TWI731079B - Method for producing water repellent fiber product - Google Patents

Abstract

The method for producing a water-repellent fiber product of the present invention includes the following steps: making at least one non-toxic material selected from the group consisting of acrylic water-repellent agents, polysiloxane-based water-repellent agents, and dendritic polymer-based water-repellent agents The fluorine-based water repellent is in contact with a _{monovalent group selected from -SO 3} M ¹ (where M ¹ represents a monovalent cation), and -COOM ² (where M ² represents a monovalent cation) The monovalent group represented and the monovalent group represented by -OP(O)(OX ¹ )(OX ² ) (where X ¹ and X ² each independently represent a hydrogen atom or an alkyl group with 1 to 22 carbon atoms) A fiber with at least one functional group in the group.

Description

Manufacturing method of water-repellent fiber products

The present invention relates to a method of manufacturing a water-repellent fiber product, and more specifically, to a method of manufacturing a water-repellent fiber product using a non-fluorine-based water-repellent agent.

Conventionally, a fluorine-based water-repellent agent having a fluorine-containing group is known, and by treating a fiber product or the like with the fluorine-based water-repellent agent, a fiber product having water repellency to the surface can be obtained. Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group. In order to fully express the water repellency, it is necessary to make the alignment of the fluoroalkyl group uniform. Generally, after the fluorine-based water repellent is attached to the fiber product, the heat treatment is performed at a temperature exceeding 130°C. However, the heat treatment at high temperature, which requires higher energy, is not ideal under the trend of energy saving in the world. In addition, the monomer having a fluoroalkyl group is not only expensive, but also difficult to decompose, and therefore has a large load on the environment.

Based on this actual situation, in recent years, research has been conducted on non-fluorine-based water repellents that do not contain fluorine. For example, Non-Patent Document 1 discloses a water repellent obtained by emulsifying and dispersing a hydrocarbon compound such as paraffin or wax, a fatty acid metal salt, or an alkyl urea. In addition, Patent Document 1 proposes a water repellent obtained by emulsifying and dispersing a specific non-fluorine-based polymer in order to impart water repellency that is not inferior to that of conventional fluorine-based water-repellent agents.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-328624

Non-patent literature

[Non-Patent Document 1] "Overall water-repellent processing, processing agents and new trends in moisture-permeable water-repellent materials", issued by Osaka Chemical Marketing Center, 1996, p.7~9

However, even with the aforementioned non-fluorine-based water-repellent agent, the performance of imparting water repellency to fiber products is still insufficient. In addition, water-repellent fiber products also require durability (durable water-repellent) that is not easily reduced by outdoor use or washing. In this respect, the aforementioned non-fluorine-based water-repellent agents are not yet sufficient. .

The present invention was completed in view of the above-mentioned actual situation, and its object is to provide a method for producing a water-repellent fiber product that can obtain a water-repellent fiber product having sufficient water repellency and sufficient durable water repellency using a non-fluorine water-repellent agent.

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive studies, and found that by using a treatment solution containing a specific non-fluorine-based water repellent to treat fibers with specific functional groups, it is possible to obtain sufficient repellency. The present invention has been completed on the basis of a water-repellent fiber product having water and sufficient durable water-repellency.

That is, the method for producing a water-repellent fiber product of the present invention includes the step of making at least one selected from the group consisting of acrylic water-repellent, silicone-based water-repellent, and dendrimer-based water-repellent The non-fluorine-based water repellent is in contact with a _{monovalent group selected from -SO 3} M ¹ (where M ¹ represents a monovalent cation) and -COOM ² (where M ² represents a monovalent cation) The monovalent group represented and the monovalent represented by -OP(O)(OX ¹ )(OX ² ) (where X ¹ and X ² each independently represent a hydrogen atom or an alkyl group with 1 to 22 carbon atoms) A fiber with at least one functional group in the group consisting of the group.

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

Preferably, the non-fluorine-based water-repellent agent includes an acrylic water-repellent agent containing a (meth)acrylate monomer (A) derived from the following general formula (A-1) ) Is a polymer of the structural unit.

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

Furthermore, it is preferable that the non-fluorine-based water repellent includes an acrylic water repellent containing a (meth)acrylate monomer (meth) derived from the formula (A-1) represented by the above-mentioned general formula (A-1). A) The polymer of the structural unit and the structural unit derived from at least one monomer (E) among vinyl chloride and vinylidene chloride.

The above-mentioned fiber may be attached with a _{monovalent group selected from -SO 3} M ¹ (where M ¹ represents a monovalent cation), and -COOM ² (where M ² represents a monovalent cation). The monovalent group and the monovalent group represented by -OP(O)(OX ¹ )(OX ² ) (where X ¹ and X ² each independently represent a hydrogen atom or an alkyl group with 1 to 22 carbon atoms) A fiber composed of at least one functional group compound in the group.

Furthermore, it is preferable that the above-mentioned compound includes a phenol-based polymer compound having a monovalent group represented by _{-SO 3} M ¹ (in the formula, 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 zeta potential of the surface of the fiber is -100 to -0.1 mV.

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

In addition, although the method of the present invention uses a non-fluorine-based water repellent that does not contain a compound having a fluoroalkyl group or a fluorine, it can obtain a water-repellent fiber product with sufficient water repellency, and can reduce the worry about the fluorine supply source or the environmental The load.

When fluorine-based water repellent is attached to fiber products, heat treatment at high temperature is usually performed. However, according to the method of the present invention, even when heat treatment is performed under mild conditions below 130°C, the performance can be adequate Water repellency, and when the heat treatment is performed at a high temperature exceeding 130°C, the heat treatment time can be made shorter than that of the fluorine-based water repellent. Therefore, the method of the present invention suppresses the heat-induced deterioration of the object to be processed, so that the texture becomes soft, and the amount of heat consumed by the heat treatment can be reduced, and it is also excellent in terms of cost.

The method of manufacturing a water-repellent fiber product of this embodiment includes the following steps: selecting at least one non-acrylic water-repellent agent, a silicone-based water-repellent agent, and a dendritic polymer-based water-repellent agent. The fluorine-based water repellent is imparted to a _{monovalent group selected from -SO 3} M ¹ (where M ¹ represents a monovalent cation), and -COOM ² (where M ² represents a monovalent cation) The monovalent group represented and the monovalent group represented by -OP(O)(OX ¹ )(OX ² ) (where X ¹ and X ² each independently represent a hydrogen atom or an alkyl group with 1 to 22 carbon atoms) A fiber of at least one type of functional group (hereinafter also referred to as a "specific functional group") in the group composed.

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

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

(i) The compound having the above-mentioned specific functional group is attached to the fiber material. Furthermore, the attachment of the compound may be a state in which a part of the compound is chemically bonded to a part of the fiber within a range where the above-mentioned specific functional group remains in a sufficient amount.

(ii) Prepare a fiber obtained by directly introducing the above-mentioned specific functional group into the material constituting the fiber.

In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the above-mentioned specific functional group.

The raw material of the fiber material is not particularly limited. Examples include natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, polyamide (nylon, etc.), polyester, and polyurethane. Synthetic fibers such as acid ester and polypropylene, as well as such composite fibers and blended fibers. The form of the fiber material can be any form such as fiber (tow, fiber bundle, etc.), yarn, knitted fabric (including mixed knitted fabric), woven fabric (including mixed woven fabric), non-woven fabric, paper, etc.

In this embodiment, from the viewpoint of improving the water repellency of the obtained fiber product, it is preferable to use a fiber material containing polyamide and polyester as raw materials, and particularly preferably to use nylon 6, nylon 6, 6, etc. Polyesters such as nylon, polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

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

[In formula (2), X ² represents -SO ₃ M ³ (where M ³ represents a monovalent cation) or the group represented by the following general formula (3), n is an integer of 20 to 3000]

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

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

As said M ⁴ , H, K, Na, or an ammonium ion which may have a substituent is mentioned.

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

Examples of the compound having the above -COOM ² include polycarboxylic acid-based polymers.

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

As a manufacturing method of a polycarboxylic acid type polymer, the method of adding a radical polymerization initiator to the aqueous solution of the said monomer and/or its salt, and heating reaction at 30-150 degreeC for 2-5 hours is mentioned, for example. At this time, alcohols such as methanol, ethanol, and isopropanol, or aqueous solvents such as acetone may be added to the aqueous solution of the above-mentioned monomer and/or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators obtained by the combination of persulfate and sodium bisulfite, and hydrogen peroxide. , Water-soluble azo polymerization initiator, etc. These radical polymerization initiators may be used individually by 1 type, or may use 2 or more types together. Furthermore, during radical polymerization, in order to adjust the degree of polymerization, a chain transfer agent (for example, octyl thioglycolate) may be added.

In radical polymerization, copolymerizable monomers other than the above-mentioned monomers can be used. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamides, acrylic esters, and methacrylic esters. The acrylic esters and methacrylic esters preferably have a hydrocarbon group having 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, and 2-hydroxyethyl methacrylate. , Propyl acrylate, Propyl methacrylate, etc. These copolymerizable monomers may be used alone or in combination of two or more kinds.

The carboxyl group in the polycarboxylic acid polymer may be free, or it may be neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, and examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

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

As the polycarboxylic acid-based polymer, commercially available products such as "NEOCRYSTAL 770" (manufactured by Nikka Chemical Co., Ltd., trade name) and "CELLOPOL PC-300" (manufactured by Sanyo Chemical Co., Ltd., trade name) can be used.

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

[In formula (4), X ¹ or X ² has the same meaning as above, and X ³ represents an alkyl group with 1 to 22 carbon atoms]

As the above-mentioned phosphoric acid ester compound, phosphoric acid monoesters, phosphoric acid diesters, and phosphoric acid triesters in which the alkyl ester portion is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

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

As the phosphoric acid ester compound, for example, commercially available products such as "PHOSPHANOL ML-200" (manufactured by Toho Chemical Industry Co., Ltd., brand name) can be used.

The pretreatment liquid containing one or more compounds having the above-mentioned specific functional group can be, for example, an aqueous solution of the above-mentioned compound. In addition, the pretreatment liquid may contain acids, alkalis, surfactants, chelating agents, and the like.

As a method of treating the fibrous material with the above-mentioned pretreatment liquid, for example, press dyeing treatment, dipping treatment, spray treatment, and coating treatment can be cited. As the press dyeing treatment, for example, it is described in the textile dyeing processing dictionary (1963, published by Nikkan Kogyo Kogyo), pages 396-397, or Seike Dyeing Chemistry III (1975, published by Shikyo Publishing Co., Ltd.), pages 256-260. Use pressure Method of dyeing device. As the coating treatment, for example, the method of using a coating machine described in pages 473 to 477 of the overview of dyeing machines (published by Textile Co., Ltd.) in 1981 can be cited. As the immersion treatment, for example, the method of using a batch dyeing machine described in pages 196 to 247 of the dyeing machine overview (published by Textile Co., Ltd.) can be used. Liquid dyeing machine, airflow dyeing machine, drum dyeing machine can be used. , Rope dyeing machine, washing dyeing machine, cheese dyeing machine, etc. As the spraying treatment, for example, a method of using an air sprayer that uses compressed air to make the treatment liquid into a mist and blows it, or an air sprayer of a hydraulic atomization method is used. The concentration of the treatment solution at this time or the treatment conditions such as the heat treatment after the application can be appropriately adjusted in consideration of various conditions such as the purpose and performance. Moreover, when the pretreatment liquid contains water, it is preferable to dry it after adhering to the fibrous material in order to remove water. The drying method is not particularly limited, and may be any of a dry heat method and a moist heat method. The drying temperature is also not particularly limited. For example, it can be dried at room temperature to 200°C for 10 seconds to several days. It can also be heat treated at a temperature of 100 to 180°C for 10 seconds to 5 minutes after drying as needed.

Furthermore, when the fiber material is to be dyed, the treatment with the pretreatment solution can be carried out before dyeing, or in the same bath as the dyeing, but in the case of reducing soaping, in the process The adsorbed compounds having the above-mentioned specific functional groups (for example, phenol-based polymer compounds, etc.) are likely to fall off, so it is preferably carried out after the reduction soaping after dyeing.

The treatment temperature in the immersion treatment can be set at 60~130°C. The processing time can be set to 5 to 60 minutes.

The functional group introduction step with the pretreatment liquid is preferably performed 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 relative to 100 parts by mass of the fiber material. If it is within this range, it is possible to have both durable water repellency and texture at a high level.

It is preferable to adjust the pH value of the pretreatment liquid to 3 to 5. For pH adjustment, pH adjusting agents such as acetic acid and malic acid can be used.

In the pretreatment liquid, in order to utilize the salting-out effect to effectively adsorb the compound having the above-mentioned specific functional group on the fiber material, a salt can also be used in combination. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

In the functional group introduction step using the pretreatment liquid, it is preferable to remove the excessively treated compound having the above-mentioned specific functional group. As the removal method, a method using water washing can be cited. By performing sufficient removal, it is possible to prevent the performance of water repellency from being hindered in the subsequent water repellency processing, and in addition, the texture of the obtained fiber product becomes better. In addition, the obtained functional group-containing fiber is preferably dried sufficiently before being contacted with a non-fluorine-based water repellent.

(Ii) The fiber obtained by directly introducing the above-mentioned specific functional group into the material constituting the fiber includes, for example, cationic dyeable polyester (CD-PET).

From the viewpoint of improving the water repellency of the obtained fiber product of the functional group-containing fiber of this embodiment, the zeta potential of the surface is preferably -100 to -0.1 mV, more preferably -50 to -1 mV. The zeta potential on the surface of the fiber can be measured using, for example, a zeta potential-particle size measuring system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

Next, the non-fluorine-based water repellent provided to the functional group-containing fiber of this embodiment will be described. The non-fluorine-based water-repellent agent can include at least one selected from the group consisting of acrylic-based water-repellent agents, silicone-based water-repellent agents, and dendrimer-based water-repellent agents.

The acrylic water repellent includes a structure containing a (meth)acrylate monomer (A) (hereinafter also referred to as "(A) component") derived from the following general formula (A-1) Unit polymer (hereinafter also referred to as "non-fluorine-based acrylic polymer").

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

Here, "(meth)acrylate" means "acrylate" or its corresponding "methacrylate", "(meth)acrylic acid", "(meth)acrylamide", etc. have the same meaning .

The (meth)acrylate monomer (A) represented by the above general formula (A-1) used in this embodiment has a monovalent hydrocarbon group with 12 or more carbon atoms that may have a substituent. The hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may further have an alicyclic or aromatic cyclic ring. Among them, the linear ones are preferred, and the linear alkyl groups are more preferred. In this case, the water repellency is more excellent. When a monovalent hydrocarbon group with 12 or more carbons has a substituent, examples of the substituent include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and (meth)acryloxy One or more of the bases. In this embodiment, in the above general formula (A-1), R ^{2 is} preferably an unsubstituted hydrocarbon group.

The carbon number of the above-mentioned hydrocarbon group is preferably 12-24. If the carbon number is 12 or more, when a non-fluorine-based acrylic polymer is attached to a fiber product or the like, it is easy to obtain excellent water repellency. On the other hand, if the carbon number is 24 or less, compared with the case where the carbon number is outside the above range, when a non-fluorinated acrylic polymer is attached to a fiber product, the texture of the fiber product is less likely to become coarse. The tendency to be hard.

The carbon number of the above-mentioned hydrocarbon group is more preferably 12-21. When the carbon number is in this range, the water repellency and texture become particularly excellent. As the hydrocarbon group, a linear alkyl group having 12 to 18 carbon atoms is particularly preferred.

As said (A) component, for example, stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, (meth) )Myristyl acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, (meth) Nonadecyl acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, behenyl (meth)acrylate, wax (meth)acrylate, (meth)acrylate ) Beeswax acrylate.

The above-mentioned 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 that can react with a crosslinking agent. In this case, the durable water repellency of the obtained fiber product can be further improved. The isocyanate group can also form a blocked isocyanate group protected by a blocking agent. In addition, when the component (A) has an amine group, the texture of the obtained fiber product can be further improved.

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

The said (A) component may be used individually by 1 type, and may be used in combination of 2 or more types.

In terms of the durable water repellency of the obtained fiber product, the aforementioned component (A) is preferably a combination of an acrylate monomer (a1) and a methacrylate monomer (a2). The ratio (a1)/(a2) of the mass of the component (a1) to the mass of the component (a2) is preferably 30/70~90/10, more preferably 40/60~85/15, and more preferably 50/50~80/20. When (a1)/(a2) is within the above range, the durable water repellency of the obtained fiber product becomes more favorable.

The non-fluorine-based acrylic polymer of this embodiment preferably contains a structural unit derived from the above-mentioned component (A) and at least one monomer (E) derived from vinyl chloride and vinylidene chloride (hereinafter also referred to as It is the structural unit of "(E) component").

At least one monomer (E) of vinyl chloride and vinylidene chloride used in this embodiment is included as a copolymer component of the non-fluorine-based acrylic polymer of this embodiment, and the obtained fiber product is In terms of water repellency and peel strength of the coating, vinyl chloride is preferred.

Regarding the content ratio of the structural unit derived from the component (A) to the structural unit derived from the component (E) in the non-fluorine-based acrylic polymer of this embodiment, the non-fluorine-based polymer of this embodiment In terms of the emulsification stability and the peel strength of the obtained fiber product for the coating, the ratio (A)/(E) of the mass of the (A) component to the mass of the (E) component (A)/(E) is preferably 40/60 ~90/10, more preferably 50/50~85/15, still more preferably 60/40~80/20. If (A)/(E) is less than 90/10, there is a tendency that the peel strength of the obtained fiber product to the coating layer is not easily reduced. If (A)/(E) is 40/60 or more, the emulsification stability of the non-fluorine-based acrylic polymer of this embodiment tends to be less likely to decrease.

In addition, the total mass of the mass of the (A) component and the mass of the (E) component to be formulated is preferably 80-100% by mass, more preferably 80-100% by mass, relative to the total amount of the monomer components constituting the non-fluorine-based acrylic polymer 85 to 99% by mass, more preferably 90 to 98% by mass.

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

In this embodiment, the melt viscosity at 105°C of the non-fluorine acrylic polymer is preferably 1000Pa. s or less. If the melt viscosity at 105°C is 1000Pa. Below s, there is a tendency that the texture of the obtained fiber product is not easy to become rough. Furthermore, the melt viscosity at 105°C is more preferably 500Pa. s or less. In this case, the obtained fiber product etc. fully exhibit water repellency, and the texture becomes more excellent.

"Melt viscosity at 105°C" refers to the use of an overhead rheometer (such as CFT-500 manufactured by Shimadzu Corporation) to fill 1g of non-fluorine-based polymer into a machine equipped with a die nozzle (length 10mm, diameter 1mm) In the cylinder, keep it at 105°C for 6 minutes and apply 100kg through the plunger. Viscosity when measured with a load of f/cm ^2.

When the weight average molecular weight of the non-fluorine-based acrylic polymer of this embodiment is equal, the higher the blending ratio of the non-fluorine-based (meth)acrylate monomer, the higher the water repellency of the attached fiber product tendency. Furthermore, by copolymerizing a copolymerizable non-fluorine-based monomer, it is possible to improve the performance of the adhered fiber product such as durable water repellency and texture.

The non-fluorinated acrylic polymer of this embodiment can improve the water repellency of the obtained fiber product and the emulsification in the composition during the emulsion polymerization or dispersion polymerization of the non-fluorine acrylic polymer of this embodiment and after the polymerization In terms of stability, it is preferable to contain (B1) HLB (Hydrophilic-Lipophilic Balance, hydrophilic-lipophilic balance) in addition to (A) component, or (A) component and (E) component. The compound represented by the following general formula (I-1) of 18, the compound represented by the following general formula (II-1) of (B2) HLB of 7 to 18, and the compound of (B3) HLB of 7 to 18 At least one reactive emulsifier (B) (hereinafter also referred to as "(B) component") in a compound obtained by adding alkylene oxides with 2 to 4 carbon atoms to fats and oils having a hydroxyl group and a polymerizable unsaturated group is used as Monomer components.

[In formula (I-1), R ³ represents hydrogen or methyl, X represents a linear or branched alkylene group with carbon number 1 to 6, and Y ¹ represents an alkylene group with carbon number 2 to 4 2-valent base]

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group with a carbon number of 13 to 17 having a polymerizable unsaturated group, and Y ² represents a divalent group containing an alkoxy group with a carbon number of 2 to 4 ]

"Reactive emulsifier" is an emulsifying and dispersing agent with free radical reactivity, that is, a surfactant with more than one polymerizable unsaturated group in the molecule, and can be copolymerized with monomers such as (meth)acrylate .

In addition, "HLB" is the HLB value calculated by the Griffin method by treating the ethoxylate group as a hydrophilic group and treating all other groups as a lipophilic group.

The HLB of the above-mentioned (B1)~(B3) compounds used in this embodiment is 7-18, and the non-fluorinated acrylic polymer of this embodiment is used in the composition during emulsion polymerization or dispersion polymerization and after polymerization In terms of emulsification stability (hereinafter referred to as emulsification stability), it is preferably 9-15. Furthermore, in terms of the storage stability of the water-repellent composition, it is more preferable to use together two or more reactive emulsifiers (B) having different HLBs within the above-mentioned range.

In the reactive emulsifier (B1) represented by the above general formula (I-1) used in this embodiment, R ³ is hydrogen or methyl. In terms of copolymerization with component (A), it is more Preferably it is methyl. X is a linear or branched alkylene having 1 to 6 carbon atoms. In terms of the emulsification stability of the non-fluorinated polymer of this embodiment, it is more preferably a linear or branched alkylene having 2 to 3 carbon atoms. base. Y ¹ is a divalent group containing an alkoxy group having 2 to 4 carbon atoms. The type, combination, and addition number of the alkoxy group in Y ¹ can be appropriately selected so as to be within the range of the above-mentioned HLB. Moreover, when there are 2 or more types of alkoxylate groups, these can have a block addition structure or a random addition structure.

The compound represented by the above general formula (I-1) is preferably a compound represented by the following general formula (I-2).

[In formula (I-2), R ³ represents hydrogen or methyl, X represents a linear or branched alkylene group with carbon number 1 to 6, and A ¹ O represents an alkoxy group with carbon number 2 to 4, m can be appropriately selected so as to be within the range of the above HLB. Specifically, it is preferably an integer of 1 to 80. When m is 2 or more, m A ¹ O may be the same or different]

In the compound represented by the general formula (I-2), R ³ is hydrogen or a methyl group, and in terms of copolymerization with the component (A), a methyl group is more preferable. X is a linear or branched alkylene group with carbon number of 1 to 6. In terms of the emulsification stability of the non-fluorinated acrylic polymer of this embodiment, it is more preferably a linear chain with carbon number of 2 to 3 Alkylene. A ¹ O is an alkoxy group with 2 to 4 carbon atoms. The type and combination of A ¹ O and the number of m can be appropriately selected so as to be within the range of the above-mentioned HLB. In terms of the emulsification stability of the non-fluorine-based acrylic polymer of this embodiment, m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ O may be the same or different. In addition, when there ^{are two or more types of A 1} O, these can have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the above general formula (I-2) can be obtained by a previously known method, and is not particularly limited. In addition, it can be easily obtained from commercially available products. For example, "LATEMUL PD-420", "LATEMUL PD-430", and "LATEMUL PD-450" manufactured by Kao Co., Ltd. can be cited.

In the reactive emulsifier (B2) represented by the above general formula (II-1) used in this embodiment, R ⁴ is a monovalent unsaturated hydrocarbon group with a carbon number of 13 to 17 having a polymerizable unsaturated group, Examples include tridecenyl, tridecadienyl, tetradecenyl, tetradecadienyl, pentadecenyl, pentadecadienyl, pentadecenyl, heptadecenyl Carbalkenyl, heptadecadienyl, heptatrienyl and the like. In terms of the emulsification stability of the non-fluorinated acrylic polymer of this embodiment, R ^{4 is more} preferably a monovalent unsaturated hydrocarbon group with 14 to 16 carbon atoms.

Y ² is a divalent group containing an alkoxy group having 2 to 4 carbon atoms. The type, combination, and number of additions of the alkoxy group in Y ² can be appropriately selected so as to be within the range of the above-mentioned HLB. Moreover, when there are 2 or more types of alkoxylate groups, these can have a block addition structure or a random addition structure. In terms of the emulsion stability of the non-fluorine-based acrylic polymer of this embodiment, the alkoxylate group is more preferably an ethoxylate group.

The compound represented by the above general formula (II-1) is preferably a compound represented by the following general formula (II-2).

[In formula (II-2), R ⁴ represents a monovalent unsaturated hydrocarbon group with a carbon number of 13 to 17 having a polymerizable unsaturated group, A ² O represents an alkoxy group with a carbon number of 2 to 4, and n can be The method to be within the range of the above HLB is appropriately selected. Specifically, it is preferably an integer of 1 to 50. When n is 2 or more, n A ² O may be the same or different]

Compound of the formula (II-2) represented by the sum of R ⁴ include the above general formula (II-1) R ⁴ in the same person.

A ² O is an alkoxy group with 2 to 4 carbon atoms. Regarding the emulsification stability of the non-fluorine-based acrylic polymer of the present embodiment, ^{the type and combination of A 2} O and the number of n can be appropriately selected so as to be within the range of the above-mentioned HLB. In terms of the emulsification stability of the non-fluorinated acrylic polymer of this embodiment, A ² O is more preferably an ethoxylate group, and n is preferably an integer of 1-50, and more preferably an integer of 5-20 , And more preferably an integer of 8-14. When n is 2 or more, n pieces of A ² O may be the same or different. In addition, when there ^{are two or more types of A 2} O, these can have a block addition structure or a random addition structure.

The reactive emulsifier (B2) represented by the above general formula (II-2) used in this embodiment can be synthesized by adding alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group by a previously known method , There is no particular limitation. For example, it can be synthesized by using alkali catalysts such as caustic soda and caustic potash and adding a specific amount of alkylene oxide at 120 to 170°C under pressure.

The above-mentioned phenols with corresponding unsaturated hydrocarbon groups include not only industrially manufactured pure products or mixtures, but also those in the form of pure products or mixtures extracted and refined from plants. For example, 3-[8(Z), 11(Z), 14-pentadecatrienyl]phenol, 3-[8(Z), 11(Z) extracted from the shell of cashew nuts, etc., collectively referred to as cardanol )-Pentadecenyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, etc.

The reactive emulsifier (B3) used in this embodiment is a compound obtained by adding an alkylene oxide having a carbon number of 2 to 4 to fats and oils having a hydroxyl group and a polymerizable unsaturated group with an HLB of 7-18. Examples of fats and oils having a hydroxyl group and a polymerizable unsaturated group include hydroxy unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid). , Docosapentaenoic acid, etc.) fatty acid monoglyceride or diglyceride, containing at least one hydroxy unsaturated fatty acid (ricinoleic acid, transricinoleic acid, 2-hydroxy tetracosenoic acid, etc.) Triglycerides of fatty acids. In terms of the emulsification stability of the non-fluorinated acrylic polymer of this embodiment, it is preferably an alkylene oxide adduct of triglyceride of fatty acid containing at least one hydroxyunsaturated fatty acid, more preferably castor The alkylene oxide adduct of sesame oil (triglyceride of fatty acid containing ricinoleic acid) with carbon number of 2 to 4 is more preferably the ethylene oxide adduct of castor oil. Furthermore, epoxy The number of added moles of alkane can be appropriately selected so as to be within the range of the above-mentioned HLB. In terms of the emulsification stability of the non-fluorinated acrylic polymer of this embodiment, it is more preferably 20-50 moles , And more preferably 25 to 45 mol. Moreover, when there are 2 or more types of alkylene oxides, these can have a block addition structure or a random addition structure.

The reactive emulsifier (B3) used in this embodiment can be synthesized by adding alkylene oxide to fats and oils having a hydroxyl group and a polymerizable unsaturated group by a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a specific amount of alkylene oxide to castor oil, which is a triglyceride of fatty acids containing ricinoleic acid, at 120-170°C under pressure using alkali catalysts such as caustic soda and caustic potash.

Regarding the composition ratio of the monomers of the component (B) in the non-fluorine-based acrylic polymer of this embodiment, it is possible to improve the water repellency of the obtained fiber product and the ratio of the non-fluorine-based acrylic polymer of this embodiment From the viewpoint of emulsion stability in the composition during emulsion polymerization or dispersion polymerization and after polymerization, the total amount of monomer components constituting the non-fluorine acrylic polymer is preferably 0.5-20% by mass, and more Preferably it is 1-15 mass %, More preferably, it is 3-10 mass %.

In terms of improving the durable water repellency of the obtained fiber product, the non-fluorine-based acrylic polymer of the present embodiment preferably contains, in addition to the (A) component and (E) component, it is also selected from the following (C1) At least one second (meth)acrylate monomer (C) (hereinafter also referred to as "C component") from the group consisting of (C2), (C3) and (C4) is used as a monomer component.

(C1) The (meth)acrylate monomer represented by the following general formula (C-1)

[In formula (C-1), R ⁵ represents hydrogen or methyl, and R ⁶ represents having selected from the group consisting of hydroxyl, amino, carboxy, epoxy, isocyanate, and (meth)acryloxy groups At least one functional group is a monovalent chain hydrocarbon group with 1 to 11 carbon atoms; wherein the number of (meth)acryloyloxy groups in the molecule is 2 or less]

(C2) The (meth)acrylate monomer represented by the following general formula (C-2)

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

(C3) Methacrylate monomer represented by the following general formula (C-3)

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

(C4) The (meth)acrylate monomer represented by the following general formula (C-4)

[In formula (C-4), R ¹⁰ represents hydrogen or methyl, p represents an integer of 2 or more, S represents a (p+1) valent organic group, and T represents a monovalent organic group with a polymerizable unsaturated group ]

The monomer of (C1) is a (meth)acrylate monomer having a monovalent chain hydrocarbon group with 1 to 11 carbon atoms in the ester portion, and the monovalent chain hydrocarbon group with 1 to 11 carbon atoms has a hydroxyl group selected from the group. At least one functional group from the group consisting of, amine group, carboxyl group, epoxy group, isocyanate group and (meth)acryloxy group. In terms of reacting with a crosslinking agent, the above-mentioned monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. At least one functional group. When the non-fluorinated acrylic polymer containing monomers (C1) having the groups that can react with the crosslinking agent and the crosslinking agent are used to process the fiber product, the texture of the obtained fiber product can be maintained And improve the durable water repellency. The isocyanate group may be a blocked isocyanate group protected by a blocking agent.

The above-mentioned chain hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, the chain hydrocarbon group may further have a substituent in addition to the above-mentioned functional group. Among them, in terms of improving the durable water repellency of the obtained fiber product, it is preferably linear and/or saturated hydrocarbon group.

Specific (C1) monomers include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 1,1 isocyanate -Bis(acryloxymethyl) ethyl ester and the like. These monomers may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, in terms of improving the durable water repellency of the obtained fiber products, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 1,1-bis(acrylic acid) isocyanate are preferred. Oxymethyl) ethyl ester. In terms of further improving the texture of the obtained fiber product, dimethylaminoethyl (meth)acrylate is preferred.

Regarding the structure of the monomer (C1) in the non-fluorine-based acrylic polymer of this embodiment From the viewpoint of the water repellency and texture of the obtained fiber product, the ratio is preferably 1-30% by mass, more preferably 3%, relative to the total amount of monomer components constituting the non-fluorine-based acrylic polymer. 25% by mass, more preferably 5-20% by mass.

基、環己基、雙環戊基等。該等環狀烴基可具有烷基等取代基。但於取代基為烴基之情形時，選擇取代基及環狀烴基之碳數之合計成為11以下之烴基。又，就提高耐久撥水性之觀點而言，較佳為該等環狀烴基與酯鍵直接鍵結。環狀烴基可為脂環式，亦可為芳香族，於脂環式之情形時，可為飽和烴基，亦可為不飽和烴基。作為具體之單體，可列舉(甲基)丙烯酸異

酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸雙環戊酯等。該等單體可單獨使用1種，亦可將2種以上組合使用。其中就能夠提高獲得之纖維製品之耐久撥水性之方面而言，較佳為(甲基)丙烯酸異

酯、甲基丙烯酸環己酯，更佳為甲基丙烯酸異

酯。 The monomer of (C2) is a (meth)acrylate monomer having a monovalent cyclic hydrocarbon group with 1 to 11 carbon atoms in the ester portion. Examples of the cyclic hydrocarbon group include various

Group, cyclohexyl, dicyclopentyl, etc. These cyclic hydrocarbon groups may have substituents such as alkyl groups. However, when the substituent is a hydrocarbon group, the total carbon number of the substituent and the cyclic hydrocarbon group is selected to be a hydrocarbon group of 11 or less. In addition, from the viewpoint of improving durable water repellency, it is preferable that these cyclic hydrocarbon groups are directly bonded to ester bonds. The cyclic hydrocarbon group may be alicyclic or aromatic. In the case of the alicyclic type, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. As a specific monomer, (meth)acrylic acid iso

Ester, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. These monomers may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, in terms of improving the durable water repellency of the obtained fiber product, (meth)acrylic acid is preferred.

Ester, cyclohexyl methacrylate, more preferably isomethacrylate

ester.

Regarding the composition ratio of the monomers (C2) in the non-fluorine-based acrylic polymer of this embodiment, from the viewpoint of the water repellency and texture of the obtained fiber product, it is relative to the monomer composition of the non-fluorine-based polymer The total amount of body ingredients is preferably 1-30% by mass, more preferably 3-25% by mass, and still more preferably 5-20% by mass.

The monomer of (C3) is a methacrylate monomer in which an unsubstituted monovalent chain hydrocarbon group with 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 chain hydrocarbon group having 3 to 4 carbon atoms are preferred. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and tertiary butyl. Specific compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and methacrylic acid. Tertiary butyl enoate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, in terms of improving the durable water repellency of the obtained fiber product, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred, and methyl methacrylate is more preferred.

Regarding the composition ratio of the monomer (C3) in the non-fluorine-based acrylic polymer of this embodiment, in terms of the water repellency and texture of the obtained fiber product, it is relative to the composition of the non-fluorine-based acrylic polymer The total amount of the monomer components is preferably 1-30% by mass, more preferably 3-25% by mass, and still more preferably 5-20% by mass.

The monomer of (C4) is a (meth)acrylate monomer having 3 or more polymerizable unsaturated groups in one molecule. In this embodiment, it is preferable that T in the general formula (C-4) is a polyfunctional (meth)acryloxy group having 3 or more (meth)acryloxy groups in one molecule. Base) acrylate monomers. In formula (C-4), p Ts may be the same or different. As specific compounds, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trihydroxymethyl Methyl propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. These monomers may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, tetramethylolmethane tetraacrylate and ethoxylated isocyanurate triacrylate are more preferable in terms of improving the durable water repellency of the obtained fiber product.

Regarding the composition ratio of the monomer (C4) in the non-fluorine-based acrylic polymer of this embodiment, from the viewpoint of the water repellency and texture of the obtained fiber product, it is relative to the monomer composition of the non-fluorine-based polymer The total amount of body ingredients is preferably 1-30% by mass, more preferably 3-25% by mass, and still more preferably 5-20% by mass.

Regarding the total composition ratio of the monomers of the above-mentioned component (C) in the non-fluorine-based acrylic polymer of this embodiment, from the viewpoint of the water repellency and texture of the obtained fiber product, it is relative to the composition of the non-fluorine-based polymer The total amount of the monomer components of the substance is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass.

The non-fluorine-based acrylic polymer of this embodiment can be copolymerized with the components (A), (E), (B), and (C) within a range that does not impair the effects of the present invention. The monofunctional monomer (D).

As the above-mentioned monomer (D), for example, (meth)acryloylmorpholine, (A) component and (C) component other than (meth)acrylate having a hydrocarbon group, (meth)acrylic acid, reverse Butenediolate, maleate, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, Ethylene monomers other than fluorine-free (E) components such as ethylene and styrene. In addition, the (meth)acrylate having a hydrocarbon group other than the component (A) and the component (C) may have substituents such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, and a blocked isocyanate group in the hydrocarbon group. , May have a quaternary ammonium group and other substituents that can react with the crosslinking agent, and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Examples of (meth)acrylates other than the (A) component and (C) component include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol diacrylate. (Meth)acrylate and the like. Among them, (meth)acrylomorpholine is more preferable in terms of improving the peel strength of the obtained fiber product to the coating.

Regarding the composition ratio of the monomer (D) in the non-fluorine-based acrylic polymer of this embodiment, in terms of the water repellency and texture of the obtained fiber product, it is relative to the composition of the non-fluorine-based acrylic polymer The total amount of the monomer components is preferably 10% by mass or less.

In terms of improving the durable water repellency of the obtained fiber products, the non-fluorine-based acrylic of this embodiment The olefinic acid polymer 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 that can react with a crosslinking agent. The isocyanate group can also form a blocked isocyanate group protected by a blocking agent. In addition, in terms of also improving the texture of the obtained fiber product, the non-fluorine-based polymer preferably has an amine group.

The non-fluorine-based acrylic polymer of this embodiment can be produced by a radical polymerization method. In addition, in the radical polymerization method, in terms of the performance and environment of the obtained water repellent, it is preferable to perform polymerization by an emulsion polymerization method or a dispersion polymerization method.

For example, it can be obtained by subjecting the (meth)acrylate monomer (A) represented by the general formula (A-1) to emulsion polymerization or dispersion polymerization in the presence of the above component (E) in a medium. Fluorine acrylic polymer. More specifically, for example, the (A) component, (E) component, and the above (B) component, the above (C) component, and the above (D) component, as well as the emulsification aid or dispersion added as necessary, are added to the medium The auxiliary agent emulsifies or disperses the mixed liquid to obtain an emulsion or dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, the polymerization reaction is started, and the monomer and the reactive emulsifier can be polymerized. Furthermore, as a means for emulsifying or dispersing the above-mentioned mixed liquid, a homomixer, a high-pressure emulsifier, an ultrasonic wave, and the like can be cited.

As the above-mentioned emulsification aid or dispersion aid, etc. (hereinafter also referred to as "emulsification aid etc."), nonionic surfactants, cationic surfactants, and anionic interfacial agents selected from the group other than the above-mentioned reactive emulsifier (B) can be used. One or more of active agents and amphoteric surfactants. The content of the emulsification aid and the like is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass relative to 100 parts by mass of all monomers. If the content of the emulsification aid etc. is 0.5 parts by mass or more, the dispersion stability of the mixed solution tends to be less likely to decrease compared with the case where the content of the emulsification aid etc. is outside the above range. If the content of the emulsification aid etc. 30 parts by mass or less, compared with the case where the content of emulsification aids etc. is outside the above range, there are some non-fluorinated acrylic polymers obtained The tendency that the water repellency is not easy to decrease.

As a medium for emulsion polymerization or dispersion polymerization, water is preferred, and water can be mixed with an organic solvent as necessary. The organic solvent at this time is not particularly limited. For example, alcohols such as methanol or ethanol, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, ethers such as diethyl ether, etc., propylene glycol, diethyl ether, etc. Glycols such as propylene glycol and tripropylene glycol. Furthermore, 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 polymerization initiators can be suitably used. Regarding the content of the polymerization initiator, the polymerization initiator is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of all monomers. If the content of the polymerization initiator is in the above range, a non-fluorine acrylic polymer having a weight average molecular weight of 100,000 or more can be produced efficiently.

In addition, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan and t-butanol may be used for the purpose of molecular weight adjustment. The content of the chain transfer agent is preferably 0.3 parts by mass or less, and more preferably 0.1 parts by mass or less with respect to 100 parts by mass of all monomers. If the content of the chain transfer agent is 0.3 parts by mass or less, the molecular weight becomes less likely to decrease, and it tends to be easy to efficiently produce a non-fluorine-based acrylic polymer having a weight average molecular weight of 100,000 or more.

Furthermore, in order to adjust the molecular weight, a polymerization inhibitor can be used. By adding a polymerization inhibitor, a non-fluorine-based acrylic polymer having a desired weight average molecular weight can be easily obtained.

The temperature of the polymerization reaction is preferably 20°C to 150°C. If the temperature is 20°C or more, the polymerization tends to become sufficient compared to the case where the temperature is outside the above range, and if the temperature is 150°C or less, the control of the reaction heat tends to be easier.

In the polymerization reaction, the weight average molecular weight of the obtained non-fluorine acrylic polymer can be By increasing or decreasing the content of the polymerization initiator, chain transfer agent, and polymerization inhibitor mentioned above, the melt viscosity at 105°C can be adjusted by the increase or decrease of the content of the polyfunctional monomer and the polymerization initiator. Adjustment. Furthermore, when it is desired to reduce the melt viscosity at 105°C, it is sufficient to reduce the content of monomers having more than two polymerizable functional groups or increase the content of the polymerization initiator.

Regarding the content of the non-fluorinated acrylic polymer in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization, in terms of the storage stability and handling properties of the composition, it is relative to the emulsion or The total amount of the dispersion is preferably 10 to 50% by mass, and 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, and methanol-modified silicone. From the viewpoint of improving the water repellency of the obtained fiber product, hydrogen silicone and amino-modified silicone are preferred.

As the hydrogen polysiloxane, commercially available products such as "DRYPON 600E" (manufactured by Nikka Chemical Co., Ltd., trade name) can be used.

As the amino-modified silicone, commercially available products such as "NEOSEED SF-200" (manufactured by Nikka Chemical Co., Ltd., trade name) can be used.

Examples of the dendrimer-based water repellent include those containing a dendritic polymer compound having a radial structure and branching regularly from the center. In order to obtain water repellency, a dendritic polymer compound having a linear or branched hydrocarbon group with a carbon number of 1 or more can be used in the branch portion of the terminal.

As the dendrimer compound, for example, "a polymer extender" disclosed in the specification of International Publication WO2014/160906 can be used. For example, it is possible to use 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) or (Ic) The compound obtained by the reaction.

In the above formula, R ²⁰ each independently represents -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) _m C(O)R ²¹ , n is independently 0-20, m is independently 0-20, and m+n exceeds 0. In addition, R ²¹ each independently represents a linear or branched alkyl group with 5 to 29 carbon atoms that may contain one or more unsaturated bonds, and R ²² each independently represents -H, or may contain one or more non-saturated bonds. Saturated bond straight or branched alkyl group with 6 to 30 carbons.

Furthermore, in formula (Ia), at least one of ^{R 20} or R ^{22 is -H.}

In the above formula, R ²³ independently represents -H, -R ²¹ , -C(O)R ²¹ , -(CH ₂ CH ₂ O(CH(CH ₃ )CH ₂ O) _m R ²² or -(CH ₂ CH ₂ O(CH(CH ₃ )CH ₂ OC(O)R ²¹ , R ²⁴ each independently represents -H, or a straight chain or branched chain with 6 to 30 carbon atoms that may contain more than one unsaturated bond Alkyl, -(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 , N'is independently 0-20, m'is independently 0-20, and m+n exceeds 0.

Furthermore, in formula (Ib), at least one of ^{R 22} , R ²³ or R ^{24 is -H.}

In the above formula, R ²⁵ represents -H, -C(O)R ²¹ or -CH ₂ C[CH ₂ OR ²⁰ ] ₃ . Furthermore, 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 or trimers of these. Can use "DESMODUR N-100" (manufactured by Bayer, product name), "DURANATE THA-100" (manufactured by Asahi Kasei Co., Ltd., product name), and "DURANATE 24A-100" (manufactured by Asahi Kasei Co., Ltd., product name) And other commercially available products. In addition, the reaction can be carried out at 80°C for 1 hour or more, for example.

The step of imparting a non-fluorine-based water repellent to a functional group-containing fiber may include, for example, the use of those selected from the group consisting of the above-mentioned acrylic water repellent, polysiloxane water repellent, and dendritic polymer water repellent. At least one kind of treatment liquid is a method for treating functional group-containing fibers.

As a method of treating the functional group-containing fiber with the above-mentioned treatment liquid, for example, processing methods such as dipping, spraying, and coating can be cited. In addition, when the treatment liquid contains water, it is preferable to perform drying in order to remove water after adhering to the functional group-containing fiber.

You may add additives etc. to the processing liquid as needed. Examples of additives include other water-repellent agents, cross-linking agents, antibacterial deodorants, flame retardants, antistatic agents, softeners, anti-wrinkle agents, and the like.

The adhesion amount of the non-fluorine-based water repellent to the functional group-containing fiber can be adjusted appropriately according to the required degree of water repellency, and it is preferably relative to 100g of the functional group-containing fiber. The non-fluorine-based water repellent contained in the treatment liquid The adhesion amount of the water repellent (for example, a non-fluorine-based acrylic polymer) is adjusted so that it becomes 0.01 to 10 g, and it is more preferably adjusted so that it becomes 0.05 to 5 g. If the adhesion amount of the non-fluorine-based water-repellent agent is 0.01g or more, compared with the case where the adhesion amount of the non-fluorine-based water-repellent agent is outside the above range, the fiber product tends to exhibit sufficient water repellency. If it is less than 10g , Compared with the case where the adhesion amount of the non-fluorine-based water repellent is outside the above range, the texture of the fiber product tends to be harder to become rough.

After the non-fluorine-based water-repellent agent of the present embodiment is applied to the functional group-containing fiber, it is preferable to appropriately perform a heat treatment. The temperature conditions are not particularly limited, and the mild conditions of 100 to 130°C can make the fiber product exhibit sufficiently good water repellency. It can also be a high-temperature treatment with a temperature condition of 130°C or higher (preferably up to 200°C). In this case, the treatment time can be shortened compared to the previous case using a fluorine-based water repellent. Therefore, according to the method of manufacturing a water-repellent fiber product of this embodiment, it is possible to suppress the deterioration of the fiber product caused by heat, the texture of the fiber product becomes soft during the water-repellent treatment, and it is under mild heat treatment conditions, that is, low-temperature curing conditions. It can impart sufficient water repellency to fiber products.

Especially when it is desired to improve the durability of water repellency, it is preferable to perform water repellency processing on the fiber product by the following method, which includes: treating the fiber containing functional group with a treatment liquid containing a non-fluorine-based water repellent The above steps; and the step of attaching a crosslinking agent represented by methylol melamine, a compound having more than one isocyanate group or blocked isocyanate group to the fiber containing functional groups and heating it. Furthermore, when it is desired to further improve the durable water repellency, the treatment liquid preferably contains a non-fluorine-based polymer obtained by copolymerizing a monomer having a functional group capable of reacting with the above-mentioned crosslinking agent.

Examples of compounds having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, toluene isocyanate, naphthalene isocyanate, toluene diisocyanate, diphenylmethane diisocyanate, Diisocyanates such as tetramethylxylylene diisocyanate and hydrogenated diphenylmethane diisocyanate, as well as trimers of isocyanurate rings and trimethylolpropane adducts. In addition, as the compound having one or more blocked isocyanate groups, a compound obtained by protecting the isocyanate group with a blocking agent for the above-mentioned compound having an isocyanate group can be mentioned. As the blocking agent used at this time, there can be mentioned organic blocking agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, internal amines, or sodium bisulfite and potassium bisulfite. Isobaric sulfite. The above-mentioned crosslinking agent may be used singly or in combination of plural kinds.

The crosslinking agent can be attached to the substrate by immersing the object (fibrous product) in a treatment solution obtained by dissolving the crosslinking agent in an organic solvent or emulsifying and dispersing in water, and drying the treatment solution attached to the object. Treatment. Then, by heating the crosslinking agent adhering to the object to be treated, the crosslinking agent can react with the object to be treated and the non-fluorine-based water repellent (especially non-fluorine-based acrylic polymer). In order to make the reaction of the crosslinking agent proceed fully and more effectively improve the washing durability, the heating at this time can be carried out at 110~180℃ for 1~5 minutes. The steps of attaching and heating the crosslinking agent can be performed simultaneously with the step of processing with the above-mentioned processing liquid. In the case of simultaneous operation, for example, a treatment liquid containing a non-fluorine-based water repellent and a cross-linking agent is attached to the object to be treated, the water is removed, and then the cross-linking agent attached to the object is heated. When considering the simplification of the water-repellent processing step, the reduction of heat, and the economic efficiency, it is preferable to perform it simultaneously with the processing step with the processing liquid.

Moreover, if the crosslinking agent is used excessively, the texture may be impaired. The above-mentioned crosslinking agent is preferably used in an amount of 0.1 to 50% by mass relative to the processed object (fiber product), and particularly preferably used in an amount of 0.1 to 10% by mass.

The water-repellent fiber product of the present embodiment obtained in this way can fully exhibit water-repellency even when it is used outdoors for a long time. Furthermore, since the water-repellent fiber product does not use fluorine-based compounds, it can be a good Environmentally friendly.

The water-repellent fiber product of this embodiment can be coated on a specific part. Examples of coating processing include moisture-permeable and waterproof processing or wind-proof processing for sports or outdoor use. As a processing method, for example, in the case of moisture-permeable and water-repellent processing, it is possible to apply a coating solution containing polyurethane resin or acrylic resin and the like to the sheet of fiber products subjected to water-repellent treatment. Noodles are dried and processed.

Above, the preferred embodiments of the present invention have been described, but the present invention is not limited to the above-mentioned embodiments.

For example, in the case of producing a non-fluorine-based acrylic polymer, in the above embodiment, the polymerization reaction is carried out by radical polymerization, but it can also be irradiated by ionizing radiation such as ultraviolet rays, electron beams, and gamma rays. Wait for photopolymerization to carry out the polymerization reaction.

[Example]

Hereinafter, the present invention will be further described with examples, but the present invention is not limited in any way by these examples.

<Preparation of polymer dispersion>

The mixed solution having the composition shown in Tables 1 and 2 (in the table, the numerical value represents (g)) was polymerized by the procedure shown below to obtain a polymer dispersion.

(Synthesis example 1)

A 500mL flask was charged with 40 g of stearyl acrylate, 20 g of vinyl chloride, 2 g of LATEMUL PD-430 (manufactured by Kao Co., Ltd., polyoxyalkylene ether, HLB=14.4), and LATEMUL PD-420 (Kao Co., Ltd.) Company manufacture, polyoxyalkylene alkenyl ether, HLB= 12.6) 2 g, 3 g of stearyl dimethylamine hydrochloride, 25 g of tripropylene glycol, and 207.70 g of water are mixed and stirred at 45° C. to prepare a mixed solution. The mixed liquid is irradiated with ultrasonic waves to emulsify and disperse all the monomers. Then, 0.3 g of azobis(isobutamidine) dihydrochloride was added to the mixed solution, and radical polymerization was carried out at 60° C. for 6 hours under a nitrogen atmosphere to obtain a non-fluorinated acrylic system with a polymer concentration of 21% by mass. The polymer dispersion is used as a non-fluorine-based water repellent.

(Synthesis example 2~10)

Except that the materials described in Tables 1 and 2 were used, polymerization was carried out in the same manner as in Example 1, and a non-fluorine-based acrylic polymer dispersion with the polymer concentration shown in Tables 1 and 2 was obtained as a non-fluorine-based water repellent. Agent.

(Synthesis examples 11 and 12)

Except that the materials described in Table 2 were used, polymerization was carried out in the same manner as in Example 1, and fluorine-based acrylic polymer dispersions having polymer concentrations shown in Table 2 were obtained as fluorine-based water-repellent agents.

In addition, each polymer in the polymer dispersion obtained in Synthesis Examples 1 to 12 was confirmed by gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation) that all the monomers contained more than 98% Aggregated.

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

LATEMUL PD-420: "LATEMUL PD-420" (manufactured by Kao Co., Ltd., trade name, polyoxyalkylene alkenyl ether, HLB=12.6)

LATEMUL PD-430: "LATEMUL PD-430" (manufactured by Kao Co., Ltd., trade name, polyoxyalkylene alkenyl ether, HLB=14.4)

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

Cardanol 8.3EO: 8.3 mol adduct of ethylene oxide of cardanol (HLB=11.0)

NOIGEN XL-100: "NOIGEN XL-100" (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., trade name, polyoxyalkylene branched decyl ether, HLB=14.7)

NOIGEN XL-60: "NOIGEN XL-60" (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., trade name, polyoxyalkylene branched decyl ether, HLB=12.5)

The "C8 fluorine group-containing acrylate" in the table is the following general formula (III): C _n F _2n+1 CH ₂ CH ₂ OCOCH=CH ₂ (III)

Shown is a mixture whose average value of n is 8 (Furthermore, compounds with n of 6, 8, 10, 12, and 14 are mixed in this mixture).

The polymer dispersion obtained above and the polymer obtained by the method shown below were evaluated.

(Evaluation of polymer properties)

The polymer was separated from the emulsifier by adding 500 mL of acetone to 50 g of the polymer dispersion obtained in Synthesis Examples 1 to 10, the polymer was filtered, and the polymer was dried under reduced pressure at 25° C. for 24 hours. The obtained polymer was evaluated as described below. The results are shown in Tables 1 and 2.

(1) Measuring method of melt viscosity

For the polymers obtained in the above examples and comparative examples, an overhead rheometer CFT-500 (manufactured by Shimadzu Corporation) was used, and 1 g of polymer was charged into a machine equipped with a die nozzle (length 10mm, diameter 1mm) In the cylinder, keep it at 105°C for 6 minutes, and apply 100kg by the plunger. With a load of f/cm ² , the melt viscosity at 105°C was measured.

(2) Measuring method of weight average molecular weight

For the polymers of the Examples and Comparative Examples obtained above, GPC (gel Permeation chromatograph (gel permeation chromatograph) device (GPC "HLC-8020" manufactured by Tosoh Co., Ltd.), using tetrahydrofuran as the eluent under the conditions of a column temperature of 40°C and a flow rate of 1.0 ml/min. For the measurement, the weight average molecular weight was measured by standard polystyrene conversion. Furthermore, the pipe string is installed by connecting three of the trade names TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation.

(Preparation of fiber materials)

As the fiber material, prepare dyed nylon 100% cloth (indicated by Ny in the table), dyed polyester 100% (made by polyethylene terephthalate) cloth (indicated by Pet in the table) and cationic Dyeable polyester (manufactured by Sedansha Co., Ltd., fiber for dyeing test "Cation dyeable polyester smooth knit (Knit Smooth) (processing line)") (indicated by CD-PET in the table).

(Preparation of pretreatment agent)

Prepare the following pretreatment agents 1~4.

Pretreatment agent 1: An aqueous solution containing a formalin condensate of phenolsulfonic acid synthesized by the following method.

Put 70g of phenol, 1.5g of phosphoric acid and 20g of formaldehyde in the reaction vessel, react at 95-100°C for 3 hours, and then add 45g of acetic anhydride dropwise over 30 minutes and then cool to 70°C. Then, 25 g of 90% sulfuric acid was added dropwise over 30 minutes, and the reaction was carried out at 100° C. for 1 hour. After the reaction, 138.5 g of water was added to obtain the pretreatment agent 1 with a formalin condensate content of phenolsulfonic acid of 38% by mass.

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

Put 100 g of bisphenol S and 45 g of acetic anhydride in the reaction vessel, and raise the temperature to 80°C. Then, after 14.5 g of 90% sulfuric acid was added dropwise over 30 minutes, the reaction was carried out at 120° C. for 6 hours. Then, after cooling to 50°C, 10.5 g of formaldehyde was added, and the reaction was carried out at 100°C for 6 hours. Then, it cooled to 70 degreeC, 147g of water was added, and the content of the formalin condensate of sulfonated bisphenol S was 40 mass %, and the pretreatment agent 2 was obtained.

Pretreatment agent 3: Aqueous solution containing sodium polyacrylate with a molecular weight of 7000 (manufactured by Nikka Chemical Co., Ltd., trade name "NEOCRYSTAL 770", content 43% by mass)

Pretreatment agent 4: Lauryl phosphate (a mixture of monoester and diester) (Toho Chemical Industry Co., Ltd. has Manufactured by a limited company, brand name "PHOSPHANOL ML-200", content 100%)

<Manufacturing of water-repellent fiber products> (Example 1)

Dyed nylon 100% cloth is immersed in a treatment bath containing pretreatment agent 1 (the amount of fiber provided is 2% owf in terms of compound concentration) at a bath ratio of 1:10, 80°C, and 20 minutes Under the conditions of processing. After the treatment, it was dried at 130°C for 2 minutes to obtain a functional group-containing fiber.

The functional group-containing fiber obtained above was immersed in the treatment solution obtained by diluting the non-fluorine-based water repellent of Synthesis Example 1 with water so that the content of the polymer became 3% by mass (liquid rate 60% by mass) Thereafter, it was dried at 130°C for 2 minutes to obtain a water-repellent fiber product.

(Examples 2-12, 14-35, Comparative Examples 3-6)

Using the fiber material, pretreatment agent, compound concentration, and water-repellent agent shown in Tables 3 to 8, water-repellent fiber products were obtained in the same manner as in Example 1. In addition, the water repellent in Examples 32 to 35 used the following.

Polysiloxane-based water repellent 1: "DRYPON 600E" (manufactured by Nikka Chemical Co., Ltd., brand name, hydrogen polysiloxane content 53% by mass)

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

(Example 13)

Except for using CD-PET as the functional group-containing fiber, a water-repellent fiber product was obtained in the same manner as in Example 1.

(Comparative example 1)

A water-repellent fiber was obtained in the same manner as in Example 1, except that the pretreatment of the fiber material was not carried out. Dimensional products.

(Comparative example 2)

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

<Various evaluations>

The following various evaluations were performed for the production of the water-repellent fiber products of the examples and comparative examples.

[Measurement of Zeta Potential on Fiber Surface]

The zeta potential/particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.) was used to measure the zeta potential on the surface of the functional group-containing fiber.

[Evaluation of Water Repellency of Fiber Products]

In accordance with the spray method of JIS L 1092 (2009), the spray water temperature was set to 20°C for the test. The result of water repellency was evaluated visually with the following grades. In addition, if the characteristics are slightly good, mark "+" at the level, and if the characteristics are slightly worse, mark "-" at the level.

Water repellency: state

5: No adhesion and wetting on the surface

4: Slightly showing adhesion and wetting on the surface

3: Show partial wetting on the surface

2: Shows wetting on the surface

1: Shows wetness on the entire surface

0: Fully wet on both sides of the front and back

[Texture Evaluation of Fiber Products]

The texture is obtained by further heat-treating the obtained fiber product at 170°C for 30 seconds Make an evaluation. The results were evaluated by hand touch with 5 levels shown below.

1: Hard ~ 5: Soft

[Test for stability of treatment bath]

The stability of the treatment bath undergoing water-repellent processing was evaluated in accordance with the following procedures. 5g of fiber material after pretreatment (CD-PET in Example 13, and fiber material without pretreatment in Comparative Examples 1 and 2) 5g, water repellent 12g, NK ASSIST FU (crosslinking agent, Nikka Chemical Co., Ltd.) (Manufactured by the company) 1 g is diluted with ion-exchanged water so that it becomes 200 mL, and the diluted solution is left at 40°C for 12 hours. Then, the fiber material was removed, maintained at 40°C, and directly stirred with a TK homomixer at 5000 revolutions per minute for 10 minutes, then filtered with a cotton cloth dyed black, and visually judged the agglomeration remaining on the surface of the cotton cloth. Things.

5; no agglomerates

4: There is a little condensate

3: Faintly whitened overall

2: White aggregate remains on the whole

1: Unable to filter

[Evaluation of Durable Water Repellency]

According to the spray method of JIS L 1092 (2009), the spray water temperature was set to 20°C for the test. In this test, the polymer content of the functional group-containing fiber is 3% by mass, and the content of UNIKA RESIN 380-K (crosslinking agent, manufactured by Union Chemical Industry Co., Ltd., trimethylol melamine resin) is 0.3 The mass% and the content of UNIKA CATALYST 3-P (surfactant, Union Chemical Industry Co., Ltd., amino alcohol hydrochloride) are 0.2% by mass, and the water repellent and the above-mentioned agents are diluted with water. After being immersed in the treatment solution (rolling rate 60% by mass), it was dried at 130°C for 2 minutes, and then When the fiber material is Pet and CD-PET, heat-treated at 170°C for 60 seconds in the case of Ny, heat-treated at 160°C for 60 seconds in the case of cloth (L-0) and 10 times (L-10) based on JIS The water repellency of the cloth after washing in the 103 method of L 0217 (1995) was evaluated in the same manner as the above water repellency evaluation method.

In Examples 1 to 35 where the functional group-containing fiber of the present invention was subjected to water-repellent processing using the specific non-fluorine-based water-repellent agent of the present invention, it was confirmed that the functional group-containing fiber of the present invention was not used in Comparative Example 1 Compared with 2, obtain fiber products with excellent water repellency and durable water repellency.

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

Furthermore, in Comparative Examples 3 and 4 using a fluorine-based water-repellent agent containing a fluorine-based acrylic polymer obtained using a reactive emulsifier, compared with Examples 1 and 2, the results of treatment bath stability were inferior. It is considered that this is because the fluorine-based water-repellent agent becomes easy to aggregate.

According to the present invention, a non-fluorine-based water-repellent agent can be used to produce a water-repellent fiber product having sufficient water repellency and sufficient durable water repellency.

Claims (12)

A method for manufacturing a water-repellent fiber product, which includes the following step A: making at least one selected from the group consisting of acrylic water-repellent, silicone-based water-repellent, and dendrimer-based water-repellent The non-fluorine-based water repellent is in contact with a _{monovalent group selected from -SO 3} M ¹ (where M ¹ represents a monovalent cation) and -COOM ² (where M ² represents a monovalent cation) The monovalent group represented and the monovalent represented by -OP(O)(OX ¹ )(OX ² ) (where X ¹ and X ² each independently represent a hydrogen atom or an alkyl group with 1 to 22 carbon atoms) A fiber with at least one functional group in the group consisting of the group. The method for producing a water-repellent fiber product according to claim 1, wherein the non-fluorine-based water-repellent agent includes an acrylic water-repellent agent, and the acrylic-based water-repellent agent includes a product derived from the following general formula (A-1) The polymer of the structural unit of (meth)acrylate monomer (A):

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group with 12 or more carbon atoms that may have a substituent]. The method for producing a water-repellent fiber product according to claim 1, wherein the non-fluorine-based water-repellent agent includes an acrylic water-repellent agent, and the acrylic-based water-repellent agent includes a product derived from the following general formula (A-1) A polymer of a structural unit of (meth)acrylate monomer (A) and a structural unit derived from at least one of vinyl chloride and vinylidene chloride (E),

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group with 12 or more carbon atoms that may have a substituent]. The method for producing a water-repellent fiber product according to claim 1, wherein the non-fluorine-based water-repellent agent includes an acrylic water-repellent agent, and the acrylic-based water-repellent agent includes a product derived from the following general formula (A-1) The structural unit of (meth)acrylate monomer (A), the structural unit derived from at least one monomer (E) among vinyl chloride and vinylidene chloride, and the structural unit derived from (B1) HLB is 7 ~18 the compound represented by the following general formula (I-1), (B2) the compound represented by the following general formula (II-1) with 7~18, and (B3) the compound represented by the following general formula (II-1) with 7~18 A polymer in which at least one type of reactive emulsifier (B) is a structural unit of a compound obtained by adding an alkylene oxide with a carbon number of 2 to 4 to a fat and oil having a hydroxyl group and a polymerizable unsaturated group,

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

[In formula (I-1), R ³ represents hydrogen or methyl, X represents a linear or branched alkylene group with carbon number 1 to 6, and Y ¹ represents an alkylene group with carbon number 2 to 4 2-valent base]

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group with a carbon number of 13 to 17 having a polymerizable unsaturated group, and Y ² represents a divalent group containing an alkoxy group with a carbon number of 2 to 4 ]. The method for manufacturing a water-repellent fiber product according to claim 3 or 4, wherein the mass ratio of the mass of the (meth)acrylate monomer (A) formulated in the polymer to the mass of the monomer (E) (A )/(E) is 40/60~90/10, and the total mass of the (meth)acrylate monomer (A) and the monomer (E) formulated in the polymer is relative to the mass of the polymer constituting the polymer The total amount of monomer components is 80% by mass or more. The method for manufacturing a water-repellent fiber product according to any one of claims 2 to 4, wherein the (meth)acrylate monomer (A) contains acrylate monomer (a1) and methacrylate monomer (a2) , And the ratio (a1)/(a2) of the mass of the acrylate monomer (a1) contained in the (meth)acrylate monomer (A) to the mass of the methacrylate monomer (a2) is 30/70~90/10. The method for producing a water-repellent fiber product according to claim 4, wherein the mass of the reactive emulsifier (B) formulated in the polymer is 0.5-20% by mass relative to the total amount of monomer components constituting the polymer. The method for manufacturing a water-repellent fiber product according to claim 1 or 2, wherein the fiber is attached with a _{monovalent group selected from -SO 3} M ¹ (where M ¹ represents a monovalent cation), -COOM ² (In the formula, M ² represents a monovalent cation) and -OP(O)(OX ¹ )(OX ² ) represented by the monovalent group (where X ¹ and X ² each independently represent a hydrogen atom or carbon A fiber of a compound of at least one functional group in the group consisting of the monovalent group represented by the number 1-22 (alkyl group). The method for producing a water-repellent fiber product according to claim 8, wherein the compound includes a phenol-based polymer compound having a monovalent group represented by _{-SO 3} M ¹ (wherein M ^{1 represents a monovalent cation).} Such as the method for manufacturing a water-repellent fiber product of claim 1 or 2, wherein the zeta potential of the surface of the fiber is -100~-0.1mV. The method for manufacturing a water-repellent fiber product according to claim 1 or 2, further comprising a step B: attaching a crosslinking agent to the fiber and heating it, the crosslinking agent is selected from methylol melamine and having one or more At least one of the group consisting of isocyanate groups or blocked isocyanate groups. Such as the method for manufacturing a water-repellent fiber product of claim 11, which comprises the above-mentioned non-fluorine The treatment liquid of the water-repellent agent and the above-mentioned crosslinking agent adheres to the above-mentioned fibers, and the above-mentioned step A and the above-mentioned step B are performed at the same time.