JP2001270907A - Method for preparing copolymer composition, and water and oil repellent agent therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copolymer composition which can prevent a metal part from rusting, has an excellent water and oil repellent performance, and is useful as a water and oil repellent agent: and a method for preparing the composition. SOLUTION: The method for preparing the composition comprises the emulsion polymerization of a monomer having a fluoroalkyl group with a monomer which can copolymerize in the presence of a compound represented by formula (1) (Wherein R1 is a 8-22C alkyl or alkenyl group, R2 and R3 are independently 1-12C alkyl groups, R4 is a 2-4C alkylene group, m is an integer of 1-5, n is an integer of 1 or 2, and Xn- is an alkyl phosphate ion).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a copolymer composition and a water / oil repellent comprising the copolymer composition obtained by this method.

[0002]

2. Description of the Related Art Conventionally, as a water and oil repellent, a copolymer obtained by emulsion polymerization of a monomer having a fluoroalkyl group and a monomer copolymerizable with the monomer having the fluoroalkyl group has been known. A polymer in which water is dispersed is used. In order to obtain this copolymer, it is known that a cationic surfactant represented by stearyltrimethylammonium chloride is used as a part of an emulsifier (JP-B-55-71779). However, the copolymer composition obtained by using such trimethylammonium chloride salts as an emulsifier has low water / oil repellency, so that a product having high water / oil repellency even at the initial stage and after repeated washing is obtained. In this method, a high-concentration water- and oil-repellent must be applied to an object to be treated, which is problematic in terms of economic efficiency.
In addition, due to the effect of chloride ions contained in the cationic surfactant used as an emulsifier, during processing, there is also a problem that rust is generated on fiber processing devices such as dryers and pin tenters and other metal devices. .

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to a copolymer useful as a water-dispersed water / oil repellent, which exhibits excellent water / oil repellency without causing rust on a metal portion of a fiber processing apparatus or the like. It is an object of the present invention to provide a method for producing a composition and a water / oil repellent using such a copolymer composition.

[0004]

That is, the present invention provides a monomer having a fluoroalkyl group and a monomer copolymerizable with the monomer having the fluoroalkyl group, represented by the following general formula [1] ]

[0005]

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(In the above formula, R ¹ represents an alkyl or alkenyl group having 8 to 22 carbon atoms, R ² and R ³ each independently represent an alkyl group having 1 to 12 carbon atoms, and R ⁴ represents 2 carbon atoms. Represents an alkylene group of 1 to 4, m is an integer of 1 to 5, n is an integer of 1 or 2, and X ^n- represents an alkyl phosphate ion) in the presence of a compound represented by the following formula:
Provided is a method for producing a copolymer composition, which comprises emulsion polymerization.

[0007] The present invention also provides a water / oil repellent comprising the copolymer composition obtained by the above method.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION
There is no particular limitation on the monomer having an oloalkyl group.
However, for example, a vinyl-based unit having a fluoroalkyl group
Monomers, acrylates or methacrylates.
Having 3 to 21 carbon atoms
Are preferable, and those having 6 to 12 carbon atoms are more preferable,
The fluoroalkyl group is a perfluoroalkyl group;
Is particularly preferred. In addition, these fluoroalkyl groups
Acrylate or methacrylate among the monomers having
Rates are more preferred. Such monomers include:
For example, the following compounds may be mentioned. 1. CF_Three(CF_Two)_FourCH_TwoOCOCH = CH_Two 2. CF_Three(CF_Two)_FourCH_TwoOCOC (CH_Three) = C
H_Two 3. CF_Three(CF_Two)₇(CH_Two)_TwoOCOCH = CH
_Two 4. CF_Three(CF_Two)₇(CH_Two)_TwoOCOC (C
H_Three) = CH_Two 5. CF_Three(CF_Two)₇(CH_Two)_FourOCOCH = CH
_Two 6. CF_Three(CF_Two)₉(CH_Two)_TwoOCOCH = CH
_Two 7. CF_Three(CF_Two)₉(CH2)_TwoOCOC (C
H_Three) = CH_Two 8. (CF_Three)_TwoCF (CF_Two)_Four(CH_Two)_TwoOCO
CH = CH_Two 9. (CF_Three)_TwoCF (CF_Two)_Four(CH_Two)_TwoOCO
C (CH_Three) = CH_Two 10. CF_Three(CF_Two)₇SO_TwoN (C_ThreeH₇) (CH
_Two)_TwoOCOCH = CH _Two 11. CF_Three(CF_Two)₇SO_TwoN (CH_Three) (C
H_Two)_TwoOCOC (CH_Three) = CH_Two 12. CF_Three(CF_Two)₇SO_TwoN (C_TwoH_Five) (CH
_Two)_TwoOCOCH = CH _Two 13. CF_Three(CF_Two)₇CONH (CH_Two)_TwoOCO
CH = CH_Two 14． CF_Three(CF_Two)₉CONH (CH_Two)_TwoOCO
C (CH_Three) = CH_Two 15. (CF_Three)_TwoCF (CF_Two)₆(CH_Two)_ThreeOC
OCH = CH_Two 16. (CF_Three)_TwoCF (CF_Two)₆CH_TwoCH (OC
OCH_Three) OCOC (CH_Three) = CH_Two 17． (CF_Three)_TwoCF (CF_Two)₆CH_TwoCH (O
H) CH_TwoOCOC (CH _Three) = CH_Two 18. (CFCl) (CF_Three) CF (CF_Two)₇CON
H (CH_Two)_TwoOCOCH = CH_Two 19. H (CF_Two)_TenCH_TwoOCOCH = CH_Two 20. (CF_TwoCl) (CF_Two)_TenCH_TwoOCOC (C
H_Three) = CH_Two 21. (CF_TwoCl) (CF_Three) CF (CF_Two)₇(C
H_Two)_TwoOCOCH = CH_Two 22. CF_Three(CF_Two)_FourCH = CH_Two 23. CF_Three(CF_Two)₇(CH_Two)_Two= CH_Two 24. (CF_Three)_TwoCF (CF_Two)_Four(CH_Two)_TwoCH
= CH_Two Having a fluoroalkyl group used in the present invention
There are no particular restrictions on monomers that can be copolymerized with the
Lauryl (meth) acrylate, stearyl (meth)
TA) acrylate, glycidyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, 2-hydro
Xyethyl (meth) acrylate, 3-chloro-2-hi
Droxypropyl (meth) acrylate, benzyl (meth
(T) Alkyl (meth) acrylates such as acrylate
Ter, ethylene di (meth) acrylate, 1,6-hex
Alkylene geos such as samethylene di (meth) acrylate
Luzi (meth) acrylate, (meth) acrylamide
, N-methylol (meth) acrylamide, diacetate
(Meth) acrylamide such as (meth) acrylamide
, Maleic acid alkyls such as dibutyl maleate
Alkyl fumarate such as ter and dibutyl fumarate
Ter, ethylene, butadiene, isoprene, vinyl chloride
, Vinylidene chloride, vinyl acetate, styrene, vinyl alcohol
Alkyl ether, halogenated vinyl alkyl ether
Any vinyl monomer is mentioned. Here, the above (
T) Acrylate is acrylate and methacrylate
(Meth) acrylic acid means acrylic acid and meth
(Meth) acrylamide is acrylic acid
Represents amide and methacrylamide.

The method for producing the copolymer composition of the present invention comprises the steps of at least one kind selected from monomers having a fluoroalkyl group and a monomer having the fluoroalkyl group as exemplified above. This is a method of obtaining a copolymer composition by subjecting at least one selected from copolymerizable monomers to emulsion polymerization in water in the presence of a compound represented by the general formula [1].

In the general formula [1], R ¹ has a carbon number of 8 to
22 alkyl or alkenyl groups, which may be linear or branched, for example, 2-ethylhexyl, octyl, lauryl, myristyl, palmityl, stearyl, eicosyl Group, behenyl group, oleyl group, elaidyl group and the like. R ¹ is particularly preferably an alkyl or alkenyl group having 12 to 18 carbon atoms.

In the general formula [1], R ² and R ³ are an alkyl group having 1 to 12 carbon atoms.
It may be branched, and may be the same or different from each other. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-
Butyl, tert-butyl, amyl, octyl, lauryl and the like. It is particularly preferred that R ² and R ³ are methyl groups.

In the general formula [1], R ⁴ has 2 to 2 carbon atoms.
And 4, for example, an ethylene group, a propylene group, a butylene group and the like, and an ethylene group is particularly preferred. In the general formula [1], m is an integer of 1 to 5. In the general formula [1], X ^n- is the following general formula [2]
Or an alkyl phosphate ion represented by [3], wherein n is 1 or 2.

[0013]

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[0014]

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In the general formulas [2] and [3], R ⁵ and R ⁶ are an alkyl group having 1 to 12 carbon atoms and may be linear or branched. , Methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, lauryl and the like, among which alkyl groups having 4 to 8 carbon atoms are particularly preferred. In the general formula [2], R ⁵ and R ⁶ may be the same as or different from each other.

The compound represented by the general formula [1] can be obtained by a conventionally known method.
As described in JP-A-9102, it can be obtained by adding an alkylene oxide to a tertiary amine in the presence of an alkyl phosphate ion. Here, the alkyl phosphate ion can be obtained, for example, by reacting an alcohol having 1 to 12 carbon atoms with phosphoric anhydride. Examples of the alcohol having 1 to 12 carbon atoms include methanol, ethanol, butyl alcohol, pentyl alcohol, octyl alcohol, lauryl alcohol and isomers thereof, and alcohols having 4 to 8 carbon atoms are particularly preferable.

The tertiary amine used in the production of the compound represented by the general formula [1] is not particularly limited, but is octyldimethylamine, octyldiethylamine, octylmethylethylamine, decyldimethylamine. , Lauryldimethylamine, lauryldiethylamine, laurylmethylethylamine, myristyldimethylamine, stearyldimethylamine, behenyldimethylamine, oleyldimethylamine, oleyldiethylamine, tri-n-octylamine, N-methyl-di-n
-Octylamine, N, N-dimethyl-2-ethylhexylamine, N, N-dibutyl-2-ethylhexylamine and the like. Further, as the alkylene oxide, ethylene oxide, propylene oxide,
Butylene oxide and the like.

In the process for producing a copolymer composition of the present invention, the compound represented by the general formula [1] is used in an amount of 100 parts by weight of the total monomer used in the emulsion polymerization. It is preferable to use 10 parts by weight. further,
In the emulsion polymerization, in addition to the compound represented by the general formula [1], a cationic surfactant such as a stearyltrimethylammonium chloride compound which has been conventionally used as an emulsifier, and the addition of an alkylene oxide to a higher alcohol or an alkylphenol. , And nonionic surfactants such as polyoxyethylene sorbitan alkyl esters.

In the monomer composition of the raw material used in the production method of the present invention, the ratio of the monomer having a fluoroalkyl group is at least 30 parts by weight based on 100 parts by weight of all monomers. And more preferably 40 to 80 parts by weight. Further, the proportion of the monomer copolymerizable with the monomer having a fluoroalkyl group is preferably 70 parts by weight or less based on 100 parts by weight of all monomers, and is preferably 60 parts by weight or less.
More preferably, it is 20 parts by weight.

The method of emulsion polymerization may be a conventionally known method. For example, a mixture of a monomer used for emulsion polymerization, an emulsifier, a solvent and the like are mixed, and water is gradually added to emulsify. A method of emulsion polymerization by further adding a polymerization initiator, a mixture of monomers used for emulsion polymerization,
A method in which an emulsifier, a solvent, and the like are mixed, and a solution obtained by gradually adding water and emulsifying the mixture is dropped into an aqueous solution of a polymerization initiator. The polymerization initiator used is not particularly limited, and for example, an organic peroxide, an azo compound, a persulfate, or the like can be used as the polymerization initiator. further,
In the emulsion polymerization, alcohols such as 3-methoxy-3-butylbutanol, ketones such as acetone, ethers such as diethylene glycol monomethyl ether and dipropylene glycol monomethyl ether are emulsified to improve the emulsification state. May be used as an agent, or an alkyl mercaptan such as n-dodecyl mercaptan may be used as a chain transfer agent.

The copolymer composition obtained by the method of the present invention can be advantageously used as a water-dispersed water / oil repellent, and therefore the present invention also provides an excellent water / oil repellent. The object to be treated with the water / oil repellent of the present invention is not particularly limited, and various objects are used. For example, textiles, glass, paper, wood, leather, fur, plastic, painted surfaces, plaster and the like can be mentioned. Textile products include natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polyethylene, and polyurethane; semi-synthetic fibers such as rayon, acetate, and triacetate; Glass fiber,
Examples include inorganic fibers such as carbon fibers and asbestos fibers, and composite fibers composed of two or more of these fibers. In addition, the form of the fiber product, fiber,
Any form such as a thread, a woven fabric, a knitted fabric, or a non-woven fabric may be used.

The water- and oil-repellent agent of the present invention can be applied to an object to be treated by any method appropriately selected according to the type of the object to be treated. For example, a method in which a water / oil repellent is attached to the surface of the object to be treated by a coating method, a spray method, a padding method, an immersion method, or the like, followed by drying can be employed. In the case of the padding method, the object to be treated is generally immersed in a treatment solution adjusted to an appropriate concentration, squeezed with a mangle, then dried and then heat-treated. Using a dyeing machine such as a dyeing machine or a liquid jet dyeing machine, the object to be treated is immersed in a treatment bath adjusted to an appropriate concentration at a temperature of about 30 to 60 ° C., dehydrated, then dried, and then heat-treated. It is common to do.

The water- and oil-repellent agent of the present invention, when the object to be treated is a fiber product, paper, leather, fur or the like, uses the copolymer as a pure component in an amount of 0.3 to 1. Preferably, it is applied in an amount of 5% by weight. The water- and oil-repellency of the object treated with the water- and oil-repellent agent of the present invention is excellent not only in the initial stage, but also after repeated washing, and thus also exhibits excellent washing durability. By using a cross-linking agent such as methylolmelamine or blocked isocyanate in combination, more excellent washing durability can be obtained. Here, as the blocked isocyanate, an isocyanate group terminal of a diisocyanate compound represented by 2,4- or 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, or the like, may be an alcohol, an amine, Stabilized by ketones and the like.

Further, the water and oil repellent of the present invention may be used in combination with other conventional water or oil repellents, if necessary, and may also be used as an insect repellent, a flame retardant, and an antistatic agent. Other processing agents such as a dye stabilizer, an anti-wrinkle agent and the like may be used in combination.

[0025]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 (Emulsifier A) 3 mol of n-butanol was charged into a reaction vessel, and 1 mol of phosphoric anhydride was gradually added at 80 ° C. or lower under a nitrogen stream while stirring. The reaction was carried out for 3 hours, and then neutralized with an aqueous solution of potassium hydroxide.
One mixture was obtained. 143 g of this mixture and 500 g of water
Was charged into a test autoclave (manufactured by Pressure Glass Corporation), neutralized by adding 260 g of lauryl dimethylamine, and then 100 g of ethylene oxide under a nitrogen atmosphere.
And reacted at 100 ° C. for 3 hours to obtain an emulsifier A.

Synthesis Example 2 (Emulsifier B) 3 mol of n-butanol was charged into a reaction vessel, and 1 mol of phosphoric anhydride was gradually added at 80 ° C. or less under a nitrogen stream while stirring. The reaction was carried out at 80 ° C. for 3 hours, and then neutralized with an aqueous potassium hydroxide solution.
One mixture was obtained. 143 g of this mixture and 600 g of water
Was charged in a test autoclave (manufactured by Pressure Glass Corporation), neutralized by adding 362 g of stearyl dimethylamine, and then ethylene oxide 100 was added under a nitrogen atmosphere.
g was charged and reacted at 100 ° C. for 3 hours to obtain an emulsifier B.

Synthesis Example 3 (Emulsifier C) 3 mol of 2-ethylhexanol was charged into a reaction vessel, and 1 mol of phosphoric anhydride was gradually added at a temperature of 80 ° C. or less under a nitrogen stream while stirring, and the addition was completed. Thereafter, the mixture was reacted at 80 ° C. for 3 hours, and then neutralized with an aqueous solution of potassium hydroxide to obtain a mixture of mono (2-ethylhexyl) phosphate and di (2-ethylhexyl) phosphate at a ratio of about 1: 1. . 143 g of this mixture and 388 g of water were charged into a test autoclave (manufactured by Pressure Glass Corporation), neutralized by adding 177 g of lauryl dimethylamine, and reacted at 100 ° C. for 3 hours under a nitrogen atmosphere to obtain an emulsifier. C was obtained.

Example 1 CH was placed in a four-necked flask equipped with a condenser._Two= CH
COOC_TwoH_FourC₈F ₁₇17g, stearyl acrylate
12 g, glycidyl methacrylate 1 g, 3-methoxy
10 g of c-3-methylbutanol, n-dodecylmerca
0.1 g of butane, ethylene oxide of stearyl alcohol
3 g of 20 mol side adduct, emulsifier obtained in Synthesis Example 1
A1 g and 55.6 g of water were charged, and an ultrasonic homogenizer was used.
-Using US-600T (Nippon Seiki Seisakusho)
And emulsified. Then, azobisisobut is used as a polymerization initiator.
0.3 g of tilamidine hydrochloride was added, and 4
The polymerization reaction was performed for a period of time to obtain a copolymer composition.

Examples 2 and 3 As an emulsifier, emulsifier B obtained in Synthesis Example 2 or emulsifier C obtained in Synthesis Example 3 was used instead of emulsifier A obtained in Synthesis Example 1. In the same manner as in Example 1,
The copolymer compositions of Examples 2 and 3, respectively, were obtained. Example 4 In an autoclave, CH ₂ ＣＨCHCOOC ₂ H ₄ C ₈ F
₁₇ 20 g, stearyl acrylate 3 g, 3-methoxy-3-methylbutanol 10 g, n-dodecyl mercaptan 0.1 g, ethylene oxide 20 mol adduct of stearyl alcohol 3 g, emulsifier A obtained in Synthesis Example 1
1 g and 42.4 g of water were charged and emulsified using an ultrasonic homogenizer US-600T (manufactured by Nippon Seiki Seisakusho). Thereafter, 0.3 parts g of azobisisobutylamidine hydrochloride was added as a polymerization initiator, 5 g of vinyl chloride was further added, and a polymerization reaction was carried out at 60 ° C. for 6 hours to obtain a copolymer composition.

Comparative Example 1 CH was placed in a four-necked flask equipped with a condenser._Two= CH
COOC_TwoH_FourC₈F ₁₇20g, stearyl acrylate
12 g, glycidyl methacrylate 1 g, 3-methoxy
10 g of c-3-methylbutanol, n-dodecylmerca
0.1 g of butane, ethylene oxide of stearyl alcohol
3 g of side 20 mol adduct, stearyl chloride as emulsifier
1 g of rutrimethylammonium compound and 55.6 g of water
And an ultrasonic homogenizer US-600T
(Nippon Seiki Seisakusho) was used to emulsify. That
After that, azobisisobutylamidine hydrochloride as a polymerization initiator
0.3 g of salt was added and polymerization reaction was carried out at 50 ° C. for 4 hours.
Thus, a copolymer composition was obtained.

The copolymer compositions obtained in Examples 1 to 4 and Comparative Example 1 were obtained by gas chromatography (GC-15APT).
F, manufactured by Shimadzu Corporation), it was confirmed that 98% or more of all the monomers used in the emulsion polymerization were polymerized. Evaluation of the copolymer compositions obtained in Examples 1 to 4 and Comparative Example 1 was performed as follows.

Sample cloth for evaluating water and oil repellency Cotton broad cloth was immersed in a 2% by weight aqueous solution of the copolymer composition of Examples 1 to 4 or Comparative Example 1 (pickup 50).
%), Dried at 120 ° C. for 1 minute, and further dried at 160 ° C.
For 1 minute to evaluate the water / oil repellency. The sample cloth obtained by the above treatment was washed in a 2 g / L aqueous solution of a detergent (Attack, Kao Corporation) at a temperature of 40 ° C. for 50 minutes, rinsed under running water for 15 minutes, dehydrated, and air-dried. . The laundry thus obtained was similarly subjected to the evaluation of water / oil repellency.

Water repellency Water repellency was evaluated according to the spray method of JIS L 1092. As a criterion, a 6-point evaluation of 5 to 0 as shown in Table 1 was used. Table 3 shows the results.

[0034]

[Table 1]

Oil repellency A few drops (approximately 5 μm in diameter) of the test solution shown in Table 2 were applied to two places on the sample cloth.
mm) and determined by the permeation state after 30 seconds (AA)
TCC-TM118-1966 method). Table 3 shows the results.

[0036]

[Table 2]

Nujol in Table 2 is liquid paraffin. Rust-preventive properties A pharmacopoeial gauze was immersed in a 5% by weight aqueous solution of the copolymer composition obtained in Examples 1 to 4 or Comparative Example 1, and 10 insect pins which had been washed with acetone beforehand were placed on the pharmacological gauze. And put 4
After standing at 0 ° C. for 48 hours, the number of insect pins for which rust was observed was determined. The results are also shown in Table 3.

[0038]

[Table 3]

[0039]

According to the present invention, a novel copolymer composition can be obtained. This composition has low corrosiveness to metals such as generation of rust, shows sufficient water / oil repellency, It is useful as a dispersion type water / oil repellent.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Koji Midori, Inventor 4- 23-1, Bunkyo, Fukui-shi, Fukui Prefecture F-term in Nichika Chemical Co., Ltd. 4H020 BA00 BA13 BA14 BA15 4J011 AA05 KA03 KA07 KA28 KB29 4J100 AA02Q AB02Q AC03Q AC04Q AC21P AE02Q AG04Q AL04Q AL05Q AL08P AL09Q AL10Q AL34Q AL62Q AM15Q AM21Q AS02Q AS03Q BA03P BA03Q BA14Q BA15P BA34P BA59P BB01P BB01Q BB12P BB13P BB18P BC43CA04

Claims (2)

[Claims] 1. A monomer having a fluoroalkyl group,
The monomer having a fluoroalkyl group and the copolymerizable monomer are represented by the following general formula [1]: (In the above formula, R ¹ represents an alkyl or alkenyl group having 8 to 22 carbon atoms, and R ² and R ³ each independently have 1 carbon atom.
Represents an alkyl group having from 12 to 12, R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms, m is an integer of 1 to 5, n is an integer of 1 or 2, and X ^n- is an alkyl phosphate ester (Representing ions) in the presence of a compound represented by the following formula: 2. A water / oil repellent comprising the copolymer composition obtained by the method according to claim 1.