering the treatment speed without reducing the water / oil repellency. And

That is, the present invention relates to a composition comprising a polymer (A) containing a polymerized unit of a polymerizable monomer having an R ^f group, a surfactant (B), and an aqueous medium (C) as essential components. In addition, the present invention provides a water / oil repellent composition wherein the surfactant (B) is a surfactant having a Dave's wetting time measured under the following conditions of more than 0 seconds and not more than 1.5 seconds. The present invention also provides fibers, treated fiber fabrics, or treated papers treated with the composition, and treatment methods.

Conditions: A bundle of eight 9-inch long cotton strands is bundled to a total weight of 5 g, and one end of the bundle is 3 g.
Attach the hook and the weight of 40 g to the length 1
Prepare a weight skein connected with a 9 mm thread. A graduated cylinder is filled with a liquid obtained by adding 0.3% by weight of the surfactant (B) to water at 25 ° C., and dropping a weight skein into the graduated cylinder, and the time required for the 19 mm long thread to bend. Measure.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In this specification, acrylate and methacrylate are collectively referred to as (meth) acrylate. Similarly, acrylamide and methacrylamide are also referred to as (meth) acrylamide. The same applies to other descriptions.

The composition of the present invention contains the polymer (A) as an essential component. The polymer (A) is a polymer containing polymerized units of a polymerizable monomer having an R ^f group.

The polymerizable monomer having an R ^f group includes R ^f
The compound is not particularly limited as long as it has a group and a polymerizable unsaturated group, and is a compound having both an R ^f group and a (meth) acryloyl group (hereinafter, this compound is referred to as a (meth) acrylate having an R ^f group). Is preferred.

Here, the R ^f group refers to a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The ^Rf group preferably has 2 to 20 carbon atoms, particularly preferably 6 to 16 carbon atoms. The R ^f group may have a linear structure or a branched structure, and a linear structure is particularly preferable. In the case of a branched structure, the branched portion is preferably present at the terminal of the R ^f group, and is preferably a short chain having about 1 to 4 carbon atoms. The structure of the terminal portion of the R ^f group includes -CF ₂ CF ₃ , -CF (C
_{F 3) 2, -CF 2 H} , -CFH 2, -CF 2 Cl and the like, -CF ₂ CF ₃ are preferred.

The R ^f group may contain a halogen atom other than a fluorine atom. Other halogen atoms include
A chlorine atom is preferred. An etheric oxygen atom or a thioetheric sulfur atom may be inserted between carbon-carbon bonds in the R ^f group.

[0015] The number of fluorine atoms in the R ^f groups, [(R ^f number of fluorine atoms in the group) / (R ^f number of hydrogen atoms contained in the alkyl group corresponding same carbon number and group)] × 100 When expressed in (%), it is preferably at least 60%, particularly preferably at least 80%. Further, the R ^f group is preferably a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (that is, a perfluoroalkyl group), or a group having a perfluoroalkyl group at a terminal portion.

The perfluoroalkyl group has 2 to 2 carbon atoms.
0 is preferable, and especially 6 to 16 is preferable. If the number of carbon atoms in the perfluoroalkyl group is small, the water / oil repellency tends to decrease, and if the number of carbon atoms in the perfluoroalkyl group is large, it may be difficult to handle a (meth) acrylate having an ^Rf group.

Specific examples of the R ^f group include the following groups. _{C 4 F 9 - [F (} CF 2) 4 -, (CF 3) 2 CFC
F ₂ —, (CF ₃ ) ₃ C—, or CF ₃ CF ₂ (CF ₃ ) C
One] structural isomers groups such F-, C ₅ F ₁₁ - [e.g. _{F (CF 2) 5 -]} , C 6 F 13 - [ e.g. F (C
_{F 2) 6 -], C} 7 F 15 - [ e.g. _{F (CF 2) 7 -]} ,
C ₈ F ₁₇ - [e.g. _{F (CF 2) 8 -]} , C 9 F 19 - [ e.g. _{F (CF 2) 9 -]} , C 10 F 21 - [ e.g. F (C
_{F 2) 10 -], C} 12 F 2 5 - [ e.g. F (CF _{2)
12 -], C 14 F 29} - [ e.g. _{F (CF 2) 14 -]} , C
₁₆ F ₃₃ - [e.g. _{F (CF 2) 16 -]} , Cl (CF 2)
_s - (wherein, s is 2-20 _{integer), H (CF 2) t} -
(Where t is an integer of 2 to 20), (CF ₃ ) ₂ CF (C
F _{2) 7} - (wherein, y is an integer of 1 to 17), and the like.

When the R ^f group is a group in which an etheric oxygen atom or a thioetheric sulfur atom is inserted between carbon-carbon bonds, the following groups may be mentioned. _{F (CF 2) 5 OCF (} CF 3) -, F [CF (C
_{F 3) CF 2 O] r} CF (CF 3) CF 2 CF 2 -, F [CF
(CF ₃ ) CF ₂ O] _z CF (CF ₃ ) —, F [CF (CF
_{3) CF 2 O] u CF} 2 CF 2 -, F (CF 2 CF 2 CF 2 O)
_{v CF 2 CF 2 -, F} (CF 2 CF 2 O) w CF 2 CF 2 -, F
_{(CF 2) 5 SCF (CF} 3) -, F [CF (CF 3) CF
_{2 S] r CF (CF 3} ) CF 2 CF 2 -, F [CF (CF 3)
_{CF 2 S] z CF (CF} 3) -, F [CF (CF 3) CF 2
_{S] u CF 2 CF 2 -} , F (CF 2 CF 2 CF 2 S) v CF 2 C
F _2- , F (CF ₂ CF ₂ S) _w CF ₂ CF _2- (r is 1 to 5
And z, u, v, and w each independently represent an integer of 1 to 6. )etc.

Examples of the polymerizable monomer having an R ^f group include R ^f
(Meth) acrylates having groups are preferred. The (meth) acrylate having R ^f group is a compound ^the R ^f group is present in the alcohol residue portion of the (meth) acrylate. As the (meth) acrylate having an R ^f group, a compound represented by the following formula 1 is preferable. Here, in the formula 1, R ^f represents an R ^f group, Q represents a divalent organic group, and R represents a hydrogen atom or a methyl group. R ^f -Q-OCOCR = CH ₂ Formula 1 R ^f in Formula 1 is preferably an R ^f group containing no etheric oxygen atom or thioetheric sulfur atom, particularly preferably a perfluoroalkyl group, and particularly preferably a linear structure. Are preferred. As the linear perfluoroalkyl group,-(CF ₂ ) _n F (however,
n is an integer of 2 to 20, preferably an integer of 6 to 16, and particularly preferably an integer of 6 to 12. ) Is preferred.

In the formula 1, Q is-(CH ₂ ) _{p + q
-, - (CH 2) p} CONR a (CH 2) -, - (CH 2) p
^{_{OCONR a (CH 2) q -}} , - (CH 2) p SO 2 NR
^a (CH ₂ ) _q -,-(CH ₂ ) _p NHCONH (CH ₂ ) _{q
-, - (CH 2) p} CH (OH) (CH 2) q -, - (CH
^{_{2) p CH (OCOR a)}} (CH 2) q - and the like are preferable. Here, Ra represents ^a hydrogen atom or an alkyl group. Also,
p and q each independently represent an integer of 0 or more;
It is an integer of 22.

Further, Q in the formula 1 is-(CH ₂ ) _{p + q
-, - (CH 2) p} CONR a (CH 2) q -, or -
(CH ₂ ) _p SO ₂ NR ^a (CH ₂ ) _q- , q is an integer of 2 or more, and p + q is preferably 2 to 6, and p + q is preferably 2 to 6. − (CH ₂ ) _{p + q}
The compound (formula 1) in the case of-(that is, ethylene group to hexamethylene group) is particularly preferable. Further, it is preferable that a fluorine atom is bonded to the carbon atom of R ^f bonded to Q in the formula 1.

The following compounds may be mentioned as (meth) acrylates having an R ^f group. However, R in the following compounds represents a hydrogen atom or a methyl group. F (CF ₂ ) ₅ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR = CH ₂ , H (CF ₂ ) ₆ CH ₂ OCOCR = CH ₂ , H (CF ₂ ) ₈ CH ₂ OCOCR = CH ₂ , H (CF ₂ ) ₁₀ CH ₂ OCOCR = CH ₂ , H (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₁₀ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₁₂ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₁₄ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₁₆ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (CH ₂ CH ₂ CH ₃ ) CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₄ OCOCR = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCR = CH ₂ , F ( CF ₂ ) ₈ SO ₂ N (CH ₂ CH ₃ ) CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₃ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OCOCH ₃ ) OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCR = C H ₂ , F (CF ₂ ) ₉ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₉ CONHCH ₂ CH ₂ OCOCR = CH ₂ .

The polymerizable unit of the polymerizable monomer having an R ^f group in the polymer (A) may be one type or two or more types. When two or more kinds are used, it is preferable that two or more kinds of polymerizable monomers having different carbon numbers of the R ^f group are used.

As the polymer (A) in the present invention, R
^a homopolymer obtained by polymerizing one kind of (meth) acrylate having an ^f group,
Copolymer obtained by polymerizing or more species, or with one or more (meth) acrylates having R ^f group having said ^the R ^f group (meth) polymerizable monomers other than acrylates (hereinafter polymerizable single A copolymer obtained by polymerizing at least one polymerizable monomer (hereinafter referred to as a polymerizable monomer (a ¹ )) (hereinafter, referred to as a copolymer (A ¹ )) is preferable, Especially copolymer (A ¹ )
Is preferred. The ratio of the polymerizable unit of the polymerizable monomer having an R ^f group in the copolymer (A ¹ ) is 50% from the viewpoint of water / oil repellency.
It is preferably from 99 to 99% by weight, particularly preferably from 55 to 98% by weight.

The polymerizable monomer (a ¹ ) is preferably a polymerizable monomer having one or two polymerizable unsaturated groups, and particularly preferably a polymerizable monomer having one polymerizable unsaturated group. preferable.
Further, the polymerizable unit of the polymerizable monomer (a ¹ ) present in the copolymer (A ¹ ) may be one type or two or more types. The polymerizable monomer (a ¹ ) is an alkyl (meth)
It is preferred that acrylate and / or vinyl halide be essential.

The alkyl (meth) acrylate is preferably an alkyl (meth) acrylate having an alkyl group portion having 1 to 22 carbon atoms. The alkyl group in the alkyl (meth) acrylate may have a linear structure, a branched structure, a ring structure, or a partially ring structure. Two or more kinds of alkyl (meth) acrylates may be used, and in the case of two or more kinds, it is preferable that two or more kinds have different structures of the alkyl group portion.

Further, the alkyl (meth) acrylate is
Alkyl (meth) acrylates having an alkyl group part having a linear or branched structure and having an alkyl group part having 1 to 18 carbon atoms are preferable, and particularly having 8 to 18 carbon atoms.
Alkyl (meth) acrylates having an alkyl group are preferred. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, octadecyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. As the vinyl halide, vinyl chloride or vinyl fluoride is preferable, and vinyl chloride is particularly preferable.

The copolymer (A) contains a polymerizable monomer (a
^It is preferred that two or more types of the polymerized unit ¹ ) are present, and that a polymerized unit of an alkyl (meth) acrylate and / or vinyl halide is essential, and a polymerizable monomer other than the polymerized unit (hereinafter, referred to as the polymerized unit) Polymerizable monomer (a)
¹¹ ). )). The polymerizable monomer (a ¹¹ ) is preferably one or more selected from the following polymerizable monomers.

Examples of the polymerizable monomer (a ¹¹ ): ethylene, vinylidene chloride, vinylidene fluoride, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, glycidyl (meth) acrylate, (meth) acrylamide,
N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N-methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene,
Isoprene, chloroprene, aziridinylethyl (meth) acrylate, benzyl (meth) acrylate, aziridinyl (meth) acrylate, polyoxyethylene mono (meth) acrylate, polyoxyalkylene mono (meth) acrylate monomethyl ether, polyoxyalkylene mono ( (Meth) acrylate mono (2-ethylhexyl) ether, polyoxyalkylene di (meth)
Acrylate, (meth) acrylate having a polydimethylsiloxane group, triallyl cyanurate, allyl glycidyl ether, allyl acetate, 2-hydroxy-3-
Chloropropyl (meth) acrylate, N-vinylcarbazole, maleimide, N-methylmaleimide, 2-
(Dimethylamino) ethyl (meth) acrylate, cycloalkyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol (meth) acrylate and the like.

Examples of the polymerizable monomer (a ¹¹ ) include vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, glycidyl (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide. ,
Diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N-methylol (meth) acrylamide, vinyl alkyl ether, (halogenated alkyl) vinyl ether, vinyl alkyl ketone, aziridinylethyl (meth) acrylate, benzyl (meth) Acrylate, aziridinyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Polyoxyethylene mono (meth) acrylate, polyoxyethylene mono (meth) acrylate monomethyl ether, polyoxyethylene mono (meth) acrylate mono (2-ethylhexyl) ether, polyoxyethylene di (meth) acrylate, allyl acetate, 2- It is preferably at least one selected from hydroxy-3-chloropropyl (meth) acrylate, N-vinylcarbazole, and 2- (dimethylamino) ethyl (meth) acrylate. The amount of the polymer (A) is preferably 1 to 50% by weight based on the aqueous medium (C) described below. The concentration can be appropriately changed depending on the purpose of use of the composition and the preparation form.

The polymer (A) in the present invention is preferably present in a composition existing as polymer particles having an average particle diameter of 10 to 1000 nm. The average particle size of the particles is 1
0 to 300 nm is particularly preferred, and 10 to 200 nm is particularly preferred. If the average particle size is too small, it is necessary to increase the amount of the surfactant (B) in order to improve the stability of the composition, which may lead to a decrease in water / oil repellency and discoloration of the processed product. There is also. On the other hand, when the average particle diameter is too large, the polymer (A) may be settled.

The composition of the present invention contains the surfactant (B) as an essential component. The surfactant (B) is a surfactant having a Dave's wetting time of more than 0 seconds and 1.5 seconds or less measured under specific conditions with the concentration of the surfactant (B) in water described below being 0.3% by weight. , And it is preferable to employ a surfactant for 0.1 second to 1.0 second. The Draves wetting time is a known measured value (Draves, 1939)
Is a value indicating the wetting performance on the fiber. As the surfactant (B) in the present invention, a surfactant having a Draves wetting time measured under the following conditions of more than 0 seconds and not more than 1.5 seconds is employed.

Conditions: Bundle eight cotton strands of 9 inches in length so that the total weight is 5 g, and 3 g at one end of the bundle.
Attach the hook and the weight of 40 g to the length 1
A weight skein connected by a 9 mm thread (preferably a flax fiber thread having a length of 19 mm) is prepared. A graduated cylinder is filled with a liquid obtained by adding 0.3% by weight of the surfactant (B) to water at 25 ° C., and dropping a weight skein into the graduated cylinder, and the time required for the 19 mm long thread to bend. Measure. The weight skein dropped into the graduated cylinder is 19 m long because the buoyancy of the skein and the settling force of the weight work at first.
The thread of m is pulled, but as time passes, the skein sinks and bends. It is known that the shorter the time until the skein begins to sink, the better the wettability.

Most of the conventionally known surfactants for water- and oil-repellent compositions have a Dave's wetting time of 10 seconds or more, whereas the present invention provides a Dave's wetting time of more than 0 second. One that is 1.5 seconds or less is used. As a result, the composition easily penetrates significantly into the object to be treated, and the foaming property of the composition can be reduced. Further, the effect can be maintained without lowering the water / oil repellency.
Further, by using the surfactant (B), it is possible to prevent the concentration of only one of the polymer (A) and the surfactant (B) contained in the composition from being extremely lowered with the processing operation. sell.

The surfactant (B) having a Draves wetting time of more than 0 second and not more than 1.5 seconds is preferably a nonionic surfactant because of the excellent performances aimed at by the present invention. A surfactant selected from nonionic surfactants comprising a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups therein and exhibiting surface activity (hereinafter referred to as nonionic surfactant ( b))
And particularly preferably a surfactant selected from nonionic surfactants comprising a compound having one carbon-carbon triple bond and one or two hydroxyl groups in the molecule.

The nonionic surfactant (b) may have a polyoxyalkylene moiety as a partial structure.
As the polyoxyalkylene portion, a polyoxyethylene portion, a polyoxypropylene portion, a portion in which oxyethylene groups and oxypropylene groups are randomly connected,
Or, a portion where polyoxyethylene and polyoxypropylene are connected in a block shape. As a specific example of the nonionic surfactant (b), a compound represented by the following formula b ¹ , b ² , b ³ , or b ⁴ is preferable.

[0037]

Embedded image

However, E ¹ , E ² and E ³ in the formulas b ¹ to b ⁴ each independently represent an alkylene group, m and n each represent an integer of 0 or more, and (m + n) represents 1 Is an integer greater than or equal to. k represents an integer of 1 or more. When m, n, or k is 2 or more, each of E ¹ , E ² , and E ³ is composed of two or more alkylene groups even if each is composed of only one alkylene group. Is also good. R ^{11 to} R ¹⁶ each independently represent a hydrogen atom or an alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 6 to 12 carbon atoms. Specific examples of the group include a methyl group, an ethyl group,
Examples include a propyl group, a butyl group, and an isobutyl group. Also, the oxyalkylene moiety preferably comprises an oxyethylene moiety, an oxypropylene moiety, or both an oxyethylene moiety and an oxypropylene moiety. The number of oxyalkylene groups in the formulas b ¹ to b ⁴ is preferably 1 to 50. Moreover, as the nonionic surfactant (b), nonionic surfactant represented by the following formula b ²⁵ are preferred. However, x and y in the formula b ²⁵
Represents an integer of 0 or more. The nonionic surfactant (formula b ²⁵ ) may be used alone or in combination of two or more.

[0039]

Embedded image

The nonionic surfactant (formula b ²⁵ ) has an (x + y) value or an average of (x + y) values of 0 to 0.
Those at 10 are preferred. The amount of the surfactant (B) is
It is preferably 0.01 to 10% by weight, particularly preferably 0.01 to 5% by weight, based on the polymer (A).

The water / oil repellent composition of the present invention may contain a surfactant other than the surfactant (B) (hereinafter, referred to as another surfactant). As the other surfactant, a nonionic surfactant other than the surfactant (B), a cationic surfactant, an anionic surfactant, or an amphoteric surfactant can be employed. When another surfactant is used, the amount is preferably 0.5 to 20% by weight based on the polymer (A), and particularly preferably 1 to 15% from the viewpoint of water / oil repellency and dispersion stability.
% By weight, especially 5 to 12% by weight. When another surfactant is used, the surfactant (B) is preferably used in an amount of 1 to 100% by weight based on the total amount of the surfactant (B) and the other surfactant. 2
It is preferably at most 80% by weight, particularly preferably at most 5% to 50% by weight.

Examples of other surfactants include the following. Examples of nonionic surfactants; alkylphenylpolyoxyethylene such as nonylphenylpolyoxyethylene and octylphenylpolyoxyethylene. Polyoxyethylene monoalkyl ethers such as polyoxyethylene monononyl ether and polyoxyethylene monooctyl ether; Alkyl polyoxyalkylene polyoxyethylene such as alkyl polyoxypropylene polyoxyethylene and alkyl polyoxybutylene polyoxyethylene; Fatty acid esters, alkylamine oxyethylene adducts, alkanoamidooxyethylene adducts, alkylamineoxyethyleneoxypropylene adducts, alkylamine oxides.

Examples of cationic surfactants: monoalkyldimethylamine hydrochloride, dialkylmonomethylamine hydrochloride, monoalkyltrimethylammonium chloride,
Dialkyldimethylammonium chloride, monoalkylamine acetate, monoalkylmonomethyldipolyoxyethyleneammonium chloride and the like. Examples of anionic surfactants; fatty acid salts, α-olefin sulfonic acid salts, alkyl benzene sulfonic acids and salts thereof, alkyl sulfate salts, alkyl ether sulfate salts, alkyl phenyl ether sulfate salts, N-acylmethyl taurine salts, Alkyl sulfosuccinates and the like. Examples of amphoteric surfactants: lauryl betaine, octadecyl betaine, lauryl dimethyl amino acetate betaine, fatty acid amidopropyl dimethyl amino acetate betaine and the like.

The aqueous medium (C) in the present invention is a medium consisting of water alone or water and a water-soluble solvent. When the aqueous medium (C) is a medium comprising water and a water-soluble solvent,
The amount of the water-soluble solvent is preferably 1 to 100% by weight, particularly preferably 1 to 50% by weight, based on water.

As the water-soluble solvent, a glycol solvent or a glycol ether solvent is preferable. Ethylene glycol, diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether , Diethylene glycol dibutyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, and propylene glycol dimethyl ether. Further, as the water-soluble solvent, those having a boiling point of 100 ° C. or higher are preferable, and dipropylene glycol monomethyl ether or tripropylene glycol is particularly preferable in terms of water / oil repellency.

When the aqueous medium (C) is composed of water, a glycol solvent or a glycol ether solvent, the dispersibility of the polymer (A) in the water / oil repellent composition is improved, and the water repellency is improved. There is an advantage that the performance such as aqueous property is improved, which is preferable.

In the composition of the present invention, components other than those described above (hereinafter referred to as other components) can be added.
It is not necessary to add an antifoaming agent. Other ingredients include
Other polymers, other water repellents, other oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents, and the like.

The method for synthesizing the polymer (A) in the present invention is preferably a method in which a polymerizable monomer is polymerized by a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method, and particularly preferably by an emulsion polymerization method. preferable. In the emulsion polymerization method, it is preferable to add a polymerization initiator to a polymerizable monomer, a surfactant, and an aqueous medium.

As the polymerization initiator, a water-soluble or oil-soluble polymerization initiator is preferable, and examples thereof include azo-based, peroxide-based, and redox-based polymerization initiators. As the polymerization initiator, a water-soluble polymerization initiator is preferable, and a polymerization initiator composed of an azo compound salt is particularly preferable. The type of the polymerization initiator can be appropriately changed according to the polymerization temperature. The polymerization temperature is preferably from 20 to 150 ° C.

In the polymerization reaction, it is preferable to include a chain transfer agent in the reaction system for the purpose of controlling the molecular weight of the polymer (A). As the chain transfer agent, an aromatic compound or a mercaptan is preferable, and an alkyl mercaptan is particularly preferable. Specific examples of the chain transfer agent include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, octadecyl mercaptan or α-methylstyrene dimer [CH ₂ CPhCH ₂ C (C
H ₃ ) ₂ Ph, where Ph is a phenyl group. Is preferred. Before the polymerization reaction, it is preferable to improve the dispersion state by subjecting the polymerizable monomer, the surfactant, and the aqueous medium to a homomixer, a high-pressure emulsifier, or the like. By improving the dispersion state before the start of polymerization, the yield of the finally obtained polymer can be improved.

The surfactant used in the emulsion polymerization may be the surfactant (B) or another surfactant.
The aqueous medium may be the same as or different from the aqueous medium (C) contained in the composition. When another surfactant or another aqueous medium is used, the surfactant (B) or the aqueous medium (C) may be used after the emulsion polymerization or during the preparation of the composition.
May be added.

The Draves wetting time of the water / oil repellent composition of the present invention is preferably 0.1 to 10 seconds, and 0.1 to 10 seconds.
It is preferably from 1.0 to 1.0 second. The Draves wetting time can be measured by the same method as the method for measuring the time in the surfactant (B). That is, under the measurement conditions of the Draves wetting time of the surfactant (B), the values are measured by the same method except that the liquid filled in the measuring cylinder is a 25 ° C. water / oil repellent composition.

The composition of the present invention can be applied to an object to be treated at any concentration. As a method for treating the composition, a dipping method is preferable, and then drying is preferable. Further, curing may be performed if necessary. Immersion time is 1 second to 1
0 seconds is preferable, and the time can be appropriately changed according to the object to be processed.

The object to be treated with the water- and oil-repellent agent of the present invention includes fibers, fiber fabrics, paper, wood, leather, fur and the like, and fibers, fiber fabrics and paper are preferred. As the fiber or fiber woven fabric, animal and plant natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; Or a mixed fiber thereof, and a woven fabric thereof.

[0055]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited thereto. The average particle diameter in the examples was measured by a laser light scattering method (ELS-800 manufactured by Otsuka Electronics Co., Ltd.). The high-pressure emulsifier used was a high-pressure homogenizer manufactured by Menton-Gaulin.

The abbreviations used in the examples have the following meanings. FA: F (CF ₂ ) _m CH ₂ CH ₂ OCOCH = CH ₂ , m
Are 6, 8, 10, 12, 14, 16 and the average of m is 9. StA: octadecyl acrylate, CHMA: cyclohexyl methacrylate, NMAM: N-methylolacrylamide, VC
L: vinyl chloride, GMA: glycidyl methacrylate,
NMAA: N-methylol methacrylate DOM: Dioctyl malate, HEA: Hydroxyethyl acrylate, DPG: Dipropylene glycol, TPG: Tripropylene glycol, PEOOE: Polyoxyethylene monooleyl ether, StTMAC: Monooctadecyl trimethyl ammonium chloride, PEONPE: Poly Oxyethylene mono (nonylphenyl) ether, H
DEO: polyoxyethylene mono hexadecyl ether, surfactants B ^1: (x + y) is the compound 10 of formula b ²⁵ (manufactured by Nissin Chemical Industry Co., Ltd. trade name Surfynol 46
5, Dorebusu wetting time measured by the following method is less than 1 second), surfactants B ^2: in the formula b ²⁵ (x + y)
(Trade name: Surfynol 104, manufactured by Nissin Chemical Industry Co., Ltd., Draves wetting time measured by the following method is 1 second or less), HDEO: polyoxyethylene mono (hexadecyl) ether, PEONPE: polyoxy Ethylene mono (nonylphenyl) ether, PEOL
E: polyoxyethylene mono (1-methylundecyl)
Ether, StSH: octadecyl mercaptan, DO
SH: n-dodecyl mercaptan.

Example 1 168 g of FA, 15.5 g of DOM, and NMA were placed in a 1 L glass reaction vessel equipped with stirring blades.
6.0 g of A, 0.5 g of DOSH, 1 of PEONPE
2.0 g, 2.4 g of StTMAC, 3.6 of HDEO
g, 418 g of ion-exchanged water and 71.7 g of DPG were added, and the mixture was stirred at 40 ° C for 30 minutes, and then emulsified at 200 kg / cm ² while maintaining the temperature at 40 to 50 ° C using a high-pressure emulsifier. Obtained. This emulsion was placed in a 1-L glass autoclave and purged with nitrogen. In addition, VCL 5
After adding 0.2 g, 2.4 g of an azo-based polymerization initiator (VA-046B, manufactured by Wako Pure Chemical Industries, Ltd.) was added. After the temperature was raised to 50 ° C., polymerization was carried out for 15 hours, and the solid content concentration was 32% by weight.
A milky white emulsion 1 having an average particle size of the polymer particles of 105 nm was obtained.

Example 2 In a 1 L glass reaction vessel equipped with a stirring blade, 154 g of FA, 90 g of StA, 12.8 g of CHMA, 0.77 g of StSH, and 1 of PEOOE
5.4 g, 5.1 g of StTMAC, 90 g of DPG,
After stirring 320 g of ion-exchanged water at 50 ° C. for 30 minutes, the mixture is kept at 40 to 50 ° C. using a high-pressure emulsifier to obtain 20
High pressure emulsification was performed at 0 kg / cm ² to obtain an emulsion. The average particle size of the emulsion in the emulsion was 230 nm. Next, this was transferred to a 1-liter glass autoclave, and the azo-based polymerization initiator (W-50, manufactured by Wako Pure Chemical Industries, Ltd., V-50) was added.
After adding 5 g, the autoclave was purged with nitrogen. Further, while stirring, the temperature was raised to 60 ° C., and polymerization was performed for 6 hours.
The solid content concentration is 38.6% by weight, and the average particle size of the polymer is 1
A milky emulsion 2 having a thickness of 10 nm was obtained.

Example 3 154 g of FA, 92 g of StA, and H were placed in a 1 L glass autoclave equipped with stirring blades.
5 g of EA, 5 g of GMA, 0.77 g of StSH, P
After adding 16.5 g of EONPE, 4.0 g of StTMAC, 330 g of ion-exchanged water, 141 g of TPG, and 0.5 g of an azo polymerization initiator (V-50, manufactured by Wako Pure Chemical Industries, Ltd.), the autoclave was purged with nitrogen. did. 60 with stirring
C., and the polymerization was carried out for 6 hours.
%, A milky white emulsion 3 having a polymer particle diameter of 110 nm.

Example 4 167 g of FA and 46.2 of StA were placed in a 1 L glass autoclave equipped with stirring blades.
g, 5.1 g of NMAA, 0.77 g of StSH, PE
OOE of 10.3 g, of the surfactant B ¹ 5.1 g, PE
5.1 g of OLE, 90 g of TPG, 3 of ion exchanged water
After adding 20 g and stirring at 50 ° C. for 30 minutes, 300 kg / cm 3 was maintained at 40 to 50 ° C. using a high-pressure emulsifier.
^The mixture was emulsified under high pressure in ² to obtain an emulsion. The particle size of the emulsion in the emulsion was 170 nm. 1 L of this emulsion
Was transferred to a glass autoclave, and 0.5 g of an azo-based polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-50) was added, and the autoclave was purged with nitrogen. 38.5 g of VCL was added thereto, and the temperature was raised to 60 ° C. with stirring, followed by polymerization for 15 hours. The solid content concentration was 38.1% by weight, and the average particle diameter of the polymer particles was 70 nm. Emulsion 4 was obtained.

[Example 5] In Example 1, PEONPE, S
Surfactant B ¹ along with tTMAC and HDEO
Was added and the polymerization was carried out in the same manner.
A milky white emulsion 5 having 3.0% by weight and an average particle diameter of the polymer of 110 nm was obtained.

[0062] In Example 6 Example 2, with PEOOE and StTMAC adding 3.6g of surfactant B ^1, carried out in the same manner as in polymerization to obtain a milky white emulsion 6.

[0063] In Example 7 Example 3, the addition of 3.6g of Surfactant B ¹ with PEONPE and StTMAC, carried out in the same manner as in polymerization to obtain a milky white emulsion 7.

[0064] In Example 8 Example 4, the addition of 3.6g of Surfactant B ¹ with PEOOE, carried out in the same manner as in polymerization to obtain a milky white emulsion 8.

[0065] The emulsion obtained in the treating agent Preparation of 1-4] Examples 1-4, in addition the surfactant B ¹ and the ion-exchanged water, respectively, a solid content of 20 wt%, surfactant B ¹ concentration to obtain a treating agent 1-4 is 1.0% by weight.

[Preparation of treating agents 5 to 8] Ion-exchanged water was added to each of the emulsions obtained in Examples 5 to 8 so that the solid content concentration became 20% by weight, thereby obtaining treating agents 5 to 8.

[Preparation of treating agents 9 to 12] To the emulsions obtained in Examples 5 to 8, surfactant B ² and ion-exchanged water were added, respectively, to give a solid content of 20% by weight. ¹ concentration of 1.0 wt%, the surfactant B ² concentration to prepare a treating agent 9-12 is 1.0 wt%.

[Preparation of treating agents 13 to 16 (comparative examples)] To the emulsions obtained in Examples 1 to 4, ion-exchanged water was added, and treating agents 13 to 1 having a solid concentration of 20% by weight were added.
6 was obtained.

[Method of Measuring Dave's Wetting Time of Surfactant] A cotton strand of 72 inches in length and 5 g in weight was folded every 9 inches to form four loops. The four loops were bundled and a stainless steel 3g hook was attached to one end of the loop. Further, the opposite end to which the hook was attached was cut with scissors. Next, 1 inch in diameter, thickness 11 /
A 64-inch lead weight of 40 g was prepared, and the weight and the hook were connected with a 19 mm flax fiber thread. A solution obtained by adding 0.3% by weight of a surfactant (B) to water and adjusting the temperature to 25 ° C.
A 500 mL graduated cylinder made of glass was filled, a weight skein was dropped into the graduated cylinder so that the whole was immersed in the liquid, and the time (unit: seconds) required for the 19 mm long thread to bend was measured.

[Evaluation of Water Repellency] JIS L-1092-
The test was performed according to the spray test of 986.2, and the water repellency grade shown in Table 1 was used. The shower water temperature was 27 ° C.

[0071]

[Table 1]

[Examples 1 to 12] 0.45 g of each of the treating agents 1 to 12 was placed in a 100 mL polyethylene beaker.
The sample was collected, and 29.55 g of ion-exchanged water was added and stirred to obtain a test solution. No bubbling was observed in the test solution. The first piece of a test cloth (nylon taffeta: dyed and fixed with a fixing agent) cut into a size of 20 cm × 20 cm was immersed in a state spread in a test solution (30 cc) filled in a vat to wet the entirety (approx. After 3 to 5 seconds), it was taken out, squeezed with a mangle (29.5% of a wet pickup when immersed once and squeezed once), dried at 110 ° C. for 1 minute, and cured at 170 ° C. for 1 minute. At this time, the remaining liquid squeezed by the mangle was collected. The remaining liquid squeezed with a mangle was used again as a test liquid, and was treated on a second test cloth in the same manner as the first test cloth. An ending test was performed for the same processing up to the eleventh test liquid. The water repellency of the obtained test cloth was evaluated. Table 2 shows the results.

[Comparative Examples 1 to 4] The same treatment as in Example 1 was carried out except that the treating agents of Example 1 were changed to treating agents 13 to 16, and the water repellency was evaluated. Table 2 shows the results.

[0074]

[Table 2]

[0075]

The water / oil repellent composition of the present invention is an excellent composition that maintains water repellency even when a large number of objects are continuously treated without adding any special additives. .
Further, when the composition of the present invention is used, bubbling and the like are not recognized, and it is not necessary to control the state of the composition,
Efficient processing work can be performed without reducing the processing speed, and sufficient performance can be exhibited with a short immersion time. That is, the composition of the present invention is a composition extremely excellent in practical use.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) D21H 21/16 D21H 21/16 // B01F 17/38 B01F 17/38 17/42 17/42 B01J 13/00 B01J 13 / 00 A F term (reference) 4D077 AA05 AB20 AC01 BA07 BA15 DC01X DC02X DC02Y DC08Z DC12X DC12Y DC15Z DC19X DC19Y DD08X DD08Y DD32X DD32Y DE02X DE02Y DE07X DE07Y DE08X DE08Y 4G065 AA01 AB13BA01 BA10X4 AC04 BA14 BA77 CA17 CA22 CA48 4L055 AG34 AG71 AG73 AG88 AG97 AH23 AH24 AH29 BE10 EA15 EA16 EA19 EA24 EA25 EA29 EA30 EA32 FA22 GA47 GA48

Claims (9)

[Claims] 1. A composition comprising a polymer (A) containing a polymerized unit of a polymerizable monomer having a polyfluoroalkyl group, a surfactant (B), and an aqueous medium (C) as essential components. A water- and oil-repellent composition, wherein the surfactant (B) is a surfactant having a Draves wetting time measured under the following conditions of more than 0 seconds and not more than 1.5 seconds. Conditions: Eight cotton threads of 9 inches in length are bundled so as to have a total weight of 5 g, a 3 g hook is attached to one end of the bundle, and the hook and a 40 g weight are combined with a 19 mm length thread. Prepare linked weight skeins. A graduated cylinder is filled with a liquid obtained by adding 0.3% by weight of the surfactant (B) to water at 25 ° C., and dropping a weight skein into the graduated cylinder, and the time required for the 19 mm long thread to bend. Measure. 2. The water / oil repellent composition according to claim 1, wherein the Draves wetting time of the composition measured under the following conditions is 0.1 to 10 seconds. Conditions: Eight cotton threads of 9 inches in length are bundled so as to have a total weight of 5 g, a 3 g hook is attached to one end of the bundle, and the hook and a 40 g weight are combined with a 19 mm length thread. Prepare linked weight skeins. A graduated cylinder is filled with a water- and oil-repellent composition at 25 ° C., a weight is placed in the graduated cylinder, and the time required for the 19 mm long yarn to bend is measured. 3. The surfactant (B) is a nonionic surfactant comprising a compound having at least one carbon-carbon triple bond and at least one hydroxyl group in a molecule and exhibiting surface activity. The water / oil repellent composition according to claim 1. 4. The water / oil repellent composition according to claim 1, wherein the amount of the surfactant (B) is 0.01 to 10% by weight of the polymer (A). 5. The water / oil repellent according to claim 1, wherein the polymer (A) in the water / oil repellent composition is present as polymer particles having an average particle diameter of 10 to 1000 nm. Composition. 6. The water / oil repellent composition according to claim 1, wherein the polymerizable monomer having a polyfluoroalkyl group is a (meth) acrylate having a polyfluoroalkyl group. 7. The water / oil repellent according to claim 1, wherein the polyfluoroalkyl group in the polymerizable monomer having a polyfluoroalkyl group is a perfluoroalkyl group having 4 to 20 carbon atoms. Composition. 8. A method for immersing fibers, fiber fabrics or paper in the water / oil repellent composition according to claim 1. 9. A treated fiber, a treated fiber fabric or a treated paper obtained by the treatment method according to claim 8.