JP2005146102A - Method for producing water / oil repellent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water and oil repellent composition excellent in emulsion stability and water and oil repellency without the need for long-time emulsification using a complicated high-pressure emulsification equipment such as a high-pressure homogenizer and a microfluidizer, and a method for producing the same provide.
(A) Formula:
CF ₃ CF ₂ — (CF ₂ CF ₂ ) _n —R ² —OCOR ¹ C═CH ₂
[Wherein, R ¹ is a hydrogen atom, a methyl group or a halogen group, R ² is a linear or branched alkylene group having 1 to 10 carbon atoms, and the average of n is 0 to 3.4. is there. ]
And (B) a monomer copolymerizable with the fluorine-containing monomer in an aqueous medium in the presence of a co-solvent that is a heterocyclic compound or a nitrogen compound. A production method comprising obtaining a fluorine-containing polymer by polymerizing the fluorine-containing monomer (A) and the copolymerizable monomer (B) after emulsifying and dispersing using the polymer.
[Selection figure] None

Description

  The present invention relates to a water-dispersed water- and oil-repellent composition having good emulsion stability and high water- and oil-repellency by only using a light emulsification dispersion method such as a homomixer or an ultramixer.

  It is known that a polymer of a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group is useful as a water / oil repellent agent for a textile fabric. In particular, the polymer is used as an emulsifier. Thus, aqueous dispersions dispersed in an aqueous medium are widely used industrially. In general, when only water is used as a dispersion medium in emulsion polymerization, the emulsion stability is very poor. Therefore, an organic solvent such as acetone has been used to improve the compatibility.

  However, due to the danger of ignition and explosion, in recent years dipropylene glycol monomethyl ether (DPM) and tripropylene glycol (TPG), which are high boiling solvents, have been used to make them non-hazardous (for example, WO00 / 37583). However, since a high boiling point solvent such as TPG is difficult to dissolve monomers, particularly fluorine-containing monomers, a complicated high-pressure emulsification equipment such as a high-pressure homogenizer or a microfluidizer is used for a long time before polymerization. It was necessary to emulsify.

  Japanese Patent Laid-Open No. 5-345810 proposes a method of polymerizing in an aqueous medium in the presence of N-alkylpyrrolidone, but it is not an industrial production method. That is, in JP-A-5-345810, a (meth) acrylic acid ester having a fluoroalkyl group and a (meth) acrylic acid alkyl ester having no fluoroalkyl group are dissolved in N-methylpyrrolidone, and then a surfactant is added. A dispersion is prepared by adding to the prepared aqueous medium and stirring. Since the emulsification is insufficient by simply stirring the monomer mixture, N-methylpyrrolidone, surfactant, and water after mixing, a complicated manufacturing process is required. Referring to the examples of JP-A-5-345810, a method of dropping an emulsified dispersion of monomers into water simultaneously with a separately prepared aqueous initiator is used, requiring a complicated manufacturing process. doing.

  The present invention is a water / oil repellent composition excellent in emulsion stability and water / oil repellency without the need for long-term emulsification using a complicated high-pressure emulsifier such as a high-pressure homogenizer or a microfluidizer, and a method for producing the same The purpose is to provide.

The present invention is a method for producing a water / oil repellent composition, which is an aqueous polymer emulsion comprising a fluoropolymer and an aqueous medium,
(A) Formula:
CF ₃ CF ₂ — (CF ₂ CF ₂ ) _n —R ² —OCOR ¹ C═CH ₂
[Wherein, R ¹ is a hydrogen atom, a methyl group or a halogen group, R ² is a linear or branched alkylene group having 1 to 10 carbon atoms, and the average of n is 0 to 3.4. is there. ]
And (B) a monomer copolymerizable with the fluorine-containing monomer in an aqueous medium in the presence of a co-solvent that is a heterocyclic compound or a nitrogen compound. The present invention relates to a production method comprising obtaining a fluorine-containing polymer by polymerizing the fluorine-containing monomer (A) and the copolymerizable monomer (B) after being emulsified and dispersed using.

  According to the present invention, a water / oil repellent composition having excellent emulsion stability and water / oil repellency without the need for long-term emulsification using a complicated high-pressure emulsifier such as a high-pressure homogenizer or a microfluidizer is provided. can get.

BEST MODE FOR CARRYING OUT THE INVENTION

The production method of the present invention generally uses (1) a fluorine-containing monomer (A) and a copolymerizable monomer (B) in the presence of an auxiliary solvent (C) in an aqueous medium using an emulsifier. Emulsifying and dispersing to form an aqueous monomer emulsion, and (2) polymerizing monomers (A) and (B) in the aqueous monomer emulsion to obtain an aqueous polymer emulsion. It becomes.

The fluorine-containing monomer (A) has the formula:
CF ₃ CF ₂ — (CF ₂ CF ₂ ) _n —R ² —OCOR ¹ C═CH ₂
[Wherein, R ¹ is a hydrogen atom, a methyl group or a halogen atom, R ² is a linear or branched alkylene group having 1 to 10 carbon atoms, and the average of n is 0 to 3.4. is there. ]
It is a compound shown by these.

Examples of the halogen atom as R ¹ are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
In the linear fluoroalkyl group (Rf group) represented by CF ₃ CF ₂ — (CF ₂ CF ₂ ) _n —, the average n number is preferably 2.0 to 3.3, more preferably 3. 0-3.3. If the average number of n in the Rf group is larger than 3.4, the compatibility with the auxiliary solvent (C) is poor and the dispersibility during emulsification is lowered. When the average number of n in the Rf group is 2.0 or more, the water / oil repellency becomes higher.
The fluorine-containing compound (A) may be one kind or a mixture of two or more kinds.

The copolymerizable monomer (B) can be copolymerized with the fluorine-containing monomer (A). Examples of the copolymerizable monomer (B) are as follows.
(1) Acrylic acid and methacrylic acid and their methyl, ethyl, butyl, isobutyl, t-butyl, propyl, 2-ethylhexyl, hexyl, decyl, lauryl, stearyl, isobornyl, β-hydroxyethyl, glycidyl ester, phenyl, benzyl , 4-cyanophenyl esters, (2) vinyl esters of fatty acids such as acetic acid, propionic acid, caprylic acid, lauric acid, stearic acid, (3) styrenes such as styrene, α-methylstyrene, p-methylstyrene Compounds, (4) vinyl halides or vinylidene compounds such as vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, (5) aliphatic such as allyl heptanoate, allyl caprylate, allyl caproate Allyl esters of (6) vinyl methyl Vinyl alkyl ketones such as ruketone and vinyl ethyl ketone; (7) acrylamides such as N-methylacrylamide and N-methylolmethacrylamide; and (8) dienes such as 2,3-dichloro-1,3-butadiene and isoprene. .

The copolymerizable monomer (B) may be a non-fluorine monomer.
The amount of the copolymerizable monomer (B) may be 5 to 150 parts by weight, for example 10 to 100 parts by weight with respect to 100 parts by weight of the fluorine-containing monomer (A).

The auxiliary solvent (C) is a heterocyclic compound or a nitrogen compound. The auxiliary solvent (C) is selected as a solvent that satisfactorily dissolves the fluorine-containing monomer (A) and the copolymerizable monomer (B).
The auxiliary solvent (C) preferably has a high boiling point, and the boiling point at normal pressure may be, for example, 60 ° C. or higher, for example, 70 to 250 ° C. The cosolvent (C) is preferably a compound having at least one (particularly one) amide group [═NC (═O) —]. An example of a heterocyclic compound is N-alkylpyrrolidone. Examples of nitrogen compounds are N, N, -dimethylacetamide and N, N-dimethylformamide. The auxiliary solvent (C) is particularly preferably N-methylpyrrolidone.
The amount of the auxiliary solvent may be 5 to 150 parts by weight, for example 10 to 100 parts by weight, based on 100 parts by weight of the polymer.

  The aqueous medium may consist essentially of water.

  In the present invention, a surfactant may be used to disperse the polymer and the organic solvent (cosolvent). As the surfactant, a cationic, anionic or nonionic emulsifier is used. Here, the surfactant is desirably a cationic emulsifier, a nonionic emulsifier, or a mixture of both (the weight ratio of the cationic emulsifier to the nonionic emulsifier is not limited). .

  Cationic emulsifiers include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi (hydropoly). Oxyethylene) ammonium chloride, benzyldodecyl di (hydropolyoxyethylene) ammonium chloride, di-cured tallow alkyl dimethyl ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride are included.

Nonionic surfactants include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C12-C16) thiol, sorbitan monofatty acid (C7-C19) or alkyl (C12-C18) amine And the like.
The amount of the surfactant (C) may be 0.01 to 30 parts by weight, for example 1 to 20 parts by weight per 100 parts by weight of the polymer.

The aqueous polymer emulsion can be produced as follows.
First, the fluorine-containing monomer (A) and the copolymerizable monomer (B) are emulsified and dispersed in an aqueous medium using an emulsifier in the presence of the auxiliary solvent (C). Form a body emulsion.
The emulsifier is preferably a homomixer or an ultramixer. The obtained aqueous monomer emulsion has a particle size of 300 nm or less. This emulsification method does not require a complicated manufacturing process, and it is not necessary to use expensive and complicated emulsification equipment such as a high-pressure homogenizer or microfluidizer, so that the cost can be reduced and in addition, the emulsification time can be shortened. It is. In addition, when a mechanical emulsification method using a homomixer or an ultramixer is not used and only stirring is performed, emulsification is insufficient, and a large amount of solid matter is generated during polymerization.

Next, the monomers (A) and (B) in the aqueous monomer emulsion are polymerized to obtain an aqueous polymer emulsion.
The polymerization is preferably performed by adding a polymerization initiator (for example, a radical polymerization initiator) to the aqueous monomer emulsion. The polymerization can be performed at 30 ° C. to 100 ° C. for 5 minutes to 30 hours, for example. The particle diameter of the obtained aqueous polymer emulsion can be made 100 nm or less.

The substrate to which the aqueous polymer emulsion is applied is a fiber product or a solid sheet. The substrate is preferably a sheet-like material such as a cloth. Examples of fiber products include fibers themselves, yarns made of fibers, and fabrics made of fibers. A solid sheet is a sheet having no voids unlike a cloth made of fibers.
Substrates may be films, fibers, yarns, woven fabrics, carpets and sheets made of filaments, fibers or yarns obtained from natural polymeric materials, modified natural polymeric materials or synthetic polymeric materials.

  In order to apply the dispersion liquid of the present invention to a substrate, it is desirable to apply by coating, dipping, spraying, padding, roll coating or a combination of these methods. For example, it is used as a pad bath by setting the solid content of the bath to 0.1 to 10% by weight. The substrate is padded with this bath and then the excess liquid is removed with a regular squeeze roll so that the dry absorption (weight of dry polymer on the substrate) is about 0.01 to 1% by weight of the substrate. The treated substrate is then preferably heated to 100-200 ° C.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The characteristics were measured as follows.
The particle size of the emulsion after emulsification and polymerization was measured using a concentrated particle size analyzer (FPAR-1000) manufactured by Otsuka Electronics.
The turbidity of the emulsion after polymerization was measured using an integrating sphere turbidimeter SEP-PT-706D manufactured by Mitsubishi Chemical.
The amount of solid matter (coagulate) generated during the polymerization was filtered through 400 mesh and the weight of the residue on the mesh was measured.

A treatment liquid is prepared by diluting the water / oil repellent polymer dispersion with water so that the solid concentration is 1% by weight. A polyester cloth is dipped in a treatment solution, wrung with a mangle, made a wet pickup 65%, dried at 100 ° C. for 2 minutes, and heat treated at 160 ° C. for 1 minute, and then the water and oil repellency of the treated cloth is evaluated.
The water repellency was measured according to the water repellent No. JIS-L-1092 spray method. (See Table 1 below).
The oil repellency is the highest point of oil repellency given by the test solution shown in Table 2 below by AATCC-TM118. Is made oil-repellent.

Water and oil repellent washing durability
Washing is repeated 3 times according to JIS L-0217-103, and the subsequent water and oil repellency is evaluated (HL-3).

A storage-stable aqueous dispersion (solid content 30% by weight) is stored at 40 ° C. for 1 month, and the occurrence of sedimentation is observed.
○: No sedimentation △: Slight sedimentation ×: Many sedimentation

Example 1
_CF 3 _CF 2 to 500cc flask _- (mixture of n = 2, 3, 4, 5 compound (average 3.15 _{n)) (CF 2 CF 2} ) n -CH 2 CH 2 OCOCH = CH 2 60g, stearyl Acrylate 40 g, N-methylolacrylamide 1 g, 3-chloro-2-hydroxypropyl methacrylate 0.6 g, pure water 120 g, N-methylpyrrolidone 50 g, ethylene glycol 10 g, acetic acid 0.3 g, octadecyltrimethylammonium chloride 4 g, polyoxyethylene 10 g of polyoxypropylene cetyl ether was added and emulsified with a homomixer at 55 ° C. for 5 minutes. After the atmosphere in the flask was replaced with nitrogen, 0.55 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer.

Example 2
_CF 3 _CF 2 to 500cc flask _- (mixture of n = 2, 3, 4, 5 compound (average 3.20 _{n)) (CF 2 CF 2} ) n -CH 2 CH 2 OCOCH = CH 2 60g, stearyl Ultra mixer And emulsified and dispersed at 55 ° C. for 5 minutes. After the atmosphere in the flask was replaced with nitrogen, 0.55 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer.

Example 3
_CF 3 _CF 2 to 500cc flask _{- (CF 2 CF 2) n} -CH 2 CH 2 OCOCH = CH 2 (n = 2.0) 60g, stearyl methacrylate 40 g, diacetone acrylamide 1.4g, pure water 120 g, N, N-dimethylformamide 55 g, acetic acid 0.3 g, and octadecyltrimethylammonium chloride 8.5 g were added and emulsified and dispersed at 55 ° C. for 5 minutes with a homomixer. After the atmosphere in the flask was replaced with nitrogen, 0.55 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer.

Example 4
In a 500 cc flask, CF ₃ CF ₂ — (CF ₂ CF ₂ ) _n —CH ₂ CH ₂ OCOCCl═CH ₂ (n = 1.0) 60 g, stearyl acrylate 20 g, 2-ethylhexyl methacrylate 20 g, N-methylol acrylamide 1 g, 3 -Chloro-2-hydroxypropyl methacrylate 0.6g, pure water 120g, N-methylpyrrolidone 50g, acetic acid 0.3g, polyoxyethylene lauryl ether 7.5g, polyoxyethylene polyoxypropylene cetyl ether 5.5g, The mixture was emulsified with an ultramixer at 55 ° C. for 5 minutes. After the atmosphere in the flask was replaced with nitrogen, 0.55 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer.

Example 5
In a 1 L autoclave, CF ₃ CF ₂ — (CF ₂ CF ₂ ) _n —CH ₂ CH ₂ OCOCH═CH ₂ (n = 3.0) 100 g, stearyl acrylate 40 g, lauryl acrylate 10 g, diacetone acrylamide 1.2 g, 3- Add 0.8 g of chloro-2-hydroxypropyl methacrylate, 160 g of pure water, 75 g of N-methylpyrrolidone, 0.3 g of acetic acid, 4 g of di-cured tallow alkyldimethylammonium chloride, 12 g of polyoxyethylene lauryl ether, and use a homomixer at 55 ° C. Emulsified and dispersed for 5 minutes. After emulsification, 1 g of n-dodecyl mercaptan was added, and 30 g of vinyl chloride was press-filled. Further, 0.75 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer.

Comparative Example 1
_CF 3 _CF 2 to 500cc flask _- (mixture of n = 2, 3, 4, 5 compound (average 3.15 _{n)) (CF 2 CF 2} ) n -CH 2 CH 2 OCOCH = CH 2 60g, stearyl Add 40 g of acrylate, 1 g of diacetone acrylamide, 0.6 g of 3-chloro-2-hydroxypropyl methacrylate, 120 g of pure water, 65 g of tripropylene glycol, 0.3 g of acetic acid, 4 g of octadecyltrimethylammonium chloride, 10 g of polyoxyethylene lauryl ether, The mixture was emulsified with a homomixer at 55 ° C. for 5 minutes. However, the average particle size after emulsification was large. After the atmosphere in the flask was replaced with nitrogen, 0.55 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. However, there was a lot of solid in the flask and the emulsion particle size and turbidity were also quite large.

Comparative Example 2
_CF 3 _CF 2 to 500cc flask _- (mixture of n = 2, 3, 4, 5 compound (average 3.15 _{n)) (CF 2 CF 2} ) n -CH 2 CH 2 OCOCH = CH 2 60g, stearyl 20 g of acrylate, 20 g of lauryl acrylate, 1.4 g of N-methylolacrylamide, 120 g of pure water, 65 g of N-methylpyrrolidone, 0.3 g of acetic acid, 4 g of octadecyltrimethylammonium chloride, 10 g of polyoxyethylene polyoxypropylene cetyl ether, and under nitrogen Stir for 1 hour. However, emulsification did not occur, and when stirring was stopped, the solution in the flask was separated into three layers. Thereafter, 0.55 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added with stirring and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. A lot of solid matter was generated in the flask.

Comparative Example 3
_CF 3 _CF 2 to 500cc flask _{- (CF} 2 _{CF 2)} a mixture of compounds of _{n -CH 2 CH 2 OCOCH = CH} 2 (n = 2,3,4,5,6,7 ( average of n 3.5) ) 60 g, stearyl acrylate 40 g, diaceton acrylamide 1 g, 3-chloro-2-hydroxypropyl methacrylate 0.6 g, pure water 200 g, N-methylpyrrolidone 50 g, ethylene glycol 10 g, acetic acid 0.3 g, di-cured tallow alkyldimethyl 4 g of ammonium chloride and 10 g of polyoxyethylene polyoxypropylene cetyl ether were added and emulsified and dispersed at 55 ° C. for 5 minutes with an ultramixer. 0.55 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of a polymer. However, the particle size and turbidity of the obtained emulsion were slightly large.

Comparative Example 4
1L autoclave _{CF 3 CF 2 - (CF 2} CF 2) a mixture of compounds of _{n -CH 2 CH 2 OCOCH = CH} 2 (n = 2,3,4,5,6,7 ( average of n 3.5) ) 100 g, stearyl acrylate 25 g, lauryl acrylate 25 g, diaceton acrylamide 1.2 g, 3-chloro-2-hydroxypropyl methacrylate 0.8 g, pure water 200 g, N-methylpyrrolidone 70 g, acetic acid 0.3 g, di-cured beef tallow 4 g of alkyldimethylammonium chloride and 12 g of polyoxyethylene lauryl ether were added and emulsified with an ultramixer at 55 ° C. for 5 minutes. After emulsification, 1 g of n-dodecyl mercaptan was added, and 30 g of vinyl chloride was press-filled. Further, 0.75 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. However, the particle size and turbidity of the obtained emulsion were slightly large.

Claims (8)

A method for producing a water / oil repellent composition, which is an aqueous polymer emulsion comprising a fluoropolymer and an aqueous medium,
(A) Formula:
CF ₃ CF ₂ — (CF ₂ CF ₂ ) _n —R ² —OCOR ¹ C═CH ₂
[Wherein, R ¹ is a hydrogen atom, a methyl group or a halogen group, R ² is a linear or branched alkylene group having 1 to 10 carbon atoms, and the average of n is 0 to 3.4. is there. ]
And (B) a monomer copolymerizable with the fluorine-containing monomer in an aqueous medium in the presence of a co-solvent that is a heterocyclic compound or a nitrogen compound. A production method comprising obtaining a fluorine-containing polymer by polymerizing the fluorine-containing monomer (A) and the copolymerizable monomer (B) after emulsifying and dispersing using the polymer.   The production method according to claim 1, wherein the average of n in the fluoropolymer (A) is 2.0 to 3.3.   The production method according to claim 1 or 2, wherein the auxiliary solvent (C) is a compound having at least one amide group.   The production method according to claim 3, wherein the auxiliary solvent (C) is N-alkylpyrrolidone, N, N-dimethylacetamide or N, N-dimethylformamide.   The process according to claim 4, wherein the auxiliary solvent (C) is N-methylpyrrolidone.   The manufacturing method according to claim 1, wherein the particle size of the aqueous polymer emulsion is 100 nm or less. (1) A fluorine-containing monomer (A) and a copolymerizable monomer (B) are emulsified and dispersed in an aqueous medium using an emulsifier in the presence of an auxiliary solvent (C). The method according to claim 1, comprising a step of forming a body emulsion, and (2) a step of polymerizing the monomers (A) and (B) in the aqueous monomer emulsion to obtain an aqueous polymer emulsion. Production method. The method according to any one of claims 1 to 7, wherein the emulsifier is a homomixer or an ultramixer.