KR20170134227A - Method for producing water repellent fiber product - Google Patents

Abstract

A water repellent fiber product manufacturing method includes a process of making at least one non-fluorine-based water repellent agent, which is selected from a group consisting of an acrylic water repellent, a silicone water repellent, and a dendrimer water repellent, be in contact with fiber including at least one functional group selected from a group formed with a monovalent group represented by -SO_3M^1 (In the formula, M^1 represents a monovalent cation), a monovalent group represented by -COOM^2 (In the formula, M^2 represents a monovalent cation), and a monovalent group represented by -O-P(O)(OX^1)(OX^2) (In the formula, X^1 and X^2 respectively and independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms). The present invention is provided to obtain a water repellent fiber product having sufficient water repellency and sufficient durability.

Description

METHOD FOR PRODUCING WATER REPELLENT FIBER PRODUCT [0001]

The present invention relates to a method for producing a water-repellent fiber product, and more particularly, to a method for producing a water-repellent fiber product using a non-fluorine-based water repellent agent.

BACKGROUND ART Conventionally, a fluorine-based water repellent agent having a fluorine-containing group is known. By treating such a fluorine-based water repellent agent with a fiber product or the like, a fiber product having water repellency on its surface can be obtained. Such a fluorine-based water repellent agent is generally prepared by polymerizing, or copolymerizing, a monomer having a fluoroalkyl group. In order to sufficiently express the water repellency, it is necessary to control the orientation property of the fluoroalkyl group. Usually, after the fluorine-based water repellent agent is attached to the fiber product, the heat treatment is performed at a temperature exceeding 130 캜. However, heat treatment at a high temperature requiring high energy is not preferable in the flow of international energy saving. Further, the monomer having a fluoroalkyl group is not only expensive, but also has a high burden on the environment because it is poorly decomposable.

In view of these circumstances, research on non-fluorine-based water repellent agents that do not contain fluorine has been conducted recently. For example, Non-Patent Document 1 discloses a water repellent agent obtained by emulsifying and dispersing a hydrocarbon compound such as paraffin or wax, a fatty acid metal salt, or an alkyl element. In addition, Patent Document 1 proposes a water repellent agent in which a specific non-fluorinated polymer is emulsified and dispersed for the purpose of giving water repellency that is comparable to that of a conventional fluorinated water repellent.

Japanese Patent Application Laid-Open No. 2006-328624

"New water-repellent processing, whole volume of processing agent and new trend of breathable waterproof material", published by Osaka Chemical Marketing Center, 1996, p.7 to 9

However, even with the conventional non-fluorine-based water repellent, the performance of imparting water repellency to the fiber product is not yet sufficient. In addition, durability (durability water repellency) which is less likely to deteriorate water repellency due to use outdoors or washing, etc. is required for the water-repellent fiber product, but the conventional non-fluoric water repellent agent is still not sufficient in this respect.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a water-repellent fiber product which can obtain a water-repellent fiber product having sufficient water repellency and sufficient endurance water repellency by using a non-fluoric water repellent agent.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies and, as a result, have found that a water-repellent fiber product having sufficient water repellency and sufficient endurance water repellency can be obtained by treating a fiber having a specific functional group with a treatment liquid containing a specific non- The present invention has been completed on the basis of this finding.

That is, the method for producing a water-repellent fiber product of the present invention comprises a monovalent group represented by -SO ₃ M ¹ (wherein M ¹ represents a monovalent cation), -COOM ^{2 wherein} M ² represents a monovalent (OX ¹ ) (OX ² ) (wherein X ¹ and X ² each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms), and -OP (O) (OX ¹ ) A water repellent agent selected from the group consisting of an acrylic water repellent agent, a silicone water repellent agent and a dendrimer water repellent agent is contacted with a fiber containing at least one functional group selected from the group consisting of a monovalent group represented by the following formula do.

The water repellent fiber product obtained by the method of the present invention can have sufficient water repellency and sufficient durability to water repellency. This water-repellent fiber product can maintain sufficient water repellency for a long period of time even when it is used outdoors for a long time or repeatedly washed.

The non-fluorine-based water repellent agent preferably includes an acrylic water repellent agent containing a polymer containing a structural unit derived from a (meth) acrylic acid ester monomer (A) represented by the following formula (A-1)

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms, which may have a substituent.]

The non-fluorine-based water repellent agent may further comprise at least one monomer (E) selected from vinyl chloride and vinylidene chloride, a structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the above formula (A- Based water repellent containing a polymer containing a constituent unit derived from an acrylic-based water repellent.

The fibers, -SO ₃ M ^{1 1-valent} group, -COOM ² represented by (wherein, M ¹ represents a monovalent cation), (wherein, M ² represents a monovalent cation), represented by a monovalent Group and a group consisting of a monovalent group represented by -OP (O) (OX ¹ ) (OX ² ) (wherein X ¹ and X ² each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) A fiber to which a compound having at least one selected functional group is attached may be used.

In addition, the compound, -SO ₃ M ¹ preferably comprises a phenolic polymer having a monovalent group represented by (wherein, M ¹ represents a monovalent cation).

In the method for producing a water repellent fiber product of the present invention, it is preferable that the surface of the fiber has a zeta potential of -100 to -0.1 mV.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing a water-repellent fiber product having sufficient water repellency and sufficient durability by using a non-fluorine-based water repellent agent.

In addition, the method of the present invention can obtain a water-repellent fiber product having sufficient water repellency while using a non-fluorine-based water repellent agent that does not contain a fluoroalkyl group or a compound having fluorine, and reduces the load on the fluorine source or the load on the environment can do.

When the fluorine-based water repellent agent is adhered to the fiber product, the heat treatment is usually performed at a high temperature. According to the method of the present invention, sufficient water repellency can be exhibited even when heat treatment is performed under mild conditions of 130 ° C or less, When the heat treatment is performed at an excessively high temperature, the heat treatment time can be made shorter than that of the fluorine-based water repellent agent. Therefore, the method of the present invention can suppress the deterioration due to heat of the article to be treated, which makes it possible to soften the feel and reduce the amount of heat applied to the heat treatment, and is also excellent in cost.

The production method of the water repellent fiber product of the present embodiment is characterized in that a monovalent group represented by -SO ₃ M ¹ (wherein M ¹ represents a monovalent cation), -COOM ² (wherein M ² represents a monovalent cation , And -OP (O) (OX ¹ ) (OX ² ) wherein X ¹ and X ² are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, A silicone-based water-repellent agent, and a dendrimer-based water-repellent agent is added to fibers containing at least one functional group selected from the group consisting of monovalent groups represented by a monovalent group represented by the following formula And a step of providing one type of non-fluorine-based water repellent agent.

Examples of M ¹ include H, K, Na or an ammonium ion which may have a substituent. Examples of M ² include H, K, Na or an ammonium ion which may have a substituent. When X ¹ or X ² is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms.

The fiber containing the specific functional group (hereinafter sometimes referred to as " functional group-containing fiber ") may be prepared, for example, by the following method.

(I) A compound having the specific functional group is attached to the fiber material. The attachment of the compound may be such that a part of the compound and a part of the fiber are chemically bonded to each other within such a range that the specific functional group is left in a sufficient amount.

(Ii) A fiber in which the specific functional group is directly introduced into the material constituting the fiber is prepared.

In the case of (i), the functional group-containing fiber can be obtained, for example, by a functional group introduction step of treating the fiber material with a pretreatment solution containing at least one compound having the specific functional group.

The fiber material is not particularly limited, and natural fibers such as cotton, hemp, dog, wool, semisynthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon), polyester, polyurethane, polypropylene, , And blended fibers. The form of the fiber material may be selected from the group consisting of fibers (tow, sliver, etc.), yarns, knitted fabrics (including knitted fabrics), fabrics Any form may be used.

In the present embodiment, it is preferable to use a fiber material containing polyamide and polyester as a raw material from the viewpoint of improving the water repellency of the obtained fiber product. In particular, nylon such as nylon 6, nylon 6,6, It is preferable to use polyester such as phthalate (PET), polytrimethyl terephthalate, and poly lactic acid, and mixed fibers containing these.

As the compound having -SO ₃ M ¹ , a phenol-based polymer can be used. Examples of such a phenol-based polymer include at least one compound represented by the following formula (2).

Wherein X ² represents -SO ₃ M ³ (wherein M ³ represents a monovalent cation) or a group represented by the following formula (3), and n is an integer of 20 to 3000.

[In the formula (3), M ⁴ represents a monovalent cation.]

Examples of the M ³ include H, K, Na or an ammonium ion which may have a substituent.

Examples of the M ⁴ include H, K, Na or an ammonium ion which may have a substituent.

The compound represented by the formula (2) may be, for example, a formalin condensate of phenolsulfonic acid, a formalin condensate of sulfonated bisphenol S, or a compound synthesized by the method described in the following Examples.

Examples of the compound having -COOM ² include a polycarboxylic acid-based polymer.

As the polycarboxylic acid polymer, for example, a polymer synthesized by conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid or the like as a monomer, or a commercially available polymer can be used.

Examples of the production method of the polycarboxylic acid polymer include a method in which a radical polymerization initiator is added to an aqueous solution of the monomer and / or a salt thereof and the mixture is subjected to a heating reaction at 30 to 150 ° C for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the monomer and / or its salt. Examples of the radical polymerization initiator include redox polymerization initiators by combination of persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, persulfates and sodium bisulfite, hydrogen peroxide, water-soluble azo-based polymerization initiators, . These radical polymerization initiators may be used singly or in combination of two or more. In the radical polymerization, a chain transfer agent (for example, octyl thioglycolate) may be added for the purpose of adjusting the polymerization degree.

As the radical polymerization, monomers copolymerizable with the above monomers may be used. Examples of the copolymerizable monomer include vinyl monomers such as ethylene, vinyl chloride and vinyl acetate, acrylamide, acrylates and methacrylates. The acrylates and methacrylates preferably have a hydrocarbon group of 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, Propyl methacrylate and the like. These copolymerizable monomers may be used singly or in combination of two or more.

The carboxyl group in the polycarboxylic acid polymer may be free or neutralized with an alkali metal or an amine compound. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, triethanolamine, and the like.

The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000 from the viewpoint of improving the water repellency of the obtained fiber product.

Commercially available products such as "Neocrystalline 770" (trade name, manufactured by Nikka Chemical Co., Ltd.) and "Cellophall PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used as the polycarboxylic acid polymer.

Examples of the compound having -OP (O) (OX ¹ ) (OX ² ) include phosphoric acid ester compounds represented by the following formula (4).

[In the formula (4), X ¹ or X ² is the same as defined above, and X ³ represents an alkyl group having 1 to 22 carbon atoms.

As the phosphate ester compound, monoesters, diesters and triesters of phosphoric acid in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and a mixture thereof can be used.

In the present embodiment, it is preferable to use lauryl phosphate ester or decyl phosphate ester from the viewpoint of improving the water repellency of the obtained fiber product.

As the phosphate ester compound, for example, a commercially available product such as " Phosphanol ML-200 " (trade name, manufactured by Tohoku Kagakukogyo Co., Ltd.) can be used.

The pretreatment liquid containing at least one compound having the specific functional group may be, for example, an aqueous solution of the compound described above. The pretreatment liquid may contain an acid, an alkali, a surfactant, a chelating agent and the like.

Examples of the method of treating the fiber material with the pretreatment liquid include padding treatment, immersion treatment, spray treatment and coating treatment. As the padding treatment, for example, a padding apparatus described in pp. 256 to 260 of Dyeing Chemistry III (published by Jikkyo Publishing Co., Ltd. in 1975), pages 396 to 397 of the fiber dyeing processing dictionary (published in 1963, Method. As the coating treatment, there can be mentioned, for example, a method using the coater described in pages 473 to 477 of Dyeing and Processing Machinery (published in 1981, Textile). Examples of the immersion treatment include a method using a batch dyeing machine described in pages 196 to 247 of Dyeing and Processing Machinery (published in 1981, Textile), and a liquid dyeing machine, an air dyeing machine, a drum dyeing machine, A washer dyeing machine, a cheese dyeing machine and the like can be used. Examples of the spray treatment include an air spray in which the treatment liquid is sprayed with the compressed air in a mist state, or a method using an air spray of a hydraulic atomizing method. The treatment conditions such as the concentration of the treatment liquid and the heat treatment after the treatment can be suitably adjusted in consideration of various conditions such as the purpose and performance. When the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid to remove water after adhering to the fiber material. The drying method is not particularly limited, and any of the dry heat method and the wet heat method may be used. The drying temperature is not particularly limited, but may be, for example, from room temperature to 200 ° C for 10 seconds to several days. If necessary, it may be subjected to heat treatment at a temperature of 100 to 180 캜 for 10 seconds to 5 minutes after drying.

In the case where the fiber material is to be dyed, the treatment with the pretreatment liquid may be carried out in a bath such as dyeing before dyeing, but when soaping is carried out, The compound having a specific functional group (for example, a phenol-based polymer compound or the like) may fall off. Therefore, it is preferable to perform the reduction after the dyeing.

The treatment temperature in the immersion treatment may be 60 to 130 占 폚. The treatment time may be 5 to 60 minutes.

The functional group introduction step by the pretreatment liquid is preferably carried out in such an amount that the adhesion amount of the compound having the specific functional group is 1.0 to 7.0 parts by mass with respect to 100 parts by mass of the fiber material. Within this range, the durability and the feeling of durability can be made compatible at a high level.

The pH of the pretreatment solution is preferably adjusted to 3 to 5. The pH adjustment may be performed using a pH adjuster such as acetic acid or malic acid.

In the pretreatment liquid, a salt may be used in combination to effectively adsorb the compound having the specific functional group to the fibrous material by the salting-out effect. Examples of the salt that can be used include sodium chloride, sodium carbonate, ammonium sulfate and sodium sulfate.

In the step of introducing a functional group by the pretreatment liquid, it is preferable to remove the excessively treated compound having the specific functional group. As a removal method, a method of washing with water may be mentioned. By performing sufficient removal, it is possible to suppress the deterioration of the water repellency in the water repellent finish of the subsequent stage, and the feeling of the obtained fiber product is improved. The obtained functional group-containing fiber is preferably sufficiently dried before coming into contact with the non-fluorine-based water repellent agent.

(Ii) Examples of the fibers into which the specific functional group is directly introduced into the material constituting the fibers include cationic fluorophosphate (CD-PET).

The zeta potential of the surface of the functional group-containing fiber according to the present embodiment is preferably -100 to -0.1 mV, more preferably -50 to -1 mV, from the viewpoint of improving the water repellency of the resulting fiber product. The zeta potential of the surface of the fiber can be measured by, for example, a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Denshi K.K.).

Next, the non-fluorine-based water repellent imparted to the functional group-containing fibers according to the present embodiment will be described. The non-fluorine-based water repellent agent may include at least one member selected from the group consisting of an acrylic water repellent agent, a silicone water repellent agent, and a dendrimer water repellent agent.

As the acrylic water repellent, a polymer containing a constituent unit derived from a (meth) acrylic acid ester monomer (A) (hereinafter also referred to as a "component (A)") represented by the following formula (A- Quot; fluorine-based acrylic polymer ").

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms, which may have a substituent.]

Here, "(meth) acrylic acid ester" refers to "acrylic acid ester" or "methacrylic acid ester" corresponding thereto and is also synonymous in "(meth) acrylic acid", "(meth) acrylamide"

The (meth) acrylic acid ester monomer (A) represented by the above formula (A-1) used in the present embodiment has a monovalent hydrocarbon group having 12 or more carbon atoms, which may have a substituent. The hydrocarbon group may be linear or branched or may be a saturated hydrocarbon group, an unsaturated hydrocarbon group, or even an alicyclic or aromatic cyclic group. Of these, straight-chain alkyl groups are preferred, and straight-chain alkyl groups are more preferred. In this case, water repellency is more excellent. When the monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, the substituent includes at least one of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a block isocyanate group and a (meth) acryloyloxy group . In the present embodiment, in the above formula (A-1), R ² is preferably an unsubstituted hydrocarbon group.

The hydrocarbon group preferably has 12 to 24 carbon atoms. When the number of carbon atoms is 12 or more, excellent water repellency tends to be obtained when the non-fluorine-containing acrylic polymer is attached to a textile product or the like. On the other hand, when the number of carbon atoms is not more than 24, when the non-fluorinated acrylic polymer is adhered to a fiber product or the like, the feeling of the fiber product tends to be hard and stiff, as compared with the case where the number of carbon atoms is out of the above range.

And the carbon number of the hydrocarbon group is more preferably 12 to 21. When the number of carbon atoms is within this range, the water repellency and feel are particularly excellent. Particularly preferred hydrocarbon groups are straight-chain alkyl groups of 12 to 18 carbon atoms.

Examples of the component (A) include stearyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, (Meth) acrylate, decyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl .

The component (A) may have at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group capable of reacting with a crosslinking agent. In this case, the endurance water repellency of the obtained fiber product can be further improved. The isocyanate group may form a blocked isocyanate group protected with a blocking agent. When the component (A) has an amino group, the feel of the resulting fiber product can be further improved.

The component (A) is preferably a monofunctional (meth) acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

The above component (A) may be used singly or in combination of two or more kinds.

The component (A) is preferably used in combination with the acrylic acid ester monomer (a1) and the methacrylic ester monomer (a2) in view of the durability of the resulting textile product. The ratio (a1) / (a2) of the mass of the component (a1) to the mass of the component (a2) is preferably 30/70 to 90/10, more preferably 40/60 to 85/15, More preferably 50/50 to 80/20. When the ratio (a1) / (a2) is within the above range, the durability water repellency of the obtained fiber product becomes better.

The non-fluorine-containing acrylic polymer according to the present embodiment is obtained by copolymerizing a constituent unit derived from the component (A) and at least one monomer (E) (hereinafter also referred to as "component (E)") of vinyl chloride and vinylidene chloride ) Containing a constituent unit derived from

At least one kind of monomer (E) of vinyl chloride and vinylidene chloride used in the present embodiment is contained as a copolymer component of the non-fluorinated acrylic polymer of the present embodiment, and the water repellency of the resulting fiber product and the peel strength Vinyl chloride is preferable.

The content ratio of the constitutional unit derived from the component (A) and the constitutional unit derived from the component (E) in the non-fluorinated acrylic polymer of the present embodiment is determined by the emulsion stability of the non-fluorinated polymer of the present embodiment, (A) / (E) of the mass of the component (A) and the mass of the component (E) to be blended is preferably 40/60 to 90/10, more preferably 50/50 to 50/50, More preferably 85/15, and still more preferably 60/40 to 80/20. When the ratio (A) / (E) is 90/10 or less, the peel strength against the coating of the resulting fiber product tends to be less likely to deteriorate. When the ratio (A) / (E) is 40/60 or more, the emulsion stability of the non-fluorine-containing acrylic polymer of the present embodiment tends to be hardly lowered.

The total mass of the mass of the component (A) and the mass of the component (E) to be blended is preferably 80 to 100 mass%, more preferably 85 to 99 mass% with respect to the total amount of the monomer components constituting the non- , And more preferably 90 to 98 mass%.

The weight average molecular weight of the non-fluorine-containing acrylic polymer of the present embodiment is preferably 100,000 or more. If the weight average molecular weight is less than 100,000, the water repellency of the resulting fiber product tends to become insufficient. Further, the weight average molecular weight of the non-fluorine-containing acrylic polymer is more preferably 500,000 or more. In this case, the obtained fiber product can exhibit water repellency more sufficiently. The upper limit of the weight average molecular weight of the non-fluorine-containing acrylic polymer is preferably about 5,000,000.

In the present embodiment, it is preferable that the non-fluorine-containing acrylic polymer has a melt viscosity at 105 캜 of 1000 Pa · s or less. If the melt viscosity at 105 DEG C is 1000 Pa · s or less, the feeling of the obtained fiber product tends to be hard and stiff. It is more preferable that the melt viscosity at 105 ° C is 500 Pa · s or less. In this case, the obtained fiber products and the like exhibit sufficient water repellency and excellent feel.

The " melt viscosity at 105 캜 " refers to a melt viscosity in a cylinder equipped with a die (length 10 mm, diameter 1 mm) using a high-priced flow tester (for example, CFT-500 manufactured by Shimadzu Corporation) Refers to the viscosity measured by adding 1 g of the fluorine-containing polymer, keeping it at 105 ° C for 6 minutes, and applying a load of 100 kg · f / cm 2 by means of a plunger.

When the non-fluorine-containing acrylic polymer of the present embodiment has the same weight average molecular weight, the water-repellency of the adhered fiber product tends to be higher as the blending ratio of the non-fluorine (meth) acrylic acid ester monomer is higher. In addition, by copolymerizing a copolymerizable non-fluorine-based monomer, the durability of the attached fiber product and the performance such as feel can be improved.

The non-fluorine-containing acrylic polymer of the present embodiment is preferably a non-fluorine-containing acrylic polymer because the water repellency of the obtained fiber product and the emulsion stability of the non-fluorine-containing acrylic polymer in the emulsion polymerization or dispersion polymerization of the present embodiment, (B1) a compound represented by the following formula (I-1) wherein the HLB is 7 to 18, (B2) a compound represented by the following formula (B3) a compound having an HLB of 7 to 18, a compound having a hydroxyl group and a compound having a polymerizable unsaturated group added with an alkylene oxide having 2 to 4 carbon atoms, and It is preferable that one type of reactive emulsifier (B) (hereinafter also referred to as " component (B) ") is contained as a monomer component.

Wherein R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y ¹ represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms Group.]

[In the formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having a polymerizable unsaturated group and having 13 to 17 carbon atoms, and Y ² represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

The "reactive emulsifier" is an emulsifying dispersant having radical reactivity, that is, a surfactant having at least one polymerizable unsaturated group in the molecule, and can be copolymerized with a monomer such as (meth) acrylic acid ester.

The term " HLB " refers to the HLB value calculated by the Griffin method, in which the ethyleneoxy group is regarded as a hydrophilic group and all others are regarded as a lipophilic group.

The HLB of the compounds (B1) to (B3) used in the present embodiment is 7 to 18, and the emulsion stability (hereinafter referred to as " emulsion stability ") in the emulsion polymerization or dispersion polymerization of the non- (Hereinafter simply referred to as " emulsion stability "). From the viewpoint of storage stability of the water repellent composition, it is more preferable to use two or more reactive emulsifiers (B) having different HLB within the above range.

In the reactive emulsifier (B1) represented by the above formula (I-1) used in this embodiment, R ³ is hydrogen or a methyl group, and more preferably a methyl group from the viewpoint of copolymerization with the component (A). X is a straight chain or branched alkylene group having 1 to 6 carbon atoms and more preferably a straight chain alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of the non-fluorinated polymer of the present embodiment. Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The kind, combination and addition number of the alkyleneoxy group in Y ¹ can be appropriately selected so as to be within the HLB range described above. When two or more kinds of alkyleneoxy groups are present, they may have a block addition structure or a random addition structure.

As the compound represented by the above-mentioned formula (I-1), a compound represented by the following formula (I-2) is preferable.

Wherein R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, A ¹ O represents an alkyleneoxy group having 2 to 4 carbon atoms, m May be appropriately selected to be in the range of the HLB, specifically, an integer of 1 to 80 is preferable, and when m is 2 or more, m A ¹ O may be the same or different.]

In the compound represented by the above formula (I-2), R ³ is hydrogen or a methyl group, and more preferably a methyl group from the viewpoint of copolymerization with the component (A). X is a straight chain or branched alkylene group having 1 to 6 carbon atoms, and a straight chain alkylene group having 2 to 3 carbon atoms is more preferable in terms of emulsion stability of the non-fluorinated acrylic polymer of the present embodiment. A ¹ O is an alkyleneoxy group having 2 to 4 carbon atoms. The kind and combination of A ¹ O and the number of m can be appropriately selected to be within the HLB range. From the viewpoint of emulsion stability of the non-fluorine-containing acrylic polymer of the present embodiment, m is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ O may be the same or different. When two or more A < ¹ > O are present, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the above formula (I-2) can be obtained by a conventionally known method and is not particularly limited. Further, examples of commercially available products include "Latex PD-420", "Latex PD-430" and "Latex PD-450" manufactured by Kao Corporation.

In the reactive emulsifier (B2) represented by the above formula (II-1) used in this embodiment, R ⁴ is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, A decanediyl group, a decadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group and a heptadecatrienyl group. R ⁴ is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms from the viewpoint of emulsion stability of the non-fluorine-containing acrylic polymer of the present embodiment.

Y ² is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The kind, combination and addition number of the alkyleneoxy group in Y ² can be appropriately selected so as to be within the HLB range described above. When two or more kinds of alkyleneoxy groups are present, they may have a block addition structure or a random addition structure. From the viewpoint of emulsion stability of the non-fluorine-containing acrylic polymer of the present embodiment, the alkyleneoxy is more preferably an ethyleneoxy group.

As the compound represented by the above formula (II-1), a compound represented by the following formula (II-2) is preferable.

Wherein R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, A ² O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n represents a range of the HLB Specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, n A ² O may be the same or different.]

R ⁴ in the compound represented by the above formula (Ⅱ-2), there may be mentioned the same as R ⁴ in the above-described formula (Ⅱ-1).

A ² O is an alkyleneoxy group having 2 to 4 carbon atoms. From the viewpoint of emulsion stability of the non-fluorine-containing acrylic polymer of the present embodiment, the kind and combination of A ² O and the number of n can be appropriately selected so as to be within the HLB range described above. In view of emulsion stability of the non-fluorine-containing acrylic polymer of the present embodiment, A ² O is more preferably an ethyleneoxy group, n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, Is more preferable. When n is 2 or more, n A ² O may be the same or different. In addition, when two or more kinds of A ² O are present, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B2) represented by the above formula (II-2) used in the present embodiment can be synthesized by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group by a conventionally known method, It is not. For example, it can be synthesized by using an alkali catalyst such as caustic soda and caustic potassium, and adding a predetermined amount of alkylene oxide at 120 to 170 ° C under pressure.

The corresponding unsaturated hydrocarbon group-containing phenol may be present as a pure product or a mixture which is extracted or purified from a plant or the like, in addition to an industrially produced pure product or a mixture thereof. For example, 3- [8 (Z), 11 (Z), 14-pentadecatetrienyl] phenol, 3- [8 (Z) 11 (Z) -pentadecadienyl] phenol, 3- [8 (Z) -pentadecenyl] phenol and 3- [11 (Z) -pentadecenyl] phenol.

The reactive emulsifier (B3) used in the present embodiment is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a hydroxyl group and a polymerizable unsaturated group-containing oil having an HLB of 7 to 18. Examples of the fat-and-oil having a hydroxyl group and a polymerizable unsaturated group may include a hydroxy unsaturated fatty acid (palmitoleic acid, oleic acid, linoleic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosa-pentaenoic acid, etc.) Triglycerides of fatty acids including mono or diglycerides of fatty acids, and at least one hydroxy unsaturated fatty acid (ricinoleic acid, ricinoleic acid, 2-hydroxytetracosic acid, etc.). In view of emulsion stability of the non-fluorine-containing acrylic polymer of the present embodiment, an alkylene oxide adduct of triglyceride of a fatty acid containing at least one hydroxy-unsaturated fatty acid is preferable, and an alkylene oxide adduct of a fatty acid Triglyceride) is more preferable, and an ethylene oxide adduct of castor oil is more preferable. The number of moles of the alkylene oxide to be added can be appropriately selected so as to be in the range of the above HLB and is preferably 20 to 50 moles, more preferably 25 to 45 moles, in view of the emulsion stability of the non-fluorinated acrylic polymer of the present embodiment Do. When two or more kinds of alkylene oxides are used, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B3) used in the present embodiment can be synthesized by adding an alkylene oxide to a hydroxyl group and a fat having a polymerizable unsaturated group by a conventionally known method, and is not particularly limited. For example, it is possible to synthesize triglycerides of fatty acids containing ricinoleic acid, that is, an alkali catalyst such as caustic soda and caustic potassium for castor oil, and adding a predetermined amount of alkylene oxide at 120 to 170 ° C under pressure can do.

The constituent ratio of the monomer of the component (B) in the non-fluorine-containing acrylic polymer of the present embodiment is not particularly limited so long as the water repellency of the obtained fiber product and the emulsion polymerization or dispersion of the non-fluorine acrylic polymer of the present embodiment, Is preferably from 0.5 to 20% by mass, more preferably from 1 to 15% by mass, and still more preferably from 3 to 10% by mass, based on the total amount of the monomer components constituting the nonfluorinated acrylic polymer from the viewpoint of improving emulsion stability Is more preferable.

(C1), (C2), (C3), and (C2), in addition to the component (A) and the component (E), from the viewpoint of improving the durability of the obtained fiber product. At least one second (meth) acrylic acid ester monomer (C) (hereinafter also referred to as " component C ") selected from the group consisting of a monomer component (C4)

(C1) a (meth) acrylic acid ester monomer represented by the following formula (C-1)

Wherein R ⁵ represents hydrogen or a methyl group and R ⁶ represents at least one group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group, Represents a monovalent straight chain hydrocarbon group having from 1 to 11 carbon atoms having a functional group of species. Provided that the number of (meth) acryloyloxy groups in the molecule is 2 or less.

(C2) a (meth) acrylic acid ester monomer represented by the following formula (C-2)

[In the formula (C-2), R ⁷ represents hydrogen or a methyl group, and R ⁸ represents a monovalent cyclic hydrocarbon group of 1 to 11 carbon atoms which may have a substituent.]

(C3) a methacrylic acid ester monomer represented by the following formula (C-3)

[In the formula (C-3), R ⁹ represents an unsubstituted monovalent straight chain hydrocarbon group having 1 to 4 carbon atoms.]

(C4) a (meth) acrylic acid ester monomer represented by the following formula (C-4)

Wherein R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents a (p + 1) -valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group.

The monomer of (C1) has 1 to 11 carbon atoms having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group in the ester moiety (Meth) acrylic acid ester monomer having a monovalent chain hydrocarbon group. The monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group in that it can react with a crosslinking agent. When the non-fluorine-containing acrylic polymer containing a monomer (C1) having a group capable of reacting with these crosslinking agents is treated with a crosslinking agent in a fiber product, the durability of water repellency can be improved while maintaining the feeling of the resulting fiber product. The isocyanate group may be a block isocyanate group protected with a blocking agent.

The chain hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The chain hydrocarbon group may further have a substituent group in addition to the functional group. Among them, it is preferably a straight chain and / or a saturated hydrocarbon group in that the durability of the resulting fiber product can be improved.

Specific examples of the monomer (C1) include 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. . These monomers may be used singly or in combination of two or more kinds. Among them, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate and 1,1-bis (acryloyloxymethyl) ethyl isocyanate are preferred because they can improve the water repellency of the obtained textile product Do. In addition, dimethylaminoethyl (meth) acrylate is preferable in that it improves the feeling of the obtained fiber product.

The constituent ratio of the monomer (C1) in the non-fluorine-containing acrylic polymer of the present embodiment is preferably from 1 to 30% by mass, more preferably from 1 to 30% by mass, with respect to the total amount of the monomer components constituting the non- , More preferably from 3 to 25 mass%, still more preferably from 5 to 20 mass%.

The monomer (C2) is a (meth) acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety. Examples of the cyclic hydrocarbon group include an isobornyl group, a cyclohexyl group and a dicyclopentanyl group. . These cyclic hydrocarbon groups may have a substituent such as an alkyl group. When the substituent is a hydrocarbon group, a hydrocarbon group in which the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is 11 or less is selected. These cyclic hydrocarbon groups are preferably bonded directly to an ester bond from the viewpoint of improvement in durability of water repellency. The cyclic hydrocarbon group may be an alicyclic group or an aromatic group, and in the case of an alicyclic group, a saturated hydrocarbon group or an unsaturated hydrocarbon group may be used. Specific examples of the monomer include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. These monomers may be used singly or in combination of two or more kinds. Among them, isobornyl (meth) acrylate and cyclohexyl methacrylate are preferable in view of improving the durability of water repellency of the obtained fiber product, and more preferred is isobornyl methacrylate.

The constituent ratio of the monomer (C2) in the non-fluorine-containing acrylic polymer of the present embodiment is preferably from 1 to 30% by weight, based on the whole amount of the monomer components constituting the non-fluorinated polymer, from the viewpoint of water repellency and feeling of the obtained fiber product More preferably from 3 to 25% by mass, and still more preferably from 5 to 20% by mass.

The monomer (C3) is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety. As the chain hydrocarbon group having 1 to 4 carbon atoms, a straight chain hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group. Specific examples of the compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and t-butyl methacrylate . These monomers may be used singly or in combination of two or more kinds. Among them, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable because it can improve the durability of water repellency of the obtained fiber product.

The proportion of the monomer (C3) in the non-fluorinated acrylic polymer of the present embodiment is preferably from 1 to 30% by weight, based on the total amount of the monomer components constituting the non-fluorinated acrylic polymer, from the viewpoint of water repellency and feeling of the obtained fiber product More preferably from 3 to 25% by mass, and still more preferably from 5 to 20% by mass.

The monomer (C4) is a (meth) acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In the present embodiment, a polyfunctional (meth) acrylic acid ester monomer having three or more (meth) acryloyloxy groups in one molecule, wherein T in the above formula (C-4) is a (meth) acryloyloxy group, is preferable Do. In formula (C-4), p T may be the same or different. Specific examples of the compound include ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, penta Erythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexa methacrylate, and the like. These monomers may be used singly or in combination of two or more kinds. Among them, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferable because they can improve the durability of water repellency of the obtained fiber product.

The proportion of the monomer (C4) in the non-fluorine-containing acrylic polymer of the present embodiment is preferably from 1 to 30% by weight, based on the total amount of the monomer components constituting the non-fluorine-containing polymer, from the viewpoint of water repellency and feeling of the obtained fiber product More preferably from 3 to 25% by mass, and still more preferably from 5 to 20% by mass.

The total constituent ratio of the above-mentioned (C) component monomer in the non-fluorine-containing acrylic polymer of the present embodiment is preferably in the range of 1 to 30 (in terms of the total amount of the monomer components constituting the non- By mass, more preferably from 3 to 25% by mass, and still more preferably from 5 to 20% by mass.

The non-fluorine-containing acrylic polymer of the present embodiment is obtained by copolymerizing a monofunctional monomer (D) copolymerizable with the component (A), the component (E), the component (B) and the component (C) And the like.

Examples of the monomer (D) include (meth) acryloylmorpholine, (meth) acrylate having a hydrocarbon group other than the component (A) and the component (C), (meth) acrylic acid, a fumaric acid ester, Vinyl monomers other than the (E) component which does not contain fluorine such as acrylic ester, fumaric acid, maleic acid, (meth) acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, . The (meth) acrylic acid ester having a hydrocarbon group other than the component (A) and the component (C) may have a substituent such as a vinyl group, a hydroxyl group, an amino group, an epoxy group and an isocyanate group or a block isocyanate group in a hydrocarbon group , A quaternary ammonium group, and the like, and may have an ether bond, an ester bond, an amide bond, a urethane bond, or the like. Examples of the (meth) acrylic acid ester other than the component (A) and the component (C) include methyl acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) . Among them, (meth) acryloylmorpholine is more preferable because it can improve the peel strength against the coating of the obtained fiber product.

The constituent ratio of the monomer (D) in the non-fluorinated acrylic polymer of the present embodiment is preferably 10% by mass or less with respect to the total amount of the monomer components constituting the non-fluorinated acrylic polymer from the viewpoint of water repellency and feeling of the obtained fiber product Do.

The non-fluorine-containing acrylic polymer of the present embodiment has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group capable of reacting with a crosslinking agent, desirable. The isocyanate group may form a blocked isocyanate group protected with a blocking agent. The non-fluorine-containing polymer is preferred because it has an amino group because it improves the feel of the resulting fiber product.

The non-fluorine-containing acrylic polymer of the present embodiment can be produced by a radical polymerization method. Among these radical polymerization methods, polymerization is preferably carried out by emulsion polymerization or dispersion polymerization in view of performance and environment of the obtained water repellent agent.

For example, a non-fluorinated acrylic polymer can be obtained by emulsion polymerization or dispersion polymerization of a (meth) acrylic acid ester monomer (A) represented by the above formula (A-1) in the presence of the above component (E) . More specifically, it is possible to use, for example, a composition containing the component (A), the component (E), and the component (B), the component (C) and the component (D) And the mixture is emulsified or dispersed to obtain an emulsion or a dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, the polymerization reaction is initiated and the monomer and the reactive emulsifier can be polymerized. Examples of means for emulsifying or dispersing the above-mentioned mixed liquid include a homomixer, a high-pressure emulsifier, and an ultrasonic wave.

Examples of the emulsifying or dispersing agent (hereinafter also referred to as "emulsifying assistant") include a nonionic surfactant other than the reactive emulsifier (B), a cationic surfactant, an anionic surfactant, and a positive surfactant Or more can be used. The content of the emulsifying aid or the like is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and further preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total monomer. When the content of the emulsifying aid or the like is 0.5 part by mass or more, the dispersion stability of the mixed liquid tends not to be lowered as compared with the case where the content of the emulsifying auxiliary is outside the above range. When the content of the emulsifying auxiliary is 30 parts by mass or less , The water repellency of the resulting non-fluorinated acrylic polymer tends to be less likely to be lowered as compared with the case where the content of the emulsifying aid or the like is outside the above range.

As a medium for emulsion polymerization or dispersion polymerization, water is preferable, and water and an organic solvent may be mixed as required. The organic solvent is not particularly limited. Examples of the organic solvent include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, Dipropylene glycol, tripropylene glycol, and the like. The ratio of water to organic solvent is not particularly limited.

As the polymerization initiator, known polymerization initiators such as azo-based, peroxide-based, or redox-based can be suitably used. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass per 100 parts by mass of the total monomer. When the content of the polymerization initiator is within the above range, a non-fluorinated acrylic polymer having a weight average molecular weight of 100,000 or more can be efficiently produced.

In the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent is preferably 0.3 parts by mass or less, more preferably 0.1 parts by mass or less based on 100 parts by mass of the total monomer. When the content of the chain transfer agent is 0.3 parts by mass or less, the molecular weight is hardly lowered, and it is easy to efficiently produce a non-fluorinated acrylic polymer having a weight average molecular weight of 100,000 or more.

A polymerization inhibitor may be used for adjusting the molecular weight. By adding the polymerization inhibitor, a non-fluorinated acrylic polymer having a desired weight average molecular weight can be easily obtained.

The temperature of the polymerization reaction is preferably 20 占 폚 to 150 占 폚. When the temperature is 20 DEG C or more, polymerization tends to be sufficient as compared with the case where the temperature is outside the above range. When the temperature is 150 DEG C or less, control of the reaction column tends to be facilitated.

In the polymerization reaction, the weight average molecular weight of the obtained non-fluorinated acrylic polymer can be adjusted by increasing or decreasing the content of the polymerization initiator, the chain transfer agent and the polymerization inhibitor, and the melt viscosity at 105 캜 is, , And the content of the polymerization initiator. When it is desired to lower the melt viscosity at 105 占 폚, the content of the monomer having two or more polymerizable functional groups may be reduced or the content of the polymerization initiator may be increased.

The content of the non-fluorine-containing acrylic polymer in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is preferably from 10 to 50 mass% with respect to the total amount of the emulsion or dispersion from the viewpoint of storage stability and handling property of the composition, More preferably 20 to 40% by mass.

Examples of the silicone-based water repellent agent include hydrogen silicone, amino-modified silicone, dimethyl silicone, epoxy-modified silicone, carbinol-modified silicone and the like. Hydrogen silicone and amino-modified silicone are preferable from the viewpoint that the water repellency of the resulting fiber product becomes good.

As the hydrogen silicone, for example, a commercially available product such as " Dry Phone 600E " (trade name, manufactured by Nikka Kagaku K.K.) can be used.

As the amino-modified silicone, a commercially available product such as " Neocide SF-200 " (trade name, manufactured by Nikka Kagaku K.K.) may be used.

As the dendrimer-based water repellent agent, there can be enumerated waterborne polymer compounds having a structure radially and regularly branched from the center. The water-based polymer compound may have a linear or branched hydrocarbon group having 1 or more carbon atoms at the end branch portion in order to obtain water repellency.

As the aqueous polymer compound, for example, " a polymer extender " disclosed in International Publication WO2014 / 160906 pamphlet may be used. At least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate or a mixture thereof, and at least one isocyanate-reactive compound selected from the following formula (Ia), (Ib) And the like can be used.

In the formula, R ^2O are each ^{independently, -H, R 21, -C (} O) R 21, - (CH 2 CH 2 O) n (CH (CH 3) CH 2 O) m R 22, or, _{- (CH 2 CH 2 O)} n (CH (CH 3) CH 2 O) represents the ^{_{m C (O) R 21,}} n is independently 0 to 20, respectively, m are each independently 0 to 20, m + n Is greater than zero. R ²¹ represents a linear or branched alkyl group having 5 to 29 carbon atoms, which may independently contain at least one unsaturated bond, and each R ²² independently represents -H or an unsaturated bond Chain or branched alkyl group having 6 to 30 carbon atoms which may have a substituent.

In formula (Ia), at least one of R ²⁰ or R ²² is -H.

Wherein R ²³ is independently selected from the group consisting of -H, -R ²¹ , -C (O) R ²¹ , - (CH ₂ CH ₂ O (CH (CH ₃ ) CH ₂ O) _m R ²² , CH ₂ CH ₂ O (CH (CH ₃ ) CH ₂ OC (O) R ²¹ and R ²⁴ each independently represent -H or a straight or branched chain having 6 or more carbon atoms, which may contain one or more unsaturated bonds an alkyl group of 1 to _{30, - (CH 2 CH 2} O) n 'CH (CH 3) CH 2 O) m' R 22, or _{- (CH 2 CH 2 O (} CH (CH 3) CH 2 OC (O) R ²¹ shows a, n 'are independently 0 to 20, respectively, m' are each independently 0 to 20, and more than a m + n is 0.

In formula (Ib), at least one of R ²² , R ²³ or R ²⁴ is -H.

In the formula, R ²⁵ represents -H, -C (O) R ²¹ , or -CH ₂ C [CH ₂ OR ²⁰ ] ₃ . In formula (Ib), at least one of R ²⁵ or R ²⁰ is -H.

The isocyanate group-containing compound is not particularly limited, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and modified polyisocyanates such as dimers and trimer thereof. "Dylanate THA-100" (trade name, manufactured by Asahi Kasei Corporation), "Dyuranate 24A-100" (trade name, manufactured by Asahi Kasei Corporation), and the like, "DESMODUR N-100" Can be used. The reaction can be carried out at 80 占 폚 for 1 hour or more, for example.

The step of imparting a non-fluorine-containing water-repellent agent to the functional group-containing fiber can be carried out, for example, by treating the functional group-containing fiber with a treatment liquid containing at least one kind selected from the group consisting of acrylic water repellent, silicone water repellent and dendrimer- Method.

Examples of the method of treating the functional group-containing fiber with the treatment liquid include a processing method such as immersion, spraying, and coating. In the case where the treatment liquid contains water, it is preferable to dry it to remove water after adhering to the functional group-containing fiber.

An additive or the like may be added to the treatment liquid as required. Examples of the additives include other water repellent agents, crosslinking agents, antibacterial deodorants, flame retardants, antistatic agents, softeners and anti-wrinkle agents.

The amount of the non-fluorine-based water repellent agent adhered to the functional group-containing fiber can be appropriately adjusted in accordance with the required degree of water repellency. However, the amount of the non-fluorine water repellent agent (for example, It is preferable to adjust the adhesion amount so as to be 0.01 to 10 g, more preferably 0.05 to 5 g. If the adhesion amount of the non-fluorinated water repellent agent is 0.01 g or more, the fiber product tends to exhibit sufficient water repellency as compared with the case where the adhesion amount of the non-fluorinated water repellent agent is out of the above range. If the adhesion amount is 10 g or less, There is a tendency that the texture of the fiber product is hard to become rough and stiff as compared with the case where it is out of the above range.

After imparting the non-fluorine-based water repellent agent of the present embodiment to the functional group-containing fiber, it is preferable that heat treatment is suitably performed. The temperature condition is not particularly limited, but it is possible to exhibit sufficiently good water repellency in a fiber product under a mild condition of 100 to 130 占 폚. The temperature condition may be a high-temperature treatment of 130 ° C or higher (preferably up to 200 ° C), but in this case, the treatment time can be shortened as compared with the conventional case using a fluorine-based water repellent. Therefore, according to the method for producing a water-repellent fiber product of the present embodiment, the deterioration of the fiber product due to heat is suppressed, the feeling of the fiber product during the water-repellent treatment becomes flexible, and further, under mild heat treatment conditions, Sufficient water repellency can be imparted.

Particularly, when it is desired to improve the durability of water repellency, the above-mentioned step of treating the functional group-containing fiber with a treatment liquid containing a non-fluorine-based water repellent agent and a step of applying a crosslinking agent represented by a compound having at least one methylol melamine, isocyanate group or block isocyanate group Containing fiber to a functional group-containing fiber and heating the functional group-containing fiber to water-repellent processing. In order to further improve the durability of water repellency, it is preferable that the treatment liquid contains a non-fluorinated polymer obtained by copolymerizing a monomer having a functional group capable of reacting with the above-mentioned crosslinking agent.

Examples of the compound having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate and naphthalene isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate And trimethylolpropane adducts, which are isocyanurate rings of these, and the like. Examples of the compound having at least one block isocyanate group include compounds in which the isocyanate group is protected with a blocking agent as the isocyanate group-containing compound. Examples of the blocking agent used herein include organic blockers such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, and lactams; and bisulfates such as sodium bisulfate and potassium bisulfite. The above-mentioned cross-linking agent may be used singly or in combination of plural kinds.

The cross-linking agent can be obtained by, for example, dissolving a cross-linking agent in an organic solvent, or immersing a to-be-treated product (fiber product) into a treatment solution obtained by emulsifying and dispersing in water, and drying the treatment solution adhered to the to- It can be attached to water. By heating the cross-linking agent attached to the object to be treated, the reaction between the cross-linking agent and the substance to be treated and the non-fluorine-based water repellent (particularly, the non-fluorine-containing acrylic polymer) can be advanced. In order to improve the washing durability more effectively by sufficiently accelerating the reaction of the crosslinking agent, the heating at this time is preferably performed at 110 to 180 DEG C for 1 to 5 minutes. The step of adhering and heating the cross-linking agent may be performed simultaneously with the step of treating with the above-mentioned treatment liquid. In the case of simultaneous execution, for example, a treatment liquid containing a non-fluorine-based water repellent agent and a cross-linking agent is attached to the object to be treated, water is removed, and then the cross-linking agent attached to the object is further heated. In view of simplification of the water-repellent processing process, reduction of heat quantity, and economical efficiency, it is preferable to perform simultaneously with the treatment process with the treatment liquid.

In addition, if the crosslinking agent is used excessively, there is a fear that the feel is damaged. The crosslinking agent is preferably used in an amount of 0.1 to 50 mass%, particularly preferably 0.1 to 10 mass%, based on the material to be treated (fiber product).

The water repellent fiber product of the present embodiment thus obtained can exhibit sufficient water repellency even when used outdoors for a long period of time. Moreover, since the water repellent fiber product does not use a fluorine compound, it can be made environmentally friendly.

The water repellent fiber product of the present embodiment can be coated with a predetermined portion. Examples of the coating process include waterproofing and windproofing in sports applications and outdoor applications. As a processing method, for example, in the case of moisture-permeable and waterproof processing, a coating liquid containing urethane resin, acrylic resin and the like and a medium may be coated on one surface of a water-repellent treated fiber product and dried.

While the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

For example, in the case of producing a non-fluorine-containing acrylic polymer, in the above-described embodiment, the polymerization reaction is carried out by radical polymerization, but polymerization reaction by irradiation with ionizing radiation such as ultraviolet ray, electron beam, .

[ Example ]

Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited at all by these examples.

≪ Preparation of polymer dispersion >

The mixture solution having the compositions shown in Tables 1 and 2 (in the table, the values are shown in (g)) was polymerized by the following procedure to obtain a polymer dispersion.

(Synthesis Example 1)

40 g of stearyl acrylate, 20 g of vinyl chloride, 2 g of Latex PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 14.4), Latex PD-420 (manufactured by Kao Corporation, 2 g of polyoxyalkylene alkenyl ether, HLB = 12.6), 3 g of stearyldimethylamine hydrochloride, 25 g of tripropylene glycol and 207.70 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.3 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution and subjected to radical polymerization at 60 ° C. for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated acrylic polymer dispersion having a polymer concentration of 21 mass% as a non-fluorinated water repellent.

(Synthesis Examples 2 to 10)

Polymerization was carried out in the same manner as in Example 1 except that the materials described in Tables 1 and 2 were used to obtain non-fluorinated acrylic polymer dispersions each having a polymer concentration shown in Tables 1 and 2 as non-fluorinated water repellent agents.

(Synthesis Examples 11 and 12)

Polymerization was carried out in the same manner as in Example 1 except that the materials listed in Table 2 were used to obtain fluorine-based acrylic polymer dispersions each having a polymer concentration shown in Table 2 as a fluorine-based water repellent agent.

It was also confirmed that 98% or more of all the monomers were polymerized by the gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation) in the polymer dispersions obtained in Synthesis Examples 1 to 12 .

Details of the materials shown in Tables 1 and 2 are as follows.

(Product name, polyoxyalkylenealkenyl ether, HLB = 12.6) manufactured by Kao Corporation), PD-420

(Product name, polyoxyalkylenealkenyl ether, HLB = 14.4) manufactured by Kao Corporation), PD-430

Cardanol 12.5 EO: 12.5 moles adduct of cardanol with ethylene oxide (HLB = 12.9)

CARDANOL 8.3 EO: ethylene oxide 8.3 mole adduct of cardanol (HLB = 11.0)

(Trade name, polyoxyalkylene branched decyl ether, HLB = 14.7, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

(Trade name, polyoxyalkylene branched decyl ether, HLB = 12.5) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

The " C8 fluoro group-containing acrylate " in the table means a compound represented by the following formula (III):

, And the average value of n is 8 (n is a mixture of compounds of 6, 8, 10, 12 and 14 in the mixture).

The polymer dispersion thus obtained and the polymer obtained by the following method were evaluated.

(Evaluation of physical properties of polymer)

To 50 g of the polymer dispersion obtained in Synthesis Examples 1 to 10, 500 mL of acetone was added to separate the polymer and the emulsifier, and the polymer was filtered, and the polymer was dried under reduced pressure at 25 캜 for 24 hours. The obtained polymer was evaluated as follows. The results are shown in Tables 1 and 2.

(1) Method of measuring melt viscosity

1 g of a polymer was put in a cylinder equipped with a die (length 10 mm, diameter 1 mm) using a high-cost flotester CFT-500 (manufactured by Shimadzu Corporation) for the polymers obtained in the above- , And maintained at 105 DEG C for 6 minutes. A load of 100 kgf / cm < 2 > was applied by a plunger to measure the melt viscosity at 105 deg.

(2) Method of measuring weight average molecular weight

The polymers obtained in the above-mentioned Examples and Comparative Examples were subjected to polymerization under the conditions of a column temperature of 40 占 폚 and a flow rate of 1.0 ml / min using a GPC apparatus (GPC "HLC-8020" manufactured by Tosoh Corporation) with tetrahydrofuran , And the weight average molecular weight was measured in terms of standard polystyrene. The columns were connected by connecting three TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation.

(Preparation of textile material)

As the fiber material, a 100% nylon cloth (represented by Ny in the table), 100% polyester (made of polyethylene terephthalate) and a cationic chlorophylic polyester (Cation-exchangeable polyester knit smooth (processed yarn)) (indicated by CD-PET in the table) was prepared.

(Preparation of pretreatment agent)

The following Pretreatment Nos. 1 to 4 were prepared.

Pretreatment 1: An aqueous solution containing formalin condensate of phenol sulfonic acid synthesized by the following method.

The reaction vessel was charged with 70 g of phenol, 1.5 g of phosphoric acid and 20 g of formaldehyde, reacted at 95 to 100 캜 for 3 hours, then 45 g of acetic anhydride was added dropwise over 30 minutes and then cooled to 70 캜. Next, 25 g of 90% sulfuric acid was added dropwise over 30 minutes, and the mixture was reacted at 100 DEG C for 1 hour. After the reaction, 138.5 g of water was added to obtain Pretreatment 1 having a content of formalin condensate of phenolsulfonic acid of 38 mass%.

Pretreatment 2: An aqueous solution containing a formalin condensate of sulfonated bisphenol S synthesized by the following method.

To the reaction vessel, 100 g of bisphenol S and 45 g of acetic anhydride were added and the temperature was raised to 80 캜. Next, 14.5 g of 90% sulfuric acid was added dropwise over 30 minutes, and the mixture was reacted at 120 DEG C for 6 hours. Next, after cooling to 50 占 폚, 10.5 g of formaldehyde was added and the reaction was carried out at 100 占 폚 for 6 hours. Thereafter, the mixture was cooled to 70 deg. C and 147 g of water was added to obtain a pretreated 2 having a content of the formalin condensate of sulfonated bisphenol S of 40 mass%.

Pretreatment 3: An aqueous solution (Neocrystalline 770, content: 43 mass%, product of Nikka Kagaku Co., Ltd.) containing sodium polyacrylate having a molecular weight of 7000

Pretreatment 4: Laurylic acid ester (mixture of monoester and diester) (trade name: " Phosphanol ML-200 ", manufactured by Toho Chemical Industries, Ltd., content: 100%

≪ Preparation of water repellent fiber product &

(Example 1)

The dyed nylon 100% fabric was immersed in a treatment bath (the amount of applied to the fiber was 2% owf in terms of compound concentration) containing the pretreatment first, and a condition of bath ratio (bath ratio) 1:10, Lt; / RTI > After the treatment, the resultant was dried at 130 ° C for 2 minutes to obtain a functional group-containing fiber.

The functional group-containing fiber obtained above was subjected to an immersion treatment (pickup ratio: 60% by mass) in a treatment liquid obtained by diluting the non-fluorine-based water repellent of Synthesis Example 1 with water so that the content of the polymer was 3% by mass, followed by drying at 130 캜 for 2 minutes , A water repellent fiber product was obtained.

(Examples 2 to 12, 14 to 35 and Comparative Examples 3 to 6)

A water repellent fiber product was obtained in the same manner as in Example 1 except that the fiber materials, the pretreatment agent, the compound concentration, and the water repellent agent shown in Tables 3 to 8 were used. As the water repellent agents in Examples 32 to 35, the following were used.

Silicone water repellent agent 1: " Dry Phone 600E " (trade name, a hydrogen silicone content: 53 mass%, manufactured by Nikka Kagaku K.K.)

Silicone-based water repellent agent 2: " Neoside SF-200 " (trade name, amino-modified silicone content 30 mass%, manufactured by Nikkagakagaku Co., Ltd.)

(Example 13)

A water-repellent fiber product was obtained in the same manner as in Example 1 except that CD-PET was used as the functional group-containing fiber.

(Comparative Example 1)

A water-repellent fiber product was obtained in the same manner as in Example 1 except that pretreatment of the fiber material was not performed.

(Comparative Example 2)

A water-repellent fiber product was obtained in the same manner as in Comparative Example 1, except that 100% polyester (made of polyethylene terephthalate) cloth dyed as a fiber material was used.

<Various Evaluation>

The following various evaluations were carried out on the production of water repellent fiber products of Examples and Comparative Examples.

[Measurement of zeta potential on fiber surface]

The zeta potential of the surface of the functional group-containing fiber was measured with a zeta potential / particle size measuring system ELSZ-1000ZS (manufactured by Otsuka Denshi K.K.).

[Evaluation of water repellency of textile products]

According to JIS L 1092 (2009) spray method, the shower water temperature was set to 20 ° C. The results of the water repellency were visually evaluated in the following grades. In addition, when the characteristics are slightly better, "+" is added to the grade, and when the characteristics are slightly lowered, "-" is added to the grade.

Water repellency: State

     5: without wetting on the surface

     4: Very slight adhesion wetting on the surface

     3: Partial wetting on the surface

     2: Wet on the surface

     1: Wetted on the entire surface

     0: Both front and back surfaces are completely wetted

[Texture evaluation of textile products]

The feel was evaluated by using the obtained fiber product which was further heat-treated at 170 캜 for 30 seconds. The results were evaluated in five steps as shown below by handling.

1: Stiffness ~ 5: Softness

[Test of treatment bath stability]

The stability of the treatment bath for water-repellent processing was evaluated by the following procedure. 5 g of the pretreated fiber material (CD-PET in Example 13, fiber materials in Comparative Examples 1 and 2, which had not been pretreated), 12 g of water repellent agent, 1 g of NK assist FU (crosslinking agent, manufactured by Nikka Kagaku K.K.) Diluted with exchange water, and the diluted solution was allowed to stand at 40 占 폚 for 12 hours. Thereafter, the fiber material was removed, and the mixture was stirred at a rotation speed of 5,000 rpm for 10 minutes with a TK homomixer while maintaining the temperature at 40 ° C. Then, the mixture was filtered with a cotton cloth dyed in black, Respectively.

5; No agglomerates

4: Very little aggregation

3: Thin whiteness as a whole

2: wholly white coagulum remains

1: Inability to filter

[Evaluation of durability of water repellency]

The test was carried out at a shower water temperature of 20 ° C in accordance with the spray method of JIS L 1092 (2009). In this test, the functional group-containing fiber was changed to a polyamic acid copolymer having a polymer content of 3% by mass, a content of UNIKA RESIN 380-K (a crosslinking agent, trimethylol melamine resin manufactured by Union Carbide Corporation) and 0.3% by mass of UNIKA CATALYST 3- (Pickup ratio: 60% by mass) to the water-repellent agent and the treatment solution diluted with water so that the content of P (surfactant, amino alcohol hydrochloride produced by Union Kagakuko K.K.) was 0.2% by mass (L-0) obtained by heat treatment at 170 ° C for 60 seconds and 160 ° C for 60 seconds in the case where the fiber material is Pet and CD-PET, and JIS L 0217 1995), the water repellency of the fabric after 10 times (L-10) was evaluated in the same manner as the above water repellency evaluation method.

In Examples 1 to 35, in which the functional group-containing fibers according to the present invention were subjected to water-repellent processing using a specific non-fluorine-based water repellent agent according to the present invention, compared with Comparative Examples 1 and 2 in which the functional group- And a durable water repellent fiber product were obtained.

In Examples 1 to 25 and 28 to 31 in which water-repellent processing was performed with an acrylic water-repellent agent containing a non-fluorine-containing acrylic polymer obtained by using a reactive emulsifier to the functional group-containing fiber according to the present invention, water repellency and durability It was confirmed that the stability of the treatment bath can be satisfied at a high level.

In addition, in Comparative Examples 3 and 4 using a fluorine-based water repellent agent containing a fluorine-containing acrylic polymer obtained by using a reactive emulsifier, the treatment bath stability was lower than in Examples 1 and 2. This is believed to be attributable to the fact that the fluorine-based water repellent agent tends to flocculate.

According to the present invention, it is possible to produce a water-repellent fiber product having sufficient water repellency and sufficient endurance repellency by using a non-fluorine-based water repellent agent.

Claims (6)

A monovalent group represented by -SO ₃ M ¹ (wherein M ¹ represents a monovalent cation), a monovalent group represented by -COOM ² (wherein M ² represents a monovalent cation) At least one group selected from the group consisting of a monovalent group represented by OP (O) (OX ¹ ) (OX ² ) (wherein X ¹ and X ² each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) A method for producing a water-repellent fiber product, comprising the step of contacting a fiber containing a functional group of a species with at least one non-fluorine-based water repellent selected from the group consisting of an acrylic water repellent agent, a silicone water repellent agent and a dendrimer water repellent agent. The non-fluorinated water repellent agent according to claim 1, wherein the non-fluorine-based water repellent agent is a water repellent agent including an acrylic water repellent containing a polymer containing a structural unit derived from a (meth) acrylic acid ester monomer (A) represented by the following formula (A- A method of manufacturing a textile product.

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms, which may have a substituent.] The non-fluorinated water repellent according to any one of claims 1 to 3, wherein the non-fluorine-containing water repellent agent is a copolymer of a constituent unit derived from a (meth) acrylic acid ester monomer (A) represented by the following formula (A- A method for producing a water repellent fiber product comprising an acrylic water repellent agent containing a polymer containing a constituent unit derived from any one kind of monomer (E).

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms, which may have a substituent.] 4. The fiber according to any one of claims 1 to 3, wherein the fiber is a monovalent group represented by -SO ₃ M ¹ (wherein M ¹ represents a monovalent cation), -COOM ² (wherein, M ² is one represented by represents a monovalent cation) valent group, and ^{-OP (O) (OX 1)} (OX 2) ( wherein, X ¹ and X ² are independently a hydrogen atom or 1 to 22 carbon atoms respectively, And a monovalent group represented by the following formula (1): wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The method for producing a water repellent fiber product according to claim 4, wherein the compound comprises a phenolic polymer compound having a monovalent group represented by -SO ₃ M ¹ (wherein M ¹ represents a monovalent cation). 6. The method according to any one of claims 1 to 5, wherein the surface of the fiber has a zeta potential of -100 to -0.1 mV.