KR20040092733A - Water-based emulsion-type water/oil repellents and their preparation method - Google Patents

Abstract

PURPOSE: A durable non-chlorine type fluorine-based water and oil repellent agent and its preparation method are provided to improve the stability of the resulted copolymer composition by using alkylisocyanate blocked with oxime. The water and oil repellent agent has a reduced risk of ignition or explosion and generates significantly reduced amount of material hazardous to the environment or human. CONSTITUTION: The durable non-chlorine type fluorine-based water and oil repellent agent is prepared by carrying out emulsion polymerization of a (meth)acrylate monomer having at least one polyfluoro alkyl group and an alkylisocyanate having double bonds which can be copolymerizable with the (meth)acrylate monomer having at least one polyfluoro alkyl group or each of the monomer blocked with oximes such as 2-butanone oxime, alcohols such as methanol, ethanol and the like, caprolactam and cyclohexanone, in an aqueous solution containing an organic solvent.

Description

Durable non-chlorine-based water and oil repellent using vinyl isocyanate with alkyl group and its preparation method {Water-based emulsion-type water / oil repellents and their preparation method}

The present invention relates to a durable non-chlorine fluorine and oil repellent using a vinyl isocyanate having a vinyl group and a method for manufacturing the same. More specifically, the present invention is applied to the surface of a fabric and the like to prevent contamination due to water repellency and oil repellency. In the emulsion,

The water- and oil-repellent agent is produced by emulsion polymerization in an aqueous solution containing an organic solvent to lower the risk of ignition due to the increase in the flash point, and to a method for producing a non-chlorine-based fluorine and oil-repellent agent that significantly reduces the adverse effects on the human body or the environment. will be.

In general, water- and oil-repellent agent is applied to various fields such as paint, fiber, paper, adhesive, resin / rubber, civil engineering / architecture, and aims for water / oil repellent of products.

These water and oil repellents are prepared through a variety of methods, among them are prepared through an aqueous copolymer of an acrylate or methacrylate monomer having a polyfluoroalkyl group, and a copolymer which is copolymerizable with and does not contain fluorine.

As such, the water- and oil-repellent oil-repellent agent is required to be synthesized with a special monomer to achieve durability (washing resistance) and bonding to the fiber at high temperature, and to achieve this, the polymer composition includes VCM (vinyl chloride) or VDC ( Vinylidend chloride) is used.

However, as described above, the polymer composition obtained by synthesizing VCM, VDC, which is applied to improve durability and bonding with fibers,

Explosion risk in the copolymer manufacturing process, as well as the production of environmental pollutants such as ozone depleting substances in the production process causes a problem that the use is gradually reduced.

However, if VCM, VDC is excluded during copolymerization to solve this problem,

The produced water-dispersible water and oil repellent agent is not applicable to products requiring frequent washing, such as clothing, because the water-repellent oil repellent weakens the bond with the fiber, causing the water-repellent oil repellency is sharply lowered after washing, which is why Due to the limited scope, it was a problem that caused economic losses due to market shrinkage.

Therefore, in the present invention was created to solve the above problems, by replacing the monomer which is dangerous to handle, such as VCM, VDC, adversely affect the environment,

By using isopropenyldimethylbenzyl isocyanate as a material that blocks 2-butanone oxime, it is possible to produce a water-dispersible water and oil repellent which is a copolymer composition that significantly lowers the explosion risk and suppresses the generation of environmental pollutants. Its purpose is to increase durability and realize eco-friendly manufacturing process.

Durable non-chlorine-based fluorine and oil repellent agent using an alkyl isocyanate having a vinyl group of the present invention for achieving the above object,

As a monomer used for the purpose of durability, the objective can be achieved by using the monomer which has a structure of following Chemical formula (1)-(2).

Chemical formula (1);

Chemical formula (2);

In Chemical Formulas (1) and (2) above;

R1; H or CH3,

R2; Alkyl group,

R3; Examples of blocking agents include oximes such as 2-butanone oxime, alcohols such as methanol and ethanol, caprolactam, and cyclohexanone.

As described above, the present invention is not a pursuit of durability through the dangerous and toxic monomers, such as VCM or VDC, when manufacturing a water- and oil-repellent agent,

A method of preparing a copolymer composition useful as a water dispersible water and oil repellent agent having a low risk of ignition and explosion and having low adverse effects on humans and the environment by using a monomer that is easy to handle, and a water / oil repellent agent using the copolymer composition to provide.

The acrylate or methacrylate monomer having a polyfluoroalkyl group used in the present invention is not particularly limited, but preferably has 3 to 21 carbon atoms, more preferably 6 to 18 carbon atoms of the polyfluoroalkyl group.

Specific examples thereof include the following compounds.

1.C _n F _{2n + 1} CH ₂ OCOCR ¹ = CH ₂

2.C _n F _{2n + 1} SO ₂ NR ² (CH ₂ ) _m OCOCR ¹ = CH ₂

3.C _n F _{2n + 1} CH ₂ CH (OH) (CH ₂ ) _m OCOCR ¹ = CH ₂

4.C _n F _{2n + 1} (CH ₂ ) _m OCOCR ¹ = CH ₂

5.ClC _n F _2n (CH ₂ ) _m OCOCR ¹ = CH ₂

6.HC _n F _2n (CH ₂ ) _m OCOCR ¹ = CH ₂

In the above formula

R ¹ ; A hydrogen atom or a methyl group,

R ² ; Methyl group, ethyl group or propyl group,

m; An integer from 2 to 6,

n; It is an integer from 3 to 21.

There is no particular limitation on the monomer which is copolymerizable with an acrylate or methacrylate monomer having a polyfluoroalkyl group used in the present invention, and the monomer which does not contain durability in the monomer which does not contain fluorine,

Examples include alkyl (meth) acrylic acid esters, alkyl (meth) acrylamides, other maleic acid alkyl esters, alkyl phthalate esters, alkylediol (meth) acrylates, ethylene, vinyl acetate, styrene, α-methylstyrene, β-methyl Styrene, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, cyclohexyl (meth) acrylate, maleic anhydride, butadiene, isoprene, chloroprene and the like.

The copolymer composition of the present invention,

When co-polymerizing with an acrylate or methacrylate monomer having a polyfluoroalkyl group and emulsifying a monomer containing no fluorine,

It is a method of emulsion-polymerizing after adding alkyl isocyanate used as the polymerizable monomer added for the purpose of durability like the said Chemical structure (1) (2), and obtaining a copolymer.

As described above, the monomer for the purpose of durability, in addition to the alkyl isocyanate having a polymerizable double bond, has been conventionally used in emulsion polymerization of VCM and VDC.

The use of these monomers can be used within the scope of not impairing the object of the present invention as these monomers are potentially explosive and produce substances harmful to the environment and the human body.

The copolymer composition of the present invention,

A monomer containing the polyfluoroalkyl group,

The solvent used to emulsify the compound which is copolymerizable with the monomer which does not contain fluorine as a main component in water is not particularly limited.

Examples thereof include acetone and polyhydric alcohols having a low molecular weight.

Conventionally, the amount of organic solvent used for emulsion polymerization required 50 to 200% by weight of the total amount of monomers used for emulsion polymerization.

In the preparation of the copolymer composition of the present invention, only 50 to 80% by weight of the total monomer can be used to obtain a safe emulsion dispersion. Therefore, this copolymer composition has a significant environmental pollution problem when used for water and oil repellent and other uses. I can alleviate it.

In the copolymer composition of the present invention, the solid content concentration is preferably 10% by weight or more, more preferably 5 to 45% by weight.

It is preferable that the monomer component containing the said polyfluoro alkyl group is 20 weight% or more of the total monomer amount, It is more preferable that it is 30 to 80 weight%,

Moreover, it is preferable that it is 80 weight% or less, and, as for the monomer which is copolymerizable with the monomer containing a polyfluoro alkyl group and does not contain fluorine, it is more preferable that it is 70 to 20 weight%.

In the copolymer production method of the present invention,

There is no particular limitation on the kind of the surfactant and the initiator, and the surfactant may be any surfactant such as nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants that have been conventionally used.

As an initiator, polymerization initiators, such as an organic peroxide, an azo compound, a persulfate, etc. can be used.

The copolymer composition of the present invention can also be used for a water and oil repellent agent and other uses, and there is no particular limitation on the object to be treated with the water and oil repellent agent, and includes various materials.

Examples include textile products, glass, paper, wood, leather, fur, plastics, painted surfaces, and gypsum. Textile products include natural fibers such as cotton, hemp, wool, and silk, polyamide, and polyester. Synthetic fibers such as polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polyethylene, and polypropylurene polyurethane; Inorganic fibers such as semi-synthetic fibers such as rayon, acetate and triacetate, glass fibers, carbon fibers and asbestos fibers; Or the composite fiber which consists of these 2 or more types of fibers, etc. are mentioned.

In addition, it is possible to process the processing object by any method selected according to the type of processing object,

For example, a method of attaching and drying a water / oil repellent agent to the surface of a workpiece by dipping, coating, spraying, and the like, and attaching it to the workpiece through curing using an appropriate crosslinking agent as necessary. Can be.

Furthermore, the water- and oil-repellent agent of the present invention can be used in combination with other water- and oil-repellent agents conventionally used, if necessary, and can be used in combination with other processing agents such as insect repellents, flame retardants, antistatic agents, dye stabilizers, and flame retardants.

The production process and features of the durable non-chlorine-based fluorine and oil repellent using an alkyl isocyanate having a vinyl group of the present invention as described above will be described in more detail.

Example 1

1000 ml of a quaternary copolymer composition of a material in which polyfluoroacrylate, butyl acrylate, methyl methacrylate and isopropenyldimethylbenzyl isocyanate are blocked with 2-butanone oxime,

135 g of C _n F _{2n + 1} CH ₂ CH ₂ OCOCH = CH ₂ (n = 6,8,10,12,14; average 8) in an autoclave,

25 g butyl acrylate,

10 g of methyl methacrylate,

20 g of a material blocking isopropenyldimethylbenzyl isocyanate with 2-butanone oxime,

710 g of distilled water,

50 g of polyoxyethylene propylene glycol mixture,

20 g of polyoxyethylene lauryl ether,

10 g stearyl trimethylammonium chloride

After the addition, the solution was stirred by stirring at 45 ° C.

Subsequently, the temperature was raised to 70 ° C., 1.5 g of the water-soluble initiator was dissolved in 37.5 g of distilled water, added to the reactor, and reacted for 20 hours to obtain a copolymer composition.

The copolymer composition is obtained in the same procedure as in Example 1, except that the isopropenyldimethylbenzyl isocyanate applied in Example 1 is used instead of the material blocking 2-butanone oxime.

The copolymer composition prepared as described above was subjected to the evaluation of the copolymer compositions of Examples and Comparative Examples 1 to 3 through the following conditions and methods.

Flash point;

The flash point of the copolymer composition was measured according to ASTM D93A, and the results as shown in Table 3 were obtained.

◎ sample for evaluation of water and oil repellency;

When the cotton cloth is padded with 3 wt% aqueous solution of the copolymer composition of Examples or Comparative Examples 1-3, dried at 120 ° C for 1 minute, and heat treated at 160 ° C for 2 minutes to evaluate water repellency and oil repellency.

◎ water repellency;

Water repellency was evaluated by JIS L 1092 Waterspray method, and the evaluation results were obtained using the six-step evaluation of 0-100 described in Table 1 as the evaluation criteria.

Durability (washing resistance);

Durability (washing resistance) was evaluated after washing 5 times by KSK0114 machine washing method, and the evaluation criteria were the same as the water repellency and oil repellency, and the results as shown in <Table 3> were obtained.

TABLE 1

Water repellency condition 100 Without adhesion to surface wet 90 Showing some adhesion wetting on the surface 80 Showing wetting on the surface in water 70 With partial wetting on the surface 50 Showing wetting on the surface 0 Showing wetting throughout the surface

Oil repellent;

The test solution shown in <Table 2> was dropped several times in two places on the specimen, and it was judged by the penetration state after 30 second (AATCC Test method 118-1966 method).

TABLE 2

Oil repellent Test solution Surface tension (dyne / cm, 25 ℃) 8 n-heptane 20.0 7 n-octane 21.8 6 n-decane 23.5 5 n-dodecane 25.0 4 n-tetradecane 26.7 3 n-hexadecane 27.3 2 n-hexadecane / Nujol (35/65) mixture 29.6 One Nujol 31.2 0 Less than 1 .

Nujol in Table 2 is liquid paraffin.

TABLE 3

In Table 3, the oil repellency '+' means that the performance is slightly better than the value, '-' means that the performance is slightly lower than the value.

Also OR; Oil repellent, WR; It means water repellency.

The durable non-chlorine fluorine and oil repellent agent using the alkyl isocyanate which has the vinyl group of this invention as described above, and its manufacturing method are the production of a stable copolymer composition using the substance which blocked the 2-butanone oxime from isopropenyl dimethylbenzyl isocyanate. Is possible,

Furthermore, the prepared composition has sufficient stability and water / oil repellency, and by using a monomer that is easy to handle, the risk of explosion or ignition during copolymerization is greatly reduced, and the generation of substances harmful to the human body or the environment is greatly reduced, thereby reducing environmental pollution. It is a useful invention that can be prevented.

Claims (5)

Acrylate or methacrylate monomers having at least one polyfluoro alkyl group, and Alkyl isocyanates having a double bond polymerizable with a monomer containing no fluorine copolymerizable with an acrylate or methacrylate monomer having at least one polyfluoro alkyl group, or Emulsification polymerization of the above monomers in an aqueous solution containing an organic solvent using oximes such as 2-butanone oxime, alcohols such as methanol and ethanol, caprolactam, cyclohexanone and the like The manufacturing method of the durable non-chlorine-type fluorine water-repellent agent using the alkyl isocyanate which has a vinyl group to make. The method of claim 1; A method for producing a durable non-chlorine fluorine and oil repellent agent using an alkyl isocyanate having a vinyl group, wherein the polyfluoroalkyl group of the acrylate or methacrylate monomer having a polyfluoroalkyl group has 3-21 carbon atoms. The method of claim 1 or 2; The acrylate or methacrylate having a polyfluoroalkyl group is a method for producing a durable non-chlorine fluorine and oil repellent using an alkyl isocyanate having a vinyl group, characterized in that consisting of at least one compound of the following chemical formula. C _n F _{2n + 1} CH ₂ OCOCR ¹ = CH ₂ C _n F _{2n + 1} SO ₂ NR ² (CH ₂ ) _m OCOCR ¹ = CH ₂ C _n F _{2n + 1} CH ₂ CH (OH) (CH ₂ ) _m OCOCR ¹ = CH ₂ C _n F _{2n + 1} (CH ₂ ) _m OCOCR ¹ = CH ₂ ClC _n F _2n (CH ₂ ) _m OCOCR ¹ = CH ₂ R ¹ ; A hydrogen atom or a methyl group, R ² ; Methyl group, ethyl group or propyl group, m; An integer of 2-6, n; It is an integer of 3-21. The method of claim 1 or 2; A monomer copolymerizable with an acrylate or methacrylate having the polyfluoroalkyl group and containing no fluorine is Lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (Meth) acrylic acid esters such as propyl (meth) acrylate, 3-chloro-2hydroxypropyl methacrylate and benzyl (meth) acrylate; (Meth) acrylamides, such as (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, and methylolated diacetone acrylamide; Other maleic acid alkyl esters, phthalic acid alkyl esters, alkylediol (meth) acrylates, vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, styrene, α-methylstyrene, β-methylstyrene, vinyl alkyl ethers, halogenated alkyl vinyls Durable non-chlorine fluorine and oil repellent agent using an alkyl isocyanate having a vinyl group comprising at least one compound of ether, vinyl alkyl ketone, cyclohexyl (meth) acrylate, maleic anhydride, butadiene, isoprene and chloroprene Manufacturing method. A durable non-chlorine fluorine and oil repellent agent using an alkyl isocyanate having a vinyl group containing a copolymer composition obtained by the method according to claim 1.