JP2017222967A - Fluorine-free water repellent, water repelling processing and water repellent fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water repellent capable of imparting a water repellent effect having excellent water repellency and excellent washing durability to a fiber products using a fluorine-free compound.SOLUTION: Provided is a water repellent being a water based dispersed body containing: an acryl-silicone based copolymer having a repeating unit induced from a long chain(meth)acrylic acid ester monomer (A) not including fluorine in which the carbon number of the ester part is 16-30 and a repeating unit including an organopolysiloxane residue induced from a fluorine-free radical reactive organopolysiloxane macromonomer (B), in which the total of the constituting ratios of the monomer (A) and the macromonomer (B) being 51-100 wt.%, and the constituting ratio of the macromonomer (B) being 0.01-50 wt% to the whole quantity of the monomer unit constituting the copolymer; and a nonionic surfactant including higher fatty acid ester.SELECTED DRAWING: None

Description

  The present invention relates to a water-repellent agent containing no acrylic and acrylic-silicone copolymer in the field of water-repellent processing of textile products, a water-repellent processing method using the same, and It relates to water-repellent fiber products.

  It is known that paraffin wax, silicone resin, or fluorine resin is used as a water repellent component in a method of treating a fiber product with an aqueous dispersion to impart water repellency. Fluorine resins exhibit water repellency superior to paraffin wax and silicone resins, and thus have been widely used industrially in methods for imparting water repellency to textiles.

  In 2000, perfluorooctane sulfonic acid (PFOS) was pointed out to be harmful, bioaccumulative, and environmental pollutant, and perfluorooctanoic acid (PFOA) and other perfluoro compounds with 8 or more carbon atoms are concerned. Came to be shown. For this reason, fluorine-based water repellent manufacturers have been developing fluorine-based water repellents that do not contain these substances and that have no fear of being generated as decomposition products.

  However, in recent years, it has been pointed out that the perfluoroalkyl group-containing compound itself is harmful and environmentally pollutant regardless of the number of carbon atoms. There has also been a movement to cancel.

  Conventionally, paraffin wax, silicone resin, and the like are well known as water-repellent compositions that do not contain fluorine. However, water repellency has been inferior to fluorine-based resins. Among these, as a technique using a composition containing no fluorine in recent years, an aqueous dispersion of a (meth) acrylic acid ester polymer in which the alkyl group of the ester moiety has 12 or more carbon atoms is an aqueous dispersion of a fluororesin. (Patent Document 1).

  Further, as a similar technique, an aqueous dispersion of a (meth) acrylic acid ester polymer characterized by not containing an N-methylol compound and a paraffin wax having a melting point in the range of 58 to 80 ° C. is a woven fabric, In particular, it has been shown to be useful in water-repellent processing for cotton, polyester or cotton-polyester blended fabric (Patent Document 2).

An acrylic-silicone copolymer water-repellent composition is disclosed as a water-repellent composition that does not contain fluorine. For example, a water-repellent treating agent using an acrylic-silicone graft copolymer having a (meth) acrylic acid ester having 8 or less carbon atoms in the ester moiety as a constituent component is disclosed. (Patent Document 3)
However, these water repellents have the actual situation that the water repellent performance is not sufficient, or the water repellent effect cannot be obtained depending on the type of dough to be treated, and is not always perfect.

JP 2006-328624 A Special table 2012-522062 gazette Japanese Patent No. 2960304

  In view of the above circumstances, the object of the present invention is to provide a water repellent effect having water repellency and excellent washing durability to a wide variety of fibers using a fluorine-free compound. It is to provide a water repellent.

  The inventors have repeatedly studied to solve the above-mentioned problems, and have used an acrylic-silicone copolymer obtained by copolymerizing an alkyl (meth) acrylate and a monomer having a polysiloxane residue. Inspired to use as a water component. And a copolymer obtained by polymerizing a (meth) acrylic acid ester having a specific number of carbon atoms in the alkyl group and a polysiloxane monomer having a specific structure at a specific ratio, and a nonionic system having a specific range. By using an aqueous dispersion containing a surfactant, it is possible to impart excellent water repellency and washing durability to various fabrics such as polyester, nylon, cotton, etc. It has been found that water repellency is not impaired even when used in combination, and has led to the present invention.

（式（１）中、Ｒ^１は水素原子またはメチル基を表す。Ｒ^２は直鎖状又は分岐状の炭化水素基であって、炭素数が１６〜３０であるものを表す。）
次式（２）で表される、フッ素を含まない単量体（Ｂ）から誘導された繰り返し単位と、

（式（２）中、Ｒ^３は互いに同一でも異なっていてもよい炭素数が１〜１０である炭化水素基又はアリール基を表す。Ｒ^４は炭素数が１〜４である炭化水素基を示す。Ｘは、酸素原子で中断されてもよい炭素数１〜１２の炭化水素基であるスペーサーを介してつながっているラジカル反応性基を表す。Ｙは互いに同一でも異なっていてもよく、上記式で表される。Ｚは炭素数１〜４の炭化水素基又はラジカル反応性基Ｘを表す。ｎは０〜１９８の整数を表し、式（２）中にｎが複数存在する場合、ｎは互いに同一でも異なっていてもよく、合計が１９８を超えない。）
を含み、前記単量体（Ａ）及び前記単量体（Ｂ）の構成割合の合計は、共重合体を構成する単量体の全量に対して５１〜１００重量％であり、前記単量体（Ｂ）の構成割合は、共重合体を構成する単量体全体の全量に対して０．０１〜５０重量％であるアクリル−シリコーン系共重合体と、
非イオン系界面活性剤とを含み、前記非イオン系界面活性剤が高級脂肪酸エステルを含む、
フッ素を含まない水系分散体であるはっ水剤。 That is, the present invention has the following configuration.
[1] A repeating unit represented by the following formula (1) derived from a fluorine-free monomer (A);

(In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a linear or branched hydrocarbon group having 16 to 30 carbon atoms.)
A repeating unit derived from a monomer (B) containing no fluorine, represented by the following formula (2):

(In Formula (2), R ³ represents a hydrocarbon group or aryl group having 1 to 10 carbon atoms which may be the same or different from each other. R ⁴ represents a hydrocarbon group having 1 to 4 carbon atoms. X represents a radical reactive group connected via a spacer which is a hydrocarbon group having 1 to 12 carbon atoms which may be interrupted by an oxygen atom, Y may be the same as or different from each other, and Z represents a hydrocarbon group having 1 to 4 carbon atoms or a radical reactive group X. n represents an integer of 0 to 198, and when a plurality of n are present in the formula (2), n May be the same or different from each other and the total does not exceed 198.)
The sum of the constituent ratios of the monomer (A) and the monomer (B) is 51 to 100% by weight based on the total amount of the monomers constituting the copolymer, The constituent ratio of the body (B) is 0.01 to 50% by weight with respect to the total amount of the whole monomers constituting the copolymer, and an acrylic-silicone copolymer,
A nonionic surfactant, and the nonionic surfactant contains a higher fatty acid ester,
A water repellent that is an aqueous dispersion containing no fluorine.

[2] The water-repellent agent according to [1], wherein the higher fatty acid ester is an ester of a fatty acid having 12 to 22 carbon atoms and a polyhydric alcohol.
[3] The water repellent according to [1] or [2], further including a cationic surfactant.

[4] The nonionic surfactant further comprises polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid alkanolamide, alkyl glucoside, higher alcohol, pluronic-type activator, alkyldimethylamine- Comprising at least one compound selected from N-oxides,
The water repellent according to any one of [1] to [3].
[5] The acrylic-silicone copolymer is further selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, a blocked isocyanate group, an amide group, an N-methylol group, and a mercapto group. The water-repellent agent according to any one of [1] to [4], comprising a repeating unit derived from a polymerizable monomer (C) containing one of the above.

[6] The above-mentioned [1] to [5], wherein the constituent ratio of the monomer (B) is 0.01% by weight or more and 40% by weight or less with respect to the total amount of the monomers constituting the copolymer. ] The water repellent of any one of.
[7] The above-mentioned [1] to [6], wherein the composition ratio of the monomer (B) is 0.01% by weight or more and 8% by weight or less based on the total amount of the monomers constituting the copolymer. ] The water repellent of any one of.
[8] The water repellent according to any one of [5] to [7], wherein the polymerizable monomer (C) is a monomer containing a hydroxyl group.

[9] With the water-repellent agent according to any one of [1] to [8],
(1) An aqueous dispersion or emulsion of a compound having a bifunctional or higher functional blocked isocyanate group and / or
(2) A water-repellent processing method for textiles using N-methylolmelamine.
[10] A step of immersing the fiber in the processing liquid containing the water repellent according to any one of [1] to [8], and a step of performing a heat treatment at a temperature of 100 ° C. or higher after the step. Water repellent processing method for textile products.
[11] A water-repellent fiber product obtained by treating the water-repellent agent according to any one of [1] to [8].

  The water repellent of the present invention does not contain fluorine, and can impart excellent water repellency and washing durability to various types of fibers. Moreover, the water repellent of the present invention can impart excellent water repellency to the fiber even when an antistatic agent is used as a concomitant drug. Moreover, the texture of the fiber processed with the water-repellent agent of the present invention is good. Furthermore, the dispersion which is the water-repellent agent of the present invention has sufficient stability for processing.

(Acrylic-silicone copolymer)
The acrylic-silicone copolymer contained in the water-repellent agent of the present invention has a repeating unit derived from the monomer (A) which is a long-chain (meth) acrylic acid ester, and has radical reactivity. An acrylic-silicone copolymer having a repeating unit containing an organopolysiloxane residue derived from a monomer (B) which is an organopolysiloxane macromonomer. The copolymer further includes at least one selected from the group consisting of a crosslinkable monomer (C), a short chain (meth) acrylate monomer (D), and another monomer (E). You may have a seed repeating unit.
In the acrylic-silicone copolymer used in the present invention, it is essential that any monomer constituting it does not contain fluorine.

Monomer (A): Long-chain (meth) acrylic acid ester The long-chain (meth) acrylic acid ester monomer is a compound represented by the formula (1).

（式（１）中、Ｒ^１は、水素原子またはメチル基を表す。Ｒ^２は、直鎖状又は分岐状の炭化水素基であって、炭素数が１６〜３０であるものを表す。）

(In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a linear or branched hydrocarbon group having 16 to 30 carbon atoms.)

In the above, R ² is preferably a linear hydrocarbon group, and the hydrocarbon group preferably has 18 to 22 carbon atoms. The hydrocarbon group may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon group. An acrylic ester monomer is more preferable than a methacrylic ester monomer from the viewpoint of water repellency.

  Examples of the monomer (A) include cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, 2-decyltetradecanyl (meth) acrylate, behenyl (meth) acrylate, and the like. And one or more of these can be used.

Monomer (B): Radical reactive organopolysiloxane macromonomer The radical reactive organopolysiloxane macromonomer is a compound represented by the formula (2).

（式（２）中、Ｒ^３は、互いに同一でも異なっていてもよい炭素数が１〜１０である炭化水素基又はアリール基を表す。Ｒ^４は、炭素数が１〜４である炭化水素基を示す。Ｘは、酸素原子で中断されてもよい炭素数１〜１２の炭化水素基であるスペーサーを介してつながっているラジカル反応性基を表す。Ｙは互いに同一でも異なっていてもよく、上記式で表される。Ｚは炭素数１〜４の炭化水素基又はラジカル反応性基Ｘを表す。ｎは０〜１９８の整数を表し、式（２）中にｎが複数存在する場合、ｎは互いに同一でも異なっていてもよく、合計が１９８を超えない。）

(In Formula (2), R ³ represents a hydrocarbon group or aryl group having 1 to 10 carbon atoms which may be the same or different from each other. R ⁴ is a hydrocarbon having 1 to 4 carbon atoms. X represents a radical reactive group connected via a spacer which is a hydrocarbon group having 1 to 12 carbon atoms which may be interrupted by an oxygen atom, and Y may be the same or different from each other. Z represents a hydrocarbon group having 1 to 4 carbon atoms or a radical reactive group X. n represents an integer of 0 to 198, and a plurality of n are present in the formula (2). , N may be the same or different from each other, and the total does not exceed 198.)

  The monomer (B) is an organopolysiloxane compound having one or more radical reactive groups in one molecule, and the radical reactive group and the organopolysiloxane structure are connected via an organic group spacer.

  In the monomer (B), the number of radical-reactive groups is 1 to 2 in one molecule, and particularly preferably one. Examples of the radical reactive group include an azo group, a mercapto group, a vinyl group, a styryl group, and a (meth) acryloyl group, and at least one of these can be used. The reactive group is preferably a (meth) acryloyl group from the viewpoint of easiness of radical copolymerization, easiness of synthesis, and availability of commercially available products.

In the organopolysiloxane structure of the monomer (B), the organic group represented by R ³ in the formula (2) is at least one of a hydrocarbon group having 1 to 10 carbon atoms or an aryl group. The organic group is particularly preferably a methyl group.
The organopolysiloxane may be either linear or branched, and the four skeleton units M (R ₃ SiO _1/2 ), D (R ₂ SiO _2/2 ), T ( The total of RSiO _3/2 ) and Q (SiO _4/2 ) is preferably 3 or more and 200 or less. When two or more polysiloxane chains are present in one molecule, the number of repeating siloxane structures n may be the same or different. If the total of the four skeleton units constituting the siloxane structure is less than 3, sufficient water repellency cannot be obtained, and if it exceeds 200, the resulting acrylic-silicone copolymer has poor film-forming properties and is durable. Sexuality gets worse.

  The monomer (B) may be synthesized by any known method, or a commercially available product may be used. There are various methods for preparing radical reactive organopolysiloxane macromonomer. For example, cyclotrisiloxane is used as a raw material, an anionic living polymerization is used to form an organopolysiloxane chain, and then one end is terminated with a chlorosilane having a radical reactive group. Examples include a method of blocking, a method of carrying out an equilibration reaction between a cyclic siloxane and a disiloxane derivative having a radical reactive group in the presence of an acid or base catalyst. Examples of commercially available products include products called silicone macromonomers and siloxane macromonomers.

Monomer (C): Crosslinkable monomer In addition to the monomer (A) and the monomer (B), the acrylic-silicone copolymer of the present invention has a crosslinkable monomer. A repeating unit derived from the body (C) may be contained. The crosslinkable monomer (C) is selected from the group consisting of a hydroxyl reactive group, an amino group, an epoxy group, a carboxylic acid group, a blocked isocyanate group, an amide group, an N-methylol group and a mercapto group. A polymerizable monomer containing at least one of the above.

  As the monomer (C), for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, (meth) acrylic acid 4 -Hydroxybutyl, (meth) acrylic acid glycidyl (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylic acid polyalkylene glycol, (meth) acrylic acid 2-[(3,5-dimethylpyrazolyl) carbonylamino ], (Meth) acrylic acid 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl, etc., and one or more kinds of polymerizable monomers selected from these groups Can be used in combination.

Monomer (D): Short-chain (meth) acrylate monomer In addition to the monomer (A) and the monomer (B), the acrylic-silicone copolymer of the present invention includes: A repeating unit derived from the short chain (meth) acrylic acid ester monomer (D) may be included.
The short chain (meth) acrylate monomer is a hydrocarbon group having 1 to 15 carbon atoms in the ester moiety. This hydrocarbon group may be linear or branched, may be saturated or unsaturated, and has an alicyclic or aromatic ring. You may do it.

  Examples of the monomer (D) include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Octyl acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (meth ) Dicyclopentanyloxyethyl acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2 (meth) acrylate -Adamantyl and the like, and one or more of these may be used.

Monomer (E): Other monomer The acrylic-silicone copolymer of the present invention contains a repeating unit derived from the other monomer (E) in addition to the monomer. Is not disturbed.
Examples of the monomer (E) include other polymerizable monomers that are not (meth) acrylic acid ester monomers, and other macromonomers other than organopolysiloxane having a radical reactive group.

  Examples thereof include styrene, vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, vinyl alkyl ether, acrylonitrile, alkylol acrylamide, maleic acid diester, methoxypolyalkylene glycol (meth) acrylate, and the like. Other monomers are not limited to these examples.

(Composition ratio of acrylic-silicone copolymer)
The amount of the monomer (A) is 50% by weight or more, preferably 75% by weight or more based on the copolymer. The amount of the monomer (A) may be 98% by weight or less, 95% by weight or less, for example 80% by weight or less, or 85% by weight or less based on the polymer. If it is 50% by weight or more, the water repellency is good, which is preferable.
The amount of the monomer (B) is 0.01% by weight or more, preferably 0.1% by weight or more based on the polymer. The amount of the monomer (B) is 50% by weight or less, preferably 40% by weight or less, more preferably 25% by weight or less, particularly preferably 8% by weight or less, and most preferably 5% by weight or less based on the polymer. It is. When the amount of the monomer (B) is larger than 50% by weight based on the polymer, the effect of further improving the water repellency cannot be obtained and the price of the water repellant becomes expensive. It is not effective in terms of effectiveness.
Moreover, the sum total of the component ratio of the said monomer (A) and the said monomer (B) is 51-100 weight% with respect to the whole quantity of the monomer which comprises a copolymer, Preferably 80- 100% by weight, more preferably 95% by weight to 100% by weight. Within this range, it becomes possible to impart excellent water repellency and washing durability to the fibers.

The amount of the monomer (C) is 0.01% by weight or more with respect to the polymer, 30% by weight or less, preferably 10% by weight or less with respect to the polymer. It is preferable to include the monomer (C) in the acrylic-silicone copolymer because the effect of washing durability becomes higher.
The amount of the monomer (D) is 0% by weight or more with respect to the polymer, 20% by weight or less, preferably 15% by weight or less with respect to the polymer.
The amount of the monomer (E) is 0% by weight or more with respect to the polymer, 50% by weight or less, preferably 40% by weight or less with respect to the polymer.

  Each of the monomers (A), (B), (C) to (E) may be used alone or in combination of two or more monomers. In addition, the acrylic-silicone copolymer contained in the water-repellent agent of the present invention may be one type of copolymer or a combination of two or more types of copolymers.

(Method for producing acrylic-silicone copolymer)
As a method for producing the above-mentioned acrylic-silicone copolymer, a known emulsion polymerization method can be used. For example, a monomer batch charging method in which monomers are charged at once, a monomer dropping method in which monomers are continuously dropped, and the like can be mentioned. In emulsification, it is preferable to use an emulsifier such as an ultrasonic wave or a homogenizer in order to make the particles smaller.

  As a surfactant used for emulsion polymerization, only a cationic surfactant, or only a nonionic surfactant, or a cationic surfactant and a nonionic surfactant can be used in combination. Furthermore, arbitrary surfactants, for example, anionic surfactants, amphoteric surfactants, polymer surfactants and the like can be used. It is particularly preferable to use a cationic surfactant and a nonionic surfactant in combination when treating the aqueous dispersion into a fiber product. Further, an anionic surfactant, a cationic surfactant or a nonionic surfactant having a radical polymerizable group generally called a reactive emulsifier may be used.

  Examples of the anionic surfactant include various fatty acid salts, alkylbenzene sulfonates, alkane sulfonates, alkyl sulfate esters, alkyl phosphate esters, polyoxyethylene alkyl ether sulfates, polyoxyethylene substituted phenyl ether sulfates. Polycarboxylates can be used, and examples of the counter ion include, but are not limited to, sodium, potassium, calcium, ammonium, triethanolamine, and the like.

  Nonionic surfactants include, for example, various fatty acid esters such as higher fatty acid glycerin, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid alkanolamide, alkyl glucoside, higher alcohol, and pluronic. Examples thereof include, but are not limited to, a type activator and alkyldimethylamine-N-oxide.

  Examples of the cationic surfactant include quaternary salts such as various alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, alkylpyridinium chloride salts, quaternized products of polyoxyethylene alkylamines, and the like. An amine salt obtained by neutralizing an amine such as an alkylamine salt, an alkyldimethylamine salt, or a polyoxyethylene alkylamine salt with an appropriate acid can be used. Examples of the counter ion include, but are not limited to, chlorine ion, bromine ion, sulfate ion, formate ion, acetate ion, methyl sulfate ion, and ethyl sulfate ion.

  As the reactive emulsifier, polyoxyethylene alkylphenyl ether as a basic structure, nonionic reactive surfactant in which radical polymerizable propenyl group is introduced into a hydrophobic group, and polyoxyethylene alkylphenyl ether sulfate ester base Examples of the structure include an anionic reactive surfactant in which a radical polymerizable propenyl group is introduced into a hydrophobic group, and a cationic reactive surfactant such as sodium alkylallylsulfosuccinate.

  Specific examples of such nonionic reactive surfactants include α-hydro-ω- (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl). ): Made by ADEKA Co., Ltd .: Trade names “ADEKA rear soap ER-10”, “ADEKA rear soap ER-20”, “ADEKA rear soap ER-30”, “ADEKA rear soap ER-40”, polyoxyethylene alkyl Propenyl phenyl ether: manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: trade name “AQUALON RN-20”, “AQUALON RN-30”, “AQUALON RN-50”, polyoxyalkylene alkenyl ether: manufactured by Kao Corporation: trade name “Latemul PD-420”, “Latemul PD-430”, “Latemul PD-450” and the like can be mentioned.

  Specific examples of the anionic reactive surfactant include α-sulfo-ω- (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt: ADEKA Co., Ltd .: Trade name “ADEKA rear soap SR-10”, “ADEKA rear soap SR-1025”, polyoxyethylene alkylpropenyl phenyl ether sulfate ammonium salt: Daiichi Kogyo Seiyaku Co., Ltd .: trade name “ Examples include Aqualon HS-10, Aqualon HS-5, Aqualon BC-10, Aqualon BC-5, and the like.

  Specific examples of cationic reactive surfactants include alkylallylsulfosuccinic acid sodium salt: Sanyo Kasei Kogyo Co., Ltd .: trade name “Eleminol JS-20”, Kao Co., Ltd .: trade name “Latemul S- 180A "," Latemul S-180 ", polyoxyalkylene alkenyl ether sulfate ammonium salt: manufactured by Kao Corporation: trade name" Latemul PD-104 "and the like.

  In emulsion polymerization, a known solvent may be used in combination for stabilizing the emulsion and improving the solubility of the polymerizable monomer. Examples of the solvent include ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and the like.

  As the polymerization initiator used for emulsion polymerization, a general radical initiator can be used. The radical polymerization initiator includes water-soluble or oil-soluble persulfates, peroxides, and azobis compounds. Specifically, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2 , 2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), and the like are preferable.

  In the polymerization, a chain transfer agent may be used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol and thioglycerol, inorganic salts such as sodium hypophosphite and sodium bisulfite.

The acrylic-silicone copolymer obtained by emulsion polymerization is an aqueous dispersion as it is or after undergoing known treatment steps such as concentration adjustment (concentration, dilution), extraction, purification, etc. as necessary. Used as a liquid medicine. The concentration of the acrylic-silicone copolymer in the water repellant is not particularly limited, and may be set as appropriate in consideration of handling properties, stability, etc. For example, the solid content concentration is 10 to 50% by weight. be able to.
For confirmation of the polymerization reaction and confirmation of the produced acrylic-silicone copolymer, known methods can be used. For example, gel permeation chromatography, gas chromatography, liquid chromatography, mass spectrometry, etc. Can be used to confirm the degree of progress of the reaction, and the molecular weight and structure of the acrylic-silicone copolymer produced using gel permeation chromatography, nuclear magnetic resonance spectroscopy, or the like can be confirmed.

(Water repellent)
The water-repellent agent of the present invention includes a nonionic surfactant together with the above acrylic-silicone copolymer, and the nonionic surfactant contains a higher fatty acid ester.

(Higher fatty acid ester)
The higher fatty acid ester contained in the water-repellent agent of the present invention is preferably an ester of a fatty acid having 12 to 22 carbon atoms and a polyhydric alcohol. An ester of a fatty acid having 12 to 22 carbon atoms and a polyhydric alcohol is a compound having one or more fatty acids in one molecule, and the number of hydroxyl groups remaining in one molecule is 0 to 2. Is more preferable. The fatty acid having 12 to 22 carbon atoms is at least one compound selected from fatty acids having 12 to 22 carbon atoms and having a linear structure and no unsaturated bond. Specifically, for example, lauric acid, myristic Examples include acid, palmitic acid, stearic acid, arachidic acid, behenic acid and the like. Palmitic acid, stearic acid and behenic acid are particularly preferred from the viewpoint of the intended effect of the present application.

  Polyhydric alcohols include butanediol, pentanediol, hexanediol, decanediol, glycerin, trimethylolethane, trimethylolpropane, erythritol, sorbitan, pentaerythritol, xylitol, glucose, fructose, sorbitol, dipentaerythritol, sucralose, maltose And adducts of these polyhydric alcohols such as ethylene oxide and propylene oxide can be used, and one or more of these can be used. The polyhydric alcohol is more preferably a polyhydric alcohol having 3 or more hydroxyl groups in one molecule.

  As esters of higher fatty acids and polyhydric alcohols, commercially available products may be used, those produced by dehydration esterification reaction of fatty acids and polyhydric alcohols, or fatty acid esters and polyhydric alcohols. You may use what was manufactured by transesterification. As a method for producing an ester of a higher fatty acid and a polyhydric alcohol by dehydration esterification, it can be produced by a conventionally known method using a supported or unsupported acid catalyst. In addition, as a production method by transesterification between a fatty acid ester and a polyhydric alcohol, a conventionally known method in which a fatty acid ester esterified with a lower alcohol and a polyhydric alcohol are reacted in the presence of an acid catalyst, a base catalyst, or an organometallic catalyst. It can manufacture by the method of.

  In the present invention, the water-repellent agent contains an ester of a fatty acid having a carbon number within the above range and the above polyhydric alcohol, so that it is excellent for various fabrics such as polyester, nylon, and cotton. It becomes possible to impart water repellency and washing durability to the fabric. As the higher fatty acid ester, sorbitan tristearate, tetraglycerin pentastearate, sucrose tetrastearate and the like are more preferably used.

  The content of the higher fatty acid ester is 1% by weight or more, preferably 2% by weight or more, and 30% by weight or less, preferably 25% by weight or less based on the acrylic-silicone copolymer. Within this range, excellent water repellency can be imparted to the fiber.

  When the higher fatty acid ester is added to the reaction system simultaneously with the production of the acrylic-silicone copolymer, an aqueous dispersion containing the acrylic-silicone copolymer and the higher fatty acid ester can be obtained. Although not bound by a specific theory, in the present invention, the higher fatty acid ester functions as an emulsifier in the aqueous dispersion and at the same time functions as a water repellant, contributing to the improvement of the water repellency of the fabric. It is thought that there is.

  In addition to the acrylic-silicone copolymer and higher fatty acid ester, the water-repellent agent that is an aqueous dispersion of the present invention includes paraffin wax, amino-modified silicone, methyl for improving water repellency and adjusting the texture. An aqueous dispersion of a non-fluorinated water repellent such as hydrogen silicone, octadecyl ethylene urea, alkyl ketene dimer, zirconyl octylate, etc. may be blended.

  In addition to the above, the aqueous dispersion of the present invention may contain any additive as long as the effects of the present invention are not impaired. Examples of the additive include textile agents such as anti-wrinkle agents, flame retardants, antistatic agents, anti-slip agents, ultraviolet absorbers, deodorants, antibacterial agents, and the like. These additives can be used singly or in appropriate combination of two or more.

(Water repellent processing method for textile products)
When the water-repellent agent of the present invention is processed into a textile product, together with the aqueous dispersion, (1) an aqueous emulsion of a bifunctional or higher functional blocked isocyanate, and (2) a crosslink such as N-methylolmelamine. It is preferable to use an agent in combination.

  (1) A bifunctional or higher functional blocked polyisocyanate can be obtained by reacting a bifunctional or higher functional isocyanate with an appropriate blocking agent by a known method. Examples of the isocyanate include 4,4'-bisisocyanatophenylmethane, toluene diisocyanate, hexamethylene diisocyanate, diisocyanate trimer and trimethylolpropane adduct.

  Examples of the isocyanate blocking agent include secondary or tertiary alcohols, active methylene compounds, phenols, oximes, substituted pyrazoles, and caprolactam. Usually, these blocked isocyanates are emulsified and dispersed using a surfactant by a known method. In addition, after blocking 70 to 95% of all isocyanate groups in advance, by reacting polyalkylene glycol having an appropriate molecular weight, particularly polyethylene glycol, with the remaining isocyanate groups, the blocked isocyanate exhibits self-emulsifying properties. It is effective not only for improving the washing durability of liquid preparations but also for improving the stability of products.

  (2) Examples of N-methylol melamine include trimethylol melamine and hexamethylol melamine.

  The water-repellent agent of the present invention is useful for imparting water repellency having excellent washing durability to fibers. For this purpose, the fibers are treated with a working fluid containing the water repellent of the present invention. The processing liquid is prepared by diluting the water-repellent containing the acrylic-silicone copolymer of the present invention, a surfactant, etc., the aforementioned blocked isocyanate, N-methylolmelamine, etc. with water to a predetermined concentration. can get. In addition, other chemicals known in the field of textile finishing, such as anti-wrinkle agents, softeners, antistatic agents, anti-slip agents, flame retardants, UV absorbers, deodorants, antibacterial agents, etc. in the processing liquid. You may contain.

  The concentration of the acrylic-silicone copolymer in the working fluid is not particularly limited and is appropriately selected according to the treatment method and conditions. For example, when the treatment is performed by a continuous method, the solid content concentration is 0.3 to It can be about 5.0% by weight. When processing by a batch method, it can be set as about 0.3-3.0% ofwf.

  The water repellency processing method is not particularly limited, and various methods can be adopted. A desired amount may be adhered to the fiber product to be water repellency processed (processed object), such as a continuous method or a batch method. Is mentioned.

  As a continuous method, first, the water-repellent agent of the present invention is diluted in water to prepare a processing liquid. Next, the processing object is continuously fed into the impregnation apparatus filled with the processing liquid, and the processing object is impregnated with the processing liquid, and then the unnecessary processing liquid is removed. The impregnation device is not particularly limited, and a padder, a spray-type applying device, a foam-type applying device, a coating-type applying device, etc. can be preferably used, and a padder type is particularly preferable.

  Subsequently, an operation of removing water remaining on the object to be processed is performed using a dryer. The dryer is not particularly limited, and a spread dryer such as a hot fluid or a tenter is preferable. The continuous method is preferably employed when the object to be treated is a fabric such as a woven fabric.

  The batch method includes a step of immersing an object to be processed in a working fluid and a step of removing water remaining on the object to be processed after the process. The batch method is preferably employed when the object to be treated is not in the form of a fabric, for example, when it is not suitable for a continuous method such as loose hair, top, yarn and the like. In the soaking step, for example, a cotton dyeing machine, a cheese dyeing machine, a liquid dyeing machine, a beam dyeing machine or the like can be used. In the operation of removing water, a hot air dryer such as a cheese dryer or a tumble dryer, a high-frequency dryer, or the like can be used.

  In either case, the drying (heat treatment) step after immersing the fibers to be treated in the processing liquid can be performed at 80 to 180 ° C., and is preferably heat treated at a temperature of 100 ° C. or higher.

  The type of fiber to be treated is not particularly limited as long as the effect of the present invention is exhibited. For example, synthetic fibers such as nylon, polyester, acrylic, and polyurethane, natural fibers such as cotton, hemp, silk, and wool, and those Can be used. The form of the fiber is not particularly limited, and water repellency can be imparted to the fabric, non-woven fabric, cotton, yarn, etc. by imparting water repellency. In particular, it is suitable as a water-repellent treatment for fabrics used for clothing and industrial materials.

  Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these examples.

(material)
The structures of radical reactive organopolysiloxane macromonomers A to D used in Examples and Comparative Examples are shown below.

Radical reactive organopolysiloxane macromonomer A

Radical reactive organopolysiloxane macromonomer B

Radical reactive organopolysiloxane macromonomer C

Radical reactive organopolysiloxane macromonomer D

[Example 1]
(Production of aqueous dispersion of acrylic-silicone copolymer containing higher fatty acid ester)
In a 500 mL flask, stearyl acrylate 116.4 g, radical reactive organopolysiloxane macromonomer A 1.2 g, 2-hydroxyethyl methacrylate 2.4 g, sorbitan tristearate 25 g, polyoxyethylene (9 mol) oleyl ether 3 g, Add 3 g of polyoxyethylene (13 mol) oleyl ether, 0.16 g of dodecyl mercaptan, 20 g of 3-methoxy-3-methyl-1-butanol and 228.41 g of ion-exchanged water, and emulsify and disperse with high-speed stirring at 50 ° C. A liquid was obtained. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.43 g of azobis [N- (2-hydroxyethyl) -2-methylpropanamide] was added, and the mixture was heated at 80 ° C. under a nitrogen atmosphere. Radical polymerization was carried out for 10 hours to obtain 400 g of a product containing a polymer concentration of 30% by weight.

[Examples 2 to 9, Comparative Examples 1 to 4]
An aqueous dispersion was produced in the same procedure as in Example 1 except that the raw materials listed in Table 1 were used.
A summary of the compositions of the aqueous dispersions of Examples 1 to 9 and Comparative Examples 1 to 4 is shown in Table 1.

  In addition, Table 2 shows the ratio of the monomers contained in the acrylic-silicone copolymers in Examples 1 to 9 and Comparative Examples 1 to 4.

[Control example]
As an example of water-repellent processing with a fluorine-based resin, AsahiGuard E-SERIES AG-E061 (manufactured by Asahi Glass Co., Ltd., fluorine-based water repellent, solid content 20% by weight) 50 g / L, Meikanate FM-1 (Blocked isocyanate manufactured by Meisei Chemical Co., Ltd.): 30% active ingredient) The processing solution diluted with water is adjusted to 10 g / L and put on polyester tropical cloth, polyester taffeta cloth, nylon taslan cloth, and cotton broad cloth. Then, nip (pickup 90%, 30%, 60%, 70%) with two rubber rollers, dried at 110 ° C for 2 minutes, and then cured at 170 ° C for 1 minute to create an evaluation fabric did. In addition, a polyester tropical cloth and a polyester taffeta cloth are processed in the same manner by using 5 g / L of Delectol AG-7 (manufactured by Meisei Chemical Industry Co., Ltd .: active ingredient 25%), which is an antistatic agent, in combination with the above processing liquid formulation. The water repellency was evaluated.

<Evaluation of water repellency>
Either 50 g / L of the acrylic-silicone copolymer of Examples 1 to 9 and the acrylic-silicone copolymer and acrylic copolymer of Comparative Examples 1 to 4, Meikanate FM-1 (manufactured by Meisei Chemical Co., Ltd.) Blocked isocyanate): 30% active ingredient) Adjust the processing solution diluted with water to 10g / L, put it on polyester tropical cloth, polyester taffeta cloth, nylon taslan cloth, and cotton broad cloth and put two rubbers A nip (pickup 90%, 30%, 60%, 70%) was made with a roller, dried at 110 ° C. for 2 minutes, and then cured at 170 ° C. for 1 minute to prepare an evaluation fabric. Water repellency was evaluated by the spray method of JIS L 1092 (2009) using the obtained evaluation cloth. In any case, the evaluation fabric was naturally dried after washing. In addition, the water repellency is expressed by a numerical value of 5 levels from 1 to 5 shown in Table 3, and when + (−) is attached to a number, it indicates that it is slightly better (bad) than the evaluation of the number. . The results are shown in Table 4.
In addition, a polyester tropical cloth and a polyester taffeta cloth are processed in the same manner by using 5 g / L of Delectol AG-7 (manufactured by Meisei Chemical Industry Co., Ltd .: active ingredient 25%), which is an antistatic agent, in combination with the above processing liquid formulation. The water repellency was evaluated. The results are shown in Table 5.

<Evaluation of water-repellent washing durability>
The created evaluation fabric was washed 0 times (HL-0), and after 10 washings (HL-10) according to the washing method described in JIS L 1092 (2009), the water repellency was similarly evaluated. did.

As shown in Table 4, Examples 1 to 9 according to the present invention are almost the same as the control example (fluorinated resin) in any of polyester tropical cloth, polyester taffeta cloth, nylon taslan cloth, and cotton broad cloth. More water repellency and washing durability were developed.
On the other hand, Comparative Examples 1 and 2 in which the radical-reactive organopolysiloxane macromonomer (monomer B) is not copolymerized are the same as the examples in both types of fabrics, both water repellency and washing durability. It was inferior. Further, Comparative Example 4 in which the (meth) acrylic acid ester (monomer A) having 16 to 30 carbon atoms in the ester portion is not copolymerized has insufficient water repellency in any type of fabric. Met. Further, Comparative Example 3 containing an acrylic-silicone copolymer but not containing a higher fatty acid ester showed higher water repellency and washing durability than Comparative Examples 2 and 4, but Examples 1 to 9 further It was excellent.

  From the results of Table 5, when antistatic agents were used in combination, Comparative Examples 1 and 2 and the control example showed a decrease in water repellency and washing durability. On the other hand, in all of Examples 1 to 9, a decrease in water repellency was suppressed even when an antistatic agent was used in combination.

  The water repellent of the present invention does not contain fluorine, can impart excellent water repellency and washing durability to various types of fibers, and is excellent when an antistatic agent is used as a concomitant drug. Since water repellency can be imparted to fibers, it has little influence on the human body and the environment, and is particularly suitable for imparting water repellency to fabrics for clothing and industrial materials. For example, textile products with water repellency can be widely applied to clothes, umbrellas, raincoats, tents, daily necessities, interiors, car seats, etc., and can be widely used for any application other than these applications. it can.

Claims (11)

A repeating unit derived from a monomer (A) containing no fluorine, represented by the following formula (1):

(In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a linear or branched hydrocarbon group having 16 to 30 carbon atoms.)
A repeating unit derived from a monomer (B) containing no fluorine, represented by the following formula (2):

(In Formula (2), R ³ represents a hydrocarbon group or aryl group having 1 to 10 carbon atoms which may be the same or different from each other. R ⁴ represents a hydrocarbon group having 1 to 4 carbon atoms. X represents a radical reactive group connected via a spacer which is a hydrocarbon group having 1 to 12 carbon atoms which may be interrupted by an oxygen atom, Y may be the same as or different from each other, and Z represents a hydrocarbon group having 1 to 4 carbon atoms or a radical reactive group X. n represents an integer of 0 to 198, and when a plurality of n are present in the formula (2), n May be the same or different from each other and the total does not exceed 198.)
The sum of the constituent ratios of the monomer (A) and the monomer (B) is 51 to 100% by weight based on the total amount of the monomers constituting the copolymer, The constituent ratio of the body (B) is 0.01 to 50% by weight with respect to the total amount of the whole monomers constituting the copolymer, and an acrylic-silicone copolymer,
A nonionic surfactant, and the nonionic surfactant contains a higher fatty acid ester,
A water repellent that is an aqueous dispersion containing no fluorine. The water-repellent agent according to claim 1, wherein the higher fatty acid ester is an ester of a fatty acid having 12 to 22 carbon atoms and a polyhydric alcohol. The water repellent according to claim 1 or 2, further comprising a cationic surfactant. The nonionic surfactant further includes polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid alkanolamide, alkyl glucoside, higher alcohol, pluronic-type activator, alkyldimethylamine-N-oxide. Comprising at least one compound selected from
The water-repellent agent according to any one of claims 1 to 3. The acrylic-silicone copolymer further contains at least one selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, a blocked isocyanate group, an amide group, an N-methylol group, and a mercapto group. The water-repellent agent according to any one of claims 1 to 4, comprising a repeating unit derived from the polymerizable monomer (C). The constituent ratio of the monomer (B) is 0.01% by weight or more and 40% by weight or less based on the total amount of the whole monomer constituting the copolymer. Water-repellent agent described in 1. The constituent ratio of the monomer (B) is 0.01% by weight or more and 8% by weight or less based on the total amount of the whole monomer constituting the copolymer. Water-repellent agent described in 1. The water repellent according to any one of claims 5 to 7, wherein the polymerizable monomer (C) is a monomer containing a hydroxyl group. With the water repellent of any one of Claims 1-8,
(1) An aqueous dispersion or emulsion of a compound having a bifunctional or higher functional blocked isocyanate group and / or
(2) A water-repellent processing method for textiles using N-methylolmelamine. A fiber comprising: a step of immersing the fiber in a processing liquid containing the water repellent according to any one of claims 1 to 8; and a step of heat-treating at a temperature of 100 ° C. or higher after the step. Water repellent processing method for products. A water-repellent fiber product obtained by treating the water-repellent agent according to any one of claims 1 to 8.