JPH07216346A - New water/oil repellent - Google Patents

Abstract

PURPOSE:To obtain a repellent excellent in the persistence of water/oil repellency. CONSTITUTION:This repellent essentially consists of a copolymer comprising repeating units derived from a polyfluoroalkyl acrylate and/or repeating units derived from a polyfluoroalkyl methacrylate and repeating units derived from a vinyl oxazoline monomer, and is desirably the one represented by the formula (wherein R<1> to R<4> each is H or CH3).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel water and oil repellent agent.

[0002]

2. Description of the Related Art In recent years, water-repellent and oil-repellent processing of clothes has been extensively performed, and various water- and oil-repellent agents have been proposed. In these compositions, the durability of water and oil repellency against washing and dry cleaning is a problem. Conventionally, for the purpose of improving the durability of water / oil repellency, a polyfluoroalkyl group-containing acrylate, vinyl chloride, and N-methylol acrylamide as a crosslinking component, or a copolymer obtained by copolymerizing glycidyl acrylamide is included. Water and oil repellent (Japanese Patent Publication No. 50-3438), or -NCO at high temperature
Water- and oil-repellent agents containing a polymer containing a functional component that releases a group (JP-A-54-131579, JP-A-54-133486, JP-A-3-8873) have been proposed.

[0003]

However, the conventional water / oil repellents are not satisfactory in terms of durability of water / oil repellency. The present invention has been made to solve the problems of conventional water and oil repellents, and provides a novel water and oil repellent.

[0004]

That is, the present invention provides a copolymer containing a polymer unit of a polyfluoroalkyl group-containing acrylate and / or a polyfluoroalkyl group-containing methacrylate and a polymer unit of an oxazoline residue-containing monomer. A water and oil repellent having a polymer as an essential component.

In the following, acrylate and methacrylate are collectively referred to as (meth) acrylate, which means both. Further, the polyfluoroalkyl group is referred to as R _f group. That is, the polyfluoroalkyl group-containing acrylate and the polyfluoroalkyl group-containing methacrylate are collectively referred to as R _f group-containing (meth) acrylate.

The R _f group-containing (meth) acrylate in the present invention refers to a (meth) acrylate having one or more R _f groups, and a (meth) acrylate having one R _f group is preferred.

The R _f group usually has a structure in which two or more hydrogen atoms of the alkyl group are substituted with fluorine atoms. The R _f group may have either a straight chain structure or a branched structure. Further, a part of the carbon atoms may be replaced with an ethereal oxygen atom.

The carbon number of the R _f group is usually 4 to 20. Among these carbon atoms, the number of carbon atoms to which a fluorine atom is bonded is 2 or more, preferably 4 to 18, particularly preferably 6 to 16.

The R _f group is a group containing two or more fluorine atoms, and usually 6 of the atoms bonded to the carbon atom.
A group in which 0% or more, preferably 80% or more is a fluorine atom is preferable. Further, the carbon atom of the R _f group may be bonded with another atom other than a fluorine atom and a hydrogen atom. As the other atom, a halogen atom is preferable, and a chlorine atom is particularly preferable.

When the R _f group contains an etheric oxygen atom, a group containing an oxyfluoroalkylene moiety is preferred. It may also be a group containing a structure in which two or more oxyfluoroalkylene moieties are connected. Examples of the oxyfluoroalkylene moiety include oxyfluoromethylene and oxyfluoropropylene.

Examples of the structure of the terminal portion of the R _f group include a trifluoromethyl group, a difluoromethyl group, a chlorodifluoromethyl group and the like, and a preferable structure is the trifluoromethyl group.

The most preferred R _f group is a perfluoroalkyl group having a structure in which all hydrogen atoms are replaced by fluorine atoms. The perfluoroalkyl group may be C _n
It is preferably a group represented by F _{2n + 1} −. here,
n is an integer of 1 to 20 and is preferably an integer of 4 to 16.

Specific examples of the R _f group-containing (meth) acrylate in the present invention are shown in Chemical formula 2, but the invention is not limited thereto.

[0014]

[Chemical 2]

However, in Chemical formula 2, R ⁵ represents a hydrogen atom or a methyl group. R _f has the same meaning as the above R _f group. In the present invention, the R _f group-containing (meth) acrylate is usually a mixture of two or more compounds having different carbon numbers of R _f . As the R _f group-containing (meth) acrylate, one kind or two or more kinds of different compounds can be used.

The water- and oil-repellent agent of the present invention contains, as an essential component, a copolymer containing a polymer unit of an R _f group-containing (meth) acrylate and a polymer unit of an oxazoline residue-containing monomer.

The monomer containing an oxazoline residue means a compound containing an oxazoline residue and a polymerizable carbon-carbon unsaturated double bond. An oxazoline residue,
The polymerizable carbon-carbon unsaturated double bond may be either directly or indirectly bonded via a bonding group, but from the viewpoint of easy availability, it is directly bonded. Is preferred.

As the oxazoline residue, one of the hydrogen atoms of 2-oxazoline, 3-oxazoline and 4-oxazoline is bonded to the carbon of the polymerizable carbon-carbon unsaturated double bond or the carbon of the divalent bonding group. It means a group replacing the binding site. Of these, in the present invention, 2-
A group in which one of the hydrogen atoms of oxazoline is replaced with a binding site is preferable, and a group in which one of the hydrogen atoms of 2-position of 2-oxazoline is replaced with a binding site is particularly preferable.

Further, a substituent may be bonded to the oxozoline residue of the present invention. Examples of the substituent include a methyl group, an ethyl group, a phenyl group and the like, but a methyl group is preferable from the viewpoint of easy availability.

As the oxazoline residue-containing monomer in the present invention, a compound represented by the following formula (1) is particularly preferable.

[0021]

[Chemical 3] However, in the formula (1), R ^{1 to} R ⁴ are respectively
Indicates a hydrogen atom or a methyl group.

Specific examples of the oxazoline residue-containing monomer in the present invention are shown in Chemical formula 4, but the present invention is not limited thereto.

[0023]

[Chemical 4]

The proportion of polymerized units of the oxazoline group-containing monomer is 0.1 to 1 based on 100 parts by weight of the copolymer of the present invention.
0 parts by weight is preferable, and 0.5 to 5 parts by weight is particularly preferable. If the proportion of polymerized units of the oxazoline residue-containing monomer is too low, the durability of the water / oil repellency may decrease. On the other hand, if the amount is too large, the water / oil repellency may decrease.
The ratio of the polymer units of the R _f group-containing (meth) acrylate is
About 30 to 90 parts by weight is preferable in 100 parts by weight of the copolymer, and particularly preferably 50 to 70 parts by weight.

Further, as the copolymer in the present invention, in addition to the above-mentioned polymer unit of the R _f group-containing (meth) acrylate and the polymer unit of the oxazoline residue-containing monomer, other copolymerizable monomers may be used. It may contain polymerized units. Examples of other polymerizable monomers include known or well-known monomers having a radical polymerizable unsaturated bond, and are not particularly limited.

Other polymerizable monomers include vinyl chloride, stearyl (meth) acrylate ethylene, vinyl acetate, vinyl fluoride, halogenated vinyl styrene, α-
Methylstyrene, p-methylstyrene, (meth) acrylic acid, (meth) acrylic acid alkyl ester, polyoxyalkylene (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, methylolated (meth) acrylamide, N- Methylol (meta)
Acrylamide, N-methylol (meth) acrylamide vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, benzyl (meth) acrylate, isocyanate ethyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, 2-
Examples thereof include ethylhexyl (meth) acrylate, hydroxyalkyl (meth) acrylate, maleic anhydride, (meth) acrylate having polysiloxane, and N-vinylcarbazole.

Of these, as the other polymerizable monomer, vinyl chloride or stearyl acrylate is preferable from the viewpoint of obtaining high water / oil repellency.

Further, it is preferable to include a polymerizable monomer having a hydroxyl group as the other polymerizable monomer. By including a polymerizable monomer containing a hydroxyl group,
The crosslinking reaction between the copolymers occurs, and the durability of water / oil repellency can be improved. As the polymerizable monomer having a hydroxyl group, methylolated (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol (meth) acrylamide vinyl alkyl ether, hydroxyalkyl (meth) acrylate and the like are preferable.

The other polymerizable monomers may be used alone or in combination of two or more, but it is preferable to use two or more kinds. When copolymerizing another polymerizable monomer, the ratio is
About 10 to 70 parts by weight, preferably 30 to 5 parts by weight of polymerized units of other polymerizable monomers, relative to 100 parts by weight of the copolymer.
0 parts by weight is preferred.

In the water- and oil-repellent agent of the present invention, a copolymer containing a polymerized unit of the R _f group-containing (meth) acrylate and a polymerized unit of the oxazoline residue-containing monomer is an essential component. When the copolymer contains polymerized units of another polymerizable monomer, when the other polymerizable monomer contains a functional group reactive with an oxazoline residue, crosslinking at the oxazoline residue portion occurs. It is believed that the reaction occurs. Therefore, when the copolymer is used as a water and oil repellent, it is considered that excellent durability is exhibited by crosslinking.

As the method for obtaining the copolymer of the present invention, various polymerization reaction methods and conditions can be arbitrarily selected. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a radiation polymerization method, a photopolymerization method or the like can be adopted.

For example, when the emulsion polymerization method is used, a method in which a mixture of polymerizable monomers to be polymerized is emulsified in water in the presence of a surfactant or the like and polymerized with stirring can be adopted. . As the polymerization initiation source, various polymerization initiators such as organic acid peroxides, azo compounds and persulfates, and ionizing radiation such as γ-rays can be used.
Further, as the surfactant, almost all of various anionic, cationic or nonionic emulsifiers can be used. Further, when carrying out solution polymerization, a method of dissolving a mixture of polymerizable monomers to be polymerized in a suitable organic solvent and polymerizing the mixture by the action of a polymerization initiation source is adopted. Examples of the organic solvent include chlorine-based and fluorine-based organic solvents such as trichlorotrifluoroethane, tetrachlorodifluoroethane, and methylchloroform, methyl isobutyl ketone, methyl ethyl ketone, butyl acetate, and ethyl acetate. The polymerization initiation source is preferably one that is soluble in the organic solvent used, and is preferably a peroxide, an azo compound, ionizing radiation or the like.

The copolymer obtained by the above-mentioned method is adjusted into a water- and oil-repellent agent of any form such as an emulsion, a solvent solution and an aerosol according to a conventional method.

For example, as in the preceding period, an aqueous emulsion can be directly prepared by emulsion polymerization and a solvent solution can be directly prepared by solution polymerization.

The water- and oil-repellent agent of the present invention can be applied to an article to be treated by any method depending on the type of the article to be treated and the adjustment form of the previous period. For example, when the water- and oil-repellent agent is an aqueous emulsion or a solvent solution, a method of adhering it to the surface of the object to be treated and drying it by a known coating method such as dip coating is employed. If necessary, curing may be performed.

Further, the water and oil repellent agent of the present invention may contain other polymers and additives. As other polymers and additives, for example, other water repellent, oil repellent, cross-linking agent, insect repellent,
Examples include flame retardants, antistatic agents, anti-wrinkle agents, and the like.

The treatment amount when applied to the article to be treated can be appropriately changed depending on the type and purpose of the article to be treated, but in the usual case, it is usually 100 parts by weight of the article to be treated. 0.01 to 2 as the solid content concentration in the water and oil repellent agent
The amount is about 0 parts by weight, preferably about 0.5 to 3.

Articles treated with the water and oil repellent of the present invention are:
Various examples can be given without particular limitation. For example,
Fiber woven fabrics, fiber knits, leathers, furs and the like. Textile fiber,
As the fiber woven fabric, natural animals and plants 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 these Woven and knitted fabrics of mixed fibers of

[0039]

EXAMPLES Next, examples of the present invention will be specifically described, but the description does not limit the present invention.

[Example 1] A perfluoroalkylethyl acrylate (hereinafter referred to as FA) [R _f CH] was placed in a glass autoclave (internal volume: 1 liter) equipped with a thermocouple type thermometer and a current stirrer. ₂ CH ₂ OCOCH = CH ₂ (the average carbon number of R _f is 9)] 120 g (60 parts by weight), 2-vinyl- (2-oxazoline) 2 g (1 part by weight), stearyl acrylate 74 g (37 parts by weight) Part), 4 g of hydroxyethyl acrylate (2 parts by weight), 12 of acetone
0 g (60 parts by weight), 350 g of water (175 parts by weight),
Nonionic surfactant [Emulgen 920 / Kao Corporation]
Manufactured by Mitsui Chemical Co., Ltd.], 6 g of stearyl trimethyl ammonium chloride, azobisdimethylisobutyramidine [V
A-061 / manufactured by Wako Kasei Co., Ltd.] was added, and nitrogen substitution was carried out for about 20 minutes while stirring. Further, the temperature was raised to 60 ° C. to start polymerization. The mixture was heated and stirred at 60 ° C for 15 hours and then cooled, and an emulsion having a solid content concentration of 31% was added to 6
90 g was obtained. The reaction rate of FA was 99.8%. The yield of the stable emulsion emulsion was 99%.

Example 2 In a glass autoclave (internal volume of 1 liter) equipped with a thermocouple type thermometer and a current type stirrer, 120 g (60 parts by weight) of the same FA as in Example 1, 2 Vinyl-4-methyl- (2-oxazoline)
2 g (1 part by weight), 2-ethylhexyl methacrylate 74 g (37 parts by weight), hydroxyethyl methacrylate 4 g (2 parts by weight), 1,1,1-trichloroethane 466 g (233 parts by weight), azobisiso 6 g of butyronitrile was added, and nitrogen substitution was carried out for about 20 minutes while stirring. Further, the temperature was raised to 60 ° C. to start polymerization. The mixture was stirred while keeping the temperature at 60 ° C. for 20 hours and then cooled to obtain a pale yellow solution having a solid content concentration of 31%. The reaction rate of FA by gas chromatography was 99.8%.

[Example 3] Polymerization was carried out in the same manner as in Example 1 except that the polymerizable monomer, emulsifier and polymerization initiator were changed. Table 1 shows the polymerizable monomers, emulsifiers and polymerization initiators used. The reaction rate of FA was 99.5%, and the yield of the stable emulsion emulsion was 99%. The nonionic surfactant A in Table 1 is Emulgen 430 (Kao Corporation).
Manufactured).

Example 4 Polymerization was carried out in the same manner as in Example 1 except that the polymerizable monomer, emulsifier and polymerization initiator were changed. Table 1 shows the polymerizable monomers, emulsifiers and polymerization initiators used. The reaction rate of FA was 99.5%, and the yield of the stable emulsion emulsion was 99%. The nonionic surfactant B in Table 1 is Emulgen 913 (Kao Corporation).
Pharmin DMC acetate (manufactured by Kao Corporation)
It is an acetic acid neutralized product of N, N-dimethyltridecaamine.

[0044]

[Table 1]

[Example 5] The polymerizable monomer and the polymerization initiator were changed, and solution polymerization was carried out in the same manner as in Example 2 to obtain a pale yellow solution having a solid content concentration of 31%. The reaction rate of FA by gas chromatography was 99.5%. The polymerizable monomers and polymerization initiators used are shown in Table 2.

[Example 6] The polymerizable monomer and the polymerization initiator were changed, and solution polymerization was carried out in the same manner as in Example 2 to obtain a pale yellow solution having a solid content concentration of 31%. The reaction rate of FA by gas chromatography was 99.5%. The polymerizable monomers and polymerization initiators used are shown in Table 2.

[0047]

[Table 2]

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that 2-vinyl- (2-oxazoline) was not used to obtain an emulsion emulsion having a solid content concentration of 30% by weight. The reaction rate of FA was 99.8%, and the yield of the stable emulsion emulsion was 99%.

[Comparative Example 2] 2-Vinyl-4-methyl-
Example 2 except that (2-oxazoline) was not used.
Polymerization was performed in the same manner as above to obtain a pale yellow solution having a solid content concentration of 31% by weight. The reaction rate of FA by gas chromatography was 99.5%.

[Embodiments 7, 9, 10] Embodiments 1, 3, 4
The emulsified emulsion obtained in 1. was adjusted with water so that the solid content concentration became 20% by weight, to prepare a stock solution. The stock solution was diluted with water, and the test solution was prepared by adjusting the ratio of the stock solution to water to 1.5%, and the test cloth was treated to evaluate the water / oil repellency. The results are shown in Table 5.

[Examples 8, 11, 12] Examples 2, 5,
The solvent obtained in 6 was adjusted with 1,1,1-trichloroethane so that the solid content concentration was 20% by weight to prepare a stock solution. The stock solution was diluted with 1,1,1-trichloroethane, and the test solution was treated with a test solution having a ratio of the stock solution to the solvent of 1.5% by weight to evaluate the water / oil repellency. The results are shown in Table 5.

[Comparative Example 3] The emulsion emulsion obtained in Comparative Example 1 was treated in the same manner as in Example 7 to evaluate the water / oil repellency. The results are shown in Table 5.

Comparative Example 4 The solution obtained in Comparative Example 1 was treated in the same manner as in Example 8 to evaluate the water / oil repellency. The results are shown in Table 5.

Reference Example The test cloth was not treated with anything, and the water and oil repellency was evaluated. The results are shown in Table 5.

A nylon taffeta cloth was used for the above water / oil repellency test. A cloth was dipped in the test liquid obtained in each of Examples 1 to 6 and the cloth was squeezed between two rubber rollers to obtain a wet pickup of 30%. Then, it was dried at 110 ° C. for 90 seconds and further heat-treated at 170 ° C. for 60 seconds.
The water and oil repellency of the obtained test cloth was measured.

The water repellency and oil repellency shown below are shown on the following scale. That is, the water repellency is JIS
It was represented by the water repellency number by the spray method of -L-1092 (Table 3 below). For oil repellency, the test solution shown in Table 4 is dropped in two places on the test cloth (diameter about 4 mm).
The sample was placed, and after 30 seconds, it was determined by the permeation state, and the highest number where no permeation was observed was noted. (AATCC-
TM118-1966). The water-repellent number and the oil-repellent number marked with + (-) indicate that their physical properties are slightly better (inferior) than the respective numbers.

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

[Table 5]

[0060]

The water and oil repellent agent of the present invention has excellent water and oil repellency. Further, it also has durability of high water / oil repellency, which cannot be achieved by the conventional water / oil repellant.

Claims (6)

[Claims] 1. A water-repellent and repellent comprising a copolymer containing a polymer unit of a polyfluoroalkyl group-containing acrylate and / or a polyfluoroalkyl group-containing methacrylate and a polymer unit of an oxazoline residue-containing monomer as essential components. Oil agent. 2. The oxazoline residue-containing monomer is represented by the following formula (1):
The water and oil repellent according to claim 1, which is a compound represented by: [Chemical 1] However, in the formula (1), R ^{1 to} R ⁴ are respectively
Indicates a hydrogen atom or a methyl group. 3. The water and oil repellent according to claim 1, which is a copolymer containing polymerized units of vinyl chloride or stearyl acrylate. 4. The water / oil repellent according to claim 1, which is a copolymer containing polymerized units of a polymerizable monomer having a hydroxyl group. 5. An article treated with the water and oil repellent according to any one of claims 1 to 4. 6. The article according to claim 5, wherein the article is a fiber or a textile product.