TW201546147A - Water-repellent agent composition, water-repellent fiber product, and manufacturing method of water-repellent fiber product - Google Patents

Abstract

The present invention relates to a water-repellent agent composition, which comprises a non-fluorine-based polymer, and the non-fluorine-based polymer contains constituent units derived from (meth)acrylate monomer (A) represented by the following general formula (A-1), and constituent units derived from reactive emulsifier (B), the reactive emulsifier (B) is selected from at least one of (B1) ~ (B3), (B1) is a compound represented by the following general formula (I-1) and has an HLB (hydrophile-lipophile babance) value of 7~18, (B2) is a compound represented by the following general formula (II-1) and has an HLB value of 7~18, and (B3) is a compound formed by adding a cycloalkoxy of 2 to 4 carbon atoms into an oil having hydrocarbon and polymerizable unsaturated groups with an HLB value of 7~18; In formula (A-1), R1 is hydrogen or methyl, R2 represents a monovalent hydrocarbon group having substituent groups of 12 carbon atoms or more. In formula (I-1), R3 is hydrogen or methyl, X represents a linear or branched alkylene having 1~6 carbon atoms, Y1 represents a divalent group of alkoxyene having carbon number of 2 ~4; [in formula (II-1), R4 is a monovalent unsaturated hydrocarbon group with 13-17 carbon atoms having polymerizable unsaturated group, and Y2 represents a divalent group of an alkoxyene of 2 ~4 carbon atoms.

Description

Water repellent composition, water-repellent fiber product and method for producing water-repellent fiber product

The present invention relates to a method for producing a water repellent composition, a water repellent fiber product, and a water repellent fiber product.

A fluorine-based water repellent having a fluorine-containing group is known in the art, and it is known that a fluorine-based water repellent is treated with a fiber product or the like to impart a water-repellent fiber product to the surface. Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group.

Although the fiber product treated with the fluorine-based water repellent exhibits excellent water repellency, in order to exhibit water repellency, since the alignment of the fluoroalkyl group must be adjusted, the fluorine-based water repellent must be attached to the fiber product to exceed 130. The heat treatment is carried out at a temperature of °C. However, heat treatment at high temperatures requires high energy, so there is a problem in the popularity of energy saving in international provinces.

Further, since the monomer having a fluoroalkyl group is expensive, it is not satisfactory in an economical aspect, and since the monomer having a fluoroalkyl group is difficult to decompose, it has a problem even in an environmental surface.

In addition, in the field of water-repellent processing of fiber products, Stabilization of quality and cost reduction, it is desirable to impart excellent water repellency to the water repellent of the fiber product even at a low concentration or a low heat treatment temperature.

Therefore, research on non-fluorine-based water repellents containing no fluorine has been conducted in recent years. For example, Non-Patent Document 1 discloses a water repellent agent which emulsifies and disperses a hydrocarbon compound such as paraffin or wax, a fatty acid metal salt or an alkyl urea.

Further, in Patent Document 1, a water repellent agent for emulsifying and dispersing a specific non-fluorine-based polymer is proposed for the purpose of imparting water repellency comparable to that of the conventional fluorine-based water repellent.

[Previous Technical Literature] [Non-patent literature]

[Non-Patent Document 1] "New Directions of Super Water-Removal, Processing Agents, and Moisture-Resistant Hydrogen-Resistant Materials", issued by Osaka Chemical Marketing Center, 1996, p.7~9

[Patent Literature]

[Patent Document 1] JP-A-2006-328624

However, in the non-fluorine water repellent described in Non-Patent Document 1, it is difficult to obtain a fiber product having the same water repellency as that used in the conventional fluorine water repellent treatment. Moreover, the treated fiber product has a hardened inclination It is not enough for the characteristics.

In the case of the non-fluorine water repellent described in Patent Document 1, In order to ensure storage stability, when a non-fluorine-based polymer is blended with a surfactant which is sufficiently emulsified and dispersed, there is a tendency to lower the water repellency of the obtained fiber product, and it is difficult to attempt storage stability and water repellency.

The present invention has been made in view of the above matters, and is provided by In addition, when the heat treatment is not performed, sufficient water repellency can be imparted to the fiber product, and the water repellent composition of the water-repellent fiber product having excellent characteristics and water repellency can be obtained, and the water repellent composition can be obtained. The purpose of the method for producing water-repellent fiber products and water-repellent fiber products is as follows.

The present invention provides a water repellent composition comprising a non-fluorine-based polymer containing a (meth) acrylate monomer derived from the following general formula (A-1) (A) The constituent unit derived from the reactive emulsifier (B), the reactive emulsifier (B) is at least one selected from the group consisting of (B1) to (B3), and the (B1) HLB is 7~ The compound represented by the following general formula (I-1) of 18, (B2) the compound represented by the following general formula (II-1) wherein HLB is 7 to 18, and the ring of (B3) addition carbon number 2 to 4; A compound in which an oxane is a lipid having a hydroxyl group and a polymerizable unsaturated group of 7 to 18 in HLB.

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

[In the formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkyl group having 1 to 6 carbon atoms, and Y ¹ represents 2 of an alkylene group having a carbon number of 2 to 4; Price base].

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

The above non-fluorine-based polymer may further contain a source selected from A constituent unit of at least one of the second (meth) acrylate monomer (C) in the group consisting of (C1), (C2), (C3), and (C4).

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

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

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

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

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

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

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

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

The present invention further provides a water repellent composition comprising a non-fluorine-based polymer obtained by emulsion polymerization or dispersion polymerization of an emulsion or a dispersion, the emulsion or dispersion comprising the above The (meth) acrylate monomer (A) and the reactive emulsifier (B) represented by the general formula (A-1), the reactive emulsifier (B) being selected from at least (B1) to (B3) (1), (B1) HLB is a compound represented by the above general formula (I-1) of 7 to 18, (B2) a compound represented by the above general formula (II-1) having an HLB of 7 to 18, and (B3) plus An alkylene oxide having a carbon number of 2 to 4 having a hydroxyl group of 7 to 18 in HLB And a compound in a fat or oil of a polymerizable unsaturated group.

The above emulsion or the above dispersion may further comprise a selected from the group consisting of A second (meth) acrylate monomer (C) of at least one selected from the group consisting of (C1), (C2), (C3) and (C4).

The water repellent composition according to the present invention has excellent storage stability At the same time, even when heat treatment is not performed, sufficient water repellency can be imparted to the fiber product or the like, and a water-repellent fiber product excellent in characteristics and water repellency can be realized.

The invention further provides a water-repellent fiber product, which is The non-fluorine-based polymer contains a constituent unit derived from the (meth) acrylate monomer (A) represented by the above general formula (A-1), and is derived from a fiber product to which a non-fluoropolymer is attached. a constituent unit of the reactive emulsifier (B), wherein the reactive emulsifier (B) is at least one selected from the group consisting of (B1) to (B3), and (B1) the above general formula (I1) wherein the HLB is from 7 to 18. 1) a compound represented by the above formula (II-1) wherein (B2) has an HLB of 7 to 18, and (B3) an alkylene oxide having an addition carbon number of 2 to 4 having an HLB of 7 to 18 A compound in a fat or oil of a hydroxyl group and a polymerizable unsaturated group.

The non-fluorine-based polymer may further contain at least one selected from the group consisting of the above (C1), (C2), (C3), and (C4) derived from the second (meth) acrylate monomer (C). The constituent unit of ).

The invention further provides a water-repellent fiber product which is formed by a fiber product to which a non-fluorine-based polymer is attached, which is obtained by emulsion polymerization or dispersion polymerization of an emulsion or a dispersion, the emulsion or The dispersion system comprises the (meth) acrylate single represented by the above general formula (A-1) The body (A) and the reactive emulsifier (B), the reactive emulsifier (B) is selected from at least one of (B1) to (B3), and the (B1) HLB is the above general formula of 7 to 18 ( The compound represented by I-1), (B2) the compound represented by the above general formula (II-1) having an HLB of 7 to 18, and the (B3) alkylene oxide having an addition carbon number of 2 to 4 are 7 to 18 in the HLB. A compound in a fat or oil having a hydroxyl group and a polymerizable unsaturated group.

The emulsion or the dispersion may further contain a second (meth) acrylate monomer (C) selected from at least one selected from the group consisting of the above (C1), (C2), (C3), and (C4). ).

The water-repellent fibrous product of the present invention can sufficiently maintain characteristics and water repellency even when used during a long period of time outside the house.

The present invention further provides a method for producing a water-repellent fibrous product, which comprises the step of treating a fibrous product with a treatment liquid comprising the above-described water repellent composition of the present invention.

According to the method for producing a water-repellent fiber product of the present invention, it is possible to impart sufficient water repellency to the water repellent composition of the present invention, such as a fiber product, even when heat treatment is not performed, by using the storage stability. It can stabilize the water-repellent fiber products with excellent manufacturing characteristics and water repellency. Further, since the method for producing a water-repellent fiber product of the present invention does not require heat treatment at a high temperature, energy saving can be achieved, and the use of a non-fluorine water-repellent agent can reduce the load on the environment.

According to the present invention, it is possible to provide a sufficient water repellency even when heat treatment is not performed. When a fiber product or the like is imparted, a water repellent composition of a water-repellent fiber product having excellent characteristics and water repellency can be obtained.

The water repellent composition of the present invention does not contain fluorine even if it The water repellent composition of the alkyl or fluorine compound also exhibits excellent water repellency, and can be used as a substitute for the fluorine water repellent, and can eliminate the suspense of the influence on the fluorine supply source or the environment. Further, after the water repellent composition is attached to the fiber product or the like, it is preferably heat treated. However, since the water repellent composition of the present invention does not use a monomer having a fluoroalkyl group, it is preferably at or below 130 ° C. When the heat treatment is carried out under mild conditions, it is also possible to exhibit high water repellency, and in the case of heat treatment at a high temperature exceeding 130 ° C, the heat treatment time can be shortened compared with the case of the fluorine water repellent. According to this, since the deterioration of the heat of the object to be treated is suppressed, the properties are soft, and the heat treatment is also excellent in reducing the cost such as the heat.

Further, according to the present invention, as a non-fluorinated polymer The emulsifying or dispersing polymerization of the emulsifying and dispersing agent can reduce the amount of the surfactant contained in the water repellent composition by using a specific reactive emulsifier instead of the usual surfactant. As a result, it is possible to suppress a decrease in the water repellency of the obtained fiber product or the like, and it is possible to achieve higher water repellency than the conventional non-fluorine water repellent. Further, since the water repellent composition of the present invention can improve the emulsification dispersibility of the non-fluorine-based polymer itself, even when it is added to the processing bath, it is easy to maintain a stable emulsified state, and it is possible to cope with various fiber processing. .

The water repellent composition of the embodiment includes non-fluorine a non-fluorine-based polymer containing a constituent unit derived from a (meth) acrylate monomer (A) (hereinafter also referred to as "(A) component") represented by the following general formula (A-1) And a constituent unit derived from the reactive emulsifier (B) (hereinafter also referred to as "(B) component)), the reactive emulsifier (B) is at least one selected from the group consisting of (B1) to (B3) (B1) HLB is a compound represented by the following general formula (I-1) of 7 to 18, (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18, and (B3) plus A compound having an alkylene oxide having 2 to 4 carbon atoms and having a hydroxyl group and a polymerizable unsaturated group in an HLB of 7 to 18.

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

[In the formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkyl group having 1 to 6 carbon atoms, and Y ¹ represents 2 of an alkylene group having a carbon number of 2 to 4; Price base].

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

Here, the term "(meth)acrylate" means "acrylate" or "methacrylate" corresponding thereto, even in "(meth)acrylic acid" or "(meth)acrylamide". Also synonymous.

In addition, the term "reactive emulsifier" means an emulsified dispersant having a radical reactivity, that is, a surfactant having one or more polymerizable unsaturated groups in the molecule, and can be made with, for example, (methyl) The acrylate monomer is copolymerized.

In addition, "HLB" means an HLB value calculated by the Griffin method, assuming that a vinyloxy group is a hydrophilic group, and all of them are assumed to be a lipophilic group.

The (meth) acrylate 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, may be a saturated hydrocarbon group, may be an unsaturated hydrocarbon group, and may have an alicyclic or aromatic ring shape. Among these, a linear one is preferable, and a linear alkyl group is more preferable. In this case, it can be more excellent in water repellency. When the monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, examples of the substituent include a hydroxyl group, an amine group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloxy group. More than one type. In the present embodiment, in the above general formula (A-1), R ^{2 is} preferably an unsubstituted hydrocarbon group.

The carbon number of the above hydrocarbon group is preferably from 12 to 24. The carbon number is less than 12 When the non-fluorine-based polymer is attached to a fiber product or the like, sufficient water repellency cannot be exhibited. In addition, when the carbon number is more than 24, when the non-fluorine-based polymer is adhered to a fiber product or the like, the properties of the fiber product tend to be rough and hard compared to the case where the carbon number is in the above range.

The carbon number of the above hydrocarbon group is more preferably 12 to 21. Carbon number for this In the range, the water repellency and characteristics are particularly excellent. As the hydrocarbon group, a linear alkyl group having a carbon number of 12 to 18 is particularly preferred.

As the component (A), for example, (meth)acrylic acid is exemplified. Stearic acid ester, hexadecyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate Esters, heptadecyl (meth) acrylate, pentadecanyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, (meth) acrylate Dialkyl ester, methyl methacrylate (meth) acrylate, beeswax (meth) acrylate.

The above component (A) may have a reaction selected from the group consisting of reacting with a crosslinking agent A functional group of at least one of a group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, and an isocyanate group. In this case, the durable water repellency of the obtained fibrous product can be further improved. The isocyanate group can be formed to be protected by a blocking agent Block isocyanate groups. Further, when the component (A) has an amine group, the properties of the obtained fiber product can be further improved.

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

The above-mentioned component (A) may be used alone or in combination of two or more.

The HLB of the compound of the above (B1) to (B3) used in the present embodiment is 7 to 18, and the non-fluorine-based polymer contained in the water repellent composition of the present embodiment (hereinafter referred to as the present embodiment) The point of emulsifying polymerization or dispersion polymerization of the non-fluorine-based polymer and the emulsion stability in the composition after polymerization (hereinafter simply referred to as emulsion stability) are preferably from 9 to 15. Further, from the viewpoint of storage stability of the water repellent composition, it is more preferred to use two or more kinds of reactive emulsifiers (B) having different HLB in the above range.

In the reactive emulsifier (B1) represented by the above general formula (I-1) used in the present embodiment, R ³ is hydrogen or a methyl group, and a point of copolymerization of the component (A) is more preferably a methyl group. . X is a linear or branched alkyl group having 1 to 6 carbon atoms. More preferably, it is a linear alkyl group having 2 to 3 carbon atoms from the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment. . Y ¹ 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 at Y ¹ can be appropriately selected within the range of the above-described HLB. Further, when two or more alkoxy groups are present, these may 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 the formula (I-2), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkyl group having 1 to 6 carbon atoms, and A ¹ O represents an alkylene group having 2 to 4 carbon atoms, m Specifically, it may be appropriately selected from the above-described HLB range, and is preferably an integer of from 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 above formula (I-2), R ³ is hydrogen or a methyl group, and more preferably a methyl group from the viewpoint of copolymerizability of the component (A). X is a linear or branched alkyl group having 1 to 6 carbon atoms. More preferably, it is a linear alkyl group having 2 to 3 carbon atoms from the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment. . A ¹ O is an alkoxy group having 2 to 4 carbon atoms. The type and combination of A ¹ O and the number of m can be appropriately selected as appropriate within the range of the above HLB. From the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment, m is preferably an integer of from 1 to 80, more preferably an integer of from 1 to 60. When m is 2 or more, m A ¹ O may be the same or different. Further, when two or more kinds of A ¹ O are used, these may have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the above general formula (I-2) can be It is obtained by a conventionally known method, and is not particularly limited. Moreover, it can be obtained more easily than a commercial product, and for example, it can be made by Kao Co., Ltd. "LATEMULPD-420", "LATEMULPD-430", "LATEMULPD-450", etc.

In the reactive emulsifier (B2) represented by the above formula (II-1) used in the present embodiment, R ⁴ is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and examples thereof include Tridecencenyl, Tridedienyl, tetradecenyl, tetradecadienyl, pentadecenyl, pentadecadienyl, pentadecene A group, a heptadecyl group, a heptadecadienyl group, a heptadecene group, and the like. From the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment, it is more preferable that R ⁴ is a monovalent unsaturated hydrocarbon group having 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 at Y ² can be appropriately selected in the range of the above-described HLB. Further, when two or more alkoxy groups are present, these may have a block addition structure or a random addition structure. From the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment, the alkoxy group is more preferably a vinyloxy group.

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

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

R in the compound (II-2) represented by the above general formula ^4, and include the R in the above general formula (II-1) ⁴ of the same person.

A ² O is an alkoxy group having a carbon number of 2 to 4. From the point of view of the emulsification stability of the non-fluorine-based polymer of the present embodiment, the type and combination of A ² O and the number of n can be appropriately selected in the range of the above-described HLB. From the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment, A ² O is more preferably a vinyloxy group, and n is preferably an integer of from 1 to 50, more preferably an integer of from 5 to 20, and furthermore. Good is an integer from 8 to 14. When n is 2 or more, n A ² O may be the same or different. Further, when two or more kinds of A ² O are used, these may have a block addition structure or a random addition structure.

In the reactive emulsifier (B2) represented by the above general formula (II-2) used in the present embodiment, an alkylene oxide can be added to the corresponding phenol having an unsaturated hydrocarbon group by a conventionally known method. The synthesis is not particularly limited. For example, an alkali catalyst such as caustic soda or caustic potash can be synthesized by adding a specific amount of alkylene oxide under pressure at 120 to 170 °C.

The phenol having the above-mentioned corresponding unsaturated hydrocarbon group is also included as a plant or the like in addition to a pure product or mixture manufactured industrially. Purified pure product or mixture exists. For example, it can be enumerated from the shell of cashew nuts, and is generally called cardanol, 3-[8(Z), 11(Z), 14-pentacarbon. Trienyl]phenol, 3-[8(Z),11(Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z ) - pentadecenyl] phenol and the like.

The reactive emulsifier (B3) used in the present embodiment, It is a compound which has an alkylene oxide having a carbon number of 2 to 4 added to a fat or oil having a hydroxyl group of 7 to 18 and an unsaturated unsaturated group. Examples of the fat or oil having a hydroxyl group and a polymerizable unsaturated group include a hydroxy unsaturated fatty acid (palmitic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, twenty a fatty acid or a diglyceride of a carbaenoic acid, docosapentaenoic acid, or the like, comprising at least one of a hydroxy unsaturated fatty acid (ricinoleic acid, ricinoleic acid (Ricinoelaidic acid), 2-hydroxy octa A triglyceride of a fatty acid such as tetraacid or the like. From the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment, it is more preferably an alkylene oxide adduct of triglyceride or a castor oil containing a fatty acid of at least one type of hydroxy unsaturated fatty acid (including The triglyceride of the fatty acid of ricinoleic acid) has an alkylene oxide adduct of 2 to 4 carbon atoms, and more preferably an ethylene oxide adduct of castor oil. Further, the addition molar number of the alkylene oxide can be appropriately selected within the range of the above-mentioned HLB, and from the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment, it is more preferably 20 to 50 moles. Ears, more preferably 25 to 45 moles. Further, when two or more kinds of alkylene oxides are used, these may have a block addition structure or a random addition structure.

The reactive emulsifier (B3) used in the present embodiment, The synthesis can be carried out by adding an alkylene oxide to a fat or oil having a hydroxyl group and a polymerizable unsaturated group by a conventionally known method, and is not particularly limited. For example, using a triglyceride containing a fatty acid of ricinoleic acid, that is, using it in castor oil An alkali catalyst such as caustic soda or caustic potash can be synthesized by adding a specific amount of alkylene oxide under pressure at 120 to 170 °C.

The non-fluorine-based polymer of the present embodiment is derived from the component (A) The content ratio of the constituent unit to the constituent unit derived from the component (B) is blended (A) from the viewpoint of the water repellency of the obtained fibrous product and the emulsion stability of the non-fluorine-based polymer of the present embodiment. The ratio (A)/(B) of the mass of the component to the mass of the component (B) is preferably 85/15 to 99/1, more preferably 90/10 to 97/3. When (A)/(B) is less than 85/15, the water repellency of the obtained fiber product tends to be insufficient. When (A)/(B) exceeds 99/1, the emulsion stability of the non-fluorine-based polymer of the present embodiment tends to be insufficient.

Moreover, the quality of the blended component (A) and the mass of the component (B) The total mass of the non-fluorine-based polymer is preferably from 80 to 100% by mass, more preferably from 85 to 99% by mass, even more preferably from 90 to 98% by mass.

Weight average molecule of the non-fluoropolymer of the present embodiment The amount is preferably 100,000 or more. When the weight average molecular weight is less than 100,000, the water repellency of the obtained fiber product tends to be insufficient. Further, the weight average molecular weight of the non-fluorine-based polymer is more preferably 500,000 or more. In this case, the obtained fibrous product can be made more fully water-repellent. The upper limit of the weight average molecular weight of the non-fluorine-based polymer is preferably about 5,000,000.

In the present embodiment, the non-fluorine-based polymer has a melt viscosity at 105 ° C, preferably 1000 Pa. s below. The melt viscosity at 105 ° C exceeds 1000 Pa. In the case of s, the properties of the obtained fibrous product tend to become coarse and hard. Further, when the melt viscosity of the non-fluorine-based polymer is too high, the non-fluorinated system is emulsified or dispersed. When the polymer is used as a water repellent composition, the non-fluorine-based polymer may precipitate and precipitate, and the storage stability of the water repellent composition tends to be lowered. Still, the melt viscosity at 105 ° C, more preferably 500Pa. s below. In this case, the obtained fiber product exhibits sufficient water repellency and is more excellent in characteristics.

The "melting viscosity at 105 ° C" refers to the use of an overhead flow tester (for example, CFT-500 manufactured by Shimadzu Corporation), and puts 1 g of non-fluorine-based polymer in a cylinder with a mold (length 10 mm, diameter 1 mm). , kept at 105 ° C for 6 minutes, added 100kg from the plunger. The viscosity of the load of f/cm ² was measured.

Weight average molecule of the non-fluoropolymer of the present embodiment When the amount is equal, the higher the blending ratio of the non-fluorine (meth) acrylate monomer, the higher the water repellency of the fiber product to which it is attached. Moreover, by copolymerizing a copolymerizable non-fluorine-based monomer, the performance of durability, water repellency, properties, and the like of the adhered fiber product can be improved.

The non-fluorine system included in the water repellent composition of the present embodiment The polymer may preferably contain, in addition to the components (A) and (B), selected from the following (C1), (C2), (C3), and the point of improving the durability of the obtained fiber product. (C4) At least one of the second (meth) acrylate monomer (C) (hereinafter also referred to as "C component") of the group is a monomer component.

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

In the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents a group selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloxy group. The at least one functional group has a monovalent chain hydrocarbon group having 1 to 11 carbon atoms. However, the number of (meth)acryloxy groups in the molecule is 2 or less].

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

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

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

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

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

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

In the non-fluorine-based polymer of the present embodiment, the content ratio of the constituent unit derived from the component (A) and the constituent unit derived from the component (B) and the constituent unit derived from the component (C) is blended (A). The ratio of the total mass of the component and the mass of the component (B) to the mass of the component (C) (A) + (B) / (C) is preferably 70/30 to 99.9 / 0.1, more preferably 75 / 25~99/1.

The single system of the above (C1) has a functional group at least one selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloxy group in the ester moiety. A (meth) acrylate monomer having a monovalent chain hydrocarbon group having 1 to 11 carbon atoms. The above-mentioned monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has a group selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group and an isocyanate group, from the viewpoint of reaction with a crosslinking agent. At least one functional group. Will contain a crosslinker that can be used with The non-fluorine-based polymer of the monomer of the reaction (C1) can directly maintain the properties of the obtained fiber product and improve the durability of water repellency when treated with the crosslinking agent in the fiber product. The isocyanate group can be a blocked isocyanate group protected with a blocking agent.

The above chain hydrocarbon group may be linear or branched. The saturated hydrocarbon group may also be an unsaturated hydrocarbon group. Further, the chain hydrocarbon group may further have a substituent in addition to the above functional group. Among them, a linear and/or saturated hydrocarbon group is preferred in view of improving the durability of the obtained fiber product.

Specific examples of the monomer (C1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-double. (acryloxymethyl)ethyl isocyanate or the like. These monomers may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(propylene oxide) are preferred from the viewpoint of improving the durability of the obtained fiber product. Methyl)ethyl isocyanate. Further, from the viewpoint of improving the properties of the obtained fiber product, dimethylaminoethyl (meth)acrylate is preferred.

The composition ratio of the monomer of the above (C1) is preferably from 0.1 to 30% by mass based on the total amount of the monomer component constituting the non-fluorine-based polymer, from the viewpoint of water repellency and characteristics of the obtained fiber product. More preferably, it is 1 to 25% by mass, and even more preferably 5 to 20% by mass.

The (C2) single system has a (meth) acrylate monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety, and is a cyclic hydrocarbon group. Examples thereof include an isomeric group, a cyclohexyl group, a dicyclopentyl group and the like. These cyclic hydrocarbon group-based alkyl groups and the like may have a substituent. However, when the substituent is a hydrocarbon group, the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is selected to be 11 or less. Further, these cyclic hydrocarbon groups may be directly bonded to an ester bond, but are preferred from the viewpoint of improving durability water repellency. The cyclic hydrocarbon group may be either alicyclic or aromatic, and in the case of an alicyclic group, it may be a saturated hydrocarbon group or a saturated hydrocarbon group. Specific examples of the monomer include isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, and bicycloalkyl (meth)acrylate. These monomers may be used alone or in combination of two or more. Among them, isodecyl (meth)acrylate and cyclohexyl methacrylate are preferable, and isodecyl methacrylate is more preferable from the viewpoint of improving the durability of the obtained fiber product.

The composition ratio of the above (C2) monomer, from the obtained fiber The total amount of the monomer components constituting the non-fluorine-based polymer is preferably from 0.1 to 30% by mass, more preferably from 1 to 25% by mass, even more preferably from 5 to 5, from the viewpoint of water repellency and characteristics of the product. 20% by mass.

The above-mentioned (C3) single system is directly bonded to the ester bond of the ester moiety An unsubstituted methacrylate monomer having a monovalent chain hydrocarbon group of 1 to 4 carbon atoms. The chain hydrocarbon group having 1 to 4 carbon atoms is preferably a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Specific examples of the compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and A. T-butyl acrylate. These monomers may be used alone or in combination of two or more. use. Among them, methyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, and more preferably methyl methacrylate are preferred from the viewpoint of improving the durability of the obtained fiber product. .

The composition ratio of the monomer of the above (C3) is made from the obtained fiber The total amount of the monomer components constituting the non-fluorine-based polymer is preferably from 0.1 to 30% by mass, more preferably from 1 to 25% by mass, even more preferably from 5 to 5, from the viewpoint of water repellency and characteristics of the product. 20% by mass.

The single system of the above (C4) has 3 or more in one molecule. A (meth) acrylate monomer which is a polymerizable unsaturated group. In the present embodiment, it is preferred that the T in the above general formula (C-4) is a (meth)acryloxy group and has a poly(oxy)oxy group having 3 or more (meth)acryloxy groups in one molecule ( Methyl) acrylate monomer. In formula (C-4), p T's may be the same or different. Specific examples of the compound include tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol. Acrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. These monomers may be used alone or in combination of two or more. Among them, tetramethylol methane tetraacrylate is more preferable from the viewpoint of improving the durability of the obtained fiber product.

The composition ratio of the monomer of the above (C4) is made from the obtained fiber From the viewpoint of water repellency and characteristics of the product, the total amount of the monomer components constituting the non-fluorine-based polymer is preferably 0.1 to 5% by mass.

The non-fluorine-based polymer contained in the water repellent composition of the present embodiment can be used in addition to the components (A), (B) and (C). Further, in the range of the effects of the present invention, a monofunctional monomer (D) copolymerizable therewith may be contained.

Examples of the monomer of the above (D) include the component (A). And (C) a hydrocarbon (meth) acrylate, (meth) acrylate, fumarate, maleate, fumaric acid, maleic acid, (meth) acrylamide, N- A vinyl monomer such as methylol acrylamide, vinyl ether, vinyl ester, vinyl chloride, vinylidene chloride, ethylene or styrene, which does not contain fluorine. Further, the (meth) acrylate 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 amine group, an epoxy group, an isocyanate group or a blocked isocyanate group in the hydrocarbon group. The substituent may have a substituent other than a group which can react with a crosslinking agent such as a fourth-order ammonium group, and may have an ether bond, an ester bond, a guanamine bond, or a urethane bond. Examples of the (meth) acrylate other than the component (A) and the component (C) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol. (Meth) acrylate, etc.

The composition ratio of the monomer of the above (D) is from the obtained fiber product From the viewpoint of water repellency and characteristics, the total amount of the monomer components constituting the non-fluorine-based polymer is preferably 10% by mass or less.

The non-fluorine-based polymer contained in the water repellent composition of the present embodiment has at least one selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, and an isocyanate group reactive with a crosslinking agent. The functional group is preferred, but it is preferred because it improves the durability of the resulting fibrous product. The isocyanate group can form a blocked isocyanate group protected with a blocking agent. Further, although the non-fluorine-based polymer has an amine group, the resulting fiber is also made. It is better to improve the characteristics of the product.

The water repellent composition of this embodiment may also be used if necessary Add additives and the like. Examples of the additive include other water repellent agents, crosslinking agents, antibacterial deodorants, flame retardants, antistatic agents, softeners, and anti-wrinkle agents.

Next, the non-fluoropolymer comprising the embodiment The method for producing the water repellent composition will be described.

A water repellent composition comprising a non-fluorinated polymer can be self-contained Manufactured by a base polymerization method. Further, in the radical polymerization method, it is preferred to carry out polymerization by an emulsion polymerization method or a dispersion polymerization method from the viewpoint of the performance of the water repellent obtained and the environment.

For example, in the media, from the combination of (B1) to (B3) above In the presence of at least one reactive emulsifier (B), the (meth) acrylate monomer (A) represented by the above general formula (A-1) can be obtained by emulsion polymerization or dispersion polymerization. Non-fluorinated polymer. More specifically, for example, the component (A), the component (B), and, if necessary, an emulsification aid or a dispersion aid are added to the medium, and the mixture is emulsified or dispersed to obtain an emulsion or a dispersion. The monomer and the reactive emulsifier can be polymerized by adding a polymerization initiator to the resulting emulsion or dispersion to initiate polymerization. Further, examples of the means for emulsifying or dispersing the above-mentioned mixed liquid include a homomixer, a high-pressure emulsifier, and an ultrasonic wave.

As the above-mentioned emulsification aid or dispersion aid, etc. It is called "emulsification adjuvant, etc."), and a nonionic surfactant other than the above-mentioned reactive emulsifier (B), a cationic surfactant, and an anion can be used. One or more of a sub-interface active agent and an amphoteric surfactant. The content of the emulsification aid or the like is preferably from 0.5 to 30 parts by mass, more preferably from 1 to 20 parts by mass, even more preferably from 1 to 10 parts by mass, per 100 parts by mass of the total monomers. When the content of the emulsification aid or the like is less than 0.5 part by mass, the content of the emulsification aid or the like tends to decrease as compared with the case of the above range, and the content of the emulsification aid or the like exceeds 30 parts by mass. In the case where the content of the emulsification aid or the like is in comparison with the above range, the water repellency of the obtained non-fluorine-based polymer tends to be lowered.

As a medium for emulsion polymerization or dispersion polymerization, it is preferably Water, if necessary, mix water with organic solvents. The organic solvent to be mixed with water is not particularly limited, and examples thereof include alcohols such as methanol and ethanol, esters such as ethyl acetate, and acetone or methyl ethyl ketone. A glycol such as a ketone or an ether such as diethyl ether or a glycol such as propylene glycol, dipropylene glycol or tripropylene glycol. Further, the ratio of water to organic solvent is not particularly limited.

As the polymerization initiator, an azo system can be suitably used. A known polymerization initiator such as a peroxide system or a redox system. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass based on 100 parts by mass of the total monomers. When the content of the polymerization initiator is in the above range, a non-fluorine-based polymer having a weight average molecular weight of 100,000 or more can be efficiently produced.

In addition, in the polymerization reaction, the molecular weight is adjusted for the purpose. A chain transfer agent such as dodecyl mercaptan, t-butyl alcohol or the like can be used. 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 monomers. The amount of chain transfer agent exceeds 0.1 When the amount is divided, the molecular weight is lowered, and it tends to be difficult to efficiently produce a non-fluorine-based polymer having a weight average molecular weight of 100,000 or more.

Further, a polymerization inhibitor can be used for molecular weight adjustment. borrow A non-fluorine-based polymer having a desired weight average molecular weight can be easily obtained by the addition of a polymerization inhibitor.

The temperature of the polymerization reaction is preferably from 20 ° C to 150 ° C. Temperature not When the temperature is 20 ° C, the polymerization tends to be insufficient as compared with the case of the above range. When the temperature exceeds 150 ° C, the control of the reaction heat becomes difficult.

In the polymerization reaction, the weight of the obtained non-fluorine-based polymer is flat The average molecular weight can be adjusted by increasing or decreasing the content of the above polymerization initiator, chain transfer agent and polymerization inhibitor. The melt viscosity at 105 ° C can be increased or decreased by the content of polyfunctional monomer and the content of polymerization initiator. To adjust. Further, in the case where the melt viscosity at 105 ° C is lowered, the content of the monomer having two or more polymerizable functional groups or the content of the polymerization initiator may be decreased.

Emulsion of the obtained polymer by emulsion polymerization or dispersion polymerization The content of the non-fluorine-based polymer of the liquid or the dispersion is preferably from 10 to 50% by mass, more preferably from 10 to 50% by mass based on the total storage of the emulsion or the dispersion. 20~40% by mass.

The water-repellent fiber product of the present embodiment is obtained by adhering the fiber product of the non-fluorine-based polymer of the present embodiment described above.

A method of producing the water-repellent fiber product of the present embodiment will be described.

The water-repellent fiber product of the embodiment, by using the fiber The product is treated with a treatment liquid containing the above-described water repellent composition, whereby a non-fluorine-based polymer can be attached to the fiber product. The material of the fiber product is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, crepe, and wool, semi-synthetic fibers such as rayon and acetate, and nylon, polyester, and polyurethane. Synthetic fibers such as polypropylene, composite fibers, blended fibers, and the like. The form of the fiber product may be any one of fiber, silk, cloth, non-woven fabric, paper, and the like.

As the side where the fiber product is treated with the above treatment liquid The method may, for example, be a processing method such as dipping, spraying, or coating. Further, when the water repellent composition contains water, it is preferred to adhere to the fibrous product and then to dry it in order to remove water.

The amount of adhesion to the fibrous product of the water repellent composition, although According to the degree of water repellency required, the amount of the non-fluorine-based polymer contained in the water repellent composition is preferably adjusted to 0.01 to 10 g, more preferably to 0.05, based on 100 g of the fiber product. ~5g. When the amount of the non-fluorine-based polymer to be adhered is less than 0.01 g, the amount of the non-fluorine-based polymer to be adhered is less than that in the above range, and the fiber product tends not to exhibit sufficient water repellency. When it exceeds 10 g, the non-fluorine-based polymer The amount of adhesion of the polymer tends to be coarser and harder than the case of the above range.

Further, the non-fluorine-based polymer of the present embodiment is attached to the fiber. After the finished product, it is preferred to carry out a suitable heat treatment. Although the temperature condition is not particularly limited, when the water repellent composition of the present embodiment is used, it is 100~ The mild condition of 130 ° C allows the fiber product to exhibit sufficient water repellency. Although the temperature condition can be a high temperature treatment of 130 ° C or higher (preferably to 200 ° C), in this case, the treatment time can be shortened more than in the conventional case of using a fluorine water repellent. According to the water-repellent fiber product of the present embodiment, the deterioration of the fiber product by the heat is suppressed, and the characteristics of the fiber product during the water repellent treatment are softened, and the mild heat treatment condition, that is, the low-temperature curing condition can be imparted. Fiber products are fully water-repellent.

Especially if you want to improve the durability of water repellency, by bag The above-mentioned step of treating the fibrous product preferably with a treatment liquid containing the water repellent composition, and a crosslinking agent represented by a compound having one or more methylol melamine, isocyanate group or blocked isocyanate group, A method of attaching to a fibrous article and heating the step of watering the fibrous product. Further, in order to further improve the durability of water repellency, it is preferred that the water repellent composition comprises a non-fluorine-based polymer which copolymerizes a monomer having a functional group reactive with the above-mentioned crosslinking agent.

As a compound having one or more isocyanate groups, Examples of monoisocyanate, methylphenylene diisocyanate, diphenylmethane diisocyanate, tetramethylbenzenedimethyl diisocyanate A diisocyanate such as a diisocyanate or a trimeric or trimethylolpropane adduct of the isocyanurate ring. Further, examples of the compound having one or more blocked isocyanate groups include a compound in which a compound having the above isocyanate group is blocked with an isocyanate group as a blocking agent. As the blocking agent used at this time, a secondary or tertiary alcohol, an active methylene group can be mentioned. An organic blocking agent such as a base compound, a phenol, an anthracene or an indoleamine; or a hydrogensulfite such as sodium hydrogen sulfite or potassium hydrogen sulfite. The above-mentioned crosslinking agent may be used alone or in combination of plural kinds.

a crosslinking agent, for example, by dissolving a crosslinking agent in an organic solvent The agent or the immersed material (fiber product) is emulsified and dispersed in the treatment liquid of water, and the method of drying and adhering to the treatment liquid of the object to be treated allows the object to be treated to adhere. Further, by heating the crosslinking agent attached to the object to be treated, a reaction between the crosslinking agent, the object to be treated, and the non-fluorine-based polymer can be performed. In order to sufficiently carry out the reaction of the crosslinking agent, the cleaning durability can be more effectively improved, and the heating at this time can be carried out at 110 to 180 ° C for 1 to 5 minutes. The step of adhering and heating the crosslinking agent may be carried out simultaneously with the step of treating the treatment liquid containing the water repellent composition. At the same time, for example, the treatment liquid containing the water repellent composition and the crosslinking agent is adhered to the object to be treated, and after removing the water, the crosslinking agent adhering to the object to be treated is heated. In consideration of simplification of the water-repellent processing step, or reduction in heat and economy, it is preferable to carry out the treatment step with the water-repellent composition.

Moreover, when the crosslinking agent is excessively used, there is a risk of damage. The crosslinking agent is preferably used in an amount of 0.1 to 50% by mass, particularly preferably 0.1 to 10% by mass, based on the object to be treated (fiber product).

The water-repellent fiber product of the embodiment thus obtained, Even when used outside the house, the water-repellent fiber product can be fully water-repellent, and the water-repellent fiber product can be environmentally friendly because it does not use a fluorine-based compound.

The above is a description of an embodiment suitable for the present invention. However, the present invention is not limited to the above embodiments.

For example, the manufacture of the water repellent composition of the present invention is included In the case of the non-fluorine-based polymer, in the above embodiment, the polymerization reaction may be carried out by radical polymerization, but polymerization may be carried out by photopolymerization such as irradiation with ultraviolet rays, electron beams, or gamma rays. reaction.

Further, in the present invention, the water repellent composition is processed into a fiber. The product is used as a water-repellent fiber product, but the product treated with the water-repellent composition is not limited to the use of the fiber product, and may be an article such as metal, glass, or resin.

Moreover, in this case, the water repellent composition is attached to the above The method of the article or the amount of the water-repellent agent can be arbitrarily determined depending on the type of the object to be treated.

[Examples]

Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited by the examples.

<Adjustment of polymer dispersion>

The mixed liquid having the compositions shown in Tables 1 to 5 (in the table, numerical values (g)) was polymerized in the order shown below to obtain a polymer dispersion.

(Example 1)

60 g of stearyl acrylate was added to a 500 mL flask. LATEMULPD-420 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=12.6) 2g, LATEMULPD-430 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=14.4) 2g, hard fat 3 g of dimethylamine hydrochloride, 20 g of tripropylene glycol, and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 2)

Into a 500 mL flask, 55 g of stearyl acrylate, LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMULPD-430 (manufactured by Kao Co., Ltd., polyoxyalkylene) Base ether, HLB=14.4) 2g, 2-hydroxyethyl acrylate 5g, stearin dimethylamine hydrochloride 3g, dodecyl mercaptan 0.15g, tripropylene glycol 20g and water 162.6g, and at 45 ° C The mixture was stirred and mixed to form a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 3)

To a 500 mL flask, 55 g of stearyl methacrylate and LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl group) were added. Ether, HLB=12.6) 2g, LATEMULPD-430 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=14.4) 2g, 2-hydroxyethyl acrylate 5g, stearin dimethylamine hydrochloride 3 g, 0.05 g of dodecyl mercaptan, 20 g of tripropylene glycol, and 162.7 g of water were mixed and stirred at 45 ° C to obtain a mixed liquid. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 4)

Into a 500 mL flask, 55 g of stearyl acrylate, LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMULPD-430 (manufactured by Kao Co., Ltd., polyoxyalkylene) Ethyl ether, HLB = 14.4) 2 g, 2 g of 2-hydroxyethyl acrylate, 3 g of stearyl dimethylamine hydrochloride, 20 g of tripropylene glycol, and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 5)

Into a 500 mL flask, 55 g of cetyl acrylate and LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl group) were added. Ether, HLB=12.6) 2g, LATEMULPD-430 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=14.4) 2g, 2-hydroxyethyl acrylate 5g, stearin dimethylamine hydrochloride 3 g, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed liquid. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 6)

In a 500 mL flask, 55 g of lauryl acrylate, LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g, LATEMULPD-430 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl ether) were added. HLB = 14.4) 2 g, 2 g of 2-hydroxyethyl acrylate, 3 g of stearyl dimethylamine hydrochloride, 20 g of tripropylene glycol, and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 7)

Adding 55 g of stearyl acrylate and 12.5 mol of ethylene oxide of cardanol to a 500 mL flask (HLB=12.9, in the table, means "cardanol" 12.5 EO") 2 g, cardanol ethylene oxide 8.3 molar addition (HLB = 11.0, in the table, "ctra-phenol 8.3 EO") 2 g, 2-hydroxyethyl acrylate 5 g, stearin dimethylamine 3 g of hydrochloride, 20 g of tripropylene glycol, and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed liquid. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 8)

Into a 500 mL flask, 55 g of stearyl acrylate, an ethylene oxide 42 molar addition of castor oil (HLB=13.3, in the table, "castor oil 42EO") 2 g, and an ethylene oxide 30 molar addition of castor oil were added. (HLB = 11.7, in the table, "castor oil 30EO") 2 g, 2-hydroxyethyl acrylate 5 g, stearic acid dimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and water 162.75 g, and carried out at 45 ° C Mix and stir to form a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 9)

In a 500 mL flask, 57 g of stearyl acrylate and LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl group) were added. Ether, HLB = 12.6) 2 g, LATEMULPD-430 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB = 14.4) 2 g, tetramethylol methane tetraacrylate 3 g, stearin dimethylamine salt 3 g of an acid salt, 20 g of tripropylene glycol, and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed liquid. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Embodiment 10)

Into a 500 mL flask, 55 g of stearyl acrylate, LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMULPD-430 (manufactured by Kao Co., Ltd., polyoxyalkylene) Base ether, HLB = 14.4) 2 g, dimethylaminoethyl methacrylate 5 g, stearic acid dimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and water 162.75 g, and mixed at 45 ° C to become Mixture. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 11)

Add 500 g of stearyl acrylate and LATEMULPD-420 (made by Kao Co., Ltd., polyoxyalkylene alkenyl group) in a 500 mL flask Ether, HLB=12.6) 2g, LATEMULPD-430 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=14.4) 2g, glycidyl methacrylate 5g, stearin dimethylamine hydrochloride 3 g, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed liquid. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Embodiment 12)

Into a 500 mL flask, 55 g of stearyl acrylate, LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMULPD-430 (manufactured by Kao Co., Ltd., polyoxyalkylene) Ethyl ether, HLB=14.4) 2g, 1,1-bis(acryloxymethyl)ethyl isocyanate, methyl ethyl ketone oxime blocker 5g, stearin dimethylamine hydrochloride 3g, three 20 g of propylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed liquid. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 13)

51 g of stearyl acrylate was added to a 500 mL flask. LATEMULPD-420 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=12.6) 4g, LATEMULPD-430 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=14.4) 4g, acrylic acid 2 5 g of hydroxyethyl ester, 3 g of stearyl dimethylamine hydrochloride, 20 g of tripropylene glycol, and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 14)

Into a 500 mL flask, 56 g of stearyl acrylate, LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB = 12.6), 0.5 g, and LATEMULPD-430 (manufactured by Kao Co., Ltd., polyoxyalkylene) were added. Alkenyl ether, HLB=14.4) 0.5g, polyoxyethylene (10 moles) lauryl ether 2g, 2-hydroxyethyl acrylate 5g, stearin dimethylamine hydrochloride 3g, tripropylene glycol 20g and water 162.75 g, and mixed and stirred at 45 ° C to form a mixed liquid. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 15)

45 g of stearyl acrylate was added to a 500 mL flask. LATEMULPD-420 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=12.6) 2g, LATEMULPD-430 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=14.4) 2g, acrylic acid 2 5 g of hydroxyethyl ester, 10 g of isodecyl acrylate, 3 g of stearyl dimethylamine hydrochloride, 20 g of tripropylene glycol, and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Embodiment 16)

In a 500 mL flask, 45 g of stearyl acrylate, LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMULPD-430 (manufactured by Kao Co., Ltd., polyoxyalkylene) Ethyl ether, HLB = 14.4) 2 g, 2-hydroxyethyl acrylate 5 g, isodecyl methacrylate 10 g, stearic acid dimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g, and carried out at 45 ° C Mix and stir to form a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Example 17)

45 g of stearyl acrylate was added to a 500 mL flask. LATEMULPD-420 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=12.6) 2g, LATEMULPD-430 (made by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB=14.4) 2g, acrylic acid 2 5 g of hydroxyethyl ester, 10 g of cyclohexyl methacrylate, 3 g of stearyl dimethylamine hydrochloride, 20 g of tripropylene glycol, and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Embodiment 18)

In a 500 mL flask, 45 g of stearyl acrylate, LATEMULPD-420 (manufactured by Kao Co., Ltd., polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMULPD-430 (manufactured by Kao Co., Ltd., polyoxyalkylene) Base ether, HLB=14.4) 2g, 2-hydroxyethyl acrylate 5g, methyl methacrylate 10g, stearin dimethylamine hydrochloride 3g, tripropylene glycol 20g and water 162.75g, and mixed at 45 ° C Stir to form a mixture. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 26% by mass. Polymer dispersion.

(Comparative Example 1)

In a 500 mL flask, the following general formula (III) is added: [Chem. 17] C _n F _2n+1 CH ₂ CH ₂ OCOCH=CH ₂ (III) , the average value of n becomes a mixture of 8 (still, in the mixture) 60 g of compound in which n is 6, 8, 10, 12, 14), 3 g of stearin dimethylamine hydrochloride, 7 g of polyoxyethylene (10 mol) lauryl ether, 20 g of tripropylene glycol, and 158.5 g of water The mixture was stirred and mixed at 45 ° C to form a mixed solution. The mixture was irradiated with ultrasonic waves to emulsifie and disperse the above mixture. Next, 1.5 g of azobis(isobutylphosphonium) 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 fluorine-based polymerization having a polymer concentration of 24% by mass. Dispersion.

(Comparative Example 2)

55 g of stearyl acrylate, 4 g of polyoxyethylene (10 mol) lauryl ether, 5 g of 2-hydroxyethyl acrylate, 3 g of stearyl dimethylamine hydrochloride, 20 g of tripropylene glycol and water 162.75 were added to a 500 mL flask. g, and mixed and stirred at 45 ° C to form a mixed liquid. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 24% by mass. Polymer dispersion.

(Comparative Example 3)

Add 500g of stearyl acrylate to the 500mL flask, polyoxyethylene (10 mol) 4 g of lauryl ether, 5 g of 2-hydroxyethyl acrylate, 7 g of stearyl dimethylamine hydrochloride, 20 g of tripropylene glycol, and 158.75 g of water, and mixed and stirred at 45 ° C to obtain a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 24% by mass. Polymer dispersion.

(Comparative Example 4)

Into a 500 mL flask, 55 g of stearyl acrylate, NOIGENXL-100 (manufactured by Daiichi Kogyo Co., Ltd., polyoxyalkylene branched mercapto ether, HLB=14.7) 2 g, NOIGENXL-60 (First Industrial Pharmaceutical Co., Ltd.) was added. , polyoxyalkylene branched decyl ether, HLB = 12.5) 2g, 2-hydroxyethyl acrylate 5g, stearic acid dimethylamine hydrochloride 3g, tripropylene glycol 20g and water 162.75g, and carried out at 45 ° C Mix and stir to form a mixed solution. The mixture is irradiated with ultrasonic waves to emulsify and disperse the whole monomer. Next, 0.25 g of azobis(isobutylphosphonium) dihydrochloride was added to the mixed solution, and the mixture was subjected to radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer having a polymer concentration of 24% by mass. Polymer dispersion.

Still, the aggregates obtained in Examples 1 to 18 and Comparative Examples 1 to 4 It was confirmed that each polymer in the dispersion liquid was polymerized by gas chromatography (G°C-15APTF, manufactured by Shimadzu Corporation), and 98% or more of all the monomers were polymerized.

For the polymer dispersion obtained above, and using the following The polymer obtained by the method shown was evaluated.

(Evaluation of physical properties of non-fluorinated polymers)

By adding 500 mL of acetone to 50 g of the polymer dispersion obtained in Examples 1 to 18 and Comparative Examples 1 to 4, the polymer was separated from the emulsifier to filter the polymer, and the polymer was dried under reduced pressure at 25 ° C. hour. The obtained polymer was evaluated as follows. The results are shown in Tables 6-9.

(1) Method for measuring melt viscosity

For the polymers of Examples 1 to 18 and Comparative Examples 2 to 4 obtained above, an overhead flow tester CFT-500 (manufactured by Shimadzu Corporation) was attached, and a cylinder (10 mm in length and 1 mm in diameter) was attached. 1 g of polymer was placed inside, kept at 105 ° C for 6 minutes, and 100 kg was added from the plunger. The load of f/cm ² was measured and the melt viscosity at 105 ° C was measured.

(2) Method for measuring weight average molecular weight

The polymer of Examples 1 to 18 and Comparative Examples 2 to 4 obtained above was a GPC apparatus (GPC "HLC-8020" manufactured by Tosoh Co., Ltd.) at a column temperature of 40 ° C and a flow rate of 1.0 ml/min. Under the conditions, the weight average molecular weight in terms of standard polystyrene was measured using tetrahydrofuran as the eluate. In addition, the pipe string system is installed with three Tosoh products under the trade names TSK-GEL G5000HHR, G4000HHR, and G3000HHR.

(Evaluation of storage stability of water repellent composition)

The stability of the polymer dispersion obtained in Examples 1 to 18 or Comparative Examples 1 to 4 at 2 ° C for 2 weeks was evaluated by the following criteria. The results are shown in Tables 6-9.

A: No change in appearance

B: It is confirmed that there is only an oil in the vicinity of the liquid surface, and there is a polymer precipitate on the wall surface of the container.

C: Confirmation of polymer sedimentation, separation, gelation

(evaluation of water repellency of fiber products)

The test was carried out in accordance with the spray method of JIS L 1092 (1998) by setting the shower water temperature to 27 °C. In this test, the dyed polyester 100% cloth or nylon 100% was disposed in the treatment of the polymer dispersions of Examples 1 to 18 or Comparative Examples 1 to 4 diluted with water to a polymer content of 3% by mass. The liquid was subjected to immersion treatment (pickup rate: 60% by mass), and then dried at 130 ° C for 2 minutes, and further heat-treated under the conditions shown in Tables 6 to 9, and the water repellency of the obtained cloth was evaluated. The results were evaluated visually on the following grades. However, when the characteristics are only slightly good, the level is marked as "+", and the characteristics are only slightly inferior, and the level is marked as "-". The results are shown in Tables 6-9.

Water repellency: status

5: No wet on the surface

4: only slightly humidified on the surface

3: Partially wet on the surface

2: showing the moister on the surface

1: showing the wetness on the whole surface

0: Both sides of the watch show complete wetness

(Feature evaluation of fiber products)

The characteristics are 100% of the polyester to be dyed, and the polymer dispersion of Examples 1 to 18 or Comparative Examples 1 to 4 is immersed in a treatment liquid in which the content of the water-diluted polymer is 3% by mass (pickup) After the rate was 60% by mass, the film was dried at 130 ° C for 2 minutes and further heat treated at 170 ° C for 30 seconds. The results were evaluated in five stages of operation as shown below. The results are shown in Tables 6-9.

1: hard ~ 5: soft

(Evaluation of durable water repellency of fiber products)

The test for changing the shower water temperature to 27 ° C was carried out in accordance with the spray method of JIS L 1092 (1998). In this test, the dyed polyester 100% cloth or nylon 100% cloth is used, and the content of the polymer is 3% by mass, UNIKA RESIN 380-K (crosslinking agent, manufactured by Union Chemical Industry Co., Ltd., trimethylol) The content of the melamine resin was 0.3% by mass, and the content of UNIKA CATALYST 3-P (surfactant, manufactured by Union Chemical Industry Co., Ltd., and the amine alcohol hydrochloride) was 0.2% by mass, and Examples 1 to 18 were used. Or the polymer dispersion liquid of Comparative Examples 1 to 4 and the treatment liquid diluted with each of the above-mentioned respective chemicals were immersed (pickup ratio: 60% by mass), and then dried at 130 ° C for 2 minutes, and further heat-treated at 170 ° C for 60 seconds. (L-0), and 10 times (L-10), the water repellency of the cloth after the cleaning by the 103 method of JIS L 0217 (1995) was evaluated in the same manner as the above-described water repellency evaluation method. price. Further, in the case of the nylon 100% cloth, the heat treatment temperature was changed from 170 ° C to 160 ° C, and the evaluation was carried out in the same manner as in the case of the polyester 100% cloth. The results are shown in Tables 6-9.

When the fiber product of the water repellent composition of Examples 1 to 18 was treated, it was confirmed that the water repellency and the durability water repellency were equal to or higher than those in the case of using the conventional fluorine water repellent (Comparative Example 1) even when the heat treatment was not performed. The characteristics are also good. Further, it was confirmed that the storage stability of the composition was also good.

Comparing Example 2 with Example 4, it was confirmed that the weight average molecular weight of the polymer was different even if it was close to the composition of the non-fluoropolymer. When the weight average molecular weight is large, the water repellency is excellent.

The water repellent composition of Comparative Example 2 has been used and is not reactive. The general surfactant of the emulsifier was confirmed to reduce the storage stability of the composition in the same amount of the surfactant amount as in Example 4 using the reactive emulsifier.

The water repellent composition of Comparative Example 3 was compared with Comparative Example 2, In order to increase the storage stability of the composition, when the amount of the emulsification aid (general surfactant) is increased, there is a tendency to reduce the water repellency of the fiber product of the treatment composition.

The water repellent composition of Comparative Example 4 was substituted for reactive emulsification The agent was confirmed to have been used in combination with a general surfactant having HLB in the preferred range of the present invention to carry out emulsion polymerization to reduce the water repellency of the treated fiber product.

From the above, according to the present invention, it is confirmed that storage stability can be provided In addition, when the heat treatment is not performed, sufficient water repellency can be imparted to the fiber product or the like, and a water repellent composition of the water-repellent fiber product having excellent characteristics and water repellency can be obtained.

[Industrial availability]

The water repellent composition of the present invention is particularly effective for use in fibrous products. When the water repellent composition of the present invention is used in a fiber product, since the fiber product is treated with a water repellent composition, it can exhibit sufficiently excellent water repellency even at a low temperature, even if it is sensitive to heat. In fiber or natural fiber, it can also be made to exhibit sufficient water repellency. Further, by using a crosslinking agent in combination or by copolymerizing a reactive monomer, durability water repellency or characteristics can be improved. Further, the water repellent composition of the present invention is low in cost and does not contain a fluorine-containing group, and is useful as a water repellent composition having little adverse effect on the human body or the environment. Moreover, compared with the conventional water-repellent agent, the amount of the surfactant used can be reduced, and it is possible to cope with various fiber processing.

Claims (9)

A water repellent composition comprising a non-fluorine-based polymer containing a constituent unit derived from a (meth) acrylate monomer (A) represented by the following general formula (A-1) And a constituent unit derived from the reactive emulsifier (B), the reactive emulsifier (B) is selected from at least one of the following (B1) to (B3), and (B1) has an HLB of 7 to 18 a compound represented by the general formula (I-1), (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18, and (B3) an alkylene oxide having an addition carbon number of 2 to 4; HLB is a compound of 7 to 18 having a hydroxyl group and a polymerizable unsaturated group; [In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having a carbon number of 12 or more which may have a substituent]; [In the formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkyl group having 1 to 6 carbon atoms, and Y ¹ represents 2 of an alkylene group having a carbon number of 2 to 4; Price base]; In the formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² represents a divalent group having an alkylene group having 2 to 4 carbon atoms] . The water repellent composition according to claim 1, wherein the non-fluoropolymer further contains at least one selected from the group consisting of (C1), (C2), (C3), and (C4) a constituent unit of the first (meth) acrylate monomer (C); (C1) a (meth) acrylate monomer represented by the following general formula (C-1) In the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents a group selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloxy group. The at least one functional group has a monovalent chain hydrocarbon group having 1 to 11 carbon atoms, but the number of (meth)acryloxy groups in the molecule is 2 or less]; (C2) the following general formula (C) -2) indicates a (meth) acrylate monomer [In the formula (C-2), R ⁷ represents hydrogen or a methyl group, and R ⁸ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent]; (C3) the following general formula (C-3) Methacrylate monomer [In the formula (C-3), R ⁹ represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms]; (C4) a (meth) acrylate monomer represented by the following general formula (C-4); [In the formula (C-4), R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents an organic group of a (p+1) valence, and T represents a monovalent organic group having a polymerizable unsaturated group] . A water repellent composition comprising a non-fluorine-based polymer obtained by emulsion polymerization or dispersion polymerization of an emulsion or a dispersion, the emulsion or dispersion comprising the following general formula ( A-1) represents a (meth) acrylate monomer (A) and a reactive emulsifier (B), and the reactive emulsifier (B) is at least one selected from the group consisting of (B1) to (B3) below. (B1) HLB is a compound represented by the following general formula (I-1) of 7 to 18, (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18, and (B3) plus a compound having a carbon number of 2 to 4 and an alkylene oxide having an HLB of 7 to 18 and having a hydroxyl group and a polymerizable unsaturated group; [In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having a carbon number of 12 or more which may have a substituent]; [In the formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkyl group having 1 to 6 carbon atoms, and Y ¹ represents 2 of an alkylene group having a carbon number of 2 to 4; Price base]; In the formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² represents a divalent group having an alkylene group having 2 to 4 carbon atoms] . The water repellent composition according to claim 3, wherein the emulsion or the dispersion further comprises at least one selected from the group consisting of (C1), (C2), (C3), and (C4) (2) (meth) acrylate monomer (C); (C1) (meth) acrylate monomer represented by the following general formula (C-1) In the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents a group selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloxy group. At least one functional group has a monovalent chain hydrocarbon group having 1 to 11 carbon atoms; however, the number of (meth)acryloxy groups in the molecule is 2 or less]; (C2) the following general formula (C) -2) indicates a (meth) acrylate monomer [In the formula (C-2), R ⁷ represents hydrogen or a methyl group, and R ⁸ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent]; (C3) the following general formula (C-3) Methacrylate monomer [In the formula (C-3), R ⁹ represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms]; (C4) a (meth) acrylate monomer represented by the following general formula (C-4); [In the formula (C-4), R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents an organic group of a (p+1) valence, and T represents a monovalent organic group having a polymerizable unsaturated group] . A water-repellent fiber product comprising a fiber product to which a non-fluorine-based polymer is contained, the non-fluorine-based polymer containing a (meth) acrylate monomer derived from the following general formula (A-1) ( The structural unit of A) and the structural unit derived from the reactive emulsifier (B), the reactive emulsifier (B) is selected from at least one of the following (B1) to (B3), and (B1) HLB is The compound represented by the following general formula (I-1) of 7 to 18, (B2) the compound represented by the following general formula (II-1) having an HLB of 7 to 18, and the (B3) addition carbon number of 2 to 4; a compound of an alkylene oxide having a hydroxyl group of 7 to 18 and having a hydroxyl group and a polymerizable unsaturated group; [In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having a carbon number of 12 or more which may have a substituent]; [In the formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkyl group having 1 to 6 carbon atoms, and Y ¹ represents 2 of an alkylene group having a carbon number of 2 to 4; Price base]; In the formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² represents a divalent group having an alkylene group having 2 to 4 carbon atoms] . The water-repellent fibrous product of claim 5, wherein the non-fluorine-based polymer further contains at least one selected from the group consisting of the following (C1), (C2), (C3), and (C4) a constituent unit of the second (meth) acrylate monomer (C); (C1) a (meth) acrylate monomer represented by the following general formula (C-1) In the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents a group selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloxy group. At least one functional group has a monovalent chain hydrocarbon group having 1 to 11 carbon atoms; however, the number of (meth)acryloxy groups in the molecule is 2 or less]; (C2) the following general formula (C) -2) indicates a (meth) acrylate monomer [In the formula (C-2), R ⁷ represents hydrogen or a methyl group, and R ⁸ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent]; (C3) the following general formula (C-3) Methacrylate monomer [In the formula (C-3), R ⁹ represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms]; (C4) a (meth) acrylate monomer represented by the following general formula (C-4); [In the formula (C-4), R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents an organic group of a (p+1) valence, and T represents a monovalent organic group having a polymerizable unsaturated group] . A water-repellent fiber product obtained by a fiber product to which a non-fluorine-based polymer is attached, wherein the emulsion or dispersion is obtained by emulsion polymerization or dispersion polymerization, and the emulsion or dispersion comprises The (meth) acrylate monomer (A) and the reactive emulsifier (B) represented by the following general formula (A-1) are selected from (B1) to (B3). At least one of (B1) HLB is a compound represented by the following general formula (I-1) of 7 to 18, and (B2) is a compound represented by the following general formula (II-1) having an HLB of 7 to 18; B3) a compound having an alkylene oxide having a carbon number of 2 to 4 and having a hydroxyl group and a polymerizable unsaturated group in an HLB of 7 to 18; [In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having a carbon number of 12 or more which may have a substituent]; [In the formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkyl group having 1 to 6 carbon atoms, and Y ¹ represents 2 of an alkylene group having a carbon number of 2 to 4; Price base]; In the formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² represents a divalent group having an alkylene group having 2 to 4 carbon atoms] ; The water-repellent fibrous product of claim 7, wherein the emulsion or the dispersion further comprises at least one selected from the group consisting of (C1), (C2), (C3), and (C4) (2) (meth) acrylate monomer (C); (C1) (meth) acrylate monomer represented by the following general formula (C-1) In the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents a group selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloxy group. At least one functional group has a monovalent chain hydrocarbon group having 1 to 11 carbon atoms; however, the number of (meth)acryloxy groups in the molecule is 2 or less]; (C2) the following general formula (C) -2) indicates a (meth) acrylate monomer [In the formula (C-2), R ⁷ represents hydrogen or a methyl group, and R ⁸ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent]; (C3) the following general formula (C-3) Methacrylate monomer [In the formula (C-3), R ⁹ represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms]; (C4) a (meth) acrylate monomer represented by the following general formula (C-4); [In the formula (C-4), R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents an organic group of a (p+1) valence, and T represents a monovalent organic group having a polymerizable unsaturated group] . A method for producing a water-repellent fibrous product, comprising the step of treating a fibrous product with a treatment liquid comprising the water repellent composition according to any one of claims 1 to 4.