JPH09291481A - Water-and oil-repellent processing agent for fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water- and oil-repellent processing agent simultaneously satisfying stain removability and antistaticity by copolymerizing a perfluoroalkyl group-containing acrylic monomer with an oxyalkylene chain-containing acrylic monomer and a (meth)acrylate ester monomer in the presence of a specific chain transfer agent. SOLUTION: This water- and oil-repellent processing agent is obtained by copolymerizing 5-50wt.% of a perfluoroalkyl group-having acrylic monomer such as a group of formula I (Rf is a 3-21C perfluoroalkyl; R<1> is H or CH3 ) or a group of formula II (R<2> is H or a 1-10C alkyl; R<3> is a 1-10C alkylene) with 10-90wt.% of an oxyalkylene chain-containing acrylic monomer of formula III [R<5> is H, CH3 or (meth)acryloyl; R<6> is a 2-30C alkylene; (n) is an integer of 1-100] and 5-40wt.% of an alkyl (meth)acrylate monomer in the presence of a chain transfer agent: 2,4-diphenyl-4-methyl-1-pentene in an amount of 0.01-20wt.% based on the total amount of the monomers.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water- and oil-repellent finishing agent for fibers which simultaneously imparts water repellency, oil repellency, stain removability, and antistatic property to fibers.

[0002]

2. Description of the Related Art Various processing agents that impart antifouling properties to fibers have been developed and put on the market. These include chemicals such as water-repellent finishing agents, oil-repellent finishing agents, stain removal (SR) finishing agents, antistatic finishing agents, etc., but they all have drawbacks and do not have sufficient performance. . In addition, examples of materials that impart water repellency to fibers include silicone-based agents, and representative ones include methylhydropolysiloxane and the like. However, those processed with conventional silicone-based agents have no effect on oily substances (oily stains) and simply prevent the adhesion of water and water-soluble substances (aqueous stains) to the fibers. There wasn't. Further, naturally, they did not have oil repellency, stain removability, and antistatic property.

[0003] Further, as a material which imparts water repellency and oil repellency at the same time, there is a material using a fluorine-containing chemical agent. For example, fluorine-containing acrylic resin, fluorine-containing urethane compound, fluorine-containing polyester resin, fluorine-containing low Examples thereof include molecular ester compounds and polytetrafluoroethylene resins. Further, recently, a fluorine-based graft copolymer or the like composed of a trunk component and a branch component has been proposed. However, although those processed with these conventional fluorine-based chemicals can reduce the adhesion of stains composed of oily substances, aqueous substances, etc., stains once attached are strongly adsorbed to the fibers and removed even after washing. Hard to do. That is, it is widely known that there is a serious defect that the stains are less likely to be removed by those rather processed without being treated with a fluorine-based chemical, which is contradictory to the expected effect of the antifouling agent. ing. Furthermore, conventional fluorine-based chemicals have to increase the content of fluorine-based compounds, which are extremely expensive raw materials.
It must be said that the oil repellency is relatively very low. Moreover, the thing having antistatic ability was not obtained.

On the other hand, for imparting stain removability,
Examples thereof include polyalkylene glycol, carboxymethyl cellulose, cationic polymers, and highly hydrophilic polyester polymers obtained by dehydration condensation from alkylene glycol, polyalkylene glycol, terephthalic acid and the like.

[0007] However, those processed with these conventional stain-removing agents make it easy to remove stains once adhering by washing or prevent re-adhesion, but do not reduce the adherence of stains at all. It was impossible. Further, the antistatic ability was extremely low.

For imparting antistatic property (antistatic property), for example, alkyl phosphate (salt), alkyl sulfate (salt), alkyl sulfonate (salt), alkyl imidazoline (salt), compound having polyethylene oxide chain, etc. Can be given. However, those processed with these conventional antistatic agents have no effect on water repellency, oil repellency, and stain removability.

By mixing (blending) the above-mentioned chemicals, among water repellency, oil repellency, stain removability and antistatic property,
Studies were also conducted on drugs with a few properties. But,
Even when the performance was limited to a few, the performance was insufficient and, of course, it was far from a drug capable of simultaneously satisfying the above four performances. In addition, it is practically impossible to simultaneously satisfy these requirements with a single compound (copolymer) instead of a mixture, and there is no drug having the above four performances at the same time and having durability. There wasn't. However, the development of such excellent drugs has long been desired by the market.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a water- and oil-repellent finishing agent for fibers, which is capable of simultaneously imparting four properties of water repellency, oil repellency, stain removability, and antistatic property to fibers. The purpose is to provide.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have used 2,4-diphenyl-4-methyl-1-pentene as an essential chain transfer agent. Then, an acrylic monomer (A) having a perfluoroalkyl group, an acrylic monomer (B) having an oxyalkylene chain, an acrylic acid alkyl ester monomer and a methacrylic acid alkyl ester monomer By using a copolymer composed of at least one of the monomers (C), it is possible to simultaneously satisfy the water repellency, oil repellency, stain removability, and antistatic property of the fiber, and solve the above problems. The present invention provides a water- and oil-repellent finishing agent for fibers which has a finding, stain removability, and antistatic property.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Main items relating to the constitution of the present invention will be described in detail below item by item.

(1) Chain Transfer Agent A copolymer, which is a water- and oil-repellent finishing agent for fibers having stain removability and antistatic property according to the present invention, is added to a series of monomer groups [(monomer When polymerizing from (A) to (C)],
2,4-diphenyl-4-methyl-1-pentene is used as an essential chain transfer agent. That is, when the above chain transfer agent is used to obtain a copolymer that imparts four properties of water repellency, oil repellency, stain removability, and antistatic property to fibers, these four properties are well balanced. It becomes possible to produce a copolymer.

When the above chain transfer agent 2,4-diphenyl-4-methyl-1-pentene is used for polymerization,
Although a copolymer having the above four performances in a well-balanced manner can be obtained as compared with a copolymer polymerized using another chain transfer agent,
There are many unclear points about the reason. The structural difference between these copolymers is not clear, nor is the reason for imparting such an effect to the fiber or the mechanism of action.

However, the inventors of the present invention used the above chain transfer agent to make a series of monomer groups [(monomer (A) to
It has been found that the copolymer polymerized from (C)] can impart four properties of water repellency, oil repellency, stain removability, and antistatic property to the fiber at the same time.

There are many unclear points about the structure of the above-mentioned copolymer and the mechanism of action on the fiber, but 2,4-diphenyl-4-
Some findings have been obtained regarding the reaction mechanism of methyl-1-pentene (hereinafter referred to as “DPMP”). It is known that DPMP has a molecular weight adjusting function, but its chain transfer mechanism is different from ordinary chain transfer agents,
Addition-fragmentation Due to chain transfer reaction.

A compound having this reaction mechanism is a compound having an allyl moiety activated by a phenyl group, an alkoxycarbonyl group and a cyano group, and a dimer of an ethylenic monomer having a methyl group at the α-position. Also obtained from
It has been reported that the cleavage site is a C-S, C-Br, or C-O bond.

As an example, FIG. 1 shows the reaction between the DPMP and a styrene monomer (monomer). First, DPMP is added to the growing radical (Addition), the C—C bond of DPMP of the growing radical at the DPMP end is split to generate a cumyl radical (Fragmentation), and this cumyl radical reacts with a styrene monomer to restart (Reinitia).
tion). A polymer (polymer) having a DPMP fragment at its end, that is, a polymer having a C = C double bond,
A polymer having a cumyl group is formed, the C = C double bond is at the tail of the polymer (the remaining portion after splitting after DPMP addition), and the cumyl group is at the head of the polymer (the first portion where polymerization is restarted). Exists in. Furthermore, it was confirmed that one C = C double bond and one cumyl group were bonded to each molecule of the polymer, and they did not exist inside the polymer. Therefore, the structural formula (1) shown in FIG. It has been reported that the polymer has a form in which polystyrene is inserted into DPMP as shown in FIG.

When the copolymer in the present invention is polymerized from a series of monomer groups [(monomers (A) to (C)] described later, the amount of the chain transfer agent DPMP used is 0.01 to 2 with respect to the total amount of (A), (B), and (C)
It is preferably set to 0% by weight, and more preferably 0.05 to 5% by weight. That is, when the amount of DPMP used is less than 0.01% by weight, the molecular weight of the copolymer becomes too large, and when it exceeds 20% by weight, the polymerization rate decreases. Therefore, outside the range of 0.01 to 20% by weight, it is difficult to obtain a copolymer that achieves the desired performance.

In the synthesis of DPMP, 2,4-diphenyl-4-methyl-2-pentene, 1,1,3-trimethyl-3-phenylindane and the like are often produced as by-products. Since these by-products have an effect as a chain transfer agent, DPMP may be a mixture with these by-products.

In the synthesis of the copolymer of the present invention, it is possible to use a chain transfer agent other than DPMP in combination. Examples of chain transfer agents other than DPMP include, for example, methanethiol, ethanethiol, propanethiol, butanethiol, octanethiol, dodecanethiol, benzenethiol, toluenethiol, α-naphthalenethiol, β-naphthalenethiol, mercaptomethanol, mercapto. Ethanol, mercaptopropanol, mercaptobutanol, thioglycolic acid,
Methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, n-octyl thioglycolate, 2-ethylhexyl thioglycolate, dodecyl thioglycolate, octadecyl thioglycolate, benzyl thioglycolate, thiol Methoxyethyl glycolate, methoxybutyl thioglycolate, β-mercaptopropionic acid, methyl β-mercaptopropionate, ethyl β-mercaptopropionate, propyl β-mercaptopropionate, butyl β-mercaptopropionate, β-mercaptopropionic acid n-octyl, 2-ethylhexyl β-mercaptopropionate, dodecyl β-mercaptopropionate, β
Thiols (mercaptans) such as octadecyl mercaptopropionate, benzyl β-mercaptopropionate, methoxyethyl β-mercaptopropionate, methoxybutyl β-mercaptopropionate, and trimethylolpropane tris- (β-mercaptopropionate)
Halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide, bromotrichloroethane, bromobenzene, trimethylamine, triethylamine, tripropylamine,
Tributylamine, N, N-dimethylaniline, N, N
Amines such as diethylaniline, nitro compounds such as m-dinitrobenzene, alcohols such as sec-butyl alcohol, aldehydes, sulfides, sulfoxides, sulfones, and others, hypophosphite, cumene, anthracene, Examples thereof include allyl compounds, diisobutylene, terpinolene, β-terpinene, γ-terpinene, 1,4-cyclohexadiene, 2-methyl-1,4-cyclohexadiene and the like. These may be used alone or in combination of two or more. These chain transfer agents can be used together in an amount that does not impair the effects of the copolymer that is the water / oil repellent finishing agent in the present invention.

(2) Acrylic monomer (A) having a perfluoroalkyl group In the monomer constituting the copolymer (water / oil repellent finishing agent) of the present invention, the monomer (A) The acrylic monomer having a fluoroalkyl group is, for example, at least one kind of monomer selected from the group consisting of monomers represented by the following general formulas (A-1) to (A-5). Is.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

[Chemical 12]

In the above general formulas (A-1) to (A-5), Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, R ¹ is hydrogen or a methyl group, and R ² is R ^{2 as described above.}
Represents hydrogen or an alkyl group having 1 to 10 carbon atoms, R ³ represents an alkylene group having 1 to 10 carbon atoms, and R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms.

Specific examples of the monomer (A) are shown below.
First, as an example of the general formula (A-1), 2- (perfluoropropyl) ethyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluoropentyl) ethyl acrylate, 2- (perfluorohexyl). ) Ethyl acrylate, 2- (perfluoroheptyl) ethyl acrylate, 2- (perfluorooctyl) ethyl acrylate, 2- (perfluorononyl)
Ethyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoroundecyl) ethyl acrylate, 2- (perfluorododecyl) ethyl acrylate, 2- (perfluorotridecyl) ethyl acrylate, 2- (perfluoro) Tetradecyl) ethyl acrylate, 2- (perfluorohexadecyl) ethyl acrylate, 2- (perfluorooctadecyl)
Examples thereof include 2- (perfluoroalkyl) ethyl acrylate such as ethyl acrylate and 2- (perfluoroicosyl) ethyl acrylate. Also, 2- (perfluoropropyl) ethyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluoropentyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluoroheptyl) ethyl. Methacrylate, 2- (perfluorooctyl) ethyl methacrylate, 2- (perfluorononyl) ethyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoroundecyl) ethyl methacrylate, 2- (perfluorododecyl) Ethyl methacrylate, 2- (perfluorotridecyl) ethyl methacrylate, 2- (perfluorotetradecyl) ethyl methacrylate, 2- (perfluorohexadecyl) ethyl methacrylate, 2- Perfluoro octadecyl) ethyl methacrylate, 2-
2 such as (perfluoroicosyl) ethyl methacrylate
An example is-(perfluoroalkyl) ethyl methacrylate.

As examples of the above general formula (A-2), N-perfluorobutylsulfonyl-N-methylaminoethyl acrylate, N-perfluorooctylsulfonyl-
N-methylaminoethyl acrylate, N-perfluorododecylsulfonyl-N-methylaminoethyl acrylate, N-perfluorobutylsulfonyl-N-ethylaminoethyl acrylate, N-perfluorooctylsulfonyl-N-ethylaminoethyl acrylate,
N-perfluorododecylsulfonyl-N-ethylaminoethyl acrylate, N-perfluorobutylsulfonyl-N-butylaminoethyl acrylate, N-perfluorooctylsulfonyl-N-butylaminoethyl acrylate, N-perfluorododecylsulfonyl-
Examples thereof include N-perfluoroalkylsulfonyl-N-alkylaminoalkyl acrylates such as N-butylaminoethyl acrylate. Further, N-perfluorobutylsulfonyl-N-methylaminoethyl methacrylate, N-perfluorooctylsulfonyl-N-methylaminoethyl methacrylate, N-perfluorododecylsulfonyl-N-methylaminoethyl methacrylate, N-perfluorobutylsulfonyl. -N-ethylaminoethyl methacrylate, N-perfluorooctylsulfonyl-N-ethylaminoethyl methacrylate,
N-perfluorododecylsulfonyl-N-ethylaminoethyl methacrylate, N-perfluorobutylsulfonyl-N-butylaminoethyl methacrylate, N-
N- such as perfluorooctylsulfonyl-N-butylaminoethylmethacrylate and N-perfluorododecylsulfonyl-N-butylaminoethylmethacrylate
Examples include perfluoroalkylsulfonyl-N-alkylaminoalkylmethacrylate.

Examples of the general formula (A-3) include 3-
3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 3-perfluorodecyl-2-hydroxypropyl acrylate, 3-perfluorododecyl-2-hydroxypropyl acrylate, etc. Fluoroalkyl-2-hydroxypropyl acrylate may be mentioned. Also, 3-perfluorohexyl-
3-perfluoroalkyl-2 such as 2-hydroxypropyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 3-perfluorodecyl-2-hydroxypropyl methacrylate, 3-perfluorododecyl-2-hydroxypropyl methacrylate -Hydroxypropyl methacrylate.

Examples of the general formula (A-4) include 3-
Perfluorohexyl-2-acetoxypropyl acrylate, 3-perfluorooctyl-2-acetoxypropyl acrylate, 3-perfluorodecyl-2-acetoxypropyl acrylate, 3-perfluorododecyl-2-acetoxypropyl acrylate, 3-perfluoro Examples thereof include 3-perfluoroalkyl-2-alkyloyloxypropyl acrylate such as octyl-2-propanoyloxypropyl acrylate. Also, 3-perfluorohexyl-2-acetoxypropyl methacrylate, 3-perfluorooctyl-2-acetoxypropyl methacrylate, 3-perfluorodecyl-2-acetoxypropyl methacrylate, 3-perfluorododecyl-2-acetoxypropyl methacrylate, 3-perfluoroalkyl-2-alkyloyloxypropyl methacrylate such as 3-perfluorooctyl-2-propanoyloxypropyl methacrylate can be mentioned.

As an example of the above general formula (A-5), N-
Perfluorononanoyl-aminoethyl acrylate,
N-perfluorotridecanoyl-N-perfluoroalkoxyyl-, such as N-methylaminoethyl acrylate
Examples thereof include aminoalkyl acrylate and N-perfluoroalkyloyl-N-alkylaminoalkyl acrylate. In addition, N-perfluorononanoyl-aminoethyl methacrylate, N-perfluorotridecanoyl-N-methylaminoethyl methacrylate, and other N-perfluoroalkyloyl-aminoalkyl methacrylates, N-perfluoroalkyloyl-N-alkyl, and the like. Aminoalkyl methacrylate can be mentioned.

These monomers (A) may be used alone or in the form of 2
Used in combination of more than one species. Among these, the general formula (A
2- (perfluoroalkyl) ethyl acrylate and 2- (perfluoroalkyl) ethyl methacrylate represented by -1) are particularly preferable from the viewpoint of easy availability of raw materials.

The amount of the acrylic monomer (A) having a perfluoroalkyl group constituting the above copolymer is preferably 5 to 50% by weight, more preferably 5% by weight based on the whole copolymer.
~ 25% by weight. That is, the amount of the monomer (A) is 5
If it is less than 50% by weight, it is difficult to obtain a copolymer having sufficient water repellency and oil repellency, and if it exceeds 50% by weight, sufficient stain removability,
This is because it is difficult to obtain antistatic property.

(3) Acrylic Monomer (B) Having Oxyalkylene Chain In the monomer constituting the copolymer (water / oil repellent finishing agent) of the present invention, oxyalkylene of the monomer (B) is used. The acrylic monomer having a chain has, for example, the following general formula (B
It is at least one monomer selected from the group consisting of monomers represented by -1).

[0035]

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In the above general formula (B-1),
Like R¹Is hydrogen or a methyl group, R^FiveIs hydrogen,
Indicates a tyl group, acryloyl group or methacryloyl group
Then R ⁶Is an alkylene group having 2 to 30 carbon atoms, and n is 1 to
Indicates an integer of 100. And R⁶The alkylene groups of
There may be one kind or two or more kinds in one compound.
Each alkylene oxide corresponding to these is attached individually
Addition, block addition, or random addition
It may be in the form.

Examples of the general formula (B-1) include hydroxyethyl acrylate, hydroxypropyl acrylate, polyoxyethylene acrylate, polyoxypropylene acrylate, polyoxybutylene acrylate, polyoxydecylene acrylate, polyoxide decylene acrylate, Polyoxytetradecylene acrylate, polyoxyhexadecylene acrylate, polyoxyoctadecylene acrylate, polyoxyicosylene acrylate, polyoxytriacontylene acrylate, polyoxyethylene polyoxypropylene acrylate, polyoxyethylene polyoxybutylene acrylate, methoxy Ethyl acrylate, methoxy polyoxyethylene acrylate, methoxy polyoxypropylene acrylate , Methoxy polyoxybutylene acrylates, methoxy polyoxyethylene decylene acrylate,
Methoxy polyoxide decylene acrylate, methoxy polyoxy tetradecylene acrylate, methoxy polyoxy hexadecylene acrylate, methoxy polyoxy octadecylene acrylate, methoxy polyoxy icosylene acrylate, methoxy polyoxytriacontylene acrylate, methoxy polyoxyethylene poly Oxypropylene acrylate, ethylene diacrylate, polyoxyethylene diacrylate, polyoxypropylene diacrylate, polyoxybutylene diacrylate, polyoxydecylene diacrylate, polyoxide decylene diacrylate, polyoxy tetradecylene diacrylate, polyoxy hexadecylene diacrylate Acrylate, polyoxy octadecylene diacrylate, polyoxy icosile Diacrylate, polyoxyethylene thoria Conch diacrylate, polyoxyethylene polyoxypropylene diacrylate, and the like.

Further, hydroxyethyl methacrylate,
Hydroxypropyl methacrylate, polyoxyethylene methacrylate, polyoxypropylene methacrylate, polyoxybutylene methacrylate, polyoxydecylene methacrylate, polyoxide decylene methacrylate, polyoxytetradecylene methacrylate, polyoxyhexadecylene methacrylate, polyoxyoctadecylene Methacrylate, polyoxyicosylene methacrylate, polyoxytriacontylene methacrylate, polyoxyethylene polyoxypropylene methacrylate, polyoxyethylene polyoxybutylene methacrylate, methoxyethyl methacrylate, methoxypolyoxyethylene methacrylate, methoxypolyoxypropylene methacrylate, methoxypolyoxybutylene Methacrylate , Methoxypolyoxydecylenemethacrylate, methoxypolyoxidedecylenemethacrylate, methoxypolyoxytetradecylenemethacrylate, methoxypolyoxyhexadecylenemethacrylate, methoxypolyoxyoctadecylenemethacrylate, methoxypolyoxyicosylenemethacrylate, methoxypolyoxytriaconti Lenmethacrylate, methoxypolyoxyethylenepolyoxypropylenemethacrylate, ethylenedimethacrylate, polyoxyethylenedimethacrylate, polyoxypropylenedimethacrylate, polyoxybutylene dimethacrylate, polyoxydecylenedimethacrylate, polyoxidedecylenedimethacrylate, polyoxytetradecyl Range methacrylate, polyoxyhexadecylene Methacrylate, polyoxyethylene octadecylcarbamoyl range methacrylate, polio alkoximinoalkyl stiffness range methacrylate, polyoxyethylene thoria Conch range methacrylate, polyoxyethylene polyoxypropylene dimethacrylate and the like.

Among the monomers represented by the above general formula (B-1), at least one monomer selected from the group consisting of the monomers represented by the following general formula (B-2). It is preferable that R ¹ is hydrogen or a methyl group and n is 1 to 100 as described in the general formula (B-2).
Indicates an integer.

[0040]

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Examples of the above general formula (B-2) include hydroxyethyl acrylate, polyoxyethylene acrylate, hydroxyethyl methacrylate, polyoxyethylene methacrylate and the like.

These monomers (B) may be used alone or in the form of 2
Used in combination of more than one species. Among these, as described above, the monomer represented by the general formula (B-2) is preferable, and polyoxyethylene acrylate and polyoxyethylene methacrylate are particularly preferable from the viewpoint of easy availability of raw materials.

The amount of the acrylic monomer (B) having a polyoxyalkylene chain which constitutes the above copolymer is 10 to 90% by weight, more preferably 20 to 90% by weight based on the whole copolymer.
The weight ratio is set to more preferably 50 to 90% by weight. That is, when the amount of the monomer (B) is less than 10% by weight, it is difficult to obtain sufficient stain removability and antistatic property, and when it exceeds 90% by weight, a copolymer having sufficient water repellency and oil repellency is obtained. This is because it is hard to be beaten.

(4) Monomer (C) Consisting of At least One of Acrylic Acid Alkyl Ester Monomers and Methacrylic Acid Alkyl Ester Monomers (C) Constituting the Copolymer (Water and Oil Repellent Processing Agent) of the Present Invention In the monomer to be used, the monomer (C) consisting of at least one of an acrylic acid alkyl ester-based monomer and a methacrylic acid alkyl ester-based monomer is, for example, the following general formula (C-1). ) Is a monomer represented by.

[0045]

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In the above general formula (C-1), as described above, R ¹ is hydrogen or a methyl group and R ⁷ is 1 carbon atom.
22 represents an alkyl group.

Specific examples of the above monomer (C) are shown below.
Examples of the general formula (C-1) include methyl acrylate, ethyl acrylate, propyl acrylate, n-
Butyl acrylate, isobutyl acrylate, sec
-Butyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, icosyl (= eicosyl) acrylate, henicosyl (= heneicosyl) ) Acrylate, docosyl acrylate and the like. In addition, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, decyl methacrylate, dodecyl methacrylate,
Examples thereof include tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, icosyl (= eicosyl) methacrylate, henicosyl (= heneicosyl) methacrylate, docosyl methacrylate and the like.

The amount of the monomer (C) comprising at least one of the alkyl acrylate-based monomer and the methacrylic acid alkyl-ester based monomer, which constitutes the above copolymer, is 5 to 5% of the total weight of the copolymer. 40% by weight, preferably 5
It is set to 30% by weight. That is, when the amount of the monomer (C) is less than 5% by weight, the adsorption to the fiber is weak, and the washing resistance and durability tend to decrease. Further, since a good copolymer itself cannot be obtained, it is difficult to obtain a copolymer having sufficient stain removability, antistatic property, water repellency and oil repellency. This is because when the amount of the monomer (C) exceeds 40% by weight, sufficient stain removability, antistatic property, water repellency and oil repellency cannot be obtained, and the performance tends to deteriorate.

(5) Copolymer (Water- and Oil-Repellent Finishing Agent for Fibers) The copolymer (water- and oil-repellent finishing agent for fibers) of the present invention comprises the above monomers (A), (B), (C) and 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, the amount of the monomer (A) is 5 to 50% by weight, and the amount of the monomer (B) is 10 to 90% by weight, the amount of the monomer (C) is 5
˜40 wt%, preferably the amount of monomer (A) is 5-2
5% by weight, the amount of the monomer (B) is 50 to 90% by weight, the amount of the monomer (C) is 5 to 30% by weight, and the chain transfer agent 2,4-diphenyl-4-methyl- The amount of 1-pentene used is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, based on the total amount of monomers, and the average molecular weight is 10%.
00 to 300,000, preferably an average molecular weight of 100
0 to 100,000. That is, the monomer (A),
This is because if the respective amounts of (B) and (C), the amount of the chain transfer agent used, and the average molecular weight are out of the above ranges, a copolymer that achieves the desired performance of the present invention cannot be obtained.

The monomers constituting the above copolymer may be polymerized in any form of block, random, alternating and graft.

The monomers constituting the above copolymer are
Monomers other than the above monomers (A), (B), and (C) may be used, and examples thereof include acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2 -Methacrylamido-2-methylpropanesulfonic acid, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, acryloylaminopropyltrimethylammonium chloride, methacryloylaminopropyltrimethylammonium chloride, acrylamide, methacrylamide, N-methylolacrylamide, N -Methylol methacrylamide, acrylonitrile, vinyl acetate, styrene, α-methylstyrene and the like. These monomers can be appropriately used within a range that does not impair the intended performance of the above copolymer.

(6) Polymerization Method The method for producing the copolymer (water- and oil-repellent finishing agent for fibers) of the present invention is not particularly limited, and any one of solution polymerization method, emulsion polymerization method and suspension polymerization method can be used. It is also possible to adopt the method. The solution polymerization method and the emulsion polymerization method are preferable, and the emulsion polymerization method is particularly preferable.

When the desired copolymer is polymerized by the above solution polymerization method or emulsion polymerization method, the polymerization solvent (medium) is water, and an organic solvent such as benzene, toluene, xylene, hexane, cyclohexane,
Heptane, octane, chloromethane, chloroethane, chlorofluoromethane, chlorofluoroethane, fluoromethane, fluoroethane, methanol, ethanol, isopropyl alcohol, butyl alcohol, ethylene glycol, glycerin, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane. ,
Examples thereof include dimethylformamide and dimethyl sulfoxide, and these solvents may be used in combination as appropriate.

Examples of the polymerization initiator include benzoyl peroxide, tert-butyl peroxide, lauroyl peroxide, cumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide,
Azobisisobutyronitrile, 2,2'-azobis-
(2,4-dimethylvaleronitrile), hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, 2,2'-azobis- (2-amidinopropane)-
Hydrochloride, redox type initiator (hydrogen peroxide-ferrous chloride, ammonium persulfate-sodium acid sulfite, etc.), o-allyl oo-t-butyl peroxycarbonate, oo-t-butyl o-2- (methacryloyloxy) ) Ethyl peroxycarbonate, t-butyl (E)
Radicals such as -3-isopropoxycarbonylperoxy acrylate, 1,1-di-t-butylperoxy-2-methylcyclohexane and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane Donors are examples. Further, radicals may be generated by photopolymerization using ultraviolet rays, electron beams, radiation, or the like. In this case, a photosensitizer or the like may be used in combination.

When the above emulsion polymerization method is adopted, a usual emulsifier may be used, and examples of the emulsifier include fatty acid salt, rosin acid salt, sulfated fatty acid salt, alkyl sulfonate, alkylbenzene sulfonate and alkyl. Naphthalene sulfonate, alkyl sulfo fatty acid ester salt,
Dialkyl sulfosuccinic acid ester salt, polyoxyalkylene alkyl ether sulfosuccinic acid monoester salt, polyoxyalkylene alkenyl ether sulfosuccinic acid monoester salt, polyoxyalkylene aryl ether sulfosuccinic acid monoester salt, alkyl diphenyl ether disulfonic acid salt, sulfated oil, sulfuric acid Fatty acid ester salt, alkyl sulfate ester salt, alkenyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl ether carboxylate salt, polyoxyalkylene alkenyl ether sulfate ester salt, polyoxyalkylene aryl ether sulfate ester salt , Alkyl phosphate ester salts, polyoxyalkylene alkyl ether phosphate ester salts, polyoxyalkyl Emissions alkenyl ether phosphate ester salts, anionic surfactants such as polyoxyalkylene aryl ether phosphoric acid ester salts, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene aryl ethers, polyoxyalkylene alkyl aryl ether,
Polyoxyalkylene alkyl ester, polyoxyalkylene alkenyl ester, polyoxyalkylene alkylaryl ester, polyoxyalkylene alkylamine, N, N-dihydroxyethylalkylamide, polyoxyalkylenealkylamide, glycerin fatty acid ester, polyglycerin fatty acid ester, penta Nonionic surfactants such as erythritol fatty acid ester, polyoxyalkylene pentaerythritol alkyl ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyalkylene sucrose fatty acid ester, polyoxyalkylene, alkylamine Salt, alkyl ammonium salt, alkyl aralkyl ammonium salt, alkyl pyridinium , Cationic surfactants such as alkyl picolinium salts, amphoteric surfactants such as amino acid type, betaine type, sulfonic acid type, sulfuric acid ester type, phosphoric acid ester type, casein, formalin condensate of β-naphthalene sulfonic acid, Polycarboxylate, polyvinyl alcohol, cellulose derivative, polyacrylamide, polymethacrylamide, styrene-maleic acid copolymer and its derivatives, polyamide-epichlorohydrin resin, amine-epichlorohydrin resin, (poly) alkylenepolyamine-epichlorohydrin resin, poly ( Examples thereof include polymer type surfactants such as diallylamine) -epichlorohydrin resin and fluorine type surfactants, and the above surfactants can be used in combination.

In addition, a pH buffer or the like may be used at the time of polymerization. Examples of the pH buffer include sodium hydrogen carbonate, sodium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate. , Sodium acetate, potassium acetate and the like.

In the polymerization of the above copolymer, the total amount of the mixture of the above-mentioned chain transfer agent, each of the monomers (A) to (C), the polymerization initiator and, if necessary, the surfactant is 5%.
To 90% by weight, preferably 10 to 80% by weight, and the balance is the medium (water, organic solvent). The polymerization temperature is 3
It is 0 to 200 ° C, preferably 50 to 100 ° C. Other conditions, methods and the like may be carried out according to general polymerization conditions and methods.For example, when mentioning a method of adding a monomer or the like to a polymerization system, a batch addition method, a continuous addition method, a divided addition method. Law, etc.

(7) Fiber Treatment with the Copolymer The type of fiber to be treated by the copolymer of the present invention is not particularly limited, but the type of fiber is, for example, polyester, acrylic (poly). Acrylonitrile-based), nylon (polyamide-based), polypropylene, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol and other synthetic fibers, cotton, wool, silk, hemp and other natural fibers, acetate, rayon and other semi-synthetic fibers,
Other examples include glass fibers, carbon fibers, metal fibers, cellulose fibers, rock wool, asbestos, and blends thereof, and the like, and are particularly effective for polyester, acrylic, nylon, polypropylene, cotton and the like.

The form of those fibers is not particularly limited, but examples thereof include cloth, yarn, felt, sliver, cotton, tow, and the like, and filaments and staples are not limited. The effect on the fabric is particularly remarkable. In the case of a cloth, examples of its form include a woven fabric, a knitted fabric, a non-woven fabric, and an intermediate product thereof.

The method for attaching the above-mentioned copolymer to the fiber structure is not particularly limited and may be a known method, for example, padding method, spray coating method, foam coating method, roller coating method, dipping method, coating method. A printing method or the like may be used. When treating the fiber by the padding method,
The concentration of the copolymer liquid (organic solvent and / or water solution, organic solvent and / or water dispersion) is 0.
It is possible to use it after diluting it to 05 to 5% by weight, preferably 0.1 to 3% by weight. After processing, after drying,
10 to 15 minutes at 120 to 220 ° C., preferably 160
It is preferable to perform heat treatment at 190 ° C. for 30 seconds to 5 minutes. This improves the firm adhesion of the copolymer to the fiber, the orientation of the perfluoroalkyl group on the fiber, and the like.
The object performance of the present invention is made more effective.

The copolymer of the present invention exerts a sufficient effect by using it alone and adhering it to the fiber. However, within the range of not impairing the effect of the above copolymer, various copolymers can be obtained. The cross-linking agent, the binder and the like may be used together for chemical bonding, and low temperature plasma treatment may be performed. Furthermore, the fibers may be impregnated with or coated with urethane resin, acrylic resin, silicone resin, melamine resin, or the like.

Further, in the treatment liquid containing the above copolymer,
If necessary, softening agents, hard finishes, water absorbing agents, antibacterial agents, flame retardants, texture modifiers, dye fixing agents, wrinkle-proofing agents, shape-retaining agents, microencapsulating agents, deodorants, insect repellents, plasticizers, It is also possible to mix one or more kinds of additives such as a film forming aid, an antioxidant, a dye, a pigment, an antistatic agent, an SR agent (dirt removal processing agent), a waterproofing agent, a water repellent, and an oil repellent. .

By using the water / oil repellent finish for fibers of the present invention, extremely excellent water repellency, oil repellency, stain removability,
It is possible to simultaneously impart the four properties of antistatic property to the fiber.

Conventionally, some processing agents for fibers which impart water repellency, oil repellency, stain removability, and antistatic property have been proposed. Compared with these, the water and oil repellent processing agent for fibers of the present invention. Is excellent in the above points. Further, the water- and oil-repellent finishing agent for fibers of the present invention is excellent in durability and durability of the above-mentioned effects, does not change the texture of the fibers, etc. It enables simultaneous development of four performances, namely, oil repellency, stain removability, and antistatic property.

Specific embodiments and effects of the present invention will be described below with reference to Examples and Comparative Examples, but the technical scope of the present invention is not limited by these exemplifications. In the following examples, parts and%
Is based on weight.

1. Example of copolymer production

[0067]

Example 1 20 parts of perfluorooctylethyl acrylate, 60 parts of polyoxyethylene methacrylate (ethylene oxide repeating unit: 8), 20 parts of n-butyl acrylate, 5 parts of DPMP, 2,2'-azobis (2
-Amidinopropane) -hydrochloride 8 parts, dodecyltrimethylammonium chloride 10 parts and water 40
0 part was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, mixed, stirred at 80 ° C. for 6 hours in a nitrogen atmosphere, cooled to 25 ° C., and then the average molecular weight was decreased. 20,000 copolymers were obtained.

[0068]

Example 2 4 parts of perfluorodecylethyl methacrylate, 1 of perfluorododecylethyl methacrylate
Parts, hydroxyethyl acrylate 65 parts, methyl methacrylate 30 parts, DPMP 0.05 part, azobisisobutyronitrile 0.5 part, polyoxyethylene nonylphenyl ether (ethylene oxide repeating unit: 2
0) 10 parts and 400 parts of water were put into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introducing tube and mixed, and after stirring under a nitrogen atmosphere at 50 ° C. for 18 hours,
After cooling to 25 ° C., a copolymer having an average molecular weight of 100,000 was obtained.

[0069]

Example 3 Perfluorobutylethyl acrylate 1
0 part, polyoxyethylene methacrylate (ethylene oxide repeating unit: 100) 85 parts, stearyl acrylate 5 parts, DPMP 0.5 part, ammonium persulfate 0.2 part, di-2-ethylhexyl sulfosuccinate sodium 1 part, sodium hydrogen carbonate 0 .3 parts and 400 parts of water were put into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introducing tube and mixed, and after stirring at 60 ° C. for 12 hours in a nitrogen atmosphere, 25 ° C. Cool down to
A copolymer having an average molecular weight of 50,000 was obtained.

[0070]

Example 4 N-perfluorooctylsulfonyl-N
-Butylaminoethyl acrylate 50 parts, polyoxypropylene dimethacrylate (propylene oxide repeating unit: 30) 25 parts, ethyl acrylate 25 parts,
A reaction in which 1 part of DPMP, 0.5 part of benzoyl peroxide, 1 part of sodium perfluorodecylethyl sulfonate, 200 parts of isopropyl alcohol, and 400 parts of water were provided with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube. Put in a container and mix, stir at 70 ° C for 10 hours in a nitrogen atmosphere, then cool to 25 ° C to give an average molecular weight of
00 was obtained.

[0071]

Example 5 30 parts of 3-perfluorohexyl-2-hydroxypropyl methacrylate, 30 parts of methoxypolyoxyethylene methacrylate (ethylene oxide repeating unit: 50), 40 parts of n-butyl methacrylate,
20 parts of DPMP, 10 parts of lauroyl peroxide, and 100 parts of methyl isobutyl ketone are placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introducing tube, and mixed, and at 100 ° C. under a nitrogen atmosphere. After stirring for 2 hours, it was cooled to 25 ° C. to obtain a copolymer having an average molecular weight of 3000.

[0072]

Example 6 45 parts of 3-perfluorononyl-2-acetoxypropyl acrylate, polyoxyethylene polyoxybutylene (block) acrylate [ethylene oxide repeating unit: 7, butylene oxide repeating unit: 3 (ester oxide on the ester bond side, terminal OH Base side butylene oxide)] 25 parts, hexadecyl acrylate 30 parts, N-methylol acrylamide 2 parts, DP
0.02 parts of MP, 0.1 parts of potassium persulfate, 0.1 part of sodium hydrogen sulfite, 4 parts of sodium lauryl sulfate, 0.3 parts of sodium phosphate, and 200 parts of water, a stirring device, a reflux condenser, and a thermometer. , And a reaction vessel equipped with a nitrogen introduction tube, and mixed.
After stirring at 0 ° C for 40 hours, the mixture was cooled to 25 ° C to obtain a copolymer having an average molecular weight of 200,000.

[0073]

Example 7 25 parts of N-perfluorodecyl-aminoethyl methacrylate, polyoxyoctadecylene methacrylate (octadecylene oxide repeating unit: 2)
10 parts, hydroxyethyl methacrylate 55 parts, lauryl acrylate 10 parts, DPMP 10 parts, o-allyl oo-t-butyl peroxycarbonate 8 parts, lauroyl peroxide 2 parts, polyoxyethylene nonylphenyl ether sulfate ammonium (ethylene oxide repeating unit: 8) 6 parts and 300 parts of water were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introducing tube and mixed, and the mixture was heated at 60 ° C. for 2 hours at 70 ° C. under a nitrogen atmosphere. After stirring for 3 hours at 90 ° C for 10 hours, 2
After cooling to 5 ° C., a copolymer having an average molecular weight of 10,000 was obtained.

[0074]

Comparative Example 1 20 parts of perfluorooctylethyl acrylate, 60 parts of polyoxyethylene methacrylate (ethylene oxide repeating unit: 8), 20 parts of n-butyl acrylate, 2,2'-azobis (2-amidinopropane) -hydrochloride 1 Parts, 10 parts of dodecyltrimethylammonium chloride, and 400 parts of water are put into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introducing tube, and mixed, and the mixture is mixed under a nitrogen atmosphere at 80 ° C. for 6 hours. After stirring, it was cooled to 25 ° C and the average molecular weight was 100,000
0 was obtained.

[0075]

Comparative Example 2 N-perfluorooctylsulfonyl-N
-Butylaminoethyl acrylate 50 parts, polyoxypropylene dimethacrylate (propylene oxide repeating unit: 30) 25 parts, ethyl acrylate 25 parts,
0.2 parts of dodecanethiol (dodecyl mercaptan),
0.2 parts of benzoyl peroxide, 1 part of sodium perfluorooctylethyl sulfonate, 200 parts of isopropyl alcohol, and 400 parts of water were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introducing tube. Were mixed and stirred in a nitrogen atmosphere at 70 ° C. for 10 hours and then cooled to 25 ° C. to obtain a copolymer having an average molecular weight of 40,000.

[0076]

Comparative Example 3 30 parts of 3-perfluorohexyl-2-hydroxypropyl methacrylate, 30 parts of methoxypolyoxyethylene methacrylate (ethylene oxide repeating unit: 50), 40 parts of n-butyl methacrylate,
Carbon tetrabromide (10 parts), lauroyl peroxide (1 part), and methyl isobutyl ketone (100 parts) were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introducing tube, and mixed, and the mixture was placed under a nitrogen atmosphere. After stirring at 100 ° C. for 2 hours and then cooling to 25 ° C., a copolymer having an average molecular weight of 3000 was obtained.

Each of the monomers used in Examples 1 to 7 and Comparative Examples 1 to 3 and their amounts, and the chain transfer agent (DPM)
P), and the average molecular weight of the obtained copolymer is summarized in Table 1 below.

[0078]

[Table 1]

2. Fiber treatment agent with copolymer

[Fiber cloth used] A processed yarn woven fabric (Georgette) made of 100% polyester is treated with 2 g / liter of a surfactant (Daisurf WS-50: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 2 g / liter of soda ash. It was immersed in the liquid (bath ratio 1:50), scoured at 98 ° C for 30 minutes, thoroughly washed with water, and dried at 130 ° C for 1 hour. The fiber cloth subjected to this pretreatment was used for the treatments of the following treatment examples 1 to 7 and comparative treatment examples 1 to 3.

[Processing Example 1] The fiber cloth was processed by a padding method (1 dip, 1 nip). After dipping the cloth in the treatment liquid prepared by diluting the copolymer liquid obtained in Example 1 to 2.5% with water, squeezing it by 80%, predrying at 120 ° C. for 2 minutes, and then curing at 170 ° C. for 1 minute. Then, a treated fabric having an adhesion amount of the copolymer (product of Example 1) of 2% owf (this is a treated fabric after 0 washing) was obtained.

Next, the following treatment was carried out in order to obtain a treated cloth for evaluating the washing resistance (durability).

The treated cloth (0 times of washing) was placed in a household electric washing machine together with a commercially available household powder detergent (Attack: Kao Co., Ltd.) 2 g / liter aqueous solution, and the bath ratio was 1:10 at 40 ° C. After washing with water for 10 minutes and dehydration, wash with water at 40 ° C for 5 minutes at 40 ° C, then dehydrate and
Dry at 30 ° C. for 30 minutes. This washing cycle is one time,
This was repeated 30 times to obtain a treated fabric after 30 times of washing.

[Treatment Examples 2 to 7] Treated Examples 2 to 7 are treated except that the copolymer liquid of Example 1 used in Treated Example 1 is replaced with the copolymer liquid obtained in Examples 2 to 7. The fiber cloth was treated in the same manner as in Example 1. The treated fabrics treated with the copolymers of Examples 2 to 7 correspond to the treated fabrics of Treatment Examples 2 to 7, respectively.

[Comparative Processing Examples 1 to 3] Comparative Processing Examples 1 to 3
Is the treatment example 1 except that the copolymer liquid of the example 1 used in the treatment example 1 is replaced with the copolymer liquid obtained in the comparative examples 1 to 3.
The fiber cloth was treated in the same manner as in the above. The treated fabrics treated with the copolymers of Comparative Examples 1 to 3 correspond to the treated fabrics of Comparative Treatment Examples 1 to 3, respectively.

Processing Examples 1 to 7 and Comparative Example Processing Examples 1 to 1
The treated fabric of No. 3 was subjected to the performance evaluation method shown below, and the performance of each fiber fabric was evaluated.

3. Performance evaluation method

[Water repellency test] Water repellency was measured according to JIS: L 1
092-1992 (Spray test method). The evaluation criteria are shown in Table 2 below. The higher the water repellency number, the better the water repellency.

[0089]

[Table 2]

[Oil Repellency Test] Oil repellency is measured by AATCC: T
It was evaluated by M118-1975. The evaluation criteria are shown in Table 3 below. The permeation resistance of the test liquid (oil) in Table 3 to the treated fabric is determined, and the higher the value, the better the oil repellency.

[0091]

[Table 3]

[Stain removal property test] Stain removal property (SR property)
Was evaluated by Japan Chemical Fiber Inspection Association: JCFATN-104. The evaluation criteria are shown in Table 4 below.

The treated fabric piece was placed flat on the polyethylene sheet with the surface facing upward, 0.1 ml of the standard soiling liquid was dropped, and this was further covered with a polyethylene sheet, and a load of 7 g / cm ² was applied on this. It was left for 1 minute. Next,
After taking out the cloth piece and thoroughly wiping off the stain liquid, 20 ° C
For 1 hour.

Next, this cloth piece was put in a household electric washing machine together with a commercially available household powder detergent (Attack: Kao Co., Ltd.) 1 g / liter aqueous solution, and a bath ratio of 1:10 was applied to 4 pieces.
After washing at 0 ° C. for 10 minutes and dehydration, it was washed with water at 40 ° C. for 5 minutes at 40 ° C., dehydrated and then dried at 80 ° C. for 30 minutes. The state of stain remaining on the fabric piece was judged by a gray scale for staining. The higher the judgment level,
It shows that the stain removability is good.

The standard stain liquid is carbon black 1
1 g of a pasty mixture consisting of 7%, 21% beef tallow hardened oil, and 62% liquid paraffin was dispersed in 100 ml of motor oil (SAE: 10W-30).

[0096]

[Table 4]

[Antistatic property test] The antistatic property (antistatic property) is
Evaluation was performed by measuring the friction electrification voltage according to JIS: L 1094-1988 (method B). The friction static voltage was measured by using a rotary static tester, applying friction of 1000 rpm to the treated fabric at 20 ° C. (40% RH) for 1 minute, and measuring the static voltage immediately after that. As the cloth to be rubbed, cotton broad cloth No. 50 was used. The lower the charged voltage, the better the antistatic property.

[Hand feeling change] The hand feeling was evaluated by using a handle odometer for two measurements in each of the machine direction and the machine direction, and the average value thereof was calculated. The relative value is shown as. The lower the value is, the softer it is and the better the texture is.

[Washing resistance] The washing resistance is measured in Treatment Examples 1 to 7,
Also, it was judged by evaluating various performances of the treated fabrics after 30 times of washing shown in Comparative Treatment Examples 1 to 3. That is, washing 30
The treated fabric after the washing is compared with that after the washing for 0 times, and the less the deterioration of the performance after 30 times of washing, the better the washing resistance is.

4. Performance Evaluation The performance evaluation results of the fiber fabrics treated with the copolymers obtained in the above Examples and Comparative Examples are shown in Tables 5 and 6 below. The performance evaluation of the treated fiber cloth shown in Table 5 shows the result of performance evaluation of the cloth after 0 times of washing,
The performance evaluation of the treated fiber cloth shown in Table 6 shows the result of performance evaluation of the cloth after 30 times of washing.

[0101]

[Table 5]

[0102]

[Table 6]

From the results of Table 5 and Table 6 above, in all the treatment examples using the products of each example, four properties of water repellency, oil repellency, stain removability, and antistatic property were simultaneously imparted to the fiber. It has a good texture. Moreover, these performances are
No sharp drop in performance even after 30 washes,
Excellent results in washing resistance (durability) were obtained for all the above performances.

[0104]

By using the water- and oil-repellent finishing agent for fibers of the present invention, four excellent properties of water repellency, oil repellency, stain removability and antistatic property are simultaneously imparted to the fibers. It becomes possible.

Conventionally, some processing agents for fibers which impart water repellency, oil repellency, stain removability, and antistatic property have been proposed, but in comparison with these, the water and oil repellency processing agent of the present invention is as described above. Is excellent in terms of. In addition, the water- and oil-repellent finishing agent of the present invention has excellent effect durability and durability, and does not change the texture of the fiber, etc. It enables simultaneous expression of four performances of stain removability and antistatic property.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a reaction state of DPMP and a styrene monomer.

Claims (7)

[Claims] 1. Use of 2,4-diphenyl-4-methyl-1-pentene as an essential chain transfer agent, which has an acrylic monomer (A) having a perfluoroalkyl group and an oxyalkylene chain. Acrylic monomer (B),
A water- and oil-repellent finishing agent for fibers, containing a copolymer comprising a monomer (C) comprising at least one of an acrylic acid alkyl ester-based monomer and a methacrylic acid alkyl ester-based monomer . 2. A chain transfer agent, 2,4-diphenyl-
The amount of 4-methyl-1-pentene used is the total amount of the monomer (A)
The water- and oil-repellent finishing agent for fibers according to claim 1, which is set to 0.01 to 20% by weight based on the total amount of (C). 3. The copolymer has an amount of the monomer (A) of 5 to 5.
The fiber according to claim 1 or 2, which is a copolymer composed of 0% by weight, the amount of the monomer (B) is 10 to 90% by weight, and the amount of the monomer (C) is 5 to 40% by weight. Water- and oil-repellent finishing agent. 4. The water- and oil-repellent finishing agent for fibers according to claim 1, which is composed of a copolymer having an average molecular weight of 1,000 to 300,000. 5. An acrylic monomer (A) having a perfluoroalkyl group as a component constituting the copolymer,
The monomer according to any one of claims 1 to 4, which is at least one kind of monomer selected from the group consisting of monomers represented by the following general formulas (A-1) to (A-5). A water- and oil-repellent finishing agent for textiles. Embedded image Embedded image Embedded image Embedded image Embedded image 6. An acrylic monomer (A) having a perfluoroalkyl group as a component constituting the copolymer,
It is at least one kind of monomer selected from the group consisting of monomers represented by the following general formula (A-1).
5. The water- and oil-repellent finishing agent for fibers according to any one of 5 above. [Chemical 6] 7. The acrylic monomer (B) having an oxyalkylene chain as a component constituting the copolymer is selected from the group consisting of monomers represented by the following general formula (B-1). The water- and oil-repellent finishing agent for fibers according to any one of claims 1 to 6, which is at least one type of monomer. Embedded image