JPH07228864A - New water-and-oil repellent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, comprising a polymer, etc., containing a polymerization unit of a monomer containing a polyfluoroalkyl group without deteriorating water-and-oil repellencies and various performances by washing or dry cleaning, hardly changing the touch feeling and curable at low temperatures. CONSTITUTION:This composition comprises (A) a polymer containing a polymerization unit of a monomer containing a polyfluoroalkyl group and (B) a polymer containing a polymerization unit of a monomer containing an oxazoline residue. Furthermore, an acrylate or a methacrylate containing the polyfluoroalkyl group is preferably used as the monomer of the component (A) and a compound expressed by the formula (R<1> to R<4> are each H or methyl) is preferably used as the component (B), which is preferably further a polymer containing a polymerization unit of a monomer containing the oxazoline residue, a polymerization unit of methyl methacrylate and a polymerization unit of styrene.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, for the purpose of imparting water / oil repellency to a fiber, the fiber has been treated with a water / oil repellent containing a polymer having a polyfluoroalkyl group. However, the conventional water and oil repellents have a problem that the water and oil repellent performance is deteriorated by washing or dry cleaning. For the purpose of solving this problem, a water / oil repellent composition in which a silicone resin, blocked isocyanate, aminoplast resin or the like is added to a conventional water / oil repellent has been proposed.

[0003]

However, the water- and oil-repellent composition containing a silicone resin has a drawback that not only the adhesive strength is lowered but also the texture of the material is impaired. In addition, blocked isocyanate and aminoblast resin not only roughen the texture, but also require a high curing temperature to crosslink the resin, and at a low temperature crosslinking does not occur, resulting in poor durability. . As described above, a water / oil repellent composition which is satisfactory in high water / oil repellency and its durability has not been obtained. The present invention has been made to solve the above problems, and provides a completely new water / oil repellent composition.

[0004]

The present invention provides a water and oil repellent agent containing a polymer containing polymerized units of a polyfluoroalkyl group-containing monomer and a polymer containing polymerized units of an oxazoline residue-containing monomer. A composition is provided.

As the polyfluoroalkyl group-containing monomer in the present invention, a polyfluoroalkyl group (hereinafter referred to as Rf group) which gives water / oil repellency and a radically polymerizable carbon-carbon unsaturated double bond are used. Known compounds or known compounds are included and are not particularly limited.

The Rf group has a structure in which two or more hydrogen atoms of a hydrocarbon group are substituted with fluorine atoms. Normally, R
The Rf group in the f group-containing monomer preferably has a linear or branched structure. The Rf group may contain one or more carbon-carbon unsaturated double bonds, or may contain an oxygen atom ether-bonded with a carbon atom.

The Rf group preferably has 4 to 20 carbon atoms.
Among the carbon atoms of the Rf group, the number of carbon atoms to which one or more fluorine atoms are bonded is 2 or more, preferably 4 to 18, particularly preferably 6 to 16. The ratio of the total number of fluorine atoms in the Rf group to the total number of hydrogen atoms in the alkyl group having the same carbon number as the Rf group is preferably 6
It is preferably 0% or more, particularly preferably 80% or more. Also, R
The f group may contain a halogen atom other than a fluorine atom. A chlorine atom is preferable as the other halogen atom.

Further, the terminal portion of the Rf group may be a group containing a hydrogen atom or a chlorine atom, or an oxypolyfluoroalkylene-containing group. For example, it is a trifluoromethyl group, a difluoromethyl group, a chlorodifluoromethyl group, and the like, but the preferred terminal structure is the trifluoromethyl group.

The structure of the terminal portion of the Rf group is preferably a perfluoroalkyl group in which all the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms. As the perfluoroalkyl group, a structure represented by C _m F _{2m + 1} (where m represents an integer of 4 to 16) is preferable, and particularly m is 6
It is preferably an integer of -12.

As the Rf group-containing monomer in the present invention, one or more, preferably one of the above Rf groups is bonded to a carbon-carbon unsaturated double bond directly or through a bonding group. It is preferable that they are bound via a linking group. The bonding group is not particularly limited, but a group containing an alkylene moiety or an ester moiety is preferable.

Particularly, the Rf group-containing monomer in the present invention is preferably an acrylate or methacrylate containing one or more Rf groups. In the following, acrylate and methacrylate are collectively referred to as (meth) acrylate, which means both. The same applies to (meth) acrylamide and the like. Further, a (meth) acrylate containing one or more Rf groups will be referred to as Rf (meth) acrylate.

Specific examples of preferable Rf (meth) acrylate include compounds represented by the following general formula (2). Rf (meth) acrylate of (2) is a known compound.

CH ₂ = CR ⁵ COO-A-Rf '(2) wherein R ⁵ is a hydrogen atom or a methyl group, A is a divalent linking group, and Rf' is Rf having 6 to 16 carbon atoms. Represents a group.

A in the general formula (2) represents a divalent linking group. -R ⁶ Examples ^{-, - R 7 N (R} 9) SO 2 -, -
R ⁸ N (R ¹⁰ ) CO— can be mentioned, but it is not limited thereto. In addition, R < ⁶ > -R < ⁸ > shows an alkylene group, respectively, and especially a C2-C6 alkylene group is preferable. R ^{6 to} R ⁸ are a hydroxyl group or -OC
It may contain an OCH ₃ group or the like. R ^{9 to} R ¹⁰ are preferably alkyl groups, particularly alkyl groups having 4 or less carbon atoms. Rf 'is a straight chain or R having a branch at the end
The f group is preferred.

Specific examples of Rf (meth) acrylate are shown below, but it goes without saying that they are not limited to these examples. However, R ⁵ and Rf 'of Chemical formula 2
Has the same meaning as in the case of the general formula (2).

[0016]

[Chemical 2]

The Rf (meth) acrylate may be used alone or in combination of two or more. When mixed and used, two or more compounds having different Rf group carbon numbers can be used.

The polymer containing polymerized units of the Rf group-containing monomer in the present invention (hereinafter referred to as the Rf group-containing polymer) is one or more polymers of the Rf group-containing monomer, or It may be a copolymer of at least one Rf group-containing monomer and at least one other polymerizable monomer. In the following, other polymerizable monomers that can be copolymerized with the Rf group-containing monomer will be referred to as comonomers.

As the comonomer, various known monomers can be mentioned. The comonomers can be used alone or in combination of two or more. Examples of comonomers include polymerizable unsaturated groups such as (meth) acrylates, (meth) acrylamides, vinyls, vinyl halides, olefins, (meth) acrylonitriles and unsaturated carboxylic acid esters. Well-known comonomers having a functional group may be mentioned.

Of these, preferred examples are (meta)
Acrylates, (meth) acrylamides, vinyl chloride can be mentioned. Further, as the (meth) acrylates, a hydroxyl group, an amino group,
Although those having a functional group such as an epoxy group may be used, it is preferable to use the comonomer having the functional group as a part of the comonomer. Among the (meth) acrylates, particularly preferable examples include those containing a long-chain hydrocarbon group having 8 or more carbon atoms in the alkyl ester moiety, such as 2-ethylhexyl (meth) acrylate and stearyl (meth) acrylate. You can

Examples of the above-mentioned comonomers include, but are not limited to, the monomers described below.

Aziridinyl (meth) acrylate, glycidyl (meth) acrylate, ethylene di (meth) acrylate, hydroxyalkyl (meth) acrylate, 3
-Chloro-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, mono- or di (meth) acrylate of polyoxypropylene diol, (meth) acrylate having an organopolysiloxane residue, N -Methylol (meth) acrylamide, diacetone (meth)
Acrylamide, methylolated diacetone (meth) acrylamide, (meth) acrylamide.

Vinyl chloride, vinyl acetate, vinyl fluoride,
Vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, ethylene, styrene,
Alkyl ester of α-methylstyrene, maleic anhydride, butadiene, isoprene, chloroprene, vinyl fluoride, acrylic acid or methacrylic acid.

The proportion of the Rf group-containing monomer and the comonomer in the copolymer is preferably 40% by weight or more, and particularly preferably 50 to 80% by weight, of the Rf group-containing monomer. The comonomer is 60 of all comonomers.
Weight% or more is (meth) acrylates or (meth)
Acrylamides are preferred. When using (meth) acrylates having a functional group as a comonomer, it is desirable to use an amount of about 1 to 10% by weight, preferably about 2 to 5% by weight, based on all monomers.

The present invention is characterized in that a water / oil repellent composition containing the above Rf group-containing polymer and a polymer containing polymerized units of an oxazoline residue-containing monomer is used.

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

As the oxazoline residue, one of the hydrogen atoms of 2-oxazoline, 3-oxazoline and 4-oxazoline is a carbon of a polymerizable carbon-carbon unsaturated double bond or a carbon of a 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 bonding site is preferable, and a group in which the hydrogen atom of 2-position of 2-oxazoline is replaced with a bonding 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 monomer containing an oxazoline residue in the present invention, a compound represented by the following formula (1) is particularly preferable.

[0030]

[Chemical 3]

However, in the formula (1), R ^{1 to} R ⁴
Represent a hydrogen atom or a methyl group, respectively.

Specific examples of the oxazoline residue-containing monomer in the present invention will be given, but the present invention is not limited thereto.

[0033]

[Chemical 4]

The polymer containing polymerized units of the oxazoline residue-containing monomer in the present invention (hereinafter referred to as the oxazoline residue-containing polymer) is one or two of the above-mentioned oxazoline residue-containing monomers. Examples thereof include polymers obtained by polymerizing one or more kinds, or ones or two or more kinds of oxazoline residue-containing monomers and one or more kinds of other polymerizable monomers. Of these, from the viewpoint of compatibility with the Rf group-containing polymer, one or more kinds of the oxazoline residue-containing monomer and one or more kinds of the other polymerizable monomer are used together. The thing polymerized is preferable.

As the other polymerizable monomer to be copolymerized with the oxazoline residue-containing monomer, the same as the above comonomer can be exemplified, but in the present invention, methyl methacrylate and styrene are adopted. Is preferred.

Further, the ratio of the polymerized units of the oxazoline residue-containing monomer in the oxazoline residue-containing polymer of the present invention is not particularly limited, but in general, it is usually 100 parts by weight of the oxazoline residue-containing polymer. It is preferably 0.1 to 40 parts by weight. The proportion of the polymer units of the comonomer to be copolymerized with the oxazoline residue-containing monomer is 60 to 99. per 100 parts by weight of the oxazoline residue-containing polymer.
About 9 parts by weight is preferable. Particularly, when methyl methacrylate is included as a comonomer, 10 to 80 parts by weight is preferable in the oxazoline residue-containing polymer, and when styrene is included, 10 to 80 parts by weight is preferable.

As the above water / oil repellent composition, a water dispersion type or a solution solvent type is preferable. As a method for producing the water / oil repellent composition, a known method can be adopted, but it is preferably produced by an emulsion polymerization method or a solution polymerization method,
In particular, the emulsion polymerization method is preferred.

Further, when water is used as a medium in the emulsion polymerization method, a water-dispersed water / oil repellent composition can be obtained. In this case, the time of adding the surfactant is not particularly limited, but it is preferable to add it as an emulsifier for polymerization during polymerization. When it is desired to further increase the dispersion stability of the polymerization product, it is preferable to carry out emulsion polymerization in an aqueous medium containing a water-soluble solvent such as alkylene glycol.

When the solution polymerization method is used, a solution solvent type water and oil repellent agent is obtained. Further, in the case where the polymer is produced by a solution polymerization method or another polymerization method and then made into a water dispersion type, it is preferable to add a surfactant when the obtained polymer is dispersed in water.

The polymerization of the above-mentioned monomers can be carried out in the usual case by adding a known polymerization initiator. For example, as a polymerization initiator at the time of emulsion polymerization, a polymerization initiator such as an organic peroxide, an azo compound or a persulfate, or an ionizing radiation such as γ-ray can be used. Further, the polymerization yield can be increased by adding an acid such as sulfuric acid or nitric acid during the polymerization.

The Rf group-containing polymer has a molecular weight of 10
The range of 00 to 1,000,000 is preferable. Particularly when the water and oil repellent is a water dispersion type, the range of about 5000 to 100,000 is preferable. In the case of a solvent solution type, 3000 to
About 30,000 is preferable. If the molecular weight of the Rf group-containing polymer is too small, the durability of water / oil repellency may be deteriorated, while if the molecular weight is too large, it is difficult to synthesize and difficult to obtain. The molecular weight of the oxazoline residue-containing polymer is not particularly limited, but in the usual case, it is 300 from the viewpoint of easy availability and easy synthesis.
About 0 to 100,000 is preferable.

The particle diameters of the Rf group-containing polymer and the oxazoline residue-containing polymer are preferably as small as possible from the viewpoint of dispersion stability, and the average particle diameter is preferably 2.0.
μ or less, particularly preferably 0.02 to 1.5 μ.

The water / oil repellent composition in the present invention contains the above-mentioned polyfluoroalkyl group-containing polymer and oxazoline residue-containing polymer. The proportion of each in the water / oil repellent composition is 0.5 to 20 parts by weight of the oxazoline residue-containing polymer with respect to 100 parts by weight of the polymer containing polymerized units of the polyfluoroalkyl group-containing monomer. About a part is preferable.

Further, the water / oil repellent composition of the present invention may contain a polymer other than the above-mentioned polymers and additives. For example, other water and oil repellents, or crosslinkers,
Examples include additives such as insect repellents, flame retardants, antistatic agents, dye stabilizers and anti-wrinkle agents.

The objects to be treated in the present invention include:
Various examples can be given without particular limitation. For example,
Textile fabrics, fiber knits, glass, paper, wood, leather, fur, asbestos, bricks, cements, metals and metal oxides, ceramic products, plastics, etc., but are not limited to these examples. Woven fibers, examples of fiber fabrics, cotton,
Natural animal and vegetable fibers such as 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, glass fibers, carbon fibers, asbestos fibers, etc. Inorganic fibers, or woven or knitted fabrics of these mixed fibers can be mentioned.

As a method for treating the article to be treated with the water / oil repellent composition of the present invention, any method can be applied depending on the type of the article to be treated, the above-mentioned preparation form and the like. For example, a method of adhering it to the surface of the object to be processed and drying it by a known coating method such as a dip coating method is adopted. Also,
If necessary, curing may be performed. The amount of the water / oil repellent composition to be treated on the article to be treated is usually
The solid content concentration of the water / oil repellent composition is about 0.01 to 10 parts by weight, preferably about 0.1 to 3 parts by weight, relative to 100 parts by weight of the object to be treated. If the solid content concentration is too low, the durability of the water / oil repellency may be deteriorated.

[0047]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples, but it goes without saying that the description does not limit the present invention. The texture, the water- and oil-repellent performance, the washing durability, and the dry cleaning durability were evaluated by the following methods.

[Evaluation Method of Texture] The texture was evaluated by making a comparison with the feel of the untreated cloth.

[Evaluation Method of Washing Durability] Washing durability was evaluated 10 times by JIS-L-0217-103 method, dried at 90 ° C. for 3 minutes, and after 10 times, water and oil repellency. The performance was evaluated by comparing with that before washing.

[Dry Cleaning Durability Evaluation Method]
The dry cleaning durability is evaluated according to JIS-L-10.
92, 3, 2 (2) method, repeated 10 times, then dried at 25 ° C. for 12 hours, and after 10 times (abbreviated as 10 times DC) water and oil repellency before dry cleaning. It was evaluated by comparing with.

The water repellency and oil repellency are shown on the following scale. That is, the water repellent performance is JIS
It is represented by the water repellency number of the spray method of L-1092 (see Table 1 below), and the oil repellency is shown by the test solution shown in Table 2 below on the test cloth in a few drops (diameter about 4 m).
m), after 30 seconds, the state of permeation was used to determine the highest number of the test solution that did not permeate (AATCC-T).
M118-1966). The water-repellent number and the oil-repellent number with + indicate that the properties are slightly better.

[Example 1] The water / oil repellency performance test was carried out using nylon taffeta cloth under the following conditions. That is, 20 parts of a copolymer of perfluoroalkylethyl acrylate (70 parts by weight) / vinyl chloride (30 parts by weight) is used.
6 parts by weight of a water-dispersed fluorine-based water and oil repellent, including 2 parts by weight
93.5 parts by weight of water was added to 0.5 parts by weight of an aqueous dispersion (Epocles K1010E / manufactured by Nippon Shokubai) containing 40 parts by weight of a vinyl- (2-oxazoline) / methyl methacrylate / styrene copolymer, What was adjusted to pH 6 was used as the treatment liquid. The treatment liquid of 20 times the weight of the treated cloth was set to 25 ° C., the test cloth was immersed therein, and the cloth was squeezed between two rubber rollers to obtain a wet pickup of 30%. Then dry at 110 ° C for 90 seconds, then 170
It heat-processed at 60 degreeC for 60 second (s). This was used as a test cloth. Table 3 shows the results of evaluation of the texture of the test cloth, the water- and oil-repellency washing durability and the dry cleaning durability.

[Embodiment 2] Epocles K10 of Embodiment 1
The same procedure as in Example 1 was carried out except that 5 parts by weight of 10E and 89 parts by weight of water were used. Table 3 shows the texture of the test cloth before and after the treatment, the washing durability of water and oil repellency, and the dry cleaning durability.

[Embodiment 3] The curing temperature of Embodiment 1 is set to 12
The treatment was performed in the same manner as in Example 1 except that the temperature was 0 ° C. Table 3 shows the texture of the test cloth before and after the treatment, the washing durability of water and oil repellency, and the dry cleaning durability.

[Embodiment 4] The curing temperature of Embodiment 2 is set to 12
The same method as in Example 1 was performed except that the temperature was 0 ° C. Table 3 shows the texture of the test cloth before and after the treatment, the washing durability of water and oil repellency, and the dry cleaning durability.

Example 5 15 parts by weight of a copolymer of perfluoroalkylethyl acrylate (60 parts by weight) / stearyl acrylate (40 parts by weight) in 1,1,1-trichloroethane (hereinafter referred to as R-113). % Of a solvent solution containing 50% of a 2-vinyl- (2-oxazoline) / butyl acrylate / styrene copolymer.
1 part by weight of a xylene solution (CX-RS-1200 / manufactured by Nippon Shokubai Co., Ltd.) containing 1% by weight was mixed and further diluted with toluene so that the solid content concentration became 1% by weight to obtain a treatment liquid. Twenty times the weight of the treated cloth is 25 ° C.,
The test cloth was dipped here, and the cloth was squeezed between two rubber rollers to obtain a wet pickup of 40%. Then, it was dried at 110 ° C. for 90 seconds and further heat-treated at 170 ° C. for 60 seconds. Table 3 shows the texture of the test cloth before and after the treatment, the washing durability of water and oil repellency, and the dry cleaning durability.

Comparative Example 1 Epocros K10 of Example 1
Instead of 10E, 3 parts by weight of an aqueous dispersion (Sumitec Resin M-3 / Melamine resin manufactured by Sumitomo Chemical Co., Ltd.) containing 75 parts by weight of a melamine resin, a catalyst (Sumitec Accelerator A)
The same method as in Example 1 was performed except that 3 parts by weight of CX / catalyst manufactured by Sumitomo Chemical Co., Ltd. and 88 parts by weight of water were used.
Table 3 shows the texture of the test cloth before and after the treatment, the washing durability of water and oil repellency, and the dry cleaning durability.

[Comparative Example 2] Epocros K10 of Example 1
Instead of 10E, an aqueous dispersion containing 40% by weight of methyl ethyl ketoxime type blocked isocyanate (BP-
11 / Meisei Kagaku Kogyo Co., Ltd.) was used, and the same procedure as in Example 1 was carried out. Table 3 shows the texture of the test cloth before and after the treatment, the washing durability of water and oil repellency, and the dry cleaning durability.

[Comparative Example 3] The curing temperature of Comparative Example 1 was set to 12
The same treatment was carried out except that the temperature was 0 ° C. Table 3 shows the texture of the test cloth before and after the treatment, the washing durability of water and oil repellency, and the dry cleaning durability.

[Comparative Example 4] The curing temperature of Comparative Example 2 was set to 12
The same treatment was carried out except that the temperature was 0 ° C. Table 3 shows the texture of the test cloth before and after the treatment, the washing durability of water and oil repellency, and the dry cleaning durability.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

The water and oil repellent composition of the present invention is a very excellent composition in which the water and oil repellent performance is not significantly deteriorated by washing or dry cleaning when it is treated on a cloth, and the texture is small. Is. Further, even when the curing temperature is lowered, the water / oil repellency and the deterioration of the performance due to washing and dry cleaning are small, and the change in the texture is small, so that there is an advantage that curing can be performed at a low temperature.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location D06M 15/356

Claims (6)

[Claims] 1. A water / oil repellent composition comprising a polymer containing polymerized units of a polyfluoroalkyl group-containing monomer and a polymer containing polymerized units of an oxazoline residue-containing monomer. 2. The water / oil repellent composition according to claim 1, wherein the polyfluoroalkyl group-containing monomer is an acrylate containing a polyfluoroalkyl group or a methacrylate containing a polyfluoroalkyl group. 3. The water / oil repellent composition according to claim 1, wherein the oxazoline residue-containing monomer is a compound represented by the formula (1). [Chemical 1] However, in the formula (1), R ^{1 to} R ⁴ are respectively
Indicates a hydrogen atom or a methyl group. 4. A polymer containing a polymerized unit of an oxazoline residue-containing monomer is a polymer containing a polymerized unit of an oxazoline residue-containing monomer, a methylmethacrylate polymerized unit, and a styrene polymerized unit. Item 5. The water / oil repellent composition according to any one of items 1 to 3. 5. An article treated with the water and oil repellent composition according to any one of claims 1 to 4. 6. The article is a fiber or a fiber product.
Goods.