JP2021070763A - Repellent agent with low content of fluorine-containing alcohol - Google Patents

Abstract

To provide a repellent agent that confers to a base material excellent oil- and/or water-repellency, particularly, excellent water resistance.SOLUTION: There is provided a repellent agent in which a content of a fluorine-containing alcohol is 2000 ppm or less relative to weight of an active ingredient of the repellent agent. Preferably the active ingredient is a fluorine-containing polymer compound, and the fluorine-containing alcohol is alcohol having a C6 fluoroalkyl group. Preferably, the fluorine-containing polymer compound being the active ingredient of the repellent agent has a fluoroalkyl group and is an acrylic polymer or an urethane polymer.SELECTED DRAWING: None

Description

The present disclosure relates to repellents having a low content of fluorinated alcohol.

Conventionally, it has been known that a fluorine-containing polymer compound can impart excellent water repellency and / or oil repellency (water and oil resistance) to a base material, for example, cloth or paper.
As the fluorine-containing polymer compound, for example, a polymer obtained by polymerizing a fluorine-containing (meth) acrylate monomer is known. The fluorine-containing (meth) acrylate monomer is produced by a method of reacting a polyfluoroalkyl alcohol having a perfluoroalkyl group with (meth) acrylic acid or the like.

Patent Document 1 (Japanese Unexamined Patent Publication No. 2001-342152) discloses a scavenger composed of a cyclic phenol sulfide sulfonic acid derivative that captures a water-soluble organic compound such as a water-soluble alcohol.
Patent Document 2 (Japanese Unexamined Patent Publication No. 2011-162369) describes that activated carbon is used for alcohol recovery.

Japanese Unexamined Patent Publication No. 2001-342152 Japanese Unexamined Patent Publication No. 2011-162369

The present disclosure provides an agent capable of imparting excellent oil repellency and / or excellent water repellency, particularly excellent water resistance, to a substrate.

The repellent containing the fluorine-containing polymer compound may have different oil repellency and water repellency that can be imparted. The present inventor considers that the difference (decrease) in oil repellency and water repellency is caused by the presence of impurities contained in the repellent, and by reducing the content of fluorinated alcohol, excellent oil repellency and / or We have found that excellent water repellency can be obtained.

The present disclosure relates to a repellent having a fluorine-containing alcohol content of 2000 ppm or less, particularly 1000 ppm or less, based on the weight of the active ingredient of the repellent.

The preferred embodiments of the present disclosure are as follows.
[1] A repellent having a fluorine-containing alcohol content of 2000 ppm or less based on the weight of the active ingredient of the repellent.
[2]
The repellent according to [1], wherein the active ingredient of the repellent is a fluorine-containing polymer compound.
[3]
The repellent according to [1] or 2], wherein the fluorinated alcohol is an alcohol having a fluoroalkyl group having 6 carbon atoms.
[4]
The repellent according to any one of [1] to [3], wherein the content of the fluorinated alcohol is 800 ppm or less with respect to the weight of the active ingredient of the repellent.
[5]
The repellent according to any one of [1] to [4], wherein the fluorine-containing polymer compound which is an active ingredient of the repellent has a fluoroalkyl group and is an acrylic polymer or a urethane polymer.
[6]
Fluorotelomer alcohol, formula:
CF _3- (CF ₂ ) _p- (CH ₂ ) _q- OH
[In the formula, p is a number from 0 to 19 and q is a number from 0 to 10. ]
The repellent according to any one of [1] to [5], which is a compound represented by.
[7]
Any of [1] to [6] including a step of removing at least a part of the fluorotelomer alcohol by bringing the raw material repellent into contact with the adsorbent to reduce the content of the fluorotelomer alcohol in the repellent. The method for producing the repellent according to.
[8]
The production method according to [7], wherein the adsorbent is at least one selected from activated carbon and an ion exchange resin.
[9]
A method for treating a base material, which comprises treating the base material with the repellent according to any one of [1] to [6].
[10]
The processing method according to [9], wherein the base material is paper.
[11]
A method for improving the water and oil repellency of a repellent, which comprises reducing the content of fluorinated alcohol in the repellent to an amount of 2000 ppm or less with respect to the weight of the active ingredient of the repellent.

The repellent can impart excellent oil repellency and / or excellent water repellency to the substrate. The repellent can impart excellent water resistance to the substrate, especially paper.

In the present specification, the "repellent" is a "liquid repellent". "Water repellent" means "water repellent", "water repellent oil repellent" or "water and oil resistant agent".

The repellent contains (1) a fluorine-containing polymer compound as an active ingredient and (2) a fluorine-containing alcohol as an impurity. The repellent also includes (3) a liquid medium. The repellent may contain (4) a surfactant and (5) other components.

(1) Fluorine-containing polymer compound The fluorine- containing polymer compound (or fluorine-containing polymer) is preferably an acrylic polymer having a fluoroalkyl group or a urethane polymer.

The fluoroalkyl group is preferably a perfluoroalkyl group. The fluoroalkyl group preferably has 1 to 12, for example 1 to 6, particularly 4 to 6, especially 6. Examples of fluoroalkyl groups are -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF _3). ) ₂ , -C (CF ₃ ) ₃ ,-(CF ₂ ) ₄ CF ₃ ,-(CF ₂ ) ₂ CF (CF ₃ ) ₂ , -CF ₂ C (CF ₃ ) ₃ , -CF (CF ₃ ) CF ₂ CF ₂ CF ₃ , − (CF ₂ ) ₅ CF ₃ , − (CF ₂ ) ₃ CF (CF ₃ ) ₂ , − (CF ₂ ) ₄ CF (CF ₃ ) ₂ , −C ₈ F ₁₇ etc.

(1-1) Acrylic Polymer The acrylic polymer has a repeating unit formed from a fluorine-containing acrylic monomer.
The fluorine-containing acrylic monomer has a general formula:
CH ₂ = C (−X) −C (= O) −Y−Z−Rf (I)
[In the formula, X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and CFX ¹ X ² groups (however, X ¹ and X). ² are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or non-substituted. Substituted benzyl group, substituted or unsubstituted phenyl group;
Y is -O- or -NH-;
Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, and a -CH ₂ CH ₂ N (R ¹ ) SO ₂ − group (however, R ^1). Is an alkyl group having 1 to 4 carbon atoms.),
-CH ₂ CH (OZ ¹ ) CH _2- (Ph-O) _p -group (where Z ¹ is a hydrogen atom or acetyl group, Ph is a phenylene group, p is 0 or 1),-(CH ₂₎ ) _N -Ph-O-group (where Ph is a phenylene group and n is 0-10),-(CH ₂ ) _m −SO ₂ − (CH ₂ ) _n − group or-(CH ₂ ) _m -S- (CH ₂ ) _n -group (where m is 1-10 and n is 0-10),
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
It is preferably an acrylate ester or acrylamide represented by.

The acrylic polymer may be formed only from the fluorine-containing acrylic monomer, but may also contain other monomers. The other monomer may be a non-fluorine non-crosslinkable acrylic monomer or a non-fluorine crosslinkable acrylic monomer. Specific examples of the non-fluorine non-crosslinkable acrylic monomer are alkyl acrylates (alkyl groups having 1 to 30 carbon atoms) and halogenated olefins (for example, vinyl chloride). The non-fluorinated crosslinkable acrylic monomer is a compound having at least two ethylenic carbon-carbon double bonds, or a compound having at least one ethylenic carbon-carbon double bond and at least one reactive group. Good. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.

The acrylic polymer may be a fluorine-silicon hybrid polymer having a silicon-containing group in addition to the fluoroalkyl group.
The amount of the fluorine-containing acrylic monomer may be 30 to 100% by weight, preferably 32 to 98% by weight, for example 35 to 95% by weight, particularly 40 to 90% by weight, based on the acrylic polymer.
The amount of the acrylic polymer may be 0.1 to 70% by weight, for example 1 to 30% by weight, based on the repellent.

(1-2) Urethane Polymer The urethane polymer is, for example, a polyurethane oligomer (a polymer having a low molecular weight (for example, a molecular weight of 5000 or less)). The urethane polymer can be produced by using a polyisocyanate having a fluoroalkyl group or a polyol having a fluoroalkyl group as a raw material of the urethane polymer. For example, by reacting a polyisocyanate having a fluoroalkyl group with a polyol having no fluoroalkyl group (or a polyol having a fluoroalkyl group), or by reacting a polyisocyanate having no fluoroalkyl group (or a polyisocyanate having a fluoroalkyl group). ) And a polyol having a fluoroalkyl group.

Polyisocyanates with fluoroalkyl groups have the formula:
R ¹¹ (-NCO) _m1
[In the formula, R ¹¹ is an m1 valent group having a fluoroalkyl group.
m1 is a number from 2 to 10. ]
It may be a compound represented by. R ¹¹ is preferably a hydrocarbon group having 1 to 20 carbon atoms, that is, a hydrocarbon group having a fluoroalkyl group.
Polyisocyanates without fluoroalkyl groups have the formula:
R ¹² (-NCO) _m2
[In the formula, R ¹² is an m2-valent organic group,
m2 is a number from 2 to 10. ]
It may be a compound represented by. R ¹² is preferably a hydrocarbon group having 1 to 20 carbon atoms.

Polyols having a fluoroalkyl group have the formula:
R ²¹ (-OH) _n1
[In the formula, R ²¹ is an n1 valent group having a fluoroalkyl group.
n1 is a number from 2 to 10. ]
It may be a compound represented by. R ²¹ is preferably a hydrocarbon group having 1 to 20 carbon atoms, that is, a hydrocarbon group having a fluoroalkyl group.
Polyols without a fluoroalkyl group have the formula:
R ²² (-OH) _n2
[In the formula, R ²² is an n2 valent organic group,
n2 is a number from 2 to 10. ]
It may be a compound represented by. R ²² is preferably a hydrocarbon group having 1 to 20 carbon atoms.

(2) Fluorotelomer alcohol The fluorotelomer alcohol may have a fluoroalkyl group having 1 to 20 carbon atoms.
Fluorotelomer alcohol is expressed in the formula:
CF _3- (CF ₂ ) _p- (CH ₂ ) _q- OH
[In the formula, p is a number from 0 to 19 and q is a number from 0 to 10. ]
It is preferably a compound represented by.
p may be a number from 1 to 18. q may be a number from 1 to 8.
In the fluoroalcohol-containing alcohol, the fluoroalkyl group (perfluoroalkyl group) preferably has 6 carbon atoms. Fluorotelomer alcohol is expressed in the formula:
CF _3- (CF ₂ ) _5- CH ₂ CH _2- OH
It is preferably a compound represented by.

The amount of fluorinated alcohol contained in the repellent is 2000 ppm or less, for example, 1000 ppm or less or 800 ppm or less, particularly 500 ppm or less, and particularly 100 ppm or less, based on the weight of the fluorine-containing polymer compound (active ingredient of the repellent). It's okay. The lower limit of the amount of fluorinated alcohol may be 1 ppm, for example 10 ppm.
Alternatively, the amount of fluorinated alcohol contained in the repellent may be 250 ppm or less, for example 200 ppm or less, particularly 100 ppm or less, and particularly 20 ppm or less, based on the weight of the repellent.

(3) Liquid medium The repellent includes a liquid medium. The liquid medium may be water or an organic solvent. The liquid medium is preferably an aqueous medium, i.e., water alone or a mixture of water and a (miscible) organic solvent. The amount of the organic solvent may be 0 to 30% by weight, for example 0 to 10% by weight (preferably 0.1% or more) with respect to the liquid medium. The liquid medium is preferably water alone. The liquid medium may be only an organic solvent.
The amount of the liquid medium may be 30 to 99% by weight, particularly 50 to 90% by weight, based on the repellent.

(4) Surfactant The repellent may contain a surfactant. When the liquid medium is an aqueous medium, the repellent preferably contains a surfactant.
The surfactant may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.

(5) Other components The repellent may contain additives as other components other than the above.
Examples of additives are silicon-containing compounds, waxes, acrylic emulsions and the like. Other examples of additives include other fluoropolymers, drying rate regulators, cross-linking agents, film-forming aids, defoamers, surfactants, antifreezes, viscosity regulators, UV absorbers, antioxidants. Agents, pH adjusters, defoamers, texture adjusters, slipperiness adjusters, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants and the like.

Method for Producing Repellent The fluorine-containing polymer compound can be produced by a usual method.
The acrylic polymer can be produced by any of the usual polymerization methods, and the conditions of the polymerization reaction can be arbitrarily selected. Examples of such a polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization.
The urethane polymer can be produced by reacting a polyisocyanate with a polyol.
The reaction product thus obtained may be used as a repellent (raw material repellent), or by adding additional components (for example, surfactant and additive) to the reaction product, the repellent (raw material repellent). May be obtained.

In order to reduce the content of the fluorine-containing alcohol in the repellent, the raw material repellent can be brought into contact with the adsorbent to obtain the repellent. By contacting the raw material repellent with the adsorbent, the fluorinated alcohol is at least partially removed to reduce the content of the fluorinated alcohol in the repellent.

The step of bringing the repellent into contact with the adsorbent is carried out under conditions sufficient to reduce the content of the fluorinated alcohol.

Examples of adsorbents are activated carbon and ion exchange resins.

Activated carbon can be produced from carbonaceous materials. The carbonaceous material may be any material that produces activated carbon by carbonization, activation, etc., wood, sawdust, charcoal, coconut husks, walnut husks and other fruit husks, fruit seeds and other plant-based materials, peat, sub-coal, brown coal, etc. Coal such as bituminous charcoal and smokeless coal, pitch such as petroleum pitch and coal pitch, tar such as coke, coal tar and petroleum tar, minerals such as petroleum distillation residue, natural materials such as cellulose fibers such as cotton and rayon, phenolic resin , Polyvinyl alcohol, synthetic materials such as polyacrylonitrile, and the like can be exemplified. The shape may be powdery, granular, fibrous, or molded.

Activated carbon is produced by carbonizing or activating carbonaceous materials. Carbonization is carried out, for example, by heating and carbonizing a carbonaceous material at a temperature of about 300 ° C. to 700 ° C. In addition, as the activation method, chemical activation with zinc chloride, phosphoric acid, sulfuric acid, calcium chloride, sodium hydroxide, potassium hydroxide, etc., gas activation with water vapor, carbon dioxide gas, oxygen gas, combustion exhaust gas, mixed gas of these, etc. are adopted. Will be done.

The size of activated carbon is generally 0.5-5.0 mm. Activation can increase the specific surface area of activated carbon. The specific surface area of the activated carbon is 500 meters ² / g or more, may be, for example 500~3000m ² / g.

Generally, the fluorinated alcohol can be adsorbed in a sufficient amount by activated carbon that has not been activated or activated carbon having a low specific surface area.

The amount of activated carbon used is preferably 1 to 50 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the repellent.

The step of bringing the repellent into contact with the activated carbon is preferably performed at 0 to 60 ° C, more preferably 0 to 40 ° C (for example, 10 to 30 ° C).

In the step of bringing the repellent into contact with the activated carbon, the contact means may be any contact means that can be appropriately selected according to the amount and concentration of the repellent. A repellent may be passed through a tower or column filled with activated carbon, and commonly used mixing, stirring, and shaking means can also be used.

As the above-mentioned contact means, a means for passing a repellent through a tower or a column filled with activated carbon is more preferable. In this case, it is preferable to use activated carbon having granular or spherical particles. The linear velocity at the time of passing the liquid is preferably 0.05 to 10 m / h, and more preferably 0.05 to 5 m / h.
When the repellent is passed through a tower or column filled with activated carbon, the repellent and the activated carbon come into contact with each other by pouring the repellent into the column or column filled with activated carbon, that is, with the contact mixed phase. Become. Then, the repellent flows out, so that the contact mixed layer is separated into a solid phase and a liquid phase. That is, the step of bringing the repellent and the activated carbon into contact and the step of separating the repellent and the activated carbon are performed at the same time.

When mixing, stirring, and shaking are performed as the above-mentioned contact means, the fluorinated alcohol in the repellent is at least partially removed by separating the obtained contact-mixed phase into a solid phase and a liquid phase. It will be. As the separation means, any separation means that can be appropriately selected according to the amount and concentration of the repellent can be used. Specific examples of the separation means include filtration using various filters, supernatant sampling, decantation, centrifugation, and separation means using a solid-liquid separation device (for example, a laval separator).

When powdered activated carbon is used, it is preferable to mix, stir, and shake as the contact means.

Examples of ion exchange resins include strongly basic anion exchange resins and weakly basic anion exchange resins as organic type anion exchangers. The strong basic anion exchange resin is a polyethylene or polystyrene main chain to which a quaternary amine is added as a functional group. Further, as the weak basic anion exchange resin, a secondary amine or a tertiary amine is added as a functional group to the polyethylene or polystyrene main chain.

The raw material repellent can be brought into contact with the adsorbent to reduce the content of the fluorinated alcohol to 2000 ppm or less or 1000 ppm or less.

The content of fluorine-containing carboxylic acid (for example, perfluorocaproic acid) in the raw material repellent can also be reduced. The content of the fluorine-containing carboxylic acid is preferably 1 ppm or less with respect to the repellent. Alternatively, the content of the fluorine-containing carboxylic acid is preferably 5 ppm or less with respect to the fluorine-containing polymer compound.

The objects to be treated with the repellent include textiles, stones, filters (eg electrostatic filters), dust masks, fuel cell parts (eg gas diffusion electrodes and gas diffusion supports), glass, paper, etc. Examples include wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, coated surfaces, and plasters. Various examples can be given as textile products. For example, animal and vegetable natural fibers 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, glass fibers and carbon fibers. , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.

The textile product may be in any form such as fiber or cloth.

Fluorine-containing polymeric compounds can be applied to fibrous substrates (eg, textiles) by any of the methods known for treating textiles with liquids. When the textile is a cloth, the cloth may be dipped in the solution, or the solution may be attached or sprayed onto the cloth. The treated textile product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.

Alternatively, the fluorine-containing polymer compound may be applied to textile products by a cleaning method, and may be applied to textile products by, for example, a washing application or a dry cleaning method.

The textile products to be processed are typically fabrics, which include textiles, knitted and non-woven fabrics, fabrics and carpets in the form of clothing, but textiles or yarns or intermediate textile products (eg, sliver or It may be blister yarn, etc.). The textile material may be a natural fiber (eg, cotton or wool), a synthetic fiber (eg, biscorayon or leocell), or a synthetic fiber (eg, polyester, polyamide or acrylic fiber), or , A mixture of fibers (eg, a mixture of natural and synthetic fibers). Fluorine-containing polymer compounds are particularly effective in making cellulosic fibers (eg, cotton or rayon, etc.) oleophobic and oil-repellent.

Alternatively, the fibrous substrate may be leather. The fluorinated polymeric compound can be added to the aqueous solution or at various stages of leather processing to make the leather hydrophobic and oleophobic, for example during the wet processing of the leather or during the finishing of the leather. It may be applied to leather from aqueous emulsions.
Alternatively, the fibrous substrate may be paper. The fluorinated polymeric compound may be applied to preformed paper or at various stages of papermaking, for example during the drying period of the paper.

The repellent can be used to treat the paper (eg, surface treatment).
The repellent can be applied to the object to be treated by a conventionally known method. Usually, a method is adopted in which the repellent is dispersed in an organic solvent or water, diluted, and adhered to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating, etc. and dried ( surface treatment). In the case of surface treatment, the fluorine-containing polymer compound may have a ratio of fluorine atoms to the weight of paper of 0.01 to 0.5% by weight, for example, 0.05 to 0.2% by weight.
The fluorine-containing polymer compound adheres well to the base material, particularly paper.

Paper can be produced by a conventionally known papermaking method. An internal addition method in which a repellent is added to the pulp slurry before papermaking or an external addition method in which the repellent is applied to the paper after papermaking can be used. The substrate thus treated, after simple drying at room temperature or high temperature, can optionally be up to 300 ° C., for example up to 200 ° C., especially in the temperature range of 80 ° C. to 180 ° C., depending on the nature of the substrate. With possible heat treatment, it exhibits excellent oil resistance and water resistance.

The present disclosure can be used in gypsum board base paper, coated base paper, medium quality paper, general liner and core, neutral pure white roll paper, neutral liner, rust preventive liner and metal interleaving paper, kraft paper and the like. It can also be used for neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral heat-sensitive paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

The pulp (pulp raw material) used as a raw material is bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as crushed wood pulp, mechanical pulp or thermomechanical pulp, used newspaper, magazine It may be any of used paper pulp such as used paper, corrugated waste paper or deinked used paper, and non-wood pulp such as bagas pulp, kenaf pulp and bamboo pulp, and may be one kind or a combination of two or more of them. Further, a mixture of a pulp raw material and one or more kinds of synthetic fibers such as asbestos, polyamide, polyimide, polyester and polyolefin can also be used.

A sizing agent can be added to improve the water resistance of the paper. Examples of sizing agents are cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (for example, acidic rosin-based sizing agents and neutral rosin-based sizing agents). The amount of sizing agent may be 0.01-5% by weight based on the pulp.

If necessary, as paper chemicals that are usually used, starch, various other modified starches mentioned above, carboxymethyl cellulose, paper strength enhancers such as polyamide polyamine-epichlorohydrin resin, yield improvers, dyes, etc. , Fluorescent dyes, slime control agents, defoamers and other additives used in the manufacture of paper can be used.

In the internal addition treatment of adding a repellent to the pulp slurry before papermaking, the pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight) can be made into paper. preferable. Additives (eg, sizing agents, paper strength agents, flocculants, yielding agents or coagulants, etc.) and fluorine-containing polymer compounds can be added to the pulp slurry. Since pulp is generally anionic, at least one of the additive and the fluorinated polymer compound is preferably cationic or amphoteric so that the additive and the fluorinated polymer compound are well anchored to the paper. Combinations where the additive is cationic or amphoteric and the fluoropolymer compound is anionic, the combination where the additive is anionic and the fluoropolymer compound is cationic or amphoteric, the additive and high fluorophore It is preferable to use a combination in which the molecular compound is cationic or amphoteric.

In addition to the repellent, other components (additives) may be used. Examples of other components are cationic coagulants, water resistant agents, paper strength enhancers, flocculants, fixers, yield improvers and the like.

As the cationic coagulant, the paper strength enhancer, the flocculant, the fixing agent, and the yield improver, a polymer or an inorganic substance having a cationic or amphoteric property can be used. Repellent composed of fluorine-containing polymer compound (1) and particles (2) with respect to pulp which can be normally anionic by a cationic coagulant, a paper strength enhancer, a flocculant, a fixing agent, and a yield improver. The agent can be effectively fixed, and the gas barrier property and / or water and oil resistance of the finally obtained pulp mold container can be enhanced.

Examples of the cationic coagulant, paper strength enhancer, flocculant, fixing agent, and yield improver include polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, and cationic polyacrylamide (acrylamide-allylamine copolymer, acrylamide). -Dimethylaminoethyl (meth) acrylate copolymer, acrylamide-diethylaminoethyl (meth) acrylate copolymer, acrylamide-4 grade dimethylaminoethyl (meth) acrylate copolymer, acrylamide-4 grade diethylaminoethyl (meth) Acrylate copolymer, etc.), Polydialyldimethylammonium chloride, polyallylamine, polyvinylamine, polyethyleneimine, N-vinylformamide-vinylamine copolymer, melamine resin, polyamide epoxy resin, sulfate band, PAC (polyaluminum chloride), Examples thereof include aluminum chloride and ferric chloride. In particular, polyamide polyamine-epichlorohydrin (PAE), polydialyldimethylammonium chloride (poly-DADMAC), polyacrylamide (PAM) and the like can be used.

"Treatment" means applying a repellent (treatment agent) to an object to be treated by dipping, spraying, coating or the like. By the treatment, the polymer which is the active ingredient of the repellent (treatment agent) penetrates into the inside of the object to be treated and / or adheres to the surface of the object to be treated.

Hereinafter, the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to these examples.
In the following, parts or% or ratios represent parts by weight or% by weight or ratios by weight unless otherwise specified.
The test procedure is as follows.

Water resistance test: Cobb test JIS P 8140
The weight (g) of water absorbed in one minute by 100 square centimeters of paper supporting a height of 1 centimeter of water is measured, and the value is converted into ^{the weight per square meter (g / m 2).}

Water resistance test: Stekihit size degree Water resistance was measured according to JIS P8122.
The longer the time (unit: seconds), the higher the water resistance.

Comparative Example 1 (Preparation of Repellent 1)
_{Fluorine-containing monomer CH 2} = CHC (= O) OCH ₂ CH ₂ C ₆ F ₁₃ (hereinafter referred to as C6SFA) in a 200 ml four-necked flask equipped with a reflux condenser, a nitrogen introduction tube, a thermometer and a stirrer. ) 35 g, dimethylaminoethyl methacrylate (hereinafter referred to as DM) 7.5 g, hydroxyethyl methacrylate (hereinafter referred to as HEMA) 7.5 g, and methyl ethyl ketone (hereinafter referred to as MEK) 50 g, 35% hydrochloric acid 0.4 g. It was charged and flowed with nitrogen for 30 minutes. After raising the internal temperature to 60-70 ° C., 0.7 g of perpivalic acid-t-butyl was added, and the polymerization reaction was carried out at 75-80 ° C. for 12 hours. Then, 286 g of 1% acetic acid water was added to the obtained solution, and MEK was distilled off under reduced pressure conditions to prepare an aqueous dispersion 1 of a fluorine-containing acrylic copolymer having a solid content concentration of about 20 wt%. .. This aqueous dispersion 1 is designated as the repellent 1.

The content of the fluorinated alcohol in the repellent 1 was 2005 ppm with respect to the repellent 1. The amount of this fluorinated alcohol corresponded to 10025 ppm with respect to the fluorinated acrylic copolymer. Acetone and water are mixed at a volume ratio of 1: 1 and 500 ppm butanol is added as an internal standard. Acetone water and a mixture of repellent 1 at a ratio of 1: 1 are measured by gas chromatography to repel the repellent. The content of fluorine-containing alcohol in 1 was measured.
A mixture of 40 and 60 parts of hardwood bleached kraft pulp and softwood bleached kraft pulp was beaten to a freeness of 450 cc (Canadian freedom).
The obtained aqueous pulp solution is diluted with water to about 2% by weight, cationized starch is added to the pulp in an amount of 0.5% by weight in terms of solid content, and then the repellent 1 is added to the pulp in terms of solid content of 1. %% by weight was added and stirred for 30 seconds. This pulp slurry was made into a paper using the hand-kneading machine described in JIS P8222. The paper-made wet paper was pressed at a pressure of 3.5 k and dried with a drum-type dryer (100 ° C./60 seconds) to obtain hand-made paper. The basis weight was about 60 g / m ² .
The water resistance of this hand-made paper was evaluated. The results are shown in Table 1.

Example 1 (Preparation of repellent 2)
Fluorotelomer alcohol is contained by contacting the repellent 1 obtained in Comparative Example 1 with activated carbon (activated carbon having a particle size of 0.5 to 2.4 mm and a specific surface area of 1200 m ² / g and not being activated). The amount was reduced. 15% of granular activated carbon was added to the repellent 1 obtained in Comparative Example 1, and a shaking test was conducted at room temperature for 12 hours. Granular activated carbon was removed to obtain repellent 2 having a solid content concentration of about 20%.
The content of the fluorinated alcohol in the repellent 2 was 195 ppm with respect to the repellent 2. The amount of this fluorinated alcohol corresponded to 975 ppm with respect to the fluorinated acrylic copolymer.
Papermaking was performed in the same manner as in Comparative Example 1 except that the repellent 2 was used instead of the repellent 1.

Example 2 (Preparation of repellent 3)
The content of the fluorinated alcohol was reduced by contacting the repellent 1 obtained in Comparative Example 1 with the strong basic anion exchange resin. A strong basic anion exchange resin of 15% was added to the repellent 1 obtained in Comparative Example 1, and a shaking test was conducted at room temperature for 12 hours. The strong basic anion exchange resin was removed to obtain a repellent 3 having a solid content concentration of about 20%.
The content of the fluorinated alcohol in the repellent 3 was 147 ppm with respect to the repellent 3. The amount of this fluorinated alcohol corresponded to 735 ppm with respect to the fluorinated acrylic copolymer.

The repellent can be used on a variety of substrates, especially paper, and imparts excellent water resistance to the substrate.

Claims (11)

A repellent having a fluorine-containing alcohol content of 2000 ppm or less based on the weight of the active ingredient of the repellent. The repellent according to claim 1, wherein the active ingredient of the repellent is a fluorine-containing polymer compound. The repellent according to claim 1 or 2, wherein the fluorinated alcohol is an alcohol having a fluoroalkyl group having 6 carbon atoms. The repellent according to any one of claims 1 to 3, wherein the content of the fluorinated alcohol is 800 ppm or less with respect to the weight of the active ingredient of the repellent. The repellent according to any one of claims 1 to 4, wherein the fluorine-containing polymer compound which is an active component of the repellent has a fluoroalkyl group and is an acrylic polymer or a urethane polymer. Fluorotelomer alcohol, formula:
CF _3- (CF ₂ ) _p- (CH ₂ ) _q- OH
[In the formula, p is a number from 0 to 19 and q is a number from 0 to 10. ]
The repellent according to any one of claims 1 to 5, which is a compound represented by. The invention according to any one of claims 1 to 6, further comprising a step of reducing the content of the fluorotelomer alcohol in the repellent by contacting the raw material repellent with the adsorbent to remove at least a part of the fluorotelomer alcohol. How to make a repellent. The production method according to claim 7, wherein the adsorbent is at least one selected from activated carbon and an ion exchange resin. A method for treating a base material, which comprises treating the base material with the repellent according to any one of claims 1 to 6. The processing method according to claim 9, wherein the base material is paper. A method for improving the water and oil repellency of a repellent, which comprises reducing the content of fluorinated alcohol in the repellent to an amount of 2000 ppm or less with respect to the weight of the active ingredient of the repellent.